Elastic fracture of polystyrene solutions

Based on the assumption of a constant critical shear strain, an expression for the critical stress at the onset of entrance fracture as a function of polymer concentration has been developed. Experimental results with 10-25 percent narrow distribution, high molecular weight polystyrene-benzene solutions show the critical stress to be much lower than that for the polymer melt and in agreement with predicted values. This result is all the more impressive when the contrast in flow behavior at the capillary entrance for melts and solutions is observed. Instead of the rotating toroidal vortices surrounding a 90-deg material entrance cone observed with polystyrene melt, cine movies of the solution flow birefringence patterns in the capillary entrance region reveal only a stagnant zone surrounding a narrow cone less than 20 deg. At fracture, the cone axis moves in a rotary path circulating about the capillary axis without undergoing the flow discontinuities typical of melt behavior.     

Critcal stress and recoverable shear for polymer melt fracture

The phenomenon of extrudate distortion, which is called melt fracture, was studied for polystyrene samples of narrow and broad molecular weight distribution, and commerical samples of polypropylene and linear and branched polyethylene. It was experimentally found that the shear stress at the onset of melt fracture (τ_cr) is of the order of 10⁶ dynes/cm² and independent of the distribution of molecular weights. As the weight average molecular weight increases the shear stress τ_cr decreases. For polystyrene extruded at τ_cr the recoverable shear strain, which is defined to be half the ration (first normal stress difference/shear stress), was found proportional to the factor M _zM _z+1/M _w² which represents the distrubution of molecular weights. The proportionality is expected to hold for other polymer systems. The polymer behavior at the onset of melt fracture was explained in terms of Graessley's entanglement theory and his correlation between true and Rouse shear compliance.     

Predicting melt flow instability from a criterion based on the behavior of polymer solutions

A criterion, based on the behavior of polymer solutions, is developed and applied for the prediction of the onset of flow anomalies observed at the capillary entrance for polymer melts. It is shown that a direct correspondence exists between the flow anomalies observed for polymer solutions and polymer melts. The onset of these anomalies can be correlated with a critical Weissenberg number which is consistent with the equality of the shear wave velocity and friction velocity. This critical condition can be employed to derive expressions useful for predicting the critical recoverable shear and critical shear stress for melt fracture.     

Effect of ultrasound on the viscoelasticity and rheology of polystyrene extruded through a slit die

The rheological and processing behavior (melt fracture performance) of polystyrene extruded through a slit die is studied as a function of the ultrasound vibration intensity. The apparent viscosity reduces 29% and die pressure reduces 22% compared with that without ultrasound vibration. The viscosity of the melt decreases exponentially as ultrasound intensity increases and an Arrhenius equation fits the data well. Ultrasound vibration also leads to a decrease of the die swell ratio and a postponement of melts fracture. Characteristic relaxation times at the onset of melt fracture are calculated according to the hypothesis that the melt fracture behavior of a polymer is affected by a balance between its viscous (viscosity) and elastic properties (recoverable shear). Ultrasound vibration shortens the relaxation time of polystyrene molecular chains. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 2907–2911, 2006     

A comparison of melt fracture initiation conditions in capillaries and slits

An experimental study was carried out with the objective of comparing the critical conditions for the onset of gross extrudate distortion, usually called melt fracture, in capillaries and slits. Narrow and broad molecular weight distribution polystyrenes as well as low- and high-density polyethylenes were used. The onset of melt fracture was observed to take place at higher shear stresses in slits than in capillaries. It is argued that the flow-average value of the recoverable shear strain should be used as the criterion for the initiation of melt fracture.     

Irregularities in steady flow for non-newtonian fluids between cone and plate

Flow irregularities have been visually observed in solutions of polyacrylamide of high molecular weight on shear in a cone-and-plate rheometry (gap angle 2.3°). This anomalous flow was found to depend on molecular weight, concentration, and solvent. The onset of flow irregularities were generally at shear rates < 5 sec^?1. A dimensional analysis shows that the elastic component of the fluid is responsible for the anomalous flow. The onset of flow irregularities has been predicted from measurements of recoverable strain as a function of shear stress.     

Measurement of the elastic properties of polymer melts

A method and apparatus for measuring the elastic and other properties of polymers in the melt state is presented. The recoverable strain magnitude and the rate of strain recovery have been measured as a function of: applied shear rate, applied shear magnitude, temperature and molecular weight. The elastic properties indicate that there is an abrupt change or “transition” in the response of polystyrene melts at temperatures well above the glass transition. This abrupt change is found to be molecular weight dependent. The results are interpreted qualitatively in terms of molecular structure and practical processing operations. The possible relationship of this “transition” to T_u, is briefly discussed.     

Effect of molecular structure on polyethylene melt rheology. III. Effects of long-chain branching and of temperature on melt elasticity in shear

The effects of long-chain branching and of temperature on the melt elasticity in shear of polyethylene were investigated using die swell measurements and relating them to recoverable shear strain, normal stress, and shear modulus. Die swell measurements, as a function of shear rate, were obtained for high- and low-density polyethylenes at temperatures ranging from 130° to 225°C. The samples were characterized by GPC and intrinsic viscosity for molecular weight distributions and degrees of long-chain branching. The importance of annealing the extrudates at temperatures above the polymer melting temperature to achieve equilibrium, or strain-free, values of die swell was demonstrated. The effect of long-chain branch was to decrease elastic deformation. At constant shear stress, the melt elasticity of both high- and low-density polyethylene was found to be essentially independent of temperature. Thus, at constant shear rate, elastic deformation decreased with increasing temperature, and it was demonstrated that this decrease could be quantitatively defined in terms of previously determined shear rate–temperature viscosity superposition shift factors.     

The source of degradation during extrusion of polystyrene

The nature and magnitude of mechanical reactions of polystyrene in capillary flow has been examined in a model extrusion process. Studies on polystyrene quantify the sensitive increase in shear degradation tendency with increasing polymer molecular weight. A molecular weight spectrum caused by the shear stress profile was measured across the extrudate radius by the new technique of solvent coring. It was further determined that an appreciable fraction of the mechanical reaction is shear induced in the capillary reservoir. This is confirmed by precision determinations of molecular weights and distributions by gel permeation chromatography on samples taken from concentric layers in the capillary reservoir after 50% sample extrusion. These results, involving traces of oxygen as a chemical probe, describe the stress profile in the reservoir and in the capillary during the pressure extrusion of high molecular weight polystyrene. Thus, changes in molecular weight and distribution may be attributable to changes in different portions of the shear geometry rather than the uniform changes generally considered. Clear evidence is also presented showing the dramatic effects of oxygen on these shear-induced changes in molecular weight and distribution.     

A study of extrudate distortion in controlled-rheology polypropylenes

The melt fracture characteristics of controlled-rheology polypropylenes (CRPP) were studied by means of capillary rheometry experiments. CRPPs were produced through reactive extrusion of a commodity polypropylene resin using various peroxide concentrations. These materials exhibited lower molecular weights and narrower molecular weight distributions than those of the starting commodity resin. The CRPP materials studied were found to exhibit only gross melt fracture. At extremely high shear rates and relatively low temperatures, a sigmoidal flexure was observed in the flow curve of certain CRPPs. Generally, it was found that the severity of melt fracture decreased with increasing shear rate for a given material and temperature and in some cases, the extrudates exhibited completely smooth surfaces. Also, the severity of surface distortions was reduced when high L/D dies were employed at a given shear rate. The critical shear stress for the melt fracture onset was found to increase with decreasing molecular weight and polydispersity, and correlations have been developed between the critical stress values and the polymer polydispersity and shear compliance.     

Effects of plasticizer on shear modification of polystyrene

The elastic and viscous properties of polymer melts may be affected by the shear history of the polymer. The extrudate swell of a polymer melt is primarily a manifestation of the elasticity of the polymer melt. In this study, a single screw extruder was used to impose different shear histories on a polystyrene polymer which was processed with and without added plasticizer. The extrudate swell and apparent viscosity of these melts were measured with a capillary rheometer. These characteristics of unplasticized polystyrene are almost not affected by the various preshearing processes. However, the extrudate swell and viscosity of polystyrene containing plasticizer are affected by plasticizer level, shear history and thermal history. After most of the plasticizer in the presheared plasticized polystyrene was extracted, the extrudate swell was still lower than that of the parent sheared polystyrene with the same shear history and the same plasticizer content. These results were obtained without significant changes in molecular weight. Shear modification by conventional process equipment may become impractical if the shear field intensity or dwell time of the material in the apparatus is limited. In such cases, shear refinability by standard process equipment may be observed if the coupling density in the polymer is reduced by some additional means, such as blending with a plasticizer.     

Capillary flow instability of ethylene polymer melts

The capillary flow instability resulting in extrudate distortion has been studied for ethylene polymer melts using a molecular structure approach. It is found that the instability initiates at a critical value of elastic strain energy independent of (average) molecular weight for linear polyethylene. Once the flow breaks down, a slip interface within the melt is formed near the capillary wall, causing an abrupt increase in volumetric throughput. The velocity gradient within the melt remains continuous through the instability, however. Low molecular weight species present in the molecular weight distribution of linear polyethylene tend to suppress slip. Blends of linear and branched polyethylene exhibit instability behavior characteristic of both components throughout the entire range of composition. Results are discussed in terms of specific molecular mechanisms.     

超声振动对PS熔体流变及黏弹行为的影响

采用Bagley入口校正等理论计算方法与实验结果相结合，讨论了超声振动对PS熔体流变及黏弹行为的影响。在口模入口处施加超声振动，降低了聚合物熔体的非牛顿性，改变其黏弹行为，使其在毛细管口模中流动时弹性形变及储能减小，形变松弛加快，黏度降低，从而使挤出加工中流动阻力变小，挤出效率得到提高。     

聚乙烯熔体的挤出畸变与非线性粘弹性的关系

采用毛细管流变仪等仪器研究了一类聚乙烯熔体的挤出畸变与熔体非线性粘弹性的关系。实验发现线形大分子或带小侧基的大分子熔体，容易发生壁滑和挤出压力振荡；而有较大侧基、或相对分子质量分布宽、或带大量短支链的熔体，挤出畸变现象较轻。挤出畸变与熔体的弹性及熔体一壁面吸附状态紧密相关：容易发生壁滑和挤出压力振荡的熔体，弹性较大(人口压力降大)；在壁面的吸附作用强(壁面临界剪切应力大).稳态剪切粘度大小与挤出畸变和压力振荡的关系不大；而拉伸应力和拉伸粘度大的熔体较易发生壁滑和挤出压力振荡。     

Shear modification of low density polyethylene

A single screw extruder was used to impose different shear histories on a low density polyethylene with broad molecular weight distribution and high molecular weight tail that had very little long chain branching. This polymer exhibits relatively high melt elasticity and the viscoelastic properties of its melt are strongly affected by preshearing. Such changes are accomplished without significant changes in molecular weight distribution or chemical structure. Measured viscous and elastic properties of the melt are different from piston-driven and screw extruder capillary rheometers. Shear modification effects in single screw extruders are enhanced by decreasing melt temperature, increased screw rotation speeds, and higher screw compression ratios. Melt elasticity can be cycled between high and relatively low values, for the particular polymer, by annealing or shearing the polymer melt.     

高分子材料动态成型过程中熔体非线性行为的研究

借助流变测量和连续介质理论,不依赖已有的本构关系,对平行叠加正弦振动条件下高分子熔体经毛细管的动态挤出过程进行了理论分析。以低密度聚乙烯(LDPE)为原材料,实验测量LDPE熔体在一定振动频率和振幅下毛细管入口压力、体积流量和挤出胀大的瞬态值,即可得到动态成型过程中高分子熔体剪切应力、剪切速率和表观粘度的变化规律:随振幅和频率的变化,LDPE熔体的表观粘度呈非线性变化趋势;在不同的振幅和频率下动态挤出LDPE熔体,跟稳态挤出时一样,壁面剪切应力与壁面剪切速率也成非线性比例关系。     

THE INFLUENCE OF POROUS MEDIA ON THE FLOW OF POLYMER MELTS IN CAPILLARIES†

Porous media placed in the entrance of capillaries were found to reduce the pressure drop across the capillaries (?P_c) by a factor of two or three for polystyrene. The reduction in ?P_c was found to be a function of the distance of the porous media from the capillary entrance, the type of porous media, the length of the capillary, and the rheological properties of the polymer melt. No significant reduction in ?P_c was observed for a polymer melt such as polyethyleneterephthalate (PET) which is nearly devoid of memory. The apparent shear rate for the onset of melt fracture was extended by a factor of three when polystyrene passed through the porous media before entering the capillary. No significant difference in die swell values was observed with the use of porous media in the entrance of the capillaries. The mechanism which accounts for these phenomena is believed to be associated with the break up of the entanglement network in the porous medium which temporarily changes the rheological properties of the polymer melt.     

Flow properties of molten ethylene–vinyl acetate copolymer and melt fracture

In an investigation of the behavior and formation mechanism of melt fracture the flow properties of molten ethylene–vinyl acetate (EVA) copolymer in the region of high shear rate were measured with a capillary-type rheometer. EVA copolymer differs slightly in flow curve from low-density polyethylene (LDPE); it seems, however, that the difference is due to the difference in molecular weight distribution (MWD) rather than to the materials themselves. The fluidity of molten EVA copolymer having a narrow MWD is equivalent to that of LDPE having a broad MWD and, generally, EVA copolymer has a higher fluidity than LDPE. It is expected that the fluidity increases with incorporation of vinyl acetate at the same MWD and the same M?_w. The critical shear rate increases with melt index and temperature. It cannot be found that the materials themselves and the MWD directly influence the critical point of melt fracture formation when the melt index is taken as a parameter. The critical viscosity (η_c) at which melt fracture forms decreases in an almost straight line with an increase of melt index. It was found from the studies of end correction and behavior of melt fracture formation that melt fracture occurs at the inlet of the die, and it is supposed that the melt fracture formation is caused by the elastic turbulence in the flow pattern due to a failure of recoverable shear strain at the die inlet.     

Extrude distortion in the capillary/slit extrusion of a molten polypropylene

Experiments were carried out in both sliding plate and capillary rheometers with a polypropylene resin to determine the conditions for the onset of slip, surface, and gross melt fracture. It was found that there was no distinction between surface and gross melt fracture, which is commonly observed in the case of polyethylenes. Furthermore, the flow curves determined by using capillaries having various diameters are diameter independent implying the absence of slip. However, experiments with slit dies having rough surfaces suggest wall slip. Further analysis has shown that the effect of viscous heating masks the detection of slip from the diameter-dependency of the flow curves. The effect of a thin layer of fluoropolymer (Teflon PA, DuPont) on the critical shear stress for the onset of wall slip and melt fracture, as well as on the relationship between the wall shlip and the shear stress, were also examined. It was found that the presence of such layers increases the slip velocity, while it decreases the critical shear stress for the onset of slip.     

Charakterisierung von Polyethylenen hoher Dichte mittels rheologischer Messungen

The melt rheological behaviour of three homologous HDPE-series, differing substantially in molecular weight distribution and each encompassing a broad molecular weight range, was investigated. The viscoelastic properties were measured by means of a sandwich-type creep rheometer and capillary viscosimeters. The zero shear viscosity is found to be proportional to the 3.6 power of the weight average molecular weight. The shear stress dependence of viscosity is related to the molecular weight distribution and is not influenced by molecular weight. The elastic behaviour (shear compliance) is also only effected by molecular polydispersity. This normal behaviour of PE is easily obscured by long chain branching. Few long chain branches cause considerable deviations of the rheological properties.