黏土/天然橡胶纳米复合材料的制备及性能

利用乳液插层法制备了黏土／天然橡胶纳米复合材料,研究了该复合材料的力学性能、应力应变行为、耐磨性、气体阻隔性和耐老化性能。结果表明,黏土／天然橡胶纳米复合材料与高耐磨炭黑(N330)、白炭黑增强橡胶相比,邵尔A型硬度、定伸应力和撕裂强度较高,拉伸强度相当。黏土、N330以及白炭黑对天然橡胶的拉伸结晶有影响,填料用量对材料拉伸强度的影响存在最佳值。黏土／天然橡胶纳米复合材料具有良好的耐磨性、气体阻隔性和耐老化性能。     

熔体法制备有机黏土/橡胶纳米复合材料的结构及性能

将有机黏土(OC)分别加入到天然橡胶(NR)、丁苯橡胶(SBR)、丁基橡胶(IIR)和三元乙丙橡胶(EPDM)中,通过熔体法制备了纳米复合材料。探讨了橡胶黏度及其分子结构对OC在复合材料中分散状况的影响,研究了复合材料的力学性能。结果表明,在以NR为基体的复合材料中。OC片层分散均匀,且剥离程度较高;在SBR,IIR,EPDM中,OC以插层结构为主,且插层效果从大到小的顺序依次为SBR,IIR,EPDM。与相应的纯胶相比,OC／NR纳米复合材料的定伸应力提高,拉伸强度和扯断伸长率有所下降;OC／SBR,OC／IIR,OC／EPDM纳米复合材料的定伸应力变化不大,拉伸强度和扯断伸长率明显提高,且OC／SBR和OC／EPDM复合材料的撕裂强度提高。     

Structure and properties of nitrile rubber (NBR)–clay nanocomposites by co‐coagulating NBR latex and clay aqueous suspension

Nitrile rubber (NBR)–clay nanocomposites were prepared by co‐coagulating the NBR latex and clay aqueous suspension. Transmission electron microscopy showed that the silicate layers of clay were dispersed in the NBR matrix at the nano level and had a planar orientation. X‐ray diffraction indicated that there were some nonexfoliated silicate layers in the NBR–clay nanocomposites. Stress–strain curves showed that the silicate layers generated evident reinforcement, modulus, and tensile strength of the NBR–clay nanocomposites, which were significantly improved with an increase in the amount of clay, and strain‐at‐break was higher than that of the gum NBR vulcanizate when the amount of clay was more than 5 phr. The NBR–clay nanocomposites exhibited an excellent gas barrier property; the reduction in gas permeability in the NBR–clay nanocomposites can be described by Nielsen's model. Compared with gum NBR vulcanizate, the oxygen index of the NBR–clay nanocomposites increased slightly. The feasibility of controlling rubber flammability via the nanocomposite approach needs to be evaluated further. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 3855–3858, 2003     

Natural rubber/poly(ethylene‐co‐vinyl acetate)‐blend‐based nanocomposites

Natural rubber (NR)/poly(ethylene‐co‐vinyl acetate) (EVA) blend–clay nanocomposites were prepared and characterized. The blend nanocomposites were prepared through the melt mixing of NR/EVA in a ratio of 40/60 with various amounts of organoclay with an internal mixer followed by compression molding. X‐ray diffraction patterns revealed that the nanocomposites formed were intercalated. The formation of the intercalated nanocomposites was also indicated by transmission electron microscopy. Scanning electron microscopy, used to study the fractured surface morphology, showed that the distribution of the organoclay in the polymer matrix was homogeneous. The tensile modulus of the nanocomposites increased with an increase in the organoclay content. However, an increase in the organoclay content up to 5 phr did not affect the tensile strength, but the organoclay reduced this property when it was increased further. This study also indicated that a low silicate content dispersed in the blend matrix was capable of increasing the storage modulus of the material. The addition of the organoclay also increased the decomposition temperature of the NR/EVA blends. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 353–362, 2006     

Dispersion and properties of natural rubber‐montmorillonite nanocomposites fabricated by novel in situ organomodified and latex compounding method

Natural rubber (NR)‐montmorillonite (MMT) nanocomposites were prepared by a novel in situ organomodified and latex compounding method, followed by melt compounding technique. Effects of cationic surfactant on MMT dispersion, curing characteristic, mechanical, and dynamical properties were investigated. The number of layers in the layered MMT stack was determined by Small‐Angle X‐Ray Scattering (SAXS). The dispersion of MMT tends to form high ordered structure in NR‐MMT masterbatch when cationic surfactant of more than 4 phr was used. The morphology of Na‐MMT shows partly intercalated and exfoliated structure in the matrix after mixing and hot pressing process with reduced number of layers compared to the pristine MMT. The use of cationic surfactant over 4 phr introduces a plasticizing effect resulting in the reduction of crosslink density, hardness and modulus, but increase in tensile strength due to higher interfacial adhesion between NR and MMT as determined by Maeir‐Goritz model and Field Emission Scanning Electron Microscopy (FESEM). The optimum cationic surfactant loading is observed at 4 phr with the highest stable bonds, which result in the highest crosslink density, tear strength and storage modulus while the lowest Payne effect and tan delta at 60°C. POLYM. ENG. SCI., 59:1830–1839, 2019. © 2019 Society of Plastics Engineers     

Mechanical properties of surface‐modified ultra‐high molecular weight polyethylene fiber reinforced natural rubber composites

The mechanical properties of ultra‐high molecular weight polyethylene (UHMWPE) fibers reinforced natural rubber (NR) composites were determined, and the effects of fiber surface treatment and fiber mass fraction on the mechanical properties of the composites were investigated. Chromic acid was used to modify the UHMWPE fibers, and the results showed that the surface roughness and the oxygen‐containing groups on the surface of the fibers could be effectively increased. The NR matrix composites were prepared with as‐received and chromic acid treated UHMWPE fibers added 0–6 wt%. The treated UHMWPE fibers increased the elongation at break, tear strength, and hardness of the NR composites, especially the tensile stress at a given elongation, but reduced the tensile strength. The elongation at break increased markedly with increasing fiber mass fraction, attained maximum values at 3.0 wt%, and then decreased. The tear strength and hardness exhibited continuous increase with increasing the fiber content. Several microfibrillations between the fiber and NR matrix were observed from SEM images of the fractured surfaces of the treated UHMWPE fibers/NR composites, which meant that the interfacial adhesion strength was improved. POLYM. COMPOS., 38:1215–1220, 2017. © 2015 Society of Plastics Engineers     

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.     

Nanomodified fillers in chloroprene‐rubber‐compatibilized natural rubber/acrylonitrile–butadiene rubber blends

Because of the structural dissimilarity, natural rubber (NR) and acrylonitrile–butadiene rubber (NBR) are immiscible, and compatibilizers are used during their blending. Neoprene or chloroprene rubber (CR) has a polar chlorine part and a nonpolar hydrocarbon part. Also, it has many advantageous properties, such as oil resistance, toughness, a dynamic flex life, and adhesion capacity. Hence, it is not less scientific to use CR as a compatibilizer in the blending of NBR with NR. Because many fewer studies on the use of neoprene as a compatibilizer in NR–NBR blend preparation are available, efforts were made to prepare 20:80 NR–NBR blends with CR with the aim of studying the effect of poly(ethylene oxide) (PEO)‐coated nano calcium silicate along with nano N‐benzylimine aminothioformamide and stearic acid coated nano zinc oxide in the sulfur vulcanization of the blends. The optimum dosage of the compatibilizer was derived by the determination of the tensile properties, tear resistance, abrasion resistance, compressions set, and swelling values. The tensile strength, tear resistance, and abrasion resistance of the gum vulcanizates of the blend were improved by the compatibilizing action of CR up to 5 parts per hundred parts of rubber (phr). In the case of the filled vulcanizates, the tear resistance, 300% modulus, hardness, and abrasion resistance increased with increasing dosage of nano calcium silicate. The elongation at break percentage decreased as expected when there was an increase in the modulus. Scanning electron microscopy was used to study the phase morphology of the blends. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Electrolytic admicellar polymerization of pyrrole on natural rubber/clay nanocomposites

Organic–inorganic composites consisting of natural rubber (NR), polypyrrole (PPy), and sodium montmorillonite (Na‐MMT) were synthesized via electrolytic admicellar polymerization. A constant potential of 9 volts was chosen for the synthesis. The PPy concentration was fixed at 100 mM, and the clay contents were varied from 1 to 7 parts per hundred of rubber (phr). The synthesized nanocomposites were characterized by Fourier transform infrared spectroscopy (FTIR), X‐ray diffraction (XRD), scanning electron microscopy, and transmission electron microscopy (TEM), together with thermal stability (TGA), mechanical properties, and electrical conductivity (σ_dc) studies. The FTIR spectra indicated the characteristic peaks of both PPy and MMT clay and also evidenced a slight interaction between the PPy chain and the clay layers, verifying the success of electrolytic admicellar polymerization. XRD and TEM results pointed out the good dispersion of clay platelets in the polymer matrix, suggesting an exfoliated structure. The morphology of the nanocomposites was greatly dependent on the amount of MMT clay, especially at a 7 phr loading. The initial modulus and tensile strength of the nanocomposites containing the 7 phr loading were about four and two times higher, compared with unfilled NR/PPy, respectively. Thermal stability studies revealed a slight improvement in the decomposition temperature for the PPy component by the clay layers, whereas the opposite trend was found for the NR component. More interestingly, the electrical conductivity of the admicelled rubber increased significantly (～ 19–32 times) with increasing clay contents from 1 to 7 phr, in comparison with unfilled NR/PPy. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

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.     

Effect of clay on properties of polyimide‐clay nanocomposites

Effect of clay on mechanical, thermal, moisture absorption, and dielectric properties of polyimide‐clay nanocomposites was investigated. Nanocomposites of polyimide (ODA‐BSAA) hybridized with two modified clay (PK‐802 and PK‐805) were synthesized for comparison. The silicate layers in the polymer matrix were intercalated/exfoliated as confirmed by wide‐angle X‐ray diffraction and transmission electron microscopy. Thermal stability, moisture absorption, and storage modulus for these nanocomposites are improved as hybridized clay increases. Reduced dielectric constants due to the hybridization of layered silicates are observed at frequencies of 1 kHz–1 MHz and temperatures of 35–150°C. The tetrahedrally substituted smectite (PK‐805) resulted in higher mechanical strength and dielectric constants than those of octahedrally substituted smectite (PK‐802), which could be attributed to their stronger ionic bonding between clay layer and polymer matrix. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 104: 318–324, 2007     

Preparation and characterization of organoclay‐rubber nanocomposites via a new route with skim natural rubber latex

Skim natural rubber latex (SNRL) is a protein rich by‐product obtained during the centrifugal concentration of natural rubber (NR) latex. A new method to recover rubber hydrocarbon and to obtain nanocomposites with organoclay (OC) was investigated. The approach involved treatment of SNRL with alkali and surfactant, leading to creaming of skim latex and removal of clear aqueous phase before addition of OC dispersion. Clay mixed latex was then coagulated to a consolidated mass by formic acid, followed by drying and vulcanization like a conventional rubber vulcanizate. X‐ray diffraction (XRD) studies revealed that NR nanocomposites exhibited a highly intercalated structure up to a loading of 15 phr (parts per hundred rubber) of OC. Transmission electron microscopy studies showed a highly exfoliated and intercalated structure for the NR nanocomposites at loadings of 3–5 phr organically modified montmorillonite (OMMT). The presence of clay resulted in a faster onset of cure and higher rheometric torque. The rubber recovered from skim latex had a high gum strength, and a low amount of OC (5 phr) improved the modulus and tensile strength of NR. The high tensile strength was supported by the tensile fractography from scanning electron microscopy. Thermal ageing at 70°C for 6 days resulted in an improvement in the modulus of the samples; the effect was greater for unfilled NR vulcanizate. The maximum degradation temperature was found to be independent of the presence and concentration of OC. The increased restriction to swelling with the loading of OC suggested a higher level of crosslinking and reinforcement in its presence. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 3277–3285, 2006     

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.     

Preparation and properties of novel natural rubber/organo‐vermiculite nanocomposites

Polymer‐layered silicate nanocomposites have an attracting increasing attention over recent years because of their unique mechanical, thermal, and other properties. In this article, a new kind of natural rubber (NR)/organo‐vermiculite (OVMT) nanocomposites were investigated. The vermiculite (VMT) was intercalated by cetyltrimethylammonium bromide with ball mill method. The intercalation led to an increase of the d₍₀₀₁₎ of VMT from 1.46 nm to 4.51 nm. NR/OVMT nanocomposites were prepared via a melt process in a HAAKE mixer and were analyzed by X‐ray diffraction and scanning electron microscope observations. The mechanical properties of the vulcanized nanocomposites were tested. It was found that the tensile strength and the elongation at the breaking point of the NR/OVMT nanocomposites loading 15 phr of the OVMT reached 28.4 MPa and 623.2%, respectively. The 300% modulus, tear strength, and hardness (Shore A) of the nanocomposites increased with the increase of the OVMT loading. The thermal properties of the nanocomposites were investigated by dynamic mechanical analysis, and the results showed that the storage modulus and the glass transition temperature of the nanocomposites were increased. POLYM. COMPOS., 2009. © 2008 Society of Plastics Engineers     

Nanocomposite systems based on unsaturated polyester and organo‐clay

Unsaturated polyester (UP) systems give rise to numerous possible approaches in synthesizing nanocomposites. A simultaneous mixing method was used to synthesize UP‐resin/organo‐clay nanocomposites. The effects of various mixing processes, using several organically‐modified clay types, were investigated. The incorporation of these organo‐clays resulted in an intercalated structure, the extent of which depended mainly on the type of the clay organic treatment. Organo‐clays that exhibited the highest intercalation levels were further studied using a sequential mixing method. The UP‐alkyd (without styrene) was mixed with different organo‐clays. Processing parameters such as mixing modes, applied shearing levels, clay contents, and mixing‐temperatures were investigated. Prolonged high shear levels promoted the intercalation and exfoliation of the silicate layers, resulting in a better dispersion of clay particles. The high shear levels effects were achieved by vigorous mechanical mixing and were intensified by using large amounts of clay and optimized matrix viscosity. Rheological studies of the nanocomposites were found complementary and in correlation with morphological and thermal characterization. This methodological approach provides a basis for understanding the structuring processes involving the formation of the UP/clay nanocomposites and establishing materials‐processing‐structure interrelations. Polym. Eng. Sci. 45:174–186, 2005. © 2005 Society of Plastics Engineers.     

Effects of PBO fiber and clay on the mechanical,morphological, and dynamic mechanical properties of NR/HDPE blends

Poly(p‐phenylene‐2,6‐benzobisoksazole) (PBO) and natural rubber (NR)/high density polyethylene (HDPE) composites were melt‐blended in a Haake internal mixer. The tensile strength, tensile modulus, and impact strength increased with fiber loading and optimized at 20%. Incorporation of clay into the NR/HDPE/PBO composites resulted in an improvement of tensile strength for NR/HDPE/PBO composites compared to the systems without clay. However, addition of clay was only effective at low contents (5–7.5%). Additional improvement of tensile strength, tensile modulus, and impact strength of the hybrid composite was observed on addition of liquid natural rubber (LNR). Scanning electron micrographs of the samples had indicated that the presence of clay decreased the domain size of the dispersed phase. Results on dynamic response showed that incorporation of clay and LNR into the composites had increased the storage modulus and reduced the tan δ. The shift of glass transition temperature (T_g) to higher values for composites also indicated good interaction between the fiber and the matrix. POLYM. ENG. SCI., 2011. © 2010 Society of Plastics Engineers.     

Research of styrene‐butadiene rubber/silicon‐aluminum oxides nanotube binary nanocomposites

A novel silicon‐aluminum oxides (Si‐Al) nanotubes with length ranging from 500 to 1000 nm were introduced to fabricate the styrene‐butadiene rubber (SBR)/Si‐Al nanotube binary nanocomposites. Scanning electron microscope observation showed the Si‐Al nanotubes up to 20 parts per hundred parts of rubber (phr) loading level were dispersed well in SBR matrix. Mechanical properties tests, thermogravimetry analysis and dynamic mechanical thermal analysis revealed that the Si‐Al nanotubes have the effects on improving shore A hardness, tensile strength, tear strength, initial decomposition temperature, and storage modulus while lower the maximum loss factor (tan δ) of the SBR/Si‐Al nanotube binary nanocomposites. FTIR spectra analysis showed that new Si O bond was generated between the hydroxyl group of Si‐Al nanotube and the coupling reagent Si69. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Preparation and properties of ethylene propylene rubber (EPR)–clay nanocomposites based on maleic anhydride‐modified EPR and organophilic clay

Ethylene propylene rubber–clay nanocomposites (EPR–CNs) were prepared by melt‐compounding maleic anhydride modified EPR (EPR‐MA) with organophilic clay, and their properties were examined. Silicate layers of organophilic clay were found to exfoliate and homogeneously disperse into the nanometer level in the nanocomposites by transmission electron microscopy observation. EPR–CNs exhibited higher tensile moduli compared to EPR‐MA and composites containing conventional fillers such as carbon black, talc. The storage moduli of EPR–CNs were also higher than those of EPR‐MA and the conventional composites. Creep resistances of EPR–CNs were much improved compared for EPR‐MA. Degree of swelling in hexadecane was remarkably restricted. Improvement of these properties is caused because dispersed silicate layers have much large interface with the EPR matrix and are thought to strongly restrain the EPR polymer chains. Nanocomposite technology using small amount of silicate layers is useful to improve properties of thermoplastic elastomer. Various kinds of thermoplastic elastomers are expected to be produced by loading of silicate layers with or without conventional fillers. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 93: 758–764, 2004     

Preparation and characteristics of nitrile rubber (NBR) nanocomposites based on organophilic layered clay

The effect of clay modification on organo‐montmorillonite/NBR nanocomposites has been studied. Organo‐montmorillonite/NBR nanocomposites were prepared through a melt intercalation process. NBR nanocomposites were characterized by X‐ray diffraction (XRD), transmission electron microscopy (TEM), dynamic mechanical thermal analysis (DMTA) and a universal testing machine (UTM). XRD showed that the basal spacing in the clay increased, which means that the NBR matrix was intercalated in the clay layer galleries. On TEM images, organo‐montmorillonite (MMT) particles were clearly observed, having been exfoliated into nanoscale layers of about 10–20 nm thickness from their original 40 µm particle size. These layers were uniformly dispersed in the NBR matrix. The DMTA test showed that for these nanocomposites the plateau modulus and glass transition temperature (T_g) increased with respect to the corresponding values of pure NBR (without clay). UTM test showed that the nanocomposites had superior mechanical properties, ie strength and modulus. These improved properties are due to the nanoscale effects and strong interactions between the NBR matrix and the clay interface. Copyright © 2003 Society of Chemical Industry     

Polypropylene–clay blends compatibilized with MAH‐g‐POE

A series of new Polypropylene (PP)–clay blends, containing 5 wt % clay, were prepared by melt compounding with maleic anhydride grafted poly(ethylene‐co‐octene) (MAH‐g‐POE) as the compatibilizer by varying its content from 0 to 20 wt %. The effect of MAH‐g‐POE on the PP–clay miscibility was examined by X‐ray diffraction (XRD), scanning electronic microscope (SEM) observation, differential scanning calorimeter (DSC) analysis, dynamic mechanical thermal analysis (DMTA), and rheological testing in sequence. The results showed that the addition of MAH‐g‐POE could improve the dispersion of clay layers in PP matrix and promoted the interaction between PP molecules and clay layers. At 10 wt % MAH‐g‐POE, the PP–clay blend exhibited a highest value of Tc,onset and Tg as well as a biggest melt storage modulus (G′), indicating the greatest PP–clay interaction. On the other hand, improved toughness and stiffness coexisted in blends with 5–10 wt % loading of MAH‐g‐POE. In view of SEM and DMTA observations, MAH‐g‐POE was well miscible with the PP matrix, even with the concentration up to 20 wt %. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 99: 2558–2564, 2006