不同改性蒙脱土对ENR/PVC共混型TPV填充效果的研究

采用熔融插层法制备了聚氯乙烯/蒙脱土(PVC/MMT)插层产物,再将该产物与环氧化天然橡胶(ENR)在密炼机中进行熔融共混制备ENR/PVC/MMT共混型热塑性弹性体(TPV),研究了不同改性MMT对共混物力学性能、热稳定性以及动态力学性能的影响。结果表明:二甲基双十八烷基铵改性蒙脱土(MMT-2C18)能显著提高ENR/PVC共混型TPV的拉伸强度,无机MMT能显著提高ENR/PVC的断裂伸长率,十八烷基铵改性蒙脱土(MMT-C18)会降低TPV的拉伸强度和断裂伸长率;有机改性MMT会促进TPV中PVC的降解,使得复合材料的热稳定性降低;动态热力学分析显示,MMT可使复合材料的储能模量增加,其中有机改性MMT使材料的损耗因数(tanδ)曲线峰强降低,峰宽变宽。     

Modification of PVC/ENR blends by electron beam irradiation

The effects of electron irradiation, with doses ranging from 20 to 100 kGy on the physical properties of poly(vinyl chloride)/epoxidised natural rubber blends (PVC/ENR50 blends) were investigated. The enhancement in tensile strength, elongation at break, hardness, and aging properties of the blends have confirmed the positive effect of irradiation on the blends. Crosslinking of the ENR50 phase proved to play a major role in the improvement of mechanical properties of blends. The results also revealed that at any blend composition the enhancement in properties depends on the irradiation dose which controls the degree of radiation-induced crosslinking. The single glass transition temperature obtained confirms that the blends remain miscible upon irradiation.     

Thermal and mechanical properties of electron beam irradiated poly(vinyl chloride)/polystyrene blends

The effect of electron beam irradiation on the thermal and mechanical properties of poly(vinyl chloride)/polystyrene (PVC/PS) blends and PVC/PS blends containing epoxidized natural rubber (ENR) was studied. The thermogravimetric analysis study showed that the thermal decomposition of the plasticized PVC individual polymer goes through two stages, whereas PS decomposes through one stage. However, the temperature of the maximum rate of reaction (T_max) of PS is much higher than that for PVC and their blends. Meanwhile, the T_max was found to increase with increasing PS ratios in the blend. The thermal stability of PVC/PS blends was greatly increased after electron beam irradiation in comparison with unirradiated blends. Moreover, the addition of ENR to PVC/PS increased the thermal stability. On the other hand, the mechanical properties in terms of tensile strength and elongation at break of PVC/PS blends are lower than pure PVC polymer because of the immiscibility. However, the addition of ENR to the PVC/PS (80/20) blend increased the elongation at break from 114 to 321% associated with a small effect on the tensile properties. These behaviors were supported by structure morphology studies observations, which indicate an improvement in the interfacial adhesion between the phases. POLYM. COMPOS., 2008. © 2008 Society of Plastics Engineers     

Irradiation Crosslinking of PVC/ENR Blend: A Comparative Study with the Respective Homopolymers

Electron beam initiated crosslinking on a 50/50 poly(vinyl chloride)/epoxidized natural rubber blend was studied in the absence and presence of 3 phr trimethylolpropane triacrylate (TMPTA). Comparative studies were made on PVC and ENR homopolymers. The samples were irradiated by using a 3.0 MeV electron beam machine at doses ranging from 20 to 200 kGy in air and room temperature. The changes in tensile strength, gel fraction and tan δ curves of the samples were investigated. The enhancement in tensile strength, gel fraction, glass transition temperature together with a concomitant decline tan δ peak revealed that under the irradiation conditions employed, the PVC/ENR blend crosslinked by electron beam irradiation. Addition of 3 phr TMPTA found to be effective in increasing the degree of crosslinking. Similar observations were also noted for the homopolymers PVC and ENR, implying that both PVC and ENR in the blend undergo crosslinking to a certain extent.     

P(MMA-MA)/OMMT纳米复合材料对PVC共混改性研究

通讨原位插层法制备聚(甲苯丙烯酸甲酯一丙烯酸甲酯)有机化蒙脱十「P(MMA-MA)/OMMT}纳米复合材料,并用其对聚氯乙烯(PVC)讲行共混改性。通讨扫描电镜(SEM)热失重分析(TGA)、动杰力学分析(DMA)拉伸和冲击等力学性能测试研究了共混物的两相相容性、热稳定性及力学性能。结果表明:共混体系两相间有很奸的相容性;随着纳米复合材料添加量的增加,共混体系的耐热性能、储能模量、玻璃化温度和力学性能逐渐增加。当纳米复合材料与PVC共混比达到20/100时,共混体系在10%失重率下的失重温度比纯PVC捍高了17.4℃,玻璃化温度比纯PVC捍高了4.7℃。当纳米复合材料与PVC共混比达到30/100时,体系的综合力学性能最奸,冲击强度和拉伸强度分别较纯PVC捍高了21. 1%和34.7%。     

Aspects of miscibility in poly(vinyl chloride)/epoxidized natural rubber blends. Part I: Mechanical and morphological properties

Miscibility in poly(vinyl chloride)/epoxidized natural rubber (PVC/ENR) blends was studied by examining evidence from tensile, impact, and physical properties. The observation of synergism in tensile strength, percent elongation at break, hardness, and relative density has reaffirmed PVC/ENR blends as miscible systems. Studies of impact properties, however, revealed that the blends are microheterogeneous in nature. This could be attributed to the large sizes of polymer molecules involved and the microgel content of ENR-50. Results from Fourier transform infrared spectroscopy (FTIR) revealed that hydrogen bonding is extensively involved in PVC/ENR systems. This evidence unveiled the exact nature of the specific interactions responsible for miscibility and hence the enhanced mechanical properties of PVC/ENR blends.     

Enhancement of PVC/ENR blend properties by poly(methyl acrylate) grafted oil palm empty fruit bunch fiber

Effect of oil palm empty fruit bunch (OPEFB) fiber and poly(methyl acrylate) grafted OPEFB on several mechanical properties of poly(vinyl chloride)/epoxidized natural rubber (PVC/ENR) blends were studied. The composites were prepared by mixing the fiber and the PVC/ENR blends using HAKEE Rheomixer at the rotor speed of 50 rpm, mixing temperature 150°C, and mixing period of 20 min. The fiber loadings were varied from 0 to 30% and the effect of fiber content in the composites on their ultimate tensile strength (UTS), Young's modulus, elongation at break, flexural modulus, hardness, and impact strength were determined. An increasing trend was observed in the Young's modulus, flexural modulus, and hardness with the addition of grafted and ungrafted fiber to the PVC/ENR blends. However the impact strength, UTS, and elongation at break of the composites were found to decrease with the increase in fiber loading. An increase in elongation at break and UTS and decrease in the flexural and Young's modulus was observed with the addition of PMA‐g‐OPEFB fiber compared to ungrafted fiber. This observation indicates that grafting of PMA onto OPEFB impart some flexibility to the blend. The morphology of cryogenically fractured and tensile fracture surfaces of the composites, examined by a scanning electron microscope shows that the adhesion between the fiber and the matrix is improved upon grafting of the OPEFB fiber. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Effects of dynamic vulcanization on tensile,morphological, and swelling properties of poly(vinyl chloride) (PVC)/epoxidized natural rubber (ENR)/(Kenaf core powder) composites

The effects of dynamic vulcanization on properties of poly(vinyl chloride) (PVC)/epoxidized natural rubber (ENR)/(kenaf core powder) composite were studied. Tensile properties indicated that the strength, elongation at break, and Young's modulus of the composites exhibited an increase for samples with dynamic vulcanization. Morphological analysis using scanning electron microscopy showed the interaction between ENR and PVC. There was no bonding between kenaf core powder and the PVC/ENR matrix owing to the different polarity of both components. Filler agglomerates increased, which leads to an increase of filler‐filler interaction and poor dispersion. Furthermore, swelling index indicated that the composite with dynamic vulcanization shows lower absorption of tolune compared with composites without dynamic vulcanization. J. VINYL ADDIT. TECHNOL., 22:206–212, 2016. © 2014 Society of Plastics Engineers     

The effect of blending sequence on the structure and properties of poly(vinyl chloride)/chicken eggshell powder composites

The effect of the blending sequence of poly(vinyl chloride)/chicken eggshell powder (PVC/ESP) composites on the processing, mechanical properties, morphology, and thermal decomposition were investigated. The compounding of composites was done by using a Rheomix mixture internal mixer at 180°C and a rotor speed of 30 rpm for 10 min to allow the mixing torque to reach a steady state. The mechanical and morphological properties of PVC/ESP composites under different blending sequences have been characterized by a lightweight tensile tester and scanning electron microscopy. The thermal stability and thermal analysis of the composites were performed by thermogravimetric and differential scanning calorimetric analysis. Good interfacial adhesion between filler and matrix in composites prepared via blending sequence 2 has improved the tensile strength and thermal stability of the PVC/ESP composite compared with blending sequence 1 as proved from scanning electron microscopy results on the tensile fracture surface of the composites. Thermogravimetric analysis results show that blending sequence 2 exhibited higher thermal stability comparable with blending sequence 1. In addition, the differential scanning calorimetric analysis results illustrate that the composites prepared via blending sequence 2 exhibit higher melting and crystallization temperature values compared with composites prepared via blending sequence 1. J. VINYL ADDIT. TECHNOL., 23:298–304, 2017. © 2015 Society of Plastics Engineers     

抗静电半硬质PVC材料的制备及性能

通过SEM、拉伸断裂行为、表面电阻、DMA(动态热机械分析)和维卡软化温度测试,研究了半硬质PVC/炭黑(CB)材料力学性能、电性能、热性能和微观形态。结果表明:随着炭黑添加量增加,PVC/CB的导电性能和拉伸强度提高,而体系的断裂伸长率降低。当炭黑添加量仅为4份时,PVC/CB即有逾渗现象发生,表面电阻大幅度降低。当炭黑的添加量为7份时,材料的表面电阻降至1×105Ω,即可满足矿山材料抗静电的要求,而材料的综合力学性能良好。炭黑可使PVC材料的玻璃化转变温度向高温区域移动,材料的耐热性能提高。     

Melt elasticity behavior and extrudate characteristics of rigid poly(vinyl chloride)/epoxidized natural rubber miscible blends

A study on the melt elasticity behavior and extrudate characteristics of melts of rigid poly(vinyl chloride), PVC, and rigid poly(vinyl chloride)/epoxidized natural rubber (ENR) miscible blends were conducted. Extrusion studies were carried out in a capillary rheometer and examinations of the surface characteristics of the extrudate were made by taking photomicrographs in a scanning electron microscope. The anomalous behavior in the die swell ratio of rigid PVC arising from the particle agglomerates continued in its blends up to 50 wt% composition of ENR. Temperature independence for high ENR blends was noted for the principal normal stress difference and elastic shear modulus, when shear stress was held constant. Recoverable shear strain and die swell ratio behaved identically in terms of blend composition and processing temperature. Factors which control the extrudate distortion and melt fracture of the melts of rigid PVC/ENR systems were fusion of particle agglomerates and strength of melts. Diamond cavitations were typical of the extrudate surface of PVC melts as those of the fracture surface of the tensile failure of PVC. Conditions to obtain a smooth extrudate surface of rigid PVC melts in blends with ENR have been found to be the low ENR content, low shear rate, or stress and high processing temperature.     

高性能聚氯乙烯复合材料的研究

以聚氯乙烯(PVC)为基体、热塑性聚氨酯弹性体(PUR–T)为增韧剂、连续玻璃纤维(GF)为增强剂,通过熔体浸渍挤出工艺制备高性能PVC复合材料,并对其力学性能、耐热性能和动态力学性能进行研究。结果表明,随着PUR–T或连续GF含量增加,复合材料的力学性能和耐热性能均得到提高,当PUR–T/PVC质量比为2/8,连续GF质量分数为30%时,复合材料的拉伸强度、缺口冲击强度、弯曲强度、弯曲弹性模量、维卡软化温度分别为83.42 MPa,19.81 k J/m2,106.33 MPa,8 823.36 MPa和74.1℃;随着连续GF含量增加,复合材料的储能模量和玻璃化转变温度提高,损耗因子降低;扫描电子显微镜测试结果表明连续GF在PVC中保持了较长的长度,分散性良好。     

Effects of chicken eggshell filler size on the processing,mechanical and thermal properties of PVC matrix composite

The effects of filler particle size of poly(vinyl chloride)/chicken eggshell powder (PVC/ESP) composites on the processing, tensile properties, morphology and thermal degradation were investigated. The mixing of composites was done using Rheomix internal mixer. The processing torque of PVC/ESP composite at a particle of 0.2 μm exhibits lower processing torque compared to that at a particle size of 7 μm due to the dispersive resistance from larger ESP filler particles. Good interfacial adhesion exists between the filler and matrix in composites prepared via a filler particle size of 0.2 μm, which has improved the tensile strength and modulus of PVC/ESP composite compared to a filler particle size of 7 μm as justified from FESEM images on the tensile fracture surface of the composites. Thermogravimetric analysis results show that the filler particle size of 0.2 μm composite exhibits higher thermal stability compared to the filler particle size of 7 μm composite.     

Oil-resistance studies of dynamically vulcanized poly(vinyl chloride)/epoxidized natural rubber thermoplastic elastomer

Dynamically vulcanized poly(vinyl chloride)/epoxidized natural rubber (PVC/ENR) thermoplastic elastomers (TPEs) were prepared with a Brabender plasticorder coupled with a mixing attachment by melt mixing. The blends were prepared at 150°C at a rotor speed of 50 rpm. Curatives concentration was steadily increased from 0 to 1 phr in order to study the vulcanization effect on the plasticized blend. The effectiveness of the dynamic vulcanization was indicated by the Brabender plastograms. The properties investigated include mass swell, tensile strength, elongation at break, modulus at 100% elongation (M100), tear strength, and hardness. The PVC/ENR samples were exposed to two types of environments, namely, air and oil under otherwise identical conditions. The effect of oil and thermooxidative aging on the mechanical properties were characterized at room temperature and 100°C. It was found that at ambient temperature the samples immersed in oil possessed similar properties to those that were exposed to air. Significant enhancement in mechanical properties were observed for both environments at 100°C. This has been attributed to the increase in crosslink density which was manifested by a steady reduction in percent mass swell with increased sulfur loading. The excellent mechanical behavior of the PVC/ENR TPEs even after immersing the samples in oil at 100°C has provided a good indication of the oil resistance of the materials. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 69: 1357–1366, 1998     

Average mixing torque,tensile and impact properties,and thermal stability of poly(vinyl chloride)/sawdust composites with different silane coupling agents

Unique explanations are given to describe changes in the mixing torque and tensile and impact properties of poly(vinyl chloride) (PVC)/wood sawdust composites affected by various types and concentrations of silane coupling agents. Concentrations of 0.5–1.0 and 1.5 wt % coupling agent are recommended for the optimization of the tensile and impact properties of the composites, respectively. Changes in the tensile and impact properties of the composites with a low sawdust content were more sensitive to the addition of silane coupling agents than those with a high sawdust content. KBM603 was suitable for improving the tensile properties, whereas KBE603 is recommended for high impact resistance of the composites. The differences in the mechanical and thermal properties of the PVC/sawdust composites were dependent on the characteristics of the functional groups in the silane coupling agents used, such as hydrophilic level, number of functional groups, self‐condensation reaction, and effectiveness of the hydrolysis reaction. Silane coupling agents above 1.0 wt % resulted in an increase in polyene sequences in the PVC structure. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 96: 213–221, 2005     

Mechanical Properties and Thermooxidative Aging of a Ternary Blend,Pvc/Enr/Nbr,Compared with the Binary Blends of Pvc

In the quest to improve the thermooxidative aging of the poly(vinyl chloride)/epoxidized natural rubber (PVC/ENR) blend, nitrile rubber (NBR) was incorporated into the blend to yield a ternary blend of PVC/ENR/NBR. A Brabender Plasticorder with a mixing attachment was used to perform the melt mixing at 150°C and 50 rpm followed by compression molding. The mechanical properties, dynamic mechanical properties, and thermooxidative aging behavior of the ternary blend were compared with those of the binary blends (i.e., PVC/ENR and PVC/NBR). It was found that the ternary blend exhibits mechanical properties which are superior to those of PVC/ENR. A single glass transition temperature (T _g) obtained from dynamic mechanical analysis coupled with synergism in the modulus and some other mechanical properties indicate that PVC, ENR, and NBR form a single phase (miscible system) in the ternary blend. Di-2-ethyl hexylphthalate (DOP) plasti-cizer improves the aging resistance of the blends generally, whereas the presence of CaCO₃ as a filler only imparts minor influences on the properties and aging resistance of the blends.     

Preparation and Electron Beam Irradiation of PVC/ENR/CNTs Nanocomposites

Poly (vinyl chloride), PVC/epoxidized natural rubber blend, ENR/carbon nanotubes, CNTs nanocomposites were prepared using melt intercalation and solution blending methods. In both preparation methods PVC: ENR: CNTs ratios were fixed at 50:50:2, while the 50/50 PVC/ENR blend without the addition of CNTs was used as control. The PVC/ENR/CNTs nanocomposites were exposed to electron beam (EB) irradiation at doses ranging from 0–200 kGy. The effects of two different preparation methods on the tensile properties, gel fraction and morphology of the PVC/ENR/CNTs nanocomposites were studied. Prior to EB irradiation, the addition of 2 phr of CNTs caused a drop in the tensile strength (Ts) of the 50/50 PVC/ENR blend, implying poor distribution of CNTs in the PVC/ENR blend matrix. However upon EB irradiation, the nanocomposites prepared by the melt blending method exhibited higher values of Ts as compared to the neat PVC/ENR blend due to occurrence of radiation-induced cross-linking in the PVC/ENR blend matrix. Transmission electron microscopy (TEM) images proved that a better dispersion of CNTs in PVC/ENR blend matrix can be achieved by melt intercalation compared to solution blending and the dispersion of CNTs was improved by irradiation. Scanning electron microscopy (SEM) results showed a distinct failure surface with formation of rough structure for the irradiated nanocomposites, which explains the higher values of tensile properties compared to the non-irradiated nanocomposites.     

Thermal and mechanical properties of phosphorylated multiwalled carbon nanotube/polyvinyl chloride composites

The fabrication of carbon nanotube/polyvinyl chloride (PVC) composites and a study of their thermal and mechanical properties are reported. Phosphorylated multiwalled carbon nanotube (p-MWCNT) and pristine MWCNT were used. The MWCNT were embedded in the polymer matrix through melt mixing. The phosphorylation of the MWCNT and their dispersion in the PVC matrix were characterized by scanning and transmission electron microscopy and Raman spectroscopy. Thermal analysis by thermal gravimetric analysis and differential scanning calorimetry, showed an increase in glass transition temperature and melting temperature for the composites with respect to pure PVC. The modulus of the MWCNT/PVC composites increased while there was a reduction in their tensile strength, indicating a decrease in polymer toughness.     

Thermal properties of graphite‐loaded nitrile rubber/poly(vinyl chloride) blends

The thermal properties (thermal conductivity, thermal diffusivity, and specific heat capacity) of nitrile rubber (NBR)/poly(vinyl chloride) (PVC) blends were measured in the temperature range of 300–425 K. The incorporation of graphite into the NBR/PVC (30/70) matrix improved its thermal properties. Moreover, these properties slightly changed with the temperature. The thermal conductivity values of the prepared samples were compared with values modeled according to the Maxwell–Eucken, Cheng–Vachon, Lewis–Nielsen, geometric mean, and Agari–Uno models. The Agari–Uno model best predicted the effective thermal conductivity for the whole range of blend ratios and for the whole range of graphite contents in NBR/PVC (30/70)/graphite composites. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

The effect of layered double hydroxides dispersion on thermal and mechanical properties of poly(vinyl chloride)/poly(methyl methacrylate) blends

Poly(vinyl chloride) (PVC)/layered double hydroxide (LDH) composites and PVC/poly(methyl methacrylate) (PMMA)/LDH composites were prepared via solution intercalation into PVC using both unmodified and organo‐modified LDHs and variable‐molecular‐weight PMMA as additional components. The LDH dispersion was investigated using X‐ray diffraction analysis and electron microscopy in scanning and transmission modes. Spotlight fourier transform infrared (FTIR) chemical imaging analysis was also used to obtain a deeper insight into the dispersion of polymer phases and LDH segregation. Thermal properties were determined using thermogravimetric analysis and differential scanning calorimetry; moreover, a preliminary investigation of mechanical properties in tensile mode and evaluation of the Vicat softening temperature were carried out. The morphological analysis of PVC/LDH and PVC/PMMA/LDH composites evidenced in both cases the presence of disordered micro‐aggregates with loss of the LDH crystallographic symmetry depending on the amount and molecular weight of PMMA. In particular, in the case of PVC/PMMA/LDH composites, the FTIR imaging analysis showed that PMMA mostly segregated in the LDH phase. However, even if the degree of LDH dispersion was not elevated (micro‐aggregates with disordered structures and size ranging from 0.5 up to 11 µm were evidenced), thermal stability and mechanical properties of the composites were improved with a synergic effect of PMMA and LDH. © 2013 Society of Chemical Industry