Structures and properties of injection moldings of crystallization nucleator-added polypropylenes. I. Structure–property relationships

Flexural test specimens were injection-molded from polypropylenes added with 0.5 wt % of calcium carbonate, talc, p-tert- dibutyl-benzoic acid monohydroxy aluminum, or p-di-methyl-benzylidene sorbitol under cylinder temperatures of 200–;320°C. Properties such as flexural modulus, flexural strength, heat distortion temperature, Izod impact strength, hardness, and mold shrinkage and higher-order structures such as crystalline texture, crystallinity, a^*-axis-oriented component fraction, and degree of crystalline orientation were measured and structure–property relationships were studied. By the addition of crystallization nucleators, the flexural modulus, flexural strength, heat distortion temperature, hardness, and mold shrinkage were increased and Izod impact strength was decreased. The degrees of crystalline orientation such as the orientation fraction OF and c-axis orientation function f_c were increased by the addition of nucleators. The degree of the increase was higher as the crystallization temperature was higher. Close relationships were observed between some properties and the degrees of crystalline orientation.     

Effects of thermal treatment on the microstructure and thermal and mechanical properties of poly(lactic acid) fibers

The microstructure and thermal and mechanical properties of poly(lactic acid) (PLA) fibers after thermal treatment under both taut and free conditions at different temperatures were studied by differential scanning calorimetry, wide‐angle X‐ray diffraction, microscopy with polarized light, an acoustic method and tensile testing. In particular, the effects of thermal treatment conditions on crystallinity, molecular orientation, and mechanical properties, as well as their interrelationships, were investigated. Both the crystal orientation and crystallinity of the PLA fibers were higher after thermal treatment under taut conditions, even though the molecular orientation was not higher. Thermal treatment relaxed orientated segments, which resulted in increasing crystallinity; however, it did not indicate that the overall molecular alignment of the chains (molecular orientation) would necessarily be high. Tensile strength and elongation were increased with increasing treatment temperature up to 150°C, which corresponded to crystallinity and chain relaxation. The crystallinity detected by XRD, enthalpy measured by DSC, birefringence, and molecular orientation were compared to distinguish the effects of crystallinity, orientation of polymer chains, and crystals. POLYM. ENG. SCI., 2013. © 2012 Society of Plastics Engineers     

Eigenschaftskennfunktionen thermisch hergestellter polystyrole unterschiedlichen molekulargewichts und unterschiedlicher molekulargewichtsverteilung

Mechanical properties and melt flow behaviour have been measured on thermal polystyrenes in order to study the effect of different molecular weight and different molecular weight distribution. The mechanical properties (impact strength, tensile strength and flexural strength) were found to depend upon a critical molecular weight M_w = 1.5 × 10⁵, where the polystyrenes reached ultimate strength. An influence of molecular weight distribution only can be observed when the average molecular weight is near the critical molecular weight limit. The broader the distribution, the poorer are mechanical properties. Injection molded specimens with different molecular weight distribution but equal average molecular weight showed different molecular orientation and different anisotropic mechanical properties. On the basis of equal orientation the narrow distributed specimens showed higher mechanical strength in direction of orientation. The broader the distribution, the higher the elastic properties of melt. An optimum of physical properties and ease of fabrication will be obtained with narrow molecular weight distributed polystyrenes with an average molecular weight slightly above the critical molecular weight limit.     

Interrelationship of strength and flow characteristics of polystyrene

This study investigated the interrelationship between strength and flow characteristics of general-purpose polystyrene (GPPS) used in injection molding applications. The ease of flow was chosen as a measure of processability and was evaluated using the melt flow rate and capillary rheometer techniques. Of the different strength tests that were examined, flexural and notched tensile strength tests were most effective in differentiating between commercial grades of high and low molecular weight GPPS. While characterizing strength of injection molded specimens, the degree of molecular orientation was taken into consideration. For unplasticized resins, increasing the weight average molecular weight by about 100,000 enhanced the flexural strength by 10%, but also increased the viscosity at low shear rates (10 to 100 s^?1). The increase in molecular weight had virtually no effect on viscosity at the highest shear rates (up to 10,000 s^?1). Plasticized resins displayed a 6% loss in flexural strength as well as a significant reduction in viscosity (throughout the shear rate range) as compared with the unplasticized resins. As expected, the improvement in strength achieved by increasing molecular weight leads to a simultaneous increase in the viscosity, i.e., a deterioration of processability. In addition, our study indicates that for samples without preferential molecular orientation, narrowing the molecular weight distribution significantly improves the balance of strength and melt flow rate properties.     

Effect of degree of saponification on the rheological properties of syndiotactic poly(vinyl alcohol)/ water solution

To identify the effect of degree of saponification (DS) of syndiotactic poly(vinyl alcohol)s (s‐PVA)s having similar tacticity and molecular weight on the rheological properties of s‐PVA/water solution, four kinds of (s‐PVA)s with assigned (DS)s, from 93.1 to 97.5%, were prepared by copolymerization of vinyl pivalate (VPi) and vinyl acetate (VAc), followed by saponifying the corresponding copoly(VPi/VAc). The DS played a significant role in rheological behavior. Over the frequency range of 10^?1 to 10² rad/s s‐PVA with higher DS shows more shear thinning at similar molecular weight and tacticity of polymer, suggesting that PVA molecules are more readily oriented as DS increases. This may provide indirect evidence of the spontaneous in situ orientation of s‐PVA molecules at the late stage of saponification. Yield stress is higher for s‐PVA with higher DS at similar molecular weight and tacticity of s‐PVA. This indicates that more domains with internal order are produced at higher saponification. These facts result from increase in stiffness of s‐PVA molecules with proceeding the saponification reaction. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 86: 463–467, 2002     

Influence of molecular weight on rheological,thermal, and mechanical properties of PEEK

This study focuses on the influence of molecular weight on the rheological, thermal, and mechanical behavior of poly(ether‐ether‐ketone) (PEEK), a semicrystalline high‐performance polymer. The results show that the molecular weight of PEEK has significant influence on its rheological, thermal, and mechanical behavior. It was found that PEEK has the unique characteristic of two shear‐thinning regions. The shear viscosity and the stress relaxation time of PEEK increase significantly as molecular weight increases. In general, the Cox‐Merz rule is valid for all grades of PEEK. As molecular weight increases, the melting temperature of PEEK decreases slightly, but its isothermal and nonisothermal crystallization temperatures drop dramatically. As molecular weight increases, the crystallinity, the crystallization rate, and the magnitude of crystallization activation energy decrease. The crystallization kinetics study indicates that PEEK tends to form spherical crystalline structures, regardless of its molecular weight. As molecular weight increases, the tensile strength at yield, the tensile modulus, and the flexural modulus of PEEK decrease slightly, whereas the tensile strength at break, the tensile strain at break, the modulus of toughness, and the impact strength of PEEK increase significantly. POLYM. ENG. SCI., 2011. © 2010 Society of Plastics Engineers     

Comparative studies of ultra high molecular weight polyethylene fiber reinforced composites

Ultra high molecular weight polyethylene fiber is a very promising material for making light-weight high strength and high impact resistant composites, especially for ballistic protective shields. Three commercially available materials designed specifically for ballistic applications are Spectra® woven cloth, Dyneema Fraglight® nonwoven felt, and Spectra Shield® Plus PCR prepreg were chosen for parallel comparisons. The high-temperature high-pressure sintering process was applied to all three materials. The physical, thermomechanical, and microstructural properties of the consolidated products were studied and compared, including their crystallinity, molecular orientation, impact resistance, interlaminar adhesion, flexural properties, and thermoformability. The differences in these materials and their structures are reflected in the different properties of the final products. The influence of different processing conditions on the properties also differs for each material. It is concluded that matrix free Spectra cloth composite has dominant advantages over the other two materials. POLYM. ENG. SCI., 47:1544–1553, 2007. © 2007 Society of Plastics Engineers     

PE-RT Ⅱ型和PE100级管材专用树脂结构与性能对比剖析

通过差示扫描量热、凝胶渗透色谱、动态力学分析及旋转流变等分析手段,研究了PE-RTⅡ型管材树脂(4731B)与PE100级管材树脂(FHMCRP100N)结构和性能上的差异,结果表明,4731B分子量分布曲线呈宽峰分布,而FHMCRP100N分子量呈双峰分布,高分子量组分含量较4731B多。与FHMCRP100N相比,4731B含有较多的共聚单体,其熔点、结晶度、屈服强度、弯曲模量、冲击强度较低,断裂伸长率略高,耐热氧老化性好。     

Influence of high molecular weight component on the hierarchical crystalline structures of injection‐molded bars of polyethylene

A small amount of high molecular weight molecules can have a dramatic influence on the flow‐induced crystallization kinetics and orientation of polymers. To elucidate the effects of the high molecular weight component under a real processing process, we prepared model blends in which high density polyethylene with a high molecular weight and wide molecular weight distribution was blended with a metallocene polyethylene with a low molecular weight and very narrow molecular weight distribution. To enhance the shear strength, gas‐assisted injection molding was utilized in producing the molded bars. The hierarchical structures and orientation behavior of the molded bars were intensively explored by using scanning electron microscopy and two‐dimensional wide‐angle X‐ray diffraction, focusing on effects of the high molecular weight component on the formation of the shish kebab structure. It was found that there exists a critical concentration of high molecular weight component for the formation of a shish kebab structure. The threshold was about 5.5–7.0 times larger than the chain overlap concentration, suggesting an important role of entanglements of the high molecular weight component. Moreover, the rheological properties of molten polyethylene melts were studied by dynamic rheological measurements and a critical characteristic relaxation time for shish kebab formation was obtained under the processing conditions adopted in this research. © 2013 Society of Chemical Industry     

Molecular,rheological, and crystalline properties of low‐density polyethylene in blown film extrusion

The molecular weight and its distribution, degree of long chain branching and cooling rate strongly influence crystallinity during processing, which in turn determines the processability and the ultimate properties of the blown film. Generally a decrease in the number of branches and molecular weight of the polymer and the cooling rate results in an increase of the crystallinity. Length of the main chain and extent of branching in low‐density polyethylene (LDPE) are also factors that affect melt rheology and film crystallinity. Long chain branched polyethylene is suitable in the blown film process due to its better melt strength for bubble stability. The objective of this article is to describe the effect of molecular properties (e.g. molecular weight and its distribution, degree of long chain branching etc) of LDPE on film crystallinity at different cooling rates of blown film extrusion. Two different grades of LDPE were selected to investigate molecular characteristics, crystallinity, and rheology. The resins were processed in a blown film extrusion pilot plant using four different cooling rates. Molecular, rheological, and crystalline properties of the resins were key parameters considered in this study. POLYM. ENG. SCI., 47:1983–1991, 2007. © 2007 Society of Plastics Engineers     

高分子量PET／60PHB热致性液晶共聚酯的结构与性能

研究了固相缩聚过程中PET/60PHB共聚酯结构性能的变化。随着反应的进行,分子量增大,分子量分布宽度指数变小;玻璃化温度略增,熔融温度增加幅度较大;热稳定性明显提高。预聚体中主要存在PET的低共熔物或部分同二质晶,固相缩聚反应使PET结晶消失,PHB结晶形成并完善。固相缩聚大大改善了共聚酯的可纺性,用[η]为0.95dL/g的共聚酯制得断裂强度达到高强范围(1GPa)的初生纤维。     

Processing and properties of solution impregnated carbon fiber reinforced polyethersulfone composites

Carbon fiber reinforced polymer composites are attractive because of their high stiffness and strength‐to‐weight ratios. In order to fully utilize the stiffness and strength of the reinforcement fiber, it is necessary to bring the polymer matrix and the reinforcement fiber together with homogeneous wetting. In this paper, a solution processing technique and the mechanical properties of carbon fiber reinforced polyethersulfone composites were investigated. The polymer was dissolved in cyclopentanone and fed onto a continuous carbon fiber tow using a drum winder. The solution‐processed composite prepregs were then layed up and compression molded into unidirectional composite panels for evaluation. The composite samples showed uniform fiber distribution and reasonably good wetting. The longitudinal flexural modulus was as high as 137 GPa, and longitudinal flexural strength 1400 MPa. In addition, the effects of polymer grade and processing conditions on the mechanical properties of the composites were discussed. It is suggested that the transverse properties and interlaminar fracture toughness could benefit from higher polymer matrix molecular weight. A careful design in the spatial distribution of the molecular weight would be necessary for practical applications.     

The influence of heat treatment on the properties of shape memory fibers. II. Tensile properties,dimensional stability,recovery force relaxation,and thermomechanical cyclic properties

Shape memory fibers (SMFs) were prepared via a melt spinning process. The fibers were subject to different heat treatments to eliminate internal stress and structure deficiency caused during the melt spinning process. The influences of heat treatments on the SMF thermal properties, molecular orientation, tensile properties, dimensional stability, recovery force relaxation, and thermomechanical cyclic properties were studied. It was found that the heat treatments increased soft segment crystallinity and phase separation while decreased molecular orientation. The low‐temperature heat treatment increased the breaking elongation, shape fixity ratios, and decreased boiling water shrinkage while shape recovery ratios were decreased. High‐temperature treatment increased both the shape recovery ratios, fixity ratios, recovery stress stability and at the same time decreasing the fiber mechanical strength. The results from differential scanning calorimetry, molecular orientation apparatus, and cyclic tensile testing were used to illustrate the mechanism governing the mechanical properties and shape memory effect. To obtain comprehensive outstanding properties, the SMF is expected to be treated at a high temperature because of the hard segment high glass transition temperature. Unfortunately, the heat treatment could not be conducted at a too high temperature because the SMF became too tacky and soft due to the melting of the soft segment phase. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

注射工艺条件对抗冲共聚聚丙烯力学性能的影响

用注塑成型方法制备了抗冲嵌段共聚聚丙(烯PP-B)试样,研究了工艺条件的改变对PP-B力学性能的影响。结果表明:注射速率和模具温度与PP-B弯曲强度、弯曲模量成正相关,而与冲击强度、拉伸强度的关系较为复杂;模具温度的升高有利于结晶度的提高,PP-B刚性上升,韧性下降;注射速率改变引起的剪切、拉伸流动使熔体发生取向流动,从而使沿取向方向上的强度升高,垂直取向方向上的强度降低;保压压力对PP-B性能的影响主要是通过熔体非晶部分在保压阶段的分子定向作用来实现的,随着保压时间的延长,PP-B塑件密度提高缺,陷减少拉,伸强度弯、曲模量呈增大趋势。     

超高分子量聚乙烯纤维性能及应用概述

超高分子量聚乙烯纤维有着高取向度,高结晶度,强力、模量高,抗冲击,耐腐蚀,耐光照,耐挠曲,耐磨损等优点。它的密度比水小,介电性能好。超高分子量聚乙烯纤维的缺点是使用温度不高,耐氧化性能差,抗蠕变性能差,表面加工困难。正是超高分子量聚乙烯纤维自身所具有的这些特点,它在抗冲击防护,低温,耐压,海洋工程,渔业等领域有着广泛地使用。     

Improvement of Flexural Strengths of Poly(L‐lactic acid) by Solid‐State Extrusion, 2. Extrusion Through Rectangular Die

Solid‐state extrusion of poly (L ‐lactic acid) (PLLA) through rectangular die was performed to produce high flexural strength plates that can be used as internal fixation devices. A single‐angle wedge‐shaped rectangular die was utilized having the die exit dimension of 4 mm × 1 mm. Billets were machined out from vacuum compression molded PLLA having different crystallinities to have various thicknesses and thus various imposed draw ratios. Solid‐state extrusion of billets was performed at various drawing rates at 130 °C, above glass transition and below melting temperature. Extruded plates had the width and thickness smaller than the die due to the further drawing outside the die. The decrease in width was larger than the decrease in thickness, and this became more prominent with increasing draw ratio and drawing rate, resulting in a significantly smaller aspect ratio. Contributions of die drawing and further drawing outside the die were estimated from the extruded plate dimensions, by which the drawing rate effect was attributed to the further drawing outside the die. As actual draw ratio increased, crystallinity, melting temperature, crystalline orientation factor, and birefringence increased. Throughout the whole process the decrease in molecular weight was largely suppressed to be about 10%. As billet crystallinity, draw ratio, and drawing rate increased, both flexural strength and flexural modulus increased up to the maxima of 202 MPa and 9.7 GPa, respectively. This enhancement in mechanical properties was correlated with structural developments.

Changes in flexural strength of solid‐state extruded PLLA plates as a function of draw ratio (the effect of drawing rate is co‐plotted by hollow symbols at corresponding draw ratio.).     

The influence of annealing treatment on the molecular structure and the mechanical properties of isotactic polypropylene fibers

An investigation was carried out on the effects of annealing treatment on the molecular structure and the mechanical properties of isotactic polypropylene fibers annealed in an air heated environment at temperatures ranging from 60 to 140°C. Analysis of the equatorial X‐ray diffraction traces showed the presence of a three phase system of amorphous‐smectic‐monoclinic forms and revealed the transformation of the metastable smectic form to the highly stable monoclinic form as the annealing temperature is increased, resulting in an enhanced degree of crystallinity and the crystallite size. The improvements in the degree of crystallinity and the crystallite size became more remarkable above 120°C. Evaluation of the crystallinity was carried out using an analysis of density, infrared spectroscopy, and X‐ray diffraction methods whereas the state of the molecular orientation was evaluated using polarized infrared spectroscopy measurements only. Polarized infra‐red spectroscopy measurements after the curve fitting procedure showed a slight increase of the molecular orientation of the helical chain segments present in the crystalline phase represented by the IR bands at 841 and 998 cm^?1 whereas the amorphous structure represented by the IR band at 974 cm^?1 showed no significant change with increasing annealing temperature. The improvement in the molecular orientation of the crystalline phase became more remarkable above 120°C. Tensile strength of the annealed fibers increased with increasing annealing temperature but the elongation at break and the initial modulus were not affected as much as the tensile strength. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011.     

UHMW-PET纤维的拉伸及结构性能研究

利用超高分子量PET进行干-湿法纺丝是目前制取高强度高模量纤维的一种重要方法。本文对超高分子量PET拉伸处理的条件以及纤维的结构性能进行了研究,认为一道拉伸应该采用低速度冷拉的方法;二道拉伸后的纤维结构完整,强度提高。     

Orientation of precrystallized poly(ethylene terephthalate)

The orientation characteristics of crystalline poly(ethylene terephthalate), PET, were studied as a function of degree of crystallinity, orientation temperature, and stretch ratio. Oriented samples were analyzed with respect to mechanical, shrinkage, and barrier properties. The results show that (a) significant impact property improvement can be achieved by orienting crystallized PET, (b) the modulus, ultimate strength, and yield stress increase with orientation of precrystallized PET, (c) the initial degree of crystallinity can affect the strain-hardening properties of PET, and (d) the total amounts of shrinkage and shrinkage stress of stretched PET increase with increasing amounts of crystallinity before orientation.