21st Annual Conference on Recent

Advances on Flame Retardancy of

Polymeric Materials
Chairman: Prof. Menachem Lewin
Polytechnic Institute of NYU
Featuring
An Intensive Short Course in Selection, Evaluation, and
Commercial Application of Flame Retardants
May 23, 2010

Main Conference
May 24-26, 2010

Contact:
Chris Ross - Conference Coordinator
Phone: (781) 489-7301 x 606
Email: [email protected]

ISBN 1-59623-619-1

BCC Research
35 Walnut St. • Wellesley, MA 02481
www.bccresearch.com
 Conference Benefits:
• Network with colleagues including expert speakers in Flame Retardancy
• Discover the latest technological advances
• Learn about leading commercial applications
• Hear the latest regulatory, environmental, and testing findings

Organized by BCC Research, 35 Walnut St., Wellesley, MA 02481

Program Chairman: Professor Menachem Lewin, Polymer Research Institute, Polytechnic University

Organized by BCC Research

Featuring an Intensive Short Course: Selection, Evaluation, and Commercial Application of Flame Retardant Polymers, Sunday May 23, 2010.
Course Director: Professor Menachem Lewin, Polymer Research Institute, Polytechnic University
The complete technical and commercial development meeting on flame retardancy
Presentations at the conference will:

Create a forum for introducing new technological achievements and developments in

the field of flame retardancy (FR)

Offer an overview of the current state of science and technology in FR

Review the applications and markets for FR products

Present recent developments in local and global standardization in testing technology

Discuss toxicity and environmental issues

Provide a unique opportunity for newcomers to become acquainted with the FR field
in all its aspects

Discuss nanoparticles effects on flammability

Address regulatory issues for flame retardancy.

 Intensive Short Course

Selection, Evaluation, and Commercial

Application of Flame Retardant Polymers
Sunday, May 23, 2010, 8:30 a.m.–5:30 p.m.
Course Director: Professor Menachem Lewin, Polymer Research Institute and Department of Chemical and
Biological Science, Polytechnic Institute of NYU, 6 MetroTech center, Brooklyn, NY 11201
The Course Instructors
Edward D. Weil, Professor, Polymer Research Institute, Polytechnic Institute of NYU, Brooklyn, NY
Sergei Levchik, Product Development Manager, ICL-IP America, Ardsley, NY
Marc L. Janssens, Director of the Fire Technology Department, Southwest Research Institute® (SwRI®),
San Antonio, TX

Who Should Attend? Topics Discussed in the Course

Chemists, engineers, physicists, polymer and material sci- (partial listing)
entists involved in research and development, production,
marketing, QC, standards, and evaluation of products and • Principles of flammability and fire hazards
their environmental impact; personnel involved in plan-
ning and design of products in building, construction, • Flame retarding polymers
automotive, aircraft, telecommunications, electronics,
computers, textile, wood products and pulp and paper and • Review of flame-retardant chemicals
other industries. For both newcomers and practitioners
who want to brush up on FR technology practices. • Mechanisms of flame retardancy

Why Attend? • Fire test methods

Flame retardancy of polymers is an active and develop-
• Survey of flame retardancy of all the significant plastics
ing field and involves several disciplines. A systematic
and textile fabrics
introduction to the field is of great importance to col-
leagues already engaged in R&D, production and
• Material flammability
marketing of polymeric materials and products, as well
as those entering the FR field, and to colleagues begin-
• Standards-setting and regulatory organizations
ning their activity in polymer technology. The course
will considerably shorten the time needed for getting
• Properties measured by fire tests
acquainted with the numerous flame retarding addi-
tives, the flammability behavior of the various polymeric
materials, the diversified applications of flame-retarded
polymers, the consumer, environmental, and regulatory
issues involved and the systems and equipment used for
production and testing. A comprehensive full-day (8:30
a.m.-5:30 p.m.) intensive, informative program, staffed
by a knowledgeable and experienced faculty steeped in
academic insight and industrial know-how.
A Certificate of Participation will be awarded to attendees

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 Conference Program
Registration— halides will be discussed. Continued progress is shown in formulat-
Sunday, May 23, 6:00-7:30 p.m. , Reception ing PVC for low smoke by use of inorganic additives, while styrenic
Monday, May 24, 7:30-8:15 a.m. systems remain a challenge. An attempt will be made to assess the
controversial environmental issues in regard to halogen-containing
plastics. A distinction is emphasized between hazard and risk, and a
May 24, 2010 judicious approach to choice of flame retardant is recommended,
8:15-8:30 a.m.—Opening Remarks considering factors such as relative efficiency, emissions in accidental
Professor Menachem Lewin fires and end-of-life issues. Progress in modern waste-to-energy facili-
Polymer Research Institute, Polytechnic Institute of NYU ties and metal smelters now affords means for safe recovery of values
from electrical and electronic scrap, including halogen-containing
Session I: General Papers and Reviews flame retardant plastics.
Chairperson: Jose Marie Lopez Cuesta, Pôle Matériaux Polymères
Avancés, Centre des Matériaux, Ecole des Mines d’Alès, France 9:30-10:00
Phosphorus Sulfur Compounds as Flame Retardants
8:30 - 9:00
Manfred Doering, Michael Ciesielski, Jochen Wagner, Institute for
Modeling Pressurization Caused by Thermal Decomposition
Technical Chemistry, Karlsruhe Research Center, Germany
of Highly Charring Foam in Sealed Containers
K. L. Erickson, A. B. Dodd, R. E. Hogan, Sandia National Labora- Commercially available phosphorus flame retardants are mostly
tories, Albuquerque, NM phosphorus oxygen compounds and can provide condensed-phase
or gas-phase activities. Replacing oxygen against sulphur in the phos-
Polymer foam encapsulants provide mechanical, electrical, and phorus flame retardants the gas-phase efficiency will be increased in
thermal isolation in engineered systems. In fire environments, epoxy resins. Recently, phosphorus compounds together with sulfur
foams, such as polyurethanes, can liquefy and flow during thermal were described as non-halogenated flame retardants for polystyrene.
decomposition, and evolved gases can cause pressurization and We will introduce new phosphorus sulphur compounds, which are
failure of sealed containers. Foam liquefaction and flow can cause particularly generated by a direct reaction of phosphorus compounds
serious modeling issues in systems safety and hazard analyses. Highly with sulfur and discuss their synergetic flame-retardant effect with
charring hybrid polyurethane epoxy cyanate ester foam was devel- sulphur compounds.
oped to mitigate modeling issues associated with foam liquefaction
and flow. A previous paper discussed the experimental and model- 10:00-10:30 Coffee
ing approach developed to predict radiation and conduction heat Chairperson: Gerald Kirschenbaum, Consultant
transfer through decomposing hybrid foam in vented containers.
This paper discusses application of a similar approach to the more 10:30-11:00
difficult problem of predicting heat transfer, foam decomposition, Parameter Sensitivity of Condensed-Phase Burning Modeling
and pressure growth in sealed containers. Model predictions will be
Nicolas Bal, Guillermo Rein, BRE Centre for Fire Safety Engineering,
compared with results from radiant heat transfer experiments involv-
The University of Edinburgh
ing encapsulated objects. All model parameters are evaluated from
independent laboratory-scale experiments such as TGA and DSC.
A one-dimensional numerical model describing the phenomena occur-
ring up to ignition for a solid fuel is used to study which mechanisms
9:00-9:30
are more important. The model solves the heat transfer equation and
Smoke and Combustion Products – Recent Progress and accounts for mass loss via multiple pyrolysis reactions. Ignition is speci-
Some Issues fied by a critical mass criterion. The model is deliberately simple and
Edward D. Weil, Polytechnic Institute of NYU, Marcelo Hirschler, follows the rule that simplifications are required where higher preci-
GBH International and Sergei Levchik, ICL-IP sion is not warranted. Comparison with a large dataset of experimental
measurements for PMMA show that the model can predict the time
Methods for smoke reduction in burning plastics will be reviewed with to ignition in or a wide range of heat fluxes from 10 to 200 kw/m^2.
emphasis on recent progress. Visual obscuration, gaseous combustion The numerical sensitivity study shows that four parameters (kinetic
product toxicology, and soot carcinogenicity will be addressed. The parameters, specific heat, density and in-depth-radiation coefficient)
dominant role of carbon monoxide in fire gases is further supported, are very important. Variations of the other parameters, in comparison,
and the relative contribution of other components such as hydrogen produce negligible changes to the time to ignition.

Program subject to change—check www.bccresearch.com/conferences.php for updates

11:00-11:30 RxnMD is introduced. In both the old and new methodologies,
Fire Retardant Polyamides- Present Technologies and potential energy surfaces of chemical reactions are constructed
Challenges from functions and parameters of a traditional (non-reactive)
force field. However, rather than predicting reactions on the
Kelvin K. Shen, Saied Kochesfahani, and Frédéric Jouffret, Rio Tinto basis of a bond breaking/making algorithm, RxnMD models
Minerals, Denver, USA pre-defined reaction types accurately by smoothly interpolating
between non-reactive potential energy terms describing reac-
Polyamides (PA) engineering plastics display excellent mechanical tants, transition states, and products. The new methodology was
properties (such as high strength at high temperatures, toughness applied to a system of ethylene oligomers of various degrees of
at low temperatures, and good wear/abrasion resistance), mold- polymerization. The results indicate that the size of the molecule
ability, and chemical resistance. They have been used in automotive is clearly a factor affecting its stability. Thus, at least for certain
parts, electrical/electronic components, and industrial markets. PA types of reaction, the knowledge of kinetics obtained from the
66, PA 6, and a variety of high temperature PA such as PA 6T/66, studies of small gas-phase molecules is not directly applicable to
PA 6T/M, PA 46, and PA 9T are commonly used for producing polymer degradation.
molded electrical parts such as electrical connectors, circuit break-
ers, relay switches, and bobbing. In these applications, PA has to 12:30-1:30 Lunch
meet a variety of flammability tests such as UL 94, Comparative
Tracking Index, and Glow Wire Test (GWFI/GWIT). This paper
will review briefly present halogen-containing PA technologies and
Session II: Halogen and Non-Halogen Flame
issues in electrical/electronic application. More importantly, recent Retardants
 hairperson: Marc Nyden, National Institute of Standards
C
advances in halogen-free PA will be presented. Special emphasis
and Technology
will be on the use of aluminum diethylphosphinate, melamine
polyphosphate, melamine cyanurate, red phosphorus, ammonium
1:30-2:00
sulfamate, Firebrake®Zinc Borates, boron phosphate, silicone, and
talc in PA. Mode of actions of these flame retardants in PA will be A New Sustainable Polymeric Fire Safety Solution for
discussed as well. Thermoplastics and Elastomers
Kumar G. Kumar, Albemarle Corporation
11:30-12:00
Environmentally Safe Flame Retardant Materials Albemarle is introducing its new generation of High Performance
Ravi Mosurkal, Jason W. Soares, Romy Kirby, Wayne S. Muller , Polymeric flame-retardants. Designed for use in a broad range of
U.S. Army Natick Soldier Research Development and Engineering plastics, this break-through technology yields products that can be
Center Natick, MA tailored to offer a unique set of physical and flame retardant proper-
Jayant Kumar, Center for Advanced Materials, University of ties in a “single-package” solution. Thanks to their non-bio accumula-
Massachusetts Lowell tive, non-toxic and excellent recyclability profiles, these products are
Lowell, MA ideal candidates for an industry striving for more environmentally
friendly and sustainable fire safety solutions.
Halogen-based flame-retardant (FR) polymers and additives have
been a cost-effective solution for FR applications. However, there 2:00-2:30
is now an increased global emphasis on discontinuing the use of Polymeric Flame Retardants
halogenated compounds due to the release of toxic gases upon S. Levchik, ICL-IP America, NY; P. Georlette, Y. Bar-Yaakov, Ita Fin-
combustion that is harmful to both humans and the environment. berg, Yaniv Hirschsohn, 2ICL-IP, Beer Sheva , Israel
Thus, there exists the need to develop human and environmentally
safe, economical polymers with efficient FR properties. We have re- Polymeric flame retardants are sustainable products in the view
cently shown that enzymatically and non-enzymatically synthesized of many national and international human health and environ-
polyborosiloxane copolymers have great potential as FR materials. mental regulations. This presentation will overview existing and
We will present simple eco-friendly synthesis, characterization includ- new polymeric bromine and phosphorus based flame retardants.
ing thermal properties, surface analysis of char, and the thermal Special attention will be given to new applications with the focus
degradation mechanism of the organic-inorganic hybrid siloxane on physical properties and safety of use of these flame retardants
copolymers. Furthermore, we will present data on new siloxane- thanks to their high thermal stability and excellent permanence
based nanocomposites. in the polymers.

12:00-12:30 2:30-3:00
Molecular Dynamics of Backbone Scission in Polyolefins Halogenated Dioxasiloles as Precursors to Flame Retardant
Stanislav Stoliarov, Department of Fire Protection Engineering, Polymers
University of Maryland, College Park, MD; Kenneth Smith, United Bob A. Howell and Young-Jun Cho, Center for Applications in
Technologies; Morgan Burns, University of Texas at Austin; Phillip Polymer Science and Department of Chemistry Central Michigan
Westmoreland, North Carolina State University; Richard Lyon, Fed- University, Mt. Pleasant, MI
eral Aviation Administration; and Marc Nyden National Institute of
Standards and Technology Certain five-membered dioxaheterocycles (heteroatoms may be
P,Si,S,etc.) contain a strained carbon-carbon bond which may un-
The past work on development and application of classical mo- dergo homolytic thermolysis at modest temperatures to generate a
lecular dynamics (MD) to simulation of chemical reactions is diradical capable of initiating vinyl polymerization. If substituents
reviewed. The next generation approach to reactive MD called contain flame retarding moieties this represents a convenient method

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for imparting flame retardancy to a polymeric material. One such 4:30-5:00
heterocycle is 2,2-diphenyl-4,4,5,5,-tetra(3,5-dibromophenyl)-1,3- Phosphorus-containing Syrenic Monomers for the
dioxa-2-silole. This compound may be prepared by treatment of Preparation of Flame Retardant Polymeric Materials
a multibrominated precursor diol with diphenyl-chlorosilane. It
Adina Dumitrascu, Bob A. Howell, Center for Applications in Polymer
may be used to generate oligomers/polymers with flame retardant
Science and Department of Chemistry, Central Michigan University,
properties.
Mt. Pleasant, MI 48859-0001
3:00-3:30 Coffee
Effective phosphorus flame retardants are attractive replacements
Chairperson: Charles Wilkie, Marquette University
for organohalogen compounds which have come under increasing
scrutiny because of their tendency to bioaccumulate when released
3:30-4:00
into the environment and to pose potential health risks. In this
Flame Retardant Synergies with Organic Phosphinates instance, five new phosphorus-containing styrene monomers have
Wolfgang Wanzke, Elke Schlosser, Sebastian Hoerold, Bernd Nass, been prepared, fully characterized, and used to generate styrene
Clariant Produkte, Deutschland; BU Additives, Development Flame copolymers containing various levels of flame-retarding comonomer.
Retardants, Gersthofen, Germany The effectiveness of the comonomers in imparting flame retardance
to the copolymers is reflected in the char yields upon thermal deg-
Fire Retardants based on organic metal phosphinates were fully com- radation and decreased peak heat release values when subjected to
mercialized in 2004, representing a new class of halogen free systems combustion.
offered in the market. The main area of application was glass fiber
reinforced polyamides at that time. In the past six years a lot of other 5:00-5:30
uses, especially in engineering plastics and elastomers were devel- Materials in Navy Applications
oped. Flame retardant polyester resins is the newest market segment
Usman Sorathia, Naval Surface Warfare Center, Carderock Division
with extended use of phosphinates in a variety of compounds. The
electrical and electronics industry recognized and appreciated the
There is a need for new bedding component materials in the U.S.
property profile of phosphinate based polyesters as a replacement for
Navy vessels. The current bedding components and their specifica-
established FR materials. More applications including adhesives and
tions are being upgraded to permit newer commercially available
thermosets have been added as well. As shown by previous analytical
materials. There is a concern for fire, smoke, and toxicity of these
studies, phosphinates can work by different mechanisms making
materials. In order to permit these new materials in the Navy con-
them versatile in polymer specific recipes. Showing a significant por-
struction, fire performance criteria are being established for many
tion of gas phase action when used on their own, a shift to more solid
applications. This paper will discuss such criteria for bedding com-
state activity by char formation can be observed when using nitrogen
ponents, including mattress, blankets, and pillows.
containing synergists and/or char stabilizing components. The most
recent work concerning metal phosphinates in combination with
5:30-6:00
different synergists in thermoplastic and elastomeric applications
will be reviewed. Morphologically Unique Magnesium Hydroxide – Preparation
and Performance in Halogen-free Flame-retardant EVA
4:00-4:30 Lijuan Lia, Zhiqi Liu a,b
Novel Phosphorus-based Flame Retardants for Epoxy Resins a. Key Laboratory of Salt Lake Resources and Chemistry, Qinghai
and Carbon Fiber Composites: Decomposition Mechanisms Institute of Salt Lakes, CAS, Qinghai, Xining810008, China;
and Fire Behavior b. Graduate University, CAS, Beijing100049, China;
Brigit Perret, Bernhard Schartel, BAM Federal Institute for Materials
Magnesium hydroxide as an ecologically sound flame retardant has
Research and Testing, Berlin, Germany; Kai Stöß, Jan Diederichs,
been widely used to fire-retard many polymers for its high decom-
Michael Ciesielski, Manfred Döring, Institute of Technical Chemistry,
position temperature, smoke suppression, non-toxicity and ability to
Karlsruhe Research Center GmbH, Karlsruhe, Germany; Johannes
neutralize with acidic gases from polymer combustion. The shape,
Krämer, Volker Altstädt, Department of Polymer Engineering, Uni-
particle size and size distribution of magnesium hydroxide have a
versity of Bayreuth, Bayreuth, Germany
great influence on the flame retardancy, smoke suppression and
mechanical properties of a flame-retardant polymeric composite.
The flame retarding action of different novel phosphorus-based
In this paper, the magnesium hydroxide with special morphological
flame retardants in different epoxy resins and their carbon fiber
features was prepared by hydrothermal modification using techni-
reinforced equivalents suitable for automotive and aviation in-
cal magnesium hydroxide as the raw material. The influence of the
dustry was investigated. Pyrolysis was studied by means of thermal
morphology-transforming agent and hydrothermal conditions on the
analysis (thermogravimetry, TG), evolved gas analysis (TG-FTIR)
magnesium hydroxide shape and size distribution was investigated.
and condensed phase analysis (linkam hot stage cell coupled with
The mechanical properties, flame property and electrical property of
FTIR). The fire behavior was studied by means of reaction to a
the EVA compounds are shown to be remarkably improved by means
small flame (flammability, LOI and UL 94) and forced flaming
of adding such morphologically unique magnesium hydroxide.
behavior (cone calorimeter). All flame retarded epoxy resins with
The SEM images and the particle size distribution of magnesium
and without carbon fibers show significant better results in forced
hydroxide obtained under different morphology-transforming
flaming behavior and flammability compared to the non-protected
agent and hydrothermal conditions. The EVA compounds and their
epoxy resins. Interactions between flame retardant and epoxy matrix
composition. Mechanical properties, flame property and electrical
were found and mechanisms and efficiency of the flame retardants
property of EVA and composites.
strongly depends on the epoxy matrix in which they are inserted.
Furthermore the influence of the carbon fibers during combustion
6:00-7:30 Reception
is of great importance.

Program subject to change—check www.bccresearch.com/conferences.php for updates

May 25, 2010 José-Marie Lopez Cuesta, Sayyed-Hossein Vahabi, Claire Longuet,
Session III: Nanocomposites and Flame Retardancy Rodolphe Sonnier, Pôle Matériaux Polymères Avancés, Centre des
Chairperson: Kelvin Shen, Rio Tinto Minerals Matériaux, Ecole des Mines d’Alès, Alès, France

8:30-9:00 Submicronic kaolinite and boehmite are investigated as fire retardant

Time to Ignition of Nanocomposites an Unpredictable fillers in PC, PC/PMMA and PC/ABS alloys. Various combinations
Puzzling Trend to be Understood with conventional flame retardant such as phosphates and hydrated
fillers are studied in order to achieve synergistic effects. A particular
A. Fina, A. Alongi, D. Battegazzore, G. Camino, Politecnico di Torino, attention is focused on the influence of interfacial treatments and
Alessandria site, Alessandria, Italy modifications of kaolinite and boehmite on the thermal degradation of
the above polymers. Nanocomposites are elaborated using a microcom-
Although the performance of polymer nanocomposites in forced pounder and characterized using scanning and transmission electron
combustion tests is well known and discussed, a limited knowledge is so microscope, thermogravimetric analysis, X-Rays diffractometry, cone
far available on fundamental mechanisms beyond the bare results. In calorimeter, combustion micro-calorimeter, epiradiateur test, and
particular, variable trends for time to ignition (TTI) of nanocomposites limiting oxygen index. Results show that water contained in the submi-
have been reported: a reduction of TTI compared to neat polymers is cronic fillers enhances the thermal degradation of polycarbonate. This
often observed, but the opposite effect is also reported in many cases. can be reduced by the incorporation of PMMA as minor component
in PC/PMMA blends. Moreover, an intercalation process involving
A number of proposals have been made to interpret reduction of DMSO, methanol and dodecylamine is also carried out on kaolinite.
TTI in nanocomposites when it occurs, such as thermal instabil- After polymerization of kaolinite/Methyl MethAcrylate compositions,
ity of nanofiller organic modifiers and/or of polymer-nanoparticles the resulting kaolinite/PMMA nanocomposites are incorporated in
compatibiliser, enhanced radiant heat absorption, improved thermal PC. An improvement of fire behaviour and transparency is noticed in
conductivity as well as viscosity increase hindering convective flow in comparison with PC/PMMA blends produced by melt blending.
the molten polymer. However, none of the interpretations supplied so
far in the literature, results in a general rule and no solid experimental 10:00-10:30 Coffee
evidences are reported. The results of a thorough investigation on igni- Chairperson: Marcelo M. Hirschler, GBH International
tion, by the measurement of ignition temperatures related to thermal
behaviour of polymers and nanocomposites, will be reported. 10:30-11:00
(Chemically Modified) Nanoparticles for Flame Retarded
9:00-9:30
Polymeric Materials
New Features in Flame Retarding PA-6 with Bromine-based
Additives in the Presence or Absence of Layered Silicates Gaelle Fontaine, Serge Bourbigot, Equipe Procédés d’Elaboration
des Revêtements Fonctionnels (PERF), Ecole Nationale Supérieure
Menachem Lewin¹*, Jin Zhang¹, Eli Pearce¹, Mauro Zammarano² de Chimie de Lille (ENSCL), France
1. Polytechnic Institute of NYU, 6 MetroTech Center, Brooklyn, NY
11201. The talk will investigate the reaction to fire of flame retarded
2. Building and Fire Research Laboratory, National Institute of Standards polymers containing novel functionalized nanoparticles. Those
and Technology, 100 Bureau Drive, Gaithersburg, MD 20899-8665, USA nanoparticles are incorporated in various polymers including ther-
*Correspondence to: Professor M. Lewin, E-mail: mlewin@duke. moplastic polyurethane (TPU), polylactic acid (PLA), and epoxy
poly.edu. resin containing flame retardants or not. The synthesis of chemi-
Tel.: +1-718-260-31632. cally modified particles like carbon nanotubes (MWNT), polyhedral
silsesquioxanes (POSS), or graphene will be presented. The effect of
Several new features encountered during the flame retardation of the chemical modifications will be examined in terms of dispersion
polyamide 6 (PA6) with bromine-based additives are discussed in light and of performance. The mechanisms of action as well as synergistic
of recent results obtained in this laboratory with pentabromobenzyl ac- aspects between the nanoparticles and the flame retardant will be
rylate (PMA). Bromine FRs were surprisingly found to behave similarly also investigated and discussed during the talk.
to clay: 1) they decrease PHRR by 2.7% for 1 wt% PMA, as compared to
9.7% for organically layered silicates; 2) the time of ignition for 10 wt% 11:00-11:30
PMA containing PA6 decreases to 39s as compared to 55s for pristine Synthesis, Thermal Behavior and Combustion of the Novel UV-
PA6. It is postulated that the bromine-based FRs migrate to the surface
Cured Flame Retardant Nanocomposite Coatings
during pyrolysis and form part of the surface barrier during combus-
tion, thus decreasing the thermal conductivity which is responsible Yuan Hu,Weiyi Xing, Lei Song, State Key Laboratory of Fire Science,
for time of ignition. 3) in the presence of 1 wt% organically layered University of Science and Technology of China, Hefei, Anhui, China
montmorillonite (OMMT), the high ratings obtained with UL-94 are
retained along with the 47% decrease in PHRR. Increasing OMMT to The novel organo-phosphorus acrylate containing acid and carbon
3 and 5 wt% brings about a drastic decrease in FR ratings. This is ac- source (BTP) was synthesized successfully. Meanwhile the novel
companied by a strong increase in the size and mass of drops formed UV-cured nanocomposite coatings containing organically modified
in the UL-94 test, indicating an increase in density and viscosity of the alpha-zirconium phosphate (OZrP) was prepared though UV irra-
pyrolysing melt; 4) the use of Na+MMT instead of OMMT retains the diation, and the synergistic effect of OZrP based on UV-cured flame
FR ratings, a high time of ignition and the mechanical properties. retardant nanocomposite coating was also studied. The structure was
characterized by FTIR, 1H NMR, XRD and TEM. The combustion
9:30-10:00 properties of the cured films were evaluated by LOI, MCC and cone
Investigation on Synergistic Effects on Fire Retardancy Using calorimeter. Thermal behavior and degradation of the cured films
Submicronic Boehmite and Kaolinite were studied by TGA, and TGA-IR. The LOI value for BTP was 39. The

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char yield was 36% at 800oC. The results of XRD and TEM indicated For the past several years, my laboratory has studied the utilization of
that an intercalated structure or exfoliated structure was formed. The nanocomposites in fire retardancy; this has included investigations
results of MCC revealed that the HRR of the films decreased with the of the effect of the various organic modifications on montmorillon-
contents of organic -ZrP (OZrP). The TGA results indicated that with ites, layered double hydroxides and other clays; the use of carbon
increasing the contents of OZrP, the char yields of UV-cured films nanotubes; the processes by which these may be effective; potentially
were enhanced. Thermal stability of flame retardant coating could synergistic combinations of nano-dimensional materials with other fire
be improved by adding OZrP. Cone tests indicated that the addition retardant materials, etc. In this talk, I will discuss new work coming out
of OZrP in flame retardant systems could reduce PHRR by 29%. from this laboratory and its implications for the future.

11:30-12:00 2:00-2:30
Characterizing Particle Emissions from Burning Polymer Non-halogenated Flame Retardant Formulations for
Nanocomposites Biodegradable Polymer Blends*
Marc R. Nyden and Nathan D. Marsh, Building and Fire Research S. Pack, M. Rafailovich, Department of Materials Science, SUNY at
Laboratory, National Institute of Standards and Technology, Gaith- Stony Brook, NY 11794-2275
ersburg, MD N. Muir, Uniondale High School, Uniondale, NY

Carbon nanotubes (CNT) and fibers (CNF) may pose significant Recently a great deal of effort has been placed in developing bio-
health and environmental risks due to their small size and ability degradable blends to replace standard polymer blends in as many
to interact with biological molecules. It has recently been suggested applications as possible. Of concern through, have been applications
that the morphology of the nanoparticles may have a special influ- where the polymers had to meet specific standards for being flame
ence on the above risks. The health risks increase with in exposure retardant. In this case it was feared that as the polymer degrades,
to fire or other forms of intense energy. In an effort to gain a better the FR formulations are released into the soil where they can leach
understanding of the potential hazards associated with the com- into nearby water supplies. As a result, the development of new and
mercialization of polymer nanocomposites, we have undertaken an environmentally safe formulations for biodegradable materials was
investigation into the nature of the particles released when these required. Here we present several options, using functionalized clays
materials are burned. The first question we hope to answer is whether in combination with other nanoparticles which have been effective
significant amounts of nanoscale additives are released (in addition in rendering biodegradable; polymer blends flame retardant with
to soot, which is a ubiquitous byproduct of gas phase combustion) UL-94 VO designation.
when polymer nanocomposites are burned. * Supported in part by the NSF-MRSEC program

12:00-12:30 2:30-3:00
An Efficiently Flame-Retardant Polycarbonate System Morphology, Thermal Stability, and Flammability Behavior
Prepared from a Novel Silicon- and Phosphorus-Containing of Polymer Composites Coated with Graphite Nanoplatelets
Flame Retardant and Montmorillonite Nanopapers
Zhi Hu, Yu-Zhong Wang, Center for Degradable and Flame-Retar- Yong Tang, Jinfeng Zhuge, Jihua Gou, Department of Mechanical,
dant Polymeric Materials (ERCEPM-MoE), College of Chemistry, Materials and Aerospace Engineering, University of Central Florida,
State Key Laboratory of Polymer Materials Engineering, Sichuan Orlando, FL
University, China
In this study, a hybrid nanopaper consisting of graphite nanoplatelets
A novel silicon- and phosphorus-containing flame retardant, P-PSi, (GNP) and ammonium polyphosphate (APP), has been fabricated
was used to prepare flame-retardant polycarbonate (PC) together through the papermaking process. The as-prepared hybrid nanopa-
with montmorillonite (MMT) via melt blending. The resulting per was then coated onto the surface of glass fiber reinforced polymer
flame-retardant PC/P-PSi/MMT organic-inorganic hybrids have matrix composites through resin transfer molding (RTM) process.
good comprehensive properties. The thermal degradation behavior The morphologies of hybrid nanopapers with and without the poly-
and flame retardancy of those hybrids were investigated with TGA, mer resin were characterized with scanning electron microscopy
limiting oxygen index (LOI), vertical burning test (UL-94), and (SEM). It can be seen that the nanopaper had a porous structure and
cone calorimeter. The LOI value of the flame-retardant PC systems the APP particles were homogeneously dispersed within the hybrid
could reach 32.8 when the content of P-PSi was 5wt%. When 2wt% nanopaper. The polymer resin penetrated the entire nanopapers
MMT was added into the hybrids containing 5wt% P-PSi, the UL-94 under a high-pressure compressed air system. The thermal decom-
rating reached V-0. Various cone parameters also showed that PC/P- position behavior of hybrid nanopapers and nanocomposites was
PSi/MMT hybrid is a good flame retardant system. A possible flame studied with real-time thermogravimetric analysis/flourier transform
retardant mode of MMT was studied via the dynamic rheological infrared spectrometry (TGA/FTIR). The test results indicate that the
properties and the morphology of the char of samples obtained after addition of APP increased the char residues of the nanocomposites.
the LOI test and the cone calorimeter test. The fire retardant performance of composite laminate coated with
hybrid nanopaper was evaluated with cone calorimeter test using a
12:30-1:30 Lunch radiated heat flux of 50 kW/m2. The cone test results indicate that
Chairperson: Richard Lyon, Federal Aviation Administration, NJ the peak heat release rate (PHRR) decreased dramatically in the
GNP-APP nanopaper coated composite laminates. The combustion
1:30-2:00 behaviors of these samples were also examined by microscale combus-
Recent Advances In Nanocomposites in Fire Retardancy tion calorimetry (MCC). The HRR obtained from MCC was consistent
Charles A. Wilkie, Department of Chemistry and the Fire Retardant with the results obtained from cone calorimeter test.
Research Facility, Marquette University, WI 53201

Program subject to change—check www.bccresearch.com/conferences.php for updates

3:00-3:30 Coffee break been prepared. Phosphorus acid is the main raw material, melamine
is the condensing agent. The two chemicals are mixed, heated and
Session IV: Consumer Focus and Industrial Applications melted at high temperature under a dry ammonia atmosphere. Some
Chairperson: Guenther Byer, Kabelwerk Eupen AG, Belgium effects, such as chemical ratio, heating temperature, time of heating
and condensing, flow and pressure of dry ammonia atmosphere are
3:30-4:00 investigated. Structural characterization of prepared product is car-
Intumescence for the Flame Retardancy of Polylactide ried out through XRD, SEM, and IR. Compared with the patterns
of industrial-grade APP with crystal form-I, form-II, form-V and cited
Serge Bourbigot, Gaëlle Fontaine and Sophie Duquesne, Equipe from literature, it is identified that the prepared product is APP with
Procédés d’Elaboration des Revêtements Fonctionnels (PERF), Ecole crystal form-V.
Nationale Supérieure de Chimie de Lille, France
5:00-5:30
Polylactide (PLA) is synthesized from renewable resources and cur-
rently deserves a particular attention in the area of environmentally
New P-based flame retardant for flexible polyurethane foams
degradable polymer materials. PLA has good mechanical proper- Alexander Koenig, Polymers and Additives Environmental Engineer-
ties, thermal plasticity and biocompatibility and is thus a promising ing, Fraunhofer Institut für Chemische Technologie, Joseph-von-
polymer for various end-use applications. In numerous applications Fraunhofer Str. 7, 76327 Pfinztal
of PLA, flame retardancy is very often required. Intumescence is
a method to provide flame retardancy to polymers and it will be The chemical nature of the flexible polyurethane foams (PUF),
investigated for PLA. Novel systems will be examined including for- their high air permeability and the high inner surface area of the
mulations based on ‘green’ products. Synergistic effects are observed foam structure cause this material to be highly flammable. In this
using nanoparticles and they will be discussed in the talk. Finally study, the influencing variables on the burning behavior of flex-
mechanism of action will be also examined. ible PUF are investigated. Additionally the synthesis, formulation,
characterization and testing of a new Phosphorus flame retardant
4:00-4:30 methyl-DOPO 9,10-Dihydro-9-oxa-methylphospha¬phenthren-10-
Intumescent Coatings for the Fire Protection of Steel - oxid in flexible PUF with low density is performed. The new flame
Influence of Inorganic Fillers on Char Structure retardant shows an excellent flame retarding behavior by acting
mainly in the gas phase. Here the vaporization of methyl-DOPO oc-
Sophie Duquesne, Serge Bourbigot, Equipe Procédés d’Elaboration curs in the same temperature region like the depolymerization of
des Revêtements Fonctionnels (PERF), Ecole Nationale Supérieure the urethane and the bisubstituted urea groups during pyrolysis of
de Chimie de Lille, France the foam. Furthermore TG-MS measurements revealed the release
of high concentrations of low molecular species like HPO, CH3PO
Intumescent coatings are widely used in the field of fire protection of or PO2 in the mentioned temperature region. This species are able
steel structures due to their high efficiency and easy of process. Their to scavenge the H- and OH-radicals in the radical chain mechanism
composition is usually based on a combination between ammonium of the flame leading to a significant increase of the CO/CO2 ratio
polyphosphate (APP), pentaerythritol and melamine. Moreover, during cone calorimeter experiments.
in most of the cases, inorganic fillers such as for example titanium
dioxide or zinc borate are added in the formulation for various 5:30-6:00
reasons. It has been demonstrated that APP is very reactive and can Flame Retardant Olefinic Polymers Containing Metal
react with most of those inorganic fillers leading to thermally stable
phosphates. The objective of this study is to investigate how the pres-
Hydroxides - Fire Performance vs. Other Properties
ence of those fillers will affect the formation and the structure of the
Optimization by Surface Modification
intumescent protective char. The influence of various inorganic fillers Tong Chen, Alex Isarov, J. M. Huber Corporation, Fairmount,
on the mechanism of intumescence will be reviewed, followed by a GA 30139
discussion on how to select the fillers for optimal properties.
Metal hydroxides such as alumina trihydrate (ATH) and magnesium
4:30-5:00 hydroxide (MDH) are used to achieve low-smoke and fire resistant
Preparation of Ammonium Polyphosphate with Crystal Form polymer compositions, which often are halogen-free. The require-
type-V from Phosphorus Acid ment for high loading levels when using the metal hydroxides contin-
ues to present concerns and challenges for industrial applications due
Gousheng Liu, School of Resources and Environmental Engineer- to undesirable reduction in mechanical properties and processing
ing, East China University of Science and Technology, Shanghai ease. Efforts have been made to design the metal hydroxide products
200237, China such that the property or performance loss as related to the high
loadings may be controlled to an acceptable range, while at same
As halogen-free and intumescent flame retardant, ammonium poly- time, the fire performance is sustained or even enhanced. One means
phosphate (APP) has been extensively applied in the field of flame to achieving such unique metal hydroxide products is to chemically
retardant materials in recent decades. In the six different kinds of modify the surface of the hydroxides. This paper will discuss recent
crystal forms from form-I to form-VI, more attentions have been paid results by J. M. Huber Corporation in exploiting surface modifica-
to form-I and form-II at home and abroad. Except form-I and form-II, tion of ATH and MDH to enable performance optimization of the
form-V APP has better stability. Until now, less study has been found fire retardant polyolefins compositions.
for APP with crystal form-V. In this study, APP with crystal form-V has

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 used in the industry have significant limitations. Most analytical
Flame Spread Rate, mm/min 17 and testing techniques are not able to measure heat release rate
(HRR), the single most important parameter in evaluating the fire
16
hazard of materials. It is difficult to measure HRR of textile fabrics
using cone calorimetry because textile fabrics are dimensionally
15
thin samples. The recently developed micro-scale calorimetry
14 (MCC) is able to measure the following flammability parameters
for textiles: heat release capacity, HRR, temperature at PHRR,
13 total heat release and char yield using milligram sample size. In
this research, we applied MCC to evaluate the flammability of
12 different textile fabrics including cotton, rayon, cellulose acetate,
0 1 2 3 4 5 silk, nylon, polyester, polypropylene, acrylic fibers, Nomex and
Ratio of low molecular weight surface treatment to
Kevlar. We also studied the textile fabrics and blends treated
polymeric surface treatment with different flame retardants. We found that MCC is able to
differentiate small differences in flammability of textile materials
treated with flame retardants. We were also be able to calculate
Figure 1. Flame spread rate as a function of the ratio of two the limiting oxygen index (LOI) using the thermal combustion
components of surface treatment (40% magnesium hydroxide properties of various textile samples measured by the MCC. The
in polypropylene). calculated LOI data have yielded good agreement with experi-
mental LOI results. Thus, we conclude that MCC is an effective
May 26, 2010 new analytical technique for measuring textile flammability and
Session IV: Consumer Focus and Industrial has great potentials in the research and development of new
Applications - continued flame retardants for textiles. The MCC studies of blend fabrics
 hairperson: Serge Bourbigot, Ecole Nationale Supérieure
C will also be included.
de Chimie de Lille, France
Session V: Testing and Standardization
8:30-9:00 Chairperson: Giovanni Camino, Politecnico di Torino,
Progress with Nanocomposites as a Flame Retardant Concept Alessandria, Italy
Guenter Beyer, Kabelwerk Eupen AG, Belgium
9:30-10:00
We will report different nanostructured fillers to generate under Differences of Polymer Nanocomposites Burning in
industrial conditions EVA-, LDPE- and PVC-nanocomposites. An Horizontal Compared to Vertical Orientation
important aspect for PVC as polymer matrix was to avoid the very S.Ukleja, M. McKee,JP. Zhang, M.A. Delichatsios, Fire Safety Engi-
early degradation of PVC by quaternary ammonium compounds neering Research and Technology Center, University of Ulster
often used in organoclays. The fire performances of the compounds
were investigated by Cone calorimeter and TGA under oxidative con- Although experiments are generally conducted in the cone calorimeter
ditions. Other intercalants than quaternary ammonium compounds in the horizontal orientation, tests in the vertical orientation can and
were investigated. We will report about the FR properties of different should be conducted for the case when the final geometry (large-scale)
PE compounds with organoclays by extrusion trials. XRD and TEM of the materials is vertical and when the material may be melting.
results will be presented and also the FR properties by cone calo- This study examines how the sample orientation affects the burning
rimeter will be reported In Europe new flame tests are introduced behaviors of a polymer nanocomposite (polypropylene modified with
by the European directive CPD (construction product directive). nanoclay, PP+NC) in the cone calorimeter. Tests are conducted at vari-
New test results will be presented which indicate the excellent flame ous heat fluxes and a comparative analysis of the results is performed
retardant properties by nanocomposites which opens the possibility in terms of ignition time, mass loss rate, heat release rate and produc-
to optimize products. tion of toxic gases (CO, CO2 and smoke). No dripping occurs in a
vertical orientation. Ignition time is twice as long. The transient HRRs
9:00-9:30 are lower. Transient results for the toxic gases are lower. Several causes
Applications of Micro-scale Combustion Calorimetry to Flame of these differences are discussed. A numerical model to explain the
Retardant Textiles Research differences between the orientations is described.
Charles Q. Yang1, Qingliang He1 and Richard E. Lyon2, 1Department
of Textiles, Merchandising and Interiors, The University of Georgia, 10:00-10:30 Coffee
Athens, 305 Dawson Hall, Georgia 30602, USA
2
Fire Research Program, FAA Fire Safety Branch AJP-6320 10:30-11:00
William J. Hughes Technical Center Fire Testing for Code Use: Steiner Tunnel Test Variations
Atlantic City International Airport, NJ 08405, USA Marcelo M. Hirschler, GBH International

Evaluating and analyzing the performance of flame retardant (FR) The Steiner tunnel is the fire test most commonly used for regula-
textiles is a critical part of research and development of new FR tory use in the USA. The standard test, ASTM E 84, is quite vague in
textile products by the industry. The testing methods commonly the explanation of how materials or products need to be mounted

Program subject to change—check www.bccresearch.com/conferences.php for updates

for testing. This has led to tests being conducted, and materials or and fume. The new regulations appear to be of vital importance to
products being approved, without the proper associated fire safety. resin manufacturers. The previous French regulations were based
This was initially addressed by developing specific variations of the on a Fire resistance part “I” using Glow wire and LOI as the main
test that applied to wires and cables (for use in plenums), sprinkler test methods and a Fume/toxicity part “F” using both toxicity and
pipes, pneumatic tubing and plastic cable raceways. In recent years opacity methods. The new norm will have 3 Hazard levels (HL)
standard practices have been issued for specimen preparation and based on type of transport and an R levels based on the type of ap-
mounting of wall/ceiling coverings, pipe and duct insulation, wood plications and the risk. The most critical R levels are discussed for
products, site-fabricated stretch systems and reflective insulation E&E applications. It is estimated that around 80-90% of application
materials. Other changes have been made, or are in progress, ad- use will be covered if HL2 level is actually reached. This paper will
dressing specimen width and thickness. This paper will present an compare results and ratings achieved using the old French regulation
update and indicate areas where added work is still needed. with new results and draft ratings made in accordance to the new
CEN/TS 45545 regulation.
11:00-11:30
Effects of an Enclosure on Burning Behavior in the 12:30-1:30 Lunch
Cone Calorimeter Chairperson: Manfred Doering
M. Janssens and C. Gomez, Southwest Research Institute, San 1:30-2:00
Antonio, TX
Ten Decades of Flame Retardancy Testing at the Forest
This paper reports on a systematic study to evaluate the effects of Products Laboratory
the enclosure on the burning behavior in the Cone Calorimeter for Robert H. White and Susan L. LeVan-Green, U.S. Forest Service,
a range of materials. Specimens of seven materials were tested in Madison, WI
air at the same heat fluxes, with and without enclosure. Some pre-
liminary tests were conducted to determine the maximum airflow The development or adoption of advances in flammability test
through the enclosure. The flow was found to be unstable at 180 equipment played a critical role in facilitating ten decades of
L/min, which is the high limit on the flow meters, and a flow rate of FPL research to improve the flammability of wood products. FPL
150 L/min was used in the experiments. Specimens of seven materi- equipment developments include the 1912-15 work of R.E. Prince
als (black PMMA, brominated FRP, carpet, flexible PVC, FR treated to expose specimens to constant temperatures to determine the
and untreated Douglas fir plywood and rigid polyisocyanurate foam) times for ignition, the fire tube apparatus in 1920’s, and the 8-ft
were tested at 50 and 75 kW/m2. The effects of the enclosure on tunnel in 1950’s. In the 1960’s, considerable fundamental research
ignition time, heat release and smoke production rates were found was conducted using thermogravimetric and differential thermal
to be statistically insignificant. Tests could not be conducted at 100 analysis. As an early promoter of the use of heat release rate as a
kW/m2 to avoid overheating of the enclosure. measure of relative flammability, FPL developed an apparatus in
the 1960’s to measure the heat released by a burning material. As
11:30-12:00 better technologies were developed to measure heat release rate,
The Limiting Oxygen Index Test (Revisited) FPL obtained such equipment to continue its efforts to properly
measure the potential contribution of wood products to a fire
R.E. Lyon, M.R. Fullmer, S. Crowley and R.N. Walters, Federal
and facilitate the development of new fire-retardant-treated wood
Aviation Administration, Airport and Aircraft Safety R&D Division,
products.
Atlantic City International Airport, NJ
2:00-2:15
Heat release rate measurements were made using oxygen consump-
tion calorimetry for several commercial plastics during the standard Heat Release Testing with the OSU Apparatus
ASTM D 2863 test to measure the minimum oxygen concentration to Timothy T. Earl, GBH International
support candle-like combustion of plastics/oxygen index. An energy
balance at the sample surface for flaming combustion can account For more than 20 years, the Federal Aviation Administration has
for the downward burning rate and extinction condition (limiting required certain materials used in the interior of passenger aircraft
oxygen index) in terms of the thermal combustion properties of the to meet maximum heat release limits. The prescribed test method
material and the effect of oxygen on flame heat flux. utilizes the Ohio State University Rate of Heat Release Apparatus.
Since then, the cone calorimeter has become much more common,
12:00-12:30 and interest in the OSU outside of the aviation industry has waned.
New EU regulations for fire safety in railways: comparison As a result, many current fire researchers have little knowledge of
with presently existing regulations. this instrument which is used as a regulatory tool in a critical appli-
cation. This paper will discuss the different configurations of the
J. W. Mitchell, F. Schutz, S.Collot, F-X.Blet, Rhodia Polyamide, Saint
OSU as specified by standards and regulations issued by the FAA,
Fons, France
ASTM, and Airbus.
The new regulations for trains in Europe are discussed. This
method replaces the previous national regulations concerning fire

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ABOUT BCC RESEARCH Short course registration includes lunch, coffee, beverages and
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Exhibits: Showcase your products or services by reserving a tabletop
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hosting one of the food functions. For details, contact Chris Ross and Connecticut. The normal fare to the Holiday Inn Stamford
at [email protected]. Downtown Stamford is $60.00 each way. Conference Attendees
will receive a discounted rate of $48 each way. Also, the discounted
REGISTRATION AND HOTEL INFORMATION companion fare is $36.80 each way for attendees travelling together
Registration and Fees: Registration fee includes copies of available using the same credit card.
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Attendance is limited and so early enrollment is advised. Room To reserve by phone, call GO Airport Shuttle at 1-203-891-1280 or
reservations should be made directly with the hotel. 1-800-377-8745. Use ID key code 20BCC to receive the discount.

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