Synthesis and characterization of nanosilica ball—PMMA hybrid composites

Organic–inorganic hybrid materials are one of the most attractive topics, which deals from fundamental researches to practical applications. In the present research, we have studied the polymerization of methyl methacrylate (MMA) on the surface of γ‐methacryloxy propyl trimethoxy silane (γ‐MPS) modified nanosilica ball (NSB). The polymeric materials were characterized by scanning electron microscope (SEM), Fourier transform infrared spectroscopy (FTIR), and thermo gravimetric analysis (TGA). The results show that new core‐shell structured materials, NSB core‐PMMA shell composites, have been synthesized. The core‐shell hybrid materials can be adjusted to form only a single spherical phase. The addition of the core‐shell hybrid materials to the clearcoat enhances the surface hardness and antiscratch property. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Surface‐modified silica nanoparticles for reinforcement of PMMA

Polymethyl methacrylate (PMMA) was introduced onto the surface of silica nanoparticles by particle pretreatment using silane coupling agent (γ‐methacryloxypropyl trimethoxy silane, KH570) followed by solution polymerization. The modified silica nanoparticles were characterized by Fourier‐transform infrared spectroscopy (FTIR), transmission electron microscopy (TEM) and thermogravimetric analysis (TGA). Sedimentation tests and lipophilic degree (LD) measurements were also performed to observe the compatibility between the modified silica nanoparticles and organic solvents. Thereafter, the PMMA slices reinforced by silica‐nanoparticle were prepared by in situ bulk polymerization using modified silica nanoparticles accompanied with an initiator. The resultant polymers were characterized by UV–vis, Sclerometer, differential scanning calorimetry (DSC). The mechanical properties of the hybrid materials were measured. The results showed that the glass transition temperature, surface hardness, flexural strength as well as impact strength of the silica‐nanoparticle reinforced PMMA slices were improved. Moreover, the tensile properties of PMMA films doped with silica nanoparticles via solution blending were enhanced. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007     

Hybridized reinforcement of natural rubber with silane‐modified short cellulose fibers and silica

Natural‐rubber‐based hybrid composites were prepared by the mixture of short cellulose fibers and silica of different relative contents with a 20‐phr filler loading with a laboratory two‐roll mill. The processability and tensile properties of the hybrid composites were analyzed. The tensile modulus improved, but the tensile strength and elongation at break decreased with increasing cellulose fiber content. The scorch safety improved with the addition of 5‐phr cellulose fiber in the composites. The Mooney viscosity significantly decreased with increasing cellulose fiber content. To modify the surface properties of the cellulose fiber and silica fillers, a silane coupling agent [bis(triethoxysilylpropyl)tetrasulfide, or Si69] was used. The effects of Si69 treatment on the processing and tensile properties of the hybrid composites were assessed. We found that the silane treatment of both fillers had significant benefits on the processability but little benefit on the rubber reinforcement. The strength of the treated hybrid composite was comparable to that of silica‐reinforced natural rubber. Furthermore, to investigate the filler surface modification and to determine the mixing effects, infrared spectroscopic and various microscopic techniques, respectively, were used. From these results, we concluded that the fillers were better dispersed in the composites, and the compatibility of the fillers and natural rubber increased with silane treatment. In conclusion, the hybridized use of short cellulose fibers from a renewable resource and silica with Si69 presented in this article offers practical benefits for the production of rubber‐based composites having greater processability and more environmental compatibility than conventional silica‐filler‐reinforced rubber. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Reinforcing effect of silica on the properties of styrene butadiene rubber–reclaim rubber blend system

Incorporation of silica into styrene butadiene rubber (SBR)–reclaim rubber (RR) blend system was carried out by sol–gel technique and conventional method. A well known silica coupling agent bis(3‐triethoxysilyl propyl) tetrasulfide was found to affect the curing characteristics and mechanical properties of SBR/RR vulcanizate. Here, the effect of RR on silica reinforcement was studied for different SBR/RR blend system. Silica incorporation by conventional mechanical mixing in absence of TESPT showed a much higher tensile properties than that of silica incorporated by the in situ sol–gel reaction of tetraethoxy silane both in presence and absence of TESPT. Studies of equilibrium swelling in a hydrocarbon solvent were also carried out. ATR study indicates that RR forms bond with silica particles due to the presence of active functional site on RR. The amount of silica incorporated by sol–gel reaction was determined through thermogravimetric analysis (TGA). Scanning electron microscopy (SEM) studies further indicate the coherency and homogeneity in the silica filled SBR/RR vulcanizate. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 99: 957–968, 2006     

Effect of silane coupling agents on basalt fiber–epoxidized vegetable oil matrix composite materials analyzed by the single fiber fragmentation technique

The fiber–matrix interfacial shear strength (IFSS) of biobased epoxy composites reinforced with basalt fiber was investigated by the fragmentation method. Basalt fibers were modified with four different silanes, (3‐aminopropyl)trimethoxysilane, [3‐(2‐aminoethylamino)propyl]‐trimethoxysilane, trimethoxy[2‐(7‐oxabicyclo[4.1.0]hept‐3‐yl)ethyl]silane and (3‐glycidyloxypropyl)trimethoxysilane to improve the adhesion between the basalt fiber and the resin. The analysis of the fiber tensile strength results was performed in terms of statistical parameters. The tensile strength of silane‐treated basalt fiber is higher than the tensile strength of the untreated basalt fiber; this behavior may be due to flaw healing effect on the defected fiber surfaces. The IFSS results on the composites confirm that the interaction between the fiber modified with coupling agents and the bio‐based epoxy resin was much stronger than that with the untreated basalt fiber. POLYM. COMPOS., 36:1205–1212, 2015. © 2014 Society of Plastics Engineers     

Some interesting phenomena in silica‐filled HNBR with the addition of silane coupling agent

Hydrogenated nitrile rubber (HNBR)/silica nanocomposites were prepared by in‐situ modification dispersion technology, and the silane coupling agent γ‐methacryloxypropyl trimethoxy silane (KH570) was chosen to promote the interfacial strength between silica particles and HNBR matrix and further improve the dispersion of silica particles. Rubber Process Analyzer (RPA2000) was used to test the Payne effect of HNBR/silica compounds, from which some interesting phenomena were found: the Payne effect became stronger after KH570 was added to HNBR/silica compound at room temperature, which was a contrary result compared to SBR/silica system. However, after stored for a month at room temperature, the Payne effect weakened, which was contrary to the traditional phenomenon of storage hardening of filled rubber. All these results are related to filler–filler interaction and filler–rubber interaction. The modulus at small strain amplitude of HNBR/silica compound with KH570 gradually decreased with the increase of times of circulatory strain sweep but that of compound without KH570 had almost no change, which was explained by Fourier Transform Infrared (FTIR) results that the reaction between silica and KH570 almost completed at the test condition: 80°C and about 1 h. The effects of silane amount, heat‐treated temperature and time on the Payne effect of compounds and the mechanical properties of vulcanizates were also investigated. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Effect of bonding agents on styrene butadiene rubber–aluminum powder composites

Effects of various bonding agents—such as the hexamethylene tetramine–resorcinol system (HR), bis[3‐ (triethoxysilyl) propyl] tetra sulfide (Si‐69), and cobalt naphthenate (CoN)—on the mechanical properties of aluminum powder filled styrene butadiene rubber composites were studied, giving emphasis on concentration of bonding agent and loading of aluminum powder. Shore A hardness, modulus, tensile strength, tear strength, heat buildup, etc., were increased by the loading of aluminum powder, and the presence of bonding agents again increased these properties. Rebound resilience and elongation at break were decreased by the addition of aluminum powder. Equilibrium swelling studies showed an improved adhesion between aluminum powder and styrene butadiene rubber (SBR) in presence of bonding agents. Among the various bonding agents used in this study, silane coupling agent (Si‐69) and hexamethylene tetramine–resorcinol (HR) system were found to be better for aluminum powder filled SBR vulcanizates. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 85: 519–529, 2002     

Plasma surface modification of silica and its effect on properties of styrene–butadiene rubber compound

The effects of surface modification of silicas by plasma‐polymerization coating, together with modification using a silane coupling agent for a comparison on the dispersion and physical properties of styrene–butadiene rubber (SBR) are reported. The chemical compositions of the plasma‐polymerization coating were characterized using FTIR and Auger spectrometer and it was found that the plasma coating was composed of C?C and C? H bonds. The surface modification of silica by either plasma polymerization or silane greatly improved the dispersion of silica particles in SBR vulcanizates. The plasma‐polymerization modification of silica improved the tensile modulus of SBR vulcanizates without deterioration of important basic properties such as tensile strength and elongation at break. © 2002 Society of Chemical Industry     

Preparation of PMMA grafted calcium carbonate whiskers and its reinforcement effect in PVC

In this study, calcium carbonate (CaCO₃) whiskers were grafted with poly(methyl methacrylate) (PMMA) by in situ emulsion polymerization using γ‐methacryloxy propyl trimethoxyl silane (γ‐MPS) as a coupling agent, and the properties of resultant whisker were determined using Fourier transform infrared (FTIR) spectroscopy, energy dispersive spectroscopy (EDS), X‐ray photoelectron spectroscopy (XPS), and thermogravimetric analysis (TGA). The results show that PMMA has been successfully grafted onto the surface of CaCO₃ whiskers and the maximum grafting degree (Gd) is 3.75%. The scanning electron microscopy (SEM) micrographs of the tensile‐fractured surfaces show that modified CaCO₃ whiskers have strong interfacial adhesion to the poly(vinyl chloride) (PVC) matrix. The tensile strength increases from 44.0 MPa for PVC composite with unmodified whisker to 49.5 MPa for that with grafted whisker. The dynamic mechanical analysis (DMA) and TGA results indicate that the composites reinforced by modified CaCO₃ whiskers have much higher modulus, glass transition temperature, and better thermal stability than their counterparts reinforced by unmodified CaCO₃ whiskers. POLYM. COMPOS., 38:2753–2761, 2017. © 2015 Society of Plastics Engineers     

Norbornylized soybean oil as a sustainable new plasticizer for rubbers with hybrid fillers

Carbon black (CB) and precipitated silica are two major reinforcing fillers in rubbers. CB/silica hybrid filler is also widely used in rubbers to provide balanced properties. CB/silica‐hybrid‐filler‐filled styrene‐butadiene rubber (SBR) containing naphthenic oil (NO), soybean oil (SO) and norbornylized SO (NSO) was investigated. The swelling and curing behavior and rheological, mechanical, thermal, aging and dynamic properties were studied and compared with earlier reported data on CB‐ or silica‐filled SBR. NSO provides better scorch safety and faster cure than SO. Compared with NO, the addition of SO and NSO enhances the thermal stability and aging resistance of SBR vulcanizates. SBR/NSO vulcanizates with hybrid filler exhibit a higher tensile and tear strength than SBR/NO and SBR/SO vulcanizates. A synergistic effect in the abrasion resistance of vulcanizates containing the hybrid filler is observed. An increase of sulfur content in the hybrid‐filler‐filled SBR/NSO vulcanizates provides further improvement in abrasion resistance, wet traction and rolling resistance. © 2017 Society of Chemical Industry     

Preparation and properties of thermosensitive organic‐inorganic hybrid gels containing modified nanosilica

A series of thermosensitive organic–inorganic hybrid gels containing nanosilica or modified nanosilica were prepared from N‐isopropylacrylamide (NIPAAm), and N,N′‐methylene‐bis‐acrylamide (NMBA) and nanosilica (AE200) or modified AE200 (mAE200); and NIPAAm, NMBA, 3‐(trimethoxysilyl) propyl methacrylate (TMSPMA) as coupling agent and AE200 or mAE200 in this study. The effect of inorganic nanosilica on the swelling behaviors and mechanical properties were investigated by adding different amount of nanosilica and modified nanosilica. Results showed that the swelling ratios of the hybrid gels decrease with increasing nanosilica content. Existence of silane coupling agent would also reduce the swelling ratios of the hybrid gels. Adding coupling agent or nanosilica would improve the gel strength. Modification of nanosilica by grafting amino‐silane via sol–gel process was carried out and the effect of addition of modified silica on gel properties was also investigated. Results showed that the hybrid gels containing modified silica would have higher swelling ratios and moduli than those containing unmodified silica. Gels containing both silane coupling agent and silica would have higher crosslinking density because the silica would be better crosslinked with coupling agent. POLYM. COMPOS., 31:1712–1721, 2010. © 2010 Society of Plastics Engineers.     

Dynamic mechanical properties and hysteresis loss of epoxidized natural rubber chemically bonded to the silica surface

High‐temperature (180°C) molding of epoxidized natural rubber (ENR) filled with precipitated silica leads to chemical bond formation between epoxy groups of ENR and silanol groups of silica. The extent of chemical bond formation is further enhanced in the presence of the silane coupling agent N‐3‐N‐(vinyl benzyl amino)ethyl‐γ‐amino‐propyl trimethoxy silane mono hydrogen chloride (trade name Z‐6032). The results of hysteresis loss measurements show that hysteresis loss increases with increase in coupling agent loading as a result of the higher modulus of the compounds compared to that of the ENR–silica mix. The dynamic mechanical property measurements show that the addition of coupling agent increases the glass‐transition temperature. Whereas strain‐dependent dynamic mechanical properties show that filler structure breakdown increases with increasing loading of coupling agent. Sulfur‐cured systems show higher filler structure breakdown compared to that of nonsulfur systems. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 84: 2171–2177, 2002     

Effect of silane coupling agent on the chemorheological behaviour of epoxidised natural rubber filled with precipitated silica

Results of measurements of physical properties and solvent swelling of the extrudates indicate that epoxidised natural rubber (ENR) interacts chemically with precipitated silica when the mix of the two was extruded at 150–170°C in a Monsanto Processability Tester (MPT). The extent of interaction between the rubber and the filler depends on the extrusion time, the volume fraction of the filler, the shear rate and the addition of the silane coupling agent, namely N-3-(N-vinyl benzyl amino) ethyl-γ-amino propyl trimethoxy silane monohydrochloride. The activation energy of the chemical interaction between ENR and silica decreases on the addition of the silane coupling agent.     

Preparation and properties of silica/styrene butadiene rubber masterbatches by latex co‐coagulating technology

Silica/styrene butadiene rubber (SBR) masterbatches were prepared by co‐coagulating SBR latex and silica aqueous suspension. The X‐ray diffraction patterns and scanning electron microscopy were employed to characterize the microstructure of the composite. The content and utilization of silica of silica/SBR masterbatches were also investigated. The highest content of silica was achieved when amount of silica is 50 g. Then the cure characteristics, swelling ratio, thermal stability, and mechanical properties of vulcanizates prepared from the masterbatches were compared with those prepared by a conventional direct mixing method. The results revealed that higher maximum torque, shorter cure time, and better swelling resistance of silica/SBR masterbatches were obtained than conventional silica filled composites. The mechanical properties of silica/SBR masterbatches exhibited greater tensile strength and hardness compared to the corresponding conventional mixes. Additionally, the silica/SBR masterbatches vulcanizates exhibited better abrasion resistance, rolling resistance and heat build‐up to those of the conventional composite. POLYM. COMPOS., 35:1212–1219, 2014. © 2013 Society of Plastics Engineers     

Decoration of graphene oxide nanosheets with amino silane‐functionalized silica nanoparticles for enhancing thermal and mechanical properties of polypropylene nanocomposites

Graphene oxide nanosheets were decorated by amino‐silane modified silica nanoparticles. An electrostatic interaction between the negative charge of oxygen‐containing groups of graphene oxide and the positive charge of amino‐silane functional groups on the surface of silica nanoparticles plays a major role for the interfacial interaction of these two materials. The hybrid material was then used as a reinforcement in polypropylene (PP) composite. The increasing tensile strength at yield, tensile, and flexural modulus of the PP composite at a graphene oxide‐ amino‐silane silica loading content of 20 wt % are about 24.81, 55.52, and 30.35%, respectively, when compared with those of PP. It is believed that GO assists the dispersion of SiO₂ nanoparticles to the polymer matrix because of its unique structure having hydrophilicity due to its oxygen functional groups and hydrophobicity owing to its backbone graphitic carbon structure. This hybrid material may also be used as the reinforcement in other polyolefins. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 44382.     

淀粉/SBR复合材料结构和性能的研究

采用淀粉水溶液与丁苯胶乳共混共凝聚的方法制备淀粉／SBR复合材料，并对其结构和性能进行研究。结果表明，与SBR相比，淀粉／SBR复合材料的焦烧时间缩短，硫化速度减慢，且随着淀粉用量的增大，复合材料的ML和MH增大，邵尔A型硬度、300％定伸应力、拉伸强度和撕裂强度显著增大；淀粉与SBR形成较好的界面结合，淀粉在SBR基体中分散粒径较小；随着淀粉用量的增大，复合材料的剪切储能模量增大，高温拉伸储能模量逐渐增大，只有一个玻璃化温度，不具有两相结构的特征。     

Mechanical and thermal behavior of styrene butadiene rubber composites reinforced with silane-treated peanut shell powder

Biocomposites of styrene butadiene rubber (SBR) reinforced with silane-treated peanut shell powder (SPSP) of different filler loadings and particle sizes were prepared by two roll mixing mills with sulfur as a vulcanizing agent. The cure characteristics of composites were studied, and they vulcanized at 160 °C. Test samples were prepared by compression moulding, and their physicomechanical properties, such as tensile strength tear strength, modulus, hardness, and abrasion resistance of SBR vulcanizates, were studied with filler loading 0, 5, 10, 15, and 20 parts per hundred rubber (phr). Composites with 10 phr filler having small particle size exhibited better properties. The interfacial adhesion between filler and matrix has a major role in the properties of composites. Surface modification of PSP was done by silane coupling agent to improve the interfacial adhesion and it characterised by FTIR, XRD, TGA, UV, and SEM. Better properties are shown by the composites with SPSP. Thermal stability of the composites was also determined using thermogravimetric analysis.     

Interfacial Interactions of Silica and Natural Rubber Enhanced by Hydroxyl Telechelic Natural Rubber as Interfacial Modifier

The incompatibility between hydrophilic silica and hydrophobic rubber is an important problem on using silica in nonpolar rubber. In this study, hydroxyl telechelic natural rubber (HTNR) that contains hydroxyl‐terminated groups was introduced into silica‐reinforced natural rubber (NR) in order to improve the bonding strength between rubber and silica. The properties of silica‐reinforced NR compounds and vulcanizates as a function of varying silica contents were evaluated at a fixed HTNR concentration at 8% wt/wt of silica content. The results show that the improvement of silica dispersion and decreasing of filler–filler interactions (Payne effect) were obtained in the NR compounds and vulcanizates with HTNR addition. The enhancements in tensile properties, crosslink density, abrasion resistance, heat build‐up, and thermal properties of the silica‐reinforced NR vulcanizates with added HTNR confirmed that HTNR performed good as interfacial modifier of silica. In the study, the optimum properties of silica‐reinforced NR vulcanizate were achieved at 30 phr silica with 2.4 phr HTNR. However, HTNR still showed poorer efficiency than the synergy between commercial silane coupling agent, bis [3‐(triethoxysilyl) propyl] tetrasulphide (TESPT) and diphenylguanidine (DPG) when used in silica‐reinforced NR vulcanizate. J. VINYL ADDIT. TECHNOL., 26:291–303, 2020. © 2019 Society of Plastics Engineers     

Dynamic mechanical properties of oil palm microfibril‐reinforced natural rubber composites

The dynamic mechanical properties of macro and microfibers of oil palm‐reinforced natural rubber (NR) composites were investigated as a function of fiber content, temperature, treatment, and frequency. By the incorporation of macrofiber to NR, the storage modulus (E') value increases while the damping factor (tan δ) shifts toward higher temperature region. As the fiber content increases the damping nature of the composite decreases because of the increased stiffness imparted by the natural fibers. By using the steam explosion method, the microfibrils were separated from the oil palm fibers. These fibers were subjected to treatments such as mercerization, benzoylation, and silane treatment. Resorcinol‐hexamethylenetetramine‐hydrated silica was also used as bonding agent to increase the fiber/matrix adhesion. The storage modulus value of untreated and treated microfibril‐reinforced composites was higher than that of macrofiber‐reinforced composites. The T_g value obtained for this microfibril‐reinforced composites were slightly higher than that of macrofiber‐reinforced composites. The activation energy for the relaxation processes in different composites was also calculated. The morphological studies using scanning electron microscopy of tensile fracture surfaces of treated and untreated composites indicated better fiber/matrix adhesion in the case of treated microfibril‐reinforced composites. Finally, attempts were made to correlate the experimental dynamic properties with the theoretical predictions. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Dynamic mechanical analysis of oil palm microfibril‐reinforced acrylonitrile butadiene rubber composites

The dynamic mechanical properties of microfibers of oil palm‐reinforced acrylonitrile butadiene rubber (NBR) composites were investigated as a function of fiber content, temperature, treatment, and frequency. The storage modulus (E′) was found to increase with weight fraction of microfibrils due to the increased stiffness imparted by the strong adhesion between the polar matrix and the hydrophilic microfibrils. The damping properties were found to decrease with increase in fiber loading. As the fiber content increases, the damping nature of the composite decreases because of the increased stiffness imparted by the natural fibers. By steam explosion method (STEX), microfibrils are separated from fibers. Natural fibers were undergone treatment such as mercerization, benzoylation, and silane treatment. The NBR is modified by the addition of resorcinol‐hexa‐hydrated silica (HRH) bonding agent. Also dicumyl peroxide (DCP) is used as an alternating vulcanizing agent in the system. In the case of composites containing chemically modified fibers, storage modulus were found to increase. Cole–Cole analysis was made to study the phase behavior of the composite samples. Activation energy for the relaxation processes in different composites was calculated. Morphological studies using scanning electron microscopy of tensile fracture surfaces of treated and untreated composites indicated better fiber matrix/adhesion in the case of treated microfibril‐reinforced composites. POLYM. COMPOS., 2010. © 2009 Society of Plastics Engineers