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Coatings for High-Temperature Structural Materials: Trends and Opportunities
Coatings for High-Temperature

Structural Materials
Trends and Opportunities
Committee of Coatings for High-Temperature Structural Materials

National Materials Advisory Board
Commission on Engineering and Technical Systems
National Research Council
NATIONAL ACADEMY PRESS

Washington, D.C. 1996
Copyright National Academy of Sciences. All rights reserved.
ii
NOTICE: The project that is the subject of this report was approved by the Governing Board of the National Research Council, whose mem-
bers are drawn from the councils of the National Academy of Sciences, the National Academy of Engineering, and the Institute of Medicine.
The members of the committee responsible for the report were chosen for their special competencies and with regard for appropriate balance.
This report has been reviewed by a group other than the authors according to procedures approved by a Report Review Committee con-
sisting of members of the National Academy of Sciences, the National Academy of Engineering, and the Institute of Medicine.
The National Academy of Sciences is a private, nonprofit, self-perpetuating society of distinguished scholars engaged in scientific and
engineering research, dedicated to the furtherance of science and technology and to their use for the general welfare. Upon the authority of
the charter granted to it by the Congress in 1863, the Academy has a mandate that requires it to advise the federal government on scientific
and technical matters. Dr. Bruce M. Alberts is president of the National Academy of Sciences.
The National Academy of Engineering was established in 1964, under the charter of the National Academy of Sciences, as a parallel
organization of outstanding engineers. It is autonomous in its administration and in the selection of its members, sharing with the National
Academy of Sciences the responsibility for advising the federal government. The National Academy of Engineering also sponsors engineer-
ing programs aimed at meeting national needs, encourages education and research, and recognizes the superior achievements of engineers.
Dr. Harold Liebowitz is president of the National Academy of Engineering.
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tive, to identify issues of medical care, research, and education. Dr. Kenneth I. Shine is president of the Institute of Medicine.
The National Research Council was organized by the National Academy of Sciences in 1916 to associate the broad community of sci-
ence and technology with the Academy’s purposes of furthering knowledge and advising the federal government. Functioning in accordance
with general policies determined by the Academy, the Council has become the principal operating agency of both the National Academy of
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communities. The Council is administered jointly by both Academies and the Institute of Medicine. Dr. Bruce M. Alberts and Dr. Harold
Liebowitz are chairman and vice chairman, respectively, of the National Research Council.
This study by the National Materials Advisory Board was conducted under Contract No. MDA-972-92-C-0028.
This report is available from the Defense Technical Information Center, Cameron Station, Alexandria, VA 22304-6145.
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ABSTRACT iii
Abstract
This report assesses coatings materials and processes for gas-turbine blades and vanes; determines potential applications
of coatings in high-temperature environments; identifies needs for improved coatings for performance enhancements, design
considerations, and fabrication processes; assesses durability of advanced coating systems in potential service environments;
and discusses required inspection, repair, and maintenance methods. Promising areas for research and development of
materials and processes for improved coating systems and approaches for increased standardization of coatings are identified,
with an emphasis on materials and processes with the potential for either improving performance, quality, or reproducibility
or significantly reducing manufacturing costs.

ABSTRACT iv

COMMITTEE ON COATINGS FOR HIGH-TEMPERATURE STRUCTURAL

MATERIALS
ROBERT V. HILLERY (chair), GE Aircraft Engines, Cincinnati, Ohio

NEIL BARTLETT, University of California, Berkeley
HENRY L. BERNSTEIN, Southwest Research Institute, San Antonio, Texas
ROBERT F. DAVIS, North Carolina State University, Raleigh
HERBERT HERMAN, State University of New York, Stony Brook, New York
LULU L. HSU, Solar Turbines, San Diego, California
WEN L. HSU, Sandia National Laboratories, Livermore, California
JOHN C. MURPHY, Johns Hopkins University, Laurel, Maryland
ROBERT A. RAPP, Ohio State University, Columbus
JEFFERY S. SMITH, Howmet Corporation, Whitehall, Michigan
JOHN STRINGER, Electric Power Research Institute, Palo Alto, California
National Materials Advisory Board Staff

ROBERT M. EHRENREICH, Senior Program Officer
CHARLIE HACH, Program Officer
JACK HUGHES, Research Associate
AIDA C. NEEL, Senior Project Assistant
ROBERT E. SCHAFRIK, NMAB Director
ROBERT SPRAGUE, Consultant
JILL WILSON, Program Officer
Technical Advisors
WILLIAM J. BRINDLEY, NASA Lewis Research Center, Cleveland, Ohio
STANLEY J. DAPKUNAS, National Institute of Standards and Technology, Gaithersburg, Maryland
Government Liasion Representatives

WILLIAM BARKER, ARPA, Arlington, Virginia
NORMAN GEYER, Wright-Patterson Air Force Base, Ohio
DAWN MIGLIACCI, Naval Air Warfare Center, Trenton, New Jersey
WILLIAM PARKS, U.S. Department of Energy, Washington, D.C.
ROBERT R. REEBER, Army Research Office, Research Triangle Park, North Carolina

vi
NATIONAL MATERIALS ADVISORY BOARD
ROBERT A. LAUDISE (chair), Lucent Technologies, Inc., Murray Hill, New Jersey
G.J. (REZA) ABBASCHIAN, University of Florida, Gainesville
JAN D. ACHENBACH, Northwestern University, Evanston, Illinois
MICHAEL I. BASKES, Sandia-Livermore National Laboratory, Livermore, California
I. MELVIN BERNSTEIN, Tufts University, Medford, Massachusetts
JOHN V. BUSCH, IBIS Associates, Inc., Wellesley, Massachusetts
HARRY E. COOK, University of Illinois, Urbana
EDWARD C. DOWLING, Cyprus AMAX Minerals Company, Englewood, Colorado
ROBERT EAGAN, Sandia National Laboratories, Albuquerque, New Mexico
ANTHONY G. EVANS, Harvard University, Cambridge, Massachusetts
CAROLYN HANSSON, University of Waterloo, Waterloo, Ontario, Canada
MICHAEL JAFFE, Hoechst Celanese Research Division, Summit, New Jersey
LIONEL C. KIMERLING, Massachusetts Institute of Technology, Cambridge
RICHARD S. MULLER, University of California, Berkeley
ELSA REICHMANIS, Lucent Technologies, Inc., Murray Hill, New Jersey
EDGAR A. STARKE, University of Virginia, Charlottesville
KATHLEEN C. TAYLOR, General Motors Corporation, Warren, Michigan
JAMES WAGNER, The Johns Hopkins University, Baltimore, Maryland
JOSEPH WIRTH, Raychem Corporation, Menlo Park, California
ROBERT E. SCHAFRIK, Director

ACKNOWLEDGMENTS vii
Acknowledgments
A great deal of work has gone into this study from its inception to the finished product. The committee is grateful for all
the help it has received and expresses thanks to everyone who has participated. Without the patience and support provided by
many individuals and organizations, this report could never have been completed.
The committee is grateful to those people who took time to brief the committee on the latest developments in coatings
for high-temperature structural materials. The information and ideas from these briefings were essential to the study.
Briefings were presented by Steve Balsone, Wright-Patterson Air Force Base; Andy Culbertson, Naval Air Warfare Center
Trenton; Jack Devan, Oak Ridge National Laboratory; Dick Novak, Engineered Coatings; Randy Sands, Naval Air Warfare
Center; Fred Soechting, Pratt & Whitney; Joseph Stephens, NASA Lewis Research Center; and Sharon Vukelich, Wright-
Patterson Air Force Base.
The staff of the Southwest Research Institute (SWRI) did an excellent job of hosting one of the committee meetings, and
the committee thanks Martin Goland, Henry Bernstein, and the SWRI staff for providing a tour of the facilities and
accommodating the many needs of the meeting.
In particular, the committee thanks William Brindley of the NASA Lewis Research Center for making information
available to the staff. The committee also thanks Stanley Dapkunas of the National Institute of Standards and Technology.
Their support as technical advisors to the committee was invaluable.
The government liaisons who served this committee were also of enormous value. The committee thanks William
Barker of ARPA, Dawn Migliacci of the Naval Air Warfare Center, William Parks of the U.S. Department of Energy, and
Robert Reeber of the Army Research Office.
The chair of the committee thanks the members for their dedication and patience during the course of this study. This
report could never have been completed without the diligence and goodwill of the members.
The committee thanks the staff of the National Materials Advisory Board, almost all of whom seemed to have been
involved in the study at one time or another. Three program officers helped guide the study. In particular, the committee
thanks Robert Ehrenreich for finishing the study. Tom Munns initiated the project and deserves thanks. Jill Wilson's support
and guidance during the course of the study is greatly appreciated by the committee, as is Robert Sprague's, whose ideas as a
consultant helped shape the report. Charles Hach and Jack Hughes were invaluable in the latter stages of the report. The
committee also thanks Robert Schafrik for his support and direction along the way. Finally, the committee gratefully
acknowledges the support of Aida C. Neel, senior project assistant.

ACKNOWLEDGMENTS viii

PREFACE ix
Preface
The U.S. Department of Defense and the National Aeronautics and Space Administration requested that the National
Research Council conduct a study and provide recommendations on future research and development needs for high-
temperature coatings systems. This report represents the work of the Committee on Coatings for High-Temperature Structural
Materials, established by the National Research Council for this purpose.
Performance improvements in high-temperature mechanical systems have resulted in increasingly severe operating
environments for high-temperature structural materials, particularly in gas turbines. This has sparked an increased demand for
more reliable coatings that possess predictable failure mechanisms, improve the performance of structural materials, and
extend the operating range of applications. With this background, the following objectives were outlined for this study:
• assess the state of the art of coatings materials and processes
• identify potential applications for coatings in high-temperature environments
• identify needs for improved coatings for performance enhancements, design considerations, and fabrication processes
• assess durability of advanced coating systems in expected service environments
• identify required inspection, repair, and maintenance methods
• recommend promising areas for materials and process research and development for improved coating systems and
identify approaches to increased coating standardization
To address these objectives, the committee considered (1) propulsion systems for commercial and military aircraft and
their marine and industrial derivatives and (2) land-based turbines for power generation and mechanical drives (excluding
automotive, diesel engines, and space applications). The committee directed its efforts toward the hot section (combustor and
turbine) of these gas-turbine systems, because this represents the most significant materials and coating challenges. To focus
the study further, the committee considered a wide range of application and technology areas that might be covered under this
broad charter and identified those that would be reviewed in detail. The intent was to concentrate on the materials systems
and degradation modes in the hottest section of the identified power-generation systems and to consider the technology and
application implications for coatings systems under these most severe conditions. A primary focus was on the needs for
advanced machines under development by the U.S. Department of Energy, the U.S. Department of Defense, and the National
Aeronautics and Space Administration sponsorship. This deliberation resulted in the list shown in table P-l, which defines the
study focus, the areas not considered, and the areas that were only referenced by association with the primary focus.
Through a series of briefings from industry and government experts, the committee reviewed current coating systems,
newly developed coating systems, and their implementation in products over the next five to eight years. To evaluate coating
needs beyond this time frame, the committee reviewed the substrate materials (e.g., ceramics and intermetallics) being
considered for future engine designs. The committee recognized that defining needs for many future systems would currently
lack clarity, but a need was perceived to anticipate any fundamental changes that may demand longer-range research, process
development, or manufacturing innovations.
This report reviews the state of the art for coating systems based on the following approach. First, the application needs
were identified and a description of the domain of use was developed. Second, the environment that currently exists and the
substrate materials that are now used in the hot section of gas-turbine engines were examined. This, in turn, led to a more
complete definition of the coatings systems required. Third, the application processes, the industrial base, and the repair and
overhaul requirements were discussed and the support capabilities (e.g., modeling, testing, and nondestructive evaluation)
were assessed. This review provided a baseline for discussion of future trends and indicated how U.S. industry, government,
and academia are planning to address the requirements of advanced propulsion systems.
To determine materials and coatings needs, advanced systems were assessed. The assessments on these advanced
systems were obtained through presentations and information provided by the program managers for three major

PREFACE x
TABLE P-1 Committee Focus

Focus Associated/Referenced Excluded
Industrial, marine, power generation, Land-based systems Auto, diesel engines, space
aircraft engine
Structural materials superalloys (Ni, Co) Refractories Titanium alloys
intermetallics composites (IMC, CMC)
monolithic ceramics
700°C + temperatures (to capture Type II
hot corrosion)
Oxidation, corrosion, erosion Seal systems degradation caused by the Tribological wear
service environment
Gas-path coatings and clearance coatings Gas-path seals
Combustor, transition piece, high-pressure Off-line combustion Compressor, fan
turbine, power turbine
Diffusion coatings, overlays, TBC, surface Functionally graded materials, claddings, Low observable coatings, fiber coatings
modifications vitreous coatings
Thermal spray, CVD, PVD, advanced Plating, C/S/N/O-resistant coatings
processes
Operating environment (air, fuel, water, Combustion, emissions
particulates)
Environmental impact: manufacturing,
service, overhaul
Repair considerations Lower-temperature coatings affected (e.g., Repairs involving brazing, welding, etc.
impact-resistant coatings)
Nondestructive evaluation (NDE)
Standards and standardization
Databases, modeling, engine condition Controls, intelligent processing of materials
sensors
Systems design (coating/substrate Material systems that might reduce or
integration): advanced concepts eliminate need for high-temperature
coatings (e.g., Lamalloy)
Customer-DOD, DOE, NASA, original Airframe manufacturers, airlines, utilities
equipment manufacturers, suppliers

PREFACE xi
TABLE P-2 Primary Performance Goals for Advanced Engine Systems

Advanced Engine System Requirements
Integrated High-Performance Turbine Engine Technology Cold section (fan and compressor): 2-3 times specific strength for
(IHPTET) materials 650-1000°C operating temperature
Hot section (the focus of this report; includes the combustor,
turbine, augmenter, and nozzle subsytems): 3-5 times specific
strength for materials 1650-2200°C with advanced cooling 1550°C
uncooled
Nonstructural (bearing and lubes) up to 825°C
High-Speed Civil Transport (HSCT) Range: 2 times greater than the Concorde Payload: 3 times greater
than the Concorde Economics: 8 times greater than the Concorde
Environmental emissions: 8 times lower than the Concorde Noise:
3 times quieter than the Concorde
Advanced Turbine Systems (ATS) High efficiency, clean gas-turbine systems initially based on
natural gas; adaptable to coal- or biomass-derived fuels
Power generation: >60% system efficiency
Industrial systems: >15% improvement
Environmental: 8 ppm NOX emissions; CO and HC < 20 ppm
Cost competitive: 10% reduction in busbar cost of electricity
government-sponsored materials efforts representing future military, commercial, and power-generation needs:
• Integrated High-Performance Turbine Engine Technology—advanced military systems
• High-Speed Civil Transport—aimed at the advanced supersonic commercial market
• Advanced Turbine Systems—advanced utility and industrial power generation
Table P-2 summarizes the primary performance goals for each of these advanced systems. For each case, the committee
obtained information on mission profile; systems needs; and specifics on time, temperature, and environmental requirements
for materials in the propulsion system. This provided a perspective on what were the ultimate materials needs for propulsion
systems reaching maturity early in the next century. In all cases, the goals underscored the demand for materials that can
withstand significantly higher operating temperatures and service life than today's state-of-the-art devices. The reviews also
provided information on significant changes that might be required as a result of new regulatory requirements, such as those
that might stipulate permissible emissions from future propulsion systems. In addition, these reviews showed those areas
common to aircraft engines and power-generation machines and changes to this commonality that might be demanded by
derivative machines as, for example, the increased use of air to combat NOX in the combustor of land-based electric utility
turbines. Some fundamental differences exist between aircraft and land-based systems that might cause a divergence in
materials (and coatings) technologies. For instance, land-based systems are less affected by weight and can be supplemented
with auxiliary systems, such as air supplies, steam supplies, or heat exchangers. The potential use of alternative fuels in
nonaircraft systems might be another divergence affecting coatings type. Both aircraft and land-based gas turbines are
moving toward higher temperatures and longer service-time requirements; this trend is causing increased emphasis on
coatings needs. Finally, the committee heard presentations on the design requirements for coating systems and the engineered
materials efforts that may have a bearing on the development and application of advanced coating systems.
In reviewing these briefings, the committee considered the following key questions:
• Can the goals for the advanced systems be achieved simply by an evolution from today's materials?
• Are programs and efforts in place to address the key potential barriers?

PREFACE xii
• Are there additional recommendations that can be made to enhance the chances for success in any of the key areas?
The committee then considered future opportunities for developing improved coatings by virtue of evolutionary
development and by way of innovative concepts. The committee developed several innovative concepts for advanced coating
systems and suggested how a wide variety of ideas could be integrated into coatings development and application advances.
The members of the committee continually posed several key questions during their considerations of innovative approaches:
• Are there concepts that have not been explored or that should be re-evaluated in light of recent knowledge?
• Are there ideas or knowledge bases in other industries that can revolutionize thinking in the gas-turbine engine coating
industry?
• Are there ideas that can shorten the development cycle of existing efforts and thereby enhance the chance for success?
• What are the latest developments in modeling, intelligent process manufacturing, and smart materials, and can these
technologies be focused in the coatings area?
• Are there new testing techniques that would be required and will new industry standards and procedures have to be
defined?
Finally, the committee provides its conclusions and recommendations for the future as well as a bibliography of cited
references and available texts.
Robert V. Hillery, chair

Committee on Coatings for High- Temperature Structural Materials

CONTENTS xiii
Contents
EXECUTIVE SUMMARY 1
1 INTRODUCTION 8
2 APPLICATION NEEDS AND TRENDS 10

Application Needs 10
Current Component Design and Base Materials 13
Advanced Materials for Engine Components 13
3 MATERIALS AND PROCESSES 19

Coatings for High-Temperature Structures 19
Coating Processes 22
Coating Process Control 24
Summary 24
4 FAILURE MODES 26
Degradation Mechanisms of Structural Materials 26
Degradation Mechanisms of Coatings 26
A Case Study: Degradation of Thermal Barrier Coatings 30
Research Opportunities 32
5 ENGINEERING CONSIDERATIONS 34
Compatibility of Coatings with Structural Materials 34
Component Coatability 36
Other Engineering Considerations 36
Concurrent Coating Development 38
6 REFURBISHMENT OF COATED STRUCTURE 39

Factors Affecting Component Life 39
Repair of High-Temperature Coatings 40
Standard Designations for Coatings 41
Nondestructive Evaluation 41
7 NEAR-TERM TRENDS AND OPPORTUNITIES 43

Thermal Barrier Coating Development 43
Coating Processes 44
8 LONG-TERM OPPORTUNITIES AND INNOVATIVE SYSTEMS 46

Innovative Coating Architectures 46
Other Innovative Concepts 48

CONTENTS xiv
REFERENCES 51
APPENDICES
A TESTING AND STANDARDS 57
B RADIATION TRANSPORT IN THERMAL BARRIER COATINGS 65
C SURVEY OF NONDESTRUCTIVE EVALUATION METHODS 67
D MODELING OF COATING DEGRADATION 72
E MANUFACTURING TECHNOLOGIES OF COATING PROCESSES 78
F EXAMPLE OF A COATING DESIGNATION SYSTEM 83
G BIOGRAPHICAL SKETCHES OF COMMITTEE MEMBERS 84

LIST OF FIGURES AND TABLES xv
List of Figures and Tables
FIGURES
1-1 Typical ranges of a coating property compared with advanced engine requirements for a property 9
2-1 Cross section of a typical modern gas-turbine engine 10
2-2 Overview of transportation gas-turbine use 11
2-3 Overview of power-generation and mechanical-drive gas-turbine use 11
2-4 Approximate increases in firing temperature capabilities from 1980 to 2010 12
2-5 Turbine blade cooling methods 15
3-1 Coating compositions as related to oxidation and corrosion resistance 21
3-2 Schematic showing the benefit of development and deployment of manufacturing process control for 25
high-temperature coatings
4-1 Types of high-temperature attack for metallic coatings (aluminide, chromide, MCrAlY, etc.) on nickel- 28
base superalloys with approximate temperature regimes and severity of attack
4-2 Micrograph of service-exposed CoCrAlY overlay coatings showing internal oxidation of coating and 29
base metal
4-3 Comparison of the microstructure of EB-PVD and plasma-sprayed TBCs 30
4-4 Photomicrograph of a plasma-sprayed TBC 31
4-5 Photomicrographs of EB-PVD TBCs before and after failure 32
5-1 Tradeoffs between first cost and operating cost 37
TABLES
P-1 Committee Focus x
P-2 Primary Performance Goals for Advanced Engine Systems, xi
2-1 Typical Duty Cycles for Various Gas-Turbine Engines 12
2-2 Nickel-and Cobalt-Base Alloys Used in Land-Based and Aircraft Gas Turbines 14
2-3 Properties of Ceramic Materials that are Candidates for Hot-Section Use 16
2-4 Selected Properties of High-Temperature-Capable Intermetallics Compared to a Conventionally Cast and a 17
Single-Crystal Superalloy
2-5 Properties of Refractory Metals and an Alloy Compared to B 1900 Nickel-Base Superalloy 18
3-1 Coating Functions and Coating Materials Characteristics 19
3-2 Types of Coatings Used in Hot-Section Components 20
3-3 Generic Information on Coating Types Used in Superalloy Hot-Section Components 21
3-4 Summary of the Benefits and Limitations of the Atomistic and Particulate Deposition Methods 22
4-1 Environmentally Induced High-Temperature Structural Material Failure Modes 27
4-2 Environmentally Induced High-Temperature Coating Failure Modes 28
6-1 Survey of Nondestructive Evaluation Techniques 42

ACRONYMS xvi
Acronyms
AISI American Iron and Steel Institute

ASM American Society for Materials
ASME American Society of Mechanical Engineers
ASTM American Society for Testing and Materials
ATS Advanced Turbine Systems
CTE coefficient of thermal expansion
CVD chemical vapor deposition
DOD U.S. Department of Defense
DOE U.S. Department of Energy
EB-PVD electron-beam physical vapor deposition
FGM functionally graded materials
HSCT High-Speed Civil Transport
HVAF high-velocity air fuel
HVOF high-velocity oxy fuel
IHPTET Integrated High-Performance Turbine Engine Technology program
ISO International Standards Organization
LPPS low-pressure plasma spraying
NASA National Aeronautics and Space Administration
NDE nondestructive evaluation
PVD physical vapor deposition
SNECMA Société National d'Etude et de Construcion de Moteurs d'Aviation
STEP Standard for the Exchange of Product
SVPA SNECMA vapor phase aluminizing
TBC thermal barrier coating

EXECUTIVE SUMMARY 1
Executive Summary
Traditionally, coatings and substrates have developed independently. Coatings have also traditionally done an excellent
job of doing what they were designed to do: prolong the life of turbine engines by protecting component parts from oxidation
and corrosion, erosion by particulate debris, and other potential hazards. Engineers now face a challenge, however. With new
technologies creating a broad range of heat-resistant materials, turbines now operate at temperatures that are significantly
higher than a decade ago. The new demands on turbine coatings and substrates make it imperative that the two be designed
interdependently; each must go hand-in-hand into the regime of ever-increasing temperatures. In this harsh environment, a
failure in one quickly leads to a failure in the other. Indeed, in some proposed designs, the coating and substrate form a
continuum, literally blurring the boundary between the surface deposit and the material it coats.
In future years, turbine engines will have the potential to reach new heights of efficiency and service life. But to keep
pace, coating technologists will have to continue moving away from the traditional way of designing coatings. The bottom
line is that coatings must be integrated into the total component design taking into full consideration the alloy composition,
casting process, and cooling scheme.
The efficiency of gas turbines, whether for industrial power generation, marine applications, or aircraft propulsion, has
steadily improved for years. These advances have come about, in large part, because the means have been found to operate
the gas-generator portion of the engine at increasingly higher temperatures. The need for greater performance from advanced
turbine engines will continue, requiring even higher operating efficiencies, longer operating lifetimes, and reduced emissions.
A large share of these improved operating efficiencies will result from still higher operating temperatures. Better engine
durability would normally require lower operating temperatures, more cooling of the hot structure, or structural materials
possessing inherently greater temperature performance. Since the first two options cause a penalty in operating efficiency, the
last approach is preferred. Achieving greater temperature performance has made imperative the use of surface protection to
extend component life and the concurrent development of the advanced structural materials and the coatings that protect the
structure from environmental degradation.
This report assesses the state of the art of turbine coatings, identifies applications for coated high-temperature structures,
identifies needs for improved coating technologies, assesses durability of coatings in expected service environments,
identifies coating life-cycle considerations, suggests innovative directions for coating systems, and presents recommendations
for coating technologies. The report concludes that coatings have become an enabling technology for advanced engines; the
development of coatings and their processes must keep pace with the broader materials and systems requirements.
TRENDS
High-Temperature Coatings Design

In the past, high-temperature coatings were selected predominantly after the component design was finalized. Current
designs require that the substrate (typically a nickel-base superalloy) have sufficient inherent resistance to the degradation
mechanisms to prevent catastrophic reduction in service lifetime in the event of coating failure. Since the materials
considered for future substrates may possess less inherent environmental resistance at higher temperatures, the importance of
coatings in achieving performance will continue to grow. In future turbine designs, coatings will be increasingly viewed as an
integral portion of the design process to meet the high demands for system performance.
High-Temperature Coating Types

Although many types of high-temperature coatings are currently in use, they generally fall into one of three types:
aluminide, chromide, and MCrAlY.1 The family of coatings that insulate the substrate from the heat of the gas path (i.e.,
thermal barrier coatings [TBCs]) is increasing in importance as they begin to be used for performance benefits. TBCs are
1 MCrAlY is a type of metallic coating in which M is a metal, usually cobalt, nickel, or a combination of the two; Cris chromium; Al is
aluminum; and Y is yttrium.

EXECUTIVE SUMMARY 2
ceramic coatings (e.g., partially stabilized zirconia) that are applied to an oxidation-resistant bondcoat, typically a MCrAlY or
aluminide.
Processes for Applying Coatings

A wide variety of processes are used to apply coatings, although they rely on one of three general methods: physical
vapor deposition, chemical vapor deposition, and thermal spray. These processes deposit a wide range of coatings between
the extremes of diffusion coatings (i.e., the deposited elements are interdiffused with the substrate during the coating process)
and overlay coatings (i.e., the deposited elements have limited interdiffusion with the substrate). Diffusion coatings are well
bonded to the substrate but have limited compositional flexibility; their usefulness is strongly dependent on substrate
chemistry. Overlay coatings are typically well bonded and have broad compositional flexibility; however, they are more
expensive and thicker than diffusion coatings. TBCs are overlay coatings and as such can be deposited on a variety of
substrates. The main difficulty with TBCs is that the abrupt change in composition and properties at the interface tends to
promote ceramic layer spallation.
Electron-beam physical vapor deposition is often favored over plasma deposition for TBCs on turbine airfoils since it
applies a smooth surface of better aerodynamic quality with less interference to cooling holes. However, the widely used
plasma-spray process has benefits, including a lower application cost, an ability to coat a greater diversity of components
with a wider composition range, and a large installed equipment base.
Coating developers must not only find a suitable coating for an application but must also develop the necessary
application processes with on-line control so that the resultant composition and microstructure of the coating is highly
reproducible and within the performance limits needed for the service requirements. Developing the relationship of the
process-to-product performance must also be a priority, near-term endeavor for advanced coating systems.
Degradation Modes
A primary consideration in selecting a coating system is determining if it provides adequate protection against the active,
in-service, environmentally induced degradation mechanism(s) experienced by the component. These degradation modes are
a function of the operating conditions and the component base materials. The degradation modes common to superalloy hot-
section components include—to varying degrees—low-cycle thermomechanical fatigue, foreign object damage, high-cycle
fatigue, high-temperature oxidation, hot corrosion, and creep.
Because of the use of thin walls and compositional design for highest strength, aircraft turbine blades with internal
cooling passages have historically had insufficient high-temperature oxidation resistance to meet required lifetimes without
the use of a coating. Coatings have been used in these circumstances to extend overhaul limits and useful life of the
component. Although the latest generation of single-crystal blades has excellent oxidation resistance compared with
conventionally cast industrial engine blades and aircraft gas-turbine blades with moderate to high chromium contents, the
blades have less tolerance for hot corrosion once the coating has been breached. Industrial gas-turbine blades, which use thick
walls and lower-strength alloys with higher corrosion resistance, generally have significant service life after the coating is
breached.
During service, coatings degrade at two fronts: the coating/gas-path interface and the coating/substrate interface.
Deterioration of the coating surface at the coating/gas-path interface is a consequence of environmental degradation
mechanisms. Solid-state diffusion at the coating/substrate interface occurs at high temperatures, causing compositional
changes at this internal interface that can compromise substrate properties and deplete the coating of critical species. In the
worst case, interdiffusion leading to the precipitation of brittle phases can cause a severe loss of fatigue resistance.
Engineering Considerations
Given that a coating system is required and that one has been identified that provides environmental protection, six
significant engineering factors must be evaluated.
1. Chemical (metallurgical) compatibility. The coating must be relatively stable with respect to the substrate material to
avoid excessive interdiffusion and chemical reactions during the service lifetime. An unstable coating can lead to
premature degradation of both the coating and the substrate through lower melting temperatures, lower creep
resistance, embrittlement, etc.
2. Coating process compatibility. The coating material may be completely compatible with the component, but the
coating process may not be compatible. This would usually occur when process conditions require high temperatures
or special precoating surface treatments.
3. Mechanical compatibility. Coatings resistant to oxidation and corrosion maintain their protectiveness only if they
remain adherent and free from through-thickness cracks. Important considerations include close match of the
coefficient of thermal expansion (CTE) of the coating with the substrate,

EXECUTIVE SUMMARY 3
strain accommodation mechanisms within the coating, coating cohesion, and coating adhesion. CTE match is the
most important factor, closely followed by the need for strain tolerance in the coating.
4. Component coatability. The ability to deposit a coating on the required surface is a function of the geometry and size
of the component, as well as the capability of the coating process. Accessibility of the surface is a consideration. For
example, some processes are line-of-sight and thus cannot coat internal passages. Size of the component is important
because some processes must be done inside an enclosed tank or reactor. The ability to apply a uniform coating must
be evaluated, particularly at edges, inside corners, and for irregular part contours. The change in part dimensions and
surface characteristics because of the coating must also be taken into account.
5. Contaminants in air and fuel (and water and steam for industrial turbines). Contaminants can combine in the hot
section to produce corrosion, erosion, and deposition under certain temperature and pressure conditions; they
contribute to accelerated degradation of high-temperature components. Limits on allowable concentrations must be
established in order to assure the effectiveness of a coating system.
6. Turbine emission levels. Gas turbines can produce harmful emissions as part of the combustion process. As
combustion technology has improved, emission levels have been reduced. These emissions include nitrogen oxides
(NO and NO2, commonly called NOX), carbon monoxide (CO), unburned hydrocarbons, sulfur oxides (mainly SO2
and SO3), and particulate matter. Coatings affect emissions primarily by reducing the need for cooling air.
In addition to the factors pertaining to the selection of an appropriate coating system, the following general engineering
considerations are also important:
• Available databases of coating and coated structure properties. Traditionally, engineering property data for high-
temperature coatings are generated after the mechanical properties of the uncoated substrate have been well
characterized. These data are generally specific to the application domain and process conditions and are usually
proprietary. Long-term data (i.e., performance of coated structures for durations greater than 50,000 hours) is sparse and
related to old technologies.
• Coating standardization. Generally, each component in the hot section of the engine has a particular coating system
optimized for the prevailing conditions. Greater consideration should be given to optimizing a coating system for many
components because of the wide variety of alloys and component systems.
Life-Cycle Factors
Hot-section structures are designed to operate at the highest possible temperatures and stresses in order to maximize
performance. As a consequence, these structures continuously degrade during service. The rate at which this degradation
occurs is crucial to the function of the component and, ultimately, to the performance and longevity of the gas turbine.
The role of the hot-section coating is to protect the substrate from the gas-path environment in order to meet
performance objectives, as manifested in the time between overhauls or the designated service. Component refurbishment
involves the economical and timely restoration of part integrity.
The types of repairs allowed to coated structures are dictated first by safety and reliability and second by economic
benefit. Repairs therefore vary greatly depending on the type of component to be refurbished. Although the replacement of
the coating is generally a small portion of the overall repair, it can be critical to meeting the intended life of the component
after it is returned to service. The wide variety of coating systems and the lack of standard designations adds complexity to
the logistical task of maintaining an engine's coated structure complex. This task will only become more difficult as advanced
coatings find their way into service.
In the past, coatings had to be capable of being removed and reapplied. This may not continue to be a requirement for
industrial turbines. If a new coating could allow higher-temperature operation (for increased efficiency), the savings in fuel
costs could possibly outweigh the extra expense of purchasing new parts versus repairing old parts. The future trends for
aircraft engine repairs will tend to parallel those of the industrial turbines with the further complication of thinner walls and
more sophisticated cooling passages. Thinner walls in advanced components may preclude any stripping of the prior coating,
potentially leading to a nonrepairable part, as is the case with many of the current turboprop and turboshaft high-pressure
turbine blades.
NEAR-TERM OPPORTUNITIES
Concurrent Development of High-Temperature Coatings and Substrate Materials

Coating and substrate development are increasingly done concurrently because the coating and the substrate are
becoming, from all the major life-cycle considerations

EXECUTIVE SUMMARY 4
(e.g. design, manufacturing, and product support), an integral entity. This concurrent development applies to the current
generation of MCrAlY coatings and, notably, to the emerging TBC technologies.
The current generation of MCrAlY coatings, as well as the emerging TBC technologies, would benefit significantly
from advances in process control. Both types of coatings are deposited by similar processes, and improvements will enhance
the performance of both coating types. Improved on-line control should be developed to ensure that the resultant behavior of
the coated structure is highly reproducible and within the performance limits needed for the service requirements.
Process control cannot be achieved, however, without understanding the relationship of the process to product
performance. Development of such knowledge must be a near-term priority for advanced coatings. While engine tests do not
necessarily provide data on individual processes, they are necessary to provide an overall qualification for a new coating
system.
The similarities in coatings needs for power generation and aircraft engines are more significant than their differences.
The view on traditional materials held that power-generation machines derive their benefits from the aircraft engine
technology. As industry, government, and academic cooperation and consortia in materials development become more
prevalent, and to the extent that the development of new coatings is done jointly among manufacturers and suppliers, there
will be a move to even more similar coatings in the marketplace.
Oxidation and Hot-Corrosion-Resistant Coating Development

The demands on coatings have evolved since coatings were first applied to gas-turbine airfoils in the 1950s. Coatings
have historically been developed to provide protection against oxidation and hot corrosion. Oxidation-resistant coatings
typically are either aluminide coatings or overlay coatings with high aluminum activity that form an adherent alumina scale.
Hot-corrosion-resistant coatings also rely on alumina as the protective scale, but in addition generally contain higher levels of
chromium to ameliorate the effects of sulfur. Incremental developments to improve the durability of oxidation and hot-
corrosion-resistant coatings for current generation engines will be made by (1) chemistry modifications to both diffusion
aluminide and overlay MCrAlY systems and (2) more stringent control of undesirable elements in both the substrate alloys
and the coatings.
The potential for higher-temperature use for superalloys is limited by their melting points. Thus, alternative component
materials are being investigated to fill the higher-temperature roles. These materials generally fall into three classes:
ceramics, intermetallics, and refractory metals. These materials significantly differ from superalloys in physical, chemical,
and mechanical properties but will still depend on coatings to protect against environmental degradation. Many of these
emerging materials, in their current form, are much less tolerant of flaws and failure in their coatings than the superalloys.
Therefore, coating of these materials presents significant challenges.
Thermal Barrier Coating Development

TBCs reduce the severity of thermal transients and lower the substrate temperature, enhancing the thermal fatigue and
creep capabilities of coated components. In addition, although TBCs do not provide significant reduction in oxygen transport
to the substrate, the lower component temperature can lead to a reduction in oxidation and hot corrosion.
TBCs are finding increased application in overall component design. Over the past 25 years, cooling technology has
contributed roughly 370°C (700°F) (from solid blades to advanced film cooling) in turbine temperature capability; further
advances may be achieved with even more sophisticated cooling schemes. Superalloy material and processing advances
(from equiaxed crystalline structure to third-generation single crystal) have added approximately 120°C (250°F). However,
superalloys now operate in some applications at 90 percent of their melting point. TBCs have the potential to reduce substrate
temperatures by 110°C (200°F) or more, even with current production methods.
Current knowledge of TBC durability and thermal performance is primarily in the form of empirical data. Surprisingly
little is understood about TBCs in the critical areas of radiative heat transfer, thermal conductivity and emissivity, and
fundamental physical and mechanical properties (i.e., fatigue, monotonic properties, or time-dependent properties). For
example, until recently, the energy transport process in TBCs has been characterized by an effective thermal conductivity
without regard to the relative contributions of radiation and true conduction.
Research is required to enhance understanding of TBC behavior (and thereby improve TBC performance) as well as to
provide reliable information for quantitative modeling. To determine the relative importance of radiative and conductive
transport in TBCs, a number of factors affecting these two thermal energy transport processes must be considered. Attention
should be given to understanding the mechanisms of energy transport in TBCs. Knowledge of the relative importance of
these mechanisms will guide research strategies aimed at reducing energy transport rates.
Reliability is a critical design factor that is in need of further development if TBCs are to be fully exploited to increase
turbine efficiency. TBCs fail as a result of erosion, impact damage, interfacial oxidation of the bondcoat, or
thermomechanical strain at the ceramic/metal interface. These factors and process variability combine to give current

EXECUTIVE SUMMARY 5
generation TBCs wide variability in service life. The lack of reliability, more than any other design factor, has slowed the
introduction of these coatings for turbines. Improved understanding of interfacial behavior is required to control coating
properties and predict performance. A more compatible and oxidation-resistant bond between the TBC and either the
metallic substrate or the bondcoat requires continued near-term emphasis. The processes by which TBCs are currently
applied, namely plasma spray and physical vapor deposition, will likely continue to be the major manufacturing methods.
Analytical Methods and Models

Coating producers and users need data and advanced analytical models. Examples include data on long-term
thermodynamic and structural stability, generic process models, and life-prediction models. Appropriate combinations of
methods must allow measurement, on the scale of the coating (which is from 1 to 30 mil), of specific materials properties
such as adhesion, fracture toughness, thermal conductivity, and elastic modulus. The availability of such methods can provide
the basis of standard test methods for coating assessment.
The coating industry needs precompetitive2 research that, particularly for TBCs, identifies critical properties and the
scale on which they are relevant. This research would provide the basis for developing standard procedures for measuring
and comparing properties of coating systems as well as providing data required for use in performance models (e.g.,
methodologies for measurement of thermal conductivity, interfacial adhesion, and microstructural characterization).
Since future engines will rely heavily on coatings to protect hot-section components, accurate models will become
essential to describe a number of coatings-related requirements, particularly:
• key attributes of the manufacturing process (e.g., microstructure, rate of coating deposition, cost, etc.)
• degradation modes (e.g., oxidation and corrosion)
• life-prediction and residual-life assessment
Process modeling is most important to coating manufacture. Degradation modeling is most important to coating design
and development. Coating life and inherent substrate environmental resistance are key determinants in setting the intervals
for engine inspection and overhaul. Few models exist in the public domain that address any of these needs.
Repair and Overhaul

Engineers currently rely heavily on visual inspection to assess the condition of coated structure. As a result, in-service
condition monitoring and repair decisions focus on deterioration at the coating/gas-path interface. Improved nondestructive
evaluation methods would provide information on when the coating has to be removed and on the extent of base-metal attack.
An important need for the repair of industrial gas-turbine components is industrywide repair specifications and
regulation of the quality of repairs. The most effective method to achieve a consensus of all interested parties is unclear.
Methods to make local repairs of coatings are needed, both during manufacture and operation. Also required are standard,
industry-accepted methods to determine the durability and properties of refurbished coatings.
Aircraft engine repair needs parallel those for the industrial turbines, with the further complexity that these coating
structure systems include more advanced designs and materials that tend to limit repair options. Incorporation of better
models and data from condition-monitoring sensors will improve repair/replace decisions. Still unclear is the extent to which
many of the advanced coatings, such as the TBCs, lend themselves to repair. Although some TBC overhaul is currently done,
the extent to which TBC-coated components can be repaired and re-used has never been fully determined.
Although generic families of coatings exist, there is no standard system of designating or defining specific coatings
within a family. Each manufacturer and vendor uses a unique nomenclature, a practice that causes confusion during the
refurbishment of the coated components. There are enough similar coatings in common use that a standard designation
system would be practical and useful.
Nondestructive Evaluation
Exploiting existing and advanced nondestructive evaluation (NDE) methods can aid significantly in developing and
qualifying coating systems, improving process control during coating operations, and characterizing the integrity of coated
structure during turbine engine manufacture, in-service condition monitoring, and repair and overhaul operations. Since each
of these applications has specialized requirements, no single NDE method will likely serve all purposes. Development
programs for advanced NDE methods should focus on supporting these key areas with the goal of bringing the new methods
into practice. The highest priority for further NDE development should be for those noncontacting methods that can examine
the interior structure of the coating system, such as the coating/substrate interface and base metal.
For aircraft engines in particular, the development of advanced NDE techniques and cost-benefit models will be
2 Precompetitive research provides data in nonproprietary areas where competing companies can comfortably collaborate. An example is
basic property data for commonly used materials.

EXECUTIVE SUMMARY 6
essential for the assessment of components that are expected to be multiwall or thin-wall structures with multilayered
coatings used as an integral part of the component design and manufacture.
LONG-TERM OPPORTUNITIES AND INNOVATIONS

Future generations of higher-performance aerospace turbine structures will require advanced materials, because
inservice superalloys are approaching the upper limit of their inherent temperature capability. Candidate materials under
consideration to replace superalloys include intermetallic compounds, monolithic and composite ceramics, and refractory
alloys. In addition, advanced cooling concepts will result in processing modifications and more complex cooling paths to
meet the demands of advanced component designs. Most advanced materials and design modifications will result in
component structures with inherently less resistance to aggressive environmental attack than current superalloys, pushing the
need for parallel development of improved coatings systems. Incremental improvements to current coating technologies are
unlikely to meet the goals of future-generation, higher-performance turbine engines. Innovative concepts are required.
In the long term (i.e., beyond five to ten years), close integration of the coating and substrate material will be standard
practice for key structural components. Control of properties at the substrate/coating interface will be critical. Future coatings
will likely have graded compositions and multiple layers. They will be expected to operate at even higher temperatures and in
steeper thermal gradients. The need for adherence and metallurgical stability completes the maze of major requirements.
Coating developers must also meet the technical requirements in a cost-effective manner.
Innovative Coating Architectures

The structural motifs for hybrid coatings include multilayered materials, materials with ordered vertical structures such
as channels, and materials with an intrinsic three-dimensional pattern such as dendrites or whiskers. In all cases, an important
element that must be considered is the stability of such structures in the high-temperature environment of an operating
engine. This stability includes the long-term ability of the material to maintain its initial mechanical properties and chemical
and microstructural morphology. Research is needed on the following issues of stability:
• Continuously graded coatings. Graded coatings, such as functionally graded materials (FGM) and nanostructures, offer
potential advances in coating performance. The need also exists for ceramic coatings that can withstand higher
temperatures. Graded coatings may demand alternative materials as well as alternative application processes. Most
significant in this area would be a critical assessment of the use of FGMs as coatings and a definition of the influence of
multilayer and nanostructure morphology on resulting properties. However, the inherent inhomogeneity in the
microscopic scale of these materials raises questions of high temperature stability that must be answered to establish the
viability of these approaches. Advanced substrates such as composites and ceramics will possess coatability
characteristics (e.g., diffusion rates and surface chemistry) very different from current superalloys. Novel concepts may
be needed for coatings and surface treatments to protect these substrate systems.
• Horizontally layered materials. Layered materials offer a number of opportunities for advanced coating concepts. For
example, the heat transfer may be reduced by making the coating a high-temperature optical multilayer interference
filter that can reflect radiation or reduce conductivity.3 If successful, such new TBC coatings would permit significantly
higher turbine engine gas temperatures. Multilayers may also permit the matching of thermal expansion coefficients to
minimize thermally induced internal stresses in the coating and at the coating/substrate interface, although this concept
requires further examination using mechanical modeling and experimentation. Again, high-temperature stability is an
issue to be resolved.
• Interphase layer. The crucial interface in any system designed to use an oxide as coating or bondcoat for protection in
high-temperature environments is the substrate-to-first-oxide layer. If this interface could be replaced by an interphase
layer, the composition of which varies continuously and gradually from the substrate metal (or ceramic) to the full oxide,
spalling of the oxide layer from its substrate could be less likely to occur. Previous attempts to use a compositionally
graded metal/ceramic interfacial layer have resulted in oxidative expansion that caused the oxidized graded layer to
buckle the coating away from the substrate (Duvall and Ruckle, 1982; DeMasi-Marcin et al., 1989). There may be
potential for other gradient schemes, however.
• Vertically layered materials. The use of vertical structure in the coating or substrate may also offer important advantages
for improved thermal isolation of the substrate from the engine environment. For example, TBCs must meet the
conflicting demands of adherence and low heat transfer between the coating and substrate. A
3 Current thinking on nanolaminates is that reduced conductivity depends more on increasing phonon scattering than increasing reflectivity.

EXECUTIVE SUMMARY 7
potential solution is to take advantage of the lithographic patterning technology that is widely used in the semiconductor
industry to create high-aspect-ratio (high depth with narrow width) trenches that limit heat transport down to the
substrate. Subsequent steps would fill in the trenches with a material that adheres poorly but has low thermal
conductivity and then cap the entire coating. Such a channel structure could also provide a means to reduce the radiative
heat load if the repetition distance between channels is commensurate with the infrared wavelength for which the
unstructured coating is transparent. This condition would lead to diffraction of infrared radiation from the channel
structure, effectively increasing the reflectance of the coating/substrate system.
• Three-dimensional structured materials. Another approach involves the formation of three-dimensional networks to
provide improved mechanical stability and possibly provide resistance to heat conduction. For example, whiskers could
be formed in situ through a phase transformation. If sintering, densification, and the desired amount of bonding between
the matrix and whisker phases can be applied successfully to ceramic coatings, the processes could yield robust
composite coatings that are strong, lightweight, highly dense, and resistant to severe environments.
• Advanced processing. Coatings processes developed in the electronics industry for the manufacture of semiconductor
devices have potential applications for coatings for high-temperature structural materials. Electronics processing relies
increasingly on in situ monitoring and process diagnostics (intelligent processing) to achieve nanoscale structural control
and characterization. Such techniques might be adapted for turbine coatings in order to improve coating quality and
increase the cost effectiveness of coating processes for the manufacture of functionally graded coatings. The committee
believes that intelligent materials processing will be required to achieve the reproducible process control necessary for
manufacture of reliable coatings. Intelligent materials processing requires the availability and integration of process
models that describe the relationships of critical process parameters with sensors that measure these parameters and
appropriate control systems. Development of all these elements is required.
Other Innovative Concepts

A variety of other approaches for improved coating/substrate systems are also possible. In most cases, there has been no
proof of concept or even prior work for these ideas. They are presented as ideas to stimulate new research directions.
• Built-in sensors for condition monitoring. Microsensors could be embedded into coatings, such as TBCs, to monitor local
temperature rises, changes in oxidation, and possibly incipient disbonding. These sensors would act as real-time
monitors of the degradation of protective coatings and may serve to warn of imminent catastrophic failure. Other sensing
technologies may use remote sensors rather than embedded sensors to achieve the same goal.
• Embedded microchannels within TBCs for cooling. Microdesigned coatings could include small cooling channels within
the TBC to reduce further the surface temperature of the substrate. A cooling fluid, such as air or helium gas, could be
forced along these channels to reduce the heat load transported to the substrate. Alternatively, a fluid (gas) that has poor
thermal conductivity might be injected into the channels to act as an insulating sheath that limits heat conduction from
the TBC.
• Coatings for refractory metals. Refractory metals are attractive potential substrates because of their high melting
temperatures and high-temperature strength. Their susceptibility to catastrophic oxidation, however, is the main obstacle
to their use in advanced turbine applications. Coatings that have an improved oxidation barrier offer improved
performance of refractory metals. New coating materials may alloy electron-rich noble metals with electron-poor metals
to form remarkably stable compounds with close-packed, or nearly close-packed, structures. These hybrid materials
could be exploited to develop a coherent, tenacious coating.

INTRODUCTION 8
1
Introduction
In future years, gas-turbine engines of all types will have the potential to reach new heights of efficiency and service life.
But to keep pace, engineers will have to design coatings concurrently with the intended substrate. Indeed, for some proposed
designs, the coating and substrate form a continuum, literally blurring the boundary between the surface deposit and the
material it coats. In selecting a coating for hot structures, the engineer will also have to keep in mind two primary criteria: the
ability of the coating to protect the component from degradation and the ability of the coating to retain, over the long term, its
protective properties in the harsh environment of the engine.
For decades, improvements in gas-turbine efficiency, whether for land-based power generation, marine applications, or
aircraft propulsion, have been primarily driven by significant increases in gas temperatures within the engine. Of particular
note have been the dramatic increases in the gas-path operating temperature within the combustor and high-pressure turbine
sections of the engine. For example, turbine inlet operating temperatures have increased by hundreds of degrees, and the
specific thrust has nearly doubled during the five decades of the existence of gas-turbine engines.
These large increases in gas temperature have been enabled by the development of highly engineered cooling schemes
for the substrate and high-performance materials technologies. Advances in cooling technology involve sophisticated
convection, impingement, and film cooling designs for turbine hardware. In many cases, these developments were facilitated
by parallel advances in materials processing technologies, such as precision casting, machining, and drilling operations.
Cooling has arguably accounted for more than 75 percent of the increased temperature capability and is still the ''first line of
defense" in new turbine designs.
The introduction of new materials and processes has also heralded a series of advances in engine technology. For
example, the transition from wrought to cast alloys provided a step improvement in high-temperature strength, a capability
further enhanced by the introduction of vacuum investment casting. Within the range of cast superalloys, further incremental
improvements occurred as directionally solidified and single-crystal alloys were developed to tolerate severe, cyclic thermal
gradients. Future improvements will occur as intermetallic compounds, ceramics, composite materials, and refractory metal
alloys are eventually incorporated in advanced engines, although significant technical barriers must still be overcome before
these new families of materials are incorporated in critical engine components.
Because seemingly modest increases in upper temperature limits translate into huge benefits for engine performance, the
large development costs associated with the introduction of new turbine blade alloys have historically been readily justified
for even modest increases in temperature capability.1 The cycle time associated with the introduction of a new alloy has
resulted in an average improvement in temperature capability of approximately 5°C (9°F) per year.
As highlighted in this report, advances in superalloy materials have gone hand-in-hand with continual improvements in
the coatings used to protect the components from environmental degradation mechanisms, particularly high-temperature
oxidation and hot corrosion. The coatings used to date have not increased the inherent temperature capability of the substrate
material, but they have protected superalloys from increasingly aggressive service environments and appreciably extended
the service lives of critical, costly components. This coating/substrate combination has provided such improved component
capability that, along with advanced cooling technology, turbine gas-path operating temperatures in localized regions exceed
the melting point of the engine's structural materials without causing catastrophic failure.
Recently, ceramic thermal barrier coatings (TBCs) deposited onto turbine alloys have been shown to have two major
benefits. First, for the same gas-path operating temperatures, the cooling air requirements can be greatly reduced. Second, for
the same cooling air flow, the hot gas temperature can be raised significantly. In practice, the designer can choose the
operating conditions between these two alternative ranges. Turbines can be operated at higher temperatures while maintaining
an acceptable temperature range within the substrate
1 Each generation of superalloy can cost $10 million or more. This rough cost estimate assumes that the new generation is based on an
incremental materials and processing change from the previous generation, however. If a step change is required, such as the change from
casting turbine blades with uniaxial grains to single crystals, the development costs would be much greater.

INTRODUCTION 9
material (i.e., TBCs are capable of providing at least 110°C [200°F] of increased capability). This latter benefit will allow
TBCs to effectively fill the gap in materials capability for advanced engines between the current family of nickel-base
superalloys (which are generally regarded as being at or close to their ultimate service temperature) and the advanced
structural materials, such as intermetallics and ceramics.
As the gas-turbine industry becomes more dependent on coatings, the scatter (variation) in coating properties is
becoming increasingly important. Figure 1-1 illustrates the scatter in performance of a given property of a coating, together
with the property values and variation required to meet a set of advanced engine requirements. A wide bell-shaped
distribution in a property such as coating adherence is tolerable—although less than optimal—when the coating is only to be
used for extending the life of the base metal. This is particularly true if the failure mode is graceful, as is the case when a
coating is protecting a superalloy that possesses inherent (but insufficient) environmental resistance.
If the coating must be relied on to last for a guaranteed time between overhauls, however, the performance of the system
will be compromised if the coating cannot provide protection on a continued, reliable basis. If the coating system was further
required to extend the temperature capability of the component system (as in the case of TBCs), scatter and unpredictability
of the coating properties become critical. In either case, a coating with too great a variation in critical properties would not be
implemented. For example, TBC life can be modeled as a broad statistical distribution, such as seen in figure 1-1. As a result,
TBCs have generally not been used for critical applications such as for high-performance turbine airfoils. A current design
criterion requires that a component not fail prior to the next scheduled inspection after local TBC spalling (Soechting, 1994).
This limits the incremental thermal advantage of TBCs to approximately 40°C (70°F) over an uncoated part. This gain is
nevertheless a significant benefit, approximating the gains typically achieved by a generation or two of alloy development.
The full potential of TBCs can only be realized, however, if these coatings can be relied on to provide thermal protection of
the substrate throughout the service life of the component. Thus, the coating must remain adherent and functional for the
extended periods between coating refurbishment.
Figure 1-1 Typical ranges of a coating property compared with advanced engine requirements for a property.
The dependence on the reliability of coatings to improve performance and extend service life places an entirely new set
of requirements on coating application processes and on coating system design. Coatings are becoming an integral part of the
materials system needed to satisfy the application requirements and component design. Critical objectives of coating
technologists, therefore, are to reduce the scatter in the property distribution curve (i.e., to enhance reliability) and to move
the minimum predicted value into the regime required by the advanced engine requirements. This theme provides the basis
for much of the discussion in this report and is a fundamental consideration of coating development and implementation on
current and future high-temperature structural materials.

APPLICATION NEEDS AND TRENDS 10
2
Application Needs and Trends
The operating requirements of gas-turbine engines dictate the future development of coatings. This chapter discusses
two areas of that influence: application needs and substrate material trends. A cross section of a typical modern gas-turbine
engine is shown in figure 2-1. As a general rule, components are only coated if system durability and reliability can be
improved. For instance, within the last several years, high-temperature coatings have been extended to additional hot-section
components in order to reduce surface degradation.
APPLICATION NEEDS
The need for coatings has evolved since they were first applied to high-pressure turbine airfoils in the early 1960s.
Coatings were initially used to protect hot structure against degradation by high-temperature oxidation and hot corrosion
(These processes are described in chapter 4). Coatings have become increasingly critical as advances in turbine technologies
have made possible substrate and gas-path temperatures that approach or even exceed the melting point of the substrate in
localized regions.
The duty cycles imposed on gas-turbine engines vary greatly depending on application. Gas-turbine engines are used in
a variety of transportation, power-generation, and mechanical-drive applications, listed in figures 2-2 and 2-3. Operating life
expectancy is principally determined by balancing the two major factors that contribute to wear: on/off cycle requirements
and time-at-temperature. Greater demand on cyclic capability generally reduces the time a system can operate at high power
(i.e., the interaction of thermomechanical fatigue and high-temperature creep of materials determine hot-section life
expectancy). Other considerations, such as environmental factors (e.g., hot corrosion and high-temperature oxidation), also
lower life expectancy.
While engine mission profiles vary with customer requirements, the typical hours of operation expected per engine start
are depicted for each generic class of operation in table 2-1. The number of engine start/stop cycles and operating time at high
temperature are the basic factors that determine when critical components are to be overhauled. The condition of hot-section
coatings is an important indicator of the extent of distress suffered by an engine. Thus, the coatings are regularly inspected.
The reliability and life expectancy of high-temperature coatings are major factors in maximizing the service life of a gas-
turbine engine.
Aircraft Turbine Needs

Two government programs, the High-Speed Civil Transport program led by NASA and the Integrated High-
Performance Turbine Engine Technology program led by DOD, are aimed at developing prototype turbines within the next
ten years that will operate at firing temperatures at least 150°C (270°F) higher than the current generation of high-
performance gas turbines. Figure 2-4 depicts the increase in firing temperatures over the past 15 years and the nominal goals
for these programs. The committee believes that incremental improvements in the durability of substrate materials will not
meet the goals of these two government programs. Success
Figure 2-1 Cross section of a typical modern gas turbine engine.

Source: Hillery (1989). Copyright General Electric Company; used with permission of the General Electric Company.

Figure 2-2 Overview of transportation gas-turbine use.
will require a much more rapid improvement in the operating temperature of materials, as depicted in figure 2-4.
Incremental development of TBC technology, however, may allow the current generation of materials to achieve a portion of
the desired increase in firing temperature.
In addition to a hot-section temperature increase, both of the advanced engine projects also seek to reduce emissions
dramatically, particularly NOX. These emission requirements affect the engineering design of the combustor and cannot be
met without advances in combustor materials and coating technology. For example, release of NOX and SOX could
potentially be controlled by the engineering of ingredients in the coating that act as catalysts for the conversion of these
pollutants immediately after their formation.
Land-Based Turbine Needs

Industrial gas turbines for power generation are distinguished from aircraft gas turbines by many characteristics that
include larger size, lower rotational speeds, longer life expectancy, longer time between overhauls, high time at full power,
few on/off duty cycles, lower quality and lower heating-value fuels, wide variety of fixed locations (e.g., arctic to tropic,
oceans to deserts, clean to polluted), and few weight penalties. The needs of large power-generation equipment essentially
determine the available technology for land-based turbines (NRC, 1986).
The Advanced Turbine Systems (ATS) program, funded as part of the fossil energy research program of DOE, seeks to
develop higher-efficiency land-based turbines that burn
Figure 2-3 Overview of power-generation and mechanical-drive gas-turbine use.

TABLE 2-1 Typical Duty Cycles for Various Gas-Turbine Engines

Typical Mission Time per Engine Start (hours)
Duty Cycle Minimum Average Maximum
Airline/Transport 1 2 8
Military/Fightera 1 2 4
Mechanical Drive 40 2,000 8,000
Base Power Generators 500 2,000 8,000
Peak Power Generators 2 4 12
a The mission profile for military aircraft has greater thermal transient and low-cycle fatigue because of periods of supersonic cruise and
combat/avoidance maneuvers.
natural gas but that are also capable of burning coal-or biomass-derived fuels (NRC, 1995a). Firing temperatures at least
150°C (270°F) higher than the current generation of gas turbines and a combined cycle efficiency of 60 percent are desired,
while maintaining the durability levels of current power-generation systems.
Fuel type is probably the most important variable affecting the selection of a coating system (NRC, 1995a). Pipeline-
quality natural gas contains virtually no hydrogen sulfide and very low sulfur content, unlike unprocessed natural gas. Coal
gasification produces a raw syngas consisting mainly of carbon monoxide and hydrogen, along with substantial quantities of
hydrogen sulfide, ammonia, and hydrogen chloride, and a few parts per million of alkali metals (NRC, 1986). To meet
environmental requirements, commercial gasification systems include clean-up systems that remove virtually all of the
hydrogen sulfide, ammonia, and hydrogen chloride; in general, the alkali metals are also removed. However, it is possible
that in the event of a degradation of the clean-up systems, some of these harmful materials may enter the turbine. The
complex chemical and electrochemical reactions that occur at high temperatures and the susceptibility of these reactions to
small changes in the coating and gaseous environment make coatings for hot-section components a critical enabling
technology. Coating degradation by hot-corrosion mechanisms is the primary concern. One goal of the ATS program is to
seek lower emission levels, similar to those discussed above for aeronautical turbines.
Marine Turbine Needs

On the ocean, gas turbines provide primary drive, auxiliary drive, and shipboard power. A new type of marine vehicle,
Figure 2-4 Approximate increases in firing temperature capabilities from 1980 to 2010.

the all-electric ship, uses a gas turbine located at mid-ship to power the motors that drive the aft propellers. Because of their
low operating cost, gas turbines are expected to become more common on ships.
Although high-quality liquid fuels are used, marine gas turbine engines operate in an environment heavily laden with
salt (sodium chloride) and are often close to other ships that burn low-quality fuels with high-sulfur concentrations, such as
Bunker C. Contaminants from these exhaust gases are drawn into the ship's intake air. Thus, hot corrosion is the primary
nemesis of gas turbines on ships. The coatings primarily developed for marine environments are aimed at increasing the
resistance of hot-section components to hot corrosion.
CURRENT COMPONENT DESIGN AND BASE MATERIALS

The operating conditions that a component is expected to encounter drives the component functional design and the
resulting choice of material. The materials that have been and continue to be used are nickel-base and cobalt-base
superalloys. A partial list of these alloys is given in table 2-2 (Gabb and Dreshfield, 1986; Backman and Williams, 1992;
Stringer and Viswanathan, 1993). These chemically complex alloys are highly developed materials with a combination of
high temperature strength, inherent environmental resistance, toughness, and fatigue resistance that are not currently available
in other alloy system (Sims, 1986). Numerous compositions and processing routes have been developed that can be tailored
to specific application needs.
Nickel-base superalloys have had more extensive development than cobalt alloys. Nickel-base superalloys enjoy high
strengths at elevated temperatures through the precipitation of a coherent phase: gamma-prime. In addition, these alloys are
strengthened by the more common mechanisms of incoherent phases and solid solutions. The result is a family of chemically
complex alloys that are capable of operating in aggressive environments at temperatures greater than 90 percent of their
incipient melting temperature. These features have made nickel-base superalloys the favored materials for use in rotating
turbine components, such as blades. These alloys are also widely used in static structure, such as case, vane, and combustor
applications.
The dramatic progress in investment-casting technology ranks as the single most important process development for
nickel-base superalloys. Progress in this technology has enabled engineers to cast directionally solidified and single-crystal
airfoils that include complex, cast-in, internal air-cooling passages. By using sophisticated cooling techniques with single-
crystal alloys, researchers have attained operating temperatures 80°C (144°F) higher than those of conventional, equiaxed
castings.
Cobalt-base superalloys are not as developed as nickelbase superalloys because coherent phase strengthening has not
been demonstrated for these materials. Although cobaltbase superalloys have less strength at comparable temperatures, they
tend to have higher melting points than comparable, conventionally cast nickel-base superalloys and can therefore function at
somewhat higher temperatures. Cobalt-base superalloys are more easily repaired by welding than are the advanced nickel-
base superalloys and also have better corrosion resistance because of higher chromium levels. For these reasons, the cobalt-
base superalloys are used for higher-temperature applications in which high strength is not the primary issue (i.e., vanes and
combustor liners). These alloys also prove valuable in certain-but not all-hot-corrosion conditions. However, the advanced
nickel-base alloys developed for single-crystal technology have significantly higher melting temperatures than the
conventional nickel-base alloys. As a result, single-crystal nickel-base superalloy vanes have replaced polycrystalline cobalt
vanes in some applications.
Design engineers seek to mitigate the impact of operating conditions on component integrity by two approaches, both of
which have become absolutely essential to the design of hot-section components. The first approach relies directly on coating
technology to extend the service life of both nickelbase and cobalt-base superalloys, as discussed in chapter 3.
In the second approach, coatings contribute indirectly, but just as significantly, to extending service life. This method
relies on component cooling to decrease the steady-state component temperatures; coatings play a key role in such cooling.
For aeronautical turbines, noncombusted air diverted from the compressor is used to cool critical components, such as airfoils
(Sims, 1991). Cooling through the use of steam or other means is also possible when engine weight is not a concern. Several
methods working in tandem make the most efficient use of the cooling air. These include convection cooling and
impingement cooling on the back sides (cold side) of hot surfaces and film cooling on the hot sides that face the combustion
gases (figure 2-5). In film cooling, air flowing out through small holes in the component wall provides a boundary layer of air
cooler than the combustion gas, thus cooling the component. These film-cooling holes may become blocked during the
application of a coating, however. Loss of cooling air may lead to local melting and serious degradation of the component.
ADVANCED MATERIALS FOR ENGINE COMPONENTS

Nickel-base and cobalt-base superalloys have served admirably in gas turbines for over 50 years, and the attractive
properties of this class of materials guarantee that superalloys will continue to serve in turbine engines well into the future
(Sims, 1986). However, current superalloys operate at 90 percent


Figure 2-5 Turbine blade cooling methods. Source: Glassman (1975).
of their incipient melting temperatures in some applications. This is both an unprecedented achievement and a graphic
illustration of the inherent limitation of these materials. The requirement for more efficient engines in the future will also
require even higher operating temperatures and, therefore, higher component temperatures. Thus, the targeted temperatures
will inevitably exceed the capabilities of current superalloys.
Variants of current superalloys, such as eutectics and superalloy matrix composites, can fill a need for increased creep
resistance and higher specific strength. These materials can also help reduce component weight and, when used as turbine
blades, lower the loads on turbine disks. However, their potential for withstanding higher temperatures is still limited by their
melting points. Thus, designers are investigating alternative materials to fill the higher-temperature roles. These materials
generally fall into three classes: ceramics, intermetallics, and refractory materials (Stoloff and Sims, 1986; Meetham, 1988;
Backman and Williams, 1992; Stringer and Viswanathan, 1993). The remainder of this chapter discusses the environmental
degradation issues that are faced for each class of these materials. Coatings for these materials are presented in chapter 3.
Ceramics
Ceramics are generally thought to hold considerable promise because they possess many of the properties desired for
higher-temperature replacements of superalloys: very high melting points, high-temperature strength, low density, and some
increased resistance to aggressive environments (table 2-3). The primary shortcoming of monolithic ceramics is their lack of
acceptable low-temperature ductility and toughness. The toughness issue is being addressed by the development of ceramic
composite systems.
Ceramics currently under development may serve as combustors in both aircraft and land-based turbine engines in the
Advanced Turbine Systems and the Integrated High-Performance Turbine Engine Technology programs. Designers are also
exploring the use of ceramics for turbine blades, an application that could become the biggest economic payoff of these
materials. Silicon carbide (SiC) and silicon nitride (Si3N4) rank as the prime candidates for making ceramic components
because of their high-temperature strength and relative resistance to thermal shock.
Although the development of the requisite mechanical properties of ceramic components continues, it is becoming
increasingly clear that these materials must be coated. Both silicon carbide and silicon nitride oxidize to form silicon oxide
surface scales, which may limit their high-temperature use unless adequate protective coatings can be applied. Under the
operating conditions envisioned for these materials, surface recession caused by active oxidation (SiO formation instead of
SiO2) is a significant problem (Jacobson, 1992). Even limited exposure to sodium-containing environments greatly
accelerates active oxidation (Jacobson et al., 1990). Coatings for a ceramic component will almost surely have to be ceramic
as well, which poses the problem of having to precisely match coefficients of thermal expansion since ceramics do not
possess the ductility to accommodate even slight mismatches in thermal expansion. In summary, coatings are needed to act as
both thermal barriers to reduce the base-material temperature (and thereby reduce the oxidation rate) and as chemical barriers
to slow oxidation.
Oxide-base ceramics are not as attractive for high-temperature structural applications since their strength and toughness
are not as high as silicon-base materials (Stoloff and Sims, 1986). Coatings are less important for these materials, however,
since oxidation is clearly not a concern, although some (e.g., zirconia and alumina) are susceptible to hot corrosion.
Intermetallics
Intermetallic compounds, especially those involving aluminum, have been heavily researched over the last several years.
Compounds of nickel (Ni), titanium (Ti), cobalt (Co), and iron (Fe) with aluminum (Al) have all shown promise, but most
studies have focused on nickel aluminides and titanium aluminides. These compounds have higher melting temperatures and
lower densities than the superalloys (table 2-4). Thus, they have the possibility of achieving both higher temperatures and
higher specific strengths than superalloys. Yet even these alloys will require coatings to excel at high temperatures.

Researchers have also begun investigating intermetallics as matrix materials for composites, adding to the specific
strength capabilities of the intermetallics. Furthermore, alloys with higher aluminum content (e.g., NiAl, TiAl, and TiAl3)
have good inherent resistance to oxidation. The oxidation resistance of NiAl is particularly excellent; NiAl is the main
component in oxidation-resistant aluminide coatings for nickel-base superalloys.
Although researchers have considered intermetallics for structural applications for over 20 years, most of the studies on
these materials have been conducted during the last decade (Dimiduk et al., 1992). Therefore, intermetallics remain relatively
immature materials that have a significant number of-technical barriers to be overcome before they could be used as hot-
section materials. Obstacles include low creep strength at high temperature and poor ductility at low temperatures(Dimiduk et
al., 1992). Despite these drawbacks, a number of research programs have improved the properties of these materials, and
intermetallics now offer the promise of less-demanding, lower-temperature applications. Indeed, studies appear to have
shifted from higher-temperature (roughly between superalloy and ceramic capabilities) to lower-temperature applications
where these materials have a chance of replacing the denser superalloys. As was the case for superalloys, intermetallics may
only attain the required mechanical properties at the expense of some of their environmental durability. Thus, intermetallics
developed for hot-section uses will require coatings to mitigate a variety o f environmentally induced problems.
Titanium aluminides that have low aluminum content (i.e., less than 40 atomic percentage) tend to grow brittle during
exposure to high temperatures in air. The high-aluminum-content titanium aluminides (TiAl) apparently do not have as
severe an embrittlement problem and have a higher resistance to oxidation than the low-aluminum titanium aluminides
(Ti3Al; McKee and Huang, 1990). Unfortunately, the relatively good oxidation resistance of TiAl does not extend to the
higher temperatures required in the hot section. Thus, TiAl will probably require a coating to perform adequately in the hot
section. The oxidation-resistant TiAl3 is brittle at low temperatures and is not currently a promising structural material (Smile
et al., 1990).
Applications for NiAl are still somewhat tentative since alloys having the requisite mechanical properties for hot-section
use are not currently available. Near-stoichiometric NiAl has excellent resistance to oxidation and therefore should not need
an oxidation-resistant coating. However, the poor strength of pure NiAl at high temperatures suggests that the

TABLE 2-4 Selected Properties of High-Temperature-Capable Intermetallics Compared to a Conventionally Cast and a Single-Crystal
Superalloy
Material TSOLIDUS Young's Modulus (GPa) Density (g/cc) Fracture Toughness @ 21 °C (MPa ` m)
(°C)a
Ti3Alb 1600 145 4.3 25
TiAlb 1460 176 3.8 25
NiAl a 1640 300 5.9 —
NiAl-eutecticb — 193 5.9 12-15
MoSi2b 1870-2030 379 6.5 4-5
FeAla 1250 260 5.6 —
CoAl a 1650 300 6.1 —
B 1900c 1274 214 8.2 »100
Single-crystal superalloya — 125 8.3 35
a Stoloff and Sims (1986).

b Dimiduk et al. (1992).
c International Nickel Company (1977).
Other intermetallics under investigation for high-temperature use include MoSi2, FeAl, and CoAl. It is expected that the
same concerns about hot-section oxidation resistance and environmentally induced problems will apply to FeAl and CoAl.
Although its high-temperature oxidation resistance is excellent (Vasudevan and Petrovic, 1992), MoSi2 has the added
environmental-resistance problem of pesting. 1
material will need to be alloyed for use in a hot section. Alloying will most likely cause some loss of oxidation
resistance. Coatings may thus be required to provide requisite oxidation resistance.
Refractory Metals
Scientists have gathered extensive data over the last few decades on the properties and environmental resistance of the
refractory materials (Stoloff and Sims, 1986). The continued interest in these materials stems from the attractive combination
of high melting point, similar to (and in some cases, higher than) ceramic materials, with some ductility at low temperatures
(table 2-5). Most of the research has been conducted on niobium, molybdenum, tantalum, and tungsten because of their
relatively low cost compared with other refractory metals. Niobium is the most attractive of the refractories since it has a
density slightly lower than nickel while still having a melting temperature approximately 1000°C (1800°F) higher than
nickel. In fact, the niobiumbase alloy C-103 has been successfully used in unmanned aircraft (Stoloff and Sims, 1986).
Although a diffusion coating of (molybdenum/tungsten)(silicon/germanium)2 has reportedly protected niobium (Mueller et
al., 1991), the extremely high oxidation rates and tendencies toward embrittlement of the refractory alloys would result in
extremely rapid degradation if the coating failed. Consequently, these materials are not currently used in long-lived, hot-
section components.
Recent work on refractory alloys has also focused on developing resistance to environmental attack. These metals have
little inherent resistance to environmental attack, which could result in a coating flaw leading to the degradation and
subsequent failure of a component. This work has included additions of aluminum and titanium, both of which tend to slow
oxidation, and additions of sufficient aluminum to form refractory metal aluminides (Stoloff and Sims, 1986). These efforts
have not produced alloys useful as hot-section components in air-breathing engines, however. If these efforts ultimately prove
successful, a coating will probably still be necessary to provide the long-term environmental resistance required for all gas-
turbine engines.
1 Pesting is a thermally activated process observed in several intermetallic compounds that results in catastrophic degradation of the
material. At an intermediate temperature range that is system specific, accelerated oxidation of the intermetallic causes large volume
increases. When oxide growth occurs in cracks, porosity, and grain boundaries, the large volume increase results in fracture and eventually
catastrophic failure of the material (Doychak, 1994).


MATERIALS AND PROCESSES 19
3
Materials and Processes
As described in chapter 2, the primary purposes of high-temperature structural coatings are to enable high temperature
components to operate at even higher temperatures, to improve component durability, and to allow use of a broader variety of
fuels in land-based and marine-based engines. Although high-temperature coatings protect the substrate, the demarcation
between coating and substrate (either metal or nonmetal) is becoming increasingly blurred. The demanding requirements of
high-temperature service in both isothermal and cyclic modes have recast the way researchers think about coated structures.
These structures can be considered part of a continuum; at the limit the coating will be a progressive modification of the
substrate and therefore must be concurrently designed with the substrate. Table 3-1 summarizes the relationship between
coating functions and coating characteristics.
There are essentially two types of high-temperature coatings. The first type is a diffusion (or conversion) coating in
which the deposited mass is diffused and/or reacted with the substrate to form a somewhat continuous gradation in
composition. The second type is an overlay coating in which material is deposited at the surface of the substrate. This chapter
discusses current and potential coatings for superalloys, ceramics, refractory metals, intermetallic materials, and metal-matrix
composites. The processes used to apply these coatings to substrate materials are also reviewed.
TABLE 3-1 Coating Functions and Coating Materials Characteristics
Functions Materials Characteristics
Reduction in surface temperature Low thermal conduction Low radiative heat transfer High emittance
Reduction in rate of oxidation Thermodynamically stable oxide formers with slow growth rates
Reduction in rate of hot corrosion Chemically stable and impervious oxide scale
Resistance to particulate erosion Hard, dense material
Increased abradability (sacrificial wear) Rub tolerance via plastic deformation (densification)
Energy transformation via fracture (material loss)
Increased abrasiveness Inclusion of hard particles to induce cutting of seal
COATINGS FOR HIGH-TEMPERATURE STRUCTURES

Coatings must maintain their performance on a continued and reliable basis, or the performance of the turbine system
could be compromised. Advanced coatings that show excessive variability and unpredictability at the required engine
operating conditions will not be employed, regardless of their potential benefits to the system. For example, thermal barrier
coatings (TBCs) are currently used to improve the performance of several engines, including GE's CF6-80C2 and CFM56-5a
and Pratt & Whitney's PW2000 and PW4000 series engines (Bose and DeMasi-Marcin, 1995). TBCs are currently relied on
for thermal insulation to improve component durability at elevated temperatures (i.e., 40°C [72°F] higher than uncoated
parts) but still below the incipient melting temperature of the substrate material. In addition, TBC patches are used to
minimize thermomechanical fatigue cracking by reducing substrate temperatures at component hot spots. However, TBCs
will not be widely accepted for use at temperatures that will result in the rapid degradation of substrate materials in order to
provide the performance benefits of which they are capable until they can be produced with predictable, reliable properties, as
discussed in chapter 1 (see figure 1-1).
The majority of hot-section components are currently made from superalloys. To achieve the aggressive performance
goals of the advanced engine programs (e.g., High-Speed Civil Transport, Integrated High-Performance Turbine Engine
Technology, and Advanced Turbine Systems programs) discussed in chapter 2, material systems with higher inherent
temperature capabilities and better oxidation and corrosion resistance are required. These systems may require the use of
advanced substrates, such as intermetallic compounds, ceramics, or refractory metals. TBCs deposited on current alloys may
allow components to operate at higher temperatures.

TABLE 3-2 Types of Coatings Used in Hot-Section Components

Coating Type
Component Aluminide Chromide MCrAlY
Blades
Gas path HL H M
Internal M
Tip L
Attachment L
Vanes
Gas path HL H M
Internal M
Shroud H H M
Combustor
Liner M M
Transition M M
NOTE: H= high use

M = medium use
L = low use
Coatings for Superalloys

In the past, coatings for superalloys formed a metallic-aluminide layer on the gas-path surfaces of high-pressure turbine
airfoils. As alloys with improved temperature and cyclic capability were synthesized, suitable coatings were developed in
parallel. These more advanced coatings were often tailored for expected environmental conditions.
Metallic coatings (i.e., aluminide, chromide, and MCrAlY) protect superalloys against aggressive environmental factors.
Ceramic oxide coatings insulate the substrate from the maximum gas-path temperatures. Table 3-2 provides an overview of
the types of coatings currently used for hot-section structures. Basic service use and application process information for each
main coating type is summarized in table 3-3. In figure 3-1, Novak (1994) schematically depicts the tradeoffs in selecting
coating compositions for an environment that requires resistance to both oxidation and corrosion.
In most applications, TBCs contain yttria-stabilized zirconia. TBCs are applied to an oxidation-resistant bondcoat,
typically a MCrAlY designed for high-temperature oxidation resistance or an aluminide modified by a platinum addition
(Smith and Boone, 1990). The platinum in an aluminide diffusion coating has been shown to improve the protective
properties of the alumina scale by (1) increasing the purity of the alumina scale by prohibiting the diffusion of the refractory
metals present in the substrate (e.g., tungsten and molybdenum) to the oxide scale; (2) increasing the diffusivity of aluminum
and promoting alumina formation; (3) improving the selective oxidation of aluminum; and (4) decreasing the activity
coefficient of aluminum in the coating. The bondcoat acts to retard a principal cause of TBC failure: oxidation of the
interface between the coating and the substrate. However, alloys currently under development have shown improved
oxidation resistance and may not require a bondcoat (Miller and Brindley, 1992; Ulion and Anderson, 1993). Furthermore,
because of its additional weight, the bondcoat can be detrimental to the creep life of the component, particularly in the case of
rotating parts. Research indicates that adherent, durable, plasma-sprayed zirconia-yttria TBCs can be deposited onto smooth
substrates (without a metallic bondcoat) if an initial layer of the TBC is applied by low-pressure plasma spraying (Miller and
Brindley, 1992). Current familiarity with TBCs will lead to improved design criteria and manufacturing experience that will
allow continual improvement and additional benefits.
Coatings for Ceramics

Current approaches for coating the silicon-based ceramic materials include the use of mullite coatings that have an
excellent expansion match with silicon carbide (Van Roode et al., 1992; Lee et al., 1994). While mullite contains silica, the
aluminum in mullite promotes formation of a solid rather than a liquid oxidation product. This cuts the weight loss in half for

TABLE 3-3 Generic Information on Coating Types Used in Superalloy Hot-Section Components
Coating Type
Information Aluminide Chromide MCrAlY Ceramic Oxide
Primary Protection Function Oxidation Hot corrosion Oxidation Thermal barrier
Thickness (µm)
Nominal 65 25 125 250
Range 25-100 25-50 125-500 > 125
Service Temperature
°C 815-1150 600-925 815-1150 980-1200
°F 1500-2100 1100-1700 1500-2100 1800-2200
Application Process Vapor phase Vapor phase Thermal spray Thermal spray
reaction reaction
air/vacuum air/vacuum
pack cementation pack cementation plasma plasma
above the pack above the pack combustion
chemical vapor Vapor deposition
deposition Vapor deposition electron beam
slurry electron beam sputtering
sputtering
Laser deposition
powder cladding
Reaction sinteringa
controlled
composition
Relative Cost 1x 1x 2x-4x 3x-5x
Commercial Availability Widely available Widely available Widely available Selectively available
a Hsu et al. (1979).
silicon carbide materials under active oxidation conditions Multilayer coatings that incorporate mullite are currently
under investigation (K. Lee, personal communication, 1996)
Coatings for Refractory Metals

Efforts to develop coatings for refractory metals have been hampered by their high reactivity. The aluminides (Stoloff
and Sims, 1986) and silicides (Mueller et al., 1991) have produced coatings that reduce environmental-induced degradation.
A new (molybdenum/tungsten)(silicon/germanium)2 diffusion coating on niobium has shown excellent cyclic oxidation
resistance (Mueller et al., 1991) but has yet to be commercially developed. Use of even excellent coatings is unlikely,
however, since flaws in the coating could severely curtail component life.
Coatings for Intermetallic Materials

In coating both the low-and high-aluminum-content titanium aluminides (i.e., Ti3Al and TiAl), researchers may have
Figure 3-1 Coating compositions as related to oxidation and corrosion resistance. Source: Novak (1994).

to contend with coating/component interdiffusion and the potential for formation of brittle intermetallic compounds at the
coating/substrate interface (Brindley et al., 1992; McKee, 1993). The high reactivity of the titanium-base alloys may require
reaction barriers between the coating and the substrate to reduce the possibility of degradation (McKee, 1993). Flaws in either
the coating or the reaction barrier could severely curtail component life.
The mechanical properties of nickel aluminide (NiAl) substrates are sensitive to compositional changes. Thus, the
potential for diffusion between the coating and the component must be considered in the use of this alloy in the coated
condition.
COATING PROCESSES
In general, the development of manufacturing processes for high-temperature coatings has paralleled the evolution of
gas-turbine materials and component design. Early turbine blades for Allison and Curtiss Wright engines in 1952 were given
a protective coating by simply dipping them into molten aluminum (Goward and Cannon, 1988). The first practical use of a
diffusion coating for turbine airfoils was in 1957 (Goward and Cannon, 1988).
As interest surged during the 1970s, processes were developed for the application of overlay coatings that offered
greater compositional flexibility than was possible with diffusion coatings. Most overlay coatings for gas-turbine applications
are currently applied using electron-beam physical vapor deposition (EB-PVD), which is an atomistic deposition method, and
low-pressure plasma spraying, which is a particulate deposition method. The benefits and limitations of the atomistic and
particulate deposition methods are summarized in table 3-4.
The features, applications, advantages, and disadvantages of the coating methods most relevant to high-temperature
structural materials are summarized in the remainder of this section. Appendix C cites a number of nondestructive evaluation
methods that could be used for process control monitoring. Appendix E reviews examples of industrial manufacturing
technologies for selected processes.
TABLE 3-4 Summary of the Benefits and Limitations of the Atomistic and Particulate Deposition Methods
Processing
Features Evaporation Sputtering CVD Electrodeposition Thermal Spraying
Deposition
Mechanism to Thermal energy Momentum transfer Chemical reaction Solution Flames or plasmas
produce depositing
species
Deposition rate Moderate (up to Low Moderate Low to high Very high
750,000 Å/min.)
Deposition species Atoms Atoms/ions Atms/ions Ions Droplets
Complex shapes Poor line of sight Good but Good Good Poor resolution
nonuniform
Deposits in small, Poor Poor Limited Limited Very limited
blind holes
Metal/alloy Yes Yes Yes Yes Yes
deposition
Refractory Yes Yes Yes Limited Yes
compounds and
ceramics
Energy of deposit- Low Can be high Can be high Can be high Can be high
species
Growth interface Not normally Yes Yes No No
perturbation
Substrate heating Yes, normally Not generally Yes No Not normally

Physical Vapor Deposition

The physical vapor deposition process is an atomistic deposition method that involves the vaporization and subsequent
deposition of coating species. It has the advantage of being able to deposit coatings of metal, alloys, and ceramics on most
materials and a wide range of shapes. Because application requires clear line-of-sight, complete coating coverage is achieved
by manipulating the part during the coating cycle with a complex mechanical system.
Electron-beam guns for EB-PVD are favored for supplying the energy necessary for evaporation because they can
achieve higher energy densities than other methods of heating. EB-PVD can successfully deposit mixed oxide coatings that
are currently of greatest benefit to high-temperature structural materials (e.g., yttria-stabilized zirconia TBCs). In this case,
the process parameters are adjusted so that the deposit has a columnar structure that is perpendicular to the interface. This
morphology maximizes resistance to strains that stem from differences in thermal expansion coefficients. Because TBCs are
porous, they allow gases and fused condensates to penetrate and, therefore, are deposited onto an underlying bondcoat
resistant to oxidation and hot corrosion (usually MCrAlY).
Most models for EB-PVD processes are primarily empirical. EB-PVD equipment is computer controlled, and regulation
of the process can often be devised by trial and error. Plasma and ion control of the vapor allows formation of the desired
coatings. The committee was unable to learn much of the processing details of EB-PVD because this information is largely
proprietary. Basic scientific understanding of vapor formation and deposition is known for simple systems but not for the
more complex, multicomponent systems that generate superalloy coatings. Particularly troublesome are components with
constituents that have vastly different vapor pressures. Deposition on parts with widely varying curvatures, such as airfoils,
also presents difficulties in processing. The committee is not aware of any mathematical models for these situations that are
available in the public domain. Additional information about this process is summarized in appendix E.
Sputtering
The primary advantage of sputtering is its ability to deposit a wide variety of materials (e.g., alloys, oxide solutions, and
intermetallics). These compositions can be derived from many types of targets. A reactive gas can be introduced with the
heavy inert gas, so that reactive sputtering occurs. Often the deposit has a columnar microstructure, with elongated grains
normal to the interface. Such a structure would be ideal for oxide TBCs. Sputtering is not yet a production coating method for
turbine hardware because current equipment deposits the coating too slowly. Appendix E provides additional information
about this process.
Thermal Spray Processes

Thermal spray processes are particulate deposition methodologies that involve the deposition of molten droplets of
material on a substrate. The coating typically begins as a powder. It is then injected into a hot carrier gas and sprayed on the
target substrate with a gun. This process can quickly deposit a wide variety of coatings. A shortcoming of traditional thermal
spray technologies has been a limitation on the thinness and smoothness of the deposit.
A wide variety of thermal spray techniques, as discussed in appendix E, can be employed to deposit metallic corrosion
and oxidation-resistant overlay coatings, bondcoats, and ceramic TBCs. Plasma spraying is the most widely used thermal
spray technique for gas-turbine component overlay coating.
The microstructure of a plasma-sprayed coating depends on the starting material and its particle size distribution, as well
as processing parameters. New and improved powder processing methods can produce starting materials with predictable and
controllable compositions and well-delineated particle size. Key plasma-spray process parameters include plasma power,
plasma gas composition, pressures and flow rates, powder injection details and carrier flow, and torch/substrate distance.
These parameters may be linked in complex ways, making process control difficult. A clear goal is to achieve on-line
feedback control of the process. This will require a much more detailed understanding of the process parameterization.
Diffusion Coating Methods

Diffusion coating is a surface modification process wherein the coating species is diffused into the substrate surface to
form a protective layer. Diffusion coatings are the most used method for providing improved hot-corrosion and oxidation
resistance for nickel-or cobalt-base superalloys. Diffusion coatings have been produced with aluminum, chromium, silicon,
hafnium, zirconium, and yttrium alloys. The

aluminum, chromium, aluminum-chromium duplex, aluminum-silicon duplex, and platinum-modified aluminide coatings are
the most commercially significant. The surface of the superalloy is typically modified to a depth of 0.5 to 5.0 mils
(thousandths of an inch) depending on the type of coating and the process parameters selected. These methods are sometimes
classified as chemical vapor deposition methods. The committee considers three primary methods for producing diffusion
coatings in this report: pack cementation, out-of-pack cementation, and chemical vapor deposition. Appendix E describes
these processes.
COATING PROCESS CONTROL

Many of the recent advancements in coating technology have been the result of improved process control. For example,
thermal spray technology has grown from an empirical art with highly variable results to a well-controlled process that gives
consistently reliable results. Reliability has been achieved through improved control of carrier gas and power, control of
feedstock material, and close monitoring of key process steps.
Process modeling, process monitoring, and real-time control must become more common if the manufacture of
improved coatings is to be realized. Process control can only be achieved by understanding the empirical relationship
between the coating process and the resulting coating. The choice of coating process should depend on a balanced approach
among the technical attributes, the coatability issues, and the performance requirements demanded from the coated
component. Developing the relationship of the process to product performance must be a priority, near-term endeavor for
advanced coating systems. Such parametric data, guided by an understanding of coating behavior and failure modes, can be
quickly and reliably acquired through rig testing, but the variability of the rig test must also be known. Rig-test modeling,
parameter sensing, and feedback control will be an evolutionary and continuing near-term activity. The NRC (1989) study of
On-Line Control of Metal Processing predicted this process evolution.
The current generation of metallic coatings, as well as the emerging TBC technologies, would benefit significantly from
advances in process control. Both types of coatings are deposited by the same basic processes (i.e., plasma spray and physical
vapor deposition), and process improvements will enhance the performance of both coating types. Improved on-line control
must be developed to help ensure that the resultant behavior of the coated structure is highly reproducible and within the
performance limits needed for the service requirements. For example, reducing the large variability in TBC performance and
extending the service life are priorities. Many emerging nondestructive evaluation methods have yet to be effectively
exploited (Murphy et al., 1993). A representative selection of methods are described in appendix C. The most promising
nondestructive evaluation methods should be further developed and applied for manufacturing process control applications.
Accurate and comprehensive in situ measurements of coating processes are often difficult and sometimes impossible,
leading to the need for process modeling. For example, in the typical direct-current plasma-spray system, powder particles are
injected at approximately right angles into a high-velocity gas flame. The powder carrier gas increases turbulence within the
flame and also disturbs its temperature distribution. Ideally, each particle becomes entrained in the flame, rapidly increases in
temperature, melts (without excessive vaporization), and impacts the substrate where rapid solidification occurs. In practice,
to formulate useful models, simplifying assumptions based on the underlying physical phenomena must be made and
validated.
Within the manufacturing domain, the committee believes that important data do not currently exist in an appropriate
form. The conceptual Taguchi Loss Function, outlined in figure 3-2, provides a starting point for developing a conceptual
framework for identifying and classifying the data needed for a robust manufacturing process. The Taguchi Loss Function is
based on the ideas of statistical process control and associates a deviation from the design-specified mean value of a
parameter as a deviation from the minimum-cost performance product (Taguchi, 1993). A first step in applying this concept
to coatings would be to chart the distribution of the parameters thought to be important to coating performance. Their
frequency of deviations from the mean could then be determined. This would guide the search for those process parameters
that must be controlled (i.e., those parameters that deviated most from the mean). Once a set of parameters needing
monitoring and control are identified, process sensors (NRC, 1995b) and control systems can narrow the deviations from the
mean. Appendix E contains more details of this approach.
SUMMARY
The majority of hot-section coatings are applied to protect superalloy components from degradation caused by the
turbine engine environment. Since current hot-section structures are produced from nickel-and cobalt-base superalloys,
substrate coatings in current engines have been optimized for superalloys. These coatings are primarily designed to protect
the superalloys from oxidation and hot corrosion. Most recently, TBCs are being designed to reduce the effects of high
temperatures and temperature gradients. Current and future generations of superalloys have extremely complex chemistries
and microstructures, carefully tailored to meet the high demand of turbine

Figure 3-2 Schematic showing the benefit of development and deployment of manufacturing process control for high-temperature
coatings.
engines. These complex substrate chemistries may be disturbed through interdiffusion with a coating, and their precisely
crafted microstructures can be thrown into disarray as a result of coating process conditions. Therefore, coating/component
combinations will have to be engineered together as a system to achieve optimum performance.
Thus the primary considerations in selecting a coating should be to protect the component and to ensure that the coating
retains its protective qualities in the engine environment. Failure modes are discussed in chapter 4. Other considerations arise
from various engineering factors, such as the requirement that the coating must also be compatible with the bulk material of
the component under the demanding conditions in a turbine engine. These factors are further discussed in chapter 5.
Materials under development for use in future advanced components will also depend on coatings to protect against
oxidation, hot corrosion, and embrittlement. Most of the new materials differ significantly from superalloys in physical,
chemical, and mechanical properties. Also, many of these emerging materials, in their current form, are much less tolerant of
flaws and failure in their coatings than the superalloys. Therefore, coating these materials presents significant challenges.
Development of new coating materials and processes should be done concurrently with the development of the emerging
materials.

FAILURE MODES 26
4
Failure Modes
As discussed in chapters 2 and 3, most hot structures are fabricated from superalloys that have been tailored to meet the
demands of turbine engine operation. Specific solutions to problems encountered under one set of operational conditions are
often in conflict with those encountered under another set (Wood and Goldman, 1986). Thus, materials specialists have
developed alloys that possess a balance of properties geared toward withstanding the most worrisome degradation
mechanisms. As a result, alloying and processing of superalloys for high-temperature structural applications has historically
focused on improving their creep resistance, with secondary goals of improving resistance to fatigue, oxidation, and hot
corrosion (Sims et al., 1986).
This chapter reviews the failure modes experienced at high temperatures by current structural materials (i.e.,
superalloys) and their coatings. A case study of the use of failure modes to improve coating design is presented, using thermal
barrier coatings (TBCs) as an example. The chapter concludes with a series of recommendations on future directions in
research on environmental degradation modes.
DEGRADATION MECHANISMS OF STRUCTURAL MATERIALS

Degradation mechanisms for structural materials are a function of the engine operating conditions, engine mechanical
design, and the component base materials. As a zero-order approximation, engine operating conditions determine operating
temperature and structural loads, while engine design determines the amount of air made available to cool the hot structure.
Table 4-1 summarizes the environmentally induced failure modes of interest (i.e., creep, fatigue, oxidation, and hot corrosion).
The first nickel-base alloys contained 20 percent chromium and successfully resisted oxidation within the operating
temperatures then used because they formed a protective layer of chromia, Cr2O3. It was soon discovered that these alloys
could be substantially strengthened with a coherent precipitate Ni3(Al, Ti), known as gamma-prime. However, the chromium
content had to be reduced to increase the volume fraction of gamma-prime. While other elements could be added to make up
for the loss in chromium, the alloys became more difficult to fabricate using existing methods (Stringer and Viswanathan,
1993).
As engine operating temperatures increased, chromia became less attractive as a protective scale because it oxidized
further to the volatile compound of CrO3. Alumina (A12O3) remained attractive, however. Unlike chromia, alumina by itself
does not protect against hot corrosion caused by molten alkali metal sulfates (Stringer and Viswanathan, 1993). Generally 4-
to 5-weight-percent aluminum suffices for both gamma-prime and alumina formation.
Grain boundaries become a weak component of the microstructure at high temperatures. Creep deformation occurs in
the grain boundaries, for example. To increase creep resistance, many of the critical hot-section airfoils are cast with the
grains aligned parallel to the direction of the principal stress axis. These are called directionally solidified castings. Ideally,
these components are selected as a single-crystal airfoil with the desired crystallographic orientation. Elements cannot
segregate to the grain boundaries in single-crystal blades and cause brittleness. Thus, alloying flexibility exists to design a
material with inherently high resistance to creep, oxidation, and hot corrosion. Single-crystal blades can be used uncoated in
certain aeronautical turbine applications, but they do not yet possess sufficient inherent corrosion resistance for industrial
turbine use, which is much more demanding on service life (Stringer and Viswanathan, 1993).
The degradation modes common to cooled hot-section superalloy components include low-cycle thermal fatigue,
oxidation, and creep, with creep being the least important factor because it is designed out. Combustor and turbine blade
components also degrade during high-cycle fatigue processes. On the other hand, noncoated components, such as low-
pressure turbine blades, are often creep limited.
DEGRADATION MECHANISMS OF COATINGS

Once it became apparent that it would be extremely difficult to develop structural materials that possessed all the desired
high-temperature mechanical properties as well as environmental resistance, the functions were uncoupled. Structural alloys
were developed to optimize mechanical properties, and coatings were developed to serve as physical

FAILURE MODES 27
TABLE 4-1 Environmentally Induced High-Temperature Structural Material Failure Modes

Failure Mode Definition
Creep Time-dependent, thermally activated inelastic deformation of a material. The rate of creep increases as
the temperature increases for constant stress.
High-Cycle Fatigue Microstructural damage mechanism that results from small stress amplitude cyclic loading, such as
vibrations; failure will occur after a relatively large number of cycles.
Low-Cycle Fatigue Microstructural damage mechanism that results from large stress amplitude cyclic loading; failure will
occur after a relatively small number of cycles. Very abrupt thermal changes, such as from engine start
and stop cycles, are the driving force for this failure mode.
High-Temperature Oxidation Solid-gas chemical reaction that produces the oxide(s) of constituents within the solid. The rate of
oxidation increases exponentially with temperature, certain oxides (notably those of aluminum and
chromium) are slow growing and protective of the underlying substrate.
Hot Corrosion Electrochemical reaction between substrate and molten salts, typically sodium and potassium sulfates.
Two forms of hot corrosion are generally recognized: Type I (high temperature), which typically occurs
between the temperatures of 820°C and 920°C (1500°F and 1700°F), with a maximum at about 870°C
(1600°F), characterized by the buildup of a nonprotective oxide layer as oxidation and sulfidation
destroy the metal substrate; and Type II (low-temperature), which typically occurs between 590°C and
820°C (1100°F and 1500°F), with a maximum at about 700°C (1300°F), often exhibiting pitting.
barriers between aggressive environments and the substrate (Stringer and Viswanathan, 1993).
The structural materials degradation modes that are moderated by the traditional metallic protective coatings include
oxidation and hot corrosion. In addition, TBCs insulate the underlying structure against the full effect of gas-path heat. They
thus retard creep degradation and reduce the severity of the thermal gradients and transients in the structure that drive low-
cycle fatigue processes. By dampening the amplitude of vibrations, some coatings can reduce high-cycle fatigue. However,
no such coating to date has been found that can survive the aggressive turbine environment.
Table 4-2 summarizes the various failure modes that pertain to the coatings themselves. Historically, metal coatings (i.e.,
alumide, chromide, and MCrAlY) have been designed to withstand three types of environmental attack: high-temperature
oxidation, high-temperature (Type I) hot corrosion, and low-temperature (Type II) hot corrosion. Figure 4-1 shows the range
of temperatures over which these attacks occur. However, it should be kept in mind that the oxidation of the aluminide and
chromide coatings at the coating/gas-path interface results in the formation of a protective oxide scale. Therefore, within this
context, high-temperature oxidation is not purely a degradation mechanism. In addition to these failure modes,
thermomechanical fatigue of coatings (and substrates) can occur as a result of cyclic and thermal loading of the component.
Thermomechanical fatigue cracking in coatings, particularly around film-cooling holes, has often been observed in advanced
engines. A TBC can reduce the magnitude of the thermomechanical fatigue strain range and can minimize or eliminate
thermomechanical fatigue cracking.
Several other damage modes cause coating loss and accelerate the overall failure mechanism:1
• mechanical distress to the coating, such as nicks and gouges, which is caused by objects ingested into the engine airstream
• solid-state diffusion of elements between coating and substrate, which can lead to the loss of critical elements from the
coating and formation of undesirable phases in the substrate
• spallation caused by differential thermal expansion between the coating and the substrate, which can lead to mechanical
failure of the coating
• rumpling of metallic coatings as a result of creep
The coating degrades at two fronts during service: the coating/gas-path interface and the coating/substrate interface. At
temperatures well below the incipient melting point of conventional superalloys, deterioration of the coating surface at the
coating/gas-path interface tends to be a consequence of oxidation or hot corrosion. As the temperature rises, diffusion across
the coating/substrate interface plays a greater role in
1 These damage modes can be addressed by proper design of the coating system (as discussed in chapter 5) and operational procedures.

FAILURE MODES 28
TABLE 4-2 Environmentally Induced High-Temperature Coating Failure Modes

Failure Mode Definition
High-Temperature Oxidation Solid-gas chemical reaction that produces the oxide(s) of constituents within the solid. The rate of
oxidation increases exponentially with temperature; certain oxides (notably those of aluminum and
chromium) are slow growing and protective of the underlying substrate.
Hot Corrosion Electrochemical reaction between metal and molten salts, typically sodium and potassium sulfates.
Two forms of hot corrosion are generally recognized: Type I (high-temperature), which typically
occurs between the temperatures of 820 and 920°C (1500°F and 1700°F), with a maximum at about
870°C (1600°F); and Type II (low-temperature), which typically occurs between 590 and 820°C (1100
and 1500°F), with a maximum at about 700°C (1300°F).
Mechanical Distress Erosion and impact damage caused by the ingestion of particles in the air stream.
Solid-State Diffusion Reduction of the aluminum content of the coating because of interdiffusion with the base metal.
Spallation Loss of protective oxide at the coating/oxide interface.
Thermomechanical Long-term (i.e., over many cycles) formation and propagation of cracks because of external mechanical
Fatigue Cracking stresses and to residual stresses from lack of thermal expansion compatibility between the substrate and
the coating
degradation; compositional changes at this interface can also compromise the structural properties of the substrate.
The remainder of this section reviews the key characteristics of coating degradation and suggests areas in which
additional knowledge is needed. The discussion is limited to commercial coatings for which service-derived experience is
available.
High-Temperature Oxidation
At high temperatures, coatings that protect against oxidation form a compact, adherent oxide scale (usually A1203) that
provides a barrier between the high-temperature gases and the underlying metal. Chromia scales (Cr203) have been used but
offer less protection than alumina above 840-870°C (15501600°F) because chromia scale tends to sublimate to CrO3 above
these temperatures. Without the protective scale, the coating, and ultimately the substrate, come under rapid attack.
The general case is that the oxide spalls repeatedly until it can no longer form. Then internal oxidation, caused by
diffusion of oxygen into the coating, degrades the protective oxide scale. Figure 4-2 shows the result of high-temperature
oxidation of a coating and its penetration to the base metal. In this example, an adherent, relatively uniform external oxide
scale remains, but internal oxidation of the coating and base metal has occurred. Recent work (Smialek, 1991; Smialek and
Tubbs, 1995) has demonstrated the enhancements to oxide adherence that can be achieved as a result of very tight control of
contaminant levels (e.g., maintaining sulfur levels in the < 1 ppm range). Segregation at the metal/scale interface causes
disruption of the bond and spallation of the oxide. In addition, oxygen-active elements such as hafnium and yttria are often
added to coatings to improve the
Figure 4-1 Types of high-temperature attack for metallic coatings (aluminide, chromide, MCrAlY, etc.) on nickel-base
superalloys with approximate temperature regimes and severity of attack. Source: EPRI (1991). Copyright 1991. Electric Power
Research Institute. EPRI GS-7334-L. Guidebook and Software for Specifying High-Temperature Coatings for Combustion
Turbines. Reprinted with permission.

FAILURE MODES 29
Figure 4-2 Micrograph of service-exposed CoCrAlY overlay coatings showing internal

oxidation of coating and base metal. Source EPRI (1991). Copyright 1991. Electric Power Research Institute. EPRI GS-7334-L.
Guidebook and Software for Specifying High-Temperature Coatings for Combustion Turbines. Reprinted with permission.
adhesion of the oxide. The mechanisms proposed for the ''reactive element" effect on scale adhesion include (1) reducing
the activity and mobility of sulfur, (2) mechanical pegging, (3) reducing void formation, (4) increasing scale plasticity, and
(5) oxide doping.
The fundamental oxide-scale formation, growth, and breakdown have been studied for several years. Although some
unresolved issues linger, high-temperature oxidation is relatively well understood. Less clear are the effects of oxidation from
secondary species in the fuel and combustion air. The role of some of these contaminants have been studied; for instance, it is
known that chlorine accelerates the rate of oxidation. However, a quantitative understanding of these effects is not well
developed.
Hot Corrosion
Hot corrosion involves attack by molten salts, typically sodium and potassium sulfates, that enter the turbine hot section
as contaminants from the air and fuel and can result in rapid loss of material (Stringer and Viswanathan, 1990). As indicated
in table 4-2, there are two forms of hot corrosion: high-temperature (Type I) and low-temperature (Type II). The basic
mechanisms of hot corrosion are relatively well understood, although there still remain areas of disagreement (Rapp and
Zhang, 1994). The role of secondary elements (e.g., impurities such as chlorine, calcium, and iron from the local
environment) is not as clear.
The key to continued protection against hot corrosion is maintaining the protective scale and keeping the hot-corrosion
process in its initial, or incubation, period. Rapid loss of the coating and the underlying metal substrate will occur once the
scale is lost or penetrated. The ideal protective scale would minimize solubility of the fused salt, a property determined by the
combustion chemistry and operational environment. This criterion for petroleum-base fuels can generally be satisfied by
either chromia or alumina, although alumina protects at higher operating temperatures than chromia.
A TBC degradation mechanism has been observed in service in which molten surface deposits can accelerate spalling of
electron-beam physical vapor deposition (EB-PVD) and plasma-sprayed TBCs. Salt species in vapors from such sources as
dirty fuel or marine environments can condense onto the coating surface. If the coating temperature is above the melting point
of the salt, it can wick through the interconnected cracks and porosity of the coating (Miller, 1986). The wicked-in salt
freezes on cooling, eliminating the strain tolerance mechanism of the coating and accelerating spallation (Palko et al., 1978;
Miller, 1986; Strangman, 1990).
Mechanical Distress
Two related failure modes-mechanically induced erosion and impact damage-merit special consideration. Erosion results
from particles in the air stream that abrade the coating and accelerate its loss. Impact damage occurs when a solid object in
the air stream strikes the coating. These failure modes are sometimes overlooked because they can often be avoided by proper
operating practice. However, these modes will become increasingly important as substrate materials are operated under
conditions in which they offer little inherent protection against oxidation or other major failure modes. These failure modes
are also a key concern in the retention of TBCs. These ceramic coatings are inherently more vulnerable to impact damage and
erosion than metallic coatings.
Creep of stand-alone metallic coatings at higher temperatures can cause rumpling of the surface of coated components
resulting in degradation of performance and durability. Application of a TBC may alleviate the problem by lowering the
temperature of the metallic coating (Bose and DeMasi-Marcin, 1995). However, plastic instability of bondcoats for TBCs is
still a potential problem at higher temperatures, and work on creep-resistant bondcoats is continuing (Brindley, 1995).
Solid-State Diffusion
The loss of aluminum in the coating, caused by diffusion of the coating with the base metal, ranks as another important
degradation mode. Diffusion of aluminum into the base metal and base-metal elements into the coating reduce the
concentration of aluminum in the coating that is available for forming alumina. A protective oxide can no longer re-form after

FAILURE MODES 30
spallation once the aluminum concentrations fall below a certain level. The basic concepts of diffusion are well understood
for simple systems, and the diffusion of complex, multielement systems containing multiple phases can be formally described
(Nesbitt and Heckel, 1984). Obtaining actual interdiffusion coefficients and predicting the interdiffusion in these systems are
formidable tasks, however. Consequently, reliance on empirical measurements of interdiffusion is necessary and usually
sufficient for engineering purposes.
Spallation
Loss of oxide scale by spallation is the major concern for all coatings and poses a particular problem for coatings based
on aluminum or chromium. Once again, a protective scale can no longer be maintained when the aluminum (or chromium)
concentration falls below a critical level, usually cited as approximately 4- to 5-weight-percent aluminum.
Loss of the protective oxide at the coating/oxide interface is most damaging since an entirely new protective scale must
be formed. Recent research indicates that spallation at this interface can be exacerbated by the presence of sulfur in the
material. With the reduction of sulfur impurities, stepwise improvements have been observed in the adherence of protective
oxides to superalloys (Smialek, 1991; Smialek and Tubbs, 1995), resulting in vastly improved oxidation resistance. Although
studies have not completely elucidated the role of sulfur, lower levels of sulfur in both the superalloy base and its coating
increase the coating's resistance to cyclic spallation.
TBC thickness is yet another concern. While it is obvious that a finite amount of TBC must be deposited in order to reap
the benefit of a thermal barrier, increasing TBC thickness adds to component weight and accelerates spallation (Bose and
DeMasi-Marcin, 1995).
Spallation of TBCs is an important failure mode. These ceramic coatings are not self-replenishing. Hence, spallation
rapidly degrades the insulating properties of the coating and can accelerate attack of the underlying metallic bondcoat or
substrate. This weakness of TBCs is discussed in greater detail in the next section.
A CASE STUDY: DEGRADATION OF THERMAL BARRIER COATINGS

Experimental and theoretical thermal characterization of TBCs has shown that they can provide significant thermal
benefits to components in operation, but only if coating integrity is maintained. TBCs are applied on top of a MCrAlY
coating; the TBC provides thermal insulation, and the MCrAlY protects the substrate against oxidation and hot corrosion.
Zirconia is extensively used as a TBC since it has low thermal conductivity and a relatively high coefficient of thermal
expansion. The zirconia used is partially stabilized in the metastable tetragonal phase with 6- to 8-weight-percent yttria. TBC
coatings are applied using one of two processes: plasma spray and EB-PVD, as discussed in chapter 3.
Maintaining coating integrity for a TBC is more difficult than for metallic coatings because of the relatively large
change in properties from the metallic substrate to the ceramic coating. The problem is exacerbated by the fact that TBCs
provide the greatest efficiency benefit at the highest operating temperatures, where TBC failure is most likely to cause
unacceptable component damage. Thus, while coatings with even lower conductivity may be possible (see chapter 8), the
high variability of TBC thermal cycle life suggests that the use of these coatings to their full potential will depend on their
susceptibility to failure.
The microstructure of the coating resulting from plasma spray differs significantly from that created by the EB-PVD
processes (see figure 4-3). Hence the coating failure modes are not the same. Unlike the other coating types that may become
ineffective through chemical degradation while the coating is still intact, the loss of the effective life of a TBC is
Figure 4-3 Comparison of the microstructure of EB-PVD and plasma-sprayed TBCs.

FAILURE MODES 31
usually marked by the physical loss of the ceramic insulating layer. This loss occurs by one of two means: ceramic layer
spallation or erosion of the ceramic layer.
Spallation
TBC spallation is a mechanical event that results in the removal of the ceramic layer by delamination from the bondcoat.
Numerous processes may trigger this mechanical event, but the two main culprits are bondcoat oxidation and the strain
generated by a thermal expansion mismatch between the ceramic top coat and the metallic components of the system (Miller
and Lowell, 1982; Strangman, 1985; Hillery et al., 1988; Demasi-Marcin et al., 1989).
Data indicate that oxidation of the bondcoat and thermal expansion mismatch strains between the ceramic top coat and
the metallic bondcoat have a synergistic effect on TBC failure. Under realistic conditions, the action of either alone cannot
cause failure of plasma-sprayed (Miller and Lowell, 1982) or EB-PVD TBCs (Manning-Meier et al., 1991). This generality
may not hold for conditions of extreme thermal transients, however, such as for rocket engine applications (Brindley and
Nesbitt, 1988). Since oxidation and thermal-cycle strains must both be present to cause TBC failure, reducing either could
dramatically improve TBC life. However, the details of degradation differ for EB-PVD and plasma-sprayed TBCs because of
their substantially different ceramic layer and interface structures.
Plasma-Sprayed TBCs
Figure 4-4 shows the microstructure of a typical plasma-sprayed TBC. Failure of a plasma-sprayed TBC generally
consists of cracking and spallation. Delamination cracking generally results from high in-plane compressive stresses that
cause significant out-of-plane tensile stresses and produce delamination cracks parallel to the interface and near the peaks of
the rough bondcoat. Finite-element analysis of a realistic rough interface of a plasma-sprayed TBC has shown that the
thermal-cycle stresses in the ceramic layer at the bondcoat peaks are roughly two orders of magnitude higher than expected at
a smooth interface (Ferguson et al., 1994). Thus the rough interface of a plasma-sprayed coating not only increases initial
adherence with the ceramic layer through mechanical interlocking but also drives its delamination and reduction in life.
Studies in which surface roughness was varied using an analytical (Evans et al., 1983) or numerical model (Ferguson et al.,
1994) have identified the radius of curvature of the bondcoat peaks as the single most important feature in generating stress.
Spacing and amplitude may also contribute.
Figure 4-4 Photomicrograph of a plasma-sprayed TBC.
Out-of-plane cracks are also present in plasma-sprayed TBCs, but these result from processing and in-plane tensions
applied to the ceramic layer during heating of the component. The out-of-plane cracks are not generally believed to be a
problem for coating durability and could even enhance the strain tolerance of the coating. The out-of-plane cracks could play
a role in spallation if they were to link major horizontal delamination cracks, and, in fact, out-of-plane cracks have been
shown to accelerate spallation in thicker coatings (Bose and DeMasi-Marcin, 1995). These cracks could also reduce coating
life by adding to the in-plane compressive stresses of the ceramic layer after cooling from high temperature. This could occur
if the cracks were to open during heating but not close on cooling because of crack-face interference or cracking debris
lodged in the crack.
Delamination in a plasma-sprayed TBC does not occur with a single cracking event but by progressive crack growth
(demise et al., 1989; Cruse et al., 1992). Since cracks, flat pores, and abundant potential crack growth paths along splat
boundaries are present in the as-processed structure, delamination cracking requires only crack growth and linkup through
thermal fatigue. No crack initiation step is required. Thus, long service lives are possible if the strain imposed on the ceramic
layer during thermal cycling is low enough. This requires a reduction in the strain imposed on the ceramic layer by thermal
expansion mismatch, oxidation, or both.
EB-PVD TBCs
EB-PVD coatings tend to fail at the alumina-scale/bondcoat interface. Finite-element analysis modeling of the thermal
cycle behavior of PVD coatings indicates that out-of-plane tensile stresses are well below the initially high adhesion strength
of the alumina and even below the adhesion strength of coatings that have been thermally cycled (Manning-Meier et al.,
1991). These low stresses primarily result

FAILURE MODES 32
Figure 4-5 Photomicrographs of EB-PVD TBCs before and after failure.
from the smoothness of the interface between the bondcoat and the alumina layer. Figure 4-5 shows an EB-PVD coating
before and after failure.
Although the calculated out-of-plane tensile stresses are lower than the adhesion strength of the coating, Manning-Meier
et al. (1991) proposed that alumina delamination proceeds by progressive interfacial cracking from in-plane strains. Since the
failure occurs at the alumina/bondcoat interface, progressive reduction of the adhesion of the alumina layer may also be
involved in spallation of the TBC.
Oxidation is a larger fraction of the failure driver for PVD coatings than for plasma-spray coatings. The difference
apparently arises because PVD coatings are less susceptible to thermal cycling damage (Manning-Meier et al., 1991).
Continued growth of the oxide scale is believed to increase the compressive stresses applied to the ceramic layer during
thermal cycling (Rigney et al., 1995). Several other mechanisms may increase the mechanical strain on the ceramic layer:
sintering (Eaton and Novak, 1987; Manning-Meier et al., 1991), formation of high-volume or low-strength oxides at the
bondcoat/ceramic interface (Lee and Sisson, 1994), and creep of the bondcoat (Hillery et al., 1988; Brindley and
Whittenberger, 1993).
Erosion
TBCs are more susceptible to erosion than fully dense ceramic coatings because the strain-tolerant structure of TBCs
includes crack like features. Furthermore, the relatively fine microstructure of the TBC coating means that the distance from
one crack like feature to another is small and the crack length required to remove small portions of the coating is also quite
small. Thus, the erosion rate, even compared with other porous ceramics, is expected to be high.
The degree of erosion depends on the density of particulates in the working gases and the angle of impingement.
Particulate loading is expected to be higher for engines operating in dusty environments (e.g., aircraft engines ingesting
debris during takeoff and landing and land-based or aircraft turbines in dusty sites or geographic regions such as the Middle
East). Erosion can also stem from the particulates generated inside the engine (e.g., coking or salt shedding from parts that
have deposited condensates). In all cases, erosion is more significant on the leading and trailing edges of rotating components
than on static components or elsewhere on turbine blades.
Erosion removes the ceramic layer of the TBC and thereby removes the insulation it provides. Current practice is to
design the leading edges of turbine blades as if no TBC were to be applied. Thus the heat load on the component will not
exceed the design temperature for the leading edge if the TBC were eroded. As operating temperatures increase and the drive
for higher efficiency continues, a solution to the leading-edge erosion problem will become increasingly important.
Fabricating thicker TBCs at high-erosion areas is not an attractive solution because of the added weight of the coating and the
increased likelihood of cooling hole blockage. A more satisfactory solution would be the development of an erosion-resistant
coating or surface layer for current TBC materials.
RESEARCH OPPORTUNITIES
Engineers have a good understanding of how high-temperature oxides form. The role of minor elements (e.g., sulfur) in
high-temperature oxidation and composition needs additional study, as do spallation of the oxide during both steady-state
operation and thermal cycling.
The mechanisms of both low-and high-temperature hot corrosion are also relatively well understood. The role of
secondary elements in hot corrosion needs additional study, as does the effect of mechanical integrity of the oxide scale
during hot corrosion. In order to develop realistic fuel specifications, the resistance of coatings to hot corrosion in biomass
and gasification environments (i.e., low sulfur but high alkali) needs clarification.

FAILURE MODES 33
Research is required to improve and apply models that can help optimize coating development and to provide more
accurate estimates of the remaining coating life for in-service engines. More specifically, advances are required in (1) the
understanding of the failure mechanisms and factors involved as a function of use conditions; and (2) the development of
qualitative and quantitative life-prediction models based on all active failure mechanisms.

ENGINEERING CONSIDERATIONS 34
5
Engineering Considerations
Choosing a high-temperature coating for a turbine engine is currently a sequential design process that is dictated by the
operating conditions of the engine. The most suitable combination of substrate cooling schemes and alloys are selected for
the hot-section components. Coating systems are then specified if they are needed to extend the performance of the
components to higher temperature regimes, to improve the durability of components, or to allow the use of fuels with a broad
range of thermal efficiencies and contaminant levels.
In addition to evaluating the coating material on its own merits, the designer must take into account several other
engineering variables to select the best high-temperature coating system. For example, coatings are typically designed to wear
out (i.e., lose their dimensional tolerance) without causing premature component replacement or unpredictable or catastrophic
structural failure. The hope is, of course, that a coating will improve all aspects of component performance, from
environmental resistance to fatigue resistance. This is not usually the case, however. Components generally perform better
with the coating but not as well as they could if the environmental degradation driver, and thus the coating, could be
eliminated. An inappropriate coating can also actually reduce performance. Thus the advantages of applying a coating must
always be weighed against the disadvantages (Wood and Goldman, 1986; Dyson, 1989).
This chapter discusses the key engineering factors that must be evaluated in specifying a coating system and, where
appropriate, emphasizes the shortcomings of the traditional, sequential design process described above.
COMPATIBILITY OF COATINGS WITH STRUCTURAL MATERIALS

The coating system must be compatible with the component's base material in order to protect against environmental
attack and to prevent degradation caused by the coating itself. Three different types of compatibility are generally considered
important: chemical (metallurgical), processing, and mechanical.
Chemical (metallurgical) Compatibility

Many coatings require some interdiffusion with the substrate to ensure adhesion (e.g., diffused aluminide and MCrAlY-
type overlay coatings), but these coatings must be relatively stable to avoid excessive coating/component interdiffusion and
chemical reaction. Simple interdiffusion can erode critical elements (e.g., the aluminum used to form the alumina scale;
Nesbitt and Heckel, 1984) and degrade the coating's protective properties. Interdiffusion with the structural alloy can create
deleterious reaction zones near the interface. Brittle intermetallic compounds and other phases often precipitate in these
zones, leading to cracking near the interface and spallation of the coating. A brittle reaction zone may also reduce component
ductility and fatigue resistance. In such an event, the coating may decrease component life. Other detrimental effects include
the formation of low melting-point (eutectic) phases and low-strength regions in the substrate material because of unwanted
changes in the local chemistry of the alloy.
Walston et al. (1993) cited a case in which a coating decreased the performance of a new superalloy. The research goal
was to develop a nickel-base alloy with higher creep strength. The work indeed demonstrated improved creep properties for
an uncoated specimen, but the application required that the component be coated to protect against oxidation. When an
aluminide coating was applied, this alloy had much lower strength and was more vulnerable to stress rupture. This poor
performance was attributed to the formation of brittle phases near the interface due to a coating/substrate reaction. The
beneficial properties of the new alloy were restored after a slight modification to the chemistry of the base material
eliminated the formation of the brittle phase (Walston et al., 1993). This case illustrates the sensitivity of carefully optimized
superalloy compositions to slight changes in chemistry. It is also one of the few reported cases in which a substrate
composition was changed to be more compatible with a coating.

Process Compatibility
The coating material may be completely compatible with the component but the coating process may be incompatible.
This can occur, for example, when the coating process requires high temperatures or a special precoating surface treatment
that changes the properties of the structural material. Incompatibility also arises if the process cannot apply a coating to the
required geometric form, reach all areas of the component (such as internal passages), provide the necessary surface finish, or
apply different thicknesses of coatings on a part, as is sometimes required.
For example, chemical vapor and physical vapor deposition processes require high temperatures to grow the correct
coating microstructure and ensure that the coating adheres to the substrate (Lammermann and Kienal, 1991). These
temperatures may impair the structural material or cause unacceptable dimensional changes in the component, such as
warping. Applying heat or mechanical straightening after coating may restore desired properties and dimensions, but
restoration may not be possible in some cases.
Some coatings require a particular surface treatment before they can be applied. Unfortunately, some pretreatments may
significantly damage the substrate. For example, thermal spray coating usually requires pretreatment with grit blasting to
roughen the surface and improve adherence. Grit blasting of a single-crystal vane or turbine blade should generally be
avoided, however, since it induces residual strains that can serve as nucleation sites for recrystallization during subsequent
operation of the turbine.
Mechanical Compatibility
To maintain the protective features of the coating, the mechanical properties of the coating must be designed to
accommodate or match those of the substrate. Factors affecting mechanical compatibility include the coefficient of thermal
expansion (CTE), coating ductility, parasitic weight, cohesion, adhesion, and surface roughness. To ensure mechanical
compatibility, the coating must have some strain tolerance to accommodate any such mismatches.
Maintaining the protective features of oxidation and hot-corrosion-resistant coatings generally depends on maintaining
adherence and a microstructure free of through-thickness cracks or other defects. For TBCs that are precracked to help
accommodate strain, continued protection generally requires that the coatings remain adherent and insulated over bondcoats
that are typically oxidation-resistant coatings.
Coating materials and processing should maximize the longevity of the component (i.e., coatings are selected with
properties that generate the lowest stresses in the coating/ substrate system). One consideration is the coating/component CTE
match. Matching the CTE of the coating and the substrate is an extremely difficult process. If the coating and substrate CTEs
match relatively closely, the stresses generated during processing and thermal cycling should be small. Under these
conditions, even a coating with low ductility will not fail catastrophically (i.e., crack), allowing it to remain adherent and
offer protection. However, if there is a large CTE mismatch, even a ductile coating may crack or spall due to the large
stresses and strains incurred during thermal cycling that result from thermal expansion mismatch. Another consideration is
environmentally enhanced thermomechanical fatigue, which is a special case of low-cycle fatigue that is not adequately
predicted with isothermal low-cycle fatigue data and models. Life-prediction methods are needed that help designers avoid
thermomechanical fatigue cracking of coated superalloy components.
All coating applications require some degree of strain tolerance. Because most coatings have less ductility than their
substrates, coated components have lower ductility. As a consequence, the strain required to initiate a crack in the structure
may prove less than that in an uncoated specimen. For example, a crack that originates in a coating (i.e. caused by
thermomechanical cycling, etc.) can trigger cracking in the base material, with a subsequent loss in ductility and fatigue life
of the component (Smialek et al., 1990).
Coatings that protect against oxidation or hot corrosion must accommodate strain and have enough ductility to keep
from cracking under operating conditions. For TBCs, the low effective modulus imparted by discontinuities in the coating
structure usually provides the strain tolerance. This tolerance allows the coating to deform locally without generating the high
stresses that would cause coating spallation.
There is often a subtle tradeoff between improved environmental performance and component life. While coatings can
improve environmental resistance, their extra mass increases stress on a rotating part. This in turn decreases the creep life and
adds to the stress imposed by thermal gradients. Furthermore, the extra mass on blades also adds to the load on the turbine
disk as well as on the turbine shaft and its bearings. Therefore, the entire rotating system must be designed to handle the
additional weight of the coatings. If not, engine life will be severely compromised.
Component degradation aside, coatings directly affect component function. For example, a coating changes part
dimensions, which can be very significant for thin sections. A coating can thicken the trailing edges of turbine blades and
vanes, causing turbulence and a loss in aerodynamic efficiency. Even components designed to allow for the added thickness
of the coating suffer mechanical degradation because of the higher trailing-edge thicknesses. Coating the leading and trailing
edges, which are important to

aerodynamic efficiency, prove especially challenging because of the combination of mechanical and thermal strains coupled
with the erosion that may occur at these highly dynamic locations.
Coatings can also change the surface finish of a component, affecting both aerodynamic drag and heat transfer rates. For
example, a recent experimental and theoretical analysis of the Space Shuttle's main engine turbopump turbine section
compared performance for two cases: turbine blades with a rough 400-micro-inch finish (Ra) and blades with a smooth 30-
micro-inch finish (Ra; Boynton et al., 1992). The analysis indicated that the efficiency of the turbine increased by an absolute
value of 2.5 percent (not 2.5 percent of the baseline) when the coating was smoothed. Thus, while the change in efficiency
varies with engine operating conditions, there was a significant advantage to a smoother surface finish.1
While smooth surfaces improve aerodynamic performance, controversy exists regarding the type of surface finish that
should be required for engine components, particularly airfoils. These components accumulate deposits and erode, which may
make costly surface finishing operations meaningless early in their service life. For some applications, original surface finish
is important, but researchers disagree on how to specify the finish. At present, surface finish is usually specified as the
arithmetic average roughness, a measure termed Ra. The value of Ra can be identical for surfaces with very different surface
profiles and potentially different aerodynamic responses. Thus, this measure alone cannot determine the aerodynamic quality
of the surface. A thorough experimental and theoretical treatment of roughness effects would benefit the coatings community.
Coating surface roughness may also affect the heat transfer rate. In particular, surface roughness generally increases the
heat transfer rate under laminar flow conditions. However, the effect of increasing roughness under turbulent conditions is
less clear. Since both component and coating degradation are generally sensitive to temperature, adding heat to a coating can
degrade the component. The few experimental studies conducted under these conditions have yielded conflicting data (Boyle
and Civinskas, 1991). Roughness effects on heat transfer require continued investigation.
COMPONENT COATABILITY
Coatability is the ability of a coating process to deposit a coating on the required surface. Expressed in these terms,
coatability is a function of geometry and size rather than base material. A primary issue is whether the process can coat all of
the surfaces required. As discussed in chapter 3, many coating processes cannot coat surfaces that are not in the line-of-sight
(e.g., the internal passages of airfoils and sharp changes in surface geometry). If a component is large enough, physical
manipulation may expose hidden surfaces to the coating source.
Uniform coating thickness is another aspect of component coatability. Most coating processes tend to produce variations
in thickness at edges, inside corners, and on irregular contours. This variation may impair the coating or reduce component
life. One obvious solution is to exclude processes that foster nonuniformity. Alternatively, it may sometimes be possible to
refinish a coating (i.e., remove regions that are too thick) to achieve a uniform thickness.
Components containing cooling holes affect the selection of the coating process. Cooling holes are often present prior to
coating. During application, the coating may partially block the holes, a phenomenon known as coat-down (i.e., coating is
deposited on the inside surfaces of the hole). Since the holes can be small (e.g., 0.5 mm in diameter), coat-down can block a
significant fraction of the hole, diminishing cooling to the outside surfaces. The preferred means for maintaining adequate
hole size is to use a coating method that limits the amount of coat-down. Other methods, such as laser drilling of holes after
coating, can also be used but are more costly.
The size of the component is another important consideration. Many current processes use enclosed tanks or reactors
(e.g., electron-beam physical vapor deposition, low-pressure plasma spray, metalorganic chemical vapor deposition, and pack-
chemical vapor deposition processing). Large parts, such as turbine blades or combustors for large-frame power-generation
engines, may not fit into some of these processing chambers. It may also be difficult for the processes that were initially
designed for small parts to achieve the same coating uniformity and coating structure for large parts. Such difficulties may
arise in maintaining uniformly high substrate temperatures, which are required for some processes. Large parts may also be
difficult to manipulate in such a way as to allow all of the surfaces to be coated.
OTHER ENGINEERING CONSIDERATIONS
Coating Databases
Traditionally, high-temperature coating data are obtained only after the mechanical properties of the uncoated substrate
have been well characterized. These data are generally specific to the application required and are often proprietary.
Moreover, the general utility of the data is limited because high-temperature coatings are applied by a variety of processes
with a variety of controls.
1 Since some coating processes, such as thermal spraying, lead to high surface roughness, surface-finishing methods have been developed
for these processes. There is also a tendency to use coating processes that inherently provide smooth surfaces, such as electron-beam physical
vapor deposition and chemical vapor deposition.

Properly structured databases could serve as effective mechanisms for the collection, organization, and dissemination of
data and experience for new coating technologies (NRC, 1995c). For example, the design criteria for TBCs can become more
sophisticated if the existing data gathered from previous laboratory experience is made available in an organized fashion to
design teams. Laboratory standards are also needed to identify and characterize the properties of materials (and coatings) over
very long (50,000+ hours) service life requirements. Standards for coatings are discussed in appendix A.
Management of Air, Fuel, and Water

Contaminants found in the fluids required to operate a gas turbine (air, fuel, or water or steam2) can combine in the hot
section to produce corrosion, erosion, and deposition under certain temperature and pressure conditions. For land-based
turbines, airborne contamination arises from particles and gases from the ambient air, from evaporative cooling of the
incoming air (for power augmentation), and from on-line engine cleaning. Regardless of the source and means by which
contaminants enter the gas path, they accelerate degradation of high-temperature components beyond that dictated by the
temperature at the component surface.
Gas turbines burn a variety of fuels, the power of which vary in form and content. The early literature was mostly
concerned with petroleum-base fuels, but the development of other fuels (e.g., coal and coal-derived fuels) has been the
subject of programs sponsored by the U.S. Department of Energy (DOE, 1992a,b; NRC, 1995a).
The petroleum-base liquid fuel used in aircraft engines is strictly controlled so that indigent fuel contaminants do not
damage the engine. Enabling gas turbines to operate on lower quality liquid fuels (i.e., residual fuels) without accelerating
deterioration from contaminants remains a challenge to the development of hot-section coatings. In contrast, most power
generating units run on natural gas and are therefore expected to suffer less degradation from fuel combustion products.
It is standard practice for turbine design engineers to specify maximum concentrations of harmful contaminants.
Addressing the combined concentration of contaminants in air, fuel, and water has proven effective in managing corrosion
and deposition for land-based turbines. This methodology involves calculating concentrations in the turbine section relative to
allowable limits. The amount that the contaminants will need to be reduced can then be calculated.
Figure 5-1 depicts the tradeoff between the initial investment in fluid cleanup and the cost of power for industrial uses.
Capital investment is directly correlated to the quality of the gas-turbine environment (represented in this case by the
concentration of alkali metals in the combustor effluent). This investment is offset by the cost of maintenance, including
turbine airfoil replacement or repair as well as the longer mean time between overhauls (Hsu, 1987, 1988).
Figure 5-1 Tradeoffs between first cost and operating cost.
Influence of Coatings on Gas-Turbine Emissions

Gas turbines can produce harmful emissions during the combustion process. These emissions include oxides of nitrogen
(NO and NO2, commonly called NOX), carbon monoxide (CO), unburnt hydrocarbons, sulfur oxides (mainly SO2 and SO3),
and particulate matter. The character of these emissions depends on a number of factors: the temperatures in the combustion
zone; the mixture of air and fuel in the combustor; the residence time, particularly in the hotter parts of the flame; and the
nature of the fuel. In general, a gas turbine operates with much more air than is required for the stoichiometric combustion of
the fuel. This air is introduced in different parts of the combustor, however. The actual air-to-fuel ratio may be close to
stoichiometric at the burner itself; secondary air is then mixed in later, and the combustor is designed to ensure good mixing
between this and the primary combustion products. Further air is added before the combustion gases enter the first row of
stationary vanes.
Poor mixing is evidenced by the passage of unburnt hydrocarbons through the turbine.3 This often happens during
startup, when the fuel-to-air ratio is high; the smell of unburnt hydrocarbons is usually detectable at airports. Incomplete
combustion of the carbon can also result in the emission of CO from the combustor, which may not oxidize to CO2
2
Some industrial turbines use water or steam injection to aid in emission control.
3Some aviation turbines deposit dense pyrolitic carbon at the combustor, and eventually this detaches and passes through the turbine
where it may cause erosion or foreign object damage.

because of the short residence time and in spite of the overall excess of oxygen. If the fuel contains sulfur, which is the case
for most hydrocarbon fuels or sulfur-containing natural gases, this will normally oxidize during combustion to SO2, which
may then oxidize further to SO3 as the temperature drops. The product mixture is usually described as SOX. Finally, and most
importantly, oxides of nitrogen may be formed during combustion. This can result from the oxidation of the nitrogen in the
combustion air or by the oxidation of fuel-bound nitrogen in liquid fuels. Again, different oxides may be formed, and the
mixture is described as NOX .
The formation of NOX is favored by high temperatures in the combustion zone and by a significant excess of oxygen. If
there is less than a stoichiometric amount of oxygen in the primary combustion zone, NOX levels will be low; but CO may be
present. As a result, there is often an inverse relationship between NOX and CO (and unburnt hydrocarbons) in the exhaust
gas. For land-based gas turbines, local environmental legislation may limit the amount of these contaminants that can be
emitted and, as a result, low-sulfur fuels are generally specified. This is true for gas-burning engines whether the gas is
natural gas or coal-derived gas.
For coal-derived gas, the fuel-bound nitrogen is converted to ammonia, which is also generally removed from the gas
during the clean-up process. Coal also contains some alkali metals, sodium and potassium, and the degree to which these are
removed depends on the clean-up processes.
Control of NOX can be achieved by reducing the maximum flame temperature, for example with water or steam
injection. This does not reduce the turbine inlet temperature. The increased mass of hot gas will result in an increase in
specific power output but lower thermal efficiency. The NOX emissions can also be controlled by a catalytic reduction
process for the exhaust gas, although this does represent a significant penalty in cost and efficiency.
An innovative concept for advanced transport engines is a "rich-lean burn" concept. The modern "dry, low-NOX"
burners often used in current generation land-based gas turbines use some version of a two-zone combustor. The first, or
primary, zone has a stoichiometric diffusion flame that stabilizes the combustion process. The second zone contains a lean
fuel-to-air mixture that burns at temperatures too low to produce NOX. A small amount of NOX is still produced in the
primary zone.
Coatings such as TBCs lower emissions by reducing the need for cooling air. 4 The less air required to cool the
combustionliner, turbine vanes, and turbine blades, the more air available to dilute the fuel-to-air ratio and achieve lean
combustion. For example, the wall temperature of a typical can combustor is moderated by cool air flowing over the inner
surface, which is known as "film cooling." Film cooling can quench gaseous reactions in the combustion process near the
wall and lead to enhanced CO and unburnt hydrocarbons emissions. TBCs 5 can be used to shield the combustor liner from
the combustion heat, reducing the amount of cooling air needed and lowering the amount of CO and unburnt hydrocarbons
formed. This effect can be further enhanced by the use of a double-walled combustor, where the inner wall is solid and
protected by an inner TBC, and the outer wall is perforated to allow impingement cooling of the inner wall.
CONCURRENT COATING DEVELOPMENT

To meet the very demanding and constantly changing requirements for high-temperature structure to support the next-
generation engines, revolutionary changes in hot-section materials and coatings will be necessary. Choosing a high-
temperature coating and determining the next step in research and development rank as a complex, iterative process. For
example, engineers must consider cost-benefit scenarios as well as structural factors in evaluating design choices. These
scenarios must include repair and maintenance costs-as well as off-line user costs-within the context of costly, idle assets and
contingency plans in the event that downtime exceeds the amount allotted for customer services (e.g., electric power or
scheduled airline service). If each step of the iteration were performed sequentially, significant time would elapse before a
design could be completed.
As a result, the sequential, separate development of structural alloys and coatings is no longer adequate. The sequential
method is being replaced by concurrent development of the total system since overall system performance is of primary
importance to the users of turbines. Thus, the design and selection of structural materials and their coating systems should be
performed concurrently by teams of experts drawn from each critical function (e.g., design disciplines, materials engineering,
manufacturing, and cost avoidance). Integrated process development, or concurrent engineering, is becoming an imperative
for coatings and will remain an imperative in the future. Life-prediction methodologies that are based on a fundamental
understanding of the key parameters that arise from engine design, anticipated application use, coating and superalloy
properties, and prior engine experience databases, could also be useful in the design of future engines. The needed
information must be available, properly measured, and defined.
4 It was thought at one time that TBCs reduced emissions directly, but there is little evidence to support this view.
5 TBCs have been used on combustion liners for many years to provide protection from hot streaking.

REFURBISHMENT OF COATED STRUCTURE 39
6
Refurbishment of Coated Structure
As described in chapter 4, a coating degrades at two interfaces: the coating/gas path and the coating/substrate.
Deterioration at the coating/gas-path interface is a consequence of oxidation or hot-corrosion mechanisms that occur at
temperatures well below the incipient melting point of conventional superalloys. As the temperature of the surface metal
increases, solid-state diffusion at the coating/substrate interface causes compositional changes that can compromise coating
protection and substrate microstructure, resulting in markedly reduced component life. Coatings are usually designed to wear
out without causing degradation of the underlying component. The conventional approach has been to ensure that the coated
component remains functional until overhaul, at which time it is fully assessed. For airfoils operating at temperatures below
the level at which diffusion is a concern, recoating with or without rework allows the part to be returned to service. Hence,
the coating serves as a renewable surface that can extend component life.
The goal of component refurbishment is to restore component integrity in an economical and timely fashion. To
accomplish this goal, engineers rely on visual nondestructive evaluation (NDE) techniques to assess the component condition
and develop a schedule of required repairs. Safety, reliability, and economic factors govern the type and extent of permissible
repairs. Repairs therefore vary greatly depending on the type and criticality of the component to be refurbished (Haafkens,
1982). Replacement of the coating is generally a small portion of the overall repair but plays a key role in ensuring that the
component endures for the remainder of its expected service life. The repair of aircraft turbines differs significantly from that
of land-based turbines. Repair facilities and practices for aircraft engine components must be certified by the military or the
Federal Aviation Administration. This generally results in industrywide minimum standards for the quality of the repair, the
repair facility, and the personnel performing the repair. No such standards currently exist for repair of industrial gas turbines.
Because of the use of thin walls and the highest-strength superalloys, aircraft turbine blades have had limited tolerance
in the past for high-temperature oxidation and virtually no tolerance for hot corrosion once the coating has been breached. For
this reason, highly distressed aircraft turbine blades are not repaired. Industrial gas turbines, which employ thick walls and
lower-strength alloys with a higher resistance to corrosion, have a higher resistance to oxidation and hot corrosion once the
coating has been breached. In this case, the blades may be able to be refurbished and returned to service if the component is
not severely distressed. The increased complexity of blades in the new generation of engines will make this more difficult.
FACTORS AFFECTING COMPONENT LIFE

For all gas-turbine applications, the minimum total service life as well as the life until an inspection interval must be
determined by engineering analyses, component testing, and any justifiable combination of verifiable methods. Determining
life expectancy often requires complex analysis of independent and interacting factors relating not only to operating
conditions but also to the reliability of the system and the quality of the finished components.
When should a component on a gas turbine be repaired or replaced, and when should the component continue to run?
These critical run/repair/replace decisions are based on a combination of turbine manufacturer recommendations, prior
experience, and, more recently, detailed analysis using modeling tools. These decisions are influenced by the amount of risk
the user is willing to tolerate, 1 the need for the equipment to continue operating, and the maintenance budget.
Run/repair/replace decisions are not an exact science, and a great deal of judgment can be involved. There has been
recent success with expert system software that assist the equipment operator and others in making these decisions. For
instance, the Electric Power Research Institute has developed software based on engineering analysis along with calibration
and verification of the predictions by the examination of field-run hardware (Bernstein, 1990).
The role of coatings in run/repair/replace decisions is crucial since the condition of the coatings often determines the
service life of the component. Thus, assessing the coating condition by calculation or inspection is critical. Algorithms for
coating degradation are under development for some of
1 Recommendations from turbine manufacturers and others are sometimes interpreted by engine operators in terms of the perceived level
of their experience and the economic benefits from additional sales of parts or services.

the industrial gas-turbine engines. Appendix C, Survey of Nondestructive Evaluation Methods, and appendix D, Modeling of
Coating Degradation, contain further information that is summarized in this chapter.
REPAIR OF HIGH-TEMPERATURE COATINGS

This section addresses the repair of coatings for industrial turbine hot structures. The criteria and practices are similar for
aircraft engine components, except that aircraft engines traditionally have made more extensive use of advanced alloys,
incorporated a higher degree of design sophistication, and had greater regulatory oversight requirements because of flight
safety concerns. These factors generally have resulted in restricting allowable repair options for aircraft engine components.
Importance and Need of Repair Technology

The single largest expense in maintaining industrial gas turbines is the cost of new hot-section components, particularly
the blades and vanes. Consequently, all possible efforts are made to repair these components instead of replacing them.
Coating replacement is one of the necessary steps in the repair of these components. Coatings must typically be removed and
reapplied a minimum of once during service life and, preferably, several times. Internal coatings must be capable of surviving
the repair process intact or being renewed. 2
It is unclear if a new coating must be capable of being refurbished in order to be a viable, commercial coating, however.
The unit cost of generating energy is the sum of the equipment acquisition and siting costs, fuel costs, and maintenance costs
divided by the energy produced. Maintenance costs include engine teardown and assembly, inspection and repairs, new parts,
and the cost associated with the unavailability of the engine. If a new coating could allow higher-temperature operation (for
increased efficiency), the savings in fuel costs could possibly outweigh the added expense of purchasing new parts versus
repairing old parts. Consequently, the ability to repair a coating may not always be a primary consideration in developing a
new coating
Current Status
Although details of repair procedures may vary, the repair steps themselves are very similar. Acid baths usually remove
aluminide coatings, while manual belting (sanding) or electrochemical processes remove overlay coatings. Water jets have
also been increasingly used to remove both aluminide and overlay coatings. The main disadvantage of the acid baths is that
they contain toxic chemicals that must be carefully handled and disposed; manual belting is costly, labor-intensive, and
difficult to control precisely. The repair procedure must remove all of the coating and deteriorated base metal; incomplete
removal can seriously shorten the service life of the new coating.3 Heat-tinting procedures work reasonably well for detecting
remnants of the old coating. Advanced, automated NDE inspection methods are needed to verify that a clean substrate has
been prepared for recoating operations.
The recoating operations generally follow the same procedures and technology as the application of the original coating.
The durability of the reapplied coating is not well quantified. Coatings applied over the base metal should be expected to
have the same durability as the original coating. Diffusion coatings applied over weld and braze repairs may have lower
durability, since the composition of the weld or braze are different from the base metal. Overlay coatings, which depend less
on the base metal for their final composition, are the least sensitive to these effects. However, manufacturing processing
sequences, such as grinding blade root platforms after coating, can present further challenges for recoating operations.
Future Directions
The most important need for the repair of industrial gas turbine components is industrywide repair specifications and
regulations of the quality of the repairs, developed by an independent, knowledgeable, and unbiased organization. These
specifications and regulations should include the removal and reapplication of the coating. Improved NDE is needed to
determine when the coating has been removed and when there is no base-metal attack.
The durability and properties of refurbished coatings are not known but are of great importance to gas-turbine operators.
Changes in airfoil composition and structure during repair cycling (e.g., brazing or welding) can affect subsequent coating
systems. As part of the knowledge, engineers need to assess the durability of coatings applied over weld and braze repairs.
Methods are needed to make local repairs of coatings during both manufacture and operation. During manufacture, some
areas of the coating may fail specification or become damaged. Methods to inspect these areas are needed. Some areas of the
coating may also become damaged during operation. If local repair procedures are available, these areas could
2 Service run coatings are typically not locally repaired, although examples of these ''mini-repairs" do exist.
3 It can be difficult to detect base-metal attack that is confined to the grain-boundary region.

be repaired on site and the component (e.g., turbine blade) returned to service.
The future of aircraft engine repairs will most likely parallel those of the industrial turbines-with the added complexity
of thinner walls and more sophisticated cooling passages (e.g., cast cool/multiwall quasi-transpiration cooling concepts). Thin
walls in advanced components can preclude any stripping of the old coating, making it unrepairable.4 Development of
advanced NDE techniques will be essential for assessing components that are expected to be multiwall/thin-wall structures
with multilayered coatings, and the coating will be an integral part of the component design and manufacture.
The ability to repair TBCs, increasingly used to improve performance, has yet to be fully assessed. Removal and
reapplication of the bondcoat should follow the same steps as for any overlay coating.
STANDARD DESIGNATIONS FOR COATINGS

Although generic types of coatings exist (e.g., aluminides, chromides, and TBCs), engineers have no standard system of
designating or defining coatings. Instead, each manufacturer and vendor has their own commercial nomenclature, meaning
the same coating may have ten or more different names. This state of affairs causes confusion for gas-turbine owners, who
have to select coatings to refurbish their components. To appreciate this confusion, one only has to imagine the situation that
would exist if there were no accepted standard designation system for steels.
For example, the U.S. Air Force believes that common designations for coatings are needed to assist in the procurement
of repairs. In the industrial gas-turbine community, the large number of coating choices is overwhelming those in charge of
maintaining the engines. A system for designating coatings would significantly reduce the current state of confusion. Other
benefits of a system that designates coatings include increased competition in the marketplace, simpler specification of
repairs to gas-turbine components, and increased access to foreign markets.
Developing a designation system for coatings could follow a path similar to that used for metals. The American Iron and
Steel Institute (AISI) system for steels provides the nominal chemistry for each type of steel and is used universally. The
Aluminum Association system for designation of aluminum alloys is similar to that of steels but includes suffixes for heat
treatments and other processing. This system for aluminum alloys is also used universally. A different approach is taken by
the American Society for Testing and Materials (ASTM). This organization develops consensus standards for materials and
other items. Its material standards, which simply use the standard number and often a subcode, designate the chemistry,
product properties, and sometimes the processing. While not intended to be a standard designation system, the ASTM
standard number has achieved the status of a material designator, such as A36 steel. Existing coatings standards published
independently by a number of organizations are listed in appendix A.
Compared with bulk metals, a coating has some unique aspects: it depends on the substrate and the process, it can be a
composite of two different coatings, and it evolves relatively rapidly. There are enough similar coatings in common use that a
designation system is practical and beneficial. Any system must have the capability of adding new coatings as they are
developed. The three systems described above for bulk metals (i.e., AISI, Aluminum Association, and ASTM) have this
capability. Some examples of potential designation systems for coatings are summarized in appendix F.
NONDESTRUCTIVE EVALUATION
NDE aims to identify defects, qualitatively or quantitatively, that could lead to failure, while not changing the material
being tested. It is often desirable to make these measurements without direct contact with the component. Recently, this goal
has been extended to include:
• assessing the after-fabrication condition of the coating system
• aiding the characterization of advanced materials
• developing process control methods to minimize the variation in quality of a manufactured part
• ensuring safe operation by assessing the in-service condition of coated components and remaining life
• evaluating the components after repair
All NDE methods use some external source to produce a measurable response from the sample without causing a
permanent change in the specimen. The information extracted by the measurement is determined both by the initial source/
specimen interaction and the detection method. The combination of source and detection methods comprises an NDE
technique. Table 6-1 lists some of the primary NDE methods used for coating inspection. Appendix C provides more detailed
discussions of these techniques.
The focus for the application of NDE methods should follow the five areas identified above. Constituencies in each area
have an interest in NDE methods; hence prioritization is difficult. At the least, it is important to retain the traditional NDE
focus on initial qualification and in-service inspection while examining opportunities in the other areas. The priority should
be on methods that can address the key issue of
4 Some of the current turboprop/turboshaft high-pressure turbine blades are not repairable.

TABLE 6-1 Survey of Nondestructive Evaluation Techniques

Source Technique Energy Form (parameters and limits) Selected Uses
Visible Light Reflected/transmitted light Surface characterization
Visual inspection Low spatial resolution semiquantitative Surface damage of substrate or coating
High resolution imaging (microscopy) Spatial resolution of surface features =1 µm Metallography, grains, surface breaking
cracks
Spectroscopy Wavelength variations in reflection/ Contaminants, oxide layers, composition
transmission
Ellipsometry Polarization state of reflected light Thickness of surface films dielectric
properties
Infrared Reflected/transmitted light Surface/bulk characterization
Imaging spectroscopy Spatial variations of reflection/ Spallation of TBC; structure of metallics;
transmission wavelength dependence of composition of coating; impurity type
optical properties
Emission spectroscopy Wavelength dependence of emission from Emittance versus wavelength for TBC
heated materials and other ceramics
X-Ray Transmitted Energy Attenuation/diffraction in bulk
Radiography Integrated attenuation along path Voids; thickness changes in metal wall
Diffraction Unit cell parameters, long-range lattice Plastic deformation; residual strain
order
Topography Single lattice reflection, spatial variations Spatial estimate of crystallinity of single-
of lattice order crystal blades/vanes
Microwave
Imaging Spatial changes in reflectivity of coating TBC contaminants, coating thickness,
and substrate substrate conductivity
Spectroscopy Wavelength dependence of optical TBC coating thickness, rotational
properties relaxation times
Electron Source Characteristic X-rays Composition thickness
Backscatter Energy selective detection of fluorescing Elemental composition, some lateral
X-ray photons resolution, layer thickness
Electromagnetic Eddy current Magnetic fields from induced/injected Factors affecting conductivity and
currents permeability
Photoinductive imaging TBC coating thickness; lateral resolution Thickness of substrates and coatings
= 250 µm
Magneto-optic imaging Lateral resolution = 10 µm; spatial Substrate crack detection residual stress;
variations in magnetic field of induced work hardening; coating thickness; crack
currents as modified by cracks, holes, etc. location/sizing; visualization of
conductivity-related defect regions in
conducting materials
Thermal with Particle or Electromagnetic Bulk and surface properties affected by Thermal parameter disbonds, voids,
Source temperature cracks, thickness
Imaging Spatial variations temperature < 10 mK, Coating thickness; coating adhesion;
emissivity > I µm thermal properties of coating and substrate
Spectroscopy b(l), R(1), e(l) throughout the Composition of substrate and coating
electromagnetic spectrum transmission regions emissivity
interface degradation, preferably without touching the specimen. Although some researchers have developed methods
that might be used to assess interfaces, studies for the most part have been preliminary and rather uncoordinated. Efforts
should be better focused and carried out at a level where some of the newer methods could be brought into practice.

NEAR-TERM TRENDS AND OPPORTUNITIES 43
7
Near-Term Trends and Opportunities
Coating technology for high-temperature turbine engine structure is advancing at a rapid rate. Engine design engineers,
materials scientists and engineers, and coating technologists are actively seeking the best alternatives to provide improved
engine performance at the lowest possible cost and risk.
To support the development of advanced aeronautical, industrial, and marine turbines, coating and substrate materials
are being increasingly developed concurrently. Until recently, the evolution of high-temperature coatings had been largely
independent of component development (e.g., alloy composition, casting process, and cooling design). This sequential
development method will be inadequate for advanced coating systems and systems where the coating and the substrate are
becoming an integral entity from a life-cycle perspective (e.g., design, materials and process development, manufacturing,
and product support). For example, concurrent development is helping match the current generation of MCrAlY coatings to
new nickel-base superalloys, as well as developing TBCs (thermal barrier coatings) to be used with a MCrAlY undercoat and
superalloy substrate.
This chapter summarizes current trends in coatings development, focusing on coatings expected to be incorporated in
engines within the next five to ten years. It also identifies critical areas of research and development that could rectify
shortcomings in coating technology. The underlying theme of this chapter is that advances in the areas highlighted in this
chapter provide the knowledge for realizing concurrent engineering of coatings and substrates.
THERMAL BARRIER COATING DEVELOPMENT

TBCs are finding increased application in overall component design. Over the past 25 years, cooling technology has
increased turbine operating temperatures by roughly 400°C (720°F; Soechting, 1995). Superalloy material and processing
advances have increased operating temperatures by approximately 120°C (215°F) because of the progression from equiaxed
superalloys to third-generation, single-crystal superalloys. Further advances will be possible with these materials through the
use of even more sophisticated cooling and casting schemes (Nealy and Reider, 1979; Turner et al., 1992; Caccavale and
Sikkenga, 1994), in conjunction with widespread use of TBCs.
Using insulating TBCs, nickel-base superalloys have been shown to support a metal temperature reduction of as much as
approximately 140°C with a 5-mil-thick TBC (Manning-Meier and Gupta, 1992). Thus, these coatings have the potential to
extend the use of superalloys into advanced engine applications. In the near term, the committee believes that TBC
technology merits most of the development and application effort. This will allow the current generation of high-temperature
structural materials to bridge the requirements gap until substrates capable of functioning at higher temperatures are fully
developed. However, the insulative effect of TBCs can be dependent on the substrate (e.g., because of substrate thermal
conductivity). As with any coating/substrate system, the coating must be tailored to the substrate material and component
design. Also, to take advantage of the reduction in substrate-metal temperature provided by TBCs as a way to optimize
turbine efficiency, TBC reliability should be considered a critical factor in need of further development.
Generating a more compatible and oxidation-resistant bond between the metallic substrate and the TBC will also need
continued effort. Pratt & Whitney Aircraft (Novak, 1994) has demonstrated improved compatibility in turbine shrouds. In this
application, a coating consisting of a graded layer acts to increase strain tolerance. Although this approach has been shown to
be effective where thick (greater than 0.050 inches) coatings are tolerable, application to rotating components, such as
airfoils, is usually impractical because of the high inertial mass added by the coating (see chapter 5). Furthermore, for use at
higher temperatures, the effects of graded layer oxidation will need to be negated in order to make graded coatings feasible
for future use in aircraft engines. The development of durable bondcoats that can accommodate thermal expansion mismatch,
combined with improved interface oxidation resistance, should be the focus of near-term research.
Current knowledge of TBC failure mechanisms lies primarily in empirical data. Although the NASA HOST reports
show significant progress toward defining a semi-empirical life-prediction methodology for TBCs, surprisingly little is
understood about TBCs in the critical areas of radiative and conductive heat transfer and emissivity, failure mechanisms, and
fundamental physical and mechanical properties (i.e., fatigue, monotonic properties, and time-dependent properties).

Research is needed to improve the understanding of TBC behavior (and thereby improve TBC performance) as well as
to provide reliable information for quantitative modeling.
Until recently, the energy transport process in ceramic TBCs has been measured by an empirical parameter: thermal
conductivity. This measure does not distinguish the relative contributions of radiation and true conduction. To determine the
relative importance of radiative and conductive transport in ceramic TBCs, a number of factors affecting the two transport
processes must be considered (see appendix B). Attention should be given to understanding the mechanisms of energy
transport in TBCs with the goal of reducing energy transport rates and increasing substrate-metal protection even further.
Knowledge of the relative importance of radiation and conduction will guide research strategies aimed at improved coating
performance. Attention should be given to understanding the mechanisms of energy transport in TBCs with the goal of
reducing energy transport rates and increasing the life of components.
The performance of TBCs depends on the characteristics of interfaces with well-understood and controlled features. For
example, the thermally grown oxide interfacial layer between the metallic bondcoat and the ceramic TBC influences adhesion
and hence coating life. Improved understanding of interfacial behavior is required to control properties and predict
performance. A more compatible and oxidation-resistant bond between the metallic substrate and the TBC should receive
continued near-term emphasis.
COATING PROCESSES
The current generation of MCrAlY coatings, as well as those emerging from new TBC technologies, would benefit
significantly from advances in process control. Both types of coatings are deposited by the same processes and both show a
similar variability in performance. Improved on-line control should be developed to ensure that the coated structure is highly
reproducible, a necessity if structures are to perform within the parameters set by service requirements. For TBCs, it is not
clear what processing factors are most important to performance or performance variability. Consequently, these must be
identified before appropriate sensors can be incorporated.
To manufacture improved coatings, process modeling, monitoring, and feedback controls will all have to become more
common. The near-term TBC effort should focus on two fronts: minimizing variability while maximizing service life. The
technical approaches by which developers choose to tackle this two-pronged challenge will no doubt vary. Iterations of
models followed by increased understanding of parametric variables, and then model modification, will be necessary.
Manufactured product uniformity will, in addition, require the development of process sensors and feedback controls, again
perhaps, by an iterative process. Application of laboratory NDE (nondestructive evaluation) concepts, such as infrared
imaging, should be applied to manufacturing process control (Murphy et al., 1993).
The two principal manufacturing processes for TBCs (i.e., plasma spray and physical vapor deposition) produce coatings
with significantly different microstructures, properties, and durabilities. In addition to these technical attributes, there are
significant coatability issues that can strongly impact the cost of the coating. The choice of coating process depends on a
balanced assessment of the technical attributes, the coatability issues, the cost, and the performance requirements demanded
from the coated component.
Process control can only be achieved if the relationship of the process-to-product performance is understood.
Development of such knowledge should be a priority, near-term endeavor for advanced coatings. Such parametric data,
guided by an understanding of coating behavior and failure modes, can be quickly and reliably acquired by rig testing, but the
variability of the rig test must also be known. Rig-test modeling, parameter sensing, and feedback control will be an
evolutionary and continuing near-term activity. 1
Although engine tests do not necessarily provide data on individual processes, they do present opportunities to test
complete (integrated) concepts in both propulsion and stationary power plants. These tests are necessary to provide an overall
qualification of a new coating system.
Repair and Overhaul

Engineers rely strongly on visual inspection to assess the condition of coatings. Improved NDE is needed to determine
when coatings should be removed and the extent of base-metal attack For aircraft engines, the development of advanced
NDE techniques and cost-benefit models will also be essential for assessing the new generation of components. These
components are expected to be multiwall/thin-wall structures with multilayered coatings used as an integral part of the
component design and manufacture. NDE, or some form of monitoring, is required to assess coating health during use. An
example of a simple monitoring method for static structures would be to use sensors to detect abrupt increases in temperature,
indicating potential TBC spalling and a need for inspection. Other more complex schemes may be available.
Analytical Methods
Because future engines will rely heavily on coatings to protect hot-section components, accurate models for coating
1 The NRC (1989) study On-Line Control of Metal Processing predicted this process evolution.

and component life will become essential. Coating life and inherent substrate environmental resistance are key determinants
in setting the frequency of engine inspections and overhauls. Coating producers and users thus have a widespread need for
general purpose data and models. Examples of these include data on long-term thermodynamic and structural stability,
generic process models, and life-prediction models. Engineers need advanced analytical techniques to measure coating
properties, including those for nanostructure materials. Appropriate combinations of methods must allow measurement on
the microstructural scale of the material relevant to specific properties (e.g., adhesion, fracture toughness, thermal
conductivity, and elastic modulus). Such methods may provide the basis of standard tests for assessing coatings.
Analytical design analysis of the mechanical stress (strains) imposed on coated components is fairly well understood and
may help in estimating service life. The degradation caused by oxidation and, to a lesser extent, corrosion is reasonably well
defined but not with high precision. The impact of other factors, such as erosion and variable environmental conditions (e.g.,
variability in air quality), is less clear. For example, the prediction of special events, such as impact damage, are not currently
factored into life models. Both users and manufacturers have a strong interest in life prediction, and refinement of these
methodologies is a continuing task. The precision of these models should improve with experience. Indeed, a better
understanding of current coatings and substrates will probably be gained more from service experience than from additional
laboratory work.
Failure to properly predict service life from laboratory tests has often resulted from variability in rig test conditions.
While rig conditions may vary, such variations are probably less than those occurring in service. Service-life variations may
also result from a factor far less understood: manufacturing variability.
There is a broad-based need for prestandards research that, particularly for TBCs, identifies critical properties and the
scale on which they are relevant. This research provides the basis for formulating a set of standards used to measure and
compare coating systems. It can also provide the data required for performance models (e.g., methodologies for measuring
thermal conductivity, interfacial adhesion, and microstructural characterization).
Modeling
Because future engines will rely heavily on coatings to protect hot-section components, accurate models will become
essential to describe a number of coatings-related requirements, particularly (1) process attributes, (2) degradation modes
(e.g., oxidation and corrosion), and (3) service-life prediction and residual-life assessment. Process modeling is most
important to coating manufacture and should be able to characterize process-dependent factors such as microstructure, rate of
coating deposition, and cost, all based on user needs. Degradation modeling is most important to coating design and
development. Coating life and inherent substrate environmental resistance are key determinants in setting engine inspection
and overhaul intervals. Few models in the public domain address any of these needs.
Coating life is determined by many factors: the mission profile, environmental conditions, accuracy of the design
analysis, the coating system selected, and the manufacturing process used. At this time, there is a good-to-excellent
understanding of the design conditions and mission profiles and a fair-to-good understanding of the environmental conditions
for conventional applications. Understanding the relationship between process parameters and in-service performance (scatter
of the properties) is fair to good for metallic coatings and currently only poor to fair for TBCs. Refinements in life prediction
will be gained through models of the entire coating life cycle, ranging from engineering analysis to component retirement.
The key factors needed to complete this model are the integration of current, specific domain models, better comprehension
of special mission-caused (random) events, and a parametric understanding of the manufacturing process. The greatest
benefit will probably be gained by defining manufacturing process capability and control, along with an improved
understanding of environmental conditions and their effects.
Nondestructive Evaluation
Advanced NDE methods are needed to characterize hot-section turbine components at inspection points during their
service life. Some methods are currently available to support decisions on repair or replacement of components, and their
application should be encouraged. In other cases, methods need to be developed for this use and as a basis for life prediction.
How useful are advanced NDE methods in assessing the fitness of turbine components following repair and
refurbishment? A comprehensive review of the currently used and candidate NDE methods could be applied to in situ process
monitoring and control, enhancing the reproducibility and cost of high-temperature coatings.

LONG-TERM OPPORTUNITIES AND INNOVATIVE SYSTEMS 46
8
Long-Term Opportunities and Innovative Systems
In the long term (i.e., beyond five to ten years), the static and dynamic components of high-temperature turbine engines
will continue to operate in harsh environments at temperatures above the incipient melting point of nickel-base superalloys.
Two primary factors are likely to increase research and development activity in advanced hot-section materials. First, the
realization is spreading that the current material systems for coated substrates are technologically mature (see chapter 7).
Second, market demand is growing for turbines with even higher efficiencies, in the aircraft engine and land-based
applications, to attract the necessary investment. The required performance levels will only be attained if one or more of the
following occurs:
• use of advanced substrate materials (e.g., ceramics)
• production of cooling schemes that impart a very low performance penalty
• development of highly reliable TBCs (thermal barrier coatings) or some other insulating technologies
Monolithic-ceramic and ceramic-composite substrate materials represent a long-term path to enhanced high-temperature
performance. These materials, however, will likely need protective coatings for long-term durability in some operating
environments. For example, silicon carbide and silicon nitride are susceptible to rapid high-temperature oxidation (as
discussed in chapter 3).
This chapter presents several innovative coating concepts that are attractive but unproven. Many are ideas borrowed
from other technology areas, such as microelectronics. They are offered to stimulate further innovative approaches by
researchers in industrial, university, and government laboratories. The committee believes that such imaginative ideas will
lead to the necessary breakthroughs for the future. The first section of the chapter presents a few architectural concepts for
advanced coatings. The second section discusses several innovative coating technology concepts.
INNOVATIVE COATING ARCHITECTURES

As stated throughout this report, close integration of coating and substrate materials will undoubtedly occur. The coated
structures emerging from this integration will be known as hybrid components, since the demarcation between substrates and
coatings will be difficult to discern. Control of interface properties for these new coatings will be a critical feature, especially
the control of the substrate/coating junction. The control of this singular interface will continue to be a key to the success of
high-temperature coating application. Advanced coatings will have multiple interfaces that must operate at higher
temperatures in steeper thermal gradients and will have to be confined to the sub-micron scale. Such structures are referred to
as nanostructures, with layer thicknesses in the 1- to 1,000-nanometer range. Adherence and metallurgical stability will also
be major requirements. In all cases, an important element is the stability of such structures in the high-temperature
environment of an operating turbine engine. Research on issues of stability is a high priority. The structural motifs for hybrid
coatings include continuously graded coatings, horizontally layered materials, interphase layer materials, vertically layered
materials, and three-dimensional structured materials.
Continuously Graded Coatings

The area of graded coatings (e.g., layered, continuously graded, and micro-or nanolayered coatings) offer the potential to
improve coating performance by providing position-dependent physical or mechanical properties. The concept of graded
coatings-more recently termed functionally graded materials (FGM; Ramesh and Markworth, 1993)-was developed and used
to improve TBC adherence in rocket engines over 30 years ago (Ingham and Shepard, 1965). The same types of thermal
spray coatings, which included both layered and continuously graded thermal spray coatings, have since been used as outer
air-seals of aircraft gas-turbine engines and thick-graded TBCs in diesel engines (Miller, 1990; Goward, 1987; Yonushonis et
al., 1987). While current thick-graded coatings are inappropriate for rotating parts in turbines, the continued improvement in
process control in thermal spray and other deposition methods (appendix E) offers the opportunity to develop thin-graded
coatings that may offer some of the benefits of grading while being sufficiently light for use on turbine blades.

FGM coatings will minimize thermal stresses in the coating caused by thermal coefficient mismatches. A continuous
compositional variation across the coating is associated with a continuous variation in the coefficient of thermal expansion
(CTE). In the ideal case, the composition of the coating would continuously vary, becoming a pure ceramic at the exposed
face of the coating. The CTE of the coating region adjacent to the substrate would match the expansion coefficient of the
substrate.
The inherent inhomogeneity in the microscopic scale of these materials raises questions about their stability at high
temperatures. These questions must be answered to establish the viability of these approaches. To spur development in this
research area, there should be a critical assessment of the use of FGMs as coatings and a definition of the influence of
multilayer and nanostructure morphology on resulting properties.
Hand-in-hand with advanced substrate materials (e.g., ceramic carbide and nitride, intermetallics, composites, and
refractory metal alloys), there exists a need for coatings capable of withstanding high temperatures.1 Meeting this demand
may require alternative coating materials as well as alternative application processes. Advanced substrates will possess
coatability characteristics (e.g., diffusion rates and surface chemistry) dramatically different from current superalloys. Novel
concepts may be needed for coatings and surface treatments to protect future advanced substrate systems.
Horizontally Layered Materials

Layered materials offer a number of opportunities for advanced coating concepts. They can be designed to reflect
thermal radiation, reduce heat transfer across an interface, and match the CTE of the coating with the substrate.
A coating may serve as a high-temperature, optical multilayer interference filter that reflects radiation. Such a system
may consist, for example, of alternating thin layers of two oxides, each having a different refractive index (e.g., zirconia-
yttria 2.07 and alumina 1.60). A process similar to Bragg diffraction reflects a very high fraction (e.g., 0.95) of the incident
radiant energy. The range of thicknesses of the deposited layers is related to a quarter wavelength of the peak wavelength of
light (about 1 to 2 microns), which corresponds to the black-body temperature of the engine. Calculations show that 95
percent of radiant energy will get reflected for only 38 microns of total coating thickness. This corresponds to about 63 pairs
of oxide layers.
Multilayered coatings may also reduce the heat-conduction load to the substrate by taking advantage of the lower rate of
heat transfer across an interface. Heat transfer across an interface is reduced if the two layers have differing thermal
effusivities.2 In a multilayer structure, the successive reductions at a series of interfaces may lead to a significant reduction in
the total heat transfer by conduction.
Multilayers also provide the opportunity to match CTE at the coating/substrate interface, possibly minimizing the
thermally induced internal stresses in the coating. The CTE of the coating layer adjacent to the substrate would closely match
the expansion coefficient of the substrate. In subsequent layers, the composition would vary in step increments, becoming a
pure ceramic at the exposed face of the coating. This concept will need to be examined from an engineering mechanics point
of view, however.
Interphase Layers
The boundary between the substrate and the first layer of oxide is the crucial interface in any system designed to afford
protection in a high-temperature environment. Separation of the oxide from its substrate is less likely to occur if this interface
is replaced by an interphase, the composition of which could vary smoothly and gradually from the substrate metal (or
ceramic) to the full oxide of one of the abundant elements of the substrate.
The full oxide layer immediately adjacent to the substrate is currently alumina (often with some chromia). In present
technology, zirconia, usually stabilized with yttria, is then deposited to provide a thermal barrier. From the standpoint of
thermal expansion, zirconia might possibly adhere better if the MCrAlY/zirconia or alumina/zirconia interface were
compositionally graded through intermediate compositions. However, previous research has shown that such a
compositionally graded metal/ceramic layer undergoes oxidative expansion, resulting in severe compressive stresses that
cause the oxidized graded layer to buckle the coating from the substrate (Duvall and Ruckle, 1982; DeMasi-Marcin et al.,
1989). There may be potential for other gradient schemes, however. Zirconia is softer and susceptible to erosion; it might be
worthwhile to top the zirconia with a graded layer as well, although this concept must be balanced against weight
considerations.
Vertically Layered Materials

Using a layered structure in the coating or substrate also improves the thermal isolation of the substrate from the engine
environment. The present design for TBCs appears to have conflicting demands—the need for adherence and for
1 Higher-temperature-capable ceramic coatings are currently being explored, for example, as part of the High-Speed Civil Transport
program.
2 Thermal effusivity is defined as the square root of the product of thermal conductivity and specific heat.

low heat transfer between coating and substrate. Adherence to the substrate (required for structural integrity) invariably
results in good transfer of heat to the substrate. One potential solution is to take advantage of the lithographic patterning
technology widely used in the semiconductor industry.
For example, the substrate could first be coated with an adherent ceramic material that has a high thermal conductivity
but can withstand high-temperature oxidation (Step A). Step B would use existing lithographic patterning techniques to form
high-aspect-ratio (high depth with narrow width) trenches in the coating. The following step (Step C) would fill in the
trenches with a poor adherent and thermally low-conducting material. This would limit heat transport down to the substrate.
The final step (Step D) would seal the outer surface.
Such a channel structure may also reduce the radiative heat load. If the repetition distance between channels is
commensurate with the infrared wavelength for which the unstructured coating is transparent, diffraction from the channel
structure will increase the reflectance of the coating/substrate system regardless of the intrinsic reflectivity of the substrate.
Three-Dimensional Structured Materials

Employing three-dimensional networks to coat microstructure can improve the mechanical stability of the coating and
possibly its resistance to heat conduction. An example is the distribution of ceramic whiskers in a ceramic matrix of a similar
composition. The whiskers could be formed in situ through a phase transformation process (e.g., silicon carbide [SiC] and
silicon nitride [Si3N4] precipitate in an acicular shape [needles or whiskers] when they transform from their beta form during
heating).
In situ formation of three-dimensional ceramic reinforcements may be applicable to coatings of ceramic-matrix
composites. SiC, Si3N4, or other ceramic materials might be incorporated as aggregates or agglomerates of beta-form
particles in the matrix powder and blended with the matrix phase before heating. 3 On heating, the aggregate phase will
transform from the beta to the alpha form and precipitate as a whisker or needle. In this way, sintering, densification, and the
desired amount of bonding between the matrix and whisker phases can be achieved, yielding a robust composite coating that
is strong, lightweight, highly dense, and resistant to severe environmental distress.
OTHER INNOVATIVE CONCEPTS

The committee identified several additional innovative technologies that may improve the coating/substrate system. In
most cases, researchers have examined these concepts, but the work has not advanced to the point where practical systems
have been developed. The committee believes that further research is warranted in these endeavors despite the lack of success.
Nanocrystalline Coatings and Substrates

Promising research of nanocrystalline substrate and coating materials, with improved high-temperature properties, may
allow for higher engine-operating temperatures and therefore improved performance in the future. For example, the SiC
nanoparticles in SiC-particle-reinforced alumina appear to facilitate crack healing, resulting in improved high-temperature
strength and creep resistance as compared to monolithic ceramics (American Ceramic Society Bulletin, 1996).
Nanocrystalline coatings consisting of TiN nanocrystallites embedded in amorphous Si3N4 are being studied for use as a wear-
resistant coating (Dias et al., 1995). Nanocrystalline structures could also potentially be developed to provide high reflectivity
to reflect radiant heat or lower conductivity because of phonon scattering.
One potential problem with using nanocrystalline materials at elevated temperatures is exaggerated grain growth, which
could result in sintering to great density (Dowding and Malghan, 1995). Sintering is problematic for TBC coatings in
particular, because a relatively porous microstructure is typically desired to accommodate strain release. Fine grain size may
be maintained by incorporating a second phase (e.g., SiC in A12O3) to inhibit grain growth (Dowding and Malghan, 1995;
American Ceramic Society Bulletin, 1996). Further research is needed to determine the optimum compositions and
processing parameters and to develop a commercial method for production of nanocrystalline materials.
Advanced Processing
Coatings processes developed by the electronics industry for the manufacture of semiconductor devices may help design
coatings for high-temperature structural materials. For example, electronics processing relies increasingly on in situ
monitoring and process diagnostics (intelligent processing) to achieve nanoscale structural control and characterization. Such
techniques might improve the quality of turbine coatings and reduce the cost of applying them. In the long term, the
committee believes that intelligent processing (i.e., in situ process control technology) will be required to achieve the
reproducible process control necessary for manufacture of reliable coatings.
3 Whiskers and fibers are generally very difficult to incorporate during powder processing, whereas aggregates of powders are not.

Intelligent processing of materials requires the availability and integration of process models that describe the
relationships of critical process parameters with sensors that measure these parameters and appropriate control systems.
Development of all these elements is required.
Built-In Sensors for Condition Monitoring

Microsensors could be embedded in TBC coatings to monitor local temperature rises, oxidation changes, and possibly
incipient debonding. These sensors would monitor in real time the degradation of protective coatings and may serve to warn
of imminent catastrophic failure. Alternatively, remote sensors rather than embedded sensors may achieve the same goal
(NRC, 1995b).
Embedded Microchannels within TBC for Cooling

Microdesigned coatings could include small cooling channels within the TBC. TBCs could provide even better thermal
insulation to the substrate by using external cooling, such as air forced along these channels. The effect of heat transfer from
ceramic to coolant must be considered along with issues associated with clogging of the channels while in service. The use of
lithographic patterning for formation of these channels should be considered.
To further enhance heat transport along these cooling channels, the use of steam, water, or even helium gas could be
considered. To limit the amount of helium that must be carried in air-based systems, closed-loop cooling would be needed;
this would be less of a concern for land-based systems. Alternatively, a fluid (gas) with poor thermal conductivity injected
into the channels might serve as an insulating sheath to limit heat conduction to the TBC.
Coatings for Refractory Metals

Refractory metals are attractive, potential substrates because of their high-temperature strength and high melting
temperatures. Their susceptibility to catastrophic oxidation, however, is the main barrier to their use in advanced turbine
applications. The coating systems for these substrate materials must be extremely reliable since the substrate rapidly
deteriorates once the coating is breached. Materials that have been explored as refractory metal coatings include
polycrystalline and amorphous silicides, as well as refractory oxides such as alumina.
Further research into refractory metal coatings may yield positive results. For example, a disilicide diffusion coating for
niobium could be modified with a small amount of germanium. The silica film that protects niobium from oxidation attack
would be modified by the dissolution of GeO2, which increases the expansion coefficient and lowers the viscosity of the
silica glass. Thus the protective glass film could form and flow into the cracks in the coating, possibly sustaining severe
temperature changes without spalling or pesting (Mueller et al., 1991).
Electron-rich noble metals (e.g., rhodium, palladium, iridium, and platinum) do not form thermodynamically stable
condensed oxides and have relatively low melting temperatures. When alloyed with electron-poor metals such as hafnium,
zirconium, and aluminum, however, they form remarkably stable compounds with close-packed, or nearly close-packed,
structures similar to those of the structural metals themselves (Brewer, 1990).4 These compounds have high thermodynamic
stability, high melting points, and low chemical activity. For example, Brewer and Wengert (1973) report that ZrIr3 melts at
2127 ± 130°C and does not interact with boiling aqua regia, molten KOH, or air at 1000°C. 5 It has the structure of AuCu3,
with a0 equal to 3.943 A. The formation of such alloys at the surface of a structural metal may provide a coherent, tenacious
coating.
4 An example is HfPt3 for which the enthalpy of formation has been evaluated as ∆Hf° = -132 ± 9 kcal mole-l (Brewer and Wengert, 1973).
5 ZrI3 has a free energy of formation of approximately ≤ -44 kcal mole-1 at 1527°C (Gibson and Wengert, 1984).


REFERENCES 51
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APPENDIX A 57
Appendix A
Testing and Standards
Broadly accepted test methods, standards, and specifications are of great value to both vendors and purchasers of coating
services and coated products. They are essential communication mechanisms for purchasers to describe the critical aspects of
required coatings and for coating suppliers to unambiguously understand the requirements.
Coatings are only used in gas turbines after a substantial testing and evaluation program by the engine manufacturer and,
where appropriate, by the coating vendor. Testing and analysis procedures are usually developed by the engine manufacturer
to:
• develop procedures, specifications, and controls for the deposition process
• serve as a quality control measure to ensure that coated products meet specified properties
• provide data for performance and lifetime prediction by evaluation under conditions simulating engine conditions
These procedures are developed by engine manufacturers to address specific conditions expected in each manufacturer's
engine. Notable examples of this approach are found in the several types of high-temperature tests developed by engine
manufacturers to simulate the corrosive behavior found in specific engines operating under specific conditions. Burner rigs of
various designs have evolved at each manufacturer that, through experience, can generate data for corrosion and thermal-
shock resistance. Many different methods of testing and analysis have evolved in the research community to develop new
coating compositions, microstructures, and processes as well as to understand coating behavior on a fundamental level.
The measurement of coating properties must be viewed in the context of a coating/substrate system. Coating
compositions and microstructures are complex and become more so during service at high temperature in corrosive
environments. Thus the use of material properties for design or lifetime prediction is usually based on the measurement of the
coating systems rather than the bulk materials, the properties of which may differ significantly from the same nominal
materials present as a coating.
While substantial efforts have been made by individual companies and research organizations to develop satisfactory
evaluation procedures, relatively few broadly accepted test methods are available for the evaluation of high-temperature
coatings. Consequently, much of the data publicly reported consist of measurements that are directly compared with the
behavior of widely used materials. This is a conservative approach suitable for the expensive turbines that are expected to
have high reliability. However, the need for increased productivity in the materials and gas-turbine fields argues for the use of
commonly accepted test methodologies that allow more cost-effective data generation and increased commonality of property
specification.
Definitions for the several terms used for standards have been developed by the American Society for Testing and
Materials (ASTM) and are followed in this discussion. A standard is defined as a rule for an orderly approach to a specific
activity, formulated and applied for the benefit and with the cooperation of all concerned. Six types of full consensus
standards are identified by the ASTM:
• Classification. A systematic arrangement or division of materials, products, systems, or services into groups based on
similar characteristics (e.g., origin, composition, properties, or use).
• Guide. A series of options or instructions that does not recommend a specific course of action.
• Practice. A definitive procedure for performing one or more specific operations or functions that does not produce a test
result.
• Specification. A precise statement of a set of requirements to be satisfied by a material, product, system, or service that
also indicates the procedures for determining whether each of the requirements is satisfied.
• Terminology. A definition or description of terms or an explanation of symbols, abbreviations, or acronyms.
• Test method. A definitive procedure for the identification, measurement, and evaluation of one or more qualities,
characteristics, or properties of a material, product, system, or service that produces a test result.
In general, company specifications dominate the commercial market and address characteristics such as composition,
microstructure, thickness, and strain-to-failure. The U.S. military has published specifications that address limited aspects of
high-temperature coatings, primarily for the thermal spray (plasma and detonation gun) processes. Broadly available
standards developed by consensus through

APPENDIX A 58
organizations such as the Society of Automotive Engineers and ASTM address feedstock composition and powder size for
thermal spray processes with limited coating property measurements. Foreign standards, notably British and German,
primarily address coating thickness with limited attention to physical or mechanical properties.
Testing standards are particularly important for thermal barrier coatings (TBCs) in that they include a ceramic layer(s)
and the inherent scatter in the mechanical properties of ceramics is accentuated by the complex microstructure produced by
thermal spraying or electron-beam physical vapor deposition (EB-PVD). The lack of standard test methods and data analysis
and interpretation techniques for relatively fundamental properties (e.g., strength, adhesion and cohesion, strain-to-failure,
and ductility) is accompanied, not unexpectedly, by a lack of standards for more complex properties (e.g., thermal shock,
fatigue, wear and erosion, corrosion, and toughness). Although basic and applied research has been conducted to understand
coating behavior and to relate processing and microstructure and microchemistry to properties and performance, little of this
effort has resulted in standards. The necessity to determine accurately appropriate properties for thermal-spray-deposited
coatings has been recognized (Berndt et al., 1992; Dapkunas, 1993), but a similar perspective for coatings applied by other
processes has not been developed. For TBCs, the lack of understanding of failure mechanisms hinders the identification of
required standards. This situation that exists for current superalloy components is also present for future materials such as
monolithic ceramics and ceramic-matrix composites, which may require coatings for oxidation protection.
The measurement of properties for use in coating micromechanical design is a significant area that has been neglected.
Measurements of properties (e.g., modulus of elasticity, coefficient of thermal expansion (CTE), inter-and intragranular
strength, and toughness) would be particularly valuable for design of TBCs and the functionally graded materials that are
similar in concept. The difficulty of measurement on the micrometer scale required for these materials is largely responsible
for this situation. Test techniques currently in development (e.g., nanoindentation) may alleviate this situation.
High-temperature coatings have not been the specific subject of standards development, and many of the standards
developed for other applications have been used where appropriate. The status of standard testing and analysis procedures
varies with the specific aspect of coating technology considered and is summarized in the following section.
NOMENCLATURE AND DESIGNATION

The description of high-temperature coating types and coating processes lacks well-defined, universally accepted
terminology. For example, the same process may be described as pack aluminizing or chemical vapor deposition. Similar
ambiguity occurs in the use of the term thermal spraying, which may inclusively refer to all high-temperature, gas-propelled
particulate applications to a substrate or specifically to high-velocity, oxygen-fueled deposition. The proprietary, rather than
commodity, nature of the coatings industry necessitates that a specific coating be designated by the manufacturer rather than
by technical or trade bodies. There are clear benefits for using commonly accepted terms to describe coating processes or
attributes, but there does not appear to be value in the development of commonly accepted coating designations.
PROCESSING
Standards, or more precisely procedures, for processing are generally developed by coating producers and users.
However, the reliance of the military on coatings to achieve desired performance objectives has fostered the issue of
specifications for both plasma spray and detonation gun deposition processes. ASTM standards developed for the minerals-
handling and powder metallurgy industries have been adopted for use where applicable by the plasma spray industry for the
analysis of powders. Although company specifications for processes (e.g., EB-PVD or sputter deposition) are used, they have
not been adopted as publicly available standards. Furthermore, suitable reference materials are not available for the
calibration of analytical instruments necessary for process control (Dapkunas, 1993).
MECHANICAL PROPERTIES
Mechanical properties, particularly as a function of temperature, are critical to the performance of a coating and
consequently are the subject of measurement in the coatings field.
The properties of greatest concern for metallic overlay or conversion coatings are ductile-to-brittle transition, fatigue,
thermal-shock resistance, adhesion, and strain-to-failure. Test procedures for these properties are generally of the elevated-
temperature uniaxial tensile, creep, stress-rupture, or fatigue type developed for metals and alloys. The evaluation of ceramic
overlay coatings used for thermal barriers focuses on adhesion to the substrate and cohesion within the coating.
Traditional methods for the qualitative evaluation of adhesion (e.g., bending, scratching, or impacting) that were
developed for less complex materials (e.g., zinc coatings) are of limited value but are nonetheless included in ASTM, British
Standards Institute, and International Standards Organization (ISO) standards. The most commonly accepted adhesion test

APPENDIX A 59
is ASTM C 633-79, the tensile tab test, which is comparable to DIN 50 160-A, AFNOR NF A91-202-79, and JIS H866680
(Berndt, 1990). This technique is limited by the use of an epoxy adhesive grip attachment at test temperatures significantly
lower than service temperatures. Brown et al. (1988) have provided a review of methods used to measure the adherence of
coatings applied by thermal spray, including flexure and fracture mechanics techniques, and conclude that widely used tests
do not provide the information required and that simulation of service conditions is vital. Thermal-shock tests can provide a
qualitative measure of adhesion and have been developed for the porcelain-coated steel industry. The importance of
determining the mechanical properties of coatings has encouraged the development of compressive, tensile fatigue techniques
for coatings removed from substrates (Beardsley, 1992). These methods have not been codified as standards.
Recognition of the importance of more subtle properties such as fracture toughness, thermal-shock response, and
thermomechanical fatigue has been manifested in research on the modeling of coating behavior and was the subject of a
recent conference (Kokini, 1993). However, standards for the measurement of these properties are not available.
Hardness is commonly used as a process control measure, and its application to coatings has been recognized in the
development of BS 5411-part 6, Vickers and Knoop microhardness, for metallic coatings. Fracture mechanics analysis has
been combined with microindentation to measure the fracture toughness of ceramics and has been applied to ceramic coatings
(Besich et al., 1993). More recently, instrumented microindenters and nanoindenters that provide data on deformation as a
function of load have been developed that can provide a measure of elastic properties. Nanoindentation offers the potential to
measure hardness and elastic modulus of specific portions of microstructures as small as several micrometers that can be
applied to modeling. None of these latter techniques have been developed into standards.
CORROSION
Metallic overlay and conversion coatings are used to impart oxidation and hot-corrosion resistance to alloy substrates.
Ceramic TBCs are expected to exhibit corrosion resistance and to protect the substrate as well.
Corrosion behavior is determined by a variety of static and dynamic tests in environments selected to simulate expected,
pertinent aspects of turbine-operating environments. Static tests in furnaces with stagnant or low gas flows provide
information on thermodynamic stability and reaction kinetics. Data usually consist of weight changes with time, corrosive
penetration determination by metallographic examination, phase-change identification, and corrosive product formation.
Dynamic testing is usually conducted in burner rigs operating at atmospheric pressure and gas velocities of less than 100
feet per second. High-velocity and elevated-pressure burner rigs that more closely simulate turbine conditions are used less
frequently. Specimen analysis of burner-rig samples usually consists of metallographic examination and compositional
analysis of corrosion products. Standards for the conduct of these tests, the specimen types, and the interpretation of data are
not available. Nonetheless, significant amounts of research have allowed the comparison of data among the different tests.
Recognition of the value of understanding the relationships among the test methodologies for hot corrosion is reflected
in the early publication of ASTM STP-421 that provides focused coverage of the tests used in the 1960s (ASTM, 1967).
Similar comparisons of more recently developed tests have not been published. The evaluation of corrosion and thermal-
shock resistance of TBCs, particularly plasma-sprayed coatings, has been the subject of considerable research. Engine
manufacturers and the NASA Lewis Research Center have used burner rigs of various designs for this purpose, and research
at the latter institution has highlighted the necessity of well-designed experiments (Miller et al., 1993).
EROSION
Although test methodologies to evaluate the erosion of coatings and substrate alloys in turbine environments have been
used extensively, standards for generally accepted techniques have not been developed. ASTM G76-83 (Standard Practice for
Conducting Erosion Tests by Solid Particle Impact Using Gas Jets), for example, uses large particles at low velocities at
temperatures of 18-28°C. Typically, evaluation tests for turbine materials are conducted in burner rigs that use particle
injection or in high-temperature furnaces using particles entrained in high-velocity gas streams. Specimen evaluation usually
consists of a measurement of surface recession and the data provide a ranking of the materials examined. The degree of
erosion damage is influenced by particle properties (e.g., size and hardness), impact angle, and velocity. These influences are
in addition to coating properties (e.g., hardness and microstructure) that may vary with temperature and long-term exposure
to operating conditions. These parametric difficulties may render standard erosion tests that provide data for accurate
performance prediction an unrealistic expectation.
THERMAL PROPERTIES
Thermal properties are a particular concern for ceramic TBCs. Knowledge of thermal conductivity, preferably at the

APPENDIX A 60
temperature of intended use, is important for design and life prediction, while knowledge of thermal expansion coefficients
are critical to understanding the adherence to the substrate and stresses in the coating.
Thermal conductivity of bulk materials and coatings is routinely measured by the use of a laser flash apparatus that
provides a controlled heat input to the front of a sample and measures surface temperature change at the back. Direct
measurements are obtained through the use of the guarded hot plate technique that uses a well-insulated apparatus to heat one
side of a specimen, while the temperature is measured on the other side. Standards for the guarded hot plate technique
(ASTM C-177) and the laser flash (ASTM E-1461) are available for uncoated specimens and may be extended to coated
specimens. The ease of the laser flash technique makes it attractive for commercial use and argues for the development of a
standard reference material that can be related to results from the guarded hot plate method.
Heat transfer through coatings is influenced by the thermal emissivity as well as the thermal conductivity of the coating.
Techniques for measuring emissivity are available and will become more important as operating temperatures increase. These
techniques are not available as standards for coatings.
The thermal comparator method has been used to determine the conductivity of films thinner than 1 micron. This work
has shown that these materials can exhibit conductivities as much as two orders of magnitude lower than bulk materials of the
same composition and that significant interfacial thermal resistance can develop (Lambropoulos et al., 1993). This observed
behavior has implications for the use of thin multilayer TBCs and warrants the evaluation of this class of materials by
techniques for which standard methods are available.
CTEs can be measured on coatings removed from a substrate using conventional dilatometry, but the graded
composition and microstructure of TBCs adds a degree of complexity that can result in specimen bowing. Although bowing
may complicate conventional measurements, this phenomena could, in principle, be used as an alternative method to
determine coating expansion. Standards for determining the CTE for coatings are unavailable.
MICROSTRUCTURE
Microstructure of coatings is routinely inspected and analyzed by metallographic preparation of cross sections. Although
examination of metallic overlay and conversion coatings is relatively straightforward, graded coatings, which can include
porosity and relatively loosely bonded material in the case of plasma-sprayed material, presents more difficulty. Special
techniques (e.g., epoxy infiltration) are required to preserve the coating microstructure. Procedures for metallographic
preparation and microstructural analysis have been developed by coating producers and users but have not been codified as
standard methods.
Porosity, manifested as coating density, has significance for coating thermomechanical behavior, corrodent penetration,
heat transfer, and centrifugal loading of turbine disks. Standards for measurement of connected porosity by use of the BET
gas absorption technique are routinely used (e.g., ASTM C-577-92-refractory permeability). Unconnected porosity is more
difficult to measure. Sophisticated techniques (e.g., small-angle neutron scattering) have been used in research to determine
pore size and distribution. This technique is not suitable for routine laboratory or production use but may provide a means to
synthesize standard materials for calibration of metallographic or other techniques.
INTERNATIONAL ACTIVITIES
Although the lack of standards for the evaluation of coatings has not impeded the development of new materials for gas
turbines, the increased emphasis on international trade may well cast standards in a new light. The greater interest in
standards developed by national standards organizations is manifested for materials generally by activities conducted under
the auspices of the Versailles Agreement on Materials and Standards that addresses prestandards research. Standards for
coatings are addressed specifically by the Committee for European Normalization Technical Committee 184 for Advanced
Technical Ceramics (Working Group 5-ceramic coatings). These standards generally correspond to the standards set by
national standards organizations. Nations that do not participate in the development of these standards are placed in the
unenviable position of having to provide test data according to procedures developed by competitors. Although this is not an
insurmountable obstacle to overseas marketing, the early presence of domestic firms in the development of these standards
allows the specific concerns of domestic firms to be accorded consideration and shape the standards finally adopted.
Participation of U.S. firms in this activity is clearly important for the long-term well-being of the domestic turbine and
coatings industries. The development of standards for analysis of coatings can have immediate, positive effects in providing
data that are more useful to the turbine industry, but long-term changes that generally affect industry should also be
considered.
ISO 9000, an international standard for certification that manufacturers have implemented quality assurance procedures,
is increasingly required for sales of products. One facet of this procedure is the identification of test and analysis procedures
that ensure that products have specified properties. The availability of standards for coating evaluation provides well-
accepted criteria for use in the certification procedure. Similarly, for many coating processes, reproducible

APPENDIX A 61
deposition relies on the skill and judgment of equipment operators. Certification of these operators, similar to that required
for welders, may be desirable in meeting the requirements of ISO 9000. This requirement has fostered the formation of the
National Aerospace and Defense Contractors Accreditation Program, which aims to develop industrywide quality
accreditation procedures.
The increased exchange of product data among manufacturers has encouraged the development of computer protocols
for the exchange of materials information. This activity is conducted under the auspices of ISO Technical Committee 104,
subcommittee 4, and is identified informally as STEP (Standard for the Exchange of Product model) and formally as ISO
10303. Completion of the program is expected by the year 2000. Although originally focused on the exchange of data for
computer-aided design, a program is in place to allow the exchange of material data from producers to users (Rumble and
Carpenter, 1992). In 1994, standards drafted by the committee for the description of materials properties were developed and
are expected to be adopted as ISO standards. Application protocols for the exchange of data relative to specific industries are
planned, with testing of polymers the likely first use. International commerce in turbine coatings could well be impacted by
this data exchange methodology and warrants participation by the domestic turbine and coating manufacturers.
SUMMARY
Relatively few standard test and analysis techniques have been developed for high-temperature coatings. The coatings
community would be well served by the availability of broadly accepted standard measurement techniques for microstructure,
mechanical, and thermal properties on scales appropriate for the design and analysis of coating systems. The Committee for
European Normalization has identified coatings measurement standards as a topic for development, and it is reasonable to
expect that these standards will be incorporated into the ISO code. The interests of producers and users of domestic coatings
would be well served by the participation of these parties in the development of standards that reflect their methods of
measurement. The current standards for coatings are listed below.
CURRENT STANDARDS
American Society for Testing and Materials
Processing
B 212-89 Standard Test Method for Apparent Density of Free-Flowing Metal Powders
B 213-90 Standard Test Method for Flow Rate of Metal Powders
B 214-92 Standard Test Method for Sieve Analysis of Granular Metal Powders
B 215-90 Standard Test Methods of Sampling Finished Lots of Metal Powders
C 702-87 Standard Practice for Reducing Field Samples of Aggregate to Testing Size
Properties
B 571-91 Standard Test Methods for Adhesion of Metallic Coatings (bend, burnishing, chisel-knife, draw, file, grind-saw, heat-
quench, impact, peel, push, scribe-grid tests, qualitative only; similar to BS 5411/Part 10)
C 177-85 Steady State Heat Flux Measurements and Thermal Transmission Properties by Means of the Guarded-Hot-Plate Apparatus
C 313 Adherence of Porcelain to Steel (discontinued)
C 633-79 Standard Test Method for Adhesion or Cohesive Strength of Flame Sprayed Coatings (reapproved 1993)
C 577-92 Standard Test Method for Permeability of Refractories
Other
D 4541-85 Standard Test Method for Pull-Off Strength of Coatings Using Portable Adhesion Testers
F 692-80 Standard Test Method for Measuring Adhesion Strength of Solderable Films to Substrates (reapproved 1991)

APPENDIX A 62
Society of Automotive Engineers
Processing
AMS 2435C Detonation Process-Tungsten Carbide/Cobalt Coating
AMS 2436B Coating, Aluminum Oxide-Detonation Deposition
AMS 2437B Coating, Plasma Spray Deposition
AMS 5791 Powder, Plasma Spray, 56. 5Co-25. 5Cr-10. 5Ni-7. 5W
AMS 5792 Powder Plasma Spray, 50(88W-12Co) + 35(70Ni-16.5Cr-4Fe-4Si-3.8B) + 15(80Ni-20Al)
AMS 5793 Powder, Plasma Spray, (95Ni-5A1)
AMS 7875 Chromium Carbide Plus Nickel-Chromium Alloy Powder, 75Cr2C3 + 25 (80Ni-20Cr Alloy)
AMS 7878 Tungsten Carbide Powder, Cobalt Coated
AMS 7879 Tungsten Carbide-Cobalt Powder, Cast and Crushed
AMS 7880 Tungsten Carbide-Cobalt Powder, Sintered and Crushed
Military Standards
Processing
MIL-C-52023 Coating: Ceramic, Refractory, for High Temperature Protection of Low Carbon Steel -1958
MIL-STD-1886 (AT) Tungsten Carbide-Cobalt Coating, Detonation Process -1992
MIL-C-81751B Coating, Metallic Ceramic
MIL-M-80141C Metallizing Outfits, Powder Guns and Accessories -1987
MIL-STD-1884A (AT) Coating, Plasma Spray Deposition -1991
MIL-Z-81572 (AS) Zirconium Oxide, Lime Stabilized, Powder and Rod, for Flame Spraying -1991
MIL-83348 Powders, Plasma Spray (CANCELED)
British Standards Institute
Properties
BS 5411 Methods of Test for Metallic and Related Coatings
Part 1 Definitions and Conventions Concerning the Measurements of Thickness
Part 2 Review of Methods for the Measurement of Thickness
Part 3 Eddy Current Method for Measurement of Thickness of Non-Conductive Coatings on Non-Magnetic Basis Materials
Part 4 Coulometric Method for the Measurement of Coating Thickness
Part 5 Measurement of Local Thickness
Part 6 Vickers and Knoop Microhardness Tests
Part 7 Profilometric Method for Measurements of Coating Thickness
Part 8 Measurement of Coating Thickness of Metallic Coatings: X-Ray Spectrometric Methods
Part 9 Measurement of Coating Thickness of Electrodeposited Nickel Coatings on Magnetic and Non-Magnetic Substrates-
Magnetic Method
Part 10 1981/ISO 2819-1980 Review of methods for testing adhesion of electrodeposited and chemically deposited metallic
coatings on metallic substrates (burnishing, ball burnishing, shot peening, peel [less than 125 microns], file, grinding and
sawing, chisel [greater than 125 microns], scribe and grid, bending, twisting, tensile, thermal shock, drawing, cathodic;
qualitative only)
Part 11 Measurement of Coating Thickness of Non-Magnetic Metallic and Vitreous or Porcelain Enamel Coatings on Magnetic
Basis Metals: Magnetic Method
Part 12 Beta Backscatter Method for Measurement of Thickness
Part 13 Chromate Conversion Coatings on Zinc and Cadmium

APPENDIX A 63
Part 14 Gravimetric Method for Determination of Coating Mass per Unit Area of Conversion Coatings on Metallic Materials
Part 15 Review of Methods of Measurement of Ductility
Part 16 Scanning Electron Microscopy Method for Measurement of Local Thickness of Coatings by Examination of Cross Sections
BSI M. 40 Aerospace Series-Methods for Measuring Coating Thickness by Non-Destructive Testing
DIN
Processing
50961-87 Electroplated Coatings: Zinc and Chromate Coatings on Iron and Steel: Chromate Treatment of Zinc and Cadmium Coatings
50966-88 Electroplated Coatings: Autocatalytic Nickel-Phosphorus Coatings on Metal in Technical Applications
50967-91 Electrodeposited Coatings of Nickel Plus Chromium and Copper Plus Nickel Plus Chromium
50968-91 Electrodeposited Coatings of Nickel and Nickel Plus Copper
Properties
50933-87 Measurement of Coating Thickness by Differential Measurement Using a Stylus
50949-84 Non-Destructive Testing of Anodic Oxidation Coatings on Pure Aluminum and Aluminum Alloys by Measurement of
Admittance
50955-83 Measurement of Coating Thickness. Measurement of Thickness of Metallic Coatings by Local Anodic Dissolution:
Coulometric Method
50976-89 Corrosion Protection: Hot Dip Batch Galvanizing: Requirements and Testing
50978-85 Testing of Metallic Coatings: Adherence of Hot Dip Zinc Coatings [up to 150 microns]
50982 PT 1-87 Principles of Coating Thickness Measurement: Terminology Associated with Coating Thickness and Measuring Areas
50982 PT 2-87 Principles of Coating Thickness Measurement: Review of Commonly Used Methods of Measurement
50982 PT 3-87 Principles of Coating Thickness Measurement: Selection Criteria and Basic Measurement Procedures
50987-87 Measurement of Coating Thickness by the X-Ray Spectrometric Method
50160-A Tensile Adhesion
Other
50960 PT 1-86 Electroplated and Chemical Coatings: Designation and Specification in Technical Documents
50960 PT 2-86 Electroplated and Chemical Coatings: Indications on Drawings
Japan Institute of Standards
Properties
H8666-90 Testing Methods for Thermal Sprayed Ceramic Coatings
R4204 Method of Testing Ceramic Coating

APPENDIX A 64
REFERENCES
ASTM (American Society for Testing and Materials). 1967. Hot Corrosion Problems Associated with Gas Turbines. Special Technical
Publication 421. Philadelphia, Pennsylvania: ASTM.
Beardsley, M.B. 1992. Thick thermal barrier coatings. Pp. 567-572 in Proceedings of the Annual Automotive Technology Development
Contractors' Coordination Meeting, Dearborn, Michigan, November 2-5. Warrendale, Pennsylvania: Society of Automotive
Engineers.
Berndt, C.C. 1990. Tensile adhesion testing methodology for thermally sprayed coatings . Journal of Materials Engineering 12:151-158.
Berndt, C.C., W. Brindley, A.N. Goland, H. Herman, D.L. Houck, K. Jones, R.A. Miller, R. Neiser, S. Sampath, M. Smith, and P. Spanne.
1992. Current problems in plasma spray processing. Journal of Thermal Spray Technology 1(4):341-356.
Besich, G.K., C.W. Florey, F.J. Worzala, and W.J. Lenling. 1993. Fracture toughness of thermal spray ceramic coatings determined by the
indentation technique. Journal of Thermal Spray Technology 2(1):35-38.
Brown, S.D., B.A. Chapman, and G.B. Wirth. 1988. Fracture kinetics and the mechanical measurement of adherence. Pp. 147-157 in
Proceedings of the National Thermal Spray Conference, October 24-27, D. Hauck, ed. Metals Park, Ohio: ASM International.
Dapkunas, S.J. 1993. NIST-Industry Workshop on Thermal Spray Coatings Research. NIST Journal of Research 98(3):383-389.
Kokini, K., ed. 1993. Ceramic coatings. In Proceedings of the 1993 ASME Winter Annual Meeting, Materials Division, New Orleans,
Louisiana, November 28-December 3. New York: American Society of Mechanical Engineers.
Lambropoulos, J.C., S.D. Jacobs, S.J. Burns, L. ShawKlein, and S.S. Hwang. 1993. Thermal conductivity of thin films: measurement and
microstructural effects. Pp. 21-32 in Thin Film Heat Transfer-Properties and Processing, Vol. 184, M.K. Alam, M.I. Slik, G.P.
Grigoropoulos, J.A.C. Humphrey, R.L. Mahajan, and V. Prasad, eds. New York: American Society of Mechanical Engineers.
Miller, R.A., G.W. Lissler, and J.M. Jobe. 1993. Characterization and Durability of Plasma Sprayed Zirconia-Yttria and Hafnia-Yttria
Thermal Barrier Coatings. NASA Technical Paper 3295. Washington, D.C.: National Aeronautics and Space Administration.
Rumble, J., and J. Carpenter. 1992. Materials STEP into the future. Advanced Materials and Processes 142(4):23-27.

APPENDIX B 65
Appendix B
Radiation Transport in Thermal Barrier Coatings
The energy transport process in ceramic thermal barrier coatings (TBCs) has been measured until recently by an
empirical parameter: thermal conductivity. This measure does not distinguish the relative contributions of radiation and true
conduction. A role for radiative transport is raised by the transparency of some of the ceramics used for TBC applications in
the infrared spectral region for wavelengths in the region of 1 to 6 µm (Thomas and Joseph, 1987; Thomas, 1989; Sova et al.,
1992). This region also corresponds to the region of maximum black-body emission for the operating temperatures of present
gas-turbine engines. Advanced engines under development in current NASA and U.S. Department of Energy programs are
expected to reach even higher temperatures with correspondingly higher levels of infrared radiation incident on the coating in
the 1- to 6-µm band from the interior of the engine. The combination of high infrared radiation density and low coating
absorption suggests that radiation may compete with conduction for energy transport across the coating.
Radiative transport of energy across a uniform coating involves a number of factors:
• the intensity and spectral distribution of infrared radiation in the engine enclosure in the 1- to 6-µm region
• infrared reflection at the coating/engine and coating/blade interfaces
• scattering and absorption within the coating
• radiation trapping in the coating by internal reflection of radiation
Regarding the source energy distribution, the radiant energy that is incident on a coated blade or vane in the engine will
have contributions from both the burning gas and the other engine surfaces. The relative contributions of these sources may
change with position in the engine and blade number. Factors influencing infrared reflection at the coating/engine interface
include a quasi-specular component associated with the difference in dielectric constants of the gas and coating as well as a
diffuse reflection associated with the structure of the coating surface. For example, coatings applied using an electron-beam
physical vapor deposition (EB-PVD) process have a polycrystalline columnar structure that leads to significant scattering in
the visible spectral region. The same coatings are partially transparent in the infrared in the 1- to 6-µm region (Murphy et al.,
1993), however, suggesting that scattering is size related via the parameter ka where a is a dimension of the crystallites in the
coating and K=2πD/λD is the characteristic size of the scatterer, and λ is the wavelength. In the case of EB-PVD coatings the
scatters are features such as the spacing and organization of columns in the coating (the coating has a columnar structure) and
individual crystallites in a column. Both of these contribute to the scattering. This result further implies that the penetration of
radiation from an external source will depend on the wavelength and angle of incidence.
Scattering has been shown to play an important role in determining the internal temperature distribution in layered
specimens (Siegel and Spuckler, 1993b). For specimens that exhibit both scattering and absorption of radiation, the
temperature distribution is affected by the albedo, which is a measure of the relative importance of scattering and absorption
(Siegel and Spuckler, 1993a). Radiation trapping caused by internal reflection was also shown to play an important role in
determining the temperature distribution (Siegel and Spuckler, 1993a). In light of the roles that scattering and radiative
transport play in reducing the temperature gradient (i.e., creating more uniform temperatures along the blade) and since
temperature gradient drives thermal conduction, any estimate of the relative importance of radiation and conduction requires
that a treatment consider both mechanisms simultaneously.
TBCs fabricated from layers of oxides of varying optical thickness have been proposed to reduce radiative transport by
selective reflection of infrared radiation in the 1- to 6-µm band (Soechting, 1994). These TBCs would form high-temperature
interference filters in the near infrared. In addition, multilayered materials will affect the rate of conductive transport
(Aamodt et al., 1990a,b). For example, multilayered structured TBCs, or more generally nanostructured TBCs, could reduce
both conductive and radiative transport. The relative importance of the two processes should be determined through more
extensive study.
REFERENCES
Aamodt, L.C., J.W.M. Spicer, and J.C. Murphy. 1990a. Analysis of characteristic thermal transit times for time

APPENDIX B 66
resolved infrared radiometry studies of multilayered coatings. Journal of Applied Physics 68(12):6087-6098.
Aamodt, L.C., J.W.M. Spicer, and J.C. Murphy. 1990b. The effect of transverse heat flow and the use of characteristic times in studying
multilayered-coatings in the time domain. Pp. 59-63 in Photoacoustic and Photothermal Phenomena II, J.C. Murphy, J.W.M. Spicer,
L.C. Aamodt, and B.S.H. Royce, eds. Berlin, Germany: Springer-Verlag.
Murphy, J.C., J.W.M. Spicer, and R. Osiander. 1993. Thermal Imaging of High-Temperature Coating. Presentation to the Committee on
Coatings for High-Temperature Structural Materials, National Materials Advisory Board, National Research Council, Washington,
D.C., October 12.
Siegel, R., and C.M. Spuckler. 1993a. Variable refractive index effects on radiation in semitransparent scattering multilayered regions.
Journal of Thermophysics and Heat Transfer 7:624-630.
Siegel, R., and C.M. Spuckler. 1993b. Refractive index effects on radiation in an absorbing, emitting and scattering laminated layer.
Transactions of American Society of Mechanical Engineers 115:194-200.
Soechting, F. 1994. Gas Turbine Design Issues. Presentation to the Committee on Coatings for High-Temperature Structural Materials,
National Materials Advisory Board, National Research Council, Washington D.C., February 17-18.
Sova, R., M.J. Linevsky, M.E. Thomas, and F.F. Mark. 1992. High temperature optical properties of oxide ceramics. Johns Hopkins APL
Technical Digest 13:369-378.
Thomas, M.E. 1989. A computer code for modeling optical properties of window materials. Proceedings of SPIE: Window and Dome
Technologies and Materials 1112:260-267.
Thomas, M.E., and R.I. Joseph. 1987. Characterization of the complex index of refraction for sapphire, spinel, alon and yttria. Proceedings of
the IRIS Specialty Group on Infrared Materials, June 9-10.

APPENDIX C 67
Appendix C
Survey of Nondestructive Evaluation Methods
For coating systems in high-temperature gas-turbine applications, the primary nondestructive evaluation (NDE) issues
are the ability to measure the stability and adherence of materials at elevated temperatures. Processes such as oxidation, hot
corrosion, creep, and solid-state diffusion degrade performance of both coating and substrate at high temperatures with
relatively high reaction rates. These processes can lead to spallation of the coating, coating/substrate interdiffusion, and crack
formation in the coating or substrate. These changes can occur at the interface between coating and substrate or at other
interior sites. Consequently an important criterion for selecting an NDE method is the ability to monitor the subsurface
condition of coated structures. However, in view of the many goals for NDE and the wide variety of coating systems, failure
modes, and component designs, no single NDE approach can meet all needs. Hence NDE methods should be selected to
address specific requirements.
This appendix surveys selected NDE methods that have been, or potentially could be, applied to coated structure.
Several promising, emerging methods are also discussed. All NDE methods use some external source to produce a response
from the sample that can be detected without causing a permanent change in the specimen. The information extracted by the
measurement is determined both by the initial source/specimen interaction and the detection method. NDE methods form
families of techniques classified by either source-detection method or source/specimen interaction. Table 6-1 lists some of the
primary NDE methods that have been used for coating inspection grouped primarily by detection method.
OPTICAL METHODS
Optical methods in this discussion refer to ultraviolet, visual, and infrared spectroscopy and imaging. Optical methods
measure light transmitted or reflected from a specimen as a function of wavelength or position on the sample for selected
polarizations or angle of incidence. From these measurements, absorption or reflection spectra can be determined if the form
of the incident light wave is known or, alternatively, if images can be formed. Since many coatings scatter light from the
voids or interfaces between grains, absorption measurements made by these techniques involve contributions from intrinsic
absorption and scattering.
In the ultraviolet and visible light case, the incident light does not penetrate far into the sample but is confined near the
coating surface by scattering. While surface cracks and other features that have a surface expression can be detected, little
information can be obtained about the coating/substrate interface. Scattering is wavelength-dependent, however, and
decreases with increasing wavelength. As a result, scattering is low enough in the near-infrared that it is possible to observe
reflection from the substrate and the interface between the substrate and coating and to identify regions where the coating
(e.g., yttria-stabilized zirconia TBCs) has disbonded from the superalloy substrate.
Emission spectra can be obtained in the infrared region for heated samples and the optical properties of TBC materials,
including the absorption coefficient, determined using Kirchoffs relations between emissivity, reflectivity, and absorptivity.
Thermally stimulated emission spectra are much more difficult to obtain in the ultraviolet to visible ranges as seen from
Planck's radiation law,
where Q is radiative flux per unit wave length, λ is the wavelength, T the temperature, and C1 and C2 are the first and
second radiation constants. For the temperature range of interest to turbine coatings applications, virtually all of the radiation
is at wavelengths longer than 1 to 1.5 µm independent of the emissivity of the specimen. For yttria-zirconia and some other
ceramics, the emissivity has been determined and the absorptivity derived (Thomas and Joseph, 1987; Thomas et al., 1988;
Thomas, 1989). There is a relatively low intrinsic absorption in the 2- to 4-µm region, and this allows the substrate to be
viewed directly if scattering is excessive. This region of transparency should be explored for other candidate TBC ceramics to
assess the prospect of inspection of the interface with the substrate as well as the coating microstructure.
A second aspect of this region of high transparency is the role of radiative transport in heat transfer across a TBC. Some
thermal-imaging methods described later in this appendix can determine the rate of heat transport by conduction. However,
the relative importance of conductive versus radiative transport does not seem to be well understood and should be studied
(see appendix B for a discussion of energy transport in these coatings). If the

APPENDIX C 68
gas-emission spectra follow a black-body law at the operating temperatures of existing and proposed engine temperatures, the
peak emissions fall within the region of coating transparency suggesting efficient radiative transport. If the radiative load is
high, then strategies to increase the thermal efficiency of the TBC must minimize both conduction and radiation.
Visual inspection is widely used for NDE of coatings. For metallic coatings, the primary goals are to determine if the
coating is spalled from the substrate and if either the coating or the substrate is cracked. The major failure mechanisms of loss
of oxidation protection by loss of the protective metal-oxide layer or by interdiffusion of coating and substrate can lead to the
attack of the coating/substrate interface and to cracking under thermal cycling. Spallation and cracking of the coating can be
identified by visual inspection in some cases. While visual inspection is not quantitative and cannot determine the useful
remaining life of the coating, it can assess current damage at some level.
Enhanced visual inspection methods may improve the quantitative aspects of the method and should be applied to in-
service inspection. Methods based on computer-aided image processing should be standard methods of inspection of engine
components for sizing of parts and location and quantification of surface defects, such as cracks and spalls. Sizing of
individual surface features may provide statistical data on qualitative changes that would aid routine inspection. The changes
of surface features with service time should be monitored to document the initial condition and the rate of change with time
with the goal of improving lifetime prediction. Technical aids such as coherent fiber optics in the visible and infrared might
allow visual inspection of some parts to be carried out in situ.
THERMAL METHODS
Thermal imaging methods use a source of energy to create a temperature field in a specimen and a detection method to
monitor the temperature changes. The information obtained depends on the initial source distribution, the subsequent thermal
diffusion, and the detection method used. The dependence on the detection method exists because detection is based on
measuring a change in some physical property of the specimen caused by temperature. Different properties may have
different temporal and spatial scales as discussed below.
Optical-Source Infrared Radiometric Detection

For optically opaque materials, amplitude-modulated (pulse or step) optical heating acts as a surface heat source equal to
a flux of heat into the specimen surface. This flux induces a change in surface temperature with time based on the magnitude
of the flux and the rate of thermal diffusion into the specimen.
For a layered specimen, the surface temperature initially follows the functional form of the uniform specimen but then
deviates in a direction that depends on the characteristics of the second layer, the interface properties, and the depth of the
second layer in the sample. The time at which the deviation occurs is the thermal transit time and can be used to determine
the coating thickness if the thermal diffusivity is known, or alternatively, the thermal diffusivity if the thickness is known. For
example, accuracy of measurement for the thickness of 200-µm TBC coatings is better than 5 percent.
This method can also confirm that an infrared image represents a disbonded region. The time-resolved thermal image
quantitatively measures the extent of the disbond, whereas the passive infrared gives rapid views of the area. These methods
may allow characterization of the coating/bondcoat/substrate interfaces as a function of time if the spatial resolution for
imaging of the interface is adequate. The results suggest that infrared source and thermal detection methods can be
complementary methods for monitoring the condition of ceramic TBCs on high-temperature substrates.
Other-Source Infrared Radiometric Detection

Other sources (i.e., non-optical) that heat internal regions of the coating or heat the substrate or bondcoat may provide
the spatial resolution needed to detect substrate cracks or changes in conductivity by thermal cycling. An illustration is the
localized induction heating (Lehtiniemi et al., 1991, 1993) of a plasma-spray-deposited ceramic on a high-temperature metal
alloy. The inductive source heats the component resistively by currents induced in the substrate. Since cracks and other
thermal features inhibit current flow and heat flow, this method can image subsurface features through the analysis of surface
temperature distribution.
Microwave-source methods also have promise for TBC characterization. Many ceramic materials are relatively
transparent to microwaves within the 10 GHz region. Hence microwaves can penetrate the coating with little loss and interact
with specific features or constituents in the coating that may be present as contaminants that were deposited during the period
of service. The resultant temperature changes may be detectable using infrared imaging methods. Thermally detected
microwave spectroscopy has already been shown to have high spatial resolution (10 µm) and the ability to determine the
presence of selected impurities in dielectric materials. As a speculative idea, perhaps the presence, or even the concentration,
of sulfur or other fuel-related species could be determined at the coating/substrate interface by this method.

APPENDIX C 69
Radiometric Methods in Coating Deposition

Radiometric methods are illustrative of the use of NDE methods in process control applications (Moreau et al., 1991,
1992). In plasma spraying, the heat source is ceramic particles that are accelerated toward a substrate through a hot plasma
flame. The particles melt in passing through the flame. The infrared emission from the particles is monitored while in passage
from flame to substrate and on the substrate itself. Using fast infrared detection methods, time-temperature profiles of
individual particles on the deposited surface can be measured as they cool. The heat transfer rate depends on the thermal
conductivity of the deposited layer and the characteristics of the particle, including particle size. Issues affected by the rate of
cooling are lateral spread on the coating, extent of crystallization, and size of crystallites. Some changes in overall
morphology can be followed. This method might be of value in providing sensor input to allow real-time control of plasma
spraying so that the desired microstructure is deposited.
Laser Acoustic Interferometric Imaging

There are a range of thermal imaging methods that use a thermal source to induce a mechanical response by thermal
expansion. Images are formed by scanning an amplitude-modulated, focused laser beam over the sample and measuring the
surface displacement of the specimen either at the point of heating or at some point close by. There are several factors that
affect the response, including the peak height of the surface deformation produced by the heating and the lateral spread and
hence the slope of the deformation. Such methods can provide information about the spatially diverse mechanical responses
of a specimen. These methods may have utility in imaging spatial changes in the stiffness of interfacial bonds.
Induced Current Methods

Induced current methods use relatively low-frequency magnetic and electric fields of varied frequency as the excitation
source. In the case of a magnetic source, the induced magnetic fields generated by the interaction of the source with a
conducting sample are measured. This interaction takes the form of eddy currents, which are dispersive waves penetrating the
specimen to a depth called the skin depth. This depth, d, can be expressed as where s is the specimen
conductivity, µ the permeability, and ω is the frequency. As in the case of thermal imaging, the depth sampling provided by
the skin depth, and especially its frequency dependence, allows buried regions of a specimen to be examined in a single-sided
measurement. Eddy-current methods can determine the electrical properties of individual layers in multilayer conducting
materials and the properties of conducting regions below a dielectric layer. They can also determine the presence of a crack in
a buried conductive layer and, in some cases, the crack density. From an NDE perspective, this could be of value in assessing
changes in the bondcoat or substrate with time because of crack formation or interdiffusion.
A derivative of the eddy-current method called photoinductive imaging (Moulder et al., 1992) offers higher spatial
resolution (micron scale) for many materials. Eddy-current methods can also measure coating thickness with good accuracy
(Smith and Stephan, 1990).
Other electromagnetic methods related to eddy currents use a variety of magnetometers and magnetometer arrays to
monitor specimen condition (Goldfine et al., 1993; Wickswo et al., 1993). These advantages derive from the ability of
nonsearch coil methods to operate at low frequencies to spatially pattern the fields in the specimen (Goldfine et al., 1993).
Injected Current Methods

Injected current methods monitor the distribution of current injected into a material or component using sensitive
magnetometer arrays. These arrays can be physical arrays, in which measurements are made in parallel, or scanned arrays.
The injected currents can be of any frequency that can be detected, and hence the depth of penetration into the specimen is
controlled. One goal of these methods is to monitor through-thickness changes in current distribution that result from spatial
variations in conductivity that are either intrinsic (e.g., caused by deformation) or extrinsic (e.g., caused by cracks). Initial
experiments suggest that these methods may have a place with further development.
Conventional Ultrasonic Methods

Ultrasonic methods monitor the amplitude, phase, and velocity of an ultrasonic wave injected into the sample. Again,
both transmission and reflection modes are available. For a layered medium, such as the coating/substrate system, in addition
to a bulk compressional and two shear waves, Rayleigh waves and other interfacial waves exist. The characteristics of these
surface and interface waves depend on the thickness of the coating and the stiffness of the mechanical bond between the
coating and the substrate. These methods offer some promise for special applications, especially if noncontact generation and
detection methods at elevated temperatures are used.
Laser Ultrasonics and Interferometric Detection

This method is related to the laser acoustic interferometric imaging discussed previously but differs in that it uses the

APPENDIX C 70
analysis techniques of ultrasonics. A pulsed laser source is used to produce an ultrasonic wave in the specimen, and the
amplitude, phase, and arrival time of the wave are measured in a typical manner. The previous work could be viewed as the
quasi-static limit of laser source ultrasonics.
X-ray Methods
X-ray methods based on radiography or tomography have clear applications to inspection of coated components.
Examples include visualization of internal passages in turbine blades, the location of casting defects, and a determination of
the crystallographic structure of substrates, especially directionally solidified and single-crystal materials. Synchotron-source
X-ray topography has the advantage of allowing the crystal orientation and structure of an entire part to be visualized in a
single measurement. While these methods require special facilities, they might be useful in process development.
Other methods are based on X-ray fluorescence and scattering (Verbinski, 1990) and are directed at the inspection of the
coating. The X-ray scattering cross section is energy-dependent with elastic scattering (Compton scattering) dominating for
low-atomic-number targets and medium energies and fluorescence dominating for high-atomic-number targets and low
energies. In the case of fluorescence, energy-selective detection methods are used to provide some discrimination of
elemental composition. Because both coating and substrate are based on high-atomic-number material, this method appears to
have some promise for composition and coating density measurements.
There is a possibility that this method could be developed to include profiling of composition with depth and to monitor
changes associated with exposure to the engine environment. In practice, however, the results have been of limited value
because of counting-rate problems and difficulties in deconvoluting fluorescence line profiles.
EMERGING NDE METHODS FOR INSPECTING COATING SYSTEMS
X-ray Thermal Imaging: Composition with Depth

Another X-ray method that has only been applied to subsurface characterization of 10-µm multilayer films uses thermal
detection to monitor X-ray absorption as a function of photon energy (Masujima et al., 1987). The energy absorbed from an
X-ray source of variable energy increases near the characteristic wavelength of specific elements. This increased heat flux
into the sample changes the volume and surface temperature of the sample. The temperature changes can be detected by
methods that monitor either the surface temperature (e.g., radiometry) or the acoustic response of the sample as discussed
earlier in this appendix. Depth profiling is possible based on the arrival time for thermal diffusion from the layer to the
surface or on the acoustic propagation time to the detector. This approach has not been tried for coating systems, but it has
been used to characterize subsurface nickel and copper multilayers in semiconductor systems. Its potential advantages are
that it is single-sided, multi-element-sensitive, preferentially responsive to high-atomic-number elements, and able to depth
profile. Its disadvantages are the need for a high flux, tunable X-ray source.
Transient Grating Characterization Methods

Transient grating characterization methods have been recently introduced for characterization of deposited layers on
surfaces. In the simplest form, they involve formation of a linear array of lines of optical or other energy on the surface of the
specimen using moire or interferometric methods. Detection is also optical through either light reflection or emission
methods. Because the grating is both a thermal and an acoustic source, several detection modalities are possible. In the first
case, thermal properties can be determined in the plane of the coating and across the coating in a single measurement. In the
second case, ultrasonic waves of known spatial and temporal structure can be launched and reflections measured at very high
rates. Thin coatings and multilayered systems can be analyzed even for submicron layers, such as those present in some of the
nanostructured coatings being considered for TBC applications. The array allows the spatial frequency of the measurement to
be varied and the spatial scale of characteristic defects to be evaluated. These methods have advantages in being noncontact,
fast, and flexible in the information presented.
An example of possible applications of transient (picoseconds to microseconds) heating in coating characterization is the
use of fast radiometric heating of TBC and NiAl coatings. In both cases, the time evolution of the temperature response under
fast pulse heating was a relaxation whose time dependence is
T(t) = t-a
where t is time and a < 0.5 (the value for one-dimensional diffusion). This result suggests that the thermal diffusion in
these coatings is geometrically constrained by the coating structure. It may be possible to infer structure using these methods,
perhaps even in the process of layer deposition.

APPENDIX C 71
Microwave Thermoreflectance
As discussed previously, many ceramics used for TBC applications are transparent to microwaves. Microwave
reflectance measurements from the coating/substrate interface can be made to temperatures in excess of 1100°C and the
reflectivity measured as a function of temperature. This raises the prospect of direct measurement of the substrate temperature
through coatings. As another feature of the method, changes in reflectivity with melting and possibly with other phase
changes in the material have been seen. This method is in the early phases of development but appears to have promise for
application in all four areas of NDE applications.
Modulated Stress Methods

Transient grating methods can also be produced by modulated stresses in the plane of the specimen (Lesniak and Boyce,
1993). These methods are at much slower time scales than the interferometric methods but provide information about the
response in the quasi-static regime for both thermal diffusion and stress relaxation. They have proven to be of value in other
materials and coating systems and should be considered for high-temperature coatings.
REFERENCES
Goldfine, N.J., A.P. Washabaugh, S.V. Dearlove, and P.A. Guggenberg. 1993. Imposed w-k magnetometer and dielectrometer. Review of
Progress in Quantitative Nondestructive Evaluation 12:1115-1122.
Lehtiniemi, R., J. Hartikainen, J. Rantala, J. Varis, and M. Luukkala. 1991. P. 441 in Review of Progress in Quantitative NDE, Vol. 11A,
D.O Thompson and D.E. Chimenti, eds. New York: Plenum.
Lehtiniemi, R., J. Hartikainen, J. Rantala, J. Varis, and M. Luukkala. 1993. P. 1931 in Review of Progress in Quantitative NDE, Vol. 12B,
D.O Thompson and D.E. Chimenti eds. New York: Plenum.
Lesniak, J., and B.R. Boyce. 1993. Forced diffusion thermography. Pp. 92-102 in the Proceedings of SPIE-The International Society for
Optical Engineering Conference on Nondestructive Inspection of Aging Aircraft, Vol. 2001, San Diego, California. Bellingham,
Washington: SPIE.
Masujima, T., H. Kawata, Y. Amemiya, N. Kamiya, T. Katsura, T. Iwamoto, H. Yoshida, H. Imai, and M. Ando. 1987. X-ray photoacoustic
effect of solid materials. Chemical Letters 973-976.
Moreau, C., P. Cielo, M. Lamontagne, S. Dallaire, J.C. Krapez, and M. Vardelle. 1991. Temperature evolution of plasma sprayed niobium
particles impacting on a substrate. Surface and Coatings Technology 46:173-187.
Moreau, C., M. Lamontagne, and P. Cielo. 1992. Influence of coating thickness of the cooling rates of plasma sprayed particles impinging on
a substrate. Surface and Coatings Technology 53:107-114.
Moulder, J.C., E. Uzal, and J.H. Rose. 1992. Thickness and conductivity of layers from eddy current measurements. Review of Science
Instruction 63:3455-3465.
Smith, K., and R. Stephan. 1990. Protective Coatings Nondestructive Evaluation. Final Report. Contract F33615-87C-5221. Wright-Patterson
Air Force Base, Ohio: U.S. Air Force Wright Research and Development Center .
Thomas, M.E. 1989. A computer code for modeling optical properties of window materials. Proceedings of SPIE: Window and Dome
Technologies and Materials 1112:260-267.
Thomas, M.E., and R.I. Joseph. 1987. Characterization of the complex index of refraction for sapphire, spinel, alon and yttria. Paper
presented at the Meeting of the IRIS Specialty Group on Infrared Materials, June 9-10.
Thomas, M.E., R.I. Joseph, and W.J. Tropf. 1988. Infrared transmission properties of sapphire, spinel, yttria, and ALON as a function of
temperature and frequency. Applied Optics 27:239-245.
Verbinski, V.V. 1990. Protective Coatings Nondestructive Evaluation. Final Report. Contract F33615-87-C-5221. Wright-Patterson Air
Force Base, Ohio.: U.S. Air Force Wright Research and Development Center.
Wickswo, J., D.C. Hurley, Y.P. Ma, S. Tan, and J.P. Wikswo, Jr. 1993. P. 633 in Review of Progress in Quantitative NDE, Vol. 12A, D.O.
Thompson and D.E. Chimenti, eds. New York: Plenum.

APPENDIX D 72
Appendix D
Modeling of Coating Degradation
The availability of accurate models for predicting the life of coatings will become essential as future engines become
increasingly reliant on coatings to protect the components from the higher firing temperatures required to improve
performance. As discussed in chapter 4, coating life at high temperature is determined by many degradation mechanisms,
primarily oxidation, hot corrosion, and fatigue.
CURRENT STATUS
Models for life prediction based on high-temperature oxidation and hot corrosion of coatings are not well developed and
are largely empirical or semi-empirical. Existing approaches test coatings in furnaces or burner rigs to determine life and to
use experience factors to relate the life in the furnace or burner rig to the life in the engine. These approaches are
unsatisfactory but are used in the absence of better methods and in the presence of a large, even if questionable, database of
test results and correlations. Problems with these approaches include the following:
• The approach does not enable the life of a coating in a new engine design to be accurately determined but only to be
estimated.
• Burner-rig tests typically exhibit a large amount of scatter and are often useful only for comparison with other laboratory
reference materials.
• Furnace testing does not simulate the high-velocity gases and high heat fluxes to which coatings are exposed and which
can be important to their behavior.
• Hot-corrosion life depends on the deposition of the corrodants on the surface. The rate of this deposition is not given by
the burner rig or other methods used to test hot-corrosion resistance.
• The actual environments, including the erosive species, to which the coatings are exposed vary widely, especially for
industrial engines. These conditions are difficult, if not impossible, to simulate in the laboratory and are not always
known.
Although not satisfactory, determination of high-temperature oxidation life by these methods can be done for existing
engines after sufficient experience has been accumulated on the engine. However, hot-corrosion life requires a determination
of the deposition of the contaminants on the surface, which depends on the environment and the flow profiles through the
engine.
Modeling of high-temperature oxidation life has been developed by Probst and Lowell (1988), based on isothermal
oxidation and thermal cycling.
where ξ is the scale thickness, W0X is the weight of the oxide scale, ∆m/A is the mass gain per unit area, kp is the
parabolic rate constant, and t is time. kp is related to temperature by an Arrhenius rate law:
where kpo is a material constant, Q is the activation energy, R is the universal gas constant, and T is the absolute
temperature in K or °R. kpo is a function of oxygen partial pressure, but it is not a strong function. The model tracks the
formation of the oxide by a parabolic growth law (although other growth kinetics can be used), and the spallation of the oxide
due to thermal cycling.
where Wspall is the weight per unit area of the oxide spalled, Q0 is an experimentally derived material constant, and
Woxide is the weight per unit area of the oxide prior to spalling. (Only a portion of the oxide may spall and some of the oxide
may remain adherent to the coating.) The spallation equations are empirical and are based on careful experimental
measurement of the weight of the spalled oxide. Barrett and Lowell (1975) have also developed a mathematical expression to
fit cyclic oxidation data. Both of these approaches rely heavily on empirical methods. The model for thermal cycling is
attractive but is based on experimental calibrations of the amount of oxide spalled instead of a more fundamental, predictive
model. Furthermore, spallation data for only one

APPENDIX D 73
chromia-forming system and one alumina-forming system are available (at least in the public domain). The committee is not
aware of any actual uses of these models.
Wright et al. (1991) have developed models for erosion modified oxidation, based on an erosion rate assumed to
increase with the thickness of the oxide.
where ξ is the scale thickness as a function of time, t is the time between erosion events, a is an oxidation rate term, c is
the Pilling-Bedworth ratio,1 ξ1 is the scale thickness after the last erosion event (ξ l = 0 at t = 0), and k is a term describing the
oxidation kinetics (k = 0 for linear kinetics and k = 1 for parabolic kinetics). A numerical solution method is used to
determine the degradation of the coating.
Chang et al. (1990) have studied the interaction of erosion and oxidation and have defined the various regimes of erosion
and oxidation. These last two models were developed for coal gasification and fluidized bed applications. Bernstein
(unpublished work) has combined the oxidation, spallation, and erosion models for industrial gas turbines and has added
erosion rate terms. An example of the approach to modeling based on correlation with engine service experience is given by
Strangman (1990). For high-temperature oxidation, Strangman computes the oxidation rate as the product of an engine
experience factor, a burner-rig calibration constant, and a term for the temperature dependence of oxidation. For hot
corrosion, Strangman uses a lengthy expression as follows:
Hot-Corrosion Rate = Salt Deposition Factor · Salt Corrosivity Factor Salt Deposition Factor = {Salt Vapor Deposition +
(Component Experience · Particulate Salt Deposition) + Fuel Salt Deposition ·
Sulfate Formation + Fuel Vanadium Deposition + Salt RetentionEvaporation}
Salt Corrosivity Factor = {(Engine Component Experience · Burner-Rig Calibration Factor · Acidic Temperature Factor ·
Acidic Sulfur Factor) + (Engine Component Experience · Burner-Rig Calibration Factor · Basic Temperature Factor · Basic Sulfur
Factor) + (Engine Component Experience . Burner-Rig Calibration Factor · Vanadate Sulfur Factor) } · Fraction Salt Molten.
The total environmental attack is the sum of the hot-corrosion rate and the oxidation rate. These equations are solved by
means of a computer program that has additional calculations for many of the terms shown above.
Nesbitt (1984, 1989) has developed a diffusion-based approach to determine the oxidation life of coatings and bulk
NiAl. For bulk materials, the model computes the flux of aluminum to the surface and the removal of aluminum by oxidation.
When the aluminum flux becomes less than the aluminum consumption by formation of Al2O3, NiAl2O4 becomes the stable
oxide. Since this spinel is not protective, the bulk metal will be attacked at this point. For coatings, the flux of aluminum in
the coating to the surface is computed and the interdiffusion of the coating with the base metal is also computed. This
interdiffusion reduces the aluminum concentration (actually aluminum activity) in the coating, shortening the life of the
coating.
Fracture mechanics approaches to modeling coating spallation have been and are continuing to be developed (Evans,
1994). They usually predict a dependence on the square of the temperature change, ∆T
However, the utility of these models to predict coating degradation, as well as their agreement with experimental data,
remain to be determined. Continuing work on modeling coating degradation by fracture mechanics may or may not prove
useful. Until a better understanding of the physical mechanisms of coating degradation and the loss of the protective oxide is
obtained, it is not possible to say if this is a fracture problem or not. It must be remembered that the oxide is in a dynamic
flux, in which its composition, morphology, and thickness are changing as a function of time, and its properties depend on the
location within the oxide scale.
The committee did not seek, nor obtain, details of proprietary models used by engine manufacturers. However, the
models used by the manufacturers, as exemplified by Strangman's model, usually are empirical in nature.
FUTURE DIRECTIONS
Thermal Barrier Coating Modeling

TBC modeling is important for life prediction, understanding TBC behavior, and design of new coatings. Life prediction
is the primary modeling issue that is needed to obtain the maximum benefit of TBCs apart from process modeling, which is
covered elsewhere in this report. In spite of the use of TBCs for over 30 years, there has been relatively little activity in
modeling their durability and reliability. In the past 10 to 15 years, there have been several large studies sponsored by NASA.
Modeling is also necessary for more efficient design of new TBCs and for examination of the complex TBC failure
mechanisms. This subsection discusses previous and current models of the life and durability of TBCs and directions for
future development.
It should be noted that most of the modeling has been for high-temperature oxidation combined with thermal cycling.
Hot corrosion of TBCs is not well understood, and there has
1 The Pilling-Bedworth ratio is the ratio of the volume of the oxide formed to the volume of the metal consumed

APPENDIX D 74
been only a limited effort in modeling the hot-corrosion life of TBCs.

Early TBC studies combined modeling and experimental work to define some of the important factors in TBC durability
(Sevcik and Stoner, 1978; Cassenti et al., 1981), which are:
• the effect of residual stress generated during processing on coating spallation
• the correlation of in-plane compressive stresses on ceramic layer spallation
• the importance of maximum operating temperatures on TBC life
An oxidation-based failure model was proposed by Miller (1984) assuming that the strains imposed on the ceramic layer
were caused by thermal-cycle effects and that time at temperature effects acted to increase the effective thermal-cycle strains
caused by oxidation.
where Nf is the number of cycles to failure, εf is the failure strain in one cycle with no oxidation, εr is the thermal
expansion mismatch strain, W is the weight gain by oxidation, and Wc is the weight gain that should cause failure in one
cycle. b and m are material constants determined from the experimental data. Miller's model correlated the cyclic life of a
specific coating system tested at 1100°C for different thermal cycle times.
In the 1980s, significant advances in TBC modeling capability occurred for applications of specific TBCs. DeMasi et al.
(1989) used a model similar to Miller's for plasma-sprayed TBCs, except that the thermal-cycle strains were included using a
finite-element analysis that incorporated a Walker constitutive model for inelastic deformation of the ceramic during thermal
cycling, and the strain to failure in one cycle, εf, changes with oxidation.
where ∆εp is the inelastic strain range, εc is εf at W = 0, and the other terms are as before. This same model was used for
life predictions of EB-PVD (electron-beam physical vapor deposition) coatings (Manning-Meier et al., 1991), except that the
EB-PVD zirconia ceramic layer was assumed elastic, the bondcoat was assumed to have inelastic behavior, and the thermal
strain of the alumina scale was included. Therefore, the important cyclic strain for the EB-PVD ceramic was between the
alumina layer and the substrate. Both models showed reasonable correlation to the experimental results.
Hillery et al. (1988) focused on the edges of TBCs as failure initiation sites for some TBC applications. Edge failures
were driven by shear stresses in addition to normal stresses and oxidation. Oxidation was included through changes in the
time-dependent material behavior and the stress state. This model was also found to give reasonable agreement with
experiment.
Strangman et al. (1987) used a linear damage rule (damage from thermal cycling, oxidation, and hot corrosion) to reduce
the strain-to-failure of the ceramic (instead of increasing the effective strain per cycle). This model reduces to a
MansonCoffin relation. Again, the agreement to the experimentally measured lives was reasonable.
For each case the intent was to develop a model that would predict life for a given coating system rather than to
determine the active degradation mechanisms. To do this, each model incorporated information known about the active
degradation mechanisms for the specific coating and application domain, which was for aircraft engines. In addition, the
models were heavily dependent on calibration to experimental data to predict the correct absolute lifetimes.
The vast majority of TBC modeling, including those models cited above, has been for current aircraft applications,
which have a much different operational profile than land-based or marine gas turbines. Thus, for nonaircraft applications, it
may be expected that the relative contributions and importance of different mechanisms to TBC failure would be different.
These mechanisms include oxidation of the bondcoat, top-coat creep, sintering of the top coat, and the mechanical behavior
of the alumina scale. These mechanisms have not yet been adequately characterized experimentally or theoretically.
A few models address long-term oxidation behavior and loss of alumina-forming capability (''wear out") of overlay
coatings (Nesbitt and Heckel, 1984) and bondcoats for TBCs (Lee and Sisson, 1994). In these models, the life of the TBC is
determined by the life of the bondcoat. While these models are not appropriate for aircraft turbines, they may address one
aspect of failure for land-based and marine-based turbines.
Comprehensive models that can predict TBC life from first principles are necessary to be able to account for the wide
range of conditions to which TBCs are exposed. Before a model can be developed to predict TBC life from first principles, a
large number of factors must first be investigated. This

APPENDIX D 75
is because many of the potential contributors to TBC failure have not been adequately characterized because of the extreme
difficulty in experimentally isolating these factors. Understanding of TBC behavior has been enhanced by computer modeling.
Computer modeling has been used to investigate TBC behavior by isolating and investigating issues not easily amenable
to experimental study. Chang et al. (1987) and Phucharoen (1990) developed a finite-element model that examined the effect
of the rough interface between the bondcoat and ceramic layer, the mechanical effects of oxidation on the stresses in ceramic
layers, and the effect of bondcoat properties on TBC life. The most important of these issues are the effect of interface
geometry and oxidation on TBC stress levels. Another recent computer model examining failure mechanisms, instead of life
prediction, used the observed bondcoat creep response (Brindley and Whittenberger, 1993) to show that bondcoat creep can
result in substantial increases in the ceramic layer delamination stresses (Brindley, 1995), which should result in decreased
TBC cyclic lives. Ferguson et al. (1994) included bondcoat and top-coat creep along with a rough interface to provide a
clearer picture of the role of these factors increasing the stresses generated in a TBC during thermal cycling. Apart from
failure mechanisms, theoretical modeling may also shed light on heat transfer through TBCs, which in turn may guide design
of more-insulating coatings.
The models discussed above have been used to guide TBC development and design. A more "design capable" model for
TBCs is necessary to facilitate more rapid development and implementation of TBCs. Such a model would need to
incorporate operating conditions, life prediction from first principles, and thermal modeling from first principles. It will also
be necessary to establish a materials property database to support the model.
High-Temperature Oxidation
The current approach to modeling high-temperature oxidation is manageable for the original equipment manufacturer
(OEM), although not desirable. It is based on laboratory testing and correlation with field experience, which has been
developed over a number of years. One of the principal difficulties is the ability to accurately predict the surface temperature
of the blading. Although not a coating issue, the difficulty of predicting surface metal temperature is a barrier that limits the
ability of any coating degradation model to properly determine the life of the coating.
There is no current approach to predicting the degradation of the coating that the operator of the engine can use. The
operator relies on OEM guidelines, which are based on design considerations and accumulated field experience. The engine
operators need models that allow them to predict the coating life for their operation. This is particularly true for industrial
engines that experience a wide range of conditions. Any models developed for the operator will also assist the OEM.
The current approaches to modeling do not provide the necessary insight that allow the development of more-oxidation-
resistant coatings. Studies of a fundamental nature, as opposed to an engineering evaluation, are needed to determine how
coatings are exposed and how they perform in the field, particularly for industrial gas turbines. Engine exposure can be
fundamentally different than laboratory testing, and the nature of the protection by the coating will depend on the local
exposure environment of the coating. Once these environments are determined and the coating response in the engine is
established, laboratory studies simulating this behavior can be conducted to understand and predict the kinetics of the
degradation of the coating. These studies can lead to the development of improved coatings and coating degradation models.
Hot Corrosion
A great deal is understood about the mechanisms and chemistry of hot corrosion, as discussed elsewhere in this report.
The prediction of hot-corrosion attack of coatings in the field cannot be reliably performed, however. This inability is due in
part to the difficulty in predicting the generation and deposition of corrodants and knowing the chemistry of the deposits and
the surface metal temperatures.
As for high-temperature oxidation, the current approaches to modeling the life of a coating also do not provide the
necessary insight that allow the development of more-corrosion-resistant coatings. (The mechanistic and chemical studies of
hot corrosion do provide this insight, however.) Studies of a fundamental nature, as opposed to an engineering evaluation, are
needed to determine the exposure environment of coatings and how they perform in the field, particularly for industrial gas
turbines. As stated above, engine exposure can be fundamentally different from laboratory testing, and the nature of the
protection of the coating will depend on the local exposure environment of the coating. Once these environments are
determined and the coating response in the engine is established, laboratory studies simulating this behavior can be conducted
to understand and predict the kinetics of the coating degradation. These studies can lead to the development of improved
coatings and coating degradation models.
Modeling of hot corrosion is currently not as important as for high-temperature oxidation for industrial gas turbines
because of the use of clean natural gas. Hot corrosion is still of importance to aircraft and marine engines, however. It will
also be of importance to industrial engines if coal gasification or biomass fuels are used. Life prediction based on hot-
corrosion attack is particularly difficult because the onset of attack may be caused by a local flaw in the protective oxide

APPENDIX D 76
that permits contact of the fused salt film with the coating. Thus the phenomenon does not obey some steady-state predictable
kinetics.
Life-Prediction Models
One important aspect of the immature status of life-prediction models deserves emphasis. The overall goal for life-
prediction models is to enable the component designer or user of the engine to make successful decisions regarding the
selection of the superalloy, coating, and coating thickness distribution. Design decisions regarding the superalloy and coating
must be made early in the engine design process (i.e., when the airfoil is still on paper). The type of information that should
be available to the designer when selecting the coating and superalloy to be used is engine design parameters (e.g., gas
temperature, velocity, and pressure; substrate and coating temperatures; fuel/air ratio; inlet filtration efficiency; stress; strain),
anticipated application usage (e.g., fuel, location, altitude, and times at duty-cycle power points), available coating and
superalloy properties, and prior engine experience knowledge bases. To make successful decisions regarding the selection of
the superalloy, coating, and coating thickness distribution, the component designer or user of the engine needs mechanistic
life-prediction methods that are expressed in terms that the designer and user of the engine can recognize, control, and, in
some cases, adjust. For instance, life-prediction methods are needed that will enable designers to avoid thermomechanical
fatigue cracking of coated superalloy components. Environmentally enhanced thermomechanical fatigue is a special case of
low-cycle fatigue that is not adequately predicted with isothermal low-cycle fatigue data and models.
RECOMMENDATIONS
The understanding of the degradation and failure mechanisms of high-temperature coatings in the field need to be
improved, particularly with respect to the effects of engine operation and environment on the coating performance (e.g.,
thermal cycling).
Qualitative and quantitative models need to be developed that predict coating life based on mechanisms observed in
operational engines. These models need to be applied to optimize coating development and to estimate more accurately the
remaining coating life for in-service engines. However, property measurements using reliable test methods are required
before modeling.
Methods to determine the deposition rate of corrodants on in-service hot-structure components need to be developed
that can be monitored by the engine operators.
REFERENCES
Barrett, C.A., and C.E. Lowell. 1975. Oxidation of Metals 9:307-355.
Brindley, W.J. 1995. Properties of plasma sprayed bond coats. Pp. 189-202 in the Proceedings of the Workshop on Thermal Barrier Coating.
NASA-CP-3312. Cleveland, Ohio: National Aeronautics and Space Administration Lewis Research Center.
Brindley, W.J., and J.D. Whittenberger. 1993. Stress relaxation of low pressure plasma-sprayed NiCrAlY alloys. Materials Science and
Engineering A 163(1):33-41.
Cassenti, B.N., A.M. Brickley, and G.C. Sinko. 1981. Thermal and stress analysis of thermal barrier coatings. In AIAA/SAE/ASME 17th
Joint Propulsion Conference, Colorado Springs, July 27-29. New York: American Institute of Aeronautics and Astronautics, Inc.
Chang, G.C., W. Phucharoen, R.A. Miller. 1987. Finite element thermal stress solutions for thermal barrier coatings. Surface Coating
Technology 32:307-325.
Chang, S.L., F.S. Pettit, and N. Birks. 1990. Interaction between erosion and high-temperature corrosion of metals: the erosion-affected
oxidation regime. Oxidation of Metals 34(1/2):23.
Evans, H.E. 1994. Modeling oxide spallation. Materials at High Temperatures 12(2-3):219-227.
DeMasi, J.T., K.D. Sheffler, and M. Ortiz. 1989. Thermal Barrier Coating Life Prediction Model Development-Phase I. Final Report. NASA-
Ferguson, B.L., G.J. Petrus, and M. Ordillas. 1994. A Software Tool to Design Thermal Barrier Coatings. Final Report. NASA Contract
NAS3-2728. Washington, D.C.: National Aeronautics and Space Administration.
Hillery, R.V., B.H. Pilsner, R.L. McKnight, T.S. Cook, and M.S. Hartle. 1988. Thermal Barrier Coating Life Prediction Model Development.
Final Report. NASA-CR180807. Washington, D.C.: National Aeronautics and Space Administration.
Lee, E.Y., and R.D. Sisson. 1994. The effect of bond coat oxidation on the failure of thermal barrier coatings: thermal spray industrial
applications. Pp. 55-59 in Proceedings of the 7th National Thermal Spray Conference, Boston, Mass., June 20-24, C.C. Berndt and
S. Sampath, eds. Materials Park, Ohio: ASM International.
Manning-Meier, S., D.M. Nissley, K.D. Sheffler, and T.A. Cruse. 1991. Thermal Barrier Coating Life Prediction Model Development.
ASME Paper 91-GT-40. New York: American Society of Mechanical Engineers.
Miller, R.A. 1984. Oxidation based model for thermal barrier coating life. Journal of the American Ceramic Society 67(8):517.

APPENDIX D 77
Nesbitt, J.A. 1989. Predicting minimum Al concentrations for protective scale formation on Ni-base alloys. Journal of the Electrochemical
Society 136(5): 1511-1527.
Nesbitt, J.A., and R.W. Heckel. 1984. Modeling of degradation and failure of Ni-Cr-Al overlay coatings. Thin Solid Films 119:281-290.
Phucharoen, W. 1990. Unpublished Ph.D. dissertation, Cleveland State University.
Probst, H.B., and C.E. Lowell. 1988. Computer simulation of cyclic oxidation. Journal of Metals 40(10):18.
Sevcik, W.R., and B.L. Stoner. 1978. An Analytical Study of Thermal Barrier Coated First Stage Blades in a JT9D Engine. NASA-
Strangman, T.E. 1990. Turbine coating life prediction model. In 1990 Proceedings of the Workshop on Coatings for Advanced Engines,
August. Washington, D.C.: U.S. Department of Energy.
Strangman, T.E., A. Liu, and J. Neumann. 1987. Thermal Barrier Coating Life-Prediction Model Development. Final Report. NASA-
Wright, I.G., V.K. Sethis, and V. Nagarajan. 1991. An approach to describing the simultaneous erosion and high-temperature oxidation of
alloys. Journal of Engineering for Gas Turbines and Power 113(0ctober):616.

APPENDIX E 78
Appendix E
Manufacturing Technologies of Coating Processes
This appendix reviews various coating process technologies: diffusion coating, thermal spray (particulate deposition),
physical vapor deposition (atomistic or molecular transfer), and sputtering (atomistic deposition). Electrospark deposition is
also discussed. Auxiliary processes and quality control procedures are also reviewed.
DIFFUSION COATING PROCESSES
Pack Cementation
In the pack-cementation process, the parts to be coated are placed inside a vented or purged retort and embedded in a
pack mixture consisting of an inert powder (e.g., aluminum oxide), a source (e.g., pure or pre-alloyed aluminum), and
typically a halide activator salt to generate the transporting vapor species. The retort is placed in a furnace and brought to the
coating temperature. A protective atmosphere (generally argon or hydrogen) contacts the pack powders to prevent their
oxidation. Pack cementation is generally conducted at temperatures between 650 and 1090°C (1200 and 2000°F) between 2
and 20 hours. Aluminizing is by far the most common process, although packs have been used to transfer chromium, silicon,
and hafnium (Goward and Cannon, 1988). Recently, zirconium and yttrium have also been reported to be codeposited with
aluminum (Bianco and Rapp, 1993).
Variants of pack cementation include slurry-fusion and electrophoretic plating where the pack is either sprayed or
electroplated onto the part to be coated. The components are then heat treated in a protective atmosphere to form the coating.
For the intended thickness and aluminum concentration, there are over 20 different production aluminizing processes in
use. The principal differences are in the type of coating desired. The effective pack aluminum activity is selected through a
choice of the source-powder composition (commonly alloys of aluminum and chromium or cobalt), the amount of the source
powder compared to the inert oxide, the respective powder size distributions, and the halide activator used. The temperature
used for forming the coating determines to a large extent the degree of outward nickel diffusion obtained during processing.
At temperatures above
-1050°C (1925°F), coatings with more outward growth, characteristic for packs with reduced thermodynamic aluminum
activity, form NiAl with lower aluminum contents. Below -1000°C (1825°F), coatings with more inward growth produce
NiAl with higher aluminum contents. The low-temperature high-activity coatings may require an additional thermal diffusion
step out-of-pack to reduce the composition and property gradients (Goward and Boone, 1971).
Out-of-Pack Methods
For the above-the-pack process, the parts to be coated are fixtured out of contact with the pack mixture. The coating
vapors are transported to the parts by an inert carrier gas or purge gas and, through the use of two packs, both internal and
external surfaces can be separately coated (Levine and Caves, 1973; Benden and Parzuchowski, 1979; Bianco and Rapp,
1993). Other variations are also in use, such as pulse aluminizing and SNECMA vapor phase aluminizing (Gauje and
Morbioli, 1982). As with pack cementation, for pulse aluminizing and SNECMA vapor phase aluminizing, the retorts are
loaded into an appropriate furnace for the thermal cycle. Because of the increased path length for vapor transport, the out-of-
pack methods favor an increased tendency for outward growth and a generally reduced deposition rate.
Chemical Vapor Deposition

In the chemical vapor deposition (CVD) process, the coating deposition reaction takes place at the part surface. The
parts to be coated are fixtured in a retort and placed in the CVD furnace. The reaction gases are metered into the reactor from
external sources. Separate sources generally supply the internal and external airfoil coating circuits. Typical precursor gases
for CVD aluminizing are HCl or HF, and these are passed over a source of aluminum under specific conditions of
temperature, pressure, and flow rate to generate gaseous aluminum chloride or fluoride compounds. By proper selection of
processing conditions, the CVD process can be varied to create the gas phase analogous to the pack-cementation coatings.
The production of the platinum-modified aluminide on the external airfoil surfaces with a simple aluminide coating on the
internal

APPENDIX E 79
passages is currently of commercial interest (Smith and Boone, 1990).
THERMAL SPRAY PROCESSES
Plasma Spraying
A plasma gun functions through the operation of a stable nontransferred direct-current electric arc between a
watercooled thoriated tungsten cathode and an annular watercooled copper anode. An inert plasma gas, which is generally
argon with a few percent of an enthalpy-enhancing gas (e.g., hydrogen), is introduced as a vortex within the interior of the
gun. The electric arc between the cathode and the anode creates a plasma arc within this gas. This ionized gas exits from the
nozzle, where ionic recombination occurs, releasing enthalpy and yielding an effective temperature of the order of 15,000 K
for the typical torch operating at 40 kW. The plasma temperature drops off rapidly from the exit of the anode. The feedstock
powder is injected either internally or externally into the exiting plasma flame. The powder particles, approximately 40
microns in diameter, are accelerated and melted in the flame on their path to the target substrate, where they impact and
undergo rapid cooling (106 K/sec) and solidification. The particle velocity can range from 100 to several hundred meters per
second depending on spray parameters and the ambient atmosphere (e.g., low-pressure plasma spray; see below).
Plasma spray is generally used to form deposits of greater than 50-microns thickness of numerous industrial materials,
including nickel-base and ferrous alloys and refractory ceramics (e.g., aluminum oxide and zirconia based ceramics). To
approach theoretical bulk density and extremely high adhesion strength for high-performance applications, the plasma spray
of metallic coatings is carried out in a reduced-pressure inert gas chamber. This vacuum plasma or low-pressure plasma spray
(LPPS) operates at pressures of between 50 and 200 mbar. Shrouded flames can also be used (e.g., as developed by Praxair),
where argon or nitrogen excludes oxygen from the vicinity of the flame and the work piece.
Although traditional plasma spray guns are gas-vortex-stabilized and operate in the 40- to 80-kW power range, it is
possible to operate at considerably higher power levels (i.e., in the range of 160 kW and beyond) by using water stabilization.
With a material throughput of about 30 times that of gas-stabilized torches, these high-production rates allow the manufacture
of thick TBCs, such as those required in abradable seal applications (Chraska and Hrabovsky, 1992).
The key features of plasma spraying include the following:
• deposition of metals, ceramics, or any combinations of these materials
• formation of microstructures with fine, noncolumnar, equiaxed grains
• ability to produce homogeneous coatings that do not change in composition with thickness (length of deposition time)
• ability to change from depositing a metal to a continuously varying mixture of metal and ceramic (i.e., functionally
graded materials)
• ability to achieve high deposition rates (>4 kg/hr)
• ability to process materials in virtually any environment (e.g., air, reduced-pressure inert gas, high pressure, under water;
see the following section)
New and improved powder-processing methods have led to powders having predictable and controllable compositions
and well-delineated particle-size distributions, an important parameter in the plasma-spray process. Ceramic powders for
plasma spray are processed in diverse ways. Both particle size and shape are important controlling variables. In particular, the
particle-size distribution has a great influence on the velocity and melt behavior in the plasma flame. These issues are
discussed extensively in the literature (Herman, 1991). The deposition efficiency (i.e., the percentage of powder that actually
becomes part of the target body) is of obvious economical importance and arguably represents a measure of deposit quality.
Extensive literature exists on feedstock alloys and ceramic materials for plasma spray.
In addition to the starting material and its particle-size distribution, the microstructure of a plasma-sprayed coating also
depends on the processing parameters, including plasma power, plasma gas composition, pressures and flow rates, powder
injection details and carrier flow, torch/substrate distance, as well as other subtle factors. These parameters are sometimes
interconnected in complex ways, leading to cross-terms in the process of parameterization. Statistical process control analysis
is used extensively in thermal spray technology. This subject has been covered extensively in papers in the annual
proceedings of the National Thermal Spray Conference (ASM International). Process control is becoming more common in
plasma-spray processing of high-performance coatings. A clear goal is to achieve on-line feedback control of the process
(i.e., intelligent processing of materials), which requires a much more detailed understanding of the process.
Low-Pressure Plasma Spray

The LPPS process was developed by Muehlberger (1973) in the early 1970s and gained widespread commercial use in
the mid-1980s. It is competitive with electron-beam physical vapor deposition (EB-PVD) for the production of high-quality
metallic (MCrAlY) coatings for certain applications because of the compositional flexibility afforded and the high coating
rates achieved through molten droplet transfer.

APPENDIX E 80
As with all thermal spray processes, LPPS is limited to line-of-sight deposition. Individual parts are fixtured on a part
manipulator inside a load-locked transfer chamber. The load lock is pumped down and the parts are preheated to about
900-1000°C before being transferred to the coating chamber. The plasma guns currently in use are in the 50- to 120-kW
range and generally use argon-helium or argon-hydrogen gas mixtures to generate the plasma jet. Prior to initiation of the
powder feed, the part is usually treated through reverse transferred arc sputtering to remove any traces of oxide that may have
formed during preheat. The part is then plasma sprayed in a nontransferred mode. The coating distribution is controlled by
the motions of the computer-controlled gun and the part. Typical parameters for turbine blade coating include a gun-to-
substrate distance of ~10 to 16 in. at a chamber pressure of 30-60 Torr and a gun power of 80 kW. Powder feed rates vary
from ~3 to 20 kg/hr, depending on the application.
The LPPS process has found its greatest use for large-power-generation turbine buckets where the coating is generally
applied in the 7to 15-mil range and in turbo-fan-blade applications in the 4- to 6-mil range.
High-Velocity Oxy-Fuel Processes

High-velocity oxy-fuel (HVOF) techniques have proven capable of depositing a wide range of hard facings, metals, and
cermets, and have demonstrated excellent deposit integrity and density (Kaufold et al., 1990). These high-velocity
combustion torches are currently competing with both LPPS and detonation gun for the production of high-performance
metallic aircraft coatings. Thus, HVOF can effectively apply bondcoats (Russo and Dorfman, 1995). More recently
developed versions of this class of guns use oxidizers other than oxygen, for example, high-velocity air fuel (HVAF). HVAF
guns offer both safer and more economical operation than HVOF and are being considered for aircraft engine applications.
PHYSICAL VAPOR DEPOSITION PROCESSES

The physical vapor deposition (PVD) process can deposit coatings of metal, alloys, and ceramics on most materials and
on a wide range of shapes. Since this is a process limited to application by line-of-sight, complete coating coverage is
achieved by manipulating the part during the coating cycle with a complex mechanical system.
Electron-beam guns are favored for supplying the energy necessary for evaporation because of their ability to achieve
very high-energy densities compared with other methods of heating. The material to be evaporated is fed into the chamber
through a water-cooled copper crucible where a rapidly scanning electron beam(s) melts the surface causing a vapor cloud to
form above the ingot. Constant pool levels are maintained through the use of continuous ingot feed and pool-height sensors.
Commercial TBCs have been successfully produced by EB-PVD. For yttria-stabilized zirconia deposition, an oxygen bleed is
introduced into the vapor cloud to maintain coating stoichiometry. Because of the high melting point of yttria-stabilized
zirconia (~3000°C), very shallow liquid pools are the norm, and temperatures at the point of beam impact are on the order of
5000°C. In PVD coatings, the structure has been found to be a strong function of the ratio of the substrate temperature to the
melting point of the material being deposited. To achieve the desired columnar ceramic coating structure, the parts must be
preheated to ~1000°C. This is typically accomplished by preheat chambers built into the load locks and through the use of
over-source heaters in the main coating chamber. For increased filament life, the electron-beam guns are generally
differentially pumped.
While the basic process of evaporation is relatively simple, there are significant differences in the equipment design for
the production of turbine blade coaters. The most significant features that make up these differences are (1) electron-beam
gun design; (2) number and location of electron-beam guns; (3) capability of the part manipulator; (4) number of load locks
and part manipulators; (5) overall layout of the guns, part manipulators, and evaporation sources; and (6) overall level of
complexity and automation of process variables.
SPUTTERING
Sputtering, an alternate vacuum process, relies on a reduced pressure and a plasma, but not evaporation, to generate a
flux of the desired composition for coating a substrate. A heavy inert working gas (usually argon) is leaked into a vacuum
chamber to provide a partial pressure of about 1-100 mTorr. This gas is ionized by imposing a voltage on the order of
500-5000 V, with the substrate charged positive with respect to a metallic target. The target consists of the elements intended
for deposition as the coating. The glow discharge from such a diode arrangement results from the ionization of the heavy gas,
and the resulting ions are accelerated at high energy to impact with the target. These collisions knock out atoms, molecules,
and clusters from the target, and these species with high kinetic energies of 10-40 eV condense to form the coating. A triode
arrangement can also be used to generate the plasma independently of the target. Direct-current voltages are generally
applied, but radio frequency potentials must be applied to overcome charge accumulation for insulating targets. Because of
the high ionization efficiency in the magnetron cavity, intense plasma discharges that provide high sputtering rates can be
maintained at moderate voltages, even for low pressures.
The primary advantage of sputtering is its ability to deposit a wide variety of materials (e.g., alloys, oxide solutions, and

APPENDIX E 81
intermetallics). These compositions can be derived from targets of many types: segments of several materials, several
different targets used simultaneously, several targets used sequentially to deposit a laminated coating, etc. While different
materials exhibit differing sputtering yields (defined as the number of target atoms ejected per incident particle), these factors
are known in the technology (Bunshah, 1982). In fact, the sputtering yields for different materials depend on the nature of the
bonding in the materials and are a function of the incident ion energy. These yields differ significantly for quite different
materials, somewhat analogously to the differing vapor pressures of components in a liquid evaporation source.
A reactive gas can be introduced with the heavy inert gas, so that reactive sputtering results, again, from reactive
collisions in the gas phase. Although the substrate can, in principle, be heated to any temperature, it is usually held at a
temperature that is too low to achieve significant interdiffusion during deposition. After cooling from the processing
temperature and heating to a higher service temperature, the inherent differences in the expansion coefficients between the
substrate and the coating generate residual stresses of opposing sign. Often the deposit achieves a columnar microstructure,
with elongated grains normal to the interface. As previously mentioned, such a structure is ideal for oxide TBCs.
Sputtering is currently not a production coating method for turbine hardware because of the slow deposition rate of
current equipment. However, the method does provide a pure coating of nearly any desired composition.
ELECTROSPARK DEPOSITION
Electrospark deposition is a microwelding process that uses pulsed electrical arcs to deposit an electrode material onto a
metallic substrate (Johnson, 1995). The process yields functionally graded coatings (with a gradient dependent on deposition
rate) by depositing material in a series of passes. Substrate materials must be electrically conductive and capable of being
melted. Coatable surface geometry is limited by access to the surface by the electrode. Electrospark deposition has mainly
been used as a repair technique for gas-turbine engine components, although electrospark deposition has been used to apply
platinum as the first step in some platinum-modified aluminide diffusion coating processes. The metallurgical bonding of
electrospark deposition has been demonstrated in tests to be more resistant to spalling than mechanically bonded coatings
(Johnson, 1995).
AUXILIARY PROCESSES
Auxiliary equipment needed for coating production using any of the above processes may also rely on chemical cleaning
(vapor degreaser, ultrasonic cleaning, and alkaline cleaning tanks), surface prep (wet or dry grit blasting), mechanical and
chemical masking for protecting noncoated areas, and vacuum heat-treatment furnaces for post-coating heat treatment.
QUALITY CONTROL
Metallurgical cross-sectioning is still the primary method used to determine conformance to overall quality
requirements, such as thickness, coating structure, interface quality, and masking transitions. Witness samples used for
metallurgical evaluations are designed to be representative of the coating batch or lot with which they were processed and are
generally scrap components. The trend in recent years has been for much tighter control of the coating process because many
components cannot be stripped and recoated if the coating is nonconforming. This has led to the use of process capability
studies prior to committing to production process qualifications, the use of statistical process control once in production to
assess manufacturing process variation, and the use of Taguchi and integrated process management to make the process more
robust (Slater, 1991; Taguchi, 1993). The process capability ratio, Cpk, is a simple but powerful measure of the ability of a
manufacturing process to meet specification requirements and is defined as Cpk = (6 standard deviation)/(specification
requirement). Ratios less than 75 percent are considered to be capable of running without significant risk of nonconformance
and ratios less than 30 percent are at world-class level. Process capability studies are not yet a part of the quality standards
used by coatings suppliers, although the process is beginning to be used for control of other manufacturing operations.
The specific trends in coating manufacturing can also be examined in terms of engine class. The small (turboprop)
engines have moved to directionally solidified and single-crystal high-pressure turbine blades and vanes, which generally use
serpentine internal cooling passages and trailing-edge and tip-cooling holes. Film cooling is not common, however, and these
designs do not contain external cooling holes. Because of the small size and thin-wall thicknesses of the components, the
possibility of stripping and recoating is limited, so coating thickness must be closely controlled.
Aluminide and platinum-modified aluminide coatings are widely used (pack or CVD if machined after coating). Limited
MCrAlY (usually EB-PVD) and some EB-PVD TBCs are now in use.
The medium-size gas-turbine engines typified by medium-range commercial aircraft propulsion are making extensive
use of directionally solidified and single-crystal high-pressure turbine blades and vanes. Serpentine internal passages and
complex film-cooling schemes are commonplace. Due to the criticality of air flow requirements, the control and shape of hole
diameter is essential. Often the

APPENDIX E 82
hole diameter must be properly sized to the coating process, and changes in the process (e.g., pack to CVD or the addition of
a TBC) necessitate a change in the targeted hole diameter. Coating process variability can also have a large impact on
meeting air flow requirements. Strip and recoat is generally restricted to one time because of wall thickness concerns. There
is widespread use of MCrAlY (LPPS) and platinum-modified aluminide (CVD) coatings in combination with internal
coatings (CVD and coatings from the Advanced Technology Program). EB-PVD TBCs are widely used in conjunction with
the above internal and external coatings.
The trends for large turbines (land-based power generation) have paralleled those for the aircraft engines. Design
engineers are moving to directionally solidified and single-crystal high-pressure turbine blades for the newest engines.
Serpentine cooling is also being considered. The platinum-modified aluminide coating is generally being replaced by thick
MCrAlYs (10-15 mils) produced by LPPS. In some cases the MCrAlY is overaluminided. Gas-phase coatings and TBCs
(plasma and EB-PVD) are being evaluated; strip and recoat is common. Internal coatings are provided by pack and slurry
methods.
REFERENCES
Benden, R., and R. Parzuchowski. 1979. Apparatus for Gas Phase Deposition of Coatings. U.S. Patent, Number 4,148,275.
Bianco, R., and R.A. Rapp. 1993. Pack cementation alumide coatings on superalloys. Codeposition of Cr and reactive elements. Journal of
the Electrochemical Society 140(4):1181-1191.
Bunshah, R.F., ed. 1982. Deposition Technologies for Films and Coatings. Park Ridge, New Jersey: Noyes.
Chraska, P., and M. Hrabovsky. 1992. An overview of water stabilized plasma guns and their applications. Pp. 81-85 in Thermal Spray:
International Advances in Coatings Technology, C.C. Berndt, ed. Materials Park, Ohio: ASM International.
Gauje, R., and R. Morbioli. 1982. Vapor-phase aluminizing to protect turbine airfoils. Journal of Metals 35(12):A12.
Goward, G.W., and D.H. Boone. 1971. Mechanisms of formation of diffusion on aluminide coatings on nickel-base superalloys. Oxidation of
Metals 3(5):475.
Goward, G.W., and L.W. Cannon. 1988. Pack Cementation Coatings for SuperalloysHistory, Theory and Practice. ASME Paper 87-GT-50.
Herman, H. 1991. Powders for thermal spray technology. Thermal Spray Technology. Powder Science and Technology 9:187-199.
Johnson, R.N. 1995. Electrospark deposited coatings for high temperature wear and corrosion applications. Pp. 265-277 in Elevated
Temperature Coatings: Science and Technology I, N.B. Dahotre, J.M. Hampikian, and J.J. Stiglich, eds. Warrendale, Pennsylvania.:
TMS.
Kaufold, R.W., A.J. Rotolico, J. Nerz, and B.A. Kushner. 1990. Deposition of coatings using a new high velocity combustion spray gun. Pp.
561-569 in Thermal Spray Research and Applications, T.F. Bernecki, ed. Materials Park, Ohio: ASM International.
Levine, S.R., and R.M. Caves. 1973. Thermodynamics and kinetics of pack aluminide coating formation. Journal of the Electrochemical
Society 120(8):C232.
Muehlberger, E. 1973 A high energy plasma coating process. In the Seventh International Metal Spraying Conference, London, September
10-14. Cambridge, England: British Welding Institute.
Russo, L., and M. Dorfman. 1995. High-temperature oxidation of MCrAlY coatings produced by HVOF. Pp. 1179-1184 in Proceedings of
the International Thermal Spray Conference, A. Ohmori, ed. Japan: High-Temperature Society of Japan.
Slater, R. 1991. Integrated Process Management: A Quality Model. New York: McGraw Hill.
Smith, J.S., and D.H. Boone. 1990. Platinum-Modified Aluminides-Present Status. Paper presented at the International Gas Turbine and
Aeroengine Congress and Exposition, Brussels, Belgium, June.
Taguchi, G. 1993. Robust Development. New York: American Society of Mechanical Engineers Press.

APPENDIX F 83
Appendix F
Example of a Coating Designation System
Any standard designation system for coatings must capture the essential features of the materials and processes being
used and be sufficiently flexible so that future materials and processes can readily be added without requiring a new
framework. A potential designation system would also have to be agreed on by all interested parties before it could be
adopted. The purpose of this appendix is to suggest some possible approaches to such a system.
An example of a standard coating designation system is a code with four elements. The code would be "XX####-X###-
T##(M or E)." The code has the flexibility to be used by the first part alone, the first two parts, the first three parts, or the
entire code. The coating is progressively better defined as more parts of the code are used.
The first part of the code, "XX," refers to the class of coating, such as AL for a simple aluminide, AS for a silicon
modified aluminide, AP for a platinum aluminide, CR for a chromide, NI for a nickel-base overlay, CO for a cobalt-base
overlay, and NC for nickel/cobalt-base overlay.
The second part of the code, "####," is four numbers that give the nominal chemical composition. For a simple
aluminide coating, this would be the aluminum level in weight percent, such as "2300" for 23-weight-percent aluminum. For
a platinum aluminide this would be the aluminum level followed by the platinum level, such as "2310" for 23-weight-percent
aluminum and 10-weight-percent platinum. For an overlay coating, the numbers would be the chromium and aluminum levels
in weight percent, such as "2308" for 23-weight-percent chromium and 8-weight-percent aluminum.
The third part of the code, "X###," refers to processing, chemistry, or base-metal requirements. They are defined by
reference to a table of terms, such as for the aluminum standards. Processing codes would start with a "P" and would refer to
a slurry process, an inward diffusion coating, an air plasma spray, a low-pressure plasma spray, etc. Chemistry codes would
start with a "C" and refer to special alloying elements, such as hafnium or silicon. Base-metal codes would start with a "B"
and would refer to the specific superalloy types for which the coating is intended. Multiple designators would be used as
needed. This portion of the code has the greatest potential for creating a very long code.
The last part of the code, "T##(M or E)," is the nominal thickness of the coating, expressed in either millimeters or mils.
The "M" is used for millimeters and the "E" is used for mils to identify the units of thickness.
Duplex coatings and thermal barrier coatings (TBCs) require that the individual parts of the coating be separately
specified. Thus a duplex coating would be called "DPXX/YY" and a TBC would be "TB-XX/YY," where XX would be the
top coating and YY the bottom coating. As an example, an aluminide on top of a NiCrAlY would be called "DP-AL/NI." A
TBC over the same bondcoat would be "TB-ZR/NI." The codes for the component coatings would still be required after this
designation.
The advantage of this coding system is that it captures the essential features of the coating. The disadvantage is its
potential for a long and ungainly designator.
Alternatives to this system are to use either a number for each coating, similar to what is currently used by vendors, or a
two-digit letter to identify the class of coating (e.g., AL, AP, CO) followed by a number for the specific type of coating. Both
of these alternatives have the advantage of a simpler designator but the disadvantage of providing little information about the
coating from the designator.

APPENDIX G 84
Appendix G
Biographical Sketches of Committee Members
ROBERT V. HILLERY, chair, is manager of Airfoil Materials in the Engineering Materials Technology Laboratories
at GE Aircraft Engines, Cincinnati, Ohio. He has a B.Sc. degree in metallurgy and a Ph.D. degree in corrosion science from
the University of Manchester. His research interests are in environmental high-temperature oxidation, corrosion-resistant
thermal barrier wear, and erosion coatings and their processing.
NEIL BARTLETT is professor of chemistry at the University of California, Berkeley. He has B.Sc. and Ph.D. degrees
in inorganic chemistry from the University of Durham. He is a foreign associate of the National Academy of Sciences and a
member of the Royal Society of London, the Gottingen Academy of Sciences, the American Academy of Arts and Science,
and the Academy of Science of France. His research concerns fluorine inorganic chemistry, noble gas chemistry, high-energy
oxidizers, X-ray crystallography, solid-state chemistry, nonaqueous solvent chemistry, and thermochemistry.
HENRY L. BERNSTEIN is a staff engineer in the Materials and Structures Division and the assistant director of the
Electric Power Research Institute's Materials Center for Combustion Turbines at Southwest Research Institute. He is a fellow
of the American Society of Mechanical Engineers. He has a B.S. degree from Ohio State University, an M.S. degree from the
University of Illinois at Urbana, and a Ph.D. degree in applied mechanics and materials science from the University of
Cincinnati. His research concerns gas-turbine durability and life prediction and the mechanical behavior of high-temperature
materials. In both of these areas, high-temperature coatings are of key interest.
ROBERT F. DAVIS is a professor of materials science and engineering at North Carolina State University. He has a
B.S. degree from North Carolina State University, an M.S. degree from Pennsylvania State University, and a Ph.D. degree in
ceramic engineering from the University of California, Berkeley. His research interests are in diffusion and high-temperature
deformation of ceramic materials, growth and characterization of wide bandgap electronic materials, and ceramic/metal
coating deposition and interface adherence.
HERBERT HERMAN is Leading Professor of materials science at the State University of New York at Stony Brook.
He has a B.S. degree from De Paul University and M.S. and Ph.D. degrees in metallurgy from Northwestern University. His
research interests are in thermal-sprayed protective coatings, intermetallic compounds, metal-and ceramic-matrix composites,
fuel cell processing, powder metallurgy and processing, and corrosion protection of transportation and marine structures.
LULU L. HSU is chief of process engineering at Solar Turbines in San Diego, California. She has a B.A. degree from
Barat College and an M.S. degree in analytical chemistry from Michigan State University. She has 19 years of experience in
the gas-turbine industry with Solar Turbines Incorporated. For 17 of these years she did work in the field of materials
engineering, where she was involved in the development, evaluation, and application of hot-section coatings for use in Solar's
fleet of industrial gas turbines. During this period, she collaborated with other turbomachinery experts and evolved a
comprehensive approach on contaminant ingestion within the context of air, fuel, and water management. Over the years, she
was also been involved with providing technical support on engine cleaning, lube oils for turbomachinery, and component
repairs, including responsibility for Solar's engineering specifications on the same subjects. In her current role as customer
services marketing manager she provides technical and commercial support to Solar's aftermarket product offerings.
WEN L. HSU is a distinguished member of the technical staff and technical coordinator of ultrahard materials for
Sandia National Laboratories in Livermore, California. He has a B.S. degree from Rensselaer Polytechnical Institute and a
Ph.D. degree in astrophysical sciences-plasma physics from Princeton University. His research concerns diamond, ceramic
materials, plasma chemical vapor deposition, and chemical vapor deposition reaction kinetics.
JOHN C. MURPHY is a professor in the Materials Science and Biomedical Engineering departments and principle
staff physicist at the Applied Physics Laboratory at Johns Hopkins University. He has a B.A. degree from the Catholic
University

APPENDIX G 85
of America and M.S. and Ph.D. degrees in physics from the University of Notre Dame. His research interests include
microwave-optical double resonance experiments on excitation migration in solids; photocatalysis; elastic wave propagation
in soils using electro-optical methods; photoacoustic spectroscopy; electron spin resonance of electrogenerated radical ions in
solution; photothermal imaging; thermal and thermoacoustic imaging and spectroscopy; microwave and magnetic properties
of solids; metrology; nondestructive evaluation of materials; and near-field imaging of organic conductors and films.
ROBERT A. RAPP is professor emeritus of materials science and engineering at Ohio State University. He has a B.S.
degree from Purdue University and M.S. and Ph.D. degrees in metallurgical engineering from the Carnegie Institute of
Technology. His research interests include the oxidation, corrosion, and coating of metals and alloys. He is a member of the
National Academy of Engineering.
JEFFERY S. SMITH is manager of surface technology at Howmet's Operhall Research Center. He has B.S. and M.S.
degrees in metallurgical engineering from the University of Wisconsin, Madison. His research interests are superalloy
processing and manufacturing methods, superalloy coating process development and performance, high-temperature
oxidation and repair technology for engine-run components. He is currently chair of the Manufacturing, Materials, and
Metallurgy Committee of the International Gas Turbine Institute of the American Society of Mechanical Engineers.
JOHN STRINGER is technical director of exploratory research at the Electric Power Research Institute. He has B.E.
and Ph.D. degrees from the University of Liverpool. His research concerns high-temperature oxidation and corrosion of
metals and alloys, fossil-fuel burning systems, hot-corrosion of gas turbines, and erosion and erosion/corrosion of metals and
alloys.

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National Research Council 1996. Coatings for High-Temperature Structural

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Coatings for High-Temperature

Committee of Coatings for High-Temperature Structural Materials

NATIONAL ACADEMY PRESS

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COMMITTEE ON COATINGS FOR HIGH-TEMPERATURE STRUCTURAL

ROBERT V. HILLERY (chair), GE Aircraft Engines, Cincinnati, Ohio

National Materials Advisory Board Staff

Government Liasion Representatives

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NATIONAL MATERIALS ADVISORY BOARD

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TABLE P-1 Committee Focus

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TABLE P-2 Primary Performance Goals for Advanced Engine Systems

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Robert V. Hillery, chair

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2 APPLICATION NEEDS AND TRENDS 10

3 MATERIALS AND PROCESSES 19

6 REFURBISHMENT OF COATED STRUCTURE 39

7 NEAR-TERM TRENDS AND OPPORTUNITIES 43

8 LONG-TERM OPPORTUNITIES AND INNOVATIVE SYSTEMS 46

Copyright National Academy of Sciences. All rights reserved.

A TESTING AND STANDARDS 57

B RADIATION TRANSPORT IN THERMAL BARRIER COATINGS 65

C SURVEY OF NONDESTRUCTIVE EVALUATION METHODS 67

D MODELING OF COATING DEGRADATION 72

E MANUFACTURING TECHNOLOGIES OF COATING PROCESSES 78

F EXAMPLE OF A COATING DESIGNATION SYSTEM 83

G BIOGRAPHICAL SKETCHES OF COMMITTEE MEMBERS 84

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LIST OF FIGURES AND TABLES xv

List of Figures and Tables

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AISI American Iron and Steel Institute

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High-Temperature Coatings Design

High-Temperature Coating Types

aluminum; and Y is yttrium.

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Processes for Applying Coatings

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Concurrent Development of High-Temperature Coatings and Substrate Materials

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Oxidation and Hot-Corrosion-Resistant Coating Development

Thermal Barrier Coating Development