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1.
The organic–inorganic hybrid composites comprising acrylic rubber and silica were synthesized through sol–gel technique at ambient temperature. The composites were generated through the acid‐catalyzed hydrolysis and subsequent condensations of inorganic tetraethoxysilane (TEOS) in the organic acrylic rubber (ACM), solvated in tetrahydrofuran. The morphology of the hybrid materials was investigated by using the transmission electron microscope (TEM) and scanning electron microscope (SEM). Transmission electron micrographs revealed that the silica particles, uniformly distributed over the rubber matrix, are of nanometer scale (20–90 nm). The scanning electron micrographs demonstrated the existence of silica frameworks dispersed in the rubber matrix of the hybrid composites. The X‐ray silicon mapping also supported that observation. There was no evidence of chemical interaction between the rubber phase and the dispersed inorganic phase, as confirmed from the infrared spectroscopic analysis and solubility measurements. Dynamic mechanical analysis indicated mechanical reinforcements within the hybrid composites. The composites containing in situ silica, formed by sol–gel technique, demonstrated superior tensile strengths and tensile modulus values at 300% elongations with increasing proportions of tetraethoxysilane. However, the improvements in physical properties with similar proportions of precipitated silica were not significant. Maximum tensile strength and tensile modulus were obtained when the rubber phase in the hybrid composites was cured with ammonium benzoate and hexamethylenediamine carbamate system, as compared with benzoyl peroxide cured system. Thermal stability of the hybrid composites was not improved appreciably with respect to the virgin rubber specimen. Residue analysis from thermogravimetric study together with infrared spectroscopic analysis indicated the presence of unhydrolyzed tetraethoxysilane in the hybrid composites. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 93: 2579–2589, 2004  相似文献   

2.
Waste rubber powder (WRP) was modified by microwave, sol–gel method, and both microwave and sol–gel method, respectively. The mechanical and dynamic mechanical properties of natural rubber (NR)/modified WRP composite were investigated. The influence of bis‐(3‐(triethoxysilyl)‐propyl)‐tetrasulfide (TESPT) content on curing characteristics and mechanical properties of vulcanizate was also studied. The results showed that NR/WRP modified by both microwave and sol–gel method composite owned the best mechanical properties. Rubber processing analyzer was used to characterize the interaction between silica and rubber chains and the dispersion of silica. With increase of TESPT content, the Payne effect decreased. Scanning electron microscopy indicated the coherency and homogeneity of in situ generated silica filled vulcanizate. Dynamic mechanical analyzer showed that NR/WRP modified by both microwave and sol–gel method composite with 5 phr TESPT exhibited the lower tan δ at temperature range of 50–80°C, compared with composite without TESPT and the higher tan δ at temperature of 0°C, compared with the conventional modification of WRP. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013  相似文献   

3.
Polyimide–silica nanocomposites were synthesized with 4,4′‐oxydianiline, 4,4′‐(4,4′‐isopropylidenediphenoxy)bis(phthalic anhydride), and fluorine‐modified silica nanoparticles. Fluorinated precursors such as 4″,4?‐(hexafluoroisopropylidene)bis(4‐phenoxyaniline) (6FBPA) and 4,4′‐(hexafluoroisopropylindene)diphenol (BISAF) were employed to modify the surface of the silica nanoparticles. The microstructures and thermal, mechanical, and dielectric properties of the polyimide–silica nanocomposites were investigated. An improvement in the thermal stability and storage modulus of the polyimide nanocomposites due to the addition of the modified silica nanoparticles was observed. The microstructures of the polyimide–silica nanocomposites containing 6FBPA‐modified silica exhibited more uniformity than those of the nanocomposites containing BISAF‐modified silica. The dielectric constants of the polyimide were considerably reduced by the incorporation of pristine silica or 6FBPA‐modified silica but not BISAF‐modified silica. The addition of a modifier with higher fluorine contents did not ensure a lower dielectric constant. The uniformity of the silica distribution, manipulated by the reactivity of the modifier, played an important role in the reduction of the dielectric constant. Using 6FBPA‐modified silica nanoparticles demonstrated an effective way of synthesizing low‐dielectric‐constant polyimide–silica nanocomposites. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 104: 882–890, 2007  相似文献   

4.
To introduce thiol–ene chemistry in the modification of composites by ionic liquid (IL), a novel functional IL, 1‐methylimidazolium mercaptopropionate (MimMP), was synthesized and investigated as a modifier for styrene–butadiene rubber/silica composites. MimMP could be hydrogen‐bonded with silica and react with the double bonds of rubber chains via thiol–ene chemistry. The filler networking, curing behavior, filler dispersion, crosslink density, and mechanical performance were fully studied. The filler networking in the uncured rubber compounds was effectively restrained. The vulcanization was largely accelerated by MimMP. The interfacial interaction was quantitatively evaluated and found to consistently increase with increasing MimMP. The mechanical performance and abrasion resistance of the modified vulcanizates improved considerably. The remarkable improvements were mainly ascribed to the improved interfacial structure comprised of MimMP–silica hydrogen bonding and MimMP–rubber covalent bonds via thiol–ene chemistry. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011  相似文献   

5.
Natural rubber–epoxidized natural rubber–silica composites were prepared by the wet masterbatch technique and the traditional dry mixing method. Performances of the composites based on different preparation methods were investigated with a moving die rheometer, an electronic universal testing machine, a dynamic mechanical analyzer, a nuclear magnetic resonance crosslink density analyzer, a rubber processing analyzer (RPA), a scanning electron microscope (SEM), and a transmission electron microscope (TEM). The RPA, SEM, and TEM analyses indicated that silica has better dispersion, lower filler–filler interaction, and better filler–rubber interaction in compounds based on the wet masterbatch technique, leading to improvements in mechanical strength and the dynamic mechanical and compression properties of the composites. It also indicates that composites prepared by the wet masterbatch technique have shorter scorch time, faster curing velocity, and higher crosslink density. The composites prepared by the wet materbatch technique also have lower rolling resistance, which is an important property for their use as a green material for the tire industry. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43571.  相似文献   

6.
In this study, we investigated the effects of untreated precipitated silica (PSi) and fly ash silica (FASi) as fillers on the properties of natural rubber (NR) and styrene–butadiene rubber (SBR) compounds. The cure characteristics and the final properties of the NR and SBR compounds were considered separately and comparatively with regard to the effect of the loading of the fillers, which ranged from 0 to 80 phr. In the NR system, the cure time and minimum and maximum torques of the NR compounds progressively increased at PSi loadings of 30–75 phr. A relatively low cure time and low viscosity of the NR compounds were achieved throughout the FASi loadings used. The vulcanizate properties of the FASi‐filled vulcanizates appeared to be very similar to those of the PSi‐filled vulcanizates at silica contents of 0–30 phr. Above these concentrations, the properties of the PSi‐filled vulcanizates improved, whereas those of the FASi‐filled compounds remained the same. In the SBR system, the changing trends of all of the properties of the filled SBR vulcanizates were very similar to those of the filled NR vulcanizates, except for the tensile and tear strengths. For a given rubber matrix and silica content, the discrepancies in the results between PSi and FASi were associated with filler–filler interactions, filler particle size, and the amount of nonrubber in the vulcanizates. With the effect of the FASi particles on the mechanical properties of the NR and SBR vulcanizates considered, we recommend fly ash particles as a filler in NR at silica concentrations of 0–30 phr but not in SBR systems, except when improvement in the tensile and tear properties is required. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 93: 2119–2130, 2004  相似文献   

7.
In this article, a series of hybrid materials consisted of epoxy resin matrix and well‐dispersed amino‐modified silica (denoted by AMS) nanoparticles were successfully prepared. First of all, the AMS nanoparticles were synthesized by performing the conventional acid‐catalyzed sol–gel reactions of tetraethyl orthosilicate (TEOS), which acts as acceded sol–gel precursor in the presence of 3‐aminopropyl trimethoxysilane (APTES), a silane coupling agent molecules. The as‐prepared AMS nanoparticles were then characterized by FTIR, 13C‐NMR, and 29Si‐NMR spectroscopy. Subsequently, a series of hybrid materials were prepared by performing in situ thermal ring‐opening polymerization reactions of epoxy resin in the presence of as‐prepared AMS nanoparticles and raw silica (RS) particles (i.e., pristine silica). AMS nanoparticles were found to show better dispersion capability in the polymer matrices than that of RS particles based on the morphological observation of transmission electron microscopy (TEM) study. The better dispersion capability of AMS nanoparticles in hybrid materials was found to lead enhanced thermal, mechanical properties, reduced moisture absorption, and gas permeability based on the measurements of thermo gravimetric analysis (TGA), differential scanning calorimetry (DSC), dynamic mechanical analysis (DMA), and gas permeability analysis (GPA), respectively. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008  相似文献   

8.
A new type of polyimide/silica (PI/SiO2) hybrid composite films was prepared by blending polymer‐modified colloidal silica with the semiflexible polyimide. Polyimide was solution‐imidized at higher temperature than the glass transition temperature (Tg) using 3,3′,4,4′‐biphenyltetracarboxylic dianhydride (BPDA) and 4,4′‐diaminodiphenyl ether (ODA). The morphological observation on the prepared hybrid films by scanning electron microscopy (SEM) pointed to the existence of miscible organic–inorganic phase, which resulted in improved mechanical properties compared with pure PI. The incorporation of the silica structures in the PI matrix also increased both Tg and thermal stability of the resulting films. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 2053–2061, 2006  相似文献   

9.
A novel method was used to synthesis nanosilica/waterborne polyurethane (WPU) hybrids by in situ hydrolysis and condensation of tetraethyl orthosilicate (TEOS) and/or 3‐aminopropyltriethoxylsilane bonding at the end of the WPU molecular chain. The hybrid was characterized by scanning electron microscopy, energy dispersive spectroscopy (EDS), transmission electron microscopy, Fourier transform infrared spectroscopy (FTIR), and X‐ray photoelectron spectroscopy (XPS). The results showed that the nanosilica/WPU hybrids with well‐dispersed nanosilica particles were synthesized, in which the particles had typical diameters of about 50 nm. In addition, XPS and FTIR analyses demonstrated that chemical interaction occurred between WPU and silica. The effects of TEOS on surface wettability, water resistance, mechanical strength, and thermal properties of the hybrid were also evaluated by contact angle measurements, water absorption tests, mechanical tests, and differential scanning calorimetry, respectively. An increase in advancing contact angles, water resistance, and tensile strength, as well as decrease in elongation at break and glass transition temperature, were obtained with the addition of TEOS. Water absorption decreased from 17.3 to 5.5%. The tensile strength increased to a maximum of 29.7 MPa, an increase of about 34%. Elongations at break of the hybrids decreased 191%. These results were attributed to the effects of the nanosilica and the chemical interaction between WPU and silica. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013  相似文献   

10.
In this study, tetraethoxysilane (TEOS) and a metallocene polyethylene–octene elastomer (POE) were chosen as the ceramic precursor and the continuous phase, respectively, for the preparation of new hybrids by an in situ sol–gel process. To obtain a better hybrid, a maleic anhydride‐grafted polyethylene–octene elastomer (POE‐g‐MAH), used as the continuous phase, was also investigated. Characterizations of POE‐g‐MAH/SiO2 and POE/SiO2 hybrids were performed by Fourier transform infrared (FTIR) and 29Si solid‐state nuclear magnetic resonance (NMR) spectrometers, a differential scanning calorimeter (DSC), a thermogravimetry analyzer, and an Instron mechanical tester. The results showed that the POE‐g‐MAH/SiO2 hybrid could improve the properties of the POE/SiO2 hybrid because the interfacial force between the polymer matrix and the silica network was changed from hydrogen bonds into covalent Si? O? C bonds through dehydration of hydroxy groups in POE‐g‐MAH with residual silanol groups in the silica network. The existence of covalent Si? O? C bonds was proved by FTIR spectra. For the POE/SiO2 and POE‐g‐MAH/SiO2 hybrids, maximum values of the tensile strength and the glass transition temperature were found at 9 wt % SiO2 since a limited content of silica might be linked with the polymer chains through the covalent bond. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 88: 966–972, 2003  相似文献   

11.
Silica as a reinforcement filler for automotive tires is used to reduce the friction between precured treads and roads. This results in lower fuel consumption and reduced emissions of pollutant gases. In this work, the existing physical interactions between the filler and elastomer were analyzed through the extraction of the sol phase of styrene–butadiene rubber (SBR)–butadiene rubber (BR)/SiO2 composites. The extraction of the sol phase from samples filled with carbon black was also studied. The activation energy (Ea) was calculated from differential thermogravimetry curves obtained during pyrolysis analysis. For the SBR–BR blend, Ea was 315 kJ/mol. The values obtained for the composites containing 20 and 30 parts of silica per hundred parts of rubber were 231 and 197 kJ/mol, respectively. These results indicated an increasing filler–filler interaction, instead of filler–polymer interactions, with respect to the more charged composite. A microscopic analysis with energy‐dispersive spectroscopy showed silica agglomerates and matched the decreasing Ea values for the SBR–BR/30SiO2 composite well. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 96: 2273–2279, 2005  相似文献   

12.
In this article, we present a facile method for the synthesis of an azo‐group‐bound silica (SiO2–azo) initiator. The azo groups were introduced onto the surface of silica (SiO2) nanoparticles via facile condensation between 4,4′‐azobis‐4‐cyanopentanoic acid and the alkyl–hydroxyl groups ‐ immobilized on the SiO2 nanoparticle surface under ambient conditions. The polystyrene (PS) chains were grafted onto the SiO2 nanoparticle surface by in situ polymerization with the resulting SiO2–azo as an initiator, and then, the SiO2–PS composite was prepared. The syntheses and properties of the SiO2–azo initiator and the composite were characterized by Fourier transform infrared spectroscopy, X‐ray photoelectron spectroscopy, thermogravimetric analysis, gel permeation chromatography, and differential scanning calorimetry techniques. The results confirm that the SiO2–azo initiator and the composite were synthesized successfully. Styrene was polymerized with the initiation of SiO2–azo, and the resulting PS domain accounted for 48.6% of the total amount of composite. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011  相似文献   

13.
The stress relaxation of silica (SiO2) filled solution‐polymerized styrene–butadiene rubber (SSBR) has been investigated at shear strains located in the nonlinear viscoelastic regions. When the characteristic separability times are exceeded, the nonlinear shear relaxation modulus can be factorized into separate strain‐ and time‐dependent functions. Moreover, the shear strain dependence of the damping function becomes strong with an increase in the SiO2 volume fraction. On the other hand, a strain amplification factor related to nondeformable SiO2 particles can be applied to account for the local strain of the rubbery matrix. Furthermore, it is believed that the damping function is a function of the localized deformation of the rubbery matrix independent of the SiO2 content. The fact that the time–strain separability holds for both the unfilled SSBR and the filled compound indicates that the nonlinear relaxation is dominated by the rubbery matrix, and this implies that the presence of the particles can hardly qualitatively modify the dynamics of the polymer. It is thought that the filler–rubber interaction induces a coexistence of the filler network with the entanglement network of the rubbery phase, both being responsible for the nonlinear relaxation. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009  相似文献   

14.
The natural rubber (NR) nanocomposites were fabricated by filling ionic liquid (1‐allyl‐3‐methyl‐imidazolium chloride, AMI) modified nano‐silica (nSiO2) in NR matrix through mechanical mixing and followed by a cure process. Based on the measurements of differential scanning calorimetry (DSC), Fourier transform infrared spectroscopy (FTIR), solid state nuclear magnetic resonance spectroscopy, and Raman spectroscopy, it was proved that AMI could interact with nSiO2 through hydrogen bonds. With the increase of AMI content, the curing rate of nSiO2/NR increased. The results of bound rubber and dynamic mechanical properties showed that polymer–filler interaction increased with the modification of nSiO2. Morphology studies revealed that modification of nSiO2 resulted in a homogenous dispersion of nSiO2 in NR matrix. AMI modified nSiO2 could greatly enhance the tensile strength and tear strength of nSiO2/NR nanocomposites. Compared to unmodified nSiO2/NR nanocomposite, the tensile strength of AMI modified nSiO2/NR nanocomposite increased by 102%. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 44478.  相似文献   

15.
Natural rubber–silica [W(NR–SiO2)] composites were prepared by wet‐compounding technology with liquid natural rubber (LNR) as a compatibilizer. The effects of the LNR content and wet‐compounding technology on the filler dispersion, Payne effect, curing characteristics, mechanical properties, and interfacial interactions were investigated. The results show that the incorporation of LNR promoted vulcanization and decreased the Payne effect of the W(NR–SiO2) composites. With the addition of 5 phr LNR, the remarkable improvements in the mechanical properties of the W(NR–SiO2) vulcanizates were correlated with the improved silica dispersion and strengthened interfacial bonding. Furthermore, the W(NR–SiO2) vulcanizates containing LNR exhibited improvements in both the wet‐skid resistance and rolling‐resistance performance. The interfacial interactions, quantitatively evaluated by the Mooney–Rivlin equation and Lorenz–Park equation on the basis of the rubber elasticity and reinforcement theory, were strengthened in the presence of LNR. Accordingly, an interfacial structural model was proposed to illustrate the improvements in the mechanical properties of the W(NR–SiO2) composites. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46457.  相似文献   

16.
The epoxy‐silica hybrids showing high Tg and thermal stability are prepared by the non‐aqueous sol–gel process initiated with borontriflouride monoethylamine. Tetramethoxysilane (TMOS) is used as a precursor of silica and 3‐glycidyloxypropyl trimethoxysilane as a coupling agent to strengthen the interphase interaction with an epoxy matrix. The basic factors governing the nonaqueous sol–gel process are studied in order to reveal the formation–structure–properties relationships and to optimize the hybrid composition as well as conditions of the nonaqueous synthesis. The formation of the hybrid, its structure, thermomechanical properties and thermal stability are followed by chemorheology experiments, NMR, DMA and TGA. The most efficient reinforcement of the epoxy network is achieved by the combination of both alkoxysilanes, showing synergy effects. The hybrids with a low content (~10 wt %) of the in situ generated silica exhibit dramatic increase in Tg and the high modulus, 335 MPa, up to the temperature 300°C. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40899.  相似文献   

17.
The effects of mixing temperature and mixing time on the reaction of 3‐octanoylthio‐1‐propyltriethoxysilane (NXT silane) during mixing with precipitated silica and natural rubber (NR) were investigated. Results showed that the reaction between NXT silane and precipitated silica can proceed at temperatures above 130°C. Because of the blocking group of NXT silane, the silane–NR coupling reactivity is low, so that the reaction of NXT silane with NR occurs only during the curing period. There is no reaction between NXT silane and NR during mixing, which showed that the mixing time of silica‐filled NR compound containing NXT silane must be longer than 10 min at 150°C to obtain the desired silane coupling efficiency. With increasing mill temperature, the coupling efficiency increases. A high mixing temperature promotes improvement of silane–silica coupling efficiency, although the tensile strength, 100% modulus, 300% modulus, and hardness of NR vulcanizates decrease. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 94: 2295–2301, 2004  相似文献   

18.
This article reports the purification and surface modification of coal ash silica and afterwards its utilization as reinforcing filler in solution‐styrene‐butadiene rubber/butadiene rubber (S‐SBR/BR). The coal ash silica free of unwanted metal ions/mineral oxides was obtained using phosphoric acid. The chemical composition of the purified coal ash silica in comparison to impure coal ash indicates the presence of characteristic hydroxyl functional group at 3440 cm?1 and an increase in the oxygen content as determined with the help of Fourier Transform Infrared and x‐ray photoelectron spectroscopy, respectively. The contact angle analysis shows that after purification the polar part of the surface energy increased to 17.5 from 12 m Jm?2. While the surface area increased to an order of magnitude, i.e., 11.6 to 110.5 m2 g?1. The modification of purified silica particles with bis(3‐triethoxysilylpropyl) tetrasulfane reveal the functionalization of hydroxyl to ‐Si‐O‐R groups as detected at 1560 cm?1. As a consequence, the modified silica based S‐SBR/BR composite resulted in improved mechanical properties due to enhanced silica‐rubber interaction. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010  相似文献   

19.
We carried out a feasibility study of the use of black rice husk ash (RHA) as a filler in epoxy resin for embedding material in electrical and electronic applications. We made a comparison by mixing RHA and two commercial fillers, fused and crystalline silica, with epoxy resin at weight fractions ranging from 20–60%. RHA‐filled epoxy resin had higher mixing viscosity, coefficient of thermal expansion, and water absorption percentage than commercial‐silica‐filled epoxy composite. However, the impact strength of all composites was comparable, but the tensile strength and elongation at break of silica‐filled epoxy were slightly superior. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 86: 3013–3020, 2002  相似文献   

20.
Oleylamine (OA) modified silica (SiO2-g-OA) was prepared using γ-(2,3-epoxypropoxy) propytrimethoxysilane (KH560) and OA, silica/natural rubber (NR) and SiO2-g-OA/NR composites were prepared by mechanical blending in an internal mixer, and SiO2-g-OA was characterized by Fourier transform infrared spectroscopy, thermal gravimetric analyzer, and contact angle analyzer. The mechanical properties, abrasion resistance, curing characteristics, Payne effect, and morphology of silica/NR and SiO2-g-OA /NR composites were investigated using universal testing machine, Akron abrasion tester, rubber processing analyzer, and scanning electron microscope, respectively. The results showed that SiO2-g-OA became more hydrophobic and had better compatibility with NR. Moreover, SiO2-g-OA/NR had weaker Payne effect, better vulcanization performance, and more excellent mechanical properties. As the content of filler was more than 30 phr, SiO2-g-OA/NR had lower rolling resistance and higher wet skid resistance. Compared with silica modified by other coupling agents, SiO2-g-OA had the best reinforcement effect on NR.  相似文献   

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