CURRENT TRENDS IN CERAMIFIABLEPOLYMER COMPOSITES DEVELOPMENT

Rafal ANYSZKA1,2, Dariusz M. BIELINSKI1, Mateusz IMIELA1, Zbigniew PEDZICH3

1Lodz University of Technology, Faculty of Chemistry, Institute of Polymer and Dye Technology, Lodz, Poland

2University of Twente, Faculty of Engineering Technology, Department of Mechanics of Solids, Surfaces & Systems (MS3), Chair of Elastomer Technology & Engineering, Enschede, The

Netherlands 3Department of Ceramics and Refractory Materials, Faculty of Material Science and

Ceramics, AGH - University of Science and Technology, Krakow, Poland

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POLYMER COMPOSIES PROPERTIESPROS & CONS

Exceptional elastic, dynamic and dumping properties Relatively easy processing and forming even into

complex shape Good mechanical properties/mass ratio Easy coloring Good chemical resistance Very good electrical resistance

Limited UV and aging resistance Limited recyclability Worse mechanical durability then metals or ceramics Low thermal stability and high combustibility

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CERAMIFICATION (CERAMIZATION)CHARACTERISTICS OF CERAMIFIABLE COMPOSITES

A process leading to irreversible transformation from viscoelasticpolymer composite to continuous, rigid ceramic structure, duringexposition of the composite on fire and/or elevated temperature.

Before ceramification: Good processability Elasticity Facile colouring Combustibility Low thermal stability

After ceramification: Incombustibility Stiffness High porosity (thermal insulation) High thermal stability

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FLAME RETARDANCY OF POLYMER COMPOSIESTYPES OF FLAME RETARDANT ADDITIVES

Main mechanisms of polymer flame retardancy

Deactivation of radicals Barrier-char formation Quenching and coolingof burning zone

Ceramification (ceramization)

http://www.hkc22.com/fireprotectionindustry_pressroom_ceram_polymerik.html

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POLYMER COMBUSTION PHENOMENAREQUIREMENTS FOR COMBUSTION MAINTAINING

G. Camino, et al. Polymer Degradation and Stability (1991) 33: 131-154.

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APPLICATION OF CERAMIFIABLE COMPOSITES

Cables assuring integrity of electrical instalation duringa fire accident: New standard for skyscrapers and specialistfireproof building applications

Fireproof glazing seal systems: Cutting off oxygen supplyinto the fire zone

Protective coatings for steel structures: Steel loseapprox. 50% of its load bearing capability at around 500 °C

Anti-ablative composites for spacecraft and rocketstructures: Providing shielding effect in high-speed/high-temperature conditions

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MECHANISMS OF CERAMIFICATIONLOW SOFTENING POINT TEMPERATURE GLASS-FRITS INITIATING CERAMIFICATION

R. Anyszka, et al. Polymer Bulletin (2017) DOI 10.1007/s00289-017-2113-0

Before ceramification After ceramification

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THERMAL DECOMPOSITION OF SILICONE RUBBERTHE BENEFITS OF USING POLYSILOXANES

Thermal degradation mechanisms of PDMS in presence of oxygen results in formation of amorphous silica

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MECHANISMS OF CERAMIFICATIONSINTERING OF MINERAL FILLERS PARTICLES

Y. Xiong, et al. Fire and Materials (2012) 36: 254-263

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MECHANISMS OF CERAMIFICATIONIN-SITU SILICA-BRIDGES FORMATION DURING SILICONE DEGRADATION

S. Hamdani, et al. Polymer Degradation and Stability (2009) 94: 465-495.R. Anyszka & D. M. Bieliński. Analysis and Performance of Engineering Materials: Key Research and Development. (2015) Apple Academic Press

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MECHANISMS OF CERAMIFICATIONLOW SOFTENING POINT TEMPERATURE GLASS-FRITS INITIATING CERAMIFICATION

J. Wang, et al. Polym. Degrad. Stabil (2015) 121: 149-156H-W. Di, et al. RSC Advances (2015) 5: 51248-51257F. Lou, et al. RSC Advances (2017) 7: 38805-38811R. Anyszka, et al. Journal of Thermal Analysis and Calorimatry (2015) 119: 111-121.R. Anyszka, et al. Polymer Bulletin (2017) DOI 10.1007/s00289-017-2113-0M. Imiela, et al. Journal of Thermal Analysis and Calorimetry (2016) 124: 197-203.R.Anyszka, et al. Przemysl Chemiczny (2014) 93: 1291-1295.R.Anyszka, et al. Przemysl Chemiczny (2014) 93: 1684-1689.R. Anyszka, et al. Materials (2016) 9: 604.

Softeningpoint

temperature

Chemical composition [wt. %] (major components >0.1 wt.%)

P2O5 Al2O3 K2O Na2O SiO2 CaO TiO2 B2O3 ZnO BaO Li2O MgO F

373.9 °C 45.13 23.82 14.05 10.03 5.47 0.91 0.41 - - - - - -

400 °C 43.4 23.9 18.0 11.6 0.4 - - - - - - - -

430 °C 28.99 9.47 22.65 - 1.42 0.37 - - - - - 26.02 9.71

450 °C(melting)

- - - - - - - 100 - - - - -

480 °C - 4.2 2.1 25.0 61.4 7.3 - - - - - - -

515 °C - 1.7 - 27.1 64.4 6.8 - - - - - - -

520 °C - 15.4 - - 69.2 6.2 - - 3.1 1.5 4.6 - -

560 °C - 2.0 - 13.7 43.1 - - 15.7 23.5 2.0 - - -

- Acidic character

- Alkaline character

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MECHANISMS OF CERAMIFICATIONIN-SITU HIGH TEMPERATURE SYNTHESIS OF CALCIUM SILICATES

S. Hamdani, et al. Polymer Degradation and Stability (2010) 95: 1911-1919.B. Gardelle, et al. Journal of Fire Science (2014) 32: 374-387.

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MECHANISMS OF CERAMIFICATIONIN-SITU FORMATION OF CONTINUOUS CERAMIC STRUCTURE

S. Hu, et al. Polymer Degradation and Stability (2016) 126: 196-203.

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MECHANISMS OF CERAMIFICATIONIN-SITU FORMATION OF CONTINUOUS CERAMIC STRUCTURE

S. Hu, et al. Polymer Degradation and Stability (2016) 126: 196-203.

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MECHANISMS OF CERAMIFICATIONCROSS-LINKING OF SILICONE LEADING TO SiOC CERAMIC FORMATION

SiOC – silicon-oxycarbideceramic formation via silicone

rubber cross-linking in high temperature

S. Hamdani, et al. Polymer Degradation and Stability (2009) 94: 465-495.G. Camino, et al. Polymer (2002) 43: 2011-2015.G. Camino, et al. Polymer (2001) 42: 2395–2402.

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MECHANISMS OF CERAMIFICATIONCROSS-LINKING OF SILICONE LEADING TO SiOC CERAMIC FORMATION

E. Delebecq, et al. ACS Applied Materials & Interfaces (2011) 3: 869-880.

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MECHANISMS OF CERAMIFICATIONSPECIFIC FILLER ARRANGEMENT AS CERAMIC STRUCTURE PRECURSOR

X. Zhang, et al. RSC Advances (2016) 6: 7970-7976.

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MECHANISMS OF CERAMIFICATIONSUMMARY

Ceramization mechanism/parameter Siliconerubber

Organicrubbers

Sintering of mineral filler particles Yes Yes

Fluxing agent application Yes Yes

Mineral fillers reaction with silica Yes ?

Deposition of silica on mineral filler surface Yes ?

Sintering of mineral fillers accompanied with bonded silicone rubber Yes No

Creation of SiOC ceramic via cross-lining of silicone rubber Yes No

Creation of SiOC ceramic on surface of silica particles Yes No

In-situ formation of continuous ceramic structure Yes ?

Specific filler arrangement as ceramic structure precursor Yes ?

Price High Various

Processability Good Various

Maximal capacity of filler ~100 phr ≤ 500 phr

Mechanical properties after addition of high amount of filler Low Avarage

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POLYMER MATRICES APPLIED FOR CERAMIFIABLECOMPOSITES

References Polymer matrix♠ Hamdani S, et al. (2010) Polym Degrad Stabil 95:1911–1919; ♠ Hamdani-Devarennes S, et al.. (2011) Polym Degrad Stabil 96:1562–1572; ♠ Hamdani-Devarennes S, et al. (2013) Polym DegradStabil 98:2021–2032; ♠ Hamdani S, et al. (2009) Polym Degrad Stabil 94:465–495; ♠ Mansouri J, et al. (2007) J Mater Sci 42:6046–6055; ♠ Mansouri J, et al. (2005) J Mater Sci 40:5741–5749; ♠ MansouriJ, et al. (2006) Mat Sci Eng A 425:7–14; ♠ Hanu LG, et al. (2004) J Mater Process Tech 153–154:401–407; ♠ Hanu LG, et al. (2006) Polym Degrad Stabil 91:1373–1379; ♠ Hanu LG, et al. (2005) Mat SciEng A 398:180–187; ♠ Wang J, et al.. (2015) Polym Degrad Stabil 121:149–156; ♠ Xiong Y, et al. (2012) Fire Mater 36:254–263; ♠ Pedzich Z, et al. (2013) J Mat Sci Chem Eng 1:43–48; ♠ Pędzich Z, et al. (2014) Key Eng Mat 602-603: 290-295; ♠ Imiela M, et al. (2016) J Therm Anal Calorim 124:197–203; ♠ Anyszka R, et al. (2015) J Therm Anal Calorim 119:111–121; ♠ Anyszka R, et al. (2014) PrzemChem 93:1291–1295; ♠ Anyszka R, et al. (2014) Przem Chem 93:1684–1689; ♠ Anyszka R, et al. (2017) Polym Bull 75: 1731-1751; ♠ Delebecq E, et al.(2011) ACS Appl Mater Interfaces 3:869–880; ♠Gardelle B, et al.(2014) J Fire Sci 32:374–387; ♠Lou F, et al. (2017) J Therm Anal Calorim 130:813–821; ♠ Guo J, et al. (2018) Polymers 10:388

Silicone rubber (PDMS)

♠ Di H-W, et al. (2015) RSC Adv 5:51248–51257; ♠ Gong X, et al. (2017) Sci Eng Compos mater24:599-608; ♠ Li Y-M, et al. (2018) Polym Degrad Stabil 153:325-332; ♠Zhao D, et al. (2018) PolymDegrad Stabil 150:140-147

Poly(ethylene-co-vinyl acetate) (EVA)

♠ Ferg EE, et al. (2017) Polym Composite 38:371–380 EVA/PDMS blend♠ Shanks RA, et al. (2010) Express Polym Lett 4:79–93 Poly(vinyl acetate)♠ Pei Y, et al. (2016) Materials Science and Environmental Engineering, Taylor & Francis 197-200; ♠Anyszka R, et al. (2017) High Temp Mater Proc 36:963-970

Ethylene-propylene-diene rubber (EPDM)

♠ Wang T, et al. (2010) Adv Compos Lett 19:175–179 Polyethylene (PE)♠ Anyszka R, et al. (2016) Materials 9:604 Styrene-butadiene rubber (SBR)♠ Shanks RA, et al. (2010) Adv Mat Res 123–125:23–26 Polyester♠ Fan S, et al. (2017) Acta Mater Compos Sinica 34:60-66; ♠ Shi M, et al. (2018) J Wuhan UnivTechnol, Mater Sci Edition 33:381-388; ♠ Wang F, et al. (2017) High Perform Polym 29:279-288

Boron phenolic resin

♠ Rybinski P, et al. (2018) J Compos Mater 52:2815-2827 Acrylonitrile-butadiene rubber (NBR)

Thank you for yourkind attention!