Effect of two types of layered silicate on mechanical and barrier properties of hydrogenated acrylonitrile butadiene rubber (HNBR)/layered silicate nanocomposites

Abstract

The role of the type of layered silicate platelets, OMMT and rectorite on the mechanical properties, aging resistance and oxygen permeation properties of HNBR/layered silicate nanocomposites was investigated. The effect of peroxide vulcanising agent on the dispersion of layered silicate in the HNBR matrix was also studied. HNBR was mechanically mixed with layered silicate via melt blending method. The results of the test show remarkable improvement in tensile strength, tear strength, aging resistance and oxygen permeation properties of HNBR nanocomposites than that of unfilled HNBR. It is obvious that the OMMT filled nanocomposites have far better properties than that of rectorite filled HNBR.     

氢化丁腈橡胶/有机蒙脱土纳米复合材料的性能

采用熔体插层法制备了氢化丁腈橡胶/有机蒙脱土纳米复合材料,采用透射电镜和X射线衍射仪对复合材料的结构进行了表征,并研究了复合材料的应力应变行为、耐老化性能、耐溶剂性能和动态力学性能。实验结果表明:制备了一种插层型纳米复合材料,复合材料的耐老化性能和耐溶剂性能良好,并且随蒙脱土含量的增大而增加;动态黏弹谱(DMA)测试显示,纳米复合材料的玻璃化转变温度升高,且具有较低的滚动阻力,复合材料的动态力学性能优良。     

氢化丁腈橡胶/有机蒙脱土纳米复合材料的结构与性能

采用机械混炼法制备氢化丁腈橡胶／有机蒙脱土纳米复合材料，并对复合材料的微观结构及性能进行了研究。透射电镜和X衍射结果显示，制得一种剥离型纳米复合材料；与纯氢化丁腈硫化橡胶相比，氢化丁腈橡胶／有机蒙脱土纳米复合材料具有优良的力学性能，并且随蒙脱土含量的增加而提高；TGA结果显示，氢化丁腈橡胶／有机蒙脱土纳米复合材料的热稳定性能提高。     

Morphology,mechanical properties,and thermal stability of rigid PVC/clay nanocomposites

PVC/Poly(ε‐caprolactone) (PCL)/organophilic‐montmorillonite (OMMT) and PVC/Polylactide (PLA)/OMMT nanocomposites were prepared by a two‐step process. PCL/OMMT and PLA/OMMT master batches were prepared by melt blending using a two‐roller mill first, and then they were blended with PVC via extrusion. PVC/OMMT nanocomposites were also prepared using a two‐roller mill. Morphology, mechanical properties, and thermal stability were investigated. The formation of exfoliated or intercalated nanocomposites was confirmed by X‐ray diffraction (XRD) and transmission electron microscopy (TEM). Only the PVC/PCL/OMMT nanocomposite showed both higher tensile strength and stiffness than unfilled PVC. Atomic force microscopy (AFM) indicated dependency of this behavior not only on the clay dispersion, but also on the adhesion between the OMMT and the polymer matrix. Furthermore, scanning electron microscopy (SEM) showed that the large plastic deformation of the PVC/PCL matrix also contributed to the strength increase of the PVC nanocomposites. The effect of PCL/OMMT on the improvement of the thermal stability of PVC was remarkable while the effect of PLA/OMMT was moderate. POLYM. ENG. SCI., 2011. © 2010 Society of Plastics Engineers.     

Solid‐state mechanical properties of polypropylene/nylon 6/clay nanocomposites

The mechanical and thermomechanical properties as well as microstructures of polypropylene/nylon 6/clay nanocomposites prepared by varying the loading of PP‐MA compatibilizer and organoclay (OMMT) were investigated. The compatibilizer PP‐MA was used to improve the adhesion between the phases of polymers and the dispersion of OMMT in polymer matrix. Improvement of interfacial adhesion between the PP and PA6 phases occurred after the addition of PP‐MA as confirmed by SEM micrographs. Moreover, as shown by the DSC thermograms and XRD results, the degree of crystallinity of PA6 decreased in the presence of PP‐MA. The presence of OMMT increased the tensile modulus as a function of OMMT loading due to the good dispersion of OMMT in the matrix. The insertion of polymer chains between clay platelets was verified by both XRD and TEM techniques. The viscosity of the nanocomposites decreased as PP‐MA loading increased due to the change in sizes of PA6 dispersed phase, and the viscosity increased as OMMT loading increased due to the interaction between the clay platelets and polymer chains. The clay platelets were located at the interface between PP and PA6 as confirmed by both SEM and TEM. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Structure,morphology, and properties of HNBR filled with N550, SiO2, ZDMA,and two of three kinds of fillers

The vulcanization properties, mechanical properties of hydrogenated nitrile rubber (HNBR) filled with carbon black (N550), zinc dimethacrylate (ZDMA), SiO₂ independently and two of three kinds of fillers together were investigated, respectively. The filler‐dispersion was characterized by the transmission electron microscopy (TEM) and dynamic mechanical properties. The results showed that HNBR composite filled with SiO₂ or ZDMA displayed high tensile strength, elongation at break and compression set. The HNBR composite filled with N550 displayed low compression set, tensile strength and elongation at break. The dispersion of SiO₂ in HNBR compound was better than that in HNBR vulcanizates because of SiO₂ particles self‐aggregation in vulcanizing processing. ZDMA particles with micron rod‐like and silky shape in HNBR compounds changed into near‐spherical poly‐ZDMA particles with nano size in HNBR vulcanizates by in situ polymerization reaction. The N550 particles morphology exhibited no much change between HNBR compounds and vulcanizates. N550/ZDMA have the most effective reinforcement to HNBR and the appropriate amount of ZDMA is about 25% of total filler amount by weights. The theory prediction for Payne effect (dispersion of the filler) shown by the dynamic properties is identical with actual state observed by TEM. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Effect of polymer matrix/montmorillonite compatibility on morphology and melt rheology of polypropylene nanocomposites

In this study, Ca²⁺‐montmorillonite (Ca²⁺‐MMT) and organo‐montmorillonite (OMMT) were modified by three compatibilizers with different degrees of polarity [poly(ethylene glycol) (PEG), alkyl‐PEG, and polypropylene (PP)‐g‐PEG]. PP/MMT nanocomposites were prepared by melt blending and characterized using X‐ray diffraction and transmission electron microscopy. The results showed the degree of dispersion of OMMT in the PP/PP‐g‐PEG/OMMT (PMOM) nanocomposite was considerably higher than those in the PP/PEG/OMMT and PP/alkyl‐PEG/OMMT nanocomposites, which indicated that the dispersion was relative to the compatibility between modified OMMT and PP matrix. Linear viscoelasticity of PP/MMT nanocomposites in melt states was investigated by small amplitude dynamic rheology measurements. With the addition of the modified MMT, the shear viscosities and storage modulus of all the PP/MMT nanocomposites decreased. It can be attributed to the plasticization effect of PEG segments in the three modifiers. This rheological behavior was different from most surfactant modified MMT nanocomposites which typically showed an increase in dynamic modulus and viscosity relative to the polymer matrix. The unusual rheological observations were explained in terms of the compatibility between the polymer matrix and MMT. In addition, the mechanical properties of PP/MMT nanocomposites were improved. A simultaneous increase in the tensile strength and toughness was observed in PP/PMOM nanocomposites. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

OMMT/ZDMA协同增强HNBR复合材料的性能研究

以离子聚合物(ZDMA)、有机蒙脱土作补强剂,采用机械混炼法制备了氢化丁腈橡胶/有机蒙脱土纳米复合材料,研究了OMMT/ZDMA协同作用对氢化丁腈橡胶纳米复合材料性能的影响,并使用扫描电镜(SEM)、热失重分析(TG)、差示扫描量热分析(DSC)及力学性能测试等方法分析了复合材料的结构和性能。结果表明,有机蒙脱土用量较少可达到纳米级分散,材料力学性能得到相应改善;用量较大时,OMMT团聚几率增大,可能形成应力集中点,影响复合材料力学性能。热性能分析表明,加入有机蒙脱土在一定程度上提高了HNBR的热稳定性。     

丁腈橡胶/有机蒙脱土纳米复合材料的结构及性能研究

通过机械共混法制备了丁腈橡胶/有机蒙脱土（NBR/OMMT）纳米复合材料。运用X射线衍射（XRD）和透射电镜（TEM）表征了复合材料的纳米结构。通过硫化仪研究了有机蒙脱土用量对复合材料硫化性能的影响,同时研究了复合材料的力学性能、热空气老化性、耐油性和热稳定性。结果表明：有机蒙脱土的加入在一定程度上提高了复合材料的力学性能、热空气老化性、耐油性及热稳定性,而且对复合材料的硫化性能有明显的影响。     

Preparation,morphology, and properties of organo‐montmorillonite/nitrile butadiene rubber nanocomposites

Organo‐montmorillonite/nitrile butadiene rubber (OMMT/NBR) nanocomposites were prepared by co‐coagulating process, and then were combined with rubber ingredient and vulcanized by traditional rubber mixing procedure. The SEM micrographs of the nanocomposites showed uniform dispersion of the OMMT particles in NBR. The ATR‐FTIR spectra illustrated the existence of montmorillonite in the nanocomposites. The XRD patterns further indicated the structure of nanocomposites, and confirmed an effective intercalation of NBR in the interlayer space of the OMMT. Moreover, the tensile strength and elongation at break of nanocomposites tended to increased rapidly with increasing OMMT loading, due to the reinforcing properties of OMMT to NBR. In addition, the TGA and DTA curves demonstrated the thermal performance of the nanocomposites enhanced. Furthermore, the addition of OMMT accelerated the vulcanization process. POLYM. COMPOS., 34:1809–1815, 2013. © 2013 Society of Plastics Engineers     

Fabrication and characterization of electrospun fibrous nanocomposite scaffolds based on poly(lactide‐co‐glycolide)/poly(vinyl alcohol) blends

Tissue engineering involves the fabrication of three‐dimensional scaffolds to support cellular in‐growth and proliferation. Ideally, the scaffolds should be similar to the native extracellular matrix (ECM). Electrospun polymer nanofibrous scaffolds are appropriate candidates for ECM mimetic materials since they mimic the nanoscale properties of ECM. Electrospun polymer nanocomposites based on poly(lactide‐co‐glycolide) (PLGA)/poly(vinyl alcohol) (PVA) and organically modified montmorillonite (OMMT) were prepared by a solution intercalation technique followed by electrospinning. The morphology of fibrous scaffolds based on these nanocomposites was investigated using scanning electron microscopy. The scaffolds showed highly porous structure within the nanofibres of diameters ranging from 400 to 700 nm. X‐ray diffractometry gave evidence of good dispersion of the OMMT in the blends with exfoliated morphology. Measurements of the water uptake and water contact angle of the fibrous scaffolds indicated significant improvement in the hydrophilicity of the scaffolds. Evaluations of the mechanical properties and unrestricted somatic stem cell culture of the electrospun fibrous nanocomposite scaffolds revealed that the PLGA90/PVA10/1.5% OMMT and PLGA90/PVA10/3% OMMT samples are the most useful from the tissue engineering application viewpoint. Copyright © 2010 Society of Chemical Industry     

溴化丁基橡胶/天然橡胶/有机蒙脱土纳米复合材料的结构与性能研究

采用机械混炼法制备了溴化丁基橡胶/天然橡胶/有机蒙脱土(BIIR/NR/OMMT)纳米复合材料,对其亚微观结构与性能进行了表征。实验结果表明:OMMT片层以剥离形式均匀分散于橡胶基体中;OMMT能够明显促进橡胶硫化反应,并使BIIR和NR两相的交联同步性加强;纳米复合材料具有优异的物理机械性能和热稳定性能。     

Preparation and properties of chlorosulfonated polyethylene/organomontmorillonite nanocomposites

Chlorosulfonated polyethylene (CSPE)/organomontmorillonite (OMMT) nanocomposites were prepared by a melt intercalation method. The microstructure of the nanocomposites was characterized by transmission electron microscopy and X‐ray diffraction. The effects of the OMMT content on the mechanical properties and swelling behavior of the nanocomposites were investigated. The improvement in the thermal stability of the nanocomposites was determined by thermogravimetric analysis. Transmission electron microscopy and X‐ray diffraction showed that CSPE was intercalated into OMMT. When the OMMT content was lower than 12 wt %, the nanocomposites showed excellent tensile properties, which was attributed to nanometer‐scale dispersion. The introduction of a small amount of OMMT also improved the thermal stability and swelling behavior, which was attributed to the gas barrier action of the OMMT layers. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

UHMWPE/organoclay nanocomposites fabricated by melt intercalation under continuous elongational flow: Dispersion,thermal behaviors and mechanical properties

The preparation of ultra‐high‐molecular weight polyethylene (UHMWPE)/organoclay nanocomposites by continuous elongational flow technique was investigated in a novel eccentric rotor extruder (ERE). The distribution and dispersion morphologies of organo‐modified montmorillonite (OMMT) layers were revealed and observed by ash determination, wide angle X‐ray diffraction and transmission electron microscopy. The thermal and thermal‐mechanical behaviors were characterized by differential scanning calorimeter, thermal gravimetric analysis and dynamic mechanical thermal analysis. The mechanical performances was measured by tensile and impact test. The morphologies of the nanocomposites evidenced that the OMMT layers can be well intercalated or/and exfoliated by UHMWPE matrix, then the fabrication mechanism of intercalated and exfoliated OMMT structures under continuous elongational flow was discussed. The ideal dispersion of OMMT in UHMWPE matrix obviously improved the crystallinity and the mechanical properties at a certain concentration of OMMT loading, indicating that the lower OMMT addition can lead an effective strengthening and toughening for UHMWPE. POLYM. ENG. SCI., 59:547–554, 2019. © 2018 Society of Plastics Engineers     

Preparation and structure and mechanical properties of poly(styrene‐b‐butadiene)/clay nanocomposites

Star‐shaped and linear block thermoplastic poly(styrene‐b‐butadiene) copolymer (SBS)/organophilic montmorillonite clays (OMMT) were prepared by a solution approach. The intercalation spacing in the nanocomposites and the degree of dispersion of nanocomposites were investigated by X‐ray diffraction (XRD) and transmission electron microscopy (TEM), respectively. The mechanical properties, dynamic mechanical properties, and thermal stability of these nanocomposites were determined. Results showed that SBS chains were well intercalated into the clay galleries and an intercalated nanocomposite was obtained. The mechanical strength of nanocomposites with the star‐shaped SBS/OMMT were significantly increased. The addition of OMMT also gave an increase of the elongation, the dynamic storage modulus, the dynamic loss modulus, and the thermal stability of nanocomposites. The increase of the elongation of nanocomposites indicates that SBS has retained good elasticity. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 3430–3434, 2004     

Effect of different nanoparticles on thermal,mechanical and dynamic mechanical properties of hydrogenated nitrile butadiene rubber nanocomposites

Organically modified and unmodified montmorillonite clays (Cloisite NA, Cloisite 30B and Cloisite 15A), sepiolite (Pangel B20) and nanosilica (Aerosil 300) were incorporated into hydrogenated nitrile rubber (HNBR) matrix by solution process in order to study the effect of these nanofillers on thermal, mechanical and dynamic mechanical properties of HNBR. It was found that on addition of only 4 phr of nanofiller to neat HNBR, the temperature at which maximum degradation took place (T_max) increased by 4 to 16°C, while the modulus at 100% elongation and the tensile strength were enhanced by almost 40–60% and 100–300% respectively, depending upon nature of the nanofiller. It was further observed that T_max was the highest in the case of nanosilica‐based nanocomposite with 4 phr of filler loading. The increment of storage modulus was highest for sepiolite‐HNBR and Cloisite 30B‐HNBR nanocomposites at 25°C, while the modulus at 100% elongation was found maximum for sepiolite‐HNBR nanocomposite at the same loading. A similar trend was observed in the case of another grade of HNBR having similar ACN content, but different diene level. The results were explained by x‐ray diffraction, transmission electron microscopy, and atomic force microscopy studies. The above results were further explained with the help of thermodynamics. Effect of different filler loadings (2, 4, 6, 8, and 16 phr) on the properties of HNBR nanocomposites was further investigated. Both thermal as well as mechanical properties were found to be highest at 8 phr of filler loading. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Influence of molecular parameters on thermal,mechanical, and dynamic mechanical properties of hydrogenated nitrile rubber and its nanocomposites

The present work derives a relationship between structure and properties of hydrogenated nitrile rubber (HNBR) in the presence as well as absence of nanofillers. Four different grades of HNBR were selected to examine the influence of polarity, unsaturation, and molecular weight on thermal, mechanical, and dynamic mechanical properties of the elastomers and particularly their nanocomposites. An increase in thermal stability, tensile strength, modulus at 100% elongation as well as storage modulus of the unfilled rubber was observed with increase in polarity (acrylonitrile content). Different nanofillers, such as montmorillonite, sepiolite, and nanosilica were used to improve the above properties of the unfilled rubber. Interestingly, a reverse trend of thermal properties was observed for the nanocomposites with acrylonitrile variation, although mechanical and dynamic mechanical properties exhibited similar trend to those of the unfilled rubber. These properties, however, gradually deteriorated as the level of unsaturation on the polymer backbone was increased. On addition of the nanofillers, it was found that the improvement in thermal and mechanical properties was higher for the elastomer having 5.5% diene content. The results were explained by X‐ray Diffraction, Atomic Force Microscopy, Energy Dispersive X‐ray mapping, and swelling studies. POLYM. ENG. SCI., 2010. © 2010 Society of Plastics Engineers     

Mechanical and rheological properties of PP/SEBS/OMMT ternary composites

The microstructure and mechanical properties of polypropylene (PP)/OMMT binary nanocomposites and PP/styrene‐6‐(ethylene‐co‐butylenes)‐6‐styrene triblock copolymer (SEBS)/OMMT ternary nanocomposites were investigated using X‐ray diffraction (XRD), transmission electron microscopy (TEM), and rheology and electromechanical testing machine. The results show that the organoclay layers are mainly intercalated and partially exfoliated in the PP‐based nanocomposites. The additions of SEBS and OMMT have no significant effect on the crystallization behavior of PP. At the same time, it can be concluded that the polymer chains of PP and SEBS have intercalated into the organoclay layers and increase the gallery distance after blending process based on the analytical results from TEM, XRD, and rheology, which result in the form of a percolated nanostructure in the PP‐based nanocomposites. The results of mechanical properties show that SEBS filler greatly improve the notched impact strength of PP, but with the sacrifice of strength and stiffness. OMMT can improve the strength and stiffness of PP and slightly enhance the notched impact strength of PP/PP‐g‐MA. In comparison with neat PP, PP/OMMT, and PP/SEBS binary composites, notched impact toughness of the PP/SEBS/OMMT ternary composites significantly increase. Moreover, the stiffness and strength of PP/SEBS/OMMT ternary nanocomposites are slightly enhanced when compared with neat PP. It is believed that the synergistic effect of both SEBS elastomer and OMMT nanoparticles account for the balanced mechanical performance of the ternary nanocomposites. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

有机蒙脱土对天然橡胶/丁苯橡胶的补强及增容作用

采用机械混炼法制备了天然橡胶(NR)/丁苯橡胶(SBR)/有机蒙脱土(OMMT)纳米复合材料,采用TEM和XRD对复合材料的亚微观结构进行了表征,并对复合材料的表观交联密度、静态力学性能、动态力学性能和硫化热效应进行了研究。结果表明,复合材料为剥离型纳米复合材料;OMMT能够明显提高纳米复合材料的交联密度和静态力学性能;OMMT导致NR/SBR共混胶动态损耗因子降低,并且能够促使NR和SBR玻璃化转变温度更为接近,起到了增容作用;OMMT实现了NR和SBR两相的同步硫化。     

Polypropylene/organically modified Sabah montmorillonite nanocomposites: Surface modification and nanocomposites characterization

The aim of the work is to extract, purify, and organically modify montmorillonite (MMT) of Lahad Datu, Sabah bentonite. The octadecylamine treated Sabah MMT (S‐OMMT) (2–8 wt%) was then melt blended with polypropylene (PP) and maleated polypropylene (PPgMAH) (10 wt%) via single screw nanomixer extruder followed by injection molding into test samples to examine the mechanical, thermal, and morphological properties of PP/S‐OMMT nanocomposites. Unmodified Sabah MMT (S‐MMT) and commercial grade MMT (Nanomer 1.30P) filled PP nanocomposites were also characterized for comparison purpose. X‐ray diffraction results showed that the interlayer spacing of S‐MMT increased after organic modification as Fourier transform infra‐red and elemental analysis evidenced the presence of octadecylamine. PP/S‐OMMT nanocomposites showed a better dispersion and strength compared to PP/Nanomer 1.30P nanocomposites due to its smaller MMT platelet size. differential scanning calorimetry and Thermogravimetry analysis revealed that the thermal stability and crystallinity of neat PP improved with the addition of all types of MMT. Dynamic mechanical analyzer showed that PP nanocomposites have higher storage modulus (E′) values than the neat PP over the whole temperature range. The new PP/S‐OMMT nanocomposites showed a comparable performance with PP/Nanomer 1.30P nanocomposites exhibiting promising future applications of S‐MMT in polymer/MMT nanocomposites. POLYM. COMPOS., 2011. © 2011 Society of Plastics Engineers