MME455: Lecture A07

Nickel Base Alloys

Topics to discuss…..
 Properties of nickel
 Physical metallurgy
 Commercially pure nickel
 Nickel base alloys
 Single crystal castings of nickel-base superalloys

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 Introduction

 Nickel and nickel-base alloys are  Nickel and its alloys, like stainless
vitally important to modern industry steels, offer a wide range of corrosion
because of their ability to withstand resistance.
a wide variety of severe operating
conditions involving corrosive  However, nickel can accommodate
environments, high temperatures, larger amount of alloying elements –
high stresses, and combination of mainly Cr, Mo, and W – in solid solution
these factors. that iron.

 Therefore, nickel based alloys in

general can be used in more severe
environments than stainless steels.

Typical properties

 Silvery shiny appearance

 High toughness and ductility Crystal structure FCC
 Good high and low temperature strength Atomic number 28
Atomic weight (g/mol) 58.71
 High oxidation resistance Density (g/cc) 8.89
 Good corrosion resistance Melting point (C) 1455
Boiling point (C) 2913
 Ferro-magnetic

Disadvantages

 Relatively high cost

 Not mixed with cheap alloying elements

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 Typical applications

 About 60% of nickel production is used as alloying elements in stainless and

nickel-alloy steels, and in other elements such as copper, cobalt, chromium, etc.

 Most of the remainders is used for high-nickel alloys and for electroplating

 Nickel and nickel alloys are used for  A number of other applications for Ni alloys
a wide variety of applications, the involve the unique physical properties of
majority of which involve corrosion special-purpose nickel-base or high-nickel
resistance and/or heat resistance alloys. These include:
chemical plant, heat exchanger, reaction • low-expansion alloys
furnace, rotary kiln, turbine blades. • electrical resistance alloys
• soft magnetic alloys
• shape memory alloys

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• Aircraft gas turbines: disks, combustion • Nuclear power systems: control rod drive
chambers, bolts, casings, shafts, exhaust mechanisms, valve stems, springs, ducting
systems, cases, blades, vanes, burner cans, • Chemical and petrochemical industries:
afterburners, thrust reversers bolts, fans, valves, reaction vessels, piping,
• Steam turbine power plants: bolts, blades, pumps
stack gas reheaters. • Pollution control equipment: scrubbers,
• Reciprocating engines: turbochargers, flue gas desulfurization equipment (liners,
exhaust valves, hot plugs, valve seat inserts fans, stack gas reheaters, ducting)
• Metal processing: hot-work tools and dies • Metals processing mills: ovens, after-
• Medical applications: dentistry uses, burners, exhaust fans
prosthetic devices • Coal gasification and liquefaction systems:
• Space vehicles: aerodynamically heated heat exchangers, reheaters, piping
skins, rocket engine parts • Pulp and paper mills: tubing, doctor blades,
• Heat-treating equipment: trays, fixtures, bleaching circuit equipment, scrubbers
conveyor belts, baskets, fans, furnace mufflers

Physical Metallurgy

 Nickel is a versatile element; alloys with most metals.

 Complete solid solubility exists between nickel and copper.
 Wide solubility ranges between iron, chromium, and nickel
 possibility of many alloy combinations

 The FCC structure of the nickel matrix (g) can be strengthened by

① solid-solution hardening
② carbide precipitation, or
③ precipitation hardening.

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 Solid solution hardening

 Co, Fe, Cr, Mo, W, V, Ti, and Al are all solid solution hardeners in nickel.

 These elements differ with nickel in atomic diameter from 1 to 13 %.

 Above 0.6Tm, which is the range of high-temperature creep, strengthening is

diffusion dependent and large, slow diffusing elements such as Mo and W
are the most effective hardeners.

Carbide strengthening

 Nickel is not a carbide former; other elements present in nickel form carbides.
 This is either a bane or a blessing to the designer of alloys. An understanding of
carbide class and its morphology is critical for alloy design.

 Most common carbides forms: MC, M6C, M7C3, and M23C6.

• MC – large blocky carbide, randomly distributed, • M7C3 – form intergranularly; beneficial if
not desired precipitated as discrete particles, or cause
embrittlement if they agglomerate and form
• M6C – blocky; formed in grain boundaries (can continuous grain-boundary films.
be used to control grain size), or precipitated in a
Widmanstaitten pattern throughout the grain • M23C6 – form as grain-boundary precipitates;
(impair ductility and rupture life) influential in enhancing rupture properties

 The alloy chemistry, its prior processing history, and the heat treatment given to the
material influence carbide precipitation and ultimately performance of the alloy.

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 Precipitation hardening

 The precipitation of g’, Ni3(AI,Ti) in a high-  The amount of g’ formed is a function of the
nickel matrix provides significant hardener content of the alloy. Al, Ti, Nb, and
strengthening to the material. Ta are strong g’ formers.
 This unique intermetallic phase has a FCC  Effective strengthening by g’ decreases above
structure similar to that of the matrix and a about 0.6Tm as the particles coarsen.
lattice constant having 1% or less
 The g’ phase can transform to other (Ni3X)
mismatch in the lattice constant with the g
precipitates if the alloy is supersaturated in Ti,
matrix. This close matching allows low
Nb, or Ta (indicated as X) and modify
surface energy and long time stability.
mechanical properties.
 Precipitation of the g’ from the
 The phases precipitated are functions of alloy
supersaturated matrix yields an increase
chemistry and the heat treatment given the
in strength with increasing precipitation
material prior to service or the
temperature, up to the overaging or
temperature/time exposure of in-service
coarsening temperature.
application.

Classification of Nickel Alloys

① Commercially pure nickel

② Nickel-copper alloys (Monels)

③ Nickel-chromium alloys

④ Nickel-iron and Nickel-chromium-iron alloys

⑤ Nickel-base superalloys

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 Commercially pure nickel
 High purity nickel contains at least 99 % Ni
 Commercially pure nickels also have Co and such impurities
like Mn, Fe, Si, and Cu to enhance specific properties.
 These alloys are non-heat treatable and may be hardened by
cold work.
 Some alloys containing Al and Ti are heat treatable and may
be strengthened by precipitation hardening Cold drawn Nickel 200
annealed at 829 C
 Microstructure consists of solid solution g phase in annealed
condition

Typical properties Applications

 Good mechanical properties and retains its  Food processing equipment
strength at elevated temperature  Electrical and electronic parts
 Excellent resistance to most corrosive  Caustic handling equipment
environment

Alloy Major Mechanical Principal Typical

Designation Composition Properties Characteristics Applications

Pure nickel 99.99 Ni (min) TS = 46 ksi

E = 30%

A nickel 99.40 Ni+Co TS = 70 ksi Used where strength in combination Chemical and soap
E = 40% of corrosion and oxidation resistance industry
HBN = 100 are required

D nickel 95.00 Ni+Co TS = 75 ksi Improve resistance to atmospheric Spark plug electrode,
4.75 Mn E = 40% attack at high temperature; ignition tube
HBN = 140 strength greater than A nickel

Duranickel 93.90 Ni+Co TS = 100 ksi High strength in combination with spring for laundry clip,
4.5 Al, 0.45 Ti E = 40% excellent corrosion resistance; jewelry parts, optical
0.55 Si HBN = 160 age hardenable frames; instrument parts

Parmanickel 98.65 Ni+Co TS = 105 ksi Strength and corrosion resistance Used in place of duranickel
0.45 Ti, E = 45% similar to duranickel; good electrical where good conductivity
0.35 Mg HBN = 160 and thermal conductivity; and magnetic properties
age hardenable are required

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 Nickel - copper alloys (Monels)
 Ni and Cu form complete solid solution Typical properties
 Ni-Cu alloy (a.k.a. Monels) contains 29-33 %  Mechanical properties higher than brasses
Cu as the major alloying element and bronzes but lower than alloy steels
 Ni-Cu alloys containing Al and Ti ( K Monel)  Good toughness and fatigue strength over a
is heat treatable and may be strengthened by range of temperature
precipitation hardening  Good formability and weldability, but poor
machinability
 Excellent corrosion resistance to acid, alkalis,
brines, waters, food products, and atmosphere
 Reduced price

Applications
 Values, pumps, marine fixtures and fasteners
Microstructure of cold drawn Monel R405 and
annealed at 829 C, showing solid solution  Chemical processing equipment
phase of Ni-Cu with sulphide stringers (black)  Oil-well drill collars and instruments

K Monel
 Addition of ~3% Al make it age hardenable
 Non-magnetic, corrosion resistant material
Constantan
with extra strength and hardness
 Uses: marine pump shaft, springs, aircraft  Contains 45% Ni and 55% Cu
instruments, ball bearings, safety tools  Highest electrical resistivity
 Uses: thermocouple

H and S Monel
 Contains 3% and 4% Si, respectively; casting alloy
 High strength, pressure tightness, corrosion resistance
 H Monel, containing less silicon has better machinability
 Uses: valve seats, pump liners, impellers

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 Ni-Cu alloys

Alloy Principal composition Condition TS, ksi 0.2PS, ksi %E in 2” BHN

Monel 66.15 Ni+Co, 31.3 Cu, 1.3 Fe Annealed 75 35 40 125

K-500 Monel 65.25 Ni+Co, 29.6 Cu, 2.75 Al Annealed 100 45 40 155

H Monel 63.0 Ni+Co, 30.5 Cu, 3.2 Si As-cast 115 70 10 265

Annealed 50 Electrical resistivity
Constantan 44-46 Ni, Bal. Cu
Cold-worked 100 = 49 mOhm-cm

Nickel - chromium alloys

 Cr forms solid solution with Ni up to ~30% at RT,  Resistivity is ~108 mohm-cm
resulting high corrosion resistance
 Change in electrical resistivity is
 Alloys containing 80Ni-20Cr compositions (Chromel not constant with temperature
A, Nichrome V) and 60Ni-16Cr-24Fe compositions
 Value depends on heat treatment;
(Chromel C, Nichrome) are used as electric
annealing improves resistivity
heating elements
 The alloy forms nickel-rich single phase solid solution
having annealing twins.

Properties Applications
 High electrical resistance  Heat exchanger tubing
 High corrosion resistance at high temperature  Heaters for electric furnace, cookers,
 High strength and workability kettles, immersion-heaters, hair-dryers,
toasters, etc.

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 Nickel-iron and Nickel-chromium-iron alloys

 Fe added to replace some of Ni

 lower cost
 lower properties (as compared with nickel base superalloy)
 used at lower temperatures
 Ni-Fe alloys contains 25-45%Ni and 15-60%Fe
 Higher Ni content increases operating temp (up to 815 C) Optical micrograph of Inconel 901
after precipitation hardening
due to improved stability but more costly

 microstructure consists of austenitic FCC matrix

 can be strengthened by solid solution strengthening
(Mo, Cr), and precipitation hardening (Ti, Nb, Al) by
forming intermetallic phases SEM micrograph of Inconel 718
after exposure at 705 C/6,048 h

Non-heat-treatable Ni-Cr-Fe alloys Heat-treatable Ni-Cr-Fe alloys

 The major alloying elements of these alloys  These alloys contains 15-22% Cr and up to
(15-22% Cr and up to 46% Fe) form single 33% Fe as the major alloying elements
phase solid solution with nickel
 May be strengthened by precipitation
 May be hardened by cold working hardening due to the presence of additional
alloying elements: Al, Be, Ti, Si
 Alloys are identified according to trade names:
Inconel, Incoloy, and Hastelloy  Trade names of some alloys:
Nimonic, Inconel X-750, Udimet,
 Good mechanical strength and high resistant Waspaloy, Rene, Astroloy
to creep combined with excellent corrosion
resistance to chloride-ion solution, sulphur  Very high mechanical strength and high
compounds and other organic and inorganic resistant to creep at temperatures up to 815
compounds C combined with good corrosion and
oxidation resistance
 Good machinability, weldability and workability
 Used for making gas turbine components,
 Used for furnace and heat treating equipment parts of nuclear steam generators, hot
(nitriding container, carburizing boxes, retorts). working tools, exhaust valves for IC engines

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 Non-heat-treatable Ni-Cr-Fe alloys

Alloy Principal composition Condition TS, MPa 0.2PS, MPa %E

Inconel Ni 72% min, Cr 14-17%, Fe 6-10% Annealed 655 310 45

Ni 30-35%, Cr 19-23%, Fe 39.5% min,

Incoloy 800 Annealed 600 275 45
Al 0.15-0.60%, Ti 0.15-0.6%

Ni 30-35%, Cr 19-23%, Fe 39.5% min,

Incoloy 800HT Annealed 560 250 45
Al 0.15-0.60%, Ti 0.15-0.6%

Ni 45-50%, Cr 20.5-23%, Fe 6-10%,

Hastelloy X Annealed 765 380 44
Mo 8-10%, W 0.2-1.0%, Co 0.5-2.5%

Heat-treatable Ni-Cr-Fe alloys

Alloy Principal composition Condition TS, MPa 0.2PS, MPa %E

Ni 69% min, Cr 18-21%, Fe 3% max,

Nimonic 80A Precip. hard. 1250 780 30
Al 1.0-1.8%, Ti 1.8-2.7%
Ni 54% min, Cr 14-16%, Fe 1% max,
Nimonic 115 Al 4.5-5.5%, Ti 3.5-4.5%, Precip. hard. 1300 850 25
Mo 3-5%, Co 13-15.5%
Ni 70% min, Cr 14-17%, Fe 5-9%,
Inconel X-750 Al 0.4-1.0%, Ti 2.25-2.75%, Precip. hard. 1250 850 30
Mo 8-10%, Nb 0.7-1.2%
Cr 18-21%, Fe 2% max, Al 1.0-1.5%,
Waspaloy Ti 2.6-3.25%, Mo 3.5-5%, Co 12-15.5%, Precip. hard. 1250 850 30
Ni balance
Cr 18-20%, Fe 5% max, Al 1.4-1.6%,
Rene 41 Ti 3.0-3.3%, Mo 9-10.5%, Co 10-12%, Precip. hard. 1420 1062 14
Ni balance

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 Nickel based superalloys

 High temperature heat-resistance Properties

alloys, which can retain high  Heat resistant and high strength
strengths at elevated temperatures at high temperature (760-980 C)
 Good corrosion resistance
 Three types of Ni superalloys
 Good oxidation resistance
① nickel base
② nickel-iron base, and
Applications
③ cobalt base containing nickel
 Aircrafts, space vehicles, rocket engines
 Alloys contain high Cr with  Industrial gas turbines, high temperature
Ti and Al to from precipitates, and applications
additions of Mo, Co, Nb, Zr, B, Fe.
 Nuclear reactors, submarines
 Complex microstructures  Steam power plants, petrochemical
equipment

 These superalloys are “super” because of the g’ precipitation strengthening effect

 g’ is an intermetallic compound (Ni3Al) with ordered fcc structure
 Amazing property of superalloys: they become stronger at higher temperature

fcc Ni g
Ni atoms
matrix
Ni atoms

Al atoms
ordered fcc g’ ppt.
(cuboid in shape)

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 Turbine blades

Turbine blades in a jet engine experience:

• Mechanical forces – (1) creep, (2) fatigue, (3) thermomechanical fatigue
• High temperature environment – (1) oxidation, (2) hot corrosion

Turbine blade heat treatment

As-cast dendritic microstructure

precipitation hardened
g’ in g matrix

precipitation hardening
(solution treatment + ageing)

g’ g

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 The major phases present in the nickel-base superalloys:
• g (gamma) phase – the continuous matrix of FCC austenite
• g’ (gamma prime) phase – the major precipitate phase (more cubic shape)
• carbides – various types, mainly M23C6 and MC (M = metal)
Note: GB carbides affect high-temp strength, ductility, creep

Single-crystal castings of nickel-base superalloys

 A major increase in strength and
temperature capability of superalloy
casting can be obtained with the
introduction of columnar-grained and
single crystal casting

equiaxed directionally single

crystal solidified crystal
columnar crystals

property comparison between polycrystal,

columnar crystal and single crystal

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Next Class

MME455: Lecture A08

Alloy steels

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