Influence of multiple processing on selected properties of poly(3‐hydroxybutyrate‐co‐4‐hydroxybutyrate)

The effect of multiple (up to 10 times) injection molding of processed poly(3‐hydroxybutyrate‐co‐4‐hydroxybutyrate) (P(3,4HB)) on its phase transition temperatures, degree of crystallinity, degradation temperature, mass flow rate, mechanical properties, dynamic mechanical properties, and Charpy's impact strength is presented. The studies have shown that the multiple injection lowers the degree of crystallinity and the thermal stability of P(3,4HB). The mass flow rate values increased with increasing the injection number. It was found that the multiple injections had no substantial effect on the tensile strength up to 10 injection cycles and the tensile strength at break, tensile strain at tensile strength, and tensile strain at break up to 6 injection cycles. The maximum value of storage modulus at 30 °C and impact strength were recorded for sample after 4 cycles of injection, while the values of storage modulus at 120 °C increased with increase of the injection cycles. Copyright © 2015 John Wiley & Sons, Ltd.     

Influence of process parameters on microstructure and mechanical properties of starch-cellulose acetate/silver sulfadiazine matrices prepared by melt extrusion

Starch-cellulose acetate matrices containing silver sulfadiazine were produced using melt extrusion for application in drug delivery devices (DDDs). The influence of the extrusion parameters (screw speed and temperature) on the morphological and mechanical properties of the matrices was evaluated at three different levels. The microstructural characterization of all matrices showed that an increase in the screw speed enhances the porosity and drug dispersion, while an increase in the extrusion temperature decreases the pore diameter of the matrices. Mechanical results did not show significant differences between the elastic modulus values for the matrices; however, a faster screw speed led to higher ultimate strength and strain at failure values. Results obtained in the dynamic mechanical analysis showed that the glass transition and loss tangent (tan δ) peak values became higher with increasing screw speed and temperature.     

Preparation of Polystyrene/Triphenyl Phosphate Composites by Suspension Polymerization and Melt Extrusion Method——A Comparative Study

Polystyrene (PS)/triphenyl phosphate (TPP) composites were prepared by both suspension polymerization and melt extrusion, and a comparative study of the flame retardance and mechanical properties was carried out. The results showed that suspension polymerization was a better technique than melt extrusion for obtaining good dispersity of the PS/TPP composite. The TPP nanoparticles, which were approximately 50 nm in size, were homogenously and uniformly dispersed in the PS matrix by suspension polymerization in one-step. However, the PS/TPP composite was partially agglomerated, exhibiting irregularly shaped micron-scale particles as a result of melt extrusion. In contrast to the melt extrusion, the limited oxygen index (LOI) of the PS/TPP nanocomposite by suspension polymerization increased to 22.6% from 21.8%, and time to ignition (TTI) increased by 12.3%, the peak heat release rate (PHRR) decreased by 8.5%, and the total heat release (THR) decreased by 11.0%. The mechanical properties of the PS/TPP nanocomposite by suspension polymerization also increased. The tensile strength, elongation at break, and flexural strength increased by 36.4%, 8.5%, and 108%, respectively.     

A temperature window of extrudability and reduced flow resistance in high-molecular weight polyethylene; interpretation in terms of flow-induced mobile hexagonal phase

An unexpected feature of melt flow behavior has been identified in high-molecular weight (≥ 4.10⁵) polyethylenes such as are being considered unprocessable at conventional temperatures (> 160°C) and at practicable extrusion rates (> 1 cm/min). In addition to a lower temperature window of smooth extrudability, lying in the range of 138–155°C already observed in previous works, we now discovered within this window a narrow temperature interval (150–152°C) of minimum flow resistance (viscosity). The new effect has the attributes of being associated with a new phase of increased fluidity. This, in turn, we attribute to a transient mesophase arising through the chain-orienting effect of the elongational flow within the extrusion orifice; from the experiments presented here, this mesophase depends critically on both molecular weight and strain rate. The hexagonal form of polyethylene, known to exist under other circumstances, is suggested as this mesophase. The relevance of the new findings for applications (extrusion, melt rheology) and for fundamentals (orientation-induced phase transformations, liquid crystals from flexible chains in particular) should be obvious and are accordingly highlighted.     

Synthesis and characterisation of branched polyarylethers

Polyarylethers (Polysulfone: PSU, Polyethersulfone: PES) belong to the group of high performance polymers, having high glass transition temperature as well as high continuous use temperature. As a consequence of their high glass transition temperature, these polymers display high melt viscosity, which limits the number of accessible applications. Since the conventional methods to improve the flow characteristics are limited, the influence of branching by incorporation of the tri-functional monomer 1,1,1-Tris-(4-hydroxyphenyl)ethane (THPE) on the flow and the mechanical performance of PES was studied. Branching enhances the flow of Polyethersulfone significantly, but has a deleterious effect on the toughness, especially Charpy impact and tensile elongation.     

Mechanical,thermal, and morphological properties of powder coating waste reinforced acetal copolymer

The present study investigates the individual effects of three different thermosetting waste materials, used as fillers, on the mechanical, thermal and flow properties of acetal copolymers (POM). Different amounts ranging from 5% to 30% by weight of hydrolyzed powder coating recyclates were mixed as filler material in POM. The matrix and the fillers were first dry-mixed and then compounds were prepared through melt extrusion. The resulting compounds were cooled, granulated, and then standard tensile test bars were produced through use of an injection-molding machine. We investigated the mechanical and thermal properties of test specimens, and tensile strength, bending strength and impact strength were evaluated as a function of type and amount of filler material in the POM matrix. In addition, the change in melt flow index of POM/filler mixtures was determined, before and after extrusion. Furthermore, the morphology of the specimens was examined via electron microscopy. The results of this investigation are encouraging and present an innovative approach to reutilize hydrolyzed electrostatic powder coating wastes with thermoset structures as fillers in acetal copolymers.     

聚丙烯/聚对苯二甲酸乙二酯共混自增强材料的研究(Ⅰ)

本文根据聚丙烯（ＰＰ）与聚对苯二甲酸乙二醇酯（ＰＥＴ）共混对在熔 融状态下．流动粘度差阳溶度参数差大的特点，用挤出造粒的方法制得 共熔成纤目增强材料。通过扫描电镜观察．证实ＰＰ／ＰＥＴ比从９５／５到 ８０／２０时。ＰＥＴ均以纤维状结构分布在ＰＰ基质中。该共熔成纤体具有 良好的机械性能。在未加偶联剂时，拉伸强度虽略比纯ＰＰ低．但抗冲击 强度与纯ＰＰ相当。该结果可用于指导ＰＰ的改性和ＰＥＴ废料再生利用 工作。     

高熔体强度聚乳酸的研究进展

聚乳酸(PLA)具有完全可再生、完全可降解、生物相容等优异的综合性能,在一次性餐具、日用品、包装材料、纺丝和3D打印等领域具有广阔应用前景。但是,由于PLA是直链脂肪族聚酯,其熔体强度低,导致PLA在使用发泡、熔融纺丝、吹膜、热成型等基于拉伸流动场的加工成型方法时工艺性能较差。因此,提高PLA的熔体强度对于改善其加工性能和促进其产业化推广具有重要的意义。本文综述了改善PLA熔体强度的技术研究进展,主要包括共聚技术、扩链改性技术、自由基反应技术和纳米技术等。     

Die swell ratio of polystyrene melt from an electro‐magnetized capillary die in an extrusion rheometer: effects of barrel diameter,shear rate and die temperature

A constant shear‐rate extrusion rheometer with an electro‐magnetized capillary die was utilized to investigate die swell behavior and flow properties of a polystyrene melt as the application of an electro‐magnetic field to the capillary die was relatively novel in polymer processing. The test conditions such as magnetic flux density, barrel diameter, extrusion rate and die temperature were studied. The results suggest that the maximum swelling of the polystyrene melt with application of the electro‐magnetic field could be enhanced up to 2.6 times (260%) whereas that without the electro‐magnetic field was 1.9 times (190%). The barrel diameter of 30 mm was found to be a critical value in the case of the die swell ratio and flow properties of the polystyrene melt were significantly affected by the magnetic flux density. This involved the number and angle of magnetic flux lines around the barrel part. Under the electro‐magnetic field, there were two mechanical forces influencing the die swell ratio and the flow properties; magnetic torque and shearing force. The die swell at wall shear rates less than 11.2 sec^?1 was caused by the magnetic torque, whereas at higher wall shear rates it was dependent on the shearing force. For a given magnetic flux density, the maximum increase in the die swell ratio as a result of the magnetic torque was calculated to be approximately 20%. Increasing the die temperature from 180 to 200°C reduced the overall die swell ratio and suppressed the effect of the magnetic flux density. Copyright © 2004 John Wiley & Sons, Ltd.     

高耐压HDPE自增强管挤出系统及试样的结构与性能

本文针对管件在输送压力流体时的特殊应力状态,提出了管材周向自增强的构想,据此设计出了自增强挤出系统.该系统利用芯棒旋转,使大分子链沿管周向取向并在适当的压力、温度条件下生成串晶结构,从而大大提高了管材的周向强度及模量.利用DSC、WAXD和SEM等检测手段对试件的凝聚态结构进行分析,找到了周向强度提高的理论依据.     

熔体中转变对四氟乙烯-六氟丙烯共聚物熔体流变性能的影响

用差示扫描量热仪与扭辨分析检出了四氟乙烯-六氟丙烯共聚物熔体中的转变。为了阐明转变的性质,用毛细管流变仪和微型平板粘度计研究了其熔体粘度的温度依赖性。发现,当温度上升到转变温度附近,熔体粘度先升高,然后下降,其粘度行为与热致型小分子液晶相似。但用偏光显微镜观察FEP共聚物熔体,未发现双折射现象。根据实验结果对转变的机制提出了解释。     

Control of Nano-Scale Structuring and Reinforcement in Rotational Molding of Polyethylene

Polyethylene (PE) resins used for Rotational Molding have usually particle sizes less than 0.8 mm and used as powders or micro-pellets. During heating in a rotating mould, these particles get fused and merge into one piece. A disadvantage of the rotomolding process is long cycle times that affect the production rate and increase thermal degradation of the polymer. One of the problems in rotomolding is bubbles of gasses trapped during sintering of the PE powders which reduce mechanical strength of the article produced. We propose to use reacting mixtures of PEG with citric acid as Processing Additive (PA) to rotomolding grades of PE. Silica fume and vinyl-silanes can be other ingredients of the additive package. The PA accelerates sintering of the PE particulates and greatly reduces number of bubbles in the melt but at high concentrations it impedes flow of the particles. Powders are characterized by low flowability while micro-pellets have too high flowability for rotomolding. To improve the rotomolding process we propose to fabricate micro-pellets by extrusion of PE resins comprising the PA at reduced temperatures and pelletizing in open air. The same PA reduces extrusion pressure and suppresses flow instabilities during pelletizing as well as adjusts flowability of micro-pellets to optimum, accelerates sintering of the PE particulates and removes bubbles from the PE melt. Mechanisms of the observed improvements are discussed.     

Liquid crystal polymers. I. Preparation and properties of p-hydroxybenzoic acid copolyesters

High molecular weight copolyesters were prepared by the acidolysis of poly(ethylene terephthalate) with p-acetoxybenzoic acid and polycondensation through the acetate and carboxyl groups. The mechanical properties of the injection-molded copolyesters containing 40–90 mole-% p-hydroxybenzoic acid (PHB) were highly anisotropic and dependent upon the PHB content, polyester molecular weight, injection-molding temperature, and specimen thickness. As the injection-molding temperature increased and the specimen thickness decreased, the tensile strength, stiffness, and Izod impact strength increased when measured along the direction of flow of the polymer melt, and the coefficient of thermal expansion was zero. In some compositions these properties were superior to those of commercial glass fiber reinforced polyesters. Maximum tensile strengths, flexural moduli, notched Izod impact strengths, and minimum melt viscosities were obtained with polyesters containing 60–70 mole-% PHB. Higher oxygen indicies (39–40) and heat deflection temperatures (150–220°C) were obtained with 80–90 mole-% PHB.     

The influence of KH-550 on properties of ammonium polyphosphate and polypropylene flame retardant composites

Ammonium polyphosphate (APP)/polypropylene (PP) composites were prepared by melt blending and extrusion in a twin-screw extruder. APP was first modified by a silane coupling agent KH-550 then added to polypropylene. The surface modification of APP by the coupling agent decreased its water solubility and its interface compatibility with the PP matrix. Limiting oxygen index (LOI) and thermogravimetric analysis (TGA) were used to characterize the flame retardant property and the thermal stability of the composites. The addition of APP improved the flame retardancy of PP remarkably. The crystal structures of APP/PP composites were characterized by X-ray diffraction (XRD). The results indicated that β-crystal phase PP may be formed. The structures and morphologies of APP, KH-550/APP and APP/PP composites were characterized by field-emission scanning electron microscope (FESEM). The mechanical property tests showed good mechanical properties of composite materials. Compared with unmodified one, the impact strength, tensile strength and elongation of modified APP/PP were all improved.     

Liquid crystal polymers. I. Preparation and properties of p-hydroxybenzoic acid copolyesters

High molecular weight copolyesters were prepared by the acidolysis of poly(ethylene terephthalate) with p-acetoxybenzoic acid and polycondensation through the acetate and carboxyl groups. The mechanical properties of the injection-molded copolyesters containing 40–90 mole- % p-hydroxybenzoic acid (PHB) were highly anisotropic and dependent upon the PHB content, polyester molecular weight, injection-molding temperature, and specimen thickness. As the injection-molding temperature increased and the specimen thickness decreased, the tensile strength, stiffness, and Izod impact strength increased when measured along the direction of flow of the polymer melt, and the coefficient of thermal expansion was zero. In some compositions these properties were superior to those of commercial glass fiber reinforced polyesters. Maximum tensile strengths, flexural moduli, notched Izod impact strengths, and minimum melt viscosities were obtained with polyesters containing 60–70 mole-% PHB. Higher oxygen indicies (39-40) and heat deflection temperatures (150-220°C) were obtained with 80–90 mole-% PHB.     

Interlaboratory comparison of melt flow rate testing of moisture sensitive plastics

The current standard for melt flow rate testing, ISO 1133, does not adequately cover the measurement of materials that degrade or further polymerise at the melt flow rate test conditions. Materials such as PET, PBT and PA tend to degrade, sometimes rapidly, at melt temperatures if they contain absorbed water. This results in poor repeatability and reproducibility of melt flow rate results. The ISO Plastics Melt Rheology Working Group (TC61/SC5/WG9) is currently developing a modified melt flow rate test method for reliable measurement of moisture sensitive materials, thereby providing an alternative to intrinsic viscosity measurements. The modified method controls more tightly the time–temperature history experienced by the material during testing and, thus, the resultant variability in measured properties due to degradation.The results of an intercomparison of testing of moisture sensitive polymers using the melt volume flow rate (MVR) and melt mass flow rate (MFR) methods are reported. A polypropylene (PP), used as a benchmark material, and five moisture sensitive materials were tested by a number of laboratories measuring either MVR or MFR, or both. For standard testing of the PP material, the repeatability and reproducibility of measurements of MVR were up to 5% and 11%, respectively, and for MFR were 7% and 21%, respectively (95% confidence level, outliers excluded). For the moisture sensitive materials the repeatability and reproducibility of measurements varied significantly, with repeatability values up to 26% and reproducibility values up to 114% being obtained. By imposing moisture and temperature control criteria in accordance with the proposed testing standard, the repeatability and reproducibility limits were significantly reduced to approximately 10% and 60%, respectively. The results suggest that both the moisture and temperature criteria were important for improving the repeatability of MVR measurements. However, the moisture content criterion was more important for improving the reproducibility of MVR measurements.The need to tightly control the sample preparation, in particular the drying and subsequent sample handing procedures, and the time–temperature history of the sample throughout the test is considered critical to further improve the precision of measurements of such materials.     

具有高灵敏性且稳定可重复的正温度系数效应的PVDF/CF导电复合材料

以碳纤维(CF)为填料,聚偏氟乙烯(PVDF)为基体,通过熔融共混法制备PVDF/CF导电复合材料.所得复合材料具有显著的正温度系数(PTC)效应,温度上升到聚合物熔点附近时,电阻率对温度变化敏感.在转折温度区间(155.5~171.0oC,(35)(28)15.5oC)内,其体积电阻率的增加速率约为1.3×105?cm K-1.在不同CF含量下,复合材料表现出不同的PTC行为.随着CF含量的增加,其峰值电阻略有下降.高导电粒子含量下,无负温度系数(NTC)效应.在冷却循环过程,导电网络的重构性良好.复合材料即使经过多次热循环,依然表现出良好的PTC特性重现性.     

Vapour pressure of DSC calibration substances

For a large number of DSC calibration substances the vapour pressure at room temperature or at transition temperature (whichever is the highest) is given. It is important to know the vapour pressure of substances, because a DSC measurement on a substance with a high vapour pressure requires encapsulation of the substance in a hermetically sealed crucible to prevent evaporation. Because the calibration procedure must be performed using the same type of sample pan as will be used during the actual measurements, the presented information allows one to decide which calibration substances and/or what type of sample pan should be used for calibration.This revised version was published online in November 2005 with corrections to the Cover Date.     

水辅助加工法制备聚丙撑碳酸酯/淀粉共混物

分别采用普通熔融共混法和水辅助加工法,制备了具有不同共混形态的聚丙撑碳酸酯(PPC)/淀粉共混物,并研究了淀粉分散形态对共混物的玻璃化转变温度(Tg)、流变以及力学性能的影响。研究结果表明,采用普通熔融共混法时,淀粉未发生糊化,并以原颗粒状分散于基体中;而采用水辅助加工法时,淀粉发生糊化,并在挤出过程中原位形成纤维结构。当淀粉以纤维形式分散于PPC基体中时,其与PPC间的界面接触面积显著增加,二者的相互作用增强,PPC/淀粉共混物的Tg、储能模量以及复合黏度显著提高。力学性能测试结果表明,当淀粉质量分数为30%,采用水辅助加工法制备的PPC/淀粉共混物的拉伸模量相比于纯PPC提高了67.7%。     

Effect of oxygen concentration and temperature on ignition time of polypropylene

The presented article deals with the assessment of combined impact of temperature and flow of oxidising atmosphere, its oxygen concentration and heat flux on the ignition time of isotactic polypropylene (PP). The ignition time was determined in a specially adapted hot air Setchkin furnace at temperatures (450 and 600?°C), density of heat flux (12.4 and?26.4?kW m^?2), flows of oxidation mixture (6 and 8?L?min^?1) and volume oxygen concentrations (3, 9, 15, 21, 27, 33, 39, 45 and 50?%). Obtained data allows us to assume that the temperature influence on PP induction period of ignition increases with decreasing flow rate of oxidising atmosphere. At the flow of oxidising mixture equal to 6?L?min^?1 and temperature of 600?°C, oxygen concentration had only a negligible impact on the the induction period of ignition in the analysed period. From the presented results, the induction period of ignition depends on the temperature and also on the flow rate of oxidising mixture and oxygen concentration in it. In addition, heat flux has a significant influence on the induction period. However, the quantification of the heat flux influence was not possible with the applied experimental device.