Three-dimensional phase morphologies in HDPE/EVA blends obtained via dynamic injection packing molding

The formation of phase morphology of injection molded HDPE/EVA blends, under the effect of shear stress, has been investigated in detail. The shear stress was induced by dynamic packing injection molding, by which a specimen is forced to move repeatedly in the model by two pistons that move reversibly with the same frequency during cooling. Two kinds of EVA with VA content 16 wt% (16EVA) and 33 wt% (33EVA) were used to investigate the effect of interfacial tension. The phase morphology was viewed both parallel and perpendicular to the shear flow direction, so one can get an overall three-dimensional phase morphology. Low shear stress provided by the pistons has a substantial effect on the phase morphology along the flow direction but is insignificant in the direction perpendicular to the flow direction. Generally, a much elongated and layer-like structure is formed along the flow direction, and spherical droplet-like morphology is formed perpendicular to the flow direction, and the degree of deformation of rubber particles also depends upon their size and elasticity as well as on the interfacial properties between matrix and dispersed phase. For static samples of HDPE/16EVA blends (without shearing), only droplet morphology is formed as 16EVA content increases from10 to 40 wt%. However, under the effect of shear stress (dynamic samples), both droplet and cylinder morphologies can be formed depending on the volume ratio. For static samples of HDPE/33EVA blends, not only droplet, but also cylinder and co-continuous morphology (perpendicular to flow direction) can be formed depending on the volume ratio. For dynamic samples of HDPE/33EVA blends, droplet, cylinder and co-continuous network (co-continuous in both parallel and perpendicular to flow direction) can be formed under the effect of shear stress. The formation of phase morphology is discussed based on interfacial interaction, viscosity ratio, shear stress, and phase inversion.     

POE/HDPE/PP三元复合材料的形貌和力学性能研究

用熔融共混法制备了高密度聚乙烯/聚丙烯(HDPE/PP)和乙烯-辛烯弹性体/高密度聚乙烯/聚丙烯(POE/HDPE/PP)复合材料。通过冲击、弯曲和拉伸测试研究了复合材料的力学性能,采用扫描电镜(SEM)观察了材料的形貌。结果表明,由于HDPE和PP的相容性有限,限制了HDPE对PP综合力学性能的提高;通过添加POE,能改善HDPE/PP共混物的相容性,使HDPE/PP复合材料在保持较高弯曲和拉伸性能的前提下,抗冲击性能获得明显提高。当HDPE/PP的含量比为12/88和POE含量为8wt%时,POE/HDPE/PP三元复合材料的综合力学性能较好。     

粘度比对PP/HDPE共混物材料形态结构与性能的影响

研究了粘度比对聚丙烯(PP)/高密度聚乙烯(HDPE)共混物的拉伸性能、弯曲性能、冲击性能以及热变形温度的影响。结果表明,随着粘度比由大到小的变化,共混物的拉伸强度、热变形温度由小到大再到小的变化;粘度比越大,冲击强度相对较高;粘度比接近1时,分散相的颗粒最小。     

Mechanical properties of blends containing HDPE and PP

The mechanical properties of binary blends of high-density polyethylene and polypropylene are quite good compared to those for blends of some other immiscible pairs. The property relationships observed depend strongly on the process used to fabricate the blends as shown by comparisons of specimens made by injection and compression molding with widely varied cooling rates in the latter. Strength and modulus may show additive behavior or have positive or negative deviations, depending on the process conditions; however, measures of ductility like impact strength or elongation at break always show negative departures from additivity and exhibit minima in some cases. Addition of an appropriate ethylene–propylene elastomer greatly improves the ductility of these blends but with a corresponding decrease in strength and modulus. The presence of weld lines has a serious detrimental effect on mechanical properties of these blends.     

Hierarchical crystalline structure of HDPE molded by gas-assisted injection molding

To understand the crystalline morphology of the parts molded by gas-assisted injection molding (GAIM), in this work, the hierarchical structures and the crystalline morphology of gas-assisted injection molded high-density polyethylene (HDPE) were investigated. According to the comparison between the results of the GAIM part and those of the conventional injection molded counterpart, it is found that gas penetration can remarkably enhance the shear rate during GAIM process and oriented lamellar structure, shish-kebab structure and common spherulites arise in the skin, subskin and gas channel region, respectively, owing to the different shear rate in these regions. Meanwhile, cooling rate also plays an important role in the formation of the oriented crystalline structure.     

Effect of flow history on poly(vinylidine fluoride) crystalline phase transformation

This study was devoted to the effect of extensional flow during film extrusion on the formation of the β‐crystalline phase and on the piezoelectric properties of the extruded poly(vinylidine fluoride) (PVDF) films after cold drawing. The PVDF films were extruded at different draw ratios with two different dies, a conventional slit die and a two‐channel die, of which the latter was capable of applying high extensional flow to the PVDF melt. The PVDF films prepared with the two‐channel die were drawn at different temperatures, strain rates, and strains. The optimum stretching conditions for the achievement of the maximum β‐phase content were determined as follows: temperature = 90°C, strain = 500%, and strain rate = 0.083 s^?1. The samples prepared from the dies were then drawn under optimum stretching conditions, and their β‐phase content and piezoelectric strain coefficient (d₃₃) values were compared at equal draw ratios. Measured by the Fourier transform infrared technique, a maximum of 82% β‐phase content was obtained for the samples prepared with the two‐channel die, which was 7% higher than that of the samples prepared by the slit die. The d₃₃ value of the two‐channel die was 35 pC/N, which was also 5 pC/N higher than that of the samples prepared with the slit die. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007     

Mechanical properties and morphologies of PP/mPE/filler composites

Because of the poor impact behavior of polypropylene (PP) at low temperatures, the blending of PP with metallocene‐polymerized polyethylene (mPE) elastomers was investigated in this study. However, a reduced modulus of the overall blend was inevitable because of the addition to elastomers. To obtain a balance of the properties, we introduced rigid inorganic fillers to PP/mPE blends. The performance of the composites was characterized with tensile and Charpy notched impact tests, and the fracture morphology was examined with scanning electron microscopy. The results showed that the effects of fillers in a brittle matrix and in a ductile matrix were quantitatively different. For PP/mPE/filler ternary composites, the dependence of Young's modulus and yield strength on CaCO₃ content was not significant compared with that of PP/filler binary composites, whereas the elongation at break and tensile toughness at room temperature for PP/mPE/filler systems were more improved. The impact strength of the PP/mPE blends filled with untreated glass beads and CaCO₃ at a low temperature was lowered because of the weak interfacial bond. However, the values of the impact strength of the PP/mPE/filler composites at a low temperature remained at a high level compared with that of pure PP. In particular, a PP/mPE blend filled with surface‐treated kaolin had a higher low‐temperature impact toughness than the unfilled blend. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 83: 3029–3035, 2002; DOI 10.1002/app.2333     

环氧液晶对木质素/聚丙烯复合材料结构和性能影响

以4,4'-二(β-羟乙氧基)联苯(BP2)、环氧氯丙烷及对苯二甲酰氯等为原料,通过取代反应合成一种小分子的环氧液晶(LCEP),将该LCEP与木质素(lignin)/聚丙烯(PP)进行共混改性,采用FT-IR、DSC、POM及TGA等对LCEP结构和液晶相转变行为进行了表征,并研究了LCEP含量对Lignin/PP复合材料物理力学性能和热性能的影响。利用SEM观察了复合材料断裂形貌,探讨其增韧增强机理。结果表明:加入4%的LCEP聚丙烯/木质素复合材料的综合性能最好,其冲击强度、弯曲强度和弯曲模量较未改性前分别提高了38.6%、30.5%和20%,热稳定性、结晶性和结晶速率也有明显提高。     

Effect of clay on the morphology and properties of PMMA/poly(styrene-co-acrylonitrile)/clay nanocomposites prepared by melt mixing

Nanocomposites of blends of polymethylmethacrylate (PMMA) and poly(styrene-co-acrylonitrile) (SAN) with natural and organically modified montmorillonite clays (Cloisite^®25A and Cloisite^®15A) were prepared by melt mixing in a twin-screw extruder and the effect of clay on the phase separation morphology and physical properties of nanocomposites was investigated. Multi-pass samples were; those extruded once (one-pass), twice (two-pass) and three times (three-pass). Dispersion of clays in the matrix polymers was investigated using XRD and TEM. Interestingly enough, the clays were observed to be mainly located at the boundaries of PMMA and SAN for most of the nanocomposites. As the number of pass increased, the phase-separated domain size became larger for nanocomposites of PMMA/SAN containing PM, while nanocomposites with clay 25A or 15A showed less degree of growth in domain size in the TEM pictures. Viscosities of the continuous phase and separated domains, and the compatibilizing effect of clays were discussed as the probable explanations for these observations. These were supported by the rheological properties measurements, where the nanocomposites with clay 25A or 15A showed the higher complex viscosities than those of PM and also showed some shear thinning behavior. DSC and TGA analyses were also conducted.     

引发剂活性和挤出温度对HDPE木塑复合材料反应增容的影响

研究试图通过引发剂与马来酸酐实现高密度聚乙烯和木粉间的反应增容,以改善木塑复合材料的热性能和力学性能。利用双螺杆挤出机同步实现了高密度聚乙烯与木粉的均匀混合、马来酸酐与高密度聚乙烯的接枝和接枝共聚物与木粉表面羟基的界面反应。通过扫描电镜观测了复合材料冲击断面的形貌,测试了复合材料的负荷变形温度和力学性能。分析了引发剂活性和挤出温度对复合材料反应增容的影响。结果表明,用中等活性的过氧化二异丙苯与马来酸酐增容后,复合材料木塑两相间的结合情况明显改善,负荷变形温度、拉伸强度、弯曲强度、缺口冲击强度和断裂伸长率明显提高;而高活性的过氧化苯甲酰与马来酸酐对复合材料的增容效果不佳。用过氧化二异丙苯与马来酸酐增容时,挤出温度升高,马来酸酐的最佳增容用量前移。     

Effect of temperature on hygroscopic thickness swelling rate of composites from lignocellolusic fillers and HDPE

Effect of temperature on hygroscopic thickness swelling rate of lignocellolusic fillers/HDPE (high density polyethylene) composites was investigated. The composites were manufactured using a dry blend/hot press method. In this method, powder of plastic and dried powder of lignocellolusic material were mixed in high‐speed mixer and then the mixed powder were pressed at 190°C. Lignocellolusic fillers/HDPE composites panels were made from virgin and recycled HDPE (as plastic) and wood sawdust and flour of rice hull (as filler) at 60% by weight filler loadings. Nominal density and dimensions of the panels were 1 g/cm³ and 35 × 35 × 1 cm³, respectively. Thickness swelling rate of manufactured wood plastic composites (WPCs) were evaluated by immersing them in water at 20, 40, and 60°C for reaching a certain value where no more thickness was swelled. A swelling model developed by Shi and Gardner [Compos. A, 37 , 1276 (2006)] was used to study the thickness swelling process of WPCs, from which the parameter, swelling rate parameter, can be used to quantify the swelling rate. The results indicated that temperature has a significant effect on the swelling rate. The swelling rate increased as the temperature increased. The swelling model provided a good predictor of the hygroscopic swelling process of WPCs immersed in water at various temperatures. From the activation energy values calculated from the Arrhenius plots, the temperature had less effect on the thickness swelling rate for the composites including wood sawdust compared with the rice hull as filler and the composites including recycled compared with the virgin HDPE as plastic. POLYM. COMPOS., 2009. © 2008 Society of Plastics Engineers     

EPDM/PP热塑性弹性体相态研究

采用透射电镜(TEM)研究动态硫化EPDM/PP热塑性弹性体制备工艺及增容改性对形态结构的影响,研究发现通过添加增容剂可使EPDM相呈颗粒分布于连续相中。     

动态硫化工艺对EPDM/PP相态结构及力学性能的影响

采用透射电镜(TEM)研究二次硫化的加工工艺对EPDM/PP热塑性弹性体相态结构及力学性能的影响,研究发现,与传统的一次硫化的加工工艺相比,采用二次硫化加工工艺制备的EPDM/PP弹性体,硫化橡胶能以颗粒态均匀分散于PP的连续相中,其力学性能也较一次硫化制备的样品有较大提高。     

N2保护对加工PP和HDPE的影响

探讨了在N2保护和无N2保护下不同抗氧剂体系对聚丙烯(PP)、高密度聚乙烯(HDPE)性能的影响.结果表明,造粒加工过程中,在N2保护下加入抗氧剂,PP的熔体流动速率变化率最高可下降46.1%,氧化诱导期最大可延长3.3 min;HDPE的氧化诱导期最大可延长19.3 min,提高了合成树脂的加工稳定性和抗氧化效果.     

弹性体的极性对高密度聚乙烯/胶粉/弹性体三元体系相结构的影响

研究了非极性弹性体乙烯-辛烯共聚物(POE)和极性弹性体乙烯-乙酸乙烯酯(EVA)对高密度聚乙烯/胶粉/弹性体三元体系相结构的影响.结果表明,POE形成包埋结构,而EVA形成分散结构.     

Crystallisation behaviour of HDPE in PA6/EPDM-g-MA/HDPE ternary blend with different phase morphology

Morphology of polyamide/maleic anhydride grafted ethylene-propylene-diene monomer/high density polyethylene (PA6/EPDM-g-MA/HDPE) blend and crystallisation behaviour of HDPE in PA6/EPDM-g-MA/HDPE blend were studied by scanning electron microscopy, transmission electron microscope and differential scanning calorimetry (DSC). Morphology observation revealed that core–shell morphology with shell of EPDM-g-MA and core of HDPE was formed in PA6 matrix. DSC test indicated that unexpected result of HDPE double crystallisation peaks emerged for ternary blend system. Also the low temperature crystallisation peak of HDPE was confirmed to be induced as a result of hindered nucleation of HDPE in fine dispersed core–shell particles and the process of crystalline shrinkage of PA6 matrix during cooling process. Furthermore, the factors influencing the crystallisation behaviour of HDPE were systematically studied in this work. The content of EPDM-g-MA and the time of melt mixing significantly affected the crystallisation behaviour of HDPE while the crystallinity of PA6 had a little effect on the crystallisation behaviour of HDPE. The results demonstrated an intimate relationship between phase morphology and crystallisation behaviour of HDPE.     

High temperature behaviour of the crystalline phases in unfilled and clay-filled nylon 6 fibers

Temperature-induced crystalline phase transitions in neat nylon 6 fibers as well as nylon 6/montmorillonite nanocomposite fibers have been studied by means of wide-angle X-ray scattering. Both types of melt spun fibers only consist of the γ crystalline phase that does not display any transition during heating up to the melt. In contrast, fibers drawn up to the maximum draw ratio at 140 °C display the single α phase with a high degree of chain orientation. During the temperature increase, the α phase undergoes a gradual structural disordering but preserves its monoclinic character up to melting. The structural evolution of the α form turned out sensitive to the thermal and mechanical treatment of the fibers. Annealing the unfilled drawn fibers at 150 °C prior to the WAXS experiment improves the thermal stability of the α form due to healing of the processing-induced crystalline defects. The montmorillonite-filled fibers display both the α and the γ crystals, which readily turn into α crystal form only upon drawing. Due to the matrix shearing between the MMT platelets, the H-bonded sheets display a higher thermal stability as compared with unfilled drawn fibers. Upon cooling from the melt, the first signs of crystallization are of γ form in the MMT-PA6 fibers, but the α form rapidly turns predominant. Crystallization kinetics considerations are put forward to account for this finding.     

Investigation on the crystalline morphologies of polyphenylene sulfide and interfacial effect in its fibre composites

Uncured polyphenylene sulfide (PPS) may form a perfect spherulite structure with a diameter of the spherulites larger than 100 μm. On the free surfaces of uncured PPS samples after isothermal crystallization a variety of spherulite patterns can be observed by means of scanning electron microscopy (SEM). However, the crystalline morphologies of PPS are greatly affected by the curing conditions. Graphite fibres, carbon fibres, and glass fibres possess the ability for inducing the transcrystallization of PPS to a different degree. The corrosive resistance of the PPS resin is not only related to its chemical structure, but also to its aggregation structure, and furthermore to the interfacial effect of carbon fibres in the composites.     

Influence of reactive blending temperature on impact toughness and phase morphologies of PLA ternary blend system containing magnesium ionomer

In this study, effects of extrusion temperature on impact toughness and phase morphologies in the reactive poly(lactic acid) (PLA)/epoxy-containing elastomer (ethylene/n-butyl acrylate/glycidyl methacrylate [EBA-GMA]) blend system with magnesium ionomer (magnesium ionomer of ethylene/methacrylic acid copolymer [EMAA-Mg]), were investigated, and the underlying origin for the dependence of morphology development on reactive blending temperature was analyzed. The extent of reactive compatibilization between PLA/EBA-GMA and crosslinking of EBA-GMA initiated by EMAA-Mg, were determined in terms of Fourier transform infrared spectra of dioxane-extracted residues, torque rheometer, dynamic mechanical analysis, and gel contents after chloroform extraction. The phase morphologies were studied by electron microscopic observation and dynamic rheological tests. Compared to the ternary blend system containing zinc-neutralized ionomer of EMAA copolymer (EMAA-Zn), the ones containing EMAA-Mg exhibited the less pronounced dependence of notched impact strength on extrusion temperature. With elevating extrusion temperature, the latter ternary blends exhibited different “salami-like” dispersed phase structure. The morphology development with reactive blending temperature was attributed to the remarkable temperature dependence of crosslinking rate of EBA-GMA phase initiated by the EMAA-Mg rather than the difference in the extent of compatibilization. The morphology development mechanism with respect to reactive blending temperature was also discussed. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 47682.     

成核剂1,3-2,4-二（3,4-二甲基）亚苄基木糖醇的合成及其对聚丙烯的改性

以3,4-二甲基苯甲醛和木糖醇为原料合成1,3-2,4-二（3,4-二甲基)亚苄基木糖醇（DMDBX）,将DMDBX作为成核剂使用溶液沉淀法制备DMDBX质量分数分别为0、0.1%、0.3%、0.5%、0.7%、0.9%的聚丙烯（PP）样品,采用红外光谱仪、差示扫描量热仪、X射线衍射仪和偏光显微镜等方法,研究了DMDBX对PP结晶结构和结晶性能的影响。结果表明,DMDBX是PP的有效α晶型诱导剂,DMDBX的加入能诱导大量球晶生成,导致结晶峰尖锐,结晶温度区间变窄,结晶度提高15％左右,FT-IR、X射线衍射和DSC等分析结果一致。在PP中添加0.3%～0.5％DMDBX时,聚丙烯的改性效果最好,结晶度达到最大值。采用修正Avrami方程Jeziorny法处理非等温结晶动力学结果表明,添加DMDBX的PP Avrami指数约为3,说明DMDBX起到了异相成核的作用,使PP结晶过程的成核和生长方式发生了改变。