Control of Polymer Properties by Entanglement: A Review

Chain entanglement, either cohesional or topological, distinguishes polymers from other engineering materials. It impedes the movement of molecular segments and influences the polymer rheology, morphology, and mechanical properties. Although a high level of entanglement can increase the polymer toughness, excessive entanglement should be avoided because it causes a high melt viscosity making the processing difficult. This review tended to elucidate the influence of entanglement on the polymer structure, determining the material properties and processability. A wide range of methods used to fine control the degrees of chain entanglement are summarized. The methods are applicable to polymers in solutions, melts, and condensed states with advantages and limitations discussed in detail. The authors also examined the effect of the entanglement on polymer crystallization—the mechanism remains a controversial issue. This review will provide general guidance to designing and processing polymer materials with desired properties via a rational route of controlling the chain entanglement.     

Liquid crystal polymer-based blends: “Universal grade” polymers?

Polymeric materials can be easily processed with different processing operations thanks to suitable rheological properties. Melt flow index, or grade, which is a measure of the fluidity of the polymers, is the most commonly parameter used to characterize the polymers from the point of view of their melt viscosity. Injection molding requires high grade materials, whereas low grade values are best suited for extrusion. Of course, it would be no doubt of interest if single “universal grade” materials could be used for all processing operations. In this paper it is demonstrated that the blends of low grade polymers with small amounts of liquid crystal polymers can be conveniently used for all processing operations. Mechanical and thermal properties of the polymer matrix are in general retained or, in some cases, improved.     

超声波在聚合物成型加工中降粘作用的研究及应用

对超声波在聚合物成型加工中的降粘机理进行了一定的研究,并对它在聚合物成型加工中的应用进行了综述.在聚合物的成型加工中,超声波的合理施加可以大幅度降低聚合物熔体的粘度,降低加工设备的要求和条件,更有利于高粘度聚合物的成型加工.     

超声波在聚合物成型加工中降粘作用的研究及应用

对超声波进行了简单的介绍,对其在聚合物成型加工中的降粘机理进行了一定的研究以及对它在聚合物成型加工中的应用进行了综述。在聚合物的成型加工中,超声波的合理施加可以大幅度的降低聚合物熔体的粘度,降低加工设备的要求和条件,更有利于高粘度聚合物的成型加工。     

注射成型过程中非牛顿塑料熔体的流变特性

在探讨塑料熔体粘度模型的基础上，根据塑料熔体在注射成型过程中的流动特点，讨论了一种能够在加工温度和压力条件下，剪切速率在l0～10^3s^-1的变化范围内，相当精确地描述高聚物流变特性的拈度模型。重点讨论了模型的参数拟合和适用范围，为注射模具设计和成型模拟提供了科学依据。     

Physical gelation of cellulose acetate propionate solutions mediated by metal carbonyl complexes

The weak physical gelation of cellulose acetate propionate-butyl butyrate solutions as a result of the in-situ decomposition of iron pentacarbonyl complexes was explored. Viscometry and infrared spectroscopy were used to monitor the iron pentacarbonyl decomposition reaction progress and its effect on viscosity. Changes in viscosity in of the cellulosic fluids in general and gelation in particular were found to be dependent upon the environment in which the Fe(CO)₅ decompositions occurred. Systems under inert atmospheres exhibited a marked increase in viscosity, while systems under oxidative atmospheres exhibited a general decrease in viscosity. We propose a hypothesis that explains the dependence of the viscosity of these cellulosic fluids as a function of the environmental conditions during the precursor decomposition. Under nitrogen atmospheres, zero-valent nanoparticles with highly reactive surfaces are synthesized, which form weak, transient bonds with the cellulosic polymer. The iron particles, under these circumstances, serve as weak bridges between adjacent polymer chains. Conversely, the primary particles synthesized under an oxidative atmosphere are metal oxides, which are less attractive to the polymer chain and, therefore, do not yield such bridges. This work demonstrates the capability to apply a simple method to control the viscosity of cellulose ester fluids.     

A macromolecular deformation model to estimate viscoelastic flow effects in polymer melts

The elastic deformation of polymer macromolecules in a shear field is used as the basis for quantitative predictions of viscoelastic flow effects in a polymer melt. Non-Newtonian viscosity, capillary end correction factor, maximum die swell, and die swell profile of a polymer melt are predicted by the model. All these effects can be reduced to generic master curves, which are independent of polymer type. Macromolecular deformation also influences the brittle failure strength of a processed polymer glass. The model gives simple and accurate estimates of practically important processing effects, and uses fitting parameters with the clear physical identity of viscoelastic constants, which follow well established trends with respect to changes in polymer composition or processing conditions.     

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.     

The effect of molecular weight and weight distribution upon polymer melt rheology

A major objective in polymer rheology is to predict a fluid's response to a general deformation from molecular information. A method has been developed which allows one to predict the viscoelastic properties of polymer melts from a limited amount of rheological and molecular data for the polymer. The input parameters are: (a) zero-shear viscosity; (b) molecular weight distribution; (c) temperature and density; and (d) constants relating Graessley's relaxation time to the Rouse relaxation time. The technique then “simulates” a discrete relaxation spectrum using G′ and G″ data from the Rouse theory and finally requires that a continuum model of polymer viscoelasticity be fit to shear viscosity data predicted by Graessley's theory. Examples of the utility of the procedure are given to illustrate the role of molecular weight and weight distribution in determining rheological behavior.     

Prediction of the viscosity reduction due to dissolved CO2 of and an elementary approach in the supercritical CO2 assisted continuous particle production of a polyester resin

The dissolution of CO₂ in a polymer causes plasticization of the polymer and hence, its viscosity is reduced. A model based on the free volume theory has been used for a polyester resin, which shows a considerable reduction in the viscosity due to dissolved CO₂. Therefore, supercritical CO₂ has been used as a processing solvent in the continuous production of micron size particles of the resin. Despite the viscosity reduction caused by the dissolved CO₂, an excess quantity of CO₂ with respect to its solubility limit has been used for micronisation of the polymer due to its high viscosity. The mixing of CO₂ and the polymer has not been possible in an extruder at high gas to polymer mass ratios and consequently, a simplified Kenics type static mixer has been used for the mixing purpose. In this study, the effect of various parameters such as temperature, pressure, nozzle diameter and gas to polymer mass ratio on the particle morphology and size has been studied. The experimental results manifest the technological as well as the theoretical insight into the particles production from a high viscosity material.     

Prediction of elongation viscosity of polymer melts

Melt extension flow is a common flow pattern during polymer processing, such as entrance converging flow in die extrusion or runner injection of polymer melts from an extruder barrel, blow molding, blowing film and melt spinning. Extensional viscosity is one of the important characterizations of the flow characteristics for polymer fluids. A new extension viscosity equation was established based on White‐Metzner model, Vinogradov‐Malkin viscosity equation and a new relaxation time equation in the present paper. The melt elongation viscosities of metallocene linear low‐density polyethylene (mLLDPE) and polyvinyl butyral (PVB) resins at 130°C were estimated applying this viscosity equation, and the predictions were compared with the measured data of mLLDPE and PVB resins at 130°C reported from reference. The results showed that calculations were close to the experimental data. The parameters in this equation were easy to be determined and the equation was convenient to use for estimating the extension viscosity of polymer melts. POLYM. ENG. SCI., 2010. © 2010 Society of Plastics Engineers     

Modification of rheological properties of a thermotropic liquid crystalline polymer by melt-state reactive processing

Thermotropic main-chain liquid crystalline polymers typically have very low melt viscosity with strong temperature dependence compared to other common thermoplastics. While this is beneficial in some processing applications, such as injection molding, it presents challenges for others, such as coextrusion. In this study, the rheological properties of a thermotropic main-chain liquid crystalline polymer (Vectra A950) were enhanced by melt-state reactive processing with triphenyl phosphite (TPP), which can react with up to three polymer chain-ends through their chain-end functionalities. The influence of processing time and TPP content on the shear viscosity and other important material properties were investigated. Optimal conditions, which increased the shear viscosity by nearly a factor of 20 over the neat polymer, were found to be 4 wt% TPP and 30 min of reaction time at 290 °C. Further results from differential scanning calorimetry, wide-angle X-ray diffraction and polarized optical microscopy confirmed that coupling with TPP did not affect the microstructure, melting/crystallization behavior or liquid crystallinity. The stability of TPP-modified samples was also studied at 80 °C in air and following melt reprocessing at 290–300 °C under N₂ or air. Samples were stable (as measured by shear viscosity) for more than one month at 80 °C in air or when reprocessed in N₂ at 290 °C for up to 10 min. However, when reprocessed at 300 °C in air, the viscosity enhancement was partially reversed due to scission of P–O bonds that were formed during the initial reaction between the polymer chain-ends and TPP.     

BIIR/NR并用的无内胎气密层混炼工艺改进

根据聚合物相容性和门尼粘度的关系,分析测试了炭黑共混物在混炼过程中影响NR和BIIR的门尼粘度的因素,通过改进生产工艺改变共混物中炭黑分布,缩减混炼温度对溴化丁基胶和天然胶门尼粘度的影响程度。结果显示,试验混炼工艺降低混炼过程中两胶橡相的门尼粘度差异,减小共混物中溴化丁基胶相和天然胶相的弹性恢复差异过大造成的影响,从而改善压延覆胶皮的过程中的工艺及外观性能。     

Melt rheology of high impact polystyrenes at high shear stresses

A study of the theological properties of commercial polystyrenes, (PS), and high impact polystyrenes (HIPS), is made in the range of shear stresses of practical interest in industrial polymer processing. A general viscosity-shear rate-temperature relationship is defined for these products, with a power law exponent of n = 0.3 and an activation energy of 27 Kcal/mol. The fluid elasticity is studied in terms of steady state shear compliance. An expression relating shear compliance, viscosity and molecular weight distribution is obtained for HIPS. As in other two-phase systems, a decrease in elasticity with viscosity is observed.     

The effect of processing on rheological and molecular characteristics of a low density polyethylene

The viscoelastic responses of some molten polymers, and particularly of low density polyethylene (LDPE), are known to vary with processing history. Reasons for the variations include the effects of shear history on morphological states of the polymer, or on its molecular weight parameters. A typical low density polyethylene has been used to test the shear-history dependence concept following a variety of processing steps. The polymer was sheared in single-screw and twin-screw extruders, and in a high speed melter / mixer (Gelimat). Samples also were precipitated from very dilute solutions in trichlorobenzene and in p-xylene. GPC analyses showed that, in general, these procedures did not affect the various moments of molecular weight. An exception was the Gelimat-mixed sample, for which mild reductions in M_n and M_w were noted. In contrast, melt viscosity and elasticity readings, the former from low shear evaluations and the latter from extrudate swelling, were affected by the various procedures. A drop in melt viscosity and in elasticity was observed, being most pronounced for precipitated and twin-screw extruded versions of the LDPE. Reductions also were observed in the specimen sheared in the Gelimat instrument. Following conditioning at the test extrusion temperature (170°C), viscous and elastic responses tended to revert to those of the unsheared control sample, the exception again being the sample sheared in the Gelimat melter / mixer. Of the various mechanisms proposed in the literature to account for transient property changes such as those reported, temporary changes in the degree of chain entanglement appear the most satisfactory explanation. Irreversible alterations in viscoelastic properties may be associated with changes in molecular weights due to processing at high shear.     

Solvent-Cast 3D Printing of Biodegradable Polymer Scaffolds

3D printing is a popular fabrication technique because of its ability to produce complex architectures. Melt-based 3D printing is widely used for thermoplastic polymers like poly(caprolactone) (PCL), poly(lactic acid) (PLA), and poly(lactic-co-glycolic acid) (PLGA) because of their low processing temperatures. However, traditional melt-based techniques require processing temperatures and pressures high enough to achieve continuous flow, limiting the type of polymer that can be printed. Solvent-cast printing (SCP) offers an alternative approach to print a wider range of polymers. Polymers are dissolved in a volatile solvent that evaporates during deposition to produce a solid polymer filament. SCP, therefore, requires optimizing polymer concentration in the ink, print pressure, and print speed to achieve desired print fidelity. Here, capillary flow analysis shows how print pressure affects the process-apparent viscosity of PCL, PLA, and PLGA inks. Ink viscosity is also measured using rheology, which is used to link a specific ink viscosity to a predicted set of print pressure and print speed for all three polymers. These results demonstrate how this approach can be used to accelerate optimization by significantly reducing the number of parameter combinations. This strategy can be applied to other polymers to expand the library of polymers printable with SCP.     

二氧化氯氧化降解三元采出液技术研究

三元复合驱采出液由于聚合物、碱、表面活性剂的存在,使采出液的粘度增加,乳化严重,油水分离困难,传统的应用于水驱、聚驱采出液的处理技术不能满足三元复合驱采出液的处理要求。本文研究了ClO2氧化降解三元采出液的效果,并且找出了ClO2的最优反应条件,结果表明,反应温度为45℃,采出液中ClO2浓度40mg·L-1,加酸量为0.5%,反应2h以上,采出液粘度可由16.65mPa·s下降到2.9mPa·s,阴离子表面活性剂浓度可由0.16mg·L-1下降到0.10mg·L-1。处理后的三元采出液的腐蚀率在腐蚀三级标准的范围内。     

Effect of reactive compatibilization on the interfacial slip in nylon‐6/EPR blends

The viscosity of uncompatibilized polymer blends often shows a negative deviation from a log‐additivity rule at shear rates relevant to processing. This deviation has been attributed to interfacial slip, which is related to the loss of entanglements at the interface. In this work interfacial slip and the effect of reactive compatibilization on this phenomenon are studied in blends consisting of ethylene‐propylene rubber and nylon‐6. The viscosity and morphology of blends with various compositions and compatibilizer content are investigated systematically. The results indicate that interfacial slip can indeed be important in uncompatibilized systems whereas it is suppressed in compatibilized blends. This is further supported by a study of the viscosity of multilayer structures. Both the effect of reactive compatibilization and of the number of layers on the rheology are studied. Again it is demonstrated that reactive compatibilization suppresses interfacial slip.     

Rheokinetics for reactive polymer processing

An important aspect of all reactive polymer processing methods, including reactive injection molding (RIM) and reactive extrusion (REX) is the dramatic increase in viscosity of the material being processed. This paper describes an instrument designed to study rheokinetics of polymerizations relevant to reactive processing. The instrument is capable of measuring simultaneously both viscosity (dynamic or “steady”) and reaction rate during isothermal polymerizations in a closed system. Design aspects of the instrument and some preliminary results are presented.     

Effects of shear rate,viscosity ratio and liquid crystalline polymer content on morphological and mechanical properties of polycarbonate and LCP blends

Studies were conducted on the effects of shear rate, viscosity ratio and liquid crystalline polymer (LCP) content on the morphological and mechanical properties of polycarbonate (PC) and LCP blends. The LCP (LC5000) used was a thermotropic liquid crystalline polymer consisting of 80/20 of parahydroxybenzoic acid and poly(ethylene terephthalate) (PHB/PET). The viscosity ratio (viscosity of LCP: viscosity of matrix) was varied by using two processing temperatures. Due to the different sensitivity of materials to temperature, variation in the processing temperature will lead to varying viscosity of the components in the blends. Based on this principle, the processing temperature could be manipulated to provide a favourable viscosity ratio of below unity for fibre formation. To study the effect of shear rate, the flow rate of the blend and the mould thickness were varied. The shear rate has a significant effect on the fibrillation of the LCP phase. The effect was more prominent when the viscosity ratio was low and the matrix viscosity was high. At 5 wt% LCP, fibrillation did not occur even at low viscosity ratios and high shear rates. It was also observed that the LCP content must be sufficiently high to allow coalescence of the dispersed phase for subsequent fibrillation to occur. © 2002 Society of Chemical Industry