Flammability and Thermophysical Characterization of ... · Thermoplastic Elastomers –...

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DISTRIBUTION A. Approved for public release; distribution unlimited The 228 The 228 th th ACS National Meeting ACS National Meeting Philadelphia, PA Philadelphia, PA August 22 August 22 - - 26, 2004 26, 2004 D. Marchant D. Marchant 1 1 , J.H. Koo , J.H. Koo 2 2 , R.L. Blanski , R.L. Blanski 3 3 , , E.H. Weber E.H. Weber 3 3 , P.N. Ruth , P.N. Ruth 1 1 , A. Lee , A. Lee 4 4 , and C.E. Schlaefer , and C.E. Schlaefer 3 3 1 1 Air Force Research Laboratory, Propulsion Materials, ERC Inc., 1 Air Force Research Laboratory, Propulsion Materials, ERC Inc., 1 0 0 Saturn Blvd., Bldg 8451, Edwards AFB, CA 93524 Saturn Blvd., Bldg 8451, Edwards AFB, CA 93524 2 The University of Texas at Austin, Department of Mechanical The University of Texas at Austin, Department of Mechanical Engineering Engineering - - C2200, Austin, TX 78712 C2200, Austin, TX 78712 3 3 Air Force Research Laboratory, Propulsion Materials, AFRL/PRSM, Air Force Research Laboratory, Propulsion Materials, AFRL/PRSM, 10 Saturn Blvd., Bldg 8451, Edwards AFB, CA 93524 10 Saturn Blvd., Bldg 8451, Edwards AFB, CA 93524 4 Michigan State University, Department of Chemical Engineering an Michigan State University, Department of Chemical Engineering an d d Materials Science, 2527 Engineering Bldg, East Lansing, MI 48824 Materials Science, 2527 Engineering Bldg, East Lansing, MI 48824 Flammability and Thermophysical Flammability and Thermophysical Characterization of Thermoplastic Elastomer Characterization of Thermoplastic Elastomer Nanocomposites Nanocomposites

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  • DISTRIBUTION A. Approved for public release; distribution unlimited

    The 228The 228thth ACS National MeetingACS National MeetingPhiladelphia, PAPhiladelphia, PA

    August 22August 22--26, 200426, 2004

    D. MarchantD. Marchant11, J.H. Koo, J.H. Koo22, R.L. Blanski, R.L. Blanski33, , E.H. WeberE.H. Weber33, P.N. Ruth, P.N. Ruth11, A. Lee, A. Lee44, and C.E. Schlaefer, and C.E. Schlaefer331 1 Air Force Research Laboratory, Propulsion Materials, ERC Inc., 1Air Force Research Laboratory, Propulsion Materials, ERC Inc., 10 0

    Saturn Blvd., Bldg 8451, Edwards AFB, CA 93524Saturn Blvd., Bldg 8451, Edwards AFB, CA 9352422 The University of Texas at Austin, Department of Mechanical The University of Texas at Austin, Department of Mechanical

    EngineeringEngineering--C2200, Austin, TX 78712C2200, Austin, TX 787123 3 Air Force Research Laboratory, Propulsion Materials, AFRL/PRSM, Air Force Research Laboratory, Propulsion Materials, AFRL/PRSM,

    10 Saturn Blvd., Bldg 8451, Edwards AFB, CA 9352410 Saturn Blvd., Bldg 8451, Edwards AFB, CA 9352444Michigan State University, Department of Chemical Engineering anMichigan State University, Department of Chemical Engineering and d

    Materials Science, 2527 Engineering Bldg, East Lansing, MI 48824Materials Science, 2527 Engineering Bldg, East Lansing, MI 48824

    Flammability and Thermophysical Flammability and Thermophysical Characterization of Thermoplastic Elastomer Characterization of Thermoplastic Elastomer

    NanocompositesNanocomposites

  • Report Documentation Page Form ApprovedOMB No. 0704-0188Public reporting burden for the collection of information is estimated to average 1 hour per response, including the time for reviewing instructions, searching existing data sources, gathering andmaintaining the data needed, and completing and reviewing the collection of information. Send comments regarding this burden estimate or any other aspect of this collection of information,including suggestions for reducing this burden, to Washington Headquarters Services, Directorate for Information Operations and Reports, 1215 Jefferson Davis Highway, Suite 1204, ArlingtonVA 22202-4302. Respondents should be aware that notwithstanding any other provision of law, no person shall be subject to a penalty for failing to comply with a collection of information if itdoes not display a currently valid OMB control number.

    1. REPORT DATE AUG 2004 2. REPORT TYPE

    3. DATES COVERED -

    4. TITLE AND SUBTITLE Flammability and Thermophysical Characterization of ThermoplasticElastomer Nanocomposites

    5a. CONTRACT NUMBER F04611-99-C-0025

    5b. GRANT NUMBER

    5c. PROGRAM ELEMENT NUMBER

    6. AUTHOR(S) D Marchant; J Koo; R Blanski; E Weber; P Ruth

    5d. PROJECT NUMBER 4847

    5e. TASK NUMBER 0249

    5f. WORK UNIT NUMBER

    7. PERFORMING ORGANIZATION NAME(S) AND ADDRESS(ES) ERC, Inc,AFRL/PRS,10 E. Saturn Blvd.,Edwards AFB,CA,93524

    8. PERFORMING ORGANIZATION REPORT NUMBER E04-082

    9. SPONSORING/MONITORING AGENCY NAME(S) AND ADDRESS(ES) 10. SPONSOR/MONITOR’S ACRONYM(S)

    11. SPONSOR/MONITOR’S REPORT NUMBER(S)

    12. DISTRIBUTION/AVAILABILITY STATEMENT Approved for public release; distribution unlimited

    13. SUPPLEMENTARY NOTES

    14. ABSTRACT N/A

    15. SUBJECT TERMS

    16. SECURITY CLASSIFICATION OF: 17. LIMITATIONOF ABSTRACT

    18. NUMBEROF PAGES

    37

    19a. NAME OFRESPONSIBLE PERSON

    a. REPORT unclassified

    b. ABSTRACT unclassified

    c. THIS PAGE unclassified

    Standard Form 298 (Rev. 8-98) Prescribed by ANSI Std Z39-18

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    Collaborators

    • AFRL/PRSM– S. Barker– M. Fernandez– T. Jones

    • 21st Century Polymers– G. Wissler

    • Texas A&M University– Z.P. Luo

    • Michigan State University– M. Namani

    • Southern Clay Products– D. Hunter

    • Applied Sciences Inc.– J. Glasglow

    • Omega Point Laboratories– S. Romo

    Financial Support: Air Force Office of Scientific Research

    Air Force Research Laboratory, Propulsion Directorate

  • 3DISTRIBUTION A. Approved for public release; distribution unlimited

    OUTLINEINTRODUCTION

    EXPERIMENTAL APPROACH

    WHAT IS NANOTECHNOLOGY?

    SELECTION OF MATERIALS

    OVERVIEW OF NANOPARTICLES

    DISCUSSION OF RESULTS

    • Processing of Materials• Microstructure Analyses of Pre-Test Materials• Thermophysical Properties• Flammability Properties• Microstructure Analyses of Post-Test Materials

    SUMMARY AND CONCLUSIONS

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    INTRODUCTION

    The introduction of inorganic nanomaterials as additives into polymer systems has resulted in polymer nanostructured materials exhibiting multifunctional, high performance polymer characteristics beyond what traditional polymer composites possess

    Selective thermoplastic elastomers have been used with montmorillonite organoclays, POSS®, carbon nanofibers to develop a flame resistant material

    Thermophysical and flammability properties of these polymer nanocomposites will be presented

  • 5DISTRIBUTION A. Approved for public release; distribution unlimited

    EXPERIMENTAL APPROACH

    A 30 mm Werner Pfleider co-rotating twin screw extruder was used and was configured for a wide variety of materials for polymer melt blendingThe extruder length/diameter (L/D) ratio can be varied from 21 to 48, with options of multiple feeds and ventsThe energy profile of the screw is optimized to meet the needs of the target productLong residence time screw designs are available for reactive productsVarieties of feeders are available to accommodate the material handling characteristics of the raw materialsStrand pelletization with low temperature chilled fluids allows processing of very soft or rubbery materialsApproximately 5 lbs of each formulation were producedSpecimens were injection molded in various configurations for measuring flammability and thermophysical properties

  • 6DISTRIBUTION A. Approved for public release; distribution unlimited

    What “Nano” Really Means?

    10 000nmhuman red blood cells

    Courtesy of Vaia

    bacteria E.coli1 000nm

    QD 7nm.

    Q-rods 30nm 10:1 aspect ratio

    virus 100nm

    polymer 40nm

    A nanometer (nm) is one billionth of a meter (10-9 m) about 4 times the diameter of an atom

  • 7DISTRIBUTION A. Approved for public release; distribution unlimited

    Nanocompositel = 1 nm

    10 nm

    Nanostructured MaterialsUniqueness

    Ultra-large interfacial area per volumeHigh fraction interfacial (interphase)

    materialShort distances between components

    NanoPolymer NanoInorganic

    Characteristics

    Reinforcement1>>h

    lInterfacial Region

    gRz

  • 8DISTRIBUTION A. Approved for public release; distribution unlimited

    10 µm

    Novamet 60 and ASI Nanotubes (inset shows ~500 tubes)

    Alexander et al.

    Micro versus Nano

  • 9DISTRIBUTION A. Approved for public release; distribution unlimited

    SELECTION OF MATERIALS

    Thermoplastic Elastomers – PELLETHANE™ 2102-90A thermoplastic polyurethane elastomer (TPU) is a polyester polycaprolactone elastomer manufactured by Dow Chemical. Its typical applications include seals, gaskets, belting, and others.Montmorillonite Nanoclays – Cloisite® 30B is a surface treated montmorillonite [Tallow bishydroxyethyl methyl, T(EOH)2M] manufactured by Southern Clay ProductsCarbon Nanofibers (CNFs) – CNFs are a form of vapor-grown carbon fibers, which is a discontinuous graphitic filament produced in the gas phase from the pyrolysis hydrocarbons manufactured by Applied Sciences. PR-19-PS CNF and PR-24-PS CNF were used.Polyhedral Oligomeric Silsesquioxane (POSS®) – Representing a merger between chemical and filler technologies, POSS nanostructured materials can be used as multifunctional polymer additives, acting simultaneously as molecular level reinforcements, processing aids, and flame retardants. Hybrid Plastics’ SO1458 Trisilanolphenyl-POSS® (C42H38O12Si7) was used.

  • 10DISTRIBUTION A. Approved for public release; distribution unlimited

    Montmorillonite Clays

    Na1/3(Al5/3Mg1/3)Si4O10(OH)2

    Na+

    Octahedral alumina layer Tetrahedral

    silicate layer

    Layer thickness is 0.96 nm

  • 11DISTRIBUTION A. Approved for public release; distribution unlimited

    Nanocomposite Classification

    U n m ix e d

    D

    E x fo lia te d

    In te rc a la te d

    d

  • 12DISTRIBUTION A. Approved for public release; distribution unlimited

    Processing Challenge of Nanoclay

    8µm Particle >1 Million Platelets

    Courtesy of Southern ClayProducts

  • 13DISTRIBUTION A. Approved for public release; distribution unlimited

    Dispersion Mechanism

    8 µm Particle~1MM Platelets

    Chemistry Chemistry/Processing Processing

    Dispersion

    Dispersion

    Tactoids/Intercalants

    Partial Dispersion

    Tactoids/Intercalants

    Tactoids/Intercalants

    Tactoids/Intercalants

    Courtesy of Southern ClayProducts

  • 14DISTRIBUTION A. Approved for public release; distribution unlimited

    Carbon Nanofibers

    Carbon nanofibers (CNFs) are a unique form of vapor-grown carbon fiber that bridges the gap in physical properties between larger, conventional PAN or pitch-based carbon fibers (5 to 10 µm in diameter) and smaller single-wall and multi-wall carbon nanotubes (1 to 10 nm in diameter)

    Pyrograf®-III is a very fine, highly graphitic carbon nanofiber manufactured by Applied Sciences Inc. that has an average diameter between 70 to 200 nm and a typical length of 50 to 100 µm

  • 15DISTRIBUTION A. Approved for public release; distribution unlimited

    Vapor-Grown Carbon Fiber

    Pyrograf-III Carbon Nanofiber Pyrograf-I VGCF

    Courtesy of Applied Sciences

  • 16DISTRIBUTION A. Approved for public release; distribution unlimited

    Pyrograf®-III TEMs

    PR-24-PS with an average diameter of 65 nm

    Courtesy of Applied Sciences

    PR-19-PS with an average diameter of 128 nm

  • 17DISTRIBUTION A. Approved for public release; distribution unlimited

    Polyhedral OligomericSilsesquioxane (POSS®)

    Represents a merger between chemical and filler technologies, POSS® nanostructured materials can be used as multifunctional polymer additives, acting simultaneously as molecular level reinforcements, processing aids, and flame retardants

    They have two unique structural features: (1) the chemical composition is a hybrid, intermediate (RSiO1.5) between that of silica (SiO2) and silicones (R2SiO); (2) POSS® molecules are nanoscopic in size, ranging from approximately 1 to 3 nm

  • 18DISTRIBUTION A. Approved for public release; distribution unlimited

    Si

    Si

    O

    O

    Si

    Si

    Si

    Si

    O

    O

    O

    O

    SiO

    Si

    O

    OO

    OO

    R R

    R

    R

    R

    R

    R X

    Anatomy of a POSS® Molecule

    May possess one or moreMay possess one or morefunctional groups suitable forfunctional groups suitable for

    polymerization or graftingpolymerization or grafting

    Thermally and chemicallyThermally and chemicallyrobust hybridrobust hybrid

    (organic(organic--inorganic) frameworkinorganic) framework

    Nanoscopic in size with anNanoscopic in size with anSiSi--Si distance of 0.5 nmSi distance of 0.5 nm

    and a Rand a R--R distance of 1.5 nmR distance of 1.5 nm

    Nonreactive organic (R)Nonreactive organic (R)groups for solubilizationgroups for solubilization

    and compatibilizationand compatibilization

    Precise threePrecise three--dimensional structure for molecular leveldimensional structure for molecular levelreinforcement of polymer segments and coilsreinforcement of polymer segments and coils

    Courtesy of Hybrid Plastics

  • 19DISTRIBUTION A. Approved for public release; distribution unlimited

    Key Aspects of POSS®Technology

    Hybrid (inorganic/organic) CompositionHybrid (inorganic/organic) Composition Nanostructured™ Chemical ReinforcementNanostructured™ Chemical Reinforcement

    POSSPOSS®® technology does not technology does not require manufacturers to require manufacturers to retool or alter existing retool or alter existing processes.processes.

    Lichtenhan et. al. Macromolecules 1993, 26, 2141.Lichtenhan, Polym. Mater. Encyclopedia 1996, 10, 7768.

    Si

    SiO

    O

    Si

    Si

    Si

    Si

    O

    O

    O

    OSi O

    Si

    O

    O

    O

    O

    O

    R

    R

    R

    R

    RR

    OO

    CH 3

    O

    CH 3

    R

    Si

    Si

    O

    O

    Si

    Si

    Si

    Si

    O

    O

    O

    O

    SiO

    Si

    O

    OO

    OO

    RR

    R

    R

    R

    R

    O O

    RTHFCatalyst

    Si

    Si

    O

    O

    Si

    Si

    Si

    Si

    O

    O

    O

    O

    SiO

    Si

    O

    O

    O

    O

    O

    RR

    R

    R

    RR

    O

    R

    O

    Si

    Si

    O

    O

    Si

    Si

    Si

    Si

    O

    O

    O

    O

    SiO

    Si

    O

    O

    O

    O

    O

    RR

    R

    R

    RR

    O

    R

    CH 3

    Use

    Tem

    pera

    ture

    &O

    xida

    tion

    Res

    ista

    nce

    Toughness, Lightweight &Ease of Processing

    Polymers

    Ceramics

    HYBRIDPROPERTIES

    Courtesy of Hybrid Plastics

  • 20

    POSS®-Molecular Silica BlendsBlended into 2 million MW Polystyrene

    Courtesy of A. LeeMichigan State University

    50 wt% loadingand transparent!

    Phase inversion

    Partial compatibilityDomain formation

    Si

    Si

    O

    O

    Si

    Si

    Si

    Si

    O

    O

    O

    O

    SiO

    Si

    O

    OO

    OO

    R R

    R

    R

    R

    R

    R R

    R = cyclopentyl

    Si

    Si

    O

    O

    Si

    Si

    Si

    Si

    O

    O

    O

    O

    SiO

    Si

    O

    OO

    OO

    R R

    R

    R

    R

    R

    R

    R = cyclopentyl

    Si

    Si

    O

    O

    Si

    Si

    Si

    Si

    O

    O

    O

    O

    SiO

    Si

    O

    OO

    OO

    R R

    R

    R

    R

    R

    R

    R = styrenyl

    Si

    Si

    O

    O

    Si

    Si

    Si

    Si

    O

    O

    O

    O

    SiO

    Si

    O

    OO

    OO

    R R

    R

    R

    R

    R

    R

    R = Phenethyl

    Cp8T8 CP7T8Styrenyl

    Styrenyl8T8

    Phenethyl8T8

  • 21DISTRIBUTION A. Approved for public release; distribution unlimited

    Thermoplastic Elastomer Nanocomposites (TPUN)

    15% PR-24-PS CNF2102-90A (85%)7

    15% PR-19-PS CNF2102-90A (85%)6

    5% PR-24-PS CNF2102-90A (95%)5

    5% PR-19-PS CNF2102-90A (95%)4

    5% Trisilanolphenyl-POSS®

    2102-90A (95%)3

    5% Cloisite® 30B2102-90A (95%)2

    None2102-90A (100%)1

    NanoparticlesPellethane™ TPUExperiments

  • 22DISTRIBUTION A. Approved for public release; distribution unlimited

    Microstructures Analyses of Pre-Test Materials

    TEM analyses were conducted on all 7 blends to examine the degree of dispersion of each type of nanoparticles in 2102-90A TPU

    PR-24-PS CNFs and PR-19-PS CNFs dispersed very well in 2102-90A TPU forming TPUNs

    In addition to TEM, the Cloisite® 30B modified materials were analyzed using WAXD

    Tests showed that the Cloisite® 30B dispersed very well in 2102-90A TPU forming intercalated/exfoliated TPU nanocomposites (TPUNs)

  • 23DISTRIBUTION A. Approved for public release; distribution unlimited

    TEMs of TPUN:5 wt% PR-19-PS CNF/95 wt% 2102-90A TPU

  • 24DISTRIBUTION A. Approved for public release; distribution unlimited

    TEMs of TPUN:15 wt% PR-19-PS CNF/85 wt% 2102-90A TPU

  • 25DISTRIBUTION A. Approved for public release; distribution unlimited

    TEMs of TPUN:5 wt% PR-24-PS CNF/95 wt% 2102-90A TPU

    500 nm 200 nm

  • 26DISTRIBUTION A. Approved for public release; distribution unlimited

    TEMs of TPUN:15 wt% PR-24-PS CNF/95 wt% 2102-90A TPU

    500 nm 200 nm 100 nm

  • 27DISTRIBUTION A. Approved for public release; distribution unlimited

    WAXDs of 5 wt% Cloisite® 30B in 2102-90A TPU

  • 28DISTRIBUTION A. Approved for public release; distribution unlimited

    TEMs of TPUN:5 wt% Cloisite® 30B/95 wt% 2102-90A TPU

  • 29DISTRIBUTION A. Approved for public release; distribution unlimited

    Properties for TPUNs

    • Thermophysical – coefficient of thermal expansion (CTE), heat capacity, thermal conductivity

    • Flammability – Cone calorimeter data

  • 30DISTRIBUTION A. Approved for public release; distribution unlimited

    Correlations of CTE of CNF and Nanoclay TPUNs

    150

    200

    250

    300

    350

    400

    0 5 10 15 20 25 30

    PR 19 PS PR 24 PS Cloisite 30B

    CTE

    (mic

    rons

    /m K

    )

    Weight % nanofiller

  • 31DISTRIBUTION A. Approved for public release; distribution unlimited

    Heat Capacity of TPUN

    0

    0.5

    1

    1.5

    2

    2.5

    none 30B PR19PS PR24PS POSS

    Cp @ 45 (J/g/ C)Cp @ 55 (J/g/ C)

    Hea

    t Cap

    acity

    (J/g

    / oC

    )

    Nanofiller

    0

    0.5

    1

    1.5

    2

    2.5

    none PR19PS PR24PS

    Cp @ 45 (J/g/ C)Cp @ 55 (J/g/ C)

    Hea

    t Cap

    acity

    (J/g

    / oC

    )

    Nanofiller

    5 wt% Nanofiller 15 wt% Nanofiller

  • 32DISTRIBUTION A. Approved for public release; distribution unlimited

    Thermal Conductivities of Thermoplastic Polyurethane Nanocomposites

    5 wt% Nanofiller 15 wt% Nanofiller

    0.15

    0.2

    0.25

    0.3

    0.35

    none 30B PR19PS PR24PS POSS

    k @ 45 C (W/ m-K)k @ 55 C (W/ m-K)

    Ther

    mal

    Con

    duct

    ivity

    (W/ m

    -K)

    NanoFiller

    0.15

    0.2

    0.25

    0.3

    0.35

    none PR19PS PR24PS

    k @ 45 C (W/(m-K)k @ 55 C (W/(m-K)

    Ther

    mal

    Con

    duct

    ivity

    (W/ m

    -K)

    Nanofiller

  • 33DISTRIBUTION A. Approved for public release; distribution unlimited

    Cone Calorimeter Data at Irradiance Heat Flux of 50 kW/m2

    Material tig (s) PHRR (kW/m2)

    Avg. HRR, 60s (kW/m2)

    Avg. HRR, 180s (kW/m2)

    Avg. Eff, Hc (MJ/kg)

    Avg. SEA (m2/kg)

    Pellethane TPU 32 2,290 406 653 30 237 Pellethane-5% Cloisite 30B TPUN

    34 664 (71% reduction)

    560 562 25 303

    Pellethane-5% PR-19-PS CNF TPUN

    27 624 (73% reduction)

    532 456 22 295

    Pellethane-5% PR-24-PS CNF TPUN

    30 911(60% reduction)

    407 554 25 283

    Pellethane-5%-Trisilanolphenyl-POSS TPUN

    31 1,637 (29% reduction)

    334 591 25 339

    tig = Time to sustained ignition PHHR = Peak heat release rate Avg. HRR = Average heat release rate after ignition Avg. Eff, Hc = Effective heat of combustion Avg. SEA = Average specific extinction area

  • 34DISTRIBUTION A. Approved for public release; distribution unlimited

    Heat Release Rate of TPUN

    0

    500

    1000

    1500

    2000

    2500

    0 50 100 150 200 250 300

    Pellethane 21025% 30_21025% PR-19-PS_21025% PR-24-PS_21025% POSS_2102

    Hea

    t Rel

    ease

    Rat

    e (k

    W/m

    2 )

    Time (s)

  • 35DISTRIBUTION A. Approved for public release; distribution unlimited

    Cone Calorimeter samples after testing

    Pellethane

    Pellethane w/ 30B

    Pellethane w/ PR19PS

  • 36DISTRIBUTION A. Approved for public release; distribution unlimited

    SUMMARY AND CONCLUSIONS

    Blending of 5 wt% of nanoclay, CNF, and POSS® and 15 wt% of CNF in Dow’s PELLETHANE™ 2102-90A TPU were conductedThermophysical and flammability properties of these TPUNs were measuredTEM analyses have demonstrated to be a very efficient way to study the degree of dispersion of nanoparticles in polymer matrixTo obtain enhanced thermophysical and flammability properties, good dispersion of the nanoparticles in the polymer matrix is essentialDow’s polyester polycaprolactone elastomer is very compatible with Cloisite® 30B nanoclay, PR-24-PS CNF, and PR-19-PS CNF as shown by TEMsTrisilanolphenyl-POSS® is not compatible with the PELLETHANE™ TPU and may actually degrade the material during process. Further investigation is underway.CTE of nanoclay TPUN increases with nanoclay to greater than 2x for 10 wt% nanoclay; and CTE of CNF TPUN goes through a maximum (~15 wt% loading) Correlations of CTE with Cloisite® 30B, PR-24-PS CNFs, and PR-19-PS CNFs were obtained as a function of nanofiller loading

  • 37DISTRIBUTION A. Approved for public release; distribution unlimited

    SUMMARY AND CONCLUSIONS (cont’d)

    Thermal conductivity increases with the addition of nanoparticlesSignificant reduction of PHRR was shown by 5 wt% PR-19-PS CNF (73%), 5 wt% Cloisite® 30B (71%), and 5 wt% PR-24-PS CNF (60%) than baselineTime to sustained ignition of Pellethane was 32s with a slight increase of tig of 34s for 5% Cloisite® 30B, all other TPUNs have a slight decrease of tigAvg. HRR, 180s was lowered for all TPUNsAvg. effective heat of combustion was lowered for all TPUNsAvg. specific extinction area was slightly higher for all TPUNs