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CURRENT TRENDS IN CERAMIFIABLE POLYMER COMPOSITES … · Main mechanisms of polimer flame...

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CURRENT TRENDS IN CERAMIFIABLE POLYMER COMPOSITES DEVELOPMENT RAFAŁ ANYSZKA 1) Chair of Elastomer Technology and Engineering, University of Twente, The Netherlands 2) Institute of Polymer and Dye Technology, Lodz University of Technology, Poland 22 September 2017, Tjuana, Mexico
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Page 1: CURRENT TRENDS IN CERAMIFIABLE POLYMER COMPOSITES … · Main mechanisms of polimer flame retardancy. Radicals deactivation. Barrier-char formation. ... Hanu LG, et al. (2006) Polym

CURRENT TRENDS IN CERAMIFIABLEPOLYMER COMPOSITES DEVELOPMENT

RAFAŁ ANYSZKA1) Chair of Elastomer Technology and Engineering, University of Twente, The Netherlands

2) Institute of Polymer and Dye Technology, Lodz University of Technology, Poland

22 September 2017,Tjuana, Mexico

Page 2: CURRENT TRENDS IN CERAMIFIABLE POLYMER COMPOSITES … · Main mechanisms of polimer flame retardancy. Radicals deactivation. Barrier-char formation. ... Hanu LG, et al. (2006) Polym

Faculty of Engineering Technology, University of Twente

Faculty of Chemistry, Lodz University of

Technology

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5/10/17 4

WORLD BENCHMARK PLASTICS/STEELSINCE 1989 WORLDWIDE PRODUCTION OF PLASTICS HAS EXCEEDED STEEL

https://committee.iso.org/files/live/sites/tc61/files/The%20Plastic%20Industry%20Berlin%20Aug%202016%20-%20Copy.pdf

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BUILDING AND CONSTRUCTION INDUSTRY CONSUME19.7 % OF PLASTIC MATERIALS IN EU

http://www.plasticseurope.org/documents/document/20161014113313-plastics_the_facts_2016_final_version.pdf

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POLYMER PROPERTIESPROS & CONS

Easy processing and forming even into complex shape Good mechanical properties/mass ratio Easy coloring Good chemical resistance Low price

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

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POLYMER COMBUSTION PHENOMENAREQUIREMENTS FOR COMBUSTION MAINTAINING

G. Camino, et al. Polymer Degradation and Stability (1991) 33: 131-154.https://image.slidesharecdn.com/opensourcebestpracticesdarpa-140206162759-phpapp02/95/open-source-best-practices-darpa-2-638.jpg?cb=1391704214

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FLAME RETARDANCY OF POLIMER MATERIALSTYPES OF FLAME RETARDANT ADDITIVES

http://www.broadview-tech.com/intumax/http://www.pcimag.com/articles/83956-foam-protects-intumescent-coatings-and-paints-for-fire-protection

Main mechanisms of polimer flame retardancy

Radicals deactivation Barrier-char formation Quenching and coolingof burning zone

Intumescent additivesCeramification (ceramization)

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

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FLAME RETARDANCY OF POLIMER MATERIALSCERAMIFICATION VS INTUMERSCENT EFFECT

X. Jin, et al. Journal of Materials Science (2017) 52:12235-12250.J. Wang, et al. Polymer Degradationa and Stability (2015) 121: 149-156.

650 °C

950 °C

Ceramifiable composites exhibitsuperior mechanical nd barier properties.

Intumescent additivesprovide excellent heatprotection

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http://www.wiki-how.in/introduction-materials-notes-science-engineering/

http://www.globalspec.com/reference/69955/203279/chapter-15-composite-materials

(a) particle reinforcement(b) short fiber reinforcement(c) continuous fiber reinforcement(d) laminate reinforcement

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CERAMIFICATION (CERAMIZATION)CHARACTERISTICS

A process leading to transformation from viscoelastic polymer composite to continuous, rigid ceramic structure, during exposition of the composite on fire or elevated temperature.

Before ceramification:• Good processability• Plsticity/elasticity• Easy to colour• Combustibility• Low thermal stability

After ceramification:•incombustibility•Stiff•Porous (thermal insulation)•Thermally stable

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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

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

Before ceramification After ceramification

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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

FTIR

XPS

XRD

R. Anyszka, et al. Polymer Bulletin (2017) DOI 10.1007/s00289-017-2113-0S. 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 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 CERAMIFICATIONNANO-POROUS STRUCTURE FORMATION

R. Anyszka, et al. Journal of Thermal Analysis and Calorimatry (2015) 119: 111-121.

Hoffman elimination reaction

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MECHANISMS OF CERAMIFICATIONADDITIONAL HEAT STEP FOR CERAMIC STRUCTURE REINFORCEMENT

M. Imiela, et al. Journal of Thermal Analysis and Calorimetry (2016) 124: 197-203.

a) s950 °C slow heating:From room temperaturę to 950 °C with heating rate of 8 °C/min.

b) 1000 °C rapid heating:Placing a sample in the owen heated beforehand to 1000 °C for 20 min.

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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 Degrad Stabil 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 Mansouri J, 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 Sci Eng 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 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) Przem Chem 93:1291–1295 Anyszka R, et al. (2014) Przem Chem 93:1684–1689 Delebecq E, et al.(2011) ACS Appl Mater Interfaces 3:869–880 Gardelle B, et al.(2014) J Fire Sci 32:374–387

Silicone rubber (PDMS)

Di H-W, et al. (2015) RSC Adv 5:51248–51257 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) Anyszka R, et al. (2017) High Temp Mater Proc DOI: 10.1515/htmp-2016-0059 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

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APPLICATION OF CERAMIFIABLE COMPOSITES

Cables assuring integrity of electrical instalation during a fire accidentfor 30, 60 or 90 minutes in accordance to DIN 4102:12 standard.

Supporting: Elevators Sprinklers Emergency exit lights Monitoring Additional emergency

systems & devices

http://www.baks.com.pl/wp-content/uploads/2015/08/e-90-cz.1-Info.pdf.S.K. Ranganathan et al. Annual Technical Conference – ANTEC, Conference Proceedings 2016

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APPLICATION OF CERAMIFIABLE COMPOSITES

Protective coatings for steelstructures: steel loose approx.50% of its load bearing capability ataround 500 °C

B. Gardelle, et al. Journal of Fire Science (2014) 32: 374-387.http://cerampolymerik.com/downloads/cp-brochure-2006-03.pdR.G. Puri and A.S. Khanna. Journal of Coatings Technology and Research (2017) 14: 1-20.f

Fireproof glazing seal systems

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APPLICATION OF CERAMIFIABLE COMPOSITES

https://contest.techbriefs.com/2014/entries/aerospace-and-defense/4586

Ablative composites for spacecraft and rocket structures

G. Zhang et al. Materials (2016) 9: 723

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22 September 2017,Tjuana, Mexico

Thank you for yourkind attention!


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