Effects of molecular weight and molecular weight distribution on creep properties of polypropylene homopolymer

The molecular weights of the industrial-grade isotactic polypropylene (i-PP) homopolymers samples were determined by the melt-state rheological method and effects of molecular weight and molecular weight distribution on solid and melt state creep properties were investigated in detail. The melt-state creep test results showed that the creep resistance of the samples increased by M_w due to the increased chain entanglements, while variations in the polydispersity index (PDI) values did not cause a considerable change in the creep strain values. Moreover, the solid-state creep test results showed that creep strain values increased by M_w and PDI due to the decreasing amount of crystalline structure in the polymer. The results also showed that the amount of crystalline segment was more effective than chain entanglements that were caused by long polymer chains on the creep resistance of the polymers. Modeling the solid-state viscoelastic structure of the samples by the Burger model revealed that the weight of the viscous strain in the total creep strain increased with M_w and PDI, which meant that the differences in the creep strain values of the samples would be more pronounced at extended periods of time.     

Influence of molecular weight distribution on the elasticity and processing properties of polypropylene melts

In a study of the flow behavior of polymer melts a semi-empirical viscometric equation has been used which contains an elasticity parameter relating the shear dependence of the viscosity to the normal-stress effect. The way in which both these effects are influenced by the molecular weight distribution of the polymers investigated is shown, and the influence of melt elasticity on polymer processing behavior is discussed. From previously published viscosity data the elasticity parameter has been determined for a number of polypropylene grades, and the possibility of classifying these grades according to a characteristic time constant is indicated.     

Effects of stearic acid on the tensile properties of ultrahigh molecular weight polyethylene fibers

For the purpose of the development of ultrahigh molecular weight polyethylene (UHMWPE) fibers with improved tensile properties, the stearic acid (SA) was added to the gel spinning of UHMWPE and acted as a lubricant film. SA addition was intended to be 0.2, 0.4, 0.6, 0.8, and 1.0 wt% of UHMWPE for forming the SA modified UHMWPE fibers. The tensile properties, thermal properties, crystallization properties, and orientation properties of the prepared UHMWPE fibers were systematically investigated. Results show that there is a more significant tensile property for UHMWPE fibers as SA addition is 0.6 wt%. Their tensile strength and tensile modulus reach 32.86 and 1580.89 cN/dtex, which are raised to an extent of 12.0% and 7.7%, respectively, compared with UHMWPE fibers alone. Moreover, the thermal properties, crystallization properties, and orientation properties of the prepared UHMWPE fibers are enhanced observably when the SA addition is 0.6 wt%.     

Influence of molecular weight and molecular weight distribution on the tensile properties of amorphous polymers

Tensile property data for polystyrene samples of varying polydispersity are correlated with various parametric measures of molecular weight. Traditional measures of molecular weight, such as M?_n, M?_w, and M?_z, are shown to be unable to account for the variation of tensile properties with molecular weight. However, a new molecular weight parameter, termed the failure property parameter, is able to provide a single relationship between tensile strength and the parameter for both the broad and narrow distribution polymers. The form of this parameter is consistent with its having origins in the view that it is the entanglement network in an amorphous polymer that provides the observed strength properties. Specifically for polystyrene, the failure property parameter results indicate that material below 60,000 molecular weight does not contribute to polymer strength. Although the results of this investigation are specifically for polystyrene, the arguments used to develop the failure property parameter are not dependent on polymer chemical structure. Consequently, we believe that both the concepts and definition of this new parameter are applicable to all amorphous polymers.     

Effect of molecular weight distribution on the rheological and mechanical properties of polypropylene

The effect of molecular weight distribution on the Theological and mechanical properties of a series of polypropylenes is evaluated. The polypropylenes tested were produced by controlled chemical degradation in a single-screw plasticating extruder. Measured properties include shear, extensional and intrinsic viscosity, melt flow index, extrudate swell, melting and crystallization temperatures, impact strength, flexural modulus, and tensile stress.     

Influence of molecular weight distribution on the structure and properties of melt-spun polypropylene filaments

The role of molecular weight distribution on the spinnability, structure, and properties of melt-spun isotactic polypropylene filaments was studied with the aim of clearly distinguishing the effect of the breadth of the distribution from the effect of the average molecular weight and resin melt flow rate (MFR). Nine resins were chosen for this purpose, ranging in MFR from 16 to 78 and in polydispersity from 2.6 to 5.4. It was observed that the spinnability, structure, and properties of the spun filaments were all strong functions of the breadth of the distribution. Spinnability decreased with increasing breadth. At given spinning conditions and polydispersity, an increase in the weight-average molecular weight (decrease in MFR) produces an increase in crystallinity, birefringence, tensile strength, and tensile modulus. But at given spinning conditions and resin MFR, broadening the molecular weight distribution (increasing the polydispersity) produces an increase in crystallinity, tensile modulus, and elongation-to-break while birefringence and tensile strength decrease. The major influence of the polydispersity on the structure and properties developed was attributed to its effect on both the elongational viscosity of the resin and the ability of high molecular weight tails in the distribution to influence the stress-induced crystallization that occurs in the spinline. © 1995 John Wiley & Sons, Inc.     

聚丙烯熔体流动指数与分子量及其分布的关系

研究了聚丙烯(PP)的熔体流动指数(MI)与聚合物不同分子量之间的关联性,对于分子量分布较窄的PP,数均分子量(Mn)、重均分子量(Mw)和粘均分子量(Mv)均能较好的关联;反之,MI与Mn关联性下降,而MI与Mn和Mv的关联性仍很好,尤其是MI与Mv的关联性受分子量分布的影响很小;MI与Z均分子量的关联性很差。同时．确定了MI与各种分子量之间的关联式,该式用于本体PP工艺反应器内氢气浓度的计算和MI的预测,与实验测量结果吻合良好。     

Influence of processing parameters and molecular weight on the mechanical properties of PVC

The role of a variety of processing parameters in determining the mechanical properties of solid PVC has been examined. Annealing pretreatment has been shown to increase both the yield stress and the modulus. It was found that the density of the material similarly increased as the annealing progressed, and when the density reached a limiting value, the yield stress and modulus also reached a limiting value. The molecular weight of the resin, as measured by its intrinsic viscosity, also affected the various mechanical properties measured. However, the yield stress increased while the modulus decreased as the molecular weight increased. This unusual behavior was thought to be a secondary effect. Finally, the addition of increasing amounts of stabilizer to the PVC resin resulted in an increase in modulus and a decrease in yield stress. This was consistent with a model for plastic deformation in which the stabilizer acted as small hard particles. The activation strain volume did not change with different concentrations of stabilizer, further supporting a model for a two-phase structure.     

The influence of processing parameters on the properties of melt‐spun polypropylene hollow fibers

Isotactic polypropylene hollow fibers were produced by melt spinning. Spinning speeds up to 1880 m/min were used, and sample hollowness (percentage void in cross section) ranged from 0 to 69%. The fiber samples were characterized using dynamic mechanical analysis, birefringence, tensile testing, and differential scanning calorimetry. The hollow fibers were found to have higher crystallinity, orientation, and strength than the analogous solid fibers. In general, the polymer orientation in a hollow fiber was larger than the orientation in a solid fiber, even when the spinning speed for the latter was much larger. For a fixed outer diameter, increasing the hollowness improved fiber properties. However, as hollowness was further increased, fiber properties declined slightly. At a given percentage hollowness, increased spinning speed increased modulus and tenacity. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 83: 1759–1772, 2002     

Experimental investigation of the influence of molecular weight distribution on the rheological properties of polypropylene melts

An experimental study of steady shear and elongational flow Theological properties of a series of polypropylene melts of varying molecular weight and distribution is reported. Broadening the molecular weight distribution increases the non-Newtonian character of the shear viscosity function and increases the principal normal stress differences at fixed shear stress. The behavior is compared to earlier rheological property-molecular weight studies. Correlations are developed for these properties in terms of molecular structure. Elongational flow studies indicate that for commercial and broader molecular weight distribution samples, ready failure by neck development occurs and the elongational viscosity appears to decrease with increasing elongation rate. For narrower molecular weight distribution samples, the elongational viscosity is an increasing function of elongation rate, The implication of these experimental results to viscoelastic fluid constitutive equations and polymer melt processing is developed.     

凝胶色谱法在聚丙烯分子量及分子量分布测定中的应用

根据聚丙烯在凝胶色谱柱上的淋洗特点,确定了测定其分子量及分子量分布试验条件;采用示差和黏度双检测凝胶色谱系统,利用普适校正方法,不需要Mark常数K、α值,可直接测定聚丙烯分子量分布并给出分子量分布曲线;采用统计方法计算数均分子量、重均分子量、黏均分子量,可以为课题研究提供一定的依据和指导。     

Effects of gamma irradiation,irradiation environment,and postirradiation aging on thermal and tensile properties of ultrahigh molecular weight polyethylene fibers

The effects of gamma irradiation in four types of irradiation environment on the thermal and tensile properties of gel-spun, ultrahigh molecular weight polyethylene fibers (Spectra™ 1000) have been investigated. The gamma irradiation was conducted at 2.5 Mrad and in air, nitrogen, acetylene, and vacuum to study the effects of irradiation media on the aforementioned properties. Thermal and tensile properties of virgin and irradiated fiber samples were examined using differential scanning calorimetry and an Instron tensile tester, respectively. The results indicate that both gamma irradiation and irradiation environment affected the properties of the polyethylene fibers, and substantial changes were observed for the oxygen-containing environment. The tensile-fractured surfaces of the fibers were examined by scanning electron microscopy. The properties of irradiated fibers were further evaluated at 160 days postirradiation and found to be affected, substantially. The postirradiation aging significantly decreased the tensile strength and elongation of the irradiated fibers, indicating that polyethylene fibers should not be exposed to gamma irradiation. © 1996 John Wiley & Sons, Inc.     

Correlations of single-point parameters of linear rheology and molecular weight distribution of polypropylene homo- and copolymers

For various purposes, it is required to compress the shape of the molecular weight distribution (MWD) of polymers into a limited set of parameters. With increasing molecular weight and polydispersity, the MWD data obtained from chromatography become increasingly unreliable due to deficiencies in the high molecular weight region, making estimation via melt rheology more preferable. A number of empirical parameters obtained from melt rheology can be related back to MWD parameters. The target of this study is to establish the reliability of such relations for polypropylene homo- and copolymers. It is found that correlations between polydispersity from rheological crossover modulus and polydispersity via chromatography are not always valid. Therefore, the range of applicability must be kept in mind when attempting predictions based on these correlations because rheological measurements are sensitive to molecular characteristics in ways different from chromatography. The use of a modified polydispersity index is shown to be more reliable.     

Study on processing of ultrahigh molecular weight polyethylene/polypropylene blends

The processing of ultrahigh molecular weight polyethylene (UHMWPE) by the addition of polypropylene (PP) and high‐density polyethylene (HDPE) was investigated. The results show that the addition of PP improves the processability of UHMWPE more effectively than does the addition of HDPE. UHMWPE/PP blends can be effectively processed with a twin‐roller and general single‐screw extruder. In the extrusion of UHMWPE/PP blends, PP is enriched at the surface of the blend adjacent to the barrel wall, thus increasing the frictional force on the wall; the conveyance of the solid down to the channel can then be carried out. The melt pool against the active flight flank exerts a considerable pressure on the UHMWPE powder in the passive flight flank, which overcomes the hard compaction of UHMWPE. The PP penetrates into the gaps between the particles, acting as a heat‐transfer agent and adhesive, thus enhancing the heat‐transfer ability in the material. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 94: 977–985, 2004     

Study on processing of ultrahigh molecular weight polyethylene/polypropylene blends: Capillary flow properties and microstructure

The capillary flow properties and morphologies of ultrahigh molecular weight polyethylene/polypropylene (UHMWPE/PP) blends were studied. The results show that UHMWPE is difficult to process. The melts flowed unsteadily at lower shear rate. With 10 wt % PP contained in the UHMWPE/PP blends, the apparent melt viscosity was much lower than that of UHMWPE. When the PP content increased to 20 and 30 wt %, no pressure vibration occurred throughout the whole shear rate range. Microstructure analysis showed that PP prefers to locate in the amorphous or low crystallinity zones of the UHMWPE matrix. The flowability of UHMWPE increased substantially with the addition of PP. The addition of PE could not effectively reduce the chain entanglement density of UHMWPE. The improvement of processability of UHMWPE by the addition of PE was rather limited. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 3894–3900, 2004     

Evolution of the molecular weight distribution and linear viscoelastic rheological properties during the reactive extrusion of polypropylene

Homogeneous and nonhomogeneous reactive extrusion of polypropylene is modeled using random chain scission statistics coupled with the double reptation mixing rule. In this manner, the evolution of both the molecular weight distribution and the linear viscoelastic material properties is quantitatively predicted for the reactive extrusion–pelletization process. Dispersion in the level of random chain scission has little impact on the MFI for a given average level of chain scission; however, dispersion does generate a marked increase in the recoverable compliance (melt elasticity) relative to the ideal homogeneous random chain scission case. Methods to quantitatively determine the degree of cracking dispersion in processing equipment are identified. Quality control issues such as blending materials of known linear viscoelastic properties to obtain a desired property set is considered in the context of known empirical relations consistent with the double reptation model. Simple mixing rules for the melt flow index and the steady-state recoverable compliance involving only single component MFI and J_e information are derived. © 1995 John Wiley & Sons, Inc.     

Ultradrawing and ultimate tensile properties of ultrahigh molecular weight polyethylene composite fibers filled with functionalized nanoalumina fillers

Ultradrawing and ultimate tensile properties of ultrahigh molecular weight polyethylene (UHMWPE) composite fibers were successfully improved by the addition of nanoalumina (NAL), acid treated nanoalumina (ATNAL), and/or functionalized nanoalumina (FNAL). As evidenced by FTIR and TEM analyses, maleic anhydride grafted polyethylene (PE_g‐MAH) molecules were successfully grafted onto ATNAL fillers. The specific surface areas of FNAL fillers reached a maximal value at 516 m²/g, as they were modified using an optimal weight ratio of PE_g‐MAH to ATNAL at 8. Achievable draw ratio (D_ra) values of UHMWPE/NAL (F₁₀₀A_y), UHMWPE/ATNAL (F₁₀₀A_x%‐8‐y) and/or UHMWPE/FNAL (F₁₀₀A_x%‐8FPE^z_y) as‐prepared fibers approached a maximal value as NAL, ATNAL, and/or FNAL contents reached an optimal value at 0.1, 0.1, and 0.075 phr, respectively. The maximal D_ra values of F₁₀₀A_x%‐8FPE^z_0.075 as‐prepared fiber specimens were significantly higher than those of F₁₀₀A_0.1 and F₁₀₀A_x%‐8‐0.1 as‐prepared fiber specimens. In which, the maximal D_ra values obtained for F₁₀₀A_x%‐8FPE^z_0.075 as‐prepared fibers reached another maximal value as FNAL fillers were modified using an optimal weight ratio of PE_g‐MAH to ATNAL at 8. The ultimate tensile strength value of F₁₀₀A_2%‐8FPE⁸_0.075 drawn fiber reached 6.4 GPa, which was about 2.4 times of that of the UHMWPE drawn fibers prepared at the same optimal UHMWPE concentration and drawing condition. POLYM. ENG. SCI., 55:2205–2214, 2015. © 2015 Society of Plastics Engineers     

Effects of sunshine UV irradiation on the tensile properties and structure of ultrahigh molecular weight polyethylene fiber

This study investigated sunlight‐simulated ultraviolet (UV) beam irradiation on the tensile properties and structure of ultrahigh molecular weight polyethylene (UHMWPE) fibers. The tensile results showed that after 300 h sunlight UV irradiation, the tensile properties of the UHMWPE fibers were obviously degraded. Investigation of morphology revealed that the crystallinity was slightly increased, whereas the overall orientation and molecular weight of the fibers were decreased. SEM observations indicated that the degradation process was nonuniform throughout the fiber and a change from a ductile to a brittle fracture mechanism was found after UV irradiation. DMA results showed two β‐relaxations and one α‐relaxation in the original single filament, and UV irradiation led to the increased intensity of the high‐temperature β‐relaxation and the lowered position of the low‐temperature β‐relaxation. This indicated that irradiation‐induced molecular scission and branching were located primarily in the amorphous and the interface areas of the fiber. Changes in the thermal behavior were also examined by DSC. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 2757–2763, 2003