Dynamic properties of star‐shaped,solution‐polymerized styrene–butadiene rubber and its cocoagulated rubber‐filled with silica/carbon black

The dynamic properties, including the dynamic mechanical properties, flex fatigue properties, dynamic compression properties, and rolling loss properties, of star‐shaped solution‐polymerized styrene–butadiene rubber (SSBR) and organically modified nanosilica powder/star‐shaped styrene–butadiene rubber cocoagulated rubber (N‐SSBR), both filled with silica/carbon black (CB), were studied. N‐SSBR was characterized by ¹H‐NMR, gel permeation chromatography, energy dispersive spectrometry, and transmission electron microscopy. The results show that the silica particles were homogeneously dispersed in the N‐SSBR matrix. In addition, the N‐SSBR/SiO₂/CB–rubber compounds' high bound rubber contents implied good filler–polymer interactions. Compared with SSBR filled with silica/CB, the N‐SSBR filled with these fillers exhibited better flex fatigue resistance and a lower Payne effect, internal friction loss, compression permanent set, compression heat buildup, and power loss. The nanocomposites with excellent flex fatigue resistance showed several characteristics of branched, thick, rough, homogeneously distributed cross‐sectional cracks, tortuous flex crack paths, few stress concentration points, and obscure interfaces with the matrix. Accordingly, N‐SSBR would be an ideal matrix for applications in the tread of green tires. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40348.     

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.     

Preparation of aromatic poly(1,3,4‐oxadiazoles) pulps and their paper properties

To improve the paper properties of the poly(1,3,4‐oxadiazoles) (POD), the POD pulps were prepared by prechemical and mechanical methods to increase their polarity, contact area, and interaction. The fibrillated degree of the staple fibers was evaluated by the Canadian Standard Freeness and the specific surface area, while the surface free energy was calculated by the Micro–wilhelmy method. Meanwhile, the functional groups and compositions on the surface of the POD fibers were confirmed by the FTIR–ATR and the X‐ray photoelectron spectroscopy, and the surface morphological structure and the crystalline structure of the POD fibers were observed by the fiber analyzer, scanning electron microscope, and Wide‐angle X‐ray diffraction, respectively. It was found that the pronounced abrasive and distinctive grooves were formed on the surface of the POD fibers after prechemical and mechanical treatment. The surface free energy of POD fibers increased 8.41%, and the polar part increased by 32.10% after treatment. It was confirmed that the polar functional groups and fibril were formed after chemical and mechanical treatment, so the interaction of the POD fibers was highly enhanced, and as a result the apparent density, tensile strength, fold endurance, and tear strength of the paper formed by those treated fibers were all improved apparently. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 39818.     

Viscoelastic properties of natural rubber composites reinforced by defatted soy flour and carbon black co‐filler

Filler mixtures of defatted soy flour (DSF) and carbon black (CB) were used to reinforce natural rubber (NR) composites and their viscoelastic properties were investigated. DSF is an abundant and renewable commodity and has a lower material cost than CB. Aqueous dispersions of DSF and CB were first mixed and then blended with NR latex to form rubber composites using freeze‐drying and compression molding methods. A 40% co‐filler reinforced composite with a 1 : 1 DSF : CB ratio exhibited a 90‐fold increase in the rubber plateau modulus compared with unfilled NR, showing a significant reinforcement effect by the co‐filler. The effect, however, is lower than that observed in the carboxylated styrene–butadiene rubber composites reported earlier, indicating a significant effect from the rubber matrix. The co‐filler composites have elastic moduli between those of DSF and CB reinforced composites. Stress softening and recovery experiments indicated that the co‐filler composites with a higher CB content tend to have a better recovery behavior; however, this can not be simply explained from the recovery behaviors of the single filler (DFS and CB) composites. CB composites prepared by freeze‐drying show a strain‐induced reorganization of fillers. Strain sweep experiment data fit with the Kraus model indicates the co‐filler composites with a higher CB content are more elastic, which is consistent with the recovery experiments. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007     

Contribution of hydrogen and/or covalent bonds on reinforcement of natural rubber latex films with surface modified silica

A macromolecular coupling agent containing hydrophilic and hydrophobic groups is made to react with precipitated silica. Interfacial interactions between  OH groups of silica and  COOH groups of macromolecule are found to be created through either hydrogen bonds alone or through hydrogen bonds and covalent bonds. Aqueous dispersions of unmodified and modified silica are prepared and the colloidal stability and particle size distribution of the dispersions are observed. The dispersions at neutral pH are incorporated into vulcanized/unvulcanized natural rubber latex. The formation of hydrogen bonds and/or covalent bonds is studied via FTIR spectroscopy and their contribution in encouraging filler‐rubber interactions is emphasized through mechanical and swelling properties. Uniform distribution and dispersion of modified filler particles throughout the rubber matrix is confirmed by the microstructures of the latex films cast from filler added natural rubber latex. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40380.     

Influence of oxygen plasma treatment on interfacial properties of poly(p‐phenylene benzobisoxazole) fiber‐reinforced poly(phthalazinone ether sulfone ketone) composite

The influence of oxygen plasma treatment on both surface properties of poly(p‐phenylene benzobisoxazole) (PBO) fibers and interfacial properties of PBO fiber reinforced poly(phthalazinone ether sulfone ketone) (PPESK) composite were investigated. Surface chemical composition, surface roughness, and surface morphologies of PBO fibers were analyzed by X‐ray photoelectron spectroscopy (XPS), Atomic force microscopy (AFM), and scanning electron microscopy (SEM), respectively. Surface free energy of the fibers was characterized by dynamic contact angle analysis (DCAA). The interlaminar shear strength (ILSS) and water absorption of PBO fiber‐reinforced PPESK composite were measured. Fracture mechanisms of the composite were examined by SEM. The results indicated that oxygen plasma treatment significantly improved the interfacial adhesion of PBO fiber‐reinforced PPESK composite by introducing some polar or oxygen‐containing groups to PBO fiber surfaces and by fiber surface roughening. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Study of crystallization behavior of neat poly(vinylidene fluoride) and transcrystallization in carbon fiber/poly(vinylidene fluoride) composite under a temperature gradient

The crystallization behavior of poly(vinylidene fluoride) (PVDF) and transcrystallization in carbon fiber (CF)/PVDF composite were investigated under a temperature gradient. The crystallization temperature (T_c) was controlled in the range of 110–180 °C. For neat PVDF, the results showed that exclusive γ phase formed at T_c above 164 °C, but coexisted with α phase at T_c ranging from 137 to 160 °C. The promotion of γ phase to nucleation of α phase at low T_c was observed for the first time. For CF/PVDF composite, a cylindrical transcrystalline (TC) layer formed on the surface of CF when T_c was between 137 and 172 °C. The TC layer was exclusively composed of γ phase at T_c above 164 °C. The hybrid nucleation was dominated by γ phase though some α phase nuclei emerged on the surface of CF when T_c was in the range of 144–160 °C. As T_c decreased, competition between the hybrid nucleation of α and γ phase became more intense. The γ phase nuclei was soon circumscribed by the rapidly developed α phase when T_c was below 144 °C. Furthermore, some α phase nuclei were induced at the surface of the γ phase TC layer, and developed into α phase TC layer when T_c was in the range of 146–156 °C, which resulted in a doubled TC layer of α and γ phase at the interface of the composite. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43605.     

Modification of poly(3‐hydroxybutyrate)‐co‐poly(3‐hydroxyvalerate) with natural rubber

Composites of poly(3‐hydroxybutyrate)‐co‐poly(3‐hydroxyvalerate) (PHBHV) with 6% of 3‐hydroxyvalerate (HV) and natural rubber (NR) were prepared by a solvent‐casting method. Different approaches were tested for the composite preparation. Both PHBHV and NR were dissolved in chloroform, followed by its evaporation, giving various layers. The mechanical properties and morphology of the obtained composites were evaluated by tensile tests and scanning electron microscopy (SEM), respectively. The obtained results demonstrated that the final composite has excellent mechanical properties when compared with PHBHV. SEM analysis unequivocally showed the excellent adhesion between the two polymeric layers. This new material was also tested as a drug delivering system using flurbiprofen as a model drug, and then the diffusion coefficients were determined. This article describes an easy method to produce a desirable composite from PHBHV and NR. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Preparation of poly(methyl methacrylate‐co‐butyl methacrylate) nanoparticles and their reinforcing effect on natural rubber

Poly(methyl methacrylate‐co‐butyl methacrylate) [P(MMA‐co‐BMA)] nanoparticles were synthesized via emulsion polymerization, and incorporated into natural rubber (NR) by latex compounding. Monodispersed, core‐shell P(MMA‐co‐BMA)/casein nanoparticles (abbreviated as PMBMA‐CA) were produced with casein (CA) as surfactant. The chemical structure of P(MMA‐co‐BMA) copolymers were confirmed by ¹H‐NMR and FTIR analyses. Transmission electron microscopy demonstrated the core–shell structure of PMBMA‐CA, and PMBMA‐CA homogenously distributed around NR particles, indicating the interaction between PMBMA‐CA and NR. As a result, the tensile strength and modulus of NR/PMBMA‐CA films were significantly enhanced. The tensile strength was increased by 100% with 10% copolymer addition, when the molar ratio of MMA:BMA was 8:2. In addition, scanning electron microscopy and atomic force microscopy results presented that the NR/PMBMA‐CA films exhibited smooth surfaces with low roughness, and PMBMA‐CA was compatible with NR. FTIR‐ATR analyses also suggested fewer PMBMA‐CA nanoparticles migrated out of NR. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43843.     

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.     

Deposition of disinfectant poly(methyl acrylate) nanocapsules onto natural rubber film via the layer‐by‐layer technique

An aqueous core containing a disinfectant agent (chlorhexidine digluconate) was encapsulated in a poly(methyl acrylate) shell with a modified nanoprecipitation technique. After redispersion of the capsules in an aqueous medium, the remaining amount of the disinfectant agent was as high as 90%. The nanocapsules were successfully adsorbed via the layer‐by‐layer technique onto a γ‐radiation‐vulcanized natural rubber latex sheet. Water contact angle measurements and scanning electron microscopy confirmed the presence of nanocapsules on the rubber surface. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Effect of microstructure on the dielectric properties of poly(vinyl alcohol)–poly(3,4‐ethylenedioxythiophene) doped with poly(styrenesulfonate) composite films

Poly(3,4‐ethylenedioxythiophene) doped with poly(styrenesulfonate) (PEDOT–PSS) was blended with poly(vinyl alcohol) (PVA) to form 0, 10, 20, 30, 40, and 50 vol % PEDOT–PSS/PVA solutions, and their freestanding films were prepared with a simple and cost‐effective solution casting technique at 27 °C in the absence of additives. Field emission scanning electron microscopy images revealed changes in the cocontinuous network to a rodlike morphology in the composite films from 10 to 50 vol % PEDOT–PSS/PVA. The alternating‐current conductivity was found to obey Jonscher's power law. The obtained values of the dielectric constant at 27 °C were relatively high, and a maximum value of 6.7 × 10⁴ at 100 Hz for 40 vol % PEDOT–PSS'/PVA was observed. The dielectric loss attained a maximum value of about 10⁶ at 100 Hz for 40 vol % PEDOT–PSS/PVA. However, a decrease in the dielectric parameters was observed at 50 vol % PEDOT–PSS/PVA because of locally induced strain in the microstructure. The variations in polarization with respect to the applied electric field (P–E) were determined for 50, 100, and 500 Hz at 500 V for the freestanding composite films of lower concentrations up to 20 vol % PEDOT–PSS/PVA. In summary, the dielectric and P–E measurements confirmed that the electrical characteristics changed in accordance to the contribution from both resistive and capacitive sites in the PEDOT–PSS/PVA composites. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 45079.     

Joining of carbon fiber reinforced polymer laminates by a novel partial cross‐linking process

Direct joining of partially cross‐linked and freshly infiltrated carbon fiber reinforced epoxy resin plates made from HTA/RTM6 is investigated as function of the partial curing degree. Partial cross‐linking maintains a certain chemical reactivity of the thermosetting resin which can be used for bonding to a second, freshly infiltrated resin part. A final curing cycle guarantees complete cross‐linking of the joined component. The bonding behavior and the interface morphology of the joined plates are analyzed by mechanical testing, acoustic emission analysis and microscopy. A significant dependence of the bonding and interfacial properties on the partial curing degree is found. Very low and very high partial curing degrees (below 70% and above 80%) result in low fracture toughness and discontinuous crack propagation. Intermediate curing degrees between 70% and 80% mainly show high fracture toughness, stable crack propagation and a ripple like interface morphology. The latter is created by the surface morphology of the partially cross‐linked plate with the typical peel‐ply imprint and results in a high contact surface and mechanical interlocking. The combination of chemical reactivity and high contact surface seems to be advantageous for the enhanced fracture toughness and the improved failure mode of samples with intermediate partial curing degree. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42159.     

Fabrication and improved performance of poly(3‐hydroxybutyrate‐co‐3‐hydroxyvalerate) for packaging by addition of high molecular weight natural rubber

The packaging industry is searching for alternative materials to attain environmental sustainability. Poly(3‐hydroxybutyrate‐co‐3‐hydroxyvalerate (PHBV) is a semicrystalline polymer that meets this sustainability goal since it is bioderived and biodegradable. However, its brittle nature and relatively high water permeation and transmission rates make it unsuitable for packaging applications. In addition, PHBV has poor mechanical, thermal, and rheological properties above 160 °C, limiting its use in cast sheets and thermo‐formed packaging applications. To improve these properties, new blends of PHBV with high molecular weight natural rubber at 5, 10, 15, and 25% by weight were fabricated, and physico‐chemical properties of the blends were characterized. The rubber in the blends aided in the following: increased thermal stability since the complex viscosities of the blends were improved by one log over pure PHBV at 170 °C, created more uniform melting peaks attesting to improved homogeneity, decreased water permeation to a level similar to that of traditional thermoplastics; increased the elongation at break, and stabilized the Young's modulus. Therefore, these blends can potentially be used in‐place of traditional, petroleum‐based thermoplastics in cast sheets and thermoforms. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43937.     

High damping epoxized natural rubber/diallyl adiallyl phthalate prepolymer (ENR/DAP‐A) blends engineered by interphase crosslinking

While a great diversity of rubber/plastic damping blends have been reported, the damping trough resulted from phase incompatibility, which usually exists between the glass transition temperatures (T_g) of each component, remains an unsolved problem by separating the effective temperature range of damping blends. Herein, we reported a new and facile way of preparing rubber/plastic binary blends with high damping property by eliminating the inherent damping trough. Specifically, we envisaged that peroxides can trigger free radical reactions both within and between epoxidized natural rubber/diallyl phthalate prepolymer moieties, which serve as the co‐vulcanizer to generate interphase reactions thus enhancing phase compatibility. Accordingly, apart from the resulting high damping epoxidized natural rubber40/diallyl phthalate prepolymer binary blends with an effective (tan δ_min > 0.35) temperature range of 178 °C from −33 to 145 °C, the proposal has also been demonstrated via the support of broadband dielectric spectrometer testing, dynamic mechanical analysis, and differential scanning calorimetry. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46300.     

Effects of the short‐fiber tip geometry and interphase properties on the interfacial debonding behavior of rubber matrix composites

An axisymmetric finite element model of a single fiber embedded in a rubber matrix was established. A cohesive zone model was used for the fiber–matrix interface because of the interfacial failure. The effect of the fiber tip shape on the interfacial debonding of short‐fiber‐reinforced rubber matrix sealing composites (SFRCs) was investigated; the shapes were flat, semi‐elliptical, hemispherical, and conoid, respectively. The initial strain of the interfacial debonding (ε₀) was obtained. We found that among the researched fiber tips, ε₀ of the SFRC reinforced with the hemispherical tip fiber appeared to be the maximum. The initial locations of interfacial debonding were also determined. The results show that the initial locations of the interfacial debonding moved from the edge to the center of the fiber tip when the ratio of the semimajor axis and semiminor axis of the semi‐elliptical fiber tip increased gradually. Further study on the effect of the interphase properties on ε₀ with the hemispherical fiber tip was conducted. The results indicate that an interphase thickness of 0.2 μm and an interphase elastic modulus of about 752 MPa were optimal for restraining the initiation of the interfacial debonding. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42774.     

Compatibilizing effect of poly(styrene)‐block‐poly(isoprene) copolymers in heterogeneous poly(styrene)/natural rubber blends

Compatibility of poly(styrene) (PS)/natural rubber (NR) blend is improved by the addition of diblock copolymer of poly(styrene) and cis‐poly(isoprene) (PS‐b‐PI). The compatibilizing effect has been investigated as a function of block copolymer molecular weight, composition and concentration. The effect of homopolymer molecular weight, processing conditions and mode of addition on the morphology of the dispersed phase have also been investigated by means of optical microscopy and scanning electron microscopy. A sharp decrease in phase dimensions is observed with the addition of a few percent of block copolymers. The effect levels off at higher concentrations. The leveling off could be an indication of interfacial saturation. For concentrations below the critical value, the particle size reduction is linear with copolymer volume fraction and agrees well with the prediction of Noolandi and Hong. The addition of the block copolymer improves the mechanical properties of the blend. An attempt is made to correlate the mechanical properties with the morphology of the blends. © 2001 Society of Chemical Industry     

Improvement of the short‐ and long‐term mechanical properties of injection‐molded poly(etheretherketone) and hydroxyapatite nanocomposites

Nanocomposites of polyetheretherketone (PEEK) and hydroxyapatite (HA) nanoparticles treated with a silane coupling agent were successfully prepared by twin screw extrusion and injection molding. Some of the samples were annealed after the injection molding. The silane treatment promoted an improvement of the short‐ and long‐term mechanical properties of the nanocomposites. A higher stress and a six times higher deformation at break and a higher impact strength were observed in the silane‐treated nanocomposites when compared to the nontreated ones. The number of cycles to fail of the treated nanocomposites was almost 200% higher than the number of cycles to fail of the nontreated samples. The treatment also decreased the glass transition temperature and amount of crystallinity of the samples. This improvement in mechanical properties obtained from the silane treatment was attributed to the strengthening of the PEEK/HA interfacial bond, to the plasticization of the PEEK matrix by silane oligomers produced during the processing and to a better dispersion of the HA nanoparticles within the PEEK matrix. Samples annealing, however, diminished all these properties due to the increase in crystallinity. Studies of the short‐ and long‐term mechanical properties of these nanocomposites under physiological conditions and of the proliferation of stem cells are under way. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 44476.     

Dielectric and microwave properties of carbon nanotubes/carbon black filled natural rubber composites

Abstract

Natural rubber (NR) based nanocomposites containing a constant amount (50 phr) of standard furnace carbon black and carbon nanotube (CNT) at a concentration from 1 to 5 phr have been prepared. Their dielectric (dielectric permittivity and dielectric loss) and microwave properties (coefficients of absorption and reflection of the electromagnetic waves and electromagnetic interference shielding effectiveness) have been investigated in the 1–12 GHz frequency range. The results achieved allow recommending CNTs as second filler for NR based composites to afford specific absorbing properties.     

Nano‐sized TiO2‐reinforced natural rubber composites prepared by latex compounding method

This paper addresses nano‐sized titanium dioxide (TiO₂) reinforced natural rubber composites. Micro‐sized TiO₂ is simultaneously prepared to make a comparison with the composites containing nano‐sized TiO₂. To improve the dispersion of TiO₂, this study also suggests a new method of incorporating TiO₂. Aqueous dispersions of micro‐ and nano‐sized TiO₂ at the loadings of 0, 2, 4, 6, and 8 parts by weight per hundred parts of resin were dispersed in natural rubber latex, and then the resulting compounds were dried prior to mixing it with other ingredients on a two‐roll mill. By applying this technique, the homogeneity of the compound is significantly improved. This can be clearly seen from the enhancement of tensile properties and morphological characteristics where the optimum loading was found at 6 parts by weight per hundred parts of resin of micro‐ and nano‐sized TiO₂. Adding TiO₂ results in delayed scorch times and curing times wherein the curing process of filled compounds is shorter than the unfilled compound. J. VINYL ADDIT. TECHNOL., 23:200–209, 2017. © 2015 Society of Plastics Engineers