It is known that Young’s modulus of elastomers increase strongly due to high filler loadings, which is critical for practical applications and processing. An experimental study was performed in order to investigate the mechanical properties of silicone rubber, which was highly filled with alumina trihydrate (ATH) under uniaxial tensile tests. Different sizes of ATH particles having different surface conditions were used. The composites were prepared in a Z-blade mixer, and the particles were partly in situ modified. In preliminary investigations, the correct amount of silane for the in situ modification was determined and the effect of the mixing time on the mechanical properties of the cured rubber was studied. Long mixing times show generally a decrease in the modulus. This is explained by the increasing formation of bound rubber. A substantial dependence of the particle size and particle surface modification on the Young’s modulus was found. This effect can be simulated using a model based on a stiff particle surrounded by a soft shell, which has a higher modulus than the polymer. Smaller particles show a stronger increase of the modulus than larger ones, which is due to (1) higher volume of interphase area and (2) shorter distance between the particles increasing the modulus of the interphase.
PachalyBAchenbachFHerzigC. Organische zwischenverbindungen, polymere. In: DittmeyerRKeimWKreysaGOberholzA (eds) Chemische Technik: Prozesse und Produkte. Weinheim: Wiley, pp. 1095–1214, 2005.
2.
ScholzMKempfM.Degussa-kieselsäure für HTV-siliconkautschuk. Degussa, 2001
3.
YuanQWMarkJE. Reinforcement of poly(dimethylsiloxane) networks by blended and in-situ generated silica fillers having various sizes, size distributions, and modified surfaces. Macromol Chem Phys1999; 200: 206–220.
4.
NielsenLE. Generalized equation for elastic moduli of composite materials. J Appl Phys1970; 41: 4626–4627.
AnsorgeSSchmuckFPapailiouKO. Improved silicone rubbers for the use as housing material in composite insulators. IEEE Trans Dielectric Electr Insul2012; 19: 209–217.
7.
GoerlUHunscheAMuellerA. Investigations into the silica/silane reaction system. Rubber Chem Technol1997; 70: 608–623.
8.
EttlingerM. Highly dispersed metallic oxides produced by the aerosil process. Degussa Tech Bull Pigments1984; 56: 12.
9.
VollenbergPHTHeikensD. Particle-size dependence of the young modulus of filled polymers.1. Preliminary experiments. Polymer1989; 30: 1656–1662.
10.
FuSYFengXQLaukeB. Effects of particle size, particle/matrix interface adhesion and particle loading on mechanical properties of particulate-polymer composites. Compos B Eng2008; 39: 933–961.
11.
JordanJJacobKITannenbaumR. Experimental trends in polymer nanocomposites - a review. Mater Sci Eng A2005; 393: 1–11.
12.
CamenzindASchweizerTSztuckiM. Structure & strength of silica-PDMS nanocomposites. Polymer2010; 51: 1796–804.
13.
EdwardsDC. Polymer-filler interactions in rubber reinforcement. J Mater Sci1990; 25: 4175–4785.
14.
GreenDWDallaviaAJ. Alumina trihydrate in polyester resin - viscosity reduction via particle size blends and surface modification. In: 46th Annual Conference, Composite Institute, Washington, 18–21 February 1991, pp. 1–5. Washington: The Society of the Plastic Industry.
15.
SternsteinSSAmanuelSShofnerML. Reinforcement mechanisms in nanofilled polymer melts and elastomers. Rubber Chem Technol2010; 83: 181–198.
16.
ArangurenMIMoraEMacoskoCW. Rheological and mechanical-properties of filled rubber - silica-silicone. Rubber Chem Technol1994; 67: 820–833.
WuCLZhangMQRongMZ. Silica nanoparticles filled polypropylene: effects of particle surface treatment, matrix ductility and particle species on mechanical performance of the composites. Compos Sci Technol2005; 65: 635–645.
19.
BoonstraBBCochraneHDannenbergEM. Reinforcement of silicone-rubber by particulate silica. Kautschuk Gummi Kunststoffe1976; 29: 29–39.
20.
SongXFYoshinoHShibataH. Mechanical properties of styrene-butadiene-styrene block copolymer composites filled with calcium carbonate treated by liquid polybutadienes. J Appl Polym Sci2009; 113: 3661–36670.
21.
SpanoudakisJYoungRJ. Crack-propagation in a glass particle-filled epoxy-resin .1. Effect of particle-volume fraction and size. J Mater Sci1984; 19: 473–486.
22.
HozojiHHorieOOgataM. Improvement of mechanical-properties for epoxy molding compounds by treatment of coupling agent on spherical filler. Kobunshi Ronbunshu. 1990; 47: 483–490.
23.
AshtonHC. Fire retardants. In: XanthosM (ed) Functional Fillers for Plastics. Weinheim: Wiley, pp. 285–315, 2005.
24.
HughesR. An introduction to colloids. In: CosgroveT (ed) Colloid Science. Chichester: Wiley, p. 1–22, 2010.
25.
DandoNRCleverTRKolekPL. Aluminum trihydroxide (ATH) as a filler for polymer composites: Comparative evaluation of precipitation and grinding on thermal stability and dehydration kinetics. In: 51st Annual Conference of the Society of the Plastics Industry, Inc (SPI), session 19-A. Cincinnati, 5–7 February 1996, American Composites Manufacturers Association (ACMA), pp. 1–9.
26.
ArangurenMIMoraEMacoskoCW. Compounding fumed silicas into polydimethylsiloxane: bound rubber and final aggregate size. J Colloid Interf Sci1997; 195: 329–337.
27.
RiggsPDParkerSBradenM. Influence of additives on the water uptake of hydrosilanized silicone rubbers. Biomaterials1997; 18: 721–726.
28.
PengYDuRNFuQ. Reinforcement of polydimethylsiloxane networks by nano-calcium carbonate. Chin J Polym Sci2005; 23: 411–416.
29.
MarkJEErmanB. Rubberlike elasticity. A molecular primer. 2nd ed. New York: Wiley-Interscience, 2007.
30.
ErmanBMarkJE. Structure and properties of rubberlike networks. New York: Oxford University Press, 1997.
31.
AndradyALLlorenteMAMarkJE. Model networks of end-linked polydimethylsiloxane chains. VII. Networks designed to demonstrate non-gaussian effects related to limited chain extensibility. J Chem Phys1980; 72: 2282–2290.
32.
LlorenteMAMarkJE. Model networks of end-linked poly(dimethylsiloxane) chains .8. Networks having cross-links of very high functionality. Macromolecules1980; 13: 681–685.
33.
NielsenLE. Simple theory of stress-strain properties of filled polymers. J Appl Polym Sci1966; 10: 97–103.
34.
DelidesCGShepherdIW. Crystallization in poly(dimethyl siloxane) networks formed by gamma-irradiation. Polymer1977; 18: 97–98.
35.
PolmanteerKELentzCW. Reinforcement studies – effect of silica structure on properties and crosslink density. Rubber Chem Technol1975; 48: 795–809.
36.
DelidesCGAdsheadA. Effect of filler on network behavior at high elongation. Polymer1979; 20: 262–264.
37.
MarkJEKatoMKoJH. Stress-strain isotherms for non-crystallizable networks at high elongation. J Polym Sci C1976; 54: 217–225.
38.
AndradyALLlorenteMAMarkJE. Model networks of end-linked polydimethylsiloxane chains. IX. Gaussian, non-gaussian, and ultimate properties of the trifunctional networks. J Chem Phys1980; 73: 1439–1445.
NingYPMarkJE. Treatment of filler-reinforced silicone elastomers to maximize increases in ultimate strength. Polym Bull1984; 12: 407–411.
41.
RadfordKC. Mechanical properties of an epoxy resin with a second phase dispersion. J Mater Sci1971; 6: 1286–1291.
42.
FarrisRJ. Dilatation of granular filled elastomers under high rates of strain. J Appl Polym Sci1964; 8: 25–35.
43.
SatoYFurukawaJ. A molecular theory of filler reinforcement based upon the conception of internal deformation (a rough approximation of the internal deformation). Rubber Chem Technol1963; 36: 1081–1106.
44.
PayneAR. Effect of dispersion on dynamic properties of filler-loaded rubbers. J Appl Polym Sci1965; 9: 2273–2284.
45.
KlüppelM. The role of disorder in filler reinforcement of elastomers on various length scales. Berlin/Heidelberg: Springer, 2003.
46.
LeblancJL. A molecular explanation for the origin of bound rubber in carbon black filled rubber compounds. J Appl Polym Sci1997; 66: 2257–2268.
47.
FurutaMHikasaTKatoE. Changes of spin–spin relaxation time for epr composites during mixing process. J Appl Polym Sci1986; 31: 2661–2666.
48.
LewisTBNielsenLE. Viscosity of dispersed and aggregated suspensions of spheres. Trans Soc Rheol1968; 12: 421–443.
49.
SindorfDWMacielGE. Solid-state NMR studies of the reactions of silica surfaces with polyfunctional chloromethylsilanes and ethoxymethylsilanes. J Am Chem Soc1983; 105: 3767–3776.
50.
SaamJC. Reinforcement in silicone elastomers. A short review. In: BaneyRHGilliomLRHiranoS-ISchmidtHK (eds) Submicron Multiphase Materials. San Francisco: Materials Research Society, pp. 91–101, 1992.
51.
SmallwoodHM. Limiting law of the reinforcement of rubber. J Appl Phys1944; 15: 758–766.
52.
GuthE. Theory of filler reinforcement. J Appl Phys1945; 16: 20–25.
53.
KernerEH. The elastic and thermo-elastic properties of composite media. Proc Phys Soc London Section B1956; 69: 808–813.
54.
NielsenLE. Relation between viscosity and moduli of filled systems. J Compos Mater1968; 2: 120–123.
55.
ScottGD. Packing of equal spheres. Nature1960; 188: 908–909.
56.
McGeeSMcCulloughRL. Combining rules for predicting the thermoelastic properties of particulate filled polymers, polyblends, and foams. Polym Compos1981; 2: 149–161.
57.
NielsenLE. Dynamic mechanical-properties of polymers filled with agglomerated particles. J Polym Sci B1979; 17: 1897–1901.
58.
TanakaTKozakoMFuseN. Proposal of a multi-core model for polymer nanocomposite dielectrics. IEEE Trans Dielectric Electr Insul2005; 12: 669–681.
59.
FelderhofBUIskePL. Mean-field approximation to the effective elastic-moduli of a solid suspension of spheres. Phys Rev A1992; 45: 611–617.
60.
HuberG. On the mechanism of hydrodynamic reinforcement in elastic composites. Macromolecules2002; 35: 9204–9210.
61.
EggersHSchummerP. Reinforcement mechanisms in carbon black and silica loaded rubber melts at low stresses. Rubber Chem Technol1996; 69: 253–265.
62.
NishiT. Effect of solvent and carbon black species on the rubber–carbon black interactions studied by pulsed NMR. J Polym Sci1974; 12: 685–693.
63.
O’BrienJCashellEWardellGE. An NMR investigation of the interaction between carbon black and cis-polybutadiene. Rubber Chem Technol1962; 50: 747–764.
64.
RaetzkeSKindersbergerJ. The effect of interphase structures in nanodielectrics. IEEJ Trans Fundam Mater2006; 126: 1044–1049.
65.
NielsenLELandelRF. Mechanical properties of polymers and composites. New York: Marcel Dekker, 1994.
