Studies on thermal, thermal ageing and morphological characteristics of EPDM-g-VTES/LLDPE

A novel graft copolymer of vinyltriethoxysilane onto ethylene propylene diene terpolymer has been developed by grafting varying contents of VTES using dicumyl peroxide as an initiator in a twin-screw extruder. Grafting of VTES and EPDM has been ascertained using FTIR. The EPDM-g-VTES developed has been blended with different weight percentage of linear low density polyethylene [LLDPE] by melt mixing. Thermal, thermal ageing and morphological behaviour of the blends are studied with respect to the effect of blend composition, static vulcanization and dynamic vulcanization with varying quantities of VTES and LLDPE. The incorporation of silane moiety onto EPDM raises the inception and final decomposition temperature. The stability EPDM-g-VTES/LLDPE blend increases with increase in concentration of EPDM-g-VTES due to thermally stable Si-O-Si linkage. It was ascertain from SEM micrograph that EPDM-g-VTES/LLDPE blends lead to formation of interpenetrating crosslinked network during hot water treatment and by treatment with DCP, respectively. The linear, statically vulcanized, dynamically vulcanized and filled blends of EPDM-g-VTES/LLDPE have been characterized to assess the suitability of the blends for high performance applications. In addition, it is also observed that the incorporation of fillers improves thermal stability of the blends.     

Thermogravimetric and dynamic mechanical analysis of LLDPE/EMA blends

The thermal stability of linear low density polyethylene (LLDPE)/ethylene methyl acrylate (EMA) blends was studied using thermogravimetry. The blend ratio as well as the presence of compatibilizer has significant effect on thermal stability of the blends. The compatibilization of the blends using LLDPE-g-MA has increased the degradation temperature. Phase morphology was found to be one of the most decisive factors that affected the thermal stability of both uncompatibilized and compatibilized blends. Dynamic mechanical behavior of the blend was studied by dynamic mechanical analysis. The storage modulus of the blends decreased with increase in EMA content. When compatibilized with LLDPE-g-MA the storage modulus of the blend increases. LLDPE-g-MA is an effective compatibilizer as it increases the thermal stability and modulus of the blend.     

紫外辐照官能化LLDPE及改性尼龙66的研究

尼龙66（PA66）是工程塑料的重要品种之一,具有高强度、耐磨、耐油、自润滑和使用温度范围广等优良特性,广泛应用于机械、汽车、电子电器等行业．但PA66在干态和低温下冲击强度偏低,吸水率大,尺寸稳定性差,使其应用范围受到一定的限制。     

CROSSLINKING AND COMPATIBILIZATION IN BLENDS OF POLYSTYRENE AND POLYETHYLENE

This paper investigated the influences of butadiene rubber (BR) and dicumylperoxide (DCP) on thermal and rheological behaviour, morphology and mechanical proper-ties of PS/LLDPE/SBS blend. Addition of DCP alone was found to decrease the mechanicalproperties of PS/LLDPE/SBS blend due to the decomposition of PS. When BR was addedtogether with DCP, it is found that the co-crosslinking of BR, SBS and PE takes place,and the decomposition of PS is reduced simultaneously because of the consumption of thefree radicals in the crosslinking process. Synergism was thus realised which resulted in theimprovement of the ductility of blend.     

Morphology and mechanical properties of blown films of a low‐density polyethylene/linear low‐density polyethylene blend

The morphologies of films blown from a low‐density polyethylene (LDPE), a linear low‐density polyethylene (LLDPE), and their blend have been characterized and compared using transmission electron microscopy, small‐angle X‐ray scattering, infrared dichroism, and thermal shrinkage techniques. The blending has a significant effect on film morphology. Under similar processing conditions, the LLDPE film has a relatively random crystal orientation. The film made from the LDPE/LLDPE blend possesses the highest degree of crystal orientation. However, the LDPE film has the greatest amorphous phase orientation. A mechanism is proposed to account for this unusual phenomenon. Cocrystallization between LDPE and LLDPE occurs in the blowing process of the LDPE and LLDPE blend. The structure–property relationship is also discussed. © 2002 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 40: 507–518, 2002; DOI 10.1002/polb.10115     

辐照法制备的醋酸乙烯酯/蒙脱土纳米复合材料与HDPE和PA6共混物的研究

利用γ射线辐射引发醋酸乙烯酯(VAc)在蒙脱土(MMT)中的原位插层聚合,X射线衍射测试与透射电子显微镜观察结果表明,PVAc/MMT复合材料为纳米复合材料.其与HDPE和PA6的共混物的扫描电镜测试结果表明,PVAc-MMT纳米复合物以微胶囊的形式存在于PVAc-MMT/HDPE/PA6共混物中,均匀分散的PVAc-MMT纳米复合物改变了复合材料的相结构.热失重测试结果显示,PVAc-MMT/HDPE/PA6的起始分解温度明显高于PVAc/HDPE/PA6,热失重过程差异较大,MMT纳米粒子的存在改变了材料的结构,使材料热性能得到了改善.在PVAc-MMT/HDPE/PA6共混物中,PVAc-MMT具有增强与增韧作用.     

PA6/HIPS/PP-g-(GMA-co-St)反应共混体系的研究

通过扫描电镜、热分析、熔体流动速率、熔融扭矩和力学性能等测试方法研究了甲基丙烯酸缩水甘油酯(GMA)和苯乙烯(St)多单体熔融接枝聚丙烯[PP-g-(GMA-co-St)]对PA6/HIPS共混物的熔融流变性能、结晶行为、相形态和力学性能的影响.结果表明,在熔融共混过程中,PP-g-(GMA-co-St)中的环氧基与PA6的端氨基原位生成的接枝共聚物有效地降低了共混物的界面张力,提高了共混物的界面粘着力,使共聚物的流动速率降低,熔融扭矩提高;PA6分子链的规整性降低,结晶完善性变差.在PP-g-(GMA-co-St)的质量分数为10%时,共混物分散相的尺寸明显减少,力学性能得到较大提高;其中冲击强度超过纯PA6,达到HIPS水平.通过反应共混,制备了力学性能均衡的PA6/HIPS/PP-g-(GMA-co-St)共混物合金.     

Microhardness and thermal stability of compatibilized LDPE/PA6 blends

Microhardness tests, water absorption and thermogravimetric measurements have been performed on blends of low density polyethylene (LDPE) with different molar mass and polyamide 6 (PA6) compatibilized with 2 pph poly(ethylene-co-acrylic acid) (Escor 5001 by Exxon). The negative deviation of Vickers microhardness from the additivity has been interpreted by changes in the crystallinity of the blend components. The hardness values of the compatibilized blends that are lower than those of the corresponding uncompatibilized blends have been explained by the decrease of the degree of crystallinity of PA6 phase in the presence of Escor. The molar mass of LDPE almost does not influence on the hardness values. The lower water absorption of the compatibilized blends, caused by the formation of a copolymer between PA6 and the compatibilizer leads to microhardness values of the wet compatibilized blends higher than those of the corresponding uncompatibilized blends. The thermogravimetric measurements demonstrate that the thermal stability of blends increases in the presence of 2 pph Escor 5001. The results confirm the compatibilizing efficiency of Escor 5001 towards LDPE/PA6 blends in a wide composition range.     

The microstructural characterization of PA6/PA12 blend specimens fabricated by selective laser sintering

This study investigates the processing of blends of polyamide 6 (PA6) and polyamide 12 (PA12) by selective laser sintering (SLS) using a CO₂ laser. Powder properties of undiluted polymers, mixture composition, and processing parameters, as well as their influence on the microstructure of the specimens manufactured, were evaluated. Polyamides showed higher absorption of laser energy during the sintering of blend specimens, with subsequent thermal energy transfer to the melting of the polymeric phases. The structure of parts obtained by SLS is dependent on the process parameters and the characteristics of the powder material to be processed. The microstructures of PA6/PA12 blend specimens were heterogeneous, with co-continuous and disperse phases depending on the quantity of PA12. The porosity and crystallinity also changed as a function of the component proportions. The use of polymeric blends can increase the range of structures and properties of SLS parts.     

Thermal degradation and crystallisation studies of reactively compatibilised polymer blends

The thermal degradation and crystallisation behaviours of polyamide12/isotactic polypropylene (PA12/PP) blends were studied. Effects of blend ratio and compatibiliser concentration on the thermal degradation properties of the blends were analysed. The activation energy for degradation in compatibilised and uncompatibilised blends computed using Horowitz-Metzger equation was reported. The blend ratio as well as the presence of compatibiliser has significant effect on the thermal stability of the blends. Phase morphology was found to be one of the decisive factors that affected the thermal stability of both uncompatibilised and compatibilised blends. Melting and crystallisation behaviours of the blends in the presence and absence of compatibiliser were evaluated. It was observed that blending has no significant effect on the melting and crystallisation properties of PA12 and PP. Compatibilisation of 70/30 and 50/50 PA12/PP blends didn't affect the crystallisation and melting behaviours of PA12 and PP even though some discrepancies were observed.     

Thermal degradation behavior of multi-walled carbon nanotubes/polyamide 6 composites

This paper focuses on the thermal degradation behavior of multi-walled carbon nanotubes (MWNTs)/polyamide 6 (PA6) composites under air and nitrogen atmosphere using thermogravimetric analysis (TGA). The results show that the dispersion of amino-functionalized MWNTs (f-MWNTs) in PA6 is more homogeneous than purified MWNTs (p-MWNTs). The presence of MWNTs improves the thermal stability of PA6 under air obviously, but has little effect on the thermal degradation behavior of PA6 under nitrogen atmosphere. The activation energies for degradation under air, E_a, estimated by Kissinger method, are 153, 165 and 169 kJ/mol for neat PA6, p-MWNTs/PA6 and f-MWNTs/PA6 composites, respectively. The p-MWNTs/PA6 composites show two-step degradation not only under air but also under nitrogen atmosphere, however, neat PA6 and the f-MWNTs/PA6 composites exhibit two-step degradation only under air.     

Synthesis and thermal behaviour of polyamide 6/bentonite/ammonium polyphosphate composites

In order to achieve acceptable levels of flame retardancy of polymers, phosphorus-based flame retardant (FR) additives at about 20-30% w/w are required which is too high for conventional synthetic fibres. To know whether more finely sized particles of conventional FRs with or without nanoclay are more effective at the same concentration, composites of PA6 with bentonite and ammonium polyphosphate (APP) have been prepared by melt processing in a twin-screw extruder. XRD peaks and TEM images of PA6/Org-bentonite composite show partially ordered intercalation and ordered exfoliation. Thermal analysis in He shows that thermal stability of PA6 nanocomposite has increased by 18 °C compared with pure PA6 during degradation after 425 °C but it has decreased by 100 °C on inclusion of APP in PA6/nanoclay composites. The char yield is increased by 20% in PA6/bentonite/APP composites. No effect on thermal stability or char yield is observed by reducing the particle size of APP.     

Evaluation of the SEBS copolymer in the compatibility of PP/ABS blends through mechanical,thermal, thermomechanical properties,and morphology

Polypropylene (PP) blends with acrylonitrile-butadiene-styrene (ABS) were prepared using the styrene-ethylene-butylene-styrene copolymer (SEBS) as a compatibilizing agent. The blends were prepared in a co-rotational twin-screw extruder and injection molded. Torque rheometry, Izod impact strength, tensile strength, heat deflection temperature (HDT), differential scanning calorimetry, thermogravimetry, and scanning electron microscopy properties were investigated. The results showed that there was an increase in the torque of PA6/ABS blends with SEBS addition. The PP/ABS/SEBS (60/25/15%) blend showed significant improvement in impact strength, elongation at break, thermal stability, and HDT compared with neat PP. The elastic modulus and tensile strength have not been significantly reduced. The degree of crystallinity and the crystalline melting temperature increased, indicating a nucleating effect of ABS. The PP/ABS blends compatibilized with 12.5% and 15% SEBS presented morphology with well-distributed fine ABS particles with good interfacial adhesion. As a result, thermal stability has been improved over pure PP and the mechanical properties have been increased, especially impact strength. In general, the addition of the SEBS copolymer as the PP/ABS blend compatibilizer has the advantage of refining the blend's morphology, increasing its toughness and thermal stability, without jeopardizing other PP properties.     

超细聚酰胺6粒子增韧聚丙烯体系的研究

采用磨盘形力化学反应器室温下制备了聚丙烯 (PP) /聚酰胺 6 (PA6 )超细粉体 ,研究了其粒度、粒度分布及PA6超细粒子填充对PP力学性能的影响 .结果表明 ,磨盘形力化学反应器可有效实现PP/PA6的粉碎 ,所得粉体平均粒径达微米级 ,初级粒子尺寸甚至可达纳米级 ,粒度分布呈双峰分布状态 .在PA6和PP熔点之间的温度下加工可制得PA6超细粒于填充的PP/PA6共混体系 ,其力学性能明显好于PP/PA6简单共混体系 ,30 %PA6用量下 ,拉伸强度由 2 3 .2MPa提高至 2 9 3MPa ,Izod缺口冲击强度由 4.6 2kJ/m2 提高到6 .34kJ/m2 .形貌分析结果表明 ,由于基本保持了PA6超细粉体的原始尺寸 ,填充体系中PA6相区尺寸小、分布均匀 ,与使用增容剂得到的相区结构类似 .     

Liquid natural rubber (LNR) as a compatibiliser in NR/LLDPE blends—II: the effects of electron-beam (EB) irradiation

Electron-beam (EB) irradiation technique has been used to improve the properties of 60/40 blends of NR/LLDPE in the presence of compatibilisers such as LNR-6 and LNR-16. Improvement in the physical properties of the blend correspond with the increase in the interactions created by EB irradiation as measured by gel content. For this blend ratio, the radiation dose of 200 kGy is found to be optimum. While LNR-6 shows some complimentary effects when it is used together with EB irradiation technique; LNR-16, however, causes an imperfection effect in the blend. The crosslinking process that takes place as a result of EB irradiation occurs at the expense of crystalline arrangement of the semi-crystalline LLDPE. For the morphological fixation purposes EB irradiation technique is found to be very effective.     

Thermogravimetric and wide angle X-ray diffraction analysis of thermoplastic elastomers from nylon copolymer and EPDM rubber

Nylon copolymer (PA6, 66) and ethylene propylene diene (EPDM) blends with and without compatibilizer were prepared by melt mixing using Brabender Plasticorder. The thermal stability of nylon copolymer (PA6, 66)/ethylene propylene diene rubber (EPDM) blends was studied using thermogravimetric analysis (TGA). The morphology of the blends was investigated using scanning electron microscopy (SEM). In this work, the effects of blend ratio and compatibilisation on thermal stability and crystallinity were investigated. The incorporation of EPDM rubber was found to improve the thermal stability of nylon copolymer. The kinetic parameters of the degradation process were also studied. A good correlation was observed between the thermal properties and phase morphology of the blends. By applying Coats and Redfern method, the activation energies of various blends were derived from the Thermogravimetric curves. The compatibilization of the blends using EPM-g-MA has increased the degradation temperature and decreased the weight loss. EPM-g-MA is an effective compatibilizer as it increases the decomposition temperature and thermal stability of the blends. Crystallinity of various systems has been studied using wide angle X-ray scattering (WAXS). The addition of EPDM decreases the crystallinity of the blend systems.     

Morphology,structure, and properties of in situ compatibilized linear low‐density polyethylene/polystyrene and linear low‐density polyethylene/high‐impact polystyrene blends

Blends of linear low‐density polyethylene (LLDPE) with polystyrene (PS) and blends of LLDPE with high‐impact polystyrene (HIPS) were prepared through a reactive extrusion method. For increased compatibility of the two blending components, a Lewis acid catalyst, aluminum chloride (AlCl₃), was adopted to initiate the Friedel–Crafts alkylation reaction between the blending components. Spectra data from Raman spectra of the LLDPE/PS/AlCl₃ blends extracted with tetrahydrofuran verified that LLDPE segments were grafted to the para position of the benzene rings of PS, and this confirmed the graft structure of the Friedel–Crafts reaction between the polyolefin and PS. Because the in situ generated LLDPE‐g‐PS and LLDPE‐g‐HIPS copolymers acted as compatibilizers in the relative blending systems, the mechanical properties of the LLDPE/PS and LLDPE/HIPS blending systems were greatly improved. For example, after compatibilization, the Izod impact strength of an LLDPE/PS blend (80/20 w/w) was increased from 88.5 to 401.6 J/m, and its elongation at break increased from 370 to 790%. For an LLDPE/HIPS (60/40 w/w) blend, its Charpy impact strength was increased from 284.2 to 495.8 kJ/m². Scanning electron microscopy micrographs showed that the size of the domains decreased from 4–5 to less than 1 μm, depending on the content of added AlCl₃. The crystallization behavior of the LLDPE/PS blend was investigated with differential scanning calorimetry. Fractionated crystallization phenomena were noticed because of the reduction in the size of the LLDPE droplets. The melt‐flow rate of the blending system depended on the competition of the grafting reaction of LLDPE with PS and the degradation of the blending components. The degradation of PS only happened during the alkylation reaction between LLDPE and PS. Gel permeation chromatography showed that the alkylation reaction increased the molecular weight of the blend polymer. The low molecular weight part disappeared with reactive blending. © 2003 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 41: 1837–1849, 2003     

BR和DCP在PS／LLDPE／SBS体系中的协同作用

ＢＲ和ＤＣＰ在ＰＳ／ＬＬＤＰＥ／ＳＢＳ体系中的协同作用方征平，许承威，项义崇（杭州大学化学系，杭州，３１００２８）关键词聚苯乙烯，聚乙烯，共混物，相分散－交联协同作用相分散（增容）－交联协同作用是提高不相容聚合物共混物性能的有效方法，我们曾将此方法成...     

Friction and wear mechanisms of polyamide 66/high density polyethylene blends

Polyamide 66 (PA66)/high density polyethylene (HDPE) blends having miscible structure were produced by compatibilization of HDPE grafted with maleic anhydride (HDPE‐g‐MAH). Mechanical and tribological properties of blends in different compositions were tested. It was found that the polymer blends greatly improved the mechanical properties of PA66 and HDPE. Blending HDPE with PA66 significantly decreased the friction coefficient of PA66; the friction coefficients of blends with different compositions were almost the same and approximately equal to that of pure HDPE; the blends with 80 vol % PA66 exhibited the best wear resistance. The transfer films, counterpart surfaces, and wear debris formed during sliding were investigated by Scanning Electron Microscopy (SEM), and Differential Scanning Calorimetry (DSC) analysis was further carried out on wear debris. These investigations indicated that the thermal control of friction model is applicable to PA66/HDPE blend, that is the friction coefficient of blend is governed by the HDPE component, which possesses a lower softening point relative to the PA66 component in this system. The wear mechanism of PA66/HDPE blend transforms from PA66 to HDPE as the HDPE content increases. PA66, as the component with higher softening point, increases the hardness of blend, enhances the ability of blend to form a transfer film on the counterface, and inhibits the formation of larger belt‐like debris of HDPE, at the same time, the presence of self‐lubricating HDPE in the system decreases the friction coefficient and the frictional heat, all of these factors are favorable for the wear resistance of PA66/HDPE blend. © 2005 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 43: 2514–2523, 2005     

PA6／PET共混体系的X射线衍射分析

用宽角Ｘ射线衍射分析,考察尼龙６／ＰＥＴ共混体系的结晶态,表明在共混物中尼龙６和ＰＥＴ是各自结晶的,即晶相分离的。研究了结晶条件,组份比等对晶态结构的影响,发现共混体系相对结晶度低于纯组份的算术加和,说明共混体系的结晶相分离过程中,由于存在相互作用导致的干扰,使结晶度下降。