Promoting the dispersibility of silica and interfacial strength of rubber/silica composites prepared by latex compounding

The dispersibility of precipitated silica and its interfacial interaction with rubber matrix can affect the performances of tires which is a difficult problem to be solved. A well-dispersed silica dispersion was obtained through ball milling and modification process followed by heat treatment to enhance the properties of NR composites prepared by latex compounding. Benefiting from the modifier Si-747, the well-dispersed silica/NR composite (Silica-MSH-C) shows excellent tensile strength of 30.8 ± 0.5 MPa, which is 17.6 ± 3.8% higher than latex compounding pure silica/NR composite (Silica-C) and 21.7 ± 4.3% higher than traditional mechanical blending pure silica/NR composite (T-Silica-C). The tan delta values indicate that Silica-MSH-C has better dynamic properties and also has stronger interface strength according to swelling tests, heat capacity curves and Mooney-Rivlin equation. The molecular dynamics (MD) simulation further shows the binding energy between NR and Si-747 modified SiO₂ is 58.88 Kcal/mol larger than the value of NR and pure silica.     

Improving blood compatibility of natural rubber by UV‐induced graft polymerization of hydrophilic monomers

Natural rubber (NR) latex films surface‐grafted with hydrophilic monomers, poly(ethylene glycol) methacrylate (PEGMA), N‐vinylpyrrolidone (VPy), and 2‐methacryloyloxyethyl phosphorylcholine (MPC), were prepared by UV‐induced graft polymerization using benzophenone as a photosensitizer. The grafting yield increases of vulcanized NR latex films as a function of time and monomer concentration were of lesser magnitude than those of the unvulcanized NR latex films. This can be explained as a result of the crosslinked network generated during vulcanization acting as a barrier to the permeation of the photosensitizer and the monomer. The appearance of a characteristic carbonyl stretching in the attenuated total reflectance‐Fourier transform infrared spectroscopy (ATR‐FTIR) spectra of NR latex films after the surface grafting of PEGMA and MPC indicates that the modification has proceeded at least to the sampling depth of ATR‐FTIR (∼ 1–2 μm). According to the water contact angle of the modified NR latex films, the surface grafting density became higher as the grafting time and monomer concentration increased. The complete absence of plasma protein adsorption and platelet adhesion on the surface‐modified NR latex films having grafting yield above 1 wt % is a strong indication of improved blood compatibility. Results from tensile tests suggest that graft polymerization does not cause adverse effects on the mechanical properties of vulcanized NR latex films. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

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     

Study on properties of natural rubber reinforced by poly(sodium‐4‐styrenesulfonate)‐decorated carbon black with a latex compounding technique

Natural rubber filled with poly(sodium‐4‐styrenesulfonate) (PSS)‐decorated carbon black (CB) by employing a latex compounding technique was prepared. The result of scanning electron microscope demonstrated that CB was uniformly dispersed in the matrix. Comparing to traditional dry compounding, an improvement in physical and mechanical properties was observed in the composites attributed to the homogeneous distribution of CB in matrix and an augment of bound rubber. Owing to the changes of the physical properties of CB surface, vulcanizate filled with oxidized CB via latex way exhibited higher mechanical properties. The resulting vulcanizates displayed a diminished interaction between fillers based on the consequence of strain dependence of storage modulus. Furthermore, a splendid wet‐skid resistance was obtained in vulcanizates fabricated by latex compounding technique in comparison with vulcanizates prepared by traditional dry compounding. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42346.     

改性氨基硅溶胶/天然乳胶膜材料的制备、结构及性能

采用阳离子乳化剂聚二烯丙基二甲基氯化铵(PDDA)对氨基硅溶胶进行改性制备改性氨基硅溶胶(MSS),然后将其与天然乳胶(NRL)进行杂凝聚制得MSS/NRL膜材料,分析了MSS,MSS/NRL膜材料的结构、粒径、Zeta电位及形态,考察了MSS/NRL膜材料的力学性能及耐紫外老化性能。结果表明,MSS与NRL共混后粒径较NRL增大;氨基硅溶胶经PDDA改性后呈弱正电性,能在杂凝聚共混环境下与带负电荷的乳胶粒子形成多层次核-壳结构;随着MSS添加量的增加,MSS/NRL膜材料的拉伸强度呈先增后减的趋势,当MSS质量分数为0.35%时,膜材料的拉伸强度达到21.98 MPa的最大值,扯断伸长率达到750%;MSS/NRL薄膜的耐紫外老化性能在老化12 h以后较NRL薄膜提高10%以上。     

Simultaneously reduced viscosity and enhanced strength of liquid silicone rubber/silica composites by silica surface modification

Silica is the most widely‐used filler to reinforce liquid silicone rubber (LSR), but the high viscosity of LSR/silica suspension significantly limits its processing flexibility. To balance the processibility and reinforcing efficiency of LSR/silica systems, two kinds of enols (propenol and 1‐undecylenyl alcohol) and a saturated alcohol (1‐undecylic alcohol) were employed to modify the silica surface. Various rheological tests were carried out to investigate the processibility as well as filler networking and crosslinking processes of the modified systems. Tensile tests were also adopted to verify the reinforcing effect. It was found that surface modification of silica by 1‐undecylenyl alcohol could significantly reduce the viscosity of its suspension with LSR. Meanwhile, the mechanical strength of LSR could be largely enhanced by six times with 10 wt % modified silica. This work will merit design and production of LSR materials with balanced processibility and mechanical performance. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 45544.     

A robust and coarse surface mesh modified by interpenetrating polymer network hydrogel for oil‐water separation

A robust and coarse surface mesh was fabricated by introducing a hydrogel coating with interpenetrating polymer network (IPN) structure on stainless steel mesh. The IPN hydrogel was prepared by crosslinking polymerization of acrylic acid (AA) followed by condensation reaction of polyvinyl alcohol (PVA) and glutaraldehyde (GA) at room temperature. As a result, the roughness of modified mesh was enhanced obviously and oil droplet underwater showed a larger contact angle. The hydrogel‐coated surface showed an underwater superoleophobicity with an oil contact angle of 153.92 ± 1.08^°. Besides, stable wettability was observed. The mesh can selectively separate oil from water with a high separation efficiency of above 99.8%. This work provides a facile method to strengthen the coating and enhance the efficiency of oil‐water separation. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41949.     

Enhanced interfacial adhesion of aramid fiber reinforced rubber composites through bio-inspired surface modification and aramid nanofiber coating

In order to improve the interfacial adhesion between aramid fiber (AF) and rubber matrix, a simple and facile method of aramid nanofiber (ANF) coating is demonstrated in this article. Tannic acid (TA) and polyethyleneimine (PEI) are polymerized in an alkaline solution to form a thin TA/PEI (TP) layer that is deposited on the surface of AF to introduce functional groups such as hydroxyl and amino groups. Then, the ANF coating is utilized to construct nanostructures on the surface of AF to improve the interfacial adhesion between the fiber and the rubber. Through hydrogen bonding and/or π-π stacking between the TP layer and the ANF, the ANF coating is firmly attached to the surface of AF. Compared with the untreated fiber, the interfacial adhesion of AF coated with ANF after 1, 3, 5, 7, 9 deposition cycles is increased by 27.8%, 29.1%, 31.5%, 43.1%, and 30.3%, and the mechanical properties of the fibers remain almost unchanged. This method shows its advantages of simple, facile, and time-effective, which is of great significance for industrial applications.     

Failure behavior of resorcinol–formaldehyde latex coated aramid short‐fiber‐reinforced rubber sealing under transverse tension

Composites composed of rubber, sepiolite fiber, and resorcinol–formaldehyde latex‐coated aramid short fibers were prepared. Mechanical and morphological characterizations were carried out. To investigate the effect of interfacial debonding on the failure behavior of short‐fiber‐reinforced rubber composites, a micromechanical representative volume element model for the composites was developed. The cohesive zone model was used to analyze the interfacial failure. We found that computational results were in good agreement with the experimental results when the interfacial fracture energy was 1 J/m² and the interfacial strength was 10 MPa. A parametrical study on the interface and interphase of the composite was conducted. The results indicate that a good interfacial strength and a choice of interphase modulus between 40 and 50 MPa enhanced the ductile behavior and strength of the composite. The ductile properties of the composite also increased with increasing interfacial fracture energy. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41672.     

Effect of interfacial pretreatment on the properties of montmorillonite/poly(vinyl alcohol) nanocomposites

This work explores the factors that control the dispersion of exfoliated montmorillonite (MMT) in poly(vinyl alcohol) (PVOH) during solution blending and solvent evaporation. Nanocomposite films were prepared by solution blending of aqueous PVOH solutions with dilute suspensions of fully exfoliated MMT platelets (as confirmed by AFM). Dynamic light scattering (DLS) indicates that addition of MMT suspensions to PVOH solutions results in undesired particle aggregation and thus poor MMT dispersion in cast films (as evidenced by transmission electron microscopic images and gas permeation measurements). We believe that PVOH bridging induces MMT platelet aggregation. To counteract bridging aggregation, we explore the novel idea of pretreating the MMT surface with a small amount of compatible polymer prior to solution blending with PVOH. We hypothesize that “pretreating” the MMT platelet surfaces with adsorbed polymer in dilute suspensions will protect the platelets from bridging aggregation during solution blending and solvent evaporation. MMT/PVOH composite films have been prepared using low‐molecular‐weight PVOH as the pretreatment polymer; and low‐, medium‐, and high‐molecular‐weight PVOH as the matrix polymer. A PEO‐PPO‐PEO triblock copolymer (F108 from the Pluronics^® family) was also evaluated as the pretreatment polymer. DLS shows that pretreated MMT platelets are less susceptible to aggregation during blending with PVOH solutions. Results compare the crystalline structure, thermal properties, dynamic mechanical properties, gas permeability, and dissolution behavior of MMT/PVOH films incorporating untreated versus pretreated MMT. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41867.     

Use of epoxidized natural rubber as a toughening agent in plastics

At present, the rubber toughening of plastics has become an attractive field of study in polymer science and technology because brittleness is known to be a drawback in many engineering plastics; it can cause premature failure during application. Among existing rubber materials, epoxidized natural rubber (ENR) has been widely used as an impact modifier or toughening agent in a large number of engineering plastics; in particular, it enhances the impact strength, which deteriorates with the incorporation of other additives, such as fillers and flame retardants. ENR is a modification product from natural rubber produced via an epoxidation reaction. ENR also has good chemical resistance. In this review, we aim to provide a concise current status in the field of ENR toughening agents for plastics with a brief discussion of their associated problems and potential applications. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42270.     

CaCO3/natural rubber latex nanometer composite and its properties

Calcium carbonate/natural rubber (NR) latex nanometer composites were prepared by adding nanometer CaCO₃ whose surface had been treated to natural rubber latex (NRL) before sulfuration. The physical, thermooxidative aging, and thermal degradation properties and the ultra‐microstructure were analyzed with a multipurpose material testing meter, a thermal analysis meter and a Philips XL‐30 SEM, respectively. The results showed that the structures and properties of nanometer composites could be clearly improved by NRL mixed with surface‐treated nanometer CaCO₃. The physical properties of the nanometer composites were best when the content of surface treatment agent was 2.5% (to nanometer CaCO₃), the nanometer CaCO₃/NRL content was 3:100, and the stirring time for treating the surface of the nanometer CaCO₃ was 20 min. Simultaneously, the thermooxidative aging resistance of the nanometer composites also was significantly improved. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 3442–3447, 2006     

A preparation method of porous surface nitrile butadiene rubber with low friction coefficient under water lubrication condition by salt leaching

Nitrile butadiene rubber is widely used in water-lubricated bearings due to its excellent performance. Generally, the friction coefficient of water-lubricated rubber bearings typically between 0.05 and 0.18. In this study, a new method for preparing nitrile butadiene rubber with micro-holes surface is developed by porous leaching with salt as pore forming agent. The possibility of using porous surface to minimize friction and wear of rubber materials is researched. The influence of structural parameters, including the hole density and size (which are determined by salt mass fraction of rubber compounds and salt grain-sized, respectively) on tribology performances are also evaluated. In a ring-on-block test, the optimal parameters of modified rubber achieved a low friction coefficient of 0.008, which reduced by 42% compared with untreated one (0.019) under the same operating condition. It can be expected that the developed method is beneficial to reduce the friction coefficient of rubber-steel friction pair under water lubricated condition.     

Natural rubber latex LbL films: Characterization and growth of fibroblasts

The recent biomedical applications of natural rubber (NR) latex, mostly in dry membranes, have motivated research into novel, more noble uses of this low-cost biomaterial. In this article, we provide the first report on the fabrication of layer-by-layer (LbL) films of NR alternated with the polyelectrolytes polyethylenimine (PEI) and polyallylamine hydrochloride (PAH). Stable (PAH/NR)_n and (PEI/NR)_n LbL films displayed similar physicochemical properties, but differed in terms of film morphology according to atomic force microscopy (AFM) and scanning electron microscopy (SEM) data. Most significantly, (PEI/NR)₅ LbL films were made of smaller and flattened particles, which were not efficient for the growth and proliferation of normal human fibroblasts (NHF). In contrast, efficient NHF proliferation could be obtained with (PAH/NR)_n LbL films, with the fibroblasts exhibiting the expected elongated morphology. Furthermore, cell growth did not occur for cast films of NR, thus demonstrating the suitability of the LbL method for this biologically related application. The differences between the two polyelectrolytes illustrate the importance of the film architecture and morphology, which open the way for exploiting the molecular control inherent in the LbL technique for further applications of NR-containing films. © 2012 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

The use of Bis-(3-triethoxysilylpropyl) tetrasulphane for surface modification of silica,ferrite and kenaf fiber filled natural rubber composites; comparison of aqueous solvent deposition,dry blend and integral blend methods

In this work, Bis-(3-triethoxysilylpropyl) tetrasulphane was employed for surface modification of silica, ferrite and kenaf fiber filled natural rubber composites using aqueous solvent deposition, dry blending and integral blend methods. The efficiency of each method and the preferred modification method for improving the mechanical performance of natural rubber composites was assessed. The appearance of the Fourier transform infrared spectroscopy peak around 1088 cm⁻¹ for all types of fillers provided evidence that silane interaction had occurred between the fillers and rubber and the formation of siloxane linkages were quantitatively determined by the crosslink density measurement. The surface treatment by dry method for silica and ferrite fillers showed significant improvement of tensile performance at approximately 67% and 34% compared to those with untreated fillers. For kenaf fiber-filled rubber composites, the surface treatment by aqueous solvent deposition showed the highest tensile improvement of 59% compared to the dry blending and integral blend method.     

Influence of modification process parameters on the properties of crumb rubber/EVA modified asphalt

Crumb rubber (CR) and ethylene vinyl acetate copolymer (EVA) were adopted as asphalt modifiers. Routine tests, softening point, penetration, and ductility were used to evaluate the basic properties of crumb rubber and ethylene vinyl acetate copolymers (CR/EVA) modified asphalt. The segregation experiment measured the storage stability. Modern test methods such as fluorescence microscopic photography technology was used to study stability of polymer modified asphalt. Infrared spectrum experiment was used to analyze the composition differences of the upper part and lower part of CR/EVA modified asphalt. Matlab software was employed to fit out the formulae of ductility, penetration, and softening point difference of modified asphalt and shearing temperature, shearing time and shearing rate separately. Compared with base asphalt, the properties of CR/EVA modified asphalt have been greatly improved. The formulae which were fitted out by Matlab software showed that the shearing time was the foremost factor affecting the properties of CR/EVA modified asphalt, followed by shearing temperature, and the last was shearing rate. The conclusions which were fitted by orthogonal experiment were basically consistent with the results of formulae which were fitted out by Matlab software. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43598.     

Effect of hollow glass beads on density and mechanical properties of silicone rubber composites

In this work, low density hollow glass beads (HGB)/silicon rubber (SR) composites were prepared by solution method and flocculation process. The prepared samples were characterized by scanning electron microscopy, Fourier transform infrared spectroscopy, tensile test, and friction test. The results show that the densities of SR composites decrease from 1.140 to 0.792 g/cm³ with the addition of HGB. By comparing theoretical density with true density, it can be estimated that the ratio of shattered HGB increase from 8.79% to 24.76%. Especially, the mechanical properties of SR composites were improved by surface modification of HGB. By adding surface-modified HGB at 5 and 10 wt%, the tensile strengths of SR composites were enhanced by 17.8% and 28.2%, respectively. In addition, tear strength, shore A hardness, compression set, and friction property were significantly ameliorated. Furthermore, the mechanism of surface-modified HGB in mechanical properties was analyzed.     

Electrospun polyurethane membrane with Ag/ZnO microparticles as an antibacterial surface on polyurethane sheets

A method of antibacterial modification of the polyurethane (PU) surface is presented in this article. An electrospun PU membrane with an incorporated antibacterial agent was applied as a coating of the PU sheets. As an antibacterial agent, a hybrid bimetallic filler was used; it combined the antibacterial effects of silver and zinc oxide. With an electrospun submicrometer‐fiber membrane, the filler was uniformly and thinly applied on the PU surface by compression molding. The antibacterial activities of three filler concentrations were tested, and they demonstrated an effective antibacterial action against Staphylococcus aureus and Escherichia coli. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43020.     

Development of biodegradable natural rubber latex composites by employing corn derivative bio-fillers

This study aims to investigate the viability of employing corn-based fillers (powdered corn grain [CG], corn flour [CF] and cornstarch [CS]) to improve the biodegradability of natural rubber latex (NRL) composites by varying filler loading from 0 to 50 phr. Notable variation in both physical and mechanical properties were observed for the different filler types, with CG-filled NRL demonstrating the better adhesion with NRL. Thus, CG-filled composites were selected for investigation of biodegradability. Increased CG loading in NRL compounds enhanced biodegradation; with over 70% degradation observed for 50 phr CG loading upon 15 weeks of soil burial. However, the trade-off between mechanical properties and biodegradability limits the CG loading in the NRL matrix to 20 phr for manufacturing NRL-based products. It was observed that NRL with CG filler loading of 20 phr conforms to the ASTM D3578 standard for manufacturing rubber gloves; with 50% biodegradation upon 15 weeks of soil burial.     

Preparation and electrochemical performance of modified Ti3C2Tx/polypyrrole composites

MXenes with a large surface area have been widely studied to improve the pseudocapacitance of electrode materials by combining conductive polymer materials. In this article, a superficial strategy to enhance the electrochemical properties by in situ polymerization of a pyrrole monomer between the Ti₃C₂T_x layers modified with 1,5-naphthalene disulfonic acid (NA) and cetyltrimethylammonium bromide (CTAB) was investigated. It is found that polypyrrole (PPy) and Ti₃C₂T_x can be combined through strong interactions between each other, and the specific capacitance of the modified Ti₃C₂T_x/PPy composite was increased to a maximum value of 437 F g⁻¹, which was more than thrice higher than that of pure PPy. The composite also exhibited good cycling performance (76% capacitance retention after 1000 cycles). Moreover, owing to the synergistic effect between the PPy and Ti₃C₂T_x layers, the composite provided better electron or ion transfer and surface redox processes than that of pure PPy, which indicated that this composite can be used as a promising electrode material for supercapacitors. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 47003.