Structure and properties of strain‐induced crystallization rubber–clay nanocomposites by co‐coagulating the rubber latex and clay aqueous suspension

Natural rubber (NR)–clay (clay is montmorillonite) and chloroprene rubber (CR)–clay nanocomposites were prepared by co‐coagulating the rubber latex and clay aqueous suspension. Transmission electron microscopy showed that the layers of clay were dispersed in the NR matrix at a nano level, and the aspect ratio (width/thickness) of the platelet inclusions was reduced and clay layers aligned more orderly during the compounding operation on an open mill. However, X‐ray diffraction indicated that there were some nonexfoliated clay layers in the NR matrix. Stress–strain curves showed that the moduli of NR were significantly improved with the increase of the amount of clay. At the same time, the clay layers inhibited the crystallization of NR on stretch, especially clay content of more than 10 phr. Compared with the carbon‐black‐filled NR composites, NR–clay nanocomposites exhibited high hardness, high modulus, high tear strength, and excellent antiaging and gas barrier properties. Similar to NR–clay nanocomposites, CR–clay nanocomposites also exhibited high hardness, high modulus, and high tear strength. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 96: 318–323, 2005     

Preparation and characterization of acrylic latex/nano‐SiO2 composites

Acrylic/nano‐silica composite latexes were prepared by blending via high shear stirring (SS) or ball milling (BM) and in situ polymerization (IS). For comparison, composites filled with micro‐silica were also prepared. The mechanical and optical properties of the polymers formed by the composite latex filled with nano‐ or micro‐silica were investigated using an Instron testing machine, by dynamic mechanical analysis, ultraviolet–visible spectrophotometry and transmission electron micrography. The results showed that SS and BM methods could obtain better nanocomposite latex and polymers than the IS method, characterized by better dispersion of nanoparticles, higher tensile strength and T_g for SS and BM than for IS. The increase in absorbance and reduction in transmittance of UV (290–400 nm wavelength) were observed as nano‐silica content increased, whereas the UV absorbance or transmittance basically were kept unchanged for the composites filled with micro‐silica. © 2002 Society of Chemical Industry     

Preparation of sulfur‐modified powdered polychloroprene rubber by inverse coagulation

Sulfur‐modified powdered polychloroprene rubber (PCR‐121) was prepared by inverse coagulation. A new coating agent (SN) was developed that could generate in situ the coating layer by inverse coagulation. The results show that this is a low‐cost, stable technology for the production of powdered rubber with a very low coating agent content. A powdering model based on the liquid–liquid stirring theory of noncoalescing, liquid–liquid dispersion was proven with uniform design testing. According to this model, the mass fraction of medium‐scale particles (1–3 mm) was only related to the agitation speed in the experimental range. Scanning electron microscopy (SEM) analysis showed that the PCR‐121 particles were single continuous particles coagulated from single chloroprene rubber latex drops. Energy spectrum analysis showed that a layer with higher Ca content was coated at the surface of PCR‐121 particles, which made PCR‐121 a free‐flowing powdered rubber. The results show that the variation of Mooney viscosity (ML₁₊₄ 100°C) from 30 to 130 had no obvious effect on the mechanical properties of PCR‐121. Compared with bale CR121, PCR‐121 had better mechanical properties. SEM analysis and energy spectrum analysis on the tensile fracture surfaces showed that the dispersion of compounding agents in PCR‐121 was better than that in bale CR121, which resulted in better mechanical properties in PCR‐121. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 98: 2109–2115, 2005     

Improvement of the mechanical and thermal properties of silica‐filled polychloroprene vulcanizates prepared from latex system

In this work, well‐dispersed silica suspension having excellent storage stability was prepared by using an ultrasonic probe. The obtained silica suspension and curatives were added into the polychloroprene (CR) latex for preparing silica‐filled CR latex compounds having various silica loadings. Then, the silica‐filled CR vulcanizates were prepared via a dipping process. The thermal and mechanical properties of the dipped CR vulcanizates containing silica dispersed by using an ultrasonic probe were compared with those of the dipped CR vulcanizates containing silica dispersed by using a mechanical stirrer. By using thermogravimetric analysis, it could be seen that thermal resistance of the dipped CR films having silica prepared by ultrasonic probe is greater than that prepared by using the mechanical stirrer. This result corresponds well with their tensile strength after aging in the hot‐air oven. In addition, modulus, tensile strength, and tear strength of the vulcanizates prepared from CR latex compounds containing silica prepared by using the ultrasonic probe are obviously greater than those prepared by using the mechanical stirrer, especially at high silica loading. This is because the silica prepared using the ultrasonic probe is uniformly distributed and dispersed throughout the CR matrix, as can be observed in the scanning electron microscope micrographs. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Investigations on the surface structure and properties of silica‐polyamine composites on the nanoscales and microscales

The structure and properties of silica polyamine composites (SPC) made from microparticles of amorphous silica gel (300–600 microns) and silica nanoparticles (10–20 nm) modified with aminopropyltrimethoxysilane (APTMS), poly(allylamine) (PAA) or poly(ethyleneimine) (PEI) have been studied. The APTMS nano‐hybrids showed batch capacities for copper equal to or better than the corresponding polymer‐based micro‐hybrids. Loading of the PEI on the nanoparticles was independent of molecular weight of the polymer. Dynamic light scattering measurements showed that the SiO₂ nanoparticles and the composites made from them aggregate in water and the degree of aggregation is dependent on the surface modification. All of the amine‐modified materials were catalysts for the Knoevenagel reaction but interestingly, the microparticles modified with APTMS were better catalysts than the corresponding nanoparticles or the polyamine modified composites. Solid‐state ¹⁹Si NMR has been used to elucidate the surface structure of the various composites. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42271.     

乳液共沉法制备离子液体改性白炭黑/SBR复合材料的研究

以1-丁基-3-甲基咪唑六氟磷酸盐( Bmim.PF6)离子液对白炭黑进行改性,采用乳液共沉法制备改性白炭黑/SBR复合材料,并对其硫化特性、物理性能和微观结构进行研究.结果表明:Bmim.PF6与白炭黑之间的相互作用为氢键作用;与未改性白炭黑/SBR复合材料相比,改性白炭黑/SBR复合材料的交联密度增大,白炭黑在橡胶基体中的分散性得到改善,拉伸强度、撕裂强度和耐磨性能均明显提高.     

High‐performance natural rubber latex composites developed by a green approach using ionic liquid‐modified multiwalled carbon nanotubes

The effect of multiwalled carbon nanotubes (MWCNTs) modified by a hydrophilic ionic liquids (ILs), including 1‐ethyl‐3‐methylimidazolium bromide and 1‐hexyl‐3‐methylimidazolium bromide, was studied. The obtained water‐suspensible carbon nanotubes (CNTs) were still homogeneously distributed in water a month after sonication. The microstructural development of filler networks and the uniform dispersion of MWCNTs in the presence of IL were analyzed by TEM. The apparent physical (cation–π/π–π) interaction between the MWCNTs and the IL was characterized by Raman spectroscopy, DSC, and TGA. Furthermore, high‐performance composites of natural rubber latex (NRL) and CNTs modified with IL were obtained by the liquid latex blending method. The CNTs were homogeneously distributed in the matrix and CNT–ILs improved the fatigue resistance and mechanical properties of the NRL/CNT–IL composites. This study demonstrates a simple and eco‐friendly approach to develop multifunctional advanced materials based on IL‐modified MWCNT elastomer composites. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46588.     

Rice husk–polyester composites: The effect of chemical modification of rice husk on the mechanical and dimensional stability properties

Rice husk was used as filler in the production of rice husk (RH)–polyester composites and was subjected to three types of chemical modification. The chemical reagents employed in this study were glycidyl methacrylate (GMA), maleic anhydride (MAH), and succinic anhydride (SAH). This study revealed that the chemical modification of RH with GMA and MAH resulted in the enhancements of tensile and flexural properties of RH–polyester composites. The reduction in these properties with respect to those modified with SAH were attributed to the absence of C?C unsaturated groups. Water immersion test showed that chemical modification of the RH improved the dimensional stability of the composites. This was shown in the GMA‐ and MAH‐modified RH–polyester composites. The modification increased the hydrophobicity as well as the crosslinking between the RH and matrix in the composites. The lower performance demonstrated by the SAH‐modified composites was due to the inability of the SAH to form crosslinking with the matrix. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 97: 1237–1247, 2005     

Preparation and characterization of polypropylene/clay nanocomposites with polypropylene‐graft‐maleic anhydride

Polypropylene (PP)/montmorillonite (MMT) nanocomposites were prepared by the esterification of propylene‐g‐maleic anhydride (MAPP) with MMT modified with α,ω‐hydroxyamines. The structural characterization confirmed the formation of ester linkages and the interaction between the silicate layers. In particular, X‐ray diffraction patterns of the modified clays and MAPP/MMT composites showed 001 basal spacing enlargement as great as 0.14–0.62 nm according to the type of α,ω‐hydroxyamine. Thermal characterization by thermogravimetric analysis for the composites revealed increased onset temperatures of thermal decomposition. The melting peak temperature decreased, and the crystallization peak temperature increased; this indicated that MMT retarded the crystallization of MAPP. Compounding PP with MAPP/MMT composites enhanced the tensile modulus and tensile strength of PP. However, the elongation at break decreased drastically even when the MMT content was as low as 0.4–2.0 wt %. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 98: 1229–1234, 2005     

Effect of styrene–butadiene latex on the bond performance of macro synthetic fiber in micro jute/macro synthetic hybrid fiber‐reinforced latex‐modified cement‐based composites

This study evaluated the effect of latex content on the pullout behavior of macro synthetic fiber in hybrid fiber‐reinforced latex‐modified cement‐based composites (HFLMCCs). A bond‐strength test which utilized dog‐bone‐shaped test specimens was used to determine the pullout behavior. Micro jute fiber was incorporated at 9.00 kg/m³ and macro synthetic fiber at 0.45 kg/m³. Latex was added at 0, 5, 10, 15, 20, and 25% of the binder weight (wt %). Pullout tests showed that latex increased the area of the debonded zone of the pullout load–displacement curve. Bond strength increased with latex content up to 15% in HFLMCCs and decreased when the latex content reached 20%. The interface toughness increased until the latex content reached 20% and decreased when the latex content was 25%. These results were confirmed by microstructural analysis of the macro synthetic fiber surface, which showed that the number of scratches increased due to friction. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci, 2013     

Particle size and morphology of poly[styrene‐co‐(butyl acrylate)]/nano‐silica composite latex

Nanocomposite latex with nano‐silica of varying particle sizes was prepared via in situ polymerization and investigated by submicron particle size analysis, transmission electron microscopy (TEM), scanning electron microscopy (SEM), Fourier‐transform infrared spectrometry (FTIR) and Raman spectrometry. It was found that nanocomposite latex exhibited a core–shell structure with nano‐silica particles enwrapped, resulting in an increase in the latex particle size. The smaller the nano‐silica particles, the more were embedded in each latex particle. The increase in the particle size of latex depended not only on the particle size of nano‐silica, but also on the number of nano‐silica particles in each latex particle. Copyright © 2004 Society of Chemical Industry     

Comparing styrene butadiene rubber–clay nanocomposites prepared by melt intercalation and latex‐coagulation methods

Among different methods for preparation of rubber–clay nanocomposites, melt intercalation and latex‐coagulation methods are more practiced. In this study, dispersion of pristine nanoclay by the latex‐coagulation method and organically modified nanoclay by the melt‐intercalation method in styrene butadiene rubber were compared, based on the same amount of mineral clay in the composites. Dispersion of nanoclay was examined by X‐ray diffraction before and after vulcanization, and by atomic force microscopy after vulcanization. It was shown that final structure of nanoclay in the composites was intercalated by both methods, with better dispersion resulting from coagulation of latex over mixing in the melt state. Dynamic–mechanical–thermal analysis and tension tests were used to further assess dispersion and polymer–filler interactions. These tests confirmed better dispersion and larger interfacial area for pristine nanoclay in the latex‐coagulated rubber through observing lower peak loss factor, higher growth of stress in stretching, and lower elongation at break when compared with those for the nanocomposite prepared by the melt mixing. © 2012 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Dispersion of carbon black in high‐abrasion furnace black filled nonsulfur modified powdered polychloroprene rubber

High‐abrasion furnace black (HAF, grade N330) filled nonsulfur modified powdered polychloroprene rubber [P(CR231/HAF)] was prepared with the method of carbon black–rubber latex coagulation using CR231 latex as raw rubber material, HAF as reinforcing filler, and polymeric resin as coating resin. The influence of the content of dispersing agent and coating resin on contact staining and dispersion properties of carbon black in P(CR231/HAF) were investigated. The results show that the addition of dispersing agent and coating resins can decrease the contact staining level of carbon black effectively. When the dispersing agent/HAF (w/w) ratio was 0.12 or 0.1, 10 phr coating resin was added, and P(CR231/HAF) without contact staining can be prepared. The analysis on scanning electron microscopy and surface energy spectrum showed that free carbon black crumb on the surface and inner of P(CR231/HAF) particles causes its contact staining. The well dispersion of carbon black in the P(CR231/HAF) can eliminate contact staining effectively. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 192–196, 2006     

Preparation and performance in paper coating of silicone‐modified styrene–butyl acrylate copolymer latex

Silicone‐modified styrene–butyl acrylate copolymer latex was synthesized by emulsion copolymerization by using octamethylcyclotetrasiloxane (D₄), styrene, and butyl acrylate as raw materials, potassium persulfate as initiator and propylmethacrylate triethoxysilane (KH‐570) as crosslinking agent. The infrared spectra studies showed that the vinyl monomers were completely copolymerized with D₄. The prepared silicone‐modified copolymer latex with the interpenetrating polymer networks tended to have higher stability, and better toluene and water resistance than styrene–butyl acrylate latex. The glossiness of coated paper was improved with silicone‐modified copolymer latex, and it was at a maximum when D₄ was about 3% of total monomers. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 79: 333–336, 2001     

Dispersion of “guava-like” silica/polyacrylate nanocomposite particles in polyacrylate matrix

A series of “guava-like” silica/polyacrylate nanocomposite particles with close silica content and different grafting degrees were prepared via mini-emulsion polymerization using 3-(trimethoxysilyl)propyl methacrylate (TSPM) modified silica/acrylate dispersion. The silica/polyacrylate composite particles were melt-mixed with unfilled polyacrylate (PA) resin to prepare corresponding silica/polyacrylate molded composites and the dispersion mechanism of these silica particles from the “guava-like” composite particles into polyacrylate matrix was studied. It was calculated that about 110 silica particles were accumulated in the bulk of every silica/polyacrylate composite latex particle. Both the solubility tests of silica/polyacrylate composite latex particles in tetrahydrofuran (THF) and the section transmission electron microscope (TEM) micrographs of silica/polyacrylate molded composites indicated that the grafting degree of silica particles played a crucial role in the dispersion of silica/polyacrylate composite particles into the polyacrylate matrix. When the grafting degree of polyacrylate onto silica was in a moderate range (ca. 20%–70%), almost all of silica particles in these “guava-like” composite particles were dispersed into the polyacrylate matrix in a primary-particle-level. However, at a lower grafting degree, massive silica aggregations were found in molded composites because of the lack of steric protection. At a greater grafting degree (i.e., 200%), a cross-linked network was formed in the silica/polyacrylate composite particles, which prevented the dispersion of composite particles in THF and polyacrylate matrix as primary particles.     

Preparation of organic–inorganic nanocomposites with core‐shell structure by inorganic powders

Organic–inorganic nanocomposites with core‐shell structure were prepared in two steps. In the first step, the latex particles in the semibatch emulsion polymerization of butyl methacrylate (BMA), in the presence of methacrylic acid (MAA), were prepared. Small amounts of acrylic acid incorporated into the latex to have better interaction between the surface of particles and inorganic phase. MAA also increased the latex stability and decreased the amount of coagulum. In the second step, the core‐shell structures were prepared by coating the latex particles with three types of inorganic powders. Pectin coated precipitated calcium carbonate, alumina, and silica. The examinations show that pectin‐coated calcium carbonate has the best response than other types of calcium carbonate. Alumina was the second type of inorganic powder that was used for coating the core particles. Silicagel and fumed silica (Aerosil) were used for coating by silica. Scanning electron microscopy and transmission electron microscopy showed the particle morphology and the core‐shell structure, respectively. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci, 2006     

Synthesis of modified silica spheres used for the preparation of dual ultraviolet‐ and thermo‐cured epoxyacrylate/silica composites

To investigate the interfacial effect on properties of epoxyacrylate–silica composites, submicron‐sized silica spheres were synthesized by sol–gel reaction under a basic environment and their surfaces were endowed with vinyl functional groups by further modification with 3‐methacryloxypropyl trimethoxy silane. The pure silica (PS) and the modified silica (MPS) spheres were characterized by Fourier transform infrared, ²⁹Si‐ and ¹³C‐nuclear magnetic resonance (NMR), scanning electron microscope (SEM), and particle size analyzer. The silica spheres were then added to the presynthesized difunctional epoxyacrylate resin with one vinyl group and one epoxide group at each end, in addition to the photo‐ and thermo‐curing agents. After cure, thermal and mechanical properties of the obtained epoxyacrylate–silica composites were measured and compared. Tensile mechanical properties including initial modulus, ultimate tensile strength, and elongation at break, as well as the fracture energy of the epoxyacrylate–silica composite were all increased by increasing the content of silica spheres. Moreover, the composites filled with MPS had stronger interfacial strength between silica sphere and matrix than those with PS and thus exhibited an additional increase of tensile mechanical properties and fracture toughness. The increase of fracture toughness was owing to the crack deflection and particle–matrix debonding as evidenced by SEM pictures on the fracture surface. POLYM. ENG. SCI., 2012. © 2012 Society of Plastics Engineers     

Thermoplastic polymers as modifiers for urea‐formaldehyde (UF) wood adhesives. II. Procedures for the preparation and characterization of thermoplastic‐modified UF wood composites

Wood composites were prepared by using wood flour (sugar maple, Acer saccharum March) and thermoplastic‐modified urea‐formaldehyde (UF) suspensions. Thermoplastic (5–10% w/v) was introduced into the UF suspension as an aqueous solution, a self‐stabilized dispersion in water, or as a surfactant‐stabilized latex. The modified suspension was blended with wood flour, and the blend was cured by using a cure cycle that was suitable for all the thermoplastic‐modified UF formulations and unmodified UF controls. The wood flour composites were tested by using a notched Izod impact strength test. All formulations containing surfactant decreased the impact strength by ～ 30–40% relative to the unmodified UF control, whereas the water‐soluble thermoplastic had no effect on the impact strength. The formulations with self‐dispersed thermoplastics all increased the notched Izod impact strength, with the greatest increase being 69% more than the UF control, except in a single instance when the molecular weight of the thermoplastic was very high, which decreased resin flow. Increasing the thermoplastic content from 5 to 10% w/v did not further improve the impact test results. Scanning electron microscopy of the fracture surfaces showed morphological differences in the systems that varied with the thermoplastic and method of thermoplastic addition to the UF suspension.© 2002 Wiley Periodicals, Inc. J Appl Polym Sci 87: 898–907, 2003     

Thiol‐containing ionic liquid for the modification of styrene–butadiene rubber/silica composites

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     

Synthesis and characterization of nanosilica/polyacrylate composite latex

The nanosilica/polyacrylate organic–inorganic composite latex was synthesized by in‐situ emulsion polymerization of methyl methacrylate (MMA) and butyl acrylate (BA) in the presence of silica nanoparticles, which were modified by silane coupling agent. The surface properties and dispersibility of silica nanoparticles modification, chemical structure, Zeta potential, diameter distribution of the composite latex prepared, surface roughness, and thermal stability of the hybrid film formed by the composite latex were investigated by fourier transform infrared spectrometer (FTIR), transmission electron microscopy (TEM), Zeta meter, ZetaPlus apparatus (dynamic light scattering method), atomic force microscopy (AFM), and thermogravimetric analysis (TGA), respectively. After modification with silane coupling agent, silane was grafted onto the surface of silica nanoparticles to form the organic layers, which was able to efficiently prevent the silica nanoparticles from aggregating to individually homogeneous disperse in the in‐situ emulsion polymerization system and improve the compatibility of silica nanoparticles with the acrylate monomers. The nanosilica/polyacrylate organic–inorganic composite latex prepared had the properties of silica nanoparticles and pure polyacrylate latex but was not simply a combination. Strong chemical bonding tethered the silica and acrylate chains to form the core/shell structural composite latex. Consequently, the hybrid film formed by nanosilica/polyacrylate composite latex exhibited a smooth surface and better thermal properties than the pure polyacrylate film. POLYM. COMPOS. 27:282–288, 2006. © 2006 Society of Plastics Engineers