Silanized Silica Nanofiller Research Articles

Developing ethylene-propylene-diene rubber compounds for industrial applications using a sulfur-bearing silanized silica nanofiller

The loading of a sulfur-bearing silanized silica nanofiller in ethylene-propylene-diene rubber with 4.5 wt % of ethylidene norbornene diene content was increased progressively to 60 parts per hundred rubber by weight. The rubber compounds were cured via the tetrasulfane groups of the silane by adding sulfenamide accelerator and zinc oxide. The hardness, tensile strength, elongation at break, stored energy density at break, tear strength, Young’s modulus, M50-M300, compression set, cyclic fatigue life and bound rubber content of the rubber vulcanizates were measured. With the exception of the elongation at break and compression set which deteriorated, the remaining properties improved and the rate of cure, optimum cure time and crosslink density benefitted also when the loading of silica was increased in the rubber. The bound rubber content was unchanged and the cyclic fatigue life of the rubber vulcanizate enhanced considerably when silica was added. Optimizing the chemical bonding between the rubber and filler via the tetrasulfane groups of TESPT reduced the chemical curatives in the rubber. This was a major improvement in health, safety and environment.

Assessing Effect of the Reagglomeration and Migration of Chemical Curatives on the Mechanical Properties of Natural Rubber Vulcanizate

Natural rubber was mixed with a high loading of a sulfur-bearing silanized silica nanofiller and cured by adding a sulfenamide accelerator and zinc oxide. The rubber was cured at 85° and 140°C, which were below and above the melting point of the accelerator, respectively, and stored at ambient temperature for up to 60 days to allow full blooming to appear. The mechanical properties of the rubber vulcanizate were measured and found to be affected by the blooming of the accelerator on the rubber surface, which also damaged the internal structure of the rubber. Below the melting point of the accelerator there was little or no reagglomeration and some migration of the accelerator, whereas above the melting point there were reagglomeration and extensive migration of the accelerator to the rubber surface. The latter was more damaging to the rubber properties than the former. © 2012 Wiley Periodicals, Inc. Adv Polym Techn 32: E153–E165, 2013; View this article online at wileyonlinelibrary.com. DOI 10.1002/adv.21259

Measuring effect of the blooming of chemical curatives on the rate of cyclic fatigue crack growth in natural rubber filled with a silanized silica nanofiller

Two rubber compounds with different amounts of chemical curatives were prepared by mixing natural rubber with a high loading of a sulfur-bearing silanized precipitated amorphous white silica nanofiller. The chemical bonding between the filler and rubber was optimized via the tetrasulfane groups of the silane by adding a sulfenamide accelerator and zinc oxide. The rubber compounds were cured and stored at ambient temperature for 65 days before they were tested. One compound showed extensive blooming as a function of storage time. Thin tensile strips of the rubber vulcanizates containing an edge crack were repeatedly stressed at constant strain amplitude and test frequency at ambient temperature and crack length c was measured as a function of the number of cycles n. The cut growth per cycle, dc/dn, was calculated and plotted against the tearing energy, T. The blooming of the chemical curatives increased dc/dn by up to an order of magnitude at a constant T. This was due to the reagglomeration of the chemical curatives in the rubber and also within a thin layer approximately 15 to 20 μm in size beneath the rubber surface. Under repeated stressing, cracks grew through the relatively weak agglomerated areas in the rubber and this caused the rate of crack growth to increase at a constant T. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012

Two advanced styrene‐butadiene/polybutadiene rubber blends filled with a silanized silica nanofiller for potential use in passenger car tire tread compound

AbstractStyrene‐butadiene rubber (SBR) and polybutadiene rubber (BR) were mixed together (75:25 by mass) to produce two SBR/BR blends. The blends were reinforced with a precipitated amorphous white silica nanofiller the surfaces of which were pretreated with bis(3‐triethoxysilylpropyl)‐tetrasulfide (TESPT). TESPT is a sulfur‐bearing bifunctional organosilane that chemically bonds silica to rubber. The rubbers were primarily cured by using sulfur in TESPT and the cure was optimized by adding non‐sulfur donor and sulfur donor accelerators and zinc oxide. The hardness, Young's modulus, modulus at different strain amplitudes, tensile strength, elongation at break, stored energy density at break, tear strength, cyclic fatigue life, heat build‐up, abrasion resistance, glass transition temperature, bound rubber and tan δ of the cured blends were measured. The blend which was cured with the non‐sulfur donor accelerator and zinc oxide had superior tensile strength, elongation at break, stored energy density at break and modulus at different strain amplitudes. It also possessed a lower heat build‐up, a higher abrasion resistance and a higher tan δ at low temperatures to obtain high‐skid resistance and ice and wet‐grip. Optimizing the chemical bonding between the rubber and filler reduced the amount of the chemical curatives by approximately 58% by weight for passenger car tire tread. This helped to improve health and safety at work and reduce damage to the environment. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012

A new method for crosslinking and reinforcing acrylonitrile–butadiene rubber using a silanized silica nanofiller

AbstractUsing a high loading of synthetic precipitated amorphous white silica nanofiller, an acrylonitrile–butadiene rubber containing 26% by weight acrylonitrile was crosslinked and its mechanical properties were measured. The silica surfaces were pre‐treated with bis(3‐triethoxysilylpropyl)tetrasulfide (TESPT) to chemically adhere silica to the rubber. To optimize the reaction between the tetrasulfane groups of TESPT and the rubber, accelerator and activator were added. The rubber was fully crosslinked and the hardness, tensile strength, stored energy density at break, elongation at break, tearing energy, and modulus increased substantially because of the filler. The bound rubber, crosslink density, tan δ, and glass transition temperature measurements indicated a strong interaction between the filler and rubber. This new method helped to substantially reduce the use of the curing chemicals and produce a safer and more cost‐effective rubber compound without compromising the good mechanical properties of the rubber, which are essential for long service life. Copyright © 2009 John Wiley & Sons, Ltd.

Effect of the blooming of chemical curatives on the cyclic fatigue life of natural rubber filled with a silanized silica nanofiller

AbstractWhen partly soluble chemical curatives are mixed with raw rubber, they migrate to the rubber surface, which can be detrimental to the rubber properties. Two rubber compounds with different amounts of curatives were prepared by mixing natural rubber with a high loading of precipitated amorphous white silica nanofiller. The silica surfaces were pretreated with bis(3‐triethoxysilylpropyl)‐tetrasulfide coupling agent to chemically adhere silica to the rubber. The chemical bonding between the filler and rubber was optimized via the tetrasulfane groups of bis(3‐triethoxysilylpropyl)‐tetrasulfide by adding accelerator and activator. The rubber compounds were cured and stored at ambient temperature for up to 65 days. One compound showed extensive blooming as a function of storage time. The cyclic fatigue life of the rubber vulcanizates was subsequently measured at a constant strain amplitude and test frequency at ambient temperature. The blooming of the chemical curatives reduced the cyclic fatigue life of the rubber vulcanizate by more than 100%. The migrated chemical curatives produced a thin layer approximately 15 μm in size beneath the rubber surface. When the rubber was stressed repeatedly in the fatigue test, cracks initiated in this layer and subsequently grew, causing the fatigue life of the vulcanizate to decrease. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011

Using a silanized silica nanofiller to reduce excessive amount of rubber curatives in styrene-butadiene rubber

In recent years, the rubber industry has come under pressure to improve health and safety at work, minimize damage to the environment, reduce costs, and increase competitiveness. Rubber compounds contain additives including curing chemicals, which are hazardous and harmful. Reducing their use or eliminating them altogether will be beneficial to rubber compounders and manufacturers of rubber articles. A styrene-butadiene rubber (SBR) was cured and reinforced with a high loading of precipitated amorphous white silica nanofiller. The silica surfaces were pretreated with bis(3-triethoxysilylpropyl) tetrasulfide (TESPT), which is a sulfur-bearing bifunctional organosilane to chemically adhere silica to the rubber. The chemical bonding between the filler and rubber was optimized via the tetrasulfane groups of TESPT by adding accelerator and activator. The rubbers were subsequently cured and their hardness, tensile strength, elongation at break, stored energy density at break, tearing energy, tensile modulus, Young's modulus, and bound rubber content were measured. This study showed that using the filler in combination with a sulfur-donor accelerator was the most efficient method for curing and reinforcing the rubber. This led to a significant reduction in the use of the curing chemicals, a faster curing cycle, and very good mechanical properties for the rubber vulcanizate. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011

Effect of silanized silica nanofiller on tack and green strength of selected filled rubbers

AbstractBACKGROUND: Tack and green strength of filled and gum (unfilled) natural rubber (NR), poly(styrene‐co‐butadiene) rubber (SBR), polybutadiene rubber (BR) and (SBR‐BR) blend with different loadings of reinforcement agent, silanized silica nanofiller (Coupsil 8113), were studied and the results compared and discussed.RESULTS: It was found that silica was fully dispersed in rubber matrix after 13 min of mixing. In addition, with some exceptions for NR and (SBR‐BR) blend, filler loading decreased the tack strength of the studied filled rubbers. Green strength and Mooney viscosity increased with filler loading for all studied filled rubbers but with different rates and amounts. The optimum filler loadings for NR and (SBR‐BR) filled blend were 30 and 10 phr, respectively. Tacks of NR filled rubbers were much higher than those of synthetic filled rubbers.CONCLUSION: It was concluded that filler loading alters substantially the tack and green strength of the rubbers under investigation. Copyright © 2009 Society of Chemical Industry

Comparing the dynamic behaviour of several rubbers filled with silanized silica nanofiller

AbstractBACKGROUND: The effect of the same amount of precipitated silica nanofiller on the curing and dynamic properties of different rubbers, including natural rubber (NR) without and with the addition of elemental sulfur (NR with S), synthetic polyisoprene (IR), polybutadiene (BR) and poly(styrene‐co‐butadiene) copolymer (SBR), was investigated. The silica surfaces were pre‐treated with bis(3‐triethoxysilylpropyl)tetrasulfane (TESPT) to chemically bond the silica to the rubber. The rubbers were primarily cured by using sulfur in TESPT with the addition of optimum accelerator (TBBS) and activator (ZnO), which helped to form sulfur chemical bonds between the rubber and filler.RESULTS: Cure properties, Mooney viscosity, glass transition temperature, bound rubber and crosslink density along with dynamic properties of the filled rubbers, including tan δ, loss modulus (G″) and storage modulus (G′), were measured as a function of double oscillation amplitude (DSA) from 15 to 1000 µm, temperature from −130 to 100 °C and frequency from 1 to 100 Hz. The results with emphasis on potential for tyre tread applications are discussed. It emerged that SBR along with BR filled rubbers had the highest rolling resistance while IR filled rubber had the least. Moreover, it was found that SBR filled rubber had the best skid resistance and BR filled rubber the worst.CONCLUSION: Interestingly, the variation of G′ with DSA showed a complicated behaviour for different filled rubbers. It emerged that in some DSA ranges the Payne effect was observed, and in the remaining ranges increments of G′ with DSA were seen. Because the bound rubber of most of the filled rubbers was more than 92%, there should be another predominant mechanism in the systems studied rather than simply de‐agglomeration or filler network breakdown, which is proposed by the Payne model. In addition, the nanoscale of the filler may be effective for this behaviour. Copyright © 2008 Society of Chemical Industry

Using modulated‐temperature differential scanning calorimetry to study interphases in blends of styrene–butadiene and polybutadiene rubbers filled with a silanized silica nanofiller

AbstractPolybutadiene and styrene–butadiene rubber compounds containing a high loading of a precipitated silica nanofiller were prepared. The silica surfaces were pretreated with bis(3‐triethoxysilylpropyl) tetrasulfide to prevent the silica from interfering with the reaction mechanism of sulfur cure in the rubber. The rubber compounds were mixed together for different times and at different temperatures to produce styrene–butadiene rubber/polybutadiene rubber blends. The mass fraction and composition of the interphase in the blends were subsequently determined with modulated‐temperature differential scanning calorimetry. At 60–65°C, the mass fraction of the interphase in the blend increased after the rubbers were mixed together for 10 min, and then it decreased significantly when the mixing time was increased to 20 min. When the two rubbers were mixed together for 7 min at 60–105°C, the mass fraction of the interphase in the blend increased slightly because of a higher mixing temperature. The composition of the interphase in the blend also changed with the mixing time and mixing temperature. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2009

Comparing effects of silanized silica nanofiller on the crosslinking and mechanical properties of natural rubber and synthetic polyisoprene

AbstractThe effect of the same amount of precipitated silica nanofiller on the curing and mechanical properties of natural rubber and synthetic polyisoprene was investigated. The silica surfaces were pretreated with bis(3‐triethoxysilylpropyl) tetrasulfide (TESPT) to chemically bond silica to rubber. The rubbers were primarily cured by using sulfur in TESPT, and the cure was optimized by the addition of accelerator and activator, which helped to form sulfur chemical bonds between the rubber and filler. Different amounts of accelerator and activator were needed to fully crosslink the filled rubbers. The hardness, tensile strength, elongation at break, stored energy density at break, tearing energy, and modulus of the vulcanizates improved substantially by the incorporation of the filler in the rubber. This was due to high level of rubber‐filler adhesion and formation of chemical bonds between the rubber and TESPT. Interestingly, natural rubber benefited more from the filler than did synthetic polyisoprene. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008

Novel technique for crosslinking and reinforcing high‐cis polybutadiene rubber using a silanized silica nanofiller

AbstractA large amount of a precipitated amorphous white silica nanofiller was mixed with a high‐cis polybutadiene rubber. The silica surfaces were pretreated with bis(3‐triethoxysilylpropyl)tetrasulfide (TESPT). TESPT is a sulfur‐containing bifunctional organosilane that chemically adheres silica to rubber. The rubber was cured primarily with sulfur in TESPT, and the cure was optimized by the addition of a sulfenamide accelerator, which helped to form sulfur chemical bonds between the rubber and the filler. The hardness, tensile properties, tear strength, abrasion resistance, modulus, and cyclic fatigue life of the cured rubber improved substantially when the filler was added. Interestingly, this new technique produced a rubber with good mechanical properties, and only one accelerator was needed to optimize the chemical bonding between the rubber and the filler and fully cure the rubber. As a result, a substantial reduction in the use of the curing chemicals was achieved. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2007

Enhancing the mechanical properties of styrene–butadiene rubber by optimizing the chemical bonding between silanized silica nanofiller and the rubber

AbstractThe reinforcing effect of a large amount of synthetic precipitated amorphous white silica nanofiller on the mechanical properties of styrene–butadiene rubber was studied. The silica surfaces were pretreated with bis(3‐triethoxysilylpropyl)tetrasulfane (TESPT). TESPT is a bifunctional organosilane that chemically adheres silica to rubber and also prevents silica from interfering with the reaction mechanism of sulfur cure in the rubber. The silica particles were fully dispersed in the rubber and the chemical bonding between the rubber and filler was optimized by the incorporation of accelerator and activator in the rubber. This study showed that the mechanical properties of the rubber vulcanizate improved substantially when the filler was added. The addition of elemental sulfur affected the rubber properties, although there was no overall advantage, as some properties improved and others deteriorated. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007