Ionic elastomer blends of zinc salts of maleated natural rubber and carboxylated nitrile rubber: Effect of grafted maleic anhydride

Zinc neutralized maleated natural rubbers (Zn‐MNR) were prepared by solution grafting and neutralization with zinc acetate in one‐step. It was later used for blending with carboxylated nitrile rubber (XNBR) in the composition of 50/50 parts by weight. The effect of grafted anhydride content (1.2, 1.6, 2.0, and 2.5% wt of NR) on the tensile properties of ionic rubber blends (Zn‐MNR/XNBR) was investigated. The tensile strength of the ionic blends was found to be greater than those of pure rubbers. The modulus, tensile, and tear strength of the blends dramatically increased with increasing levels of grafted anhydride. The ionic rubber blends also possessed superior physical properties compared to those of the corresponding nonionic rubber blends (MNR/XNBR). Dynamic mechanical thermal analysis and scanning electron microscopic studies were performed to verify the process of mixing. Fourier transform infrared spectroscopic studies were carried out to characterize the nature of specific intermolecular interactions between Zn‐MNR and XNBR chain segments. The results indicated that the ion‐ion (Zn⁺ ‐COO^?) interactions between Zn‐MNR and XNBR are formed at the interface, which provides the mean of compatibilization in the ionic rubber blends. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007     

Phenolic resin‐crosslinked natural rubber/clay nanocomposites: Influence of clay loading and interfacial adhesion on strain‐induced crystallization behavior

Nanocomposites of natural rubber (NR) and pristine clay (clay) were prepared by latex mixing, then crosslinked with phenolic resin (PhOH). For comparative study, the PhOH‐crosslinked neat NR was also prepared. Influence of clay loading (i.e., 1, 3, 5, and 10 phr) on mechanical properties and structural change of PhOH‐crosslinked NR/clay nanocomposites was studied through X‐ray diffraction (XRD), transmission electron microscopic (TEM), wide‐angle X‐ray diffraction (WAXD), tensile property measurement, and Fourier transform infrared spectroscopy (FTIR). XRD and TEM showed that the clay was partly intercalated and aggregated, and that the dispersion state of clay was non‐uniform at higher clay loading (>5 phr). From tensile test measurement, it was found that the pronounced upturn of tensile stress was observed when the clay loading was increased and a maximum tensile strength of the PhOH‐crosslinked NR/clay nanocomposites was obtained at 5 phr clay. WAXD observations showed that an increased addition of clay induced more orientation and alignment of NR chains, thereby lowering onset strain of strain‐induced crystallization and promoting crystallinity of the NR matrix during tensile deformation. FTIR investigation indicated a strong interfacial adhesion between NR matrix and clay filler through a phenolic resin bridge. This suggested that the PhOH did not only act as curative agent for crosslinking of NR, but it also worked as coupling agent for promoting interfacial reaction between NR and clay. The presence of strong interfacial adhesion was found to play an important role in the crystallization process, leading to promotion of mechanical properties of the PhOH‐crosslinked NR/clay nanocomposites. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43214.     

Morphological evolution and mechanical property enhancement of natural rubber/polypropylene blend through compatibilization by nanoclay

Nanocomposites of natural rubber (NR)/polypropylene (PP) (80/20 wt %) blends filled with 5 phr pristine clay were prepared by melt‐mixing process. Effects of clay incorporation technique via conventional melt‐mixing (CV) and masterbatch mixing (MB) methods on nanostructure and properties of the blend nanocomposites were investigated. The XRD, SAXS, WAXD, and TEM results showed that the clays in the NR/PP blend nanocomposites were presented in different states of dispersion and were locally existed at the interface between NR and PP as well as dispersed in the NR matrix. The presence of clay caused unique morphological evolution such as fine fibrillar PP domains. The tensile strength was improved over the unfilled NR/PP blends by 53% and 224%, and the storage modulus at 25 °C was increased by 78% and 120% for the NR/PP/clay nanocomposites prepared by CV and MB methods, respectively. Significant improvement in both properties was particularly obtained from the MB method due to finer dispersion fibrillar PP phase in the NR matrix and stronger interfacial adhesion between NR and PP fibers, as suggested from DMA. The oil resistance of blend nanocomposites was also improved over that of the unfilled NR/PP blend, and this property was further progressed by the masterbatch mixing method. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 44574.     

Influence of incorporation sequence of silica nanoparticles on morphology,crystallization behavior,mechanical properties,and thermal resistance of melt blended thermoplastic natural rubber

Thermoplastic natural rubber nanocomposites based on epoxidized natural rubber (ENR) and polypropylene blends at a fixed blend ratio of 50/50 wt% reinforced with small amount (2.5 wt%) of nanosilica (SiO₂) were prepared by melt‐mixing through three different incorporation sequences in an internal mixer. The effects of incorporation techniques on morphology, crystallization behavior, mechanical properties, dynamic, rheological characteristics, and thermal resistance of thermoplastic natural rubber (TPNR) nanocomposites were investigated. It was found that the dispersion of nanosilica in TPNRs was significantly dependent on the incorporation sequence. In the case where SiO₂ was premixed in ENR before blending with polypropylene (PP), the final morphology showed the good dispersion of SiO₂ in ENR phase, while the SiO₂ particles were localized near the PP interface when SiO₂ was premixed the in PP first. Whereas, when the three components were simultaneously mixed, the SiO₂ particles were mainly dispersed in the PP phase. It was also found that the improvements of Young's modulus, tensile strength, damping behavior, and thermal stability of TPNR nanocomposites were more pronounced when the SiO₂ particles localized in ENR phase. By contrast, the presence of SiO₂ particles in PP domain either near the interface or inside the PP phase affected the reduction in crystallinity of PP phase and showed a negative effect on mechanical properties due to the poor interface interaction between PP and SiO₂ particles. POLYM. COMPOS., 33:1911–1920, 2012. © 2012 Society of Plastics Engineers     

Stress Transfer Function for Interface Assessment in Composites with Plasma Copolymer Functionalized Carbon Fibres

Radio-frequency-induced plasma copolymerization of acrylic acid/1,7-octadiene was used to produce a range of functionalized plasma copolymer coatings with controlled degree of adhesion. The single-fibre fragmentation test was used to characterize the adhesion of plasma copolymer coated fibres to epoxy resin. The cumulative stress transfer function (CSTF) and Kelly-Tyson approaches were used to evaluate the degree of adhesion. By continuous monitoring of the fragmentation process, it was found that the mechanical performance of a composite material could be evaluated using the CSTF methodology at strain well below saturation. The degree of debonding was a good measure of relative interface/interphase adhesive strength. The trend in the CSTF is consistent with the propagation of interfacial debonds during the test. For a completely debonded fibre a normalized CSTF value, referred as stress transfer efficiency (STE), was found to provide a more consistent analysis that was able to differentiate between fibres with similar degrees of debonding. The calculated values of interfacial shear strength (IFSS) were only valid for a fully debonded fibre (1,7-octadiene plasma homopolymer coating) where the assumption of a constant shear stress, as in the Kelly-Tyson model, applied. However, IFSS did not provide the same ranking. Where debonding does not occur, the stress transfer efficiency also provides a sensitive measure of the interface/interphase performance. Improved adhesion over the untreated-unsized carbon fibre was observed for both of the plasma copolymer-coated and commercially treated carbon fibres. Since there is a concentration dependence of carboxyl groups on adhesion, the mechanism appears to relate to covalent bond formation with the epoxy group. Plasma copolymer coatings on carbon fibres also causes an increased tensile strength and Weibull modulus.     

Performance of pineapple leaf fiber–natural rubber composites: The effect of fiber surface treatments

Composites of natural rubber (NR) and short pineapple leaf fiber (PALF) were prepared on a laboratory two‐roll mill. The influences of untreated fiber content and orientation on the processing and mechanical properties of the composites were investigated. The dependence of extent of orientation on fiber concentration was also established. Sodium hydroxide (NaOH) solutions (1, 3, 5, and 7% w/v) and benzoyl peroxide (BPO) (1, 3, and 5 wt % of fiber) were used to treat the surfaces of PALFs. FTIR and scanning electron microscope (SEM) observations were made of the treatments in terms of chemical composition and surface structure. The tensile strength and elongation at break of the composites were later studied. The fiber–matrix adhesion was also investigated using SEM technique. It was found that all surface modifications enhanced adhesion and tensile properties. The treatments with 5% NaOH and 1% BPO provided the best improvement of composite strength (28 and 57% respectively) when compared with that of untreated fiber. The PALF‐NR composites also exhibited better resistance to aging than its gum vulcanizate, especially when combined with the treated fibers. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 1974–1984, 2006     

Influence of fiber modification on interfacial adhesion and mechanical properties of pineapple leaf fiber‐epoxy composites

Three kinds of surface treatment, that is, the alkalization (5% w/v NaOH aqueous solution), the deposition of diglycidyl ether of bisphenol A (DGEBA) from toluene solution (1% w/v DGEBA), and the alkalization combined with the deposition of DGEBA (5% w/v NaOH/1% w/v DGEBA) were applied to modify interfacial bonding and to enhance mechanical properties of pineapple leaf fiber (PALF) reinforced epoxy composites. The fiber strength and strain were measured by single fiber test and the fiber strength variation was assessed using Weibull modulus. Furthermore, a fragmentation test was used to quantify the interfacial adhesion of PALF‐epoxy composite. It was verified that the interfacial shear strength of modified PALFs was substantially higher than that of untreated PALF by almost 2–2.7 times because of the greater interaction between the PALFs and epoxy resin matrix. The strongest interfacial adhesion was obtained from the fibers that had been received the alkalization combined with DGEBA deposition. Moreover, the flexural and impact properties of unidirectional PALF‐epoxy composites were greatly enhanced when reinforced with the modified PALFs due to an improvement in interfacial adhesion, particularly in the synergetic use of 5% NaOH and 5% NaOH/1% DGEBA. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Strain‐induced crystallization behavior of phenolic resin crosslinked natural rubber/clay nanocomposites

Nanocomposites of natural rubber (NR) and unmodified clay were prepared by latex compounding method. Phenolic resin (PhOH) was used to crosslink NR. Crosslinked neat NR was also prepared for comparison. The structure–property relationship of uncrosslinked and crosslinked NR/clay nanocomposites was examined to verify the reinforcement mechanism. Microstructure of NR/clay nanocomposites was studied by using transmission electron microscopic (TEM), X‐ray diffraction (XRD), wide angle X‐ray diffraction (WAXD), and small angle X‐ray scattering (SAXS) analyses. The results showed the evidence of intercalated clay together with clay tactoids for the nanocomposite samples. The highest tensile strength was achieved for the crosslinked NR/clay nanocomposite. The onset strain of deformation induced the crystallization of NR for nanocomposites was found at almost the same strain, and furthermore their crystallization was developed at lower strain than that of the crosslinked neat NR because of the clay orientation and alignment. However, at high strain region, the collaborative crystallization process related to the clay dispersion and conventional crosslink points in the NR was responsible to considerably high tensile strength of the crosslinked NR/clay nanocomposite. Based on these analyses, a mechanistic model for the strain‐induced crystallization and orientational evolution of a network structure of PhOH‐crosslinked NR/clay nanocomposite was proposed. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42580.     

The role of nanofillers on (natural rubber)/(ethylene vinyl acetate)/clay nanocomposite in blending and foaming

Nanocomposite foams were fabricated from 60/40 wt% ethylene vinyl acetate (EVA)/natural rubber (NR) blends by using azodicarbonamide as a blowing agent. Two different nanofillers (sodium montmorillonite and organoclay) were employed to study their effects on foam properties. The results were also compared with conventional (china clay)‐filled foams. Transmission electron microscopy, X‐ray diffraction, scanning electron microscopy, and three‐dimensional Microfocus X‐ray computed tomography scanning analysis were performed to characterize the EVA/NR blend morphology and foam structures. The results revealed that the nanofiller acted as a blend compatibilizer. Sodium montmorillonite was more effective in compatibilization, generating better phase‐separated EVA/NR blend morphology and improving foam structure. Higher filler loading increased the specific tensile strength of rubber foams. The rubber nanocomposite foam showed superior specific tensile strength to the conventional rubber composite foam. The elastic recovery and compressive strength of the nanocomposite foams decreased with increasing filler content, whereas the opposite trend was observed for the conventional composite foams with china clay. The thermal conductivity measurement indicated that the nanofiller had better beneficial effect on thermal insulation over china clay filler. From the present study, the nanofillers played an important role in obtaining better blend morphology as compatibilizer, rather than the nucleating agent and the nanofiller content of 5 phr (parts by weight per hundred parts of rubber) was recommended for the production of EVA/NR nanocomposite foams. J. VINYL ADDIT. TECHNOL., 21:134–146, 2015. © 2014 Society of Plastics Engineers     

Influence of incorporation methods of ATH on microstructure,elastomeric properties,flammability, and thermal decomposition of dynamically vulcanized NR/PP blends

Flame‐retardant thermoplastic vulcanizates (TPVs) of natural rubber (NR)/polypropylene (PP) (60/40 wt %) blends filled with alumina trihydrate (ATH) were prepared with an internal mixer. To increase the properties of flame‐retardant NR/PP TPV, the new mixing method, stepwise masterbatch mixing (SMB) method was adopted. The effects of SMB method along with different ATH loadings on microstructure and properties of NR/PP TPVs were investigated. Conventional one‐step mixing (CV) method was also studied for comparison. Transmission electron microscopy analysis showed that different processes led to a variation in microstructural homogeneity, which imposed various effects on blend properties. The mechanical properties of TPVs changed with ATH loading, and the strength of the samples obtained from SMB method was higher than those of CV method. LOI and cone calorimetry tests revealed that the flame retardancy of NR/PP blends dramatically increased at higher ATH loading. Furthermore, the increment level of flame retardancy was accelerated in the blends produced particularly through SMB method, resulting from homogeneity of local ATH distribution in NR/PP blend. Greater combustion resistance of blends prepared from SMB route were confirmed by thermogravimetry and pyrolysis‐gas chromatography–mass spectrometry techniques. Finally, a burning mechanism between filler structure and flammability of NR/PP TPVs obtained from CV and SMB methods was discussed. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46231.