Morphology and properties of acrylate styrene acrylonitrile/polybutylene terephthalate blends

The structure and mechanical properties of acrylate styrene acrylonitrile (ASA) and ASA/polybutylene terephthalate (PBT) blends have been studied. The morphology of ASA is found to conform to a previous model. 40/60 and 60/40 blends of ASA/PBT have a two-phase, dispersed morphology while the 50/50 blend is shown to have a co-continuous structure. As processing temperature is increased, the mechanical properties decrease, due to PBT degradation. The 60/40 ASA/PBT blend has very poor impact resistance because of the continuous, degraded PBT matrix. Better mechanical properties are observed for blends with a continuous ASA matrix, particularly in the 50/50 blend. Fracture surface analysis reveals a unique morphology of mushroom-like PBT fibrils for the low processing temperature samples near the crack tip. This is thought to occur due to the competition of cohesion and adhesion of the PBT with the ASA matrix.     

Thermomechanical properties of a polymer blend: Investigation of a third phase

This paper deals with immiscible blends of poly(ethylene terephthalate) with polycarbonate obtained by melt mixing. Miscibility of the polyester blends is influenced by transesterification reactions, that are catalyzed either by catalyst residues in the polyesters or by catalysts added on purpose in the blend. These reactions convert the initial homopolymers into block and even random copolymers and affect both the miscibility of the system and the adhesion between the phases. The effect of catalysts and stabilizers on the morphology of PET/PC 50/50 blends was investigated using dynamic mechanical thermal analysis, rheology, microscopy and tensile tests. PET/PC 50/50 containing 0.05 wt.% of lanthanide acetyl acetonate exhibit a irreversible transition occurring at temperature higher than the glass transitions of PET and PC. This transition induces a large increase of the shear modulus and it was attributed to the formation of a third phase in the blend.     

具有高界面压应力的高分子共混物Ⅰ.制备和拉伸性能

考察了高界面压应力对不相容聚对苯二甲酸乙二醇酯(PET)/聚乙烯(PE)和聚碳酸酯(PC)/PE共混物拉伸性能的影响.高界面压应力是共混物低温成型(PE的成型温度)时,分散相与基体从加工温度冷却到室温过程中基体的收缩比分散相粒子大产生的.尽管PET/PE和PC/PE共混物极不相容,但拉伸强度和模量随着PET和PC含量增加而增加.PET与PC含量相同时,PC/PE的拉伸强度和模量高于PET/PE的.采用Takayanangi方程计算共混物的拉伸模量时,具有高界面压应力的PC/PE共混物的拉伸强度高于界面有良好粘结的共混物的理论值,表明在不添加增容剂时,可通过控制加工条件改善共混物界面相互作用,提高共混材料的性能.     

具有高界面压应力的高分子共混物Ⅱ.拉伸过程中形态演化与增强机理

研究了聚对苯二甲酸乙二醇酯(PET)/聚乙烯(PE)和聚碳酸酯(PC)/PE共混物在拉伸过程中形态的演化和增强机理.结果表明,高界面压应力是共混物在基体加工温度成型时,从成型温度冷却到室温过程中基体收缩比分散相大产生的;两种共混物在拉伸中有不同的形态演化过程:PC粒子原位形成了微纤,粒子与基体间没有明显的界面滑动,而PET粒子只产生较小的塑性变形,成为椭球状粒子,粒子与界面间存在滑动.PC对基体PE的增强效果比PET的更好,因为PC/PE共混物拉伸过程中形成了良好增强作用的原位微纤.在拉伸过程中,PET/PE试样的细颈在靠近非浇口端形成,并从此扩展开.部分拉伸后,PC/PE试样比PET/PE试样的弹性回复大,回复到平衡状态时间长,这是两种共混物分散相变形机理不同引起的.     

PET/PCTG/SiO2 共混材料热性能研究

目的 PET与PCTG和Si O_2共混是提高PET综合性能的一种途径,研究共混材料的热性能的变化规律来为共混材料的共混工艺提供理论基础。方法测定PET与PCTG及不同粒径Si O_2的共混材料的升温和降温DSC分析曲线,研究PCTG和Si O_2的粒径和用量对PET/PCTG/Si O_2共混材料的冷、热结晶性能的影响。结果 PET与PCTG和Si O_2共混,PCTG和Si O_2的加入会降低PET的冷结晶温度,提高热结晶温度,Si O_2用量越大,冷结晶温度降低和热结晶温度提高的幅度越大。结论PCTG和Si O_2对冷、热结晶温度的协同影响较大,Si O_2的粒度对PET/PCTG/Si O_2冷结晶温度影响较小,对热结晶温度影响较大,Si O_2的粒度越小,热结晶温度越高。     

Synchrotron infrared microspectroscopy characterization of heterogeneities in solid-state blended polymers

Immiscible polymers, including polystyrene (PS) and polyethylene terephthalate (PET), were blended in the solid state via mechanical attrition, the first step of a near net-shape manufacturing (NNSM) technique. Subsequent analysis via Fourier Transform Infrared Spectroscopy (FT-IR) with synchrotron radiation successfully distinguished between blend components. Characteristic absorbance peaks for each polymer allowed both qualitative and quantitative mapping within prepared samples. Reproducible area maps were created for 50/50 blends of polymethylmethacrylate (PMMA)/PET and PET/PS, which exhibited areas of macroscopic phase separation. Fluctuations in blend concentration were particularly evident for PS/PMMA. However, spatial resolution was shown to limit the detection of heterogeneities. Further modifications with the synchrotron IR apparatus will improve resolution and allow for the direct comparison of NNSM-processed and melt-blended polymers.     

亚磷酸三苯酯扩链制备PBT/PET合金

采用亚磷酸三苯酯(TPPi)作为扩链剂熔融共混制备了聚对苯二甲酸丁二醇酯(PBT)/聚对苯二甲酸乙二醇酯(PET)合金.通过力学性能测试、毛细管流变仪、差示扫描量热法(DSC)研究了TPPi的用量对PBT/PET体系力学性能、流变行为及结晶性能的影响.结果表明,加入TPPi后PBT/PET体系的拉伸强度提高至60MPa...     

Effects of nematic polymer liquid crystal on crystallization and structure of PET/Vectra blends

We investigate the effects of a nematic liquid crystalline polymer, Vectra A, on the structure and properties of its blends with a semicrystalline polymer, poly(ethylene terephthalate),PET. PET/Vectra blend composition ranged from 100/0 to 60/40. Real-time, in situ studies ofisothermal and non-isothermal melt crystallizations of these blends were conducted usingsimultaneous wide and small angle X-ray scattering (WAXS and SAXS), differentialscanning calorimetry (DSC), and quantitative polarizing optical microscopy. All techniquesconfirm that the addition of Vectra nematic liquid crystal delays the onset of crystallization,and affects the degree of crystallinity and structural parameters such as Bragg long period,lamellar thickness and linear stack crystallinity. SAXS results indicate that some of theVectra component penetrates into the interlamellar regions of the crystal stacks. Vectrainterrupts the entangled polymer network making it more difficult for lamellar crystals tonucleate. Slower nucleation and growth result in increased perfection of the PET crystalsgrown isothermally, but reduces the crystallization temperature of PET crystals grownnon-isothermally causing these crystals to be less perfect.     

HDPE/PET共混物的原位反应增容

采用"一步挤出法"制备了高密度聚乙烯/聚对苯二甲酸乙二(醇)酯(HDPE/PET)共混物。通过傅里叶变换红外光谱(FT-IR)分析证明了HDPE与甲基丙烯酸缩水甘油酯(GMA)的接枝共聚物HDPE-g-GMA的形成。通过力学性能测试、扫描电镜(SEM)观察、差示扫描量热(DSC)分析和维卡软化点测试评价了共混物的增容效果。结果表明,过氧化二异丙苯(DCP)含量对体系增容效果的影响要大于单体含量的影响;当DCP含量不超过0.25phr时,增容效果随其含量的增加而提高,但当DCP含量为0.30phr时增容效果有所下降。采用"一步挤出法"进行HDPE/PET共混物的原位反应增容是可行的。     

Fibrillar polymer–polymer composites: morphology, properties and applications

Micro- or nano-fibrillar composites (MFCs or NFCs) are created by blending two homopolymers (virgin or recycled) with different melting temperatures such as polyethylene (PE) and poly(ethylene terephthalate) (PET), and processing the blend under certain thermo-mechanical conditions to create in situ fibrils of the polymer that has the higher-melting temperature. These resulting fibrillar composites have been reported to possess excellent mechanical properties and can have wide ranging applications with suitable processing under controlled conditions. However, the properties and applications very much depend on the morphology of created polymer fibrils and their thermal stability. The present paper develops an understanding of the mechanism of micro-/nano-fibril formation in PE/PET and polypropylene (PP)/PET blends by studying their morphology at various stages of extrusion and drawing. It is revealed that this subsequent mechanical processing stretches the polymer chains and creates fibrils of very high aspect ratios, thus resulting in superior mechanical performance of the composites compared to the raw blends. The study also identifies the primary mechanical properties of the main types of MFCs, as well as quantifying their enhanced resistance to oxygen permeability. Furthermore, the failure phenomena of these composites are studied via application of the modified Tsai–Hill criterion. In addition to their usage as input materials in different manufacturing processes, possible applications of these fibrillar composites in two different areas are also discussed, namely food packaging with controlled oxygen barrier properties and biomedical tissue scaffolding. Results indicate a significant scope for using these materials in both areas.     

热致液晶共聚酯酰胺／PET共混物的相容性和形态结构

用溶解度参数预测热致液晶共聚酯酰胺（ＰＥＡ）与聚对苯二甲酸乙二酯（ＰＥＴ）共混物的相容性。采用偏光显微镜、扫描电镜研究其形态结构。结果表明：ＰＥＡ／ＰＥＴ共混物虽然在理论上是热力学相容的，但因ＰＥＡ的热致液晶性，从液晶有序相变为各向同性存在热效应，致使理论预测与实验结果产生偏差。ＰＥＡ／ＰＥＴ共混物呈两相结构，当ＰＥＡ含量少时，两相之间具有一定的相容性。共混物熔体在剪切力作用下，液晶相形成取向微纤     

Effect of composition on transcrystallization with reorientation of polypropylene in drawn PET/PP blend

The crystallization behaviour of three blend compositions of poly(ethylene terephthalate)/polypropylene (PET/PP), namely 30/70, 50/50 and 70/30 wt.% was studied. The samples were heated up to temperature between the melting temperatures of the blend components and then cooled to 30 °C. X-ray pictures were taken at every stage and it was shown that a recrystallization with reorientation of the PP crystallites took place during the nonisothermal recrystallization. The PP crystallites in the PET/PP blend reorient with molecular axis tilted at aprox. 49° against the FA during the recrystallization. The amount of PP in the blend does not directly affect the process of trancrystallization with reorientation but has only a masking effect. Such reorientation was observed for all three blends. No reorientation occurs if the PET crystallites have been melted before the recrystallization, i.e., when oriented they induce the reorientation of the PP crystallites.     

High density polyethylene and poly(ethylene terephthalate) in situ sub-micro-fibril blends as a matrix for wood plastic composites

Wood plastic composites were prepared based on in situ formed poly(ethylene terephthalate) (PET) sub-micro-fibril reinforced high density polyethylene (HDPE) matrices, using a two-step reactive extrusion technology. The use of ethylene-glycidyl methacrylate (E-GMA) copolymer improved phase compatibility in the sub-micro-fibril blends (SMFBs) with 75% HDPE and 25% PET. Most of in situ formed PET fibrils were less than 500 nm in diameter. The PET fibrils obviously increased mechanical properties of the blend, especially the moduli. The subsequent addition of 40 wt.% wood flour did not influence the size and morphology of PET fibrils, and the fibrils and wood fibers had a synergic reinforcement effect on composite properties. Compared with the HDPE/wood composites, the SMFB/wood system had 65% higher tensile strength, 95% higher tensile modulus, 42% higher flexural strength, and 64% higher flexural modulus, respectively. The technology offers a way to use engineering plastics (i.e., PET) for high performance WPC manufacturing.     

Morphological control of LCP/PET blends using a melt mixer equipped with a milling part

The morphology of liquid crystalline polymer (LCP)/poly(ethylene terephthalate) (PET) blends using a melt mixer equipped with a gap-adjustable milling part was investigated. From the scanning electron microscopic (SEM) observation, the isotropic structure in which spherical LCP domains were dispersed homogeneously in a PET matrix was attained in this study, if the LCP component was 50% or below. The wide-angle X-ray diffraction (WAXD) pattern of the LCP/PET=50/50 blend extrudate suggested that the LCP phase had an unoriented structure, showing a single reflection of 0.45 nm. In the case of the LCP/PET=50/50 blend extrudate, the difference between the linear expansion coefficient (α) parallel to the machine direction, α (MD), and that perpendicular to the MD, α (TD), was estimated to be very small; the α (TD)/α (MD) ratio was 1.153. These results are in agreement with the results of the WAXD profile, and clearly suggest that the anisotropy in the α of the blend extrudate is significantly reduced by the use of a melt mixer equipped with a milling part.     

Morphology-tensile behavior relationship in injection molded poly(ethylene terephthalate)/polyethylene and polycarbonate/polyethylene blends (I) Part I Skin-core Structure

The skin-core structure of injection molded poly(ethylene terephthalate) (PET)/polyethylene (PE) and polycarbonate (PC)/PE blends was investigated. The results indicate that both shape and size of the PET and PC phases depended not only on the nature properties of PET/PE and PC/PE blends, but also on the injection molding parameters such as injection speed and the positions in the molded bars. The morphology in the section perpendicular to the melt flow direction included four layers, surface, sub-skin, intermediate layers as well as core zone. The surface layer was ignored in the present study. The sub-skin layer contained more or less fibrous structure and its thickness gradually decreased along the molded bar from the gate toward the non-gate end. At the same injection speed, the concentration of the injection-induced fibers in PC/PE blend was much higher than that in PET/PE blend. In the core region, the dispersed phase was mainly composed of spherical particles whose diameter increased along the melt flow pathway. Between these two layers, there was an intermediate layer where the dispersed particles mainly assumed the form of fibers, ellipsoids or spheres. Generally, no matter whether the dispersed particles were elongated or not during injection molding, the PET particles were larger than PC ones.     

Phase behaviour, mechanical properties and thermal stability of thermosetting polymer blends of unsaturated polyester resin and poly(ethylene oxide)

The results of dynamic mechanical analysis reveal that crosslinked polyester resin (PER)/poly(ethylene oxide) (PEO) blends show a composition dependent glass transition temperature, Tg, which suggests that the blends studied are homogeneous in the amorphous state. The initial dynamic storage modulus, E', decreases with increasing PEO content up to 30 wt% in the blends, whereas E for both the 60/40 and 40/60 PER/PEO blends is close to that for the 80/20 PER/PEO blend and much larger than that for the 70/30 PER/PEO blend. The addition of crystalline PEO has a remarkable effect on the mechanical properties of crosslinked PER. Tensile testing shows that the elongation at break first increases greatly and then decreases slightly, whereas the Young's modulus and the tensile strength first decrease and then increase slightly with increasing PEO content in the blends. The variation of tensile properties was considered to be due to both the plasticization effect and the crystallization effect of PEO in the blends. The impact strength remains almost unchanged with increasing PEO content in the blends studied. No dramatic decrease of thermal stability for PER/PEO blends was observed for the blends with PEO content up to 30 wt%.     

界面粘结对PET／尼龙66共混物结晶行为和力学性能的影响

利用ＳＥＭ、ＤＳＣ等方法，比较了尼龙６和尼龙６６对ＰＥＴ结晶的异相成核作用，研究了界面粘结状况对ＰＥＴ／尼龙６６共混物结晶行为及力学性能的影响。结果表明，尼龙６６对ＰＥＴ结晶的成核能力优于尼龙６。虽然界面粘结听改善不利于ＰＥＴ／尼龙６６共混物的结晶，但是经明显提高了共混物的力学性能。     

PET/PE原位微纤化共混物的形态与性能

用“熔融挤出—热拉伸—淬冷”方法制备了聚对苯二甲酸乙二醇酯(PET)／聚乙烯(PE)原位微纤化共混物(MCB)，研究了热拉伸比恒定时组成对MCB形态和力学性能的影响，形态观察发现，MCB形成了良好的纤维结构，热拉伸比恒定时，纤维的形态特征(如直径及其分布等)主要受PET含量影响，MCB拉伸模量和强度较通常共混物有显著提高，但太低和太高PET含量，增强效果有所减弱，随着PET含量的提高，MCB经历了从韧性拉伸断裂到脆性拉伸断裂的转变。     

New aspects of the microstructure of glassy PET/PEN blends as revealed by microhardness

The microhardness of films of poly(ethylene terephthalate) (PET) and poly(ethylene naphthalene-2,6-dicarboxylate) (PEN) blends prepared by co-precipitation from solution followed by melt-pressing and quenching was determined. The miscibility, transesterification and crystallization properties of these blended films were reported previously [1]. The PET/PEN compositions chosen were 10/90, 30/70, 44/56, 60/40, 70/30 and 90/10. The microhardness of films was notably affected by the composition. It is shown that the deviation of microhardness from the additivity law of the single components depends on the time for which the blend was melt-pressed before quenching in ice water. The results are discussed in light of changes occurring from the initial two-phase structure of the single components through the one-phase structure up to the PET-co-PEN obtained by transesterification of the two components. This revised version was published online in November 2006 with corrections to the Cover Date.     

Cold crystallization studies on PET/PEN blends as revealed by microhardness

The cold crystallization of amorphous films of poly(ethylene terephthalate) (PET) and poly(ethylene naphthalene-2,6-dicarboxylate) (PEN) blends, with different composition, prepared by co-precipitation from solution followed by melt-pressing for 2 min at 280°C and quenching in ice-water, was followed by measuring the microhardness, H, in real time as a function of crystallization temperature and time. An analytical model was derived, relating properties of the individual components to the blend microhardness based on an Avrami-type equation to account for the crystallization of the components upon heating. Fitting of the model to the experimental results revealed a two-step hardening process of the blends. The degree of transesterification of the blends, can be estimated with this model. Finally, a removal of the physical ageing, inducing a decrease in H of PET in the blend, was observed upon heating above its glass transition temperature. This revised version was published online in November 2006 with corrections to the Cover Date.