Peel Adhesion of Natural Rubber Bonded to Polyethylene Terephthalate: Effect of Crosslinking on Rate/Temperature Response

Laminates consisting of natural rubber (NR) sandwiched between cloth fabric and polyester film were pulled apart at various rates and temperatures in a T-peel geometry. Peel energies for joints containing uncrosslinked or lightly-crosslinked NR did not obey simple time-temperature superposition. This behavior is attributed to strain-induced crystallization during peeling. However, when the rubber was highly crosslinked, strain crystallization seems to be absent, as peel energies now can be WLF shifted to form a mastercurve.     

Preparation of graphene oxide/natural rubber composites by latex cocoagulation: Relationship between microstructure and reinforcement

Graphene oxide(GO) has recently attracted substantial interest as a possible reinforcing agent for next generation rubber composite materials. In this research, GO was incorporated in natural rubber(NR) composites through latex co-coagulation technique. The microstructures of GO/NR composites were characterized through a combination of transmission electron microscope, scanning electron microscope, X-ray diffraction, Fourier transform infrared spectroscopy, and Differential scanning calorimeter. The results showed that highly exfoliated GO sheets were finely dispersed into NR rubber matrix with strong interface interaction between GO and NR. The mechanical properties of the GO/NR composites were further evaluated. The results showed that the tensile strength, tear strength and modulus can be significantly improved at a content of less than 2 phr. Especially,GO exhibited specific reinforce mechanism in NR due to the stress-induced crystallization effects of NR. The stress transfer from the NR to the GO sheets and the hindrance of GO sheets to the stress-induced crystallization of NR were further displayed in stress–strain behavior of GO/NR composites. These enhanced properties were attributed to the high surface area of GO sheets and highly exfoliated microstructures of GO sheets in NR.     

两种橡胶/有机累托石纳米复合材料的结构与性能

比较了用熔体法制备的有机累托石(OR)/丁苯橡胶(SBR)以及有机累托石(OR)/天然橡胶(NR)2种纳米复合材料的结构与性能.TEM和XRD对材料的分析显示,由于橡胶基体的性质差异,OR/SBR为典型的插层型结构,而OR/NR为插层型和部分剥离型混合结构.应力应变行为的研究表明,随着OR用量的增加,OR/SBR的拉伸强度和拉断伸长率均增大,这主要是分子链滑移和填料的取向造成的.对于拉伸结晶型橡胶NR,由于部分剥离型填料的增强作用,NR的定伸应力随填料用量的增加而逐渐提高.由于对结晶的阻碍作用,当OR用量为20份时,OR/NR的拉伸强度有所降低.纳米累托石的加入可以显著提高SBR和NR的硬度和撕裂强度.热失重分析表明,OR/橡胶纳米复合材料与相应的纯橡胶相比,热稳定性提高,在NR体系中更为显著.     

“Mechanism of the self-reinforcement of cross-linked NR generated through the strain-induced crystallization”

The author proposed new models and concept for the self-reinforcement of NR. The first model indicates that general rubber vulcanizate consists of the heterogeneous structure, partially continuous cross-linked phase (75%) and continuous uncross-linked phase (25%). In addition, the author proposed other new models and concept for the strain-induced crystallization in vulcanized NR, in which the strain-induced crystallization takes place in the uncross-linked phase in cross-linked rubber. In the uncross-linked phase under large extension, molecular flow and orientation occur due to the very high compressive, shear and tensile stresses generated by the surrounding hard cross-linked phases, which makes the strain-induced crystallization possible in the uncross-linked phase. As macroscopic extension increases, the crystallization spreads over the whole uncross-linked phases, thus the uncross-linked phase changes its character from original soft rubber to the strong super network consisting of a bundle of extended molecules interconnected at the crystals. The characteristic phenomena observed in the stress-strain relation of NR such as the stress-upturn, high tensile strength and large stress-softening (Mullins effect) can be reasonably explained using these models and concepts.     

Effect of non‐rubber substances on vulcanization kinetics of natural rubber

Effect of non‐rubber components on vulcanization kinetics of natural rubber was studied with the use of a Rheometer MDR‐2000. The results show that the rate constants of induction period and curing period of natural rubber (NR) are greater than that of natural rubber extracted with acetone (NR_E), and the activation energies of induction period and curing period of NR are lower than that of NR_E. The activation energy of induction period of NR is reduced by16.9% and the activation energy of curing period of NR is reduced by 3.2% compared to the activation energies of NR_E. The time t_dis of NR is shorter than that of NR_E at the same temperature. © 2012 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Crystallization behavior and spherulite growth rate of isotactic polypropylene in isotactic polypropylene/natural rubber based thermoplastic elastomers

The melting and crystallization behavior of isotactic polypropylene/natural rubber (PP/NR) based thermoplastic elastomers (TPEs) were investigated using differential scanning calorimetry. The samples were scanned at a heating rate of 10°C/min under nitrogen atmosphere. The effects of blend ratio on the melting and crystallization characteristics of the blends were analyzed. Normalized crystallinity is unchanged by the addition of small amount of NR, but as the amount of rubber increases crystallinity increased for the 30/70 NR/PP and lowered for the 50/50 NR/PP blend system. Morphology of the blend was analyzed using scanning electron microscopy (SEM). Blend ratio showed a pronounced influence on the phase morphology of the NR/PP TPEs. As the amount of NR increases more than 50 wt % the system changes from dispersed to cocontinuous structure. Hot‐stage polarizing optical microscopy (POM) was used to study the radial growth of spherulite as a function of blend ratio, cooling rate, and crystallization temperature. Spherulite growth rate is marginally influenced by the rubber inclusions. The spherulite morphology observed under polarized optical microscopy is influenced by the blend morphology. It was found that for the cocontinuous 50/50 blend system, spherulites are much different from the usual appearance under polarized light. Attempts have been made to correlate the crystallization behavior with the morphology of the blend. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Improved mechanical properties and special reinforcement mechanism of natural rubber reinforced by in situ polymerization of zinc dimethacrylate

The peroxide‐cured natural rubber (NR) was reinforced by in situ polymerization of zinc dimethacrylate (ZDMA). The experimental results showed NR could be greatly reinforced by ZDMA. The tensile strength and the hardness of NR/ZDMA composites increased with the content of ZDMA. The reinforcement mechanism was studied further. Both high crosslinking density provided by ionic crosslinking and strain‐induced crystallization improved the mechanical properties. The crosslinking density was determined by an equilibrium swelling method and the crystallization index was measured by Wide‐angle X‐ray diffraction (WXRD). When the amount of ZDMA was high, the ability of strain‐induced crystallization decreased, due to the strong interactions between the rubber phase and the hard poly‐ZDMA (PZDMA) nanodispersions. At the moment, the increasing ionic crosslinking density made up for the effect of the drop of the strain‐induced crystallization, and played a more important role in the reinforcement. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

生胶挤出中的动态结晶及应力振荡行为

用Instron毛细管流变仪研究了NR、BR和NR/BR并用胶的流动行为,讨论了一定条件下形成不稳定流动的原因及影响因素。发现在较低温度下NR由于动态结晶而产生压力突增现象及不规则应力振荡;在较高温度下BR由于粘滑效应而产生规则应力振荡。这两种振荡都不可能在一般加工温度和剪切速率范围内完全加以避免,因此采用NR/BR并用胶是解决高含胶率胶料稳定挤出的有效途径。     

Static deformation of low structure HAF black‐loaded (SBR+NR) rubber blend

The stress‐strain behavior of different concentrations of low‐structure high abrasion furnace black (HAF‐LS, N326)‐loaded rubber blend of styrene butadiene rubber and natural rubber (SBR+NR) of equal parts was measured. Moduli of elasticity and the n‐measure of such blends were calculated using different approaches. An anomaly, of modulus of elasticity, found at 50 phr may be attributed to carbon black reinforcement and to an early crystallization of stretched natural rubber (NR) in the blend. These assumptions are confirmed through the measurement of the swelling factor as a function of time of swelling in kerosene.     

Natural rubber/nitrile butadiene rubber/hindered phenol composites with high-damping properties

New natural rubber (NR)/nitrile butadiene rubber (NBR)/hindered phenol (AO-80) composites with high-damping properties were prepared in this study. The morphological, structural, and mechanical properties were characterized by atomic force microscopy (AFM), polarized Fourier transform infrared spectrometer (FTIR), dynamic mechanical thermal analyzer (DMTA), and a tensile tester. Each composite consisted of two phases: the NR phase and the NBR/AO-80 phase. There was partial compatibility between the NR phase and the NBR/AO-80 phase, and the NR/NBR/AO-80 (50/50/20) composite exhibited a co-continuous morphology. Strain-induced crystallization occurred in the NR phase at strains higher than 200%, and strain-induced orientation appeared in the NBR/AO-80 phase with the increase of strain from 100% to 500%. The composites had a special stress–strain behavior and mechanical properties because of the simultaneous strain-induced orientation and strain-induced crystallization. In the working temperature range of a seismic isolation bearing, the composites (especially the NR/NBR/AO-80 (50/50/20) composite) presented a high loss factor, high area of loss peak (TA), and high hysteresis energy. Therefore, the NR/NBR/AO-80 rubber composites are expected to have important application as a high-performance damping material for rubber bearing.     

Synergistic reinforcement of nanoclay and carbon black in natural rubber

The synergistic reinforcement of nanoclay (NC) and carbon black (CB) in natural rubber (NR) has not been much studied. Therefore, the reinforcement mechanism was probed using synchrotron wide‐angle X‐ray diffraction and transmission electron microscopy (TEM) observation and analyzed in terms of tube model theory. A synergistic effect in reinforcement between NC and CB was proved by the marked enhancement in tensile strength from 11.4 MPa for neat NR to 28.2 MPa for NR nanocomposite with 5 wt% NC and 20 wt% CB. From a study of crystallization under deformation it was found that crystallization plays a less important role in the reinforcement of NR/NC/CB. Analysis using tube model theory provided more evidence for the synergistic effect. NR containing a combination of NC and CB exhibited an increase of topological tube‐like constraints in comparison with NR/CB. That is to say, in NR/NC/CB nanocomposites, a CB–NC local filler network, as indicated by TEM images, induced a more entangled structure in which mobility of rubber chains was hindered for lateral fluctuations by the presence of neighboring chains. The synergistic reinforcement of NC and CB in NR/NC/CB nanocomposites can be reasonably understood as due to the formation CB–NC local filler networks. Copyright © 2010 Society of Chemical Industry     

Effects of Characteristics of Rubber,Mixing and Vulcanization on the Structure and Properties of Rubber/Clay Nanocomposites by Melt Blending

Summary: Three rubber‐based nanocomposites, natural rubber (NR), styrene‐butadiene rubber (SBR), and ethylene‐propylene‐diene rubber (EPDM) matrixes, were prepared with octadecylamine modified fluorohectorite (OC) by melt blending. X‐ray diffraction (XRD) revealed that the SBR/OC and EPDM/OC nanocomposites exhibited a well‐ordered intercalated structure and a disordered intercalated structure, respectively. In the case of the NR/OC nanocomposite, it exhibited an intermediate intercalated and even exfoliated structure. These results were in good agreement with transmission electron microscopy (TEM) observations. Furthermore, in the NR/OC and SBR/OC systems, the mixing process played a predominant role in the formation of nanometer‐scale dispersion structure, whereas the intercalated structure of EPDM/OC formed mainly during the vulcanization process. The tensile strength of SBR/OC and EPDM/OC nanocomposites loading 10 phr OC was 4–5 times higher than the value obtained for the corresponding pure rubber vulcanizate, which could be ascribed to the slippage of the rubber molecules and the orientation of the intercalated OC. For the strain‐induced crystallization NR, the exfoliated OC efficiently improved the modulus of the NR/OC nanocomposite relative to the pure NR. However, its hindrance on NR crystallization during the tensile process may be the main reason for the decrease in tensile strength of NR/OC.

XRD diffraction patterns of three nanocomposites containing 10 phr organoclay.     

国产稀土异戊橡胶的性能

研究了国产稀土异戊橡胶(NdIR)生胶、硫化胶的的应变/应力、混炼、生热以及磨耗性能,并与天然橡胶(NR)和俄罗斯产钛系异戊橡胶(TiIR)进行了对比。结果表明:当顺式-1,4结构含量和门尼粘度超过临界值时,异戊橡胶生胶能产生"应变诱导结晶"现象。NdIR的硫化特性与NR和TiIR相当,且炭黑分散性和物理机械性能也与二者接近。从动态粘弹谱图可以预测,NdIR硫化胶的抗湿滑性优于NR和TiIR,滚动阻力接近NR和TiIR,是一种值得期待的适宜轮胎使用的新型胶种。     

高抗疲劳性轿车轮胎胎侧胶的配方设计与性能研究

研究反式-1,4-丁二烯-异戊二烯共聚橡胶(TBIR)的结晶性能、加工性能以及NR/BR/TBIR并用胶在轿车轮胎胎侧胶中的应用。结果表明:相比反式-1,4-聚异戊二烯(TPI),TBIR的结晶性能微弱、玻璃化温度更低;相比天然橡胶(NR)和顺丁橡胶(BR),TBIR具有优异的加工性能;相比NR,BR和TPI,TBIR的耐老化性能优异;相比NR/BR和NR/BR/TPI并用胶,NR/BR/TBIR(并用比为45/35/20)并用胶的物理性能优异,生热降低,耐裂口扩展性能显著提高。TBIR作为一种新型合成橡胶材料可应用于高耐疲劳轿车轮胎。     

Effect of fatty acids on the strain‐induced crystallization of natural rubber detected by tear energy measurements

The strain‐induced crystallization of natural rubber (NR) was investigated by the measurement of the tear energy of a crosslinked blend consisting of NR and noncrystalline styrene–butadiene rubber (SBR). When NR was dispersed into the SBR matrix, the tear energy of SBR increased at various temperatures and tear rates. After the application of the principle of time–temperature superposition to the tear energy according to the Williams–Landel–Ferry equation, two distinct curves were found for the NR/SBR blend with respect to the reduced tear rate, despite the fact that the tear energy of SBR or the SBR/SBR blend gave its own single composite curve. When the fatty acid in the NR/SBR blend was removed by acetone extraction, the tear energy of the blend drew a single composite curve. The conversion of the two curves into the single composite curve for the NR/SBR blend suggested that the tear energy depended on the strain‐induced crystallization of NR dispersed in the SBR matrix, which was suppressed by the removal of the fatty acid. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 98: 613–619, 2005     

Quantification of the distribution of carbon black in natural rubber/polybutadiene blends by differential scanning calorimetry

The distribution of carbon black (CB) in uncured blends of natural rubber (NR) and polybutadiene (PB) can be quantified using DSC. The crystallization temperature of PB containing CB, measured during cooling from the melt, increases with the CB loading. This phenomenon was used to calculate the CB content in PB and conversely in NR in NR/PB/CB mixtures. Two different blends containing N550 CB were studied. A deeper analysis was performed over the entire composition range of NR/PB blends filled with N234 CB. Two different trends were highlighted depending on composition. Below 50 wt% of NR in the elastomer phase, the crystallization temperature of PB is higher than that of pure PB indicating that a part of the CB is dispersed in PB. Above 50 wt% of NR, the crystallization temperature of PB is lower than that of pure PB, indicating that the whole CB is in the NR phase and that fractionated crystallization of PB simultaneously occurs. Both phenomena are consistent as the dispersed phase morphology is favored by a large increase of the matrix viscosity by the filler. For both CBs, the results indicate that CB has larger affinity for NR than for PB. This tendency was confirmed by transmission electron microscopy. POLYM. ENG. SCI., 2009. © 2009 Society of Plastics Engineers     

Molecular weight between physical entanglements in natural rubber: A critical parameter during strain-induced crystallization

The purpose of this paper is to clarify the role of crosslink density of natural rubber on its strain-induced crystallization. A series of new in situ synchrotron X-ray diffraction experiments were performed during the stretching process of weakly and highly vulcanized natural rubber samples. The experimental data have been analysed in terms of both crystallite size and crystallization rate. Moreover, a careful treatment of previously published data that might appear contradictory has been done. The comparison between all these data, coming from NR of different origins and with different crosslinking states, demonstrates that the molecular weight between physical entanglements in natural rubber appears as a key parameter for strain-induced crystallization (SIC).     

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.     

Crack growth resistance of natural rubber reinforced with carbon nanotubes

Carbon nanotubes (CNTs)/natural rubber (NR) composites are prepared through ultrasonically assisted latex mixing combined with a two-roll mixing process, and their crack growth behavior is examined to evaluate their fatigue properties. CNTs/NR shows a reinforcement of crack growth resistance compared to unfilled NR. The measurements of the tearing energy and the hysteresis loss show that CNTs/NR exhibits more energy dissipation than NR. Also, strain-induced crystallization (SIC) around the crack tip of CNTs/NR and NR composite was examined at different fatigue strains. CNTs positioned at the crack tip led to a crack branching at low fatigue strain, which is responsible for the improvement of the crack growth resistance of CNTs/NR. However, the inclusion of CNTs renders NR higher crystallinity and larger crystallization zones in front of the crack tip at high fatigue strains, which allows more energy dissipation during crack growth. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2020 , 137, 48447.     

Parameters governing strain induced crystallization in filled natural rubber

A series of in situ synchrotron X-ray diffraction experiments are performed during the stretching of weakly and highly vulcanized carbon black (CB), silica and grafted silica filled natural rubber sample (NR). Conversely to literature, Mullins effect observed after one stretching cycle modifies the strain induced crystallization (SIC) behaviour of the sample. The onset of crystallization is ruled by the strain amplification induced by the filler presence. Moreover, fillers (CB and silica) behave as additional crosslinks into NR network, through filler-rubber interactions that either accelerate or slow down the crystallization rate depending on NR matrix chemical crosslink density. This is consistent with the assumption that effective network density, which is due to chemical crosslinks, entanglements, and filler-rubber interactions, controls the crystallization rate.