PET熔融挤出后的特性黏数变化

分别使用单螺杆挤出机、双螺杆挤出机、反应型挤出机挤出聚对苯二甲酸乙二酯(PET),研究其在不同挤出温度、不同螺杆转速下熔融挤出后PET的特性黏数变化情况。使用双螺杆挤出机时,PET降解最严重,特性黏数平均降低23.5%。使用单螺杆挤出机:在较低挤出温度时挤出产物基本不降解;在高温时挤出产物降解明显,挤出温度每提高10℃,产物特性黏数平均降低5.8%;较高的螺杆转速有利于防止PET的降解;原料含水量越低,PET分子越不易降解。使用反应型挤出机时,PET热降解程度大于使用单螺杆挤出机。PET最适合使用单螺杆挤出机,在较低挤出温度、较高螺杆转速、物料经过烘干的情况下进行熔融挤出加工。     

Distribution of chain defects and microstructure of melt crystallized polyethylene

A combined study using wide-angle X-ray diffraction (WAXD) and small-angle X-ray diffraction (SAXD) of a series of mostly low density polyethylenes with a wide range of chain defect concentrations (0.1–7%) crystallized from the melt is reported. The data presented here complement the earlier results obtained by Swan⁷ and Holdsworth and Keller⁸ for copolymers. The concurrent unit cell expansion and long period decrease with increasing chain defect concentration leads to a picture of chain defects (branches, unsaturations) being distributed between the crystalline lamellae and the surface layer. Based on a model which assumes inclusion of defects within the lattice by means of a generation of 2gl kinks, (supported by the parallel increase of paracrystallinity) an estimation of the concentration of chain defects, ?_c, incorporated into the crystal lattice (<1%) is attempted. The density of defects in the non-crystalline regions, ?_a, turns out to be substantially larger than ?_c and supports the view of a clustering of defects, ?_c and ?_a are both increasing functions of ? with a tendency to level off for ? > 6. According to this model, the fraction of defects incorporated into the lattice does not exceed 20% of the total number of defects in any of the samples investigated. The fraction of defects excluded from the lattice (>80%), on the other hand, sets a higher permissable limit to the crystal thickness value achieved.     

Impact of organoclay and maleated polyethylene on the rheology and instabilities in the extrusion of high density polyethylene

The impact of organoclay on the rheology and extrusion of high density polyethylene (HDPE) was studied. Organoclay effect was studied at very low clay loading (≤0.1 wt %) while serving as a processing aid. A special design slit die with three transducers was used in the study of the extrusion melt instabilities. The rheological results showed that normal stress difference of HDPE was reduced during steady shear rate and stress growth tests when organoclay (≤0.1 wt %) was added. The extensional strain and stress growth of HDPE reduced with the addition of organoclay. So, organoclay (≤0.1 wt %) has an effect on the shear and extensional rheology of HDPE. The intensity of the melt instability was characterized with both a moment analysis and distortion factor (DF) from an advanced Fourier transform analysis. Both showed the same trends in the characterization of the pressure fluctuations in the die. Generally, addition of organoclay (≤0.1 wt %) to HDPE led to the reduction in DF. The ratio of first and second moment analyses became reduced as well. The results quantified the extent of elimination of gross melt fracture in HDPE by organoclay. Also, the extrusion pressure was reduced with organoclay (≤0.1 wt %) inclusion hence more throughput. There was a good correlation between rheology and extrusion. Both showed that the platy‐like organoclay streamlined the melt flow. However, the maleated polyethylene added as a compatibilizer did not give substantial synergistic effect. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

New developments in melt rheology aid formulating rigid vinyl compounds with improved extrusion processing

This paper describes a new approach to the rheological characterization of PVC compounds using a capillary rheometer. Since the control of the thermal degradation rate of rigid PVC is very critical in extrusion, a new quantitative method of measuring the true degradation rate of PVC is proposed for formulating rigid vinyl compounds. The usefulness of this new technique is demonstrated in formulating PVC compounds with the lowest rate of degradation measured on the Kayeness capillary rheometer. This study shows a very good correlation between the capillary rheometer data and the extrusion melt temperature, melt viscosity, and the rate of degradation of PVC. The ideal melt temperature for extrusion is determined from the rheology data of each PVC compound to attain the longest run time. The study also shows how to measure the true melt temperature in extrusion, an important variable, to control the rate of degradation in processing. The results of this study show how the new rheology technique can be used as a practical tool for product development, quality control of the PVC compounds, and the development of optimum extrusion parameters.     

The effect of materials' rheology on process energy consumption and melt thermal quality in polymer extrusion

Polymer extrusion is an important but an energy intensive method of processing polymeric materials. The rapid increase in demand of polymeric products has forced manufactures to rethink their processing efficiencies to manufacture good quality products with low-unit-cost. Here, analyzing the operational conditions has become a key strategy to achieve both energy and thermal efficiencies simultaneously. This study aims to explore the effects of polymers' rheology on the energy consumption and melt thermal quality (ie, a thermally homogeneous melt flow in both radial and axil directions) of extruders. Six commodity grades of polymers (LDPE, LLDPE, PP, PET, PS, and PMMA) were processed at different conditions in two types of continuous screw extruders. Total power, motor power, and melt temperature profiles were analyzed in an industrial scale single-screw extruder. Moreover, the active power (AP), mass throughput, torque, and power factor were measured in a laboratory scale twin-screw extruder. The results confirmed that the specific energy consumption for both single and twin screw extruders tends to decrease with the processing speed. However, this action deteriorates the thermal stability of the melt regardless the nature of the polymer. Rheological characterization results showed that the viscosity of LDPE and PS exhibited a normal shear thinning behavior. However, PMMA presented a shear thickening behavior at moderate-to-high shear rates, indicating the possible formation of entanglements. Overall, the findings of this work confirm that the materials' rheology has an appreciable correlation with the energy consumption in polymer extrusion and also most of the findings are in agreement with the previously reported investigations. Therefore, further research should be useful for identifying possible correlations between key process parameters and hence to further understand the processing behavior for wide range of machines, polymers, and operating conditions.     

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.     

Temperature dependence of polyolefin melt rheology

The rheology of polymer melts depends strongly on temperature. Quantifying this temperature dependence is very important for fundamental, as well as practical, reasons. The purpose of this paper is to present a unified framework for handling the temperature dependence of rheological data. We considered the case (by far the most common in polymer melts) where all relaxation times (in the context of linear viscoelasticity) have the same temperature dependence (characterized by a “horizontal shift activation energy”) and all relaxation moduli have the same temperature dependence (characterized by a “vertical shift activation energy”). The horizontal and vertical activation energies were extracted from loss tangent vs. frequency and loss tangent vs. complex modulus data, respectively. This is the recommended method of calculation, as it allows independent estimation of the two activation energies (statistically uncorrelated). It was shown theoretically, and demonstrated experimentally, that neglect of the vertical shift leads to a stress (or modulus) dependent activation energy and necessitates different activation energies for the superposition of loss and storage modulus data. The long standing problem of a stress-dependent activation energy in long chain branched LDPE was identified as originating from the neglect of the vertical shift. The theory was applied successfully to many polyolefin melts, including HDPE, LLDPE, PP, EVOH, LDPE, and EVA. Linear polymers (HDPE, LLDPE, PP) and EVOH do not require a vertical shift, but long chain branched polymers do (LDPE, EVA). Steady-shear viscosity data can be superimposed using activation energies extracted from dynamic data.     

Pressure effects in polymer melt rheology

Wide ranges of pressure and temperature are encountered in polymer processing operations, as, for example, in injection molding. While the temperature dependence of viscosity has been widely studied, the pressure dependence has not. The present work focuses on the measurement of the melt viscosity of polystyrene at high pressures (up to 124 MPa or 18,000 psi) and high shear rates (1–100 s^?1) at 180°C. The apparatus was a capillary rheometer with the downstream chamber being held at a high back pressure by means of a needle valve. The data so obtained were combined with zero shear viscosity data from the literature; and then correlated with a shear-dependent rheological model of the authors, using a shift factor suggested by Utracki (based on the Simha–Somcynsky equation of state). The final correlation calls for making both the elastic modulus and the time constant dependent on pressure, with the modulus being the dominant factor at high shear rates.     

Elongational rheology of polyethylene melts

Effective elongational viscosities were measured for high‐ and low‐density polyethylene samples using a capillary rheometer fitted with semihyperbolic dies. These dies establish a purely elongational flow field at constant elongational strain rate. The effective elongational viscosities were evaluated under the influence of the process strain rate, Hencky strain, and temperature. Enthalpy and entropy changes associated with the orientation development of semihyperbolic‐processed melts were also estimated. The results showed that elongational viscosities were primarily affected by differences in the weight‐average molecular weight rather than in the degree of branching. This effect was process‐strain‐rate‐ as well as temperature‐dependent. An investigation of the melt‐pressure relaxation and the associated first decay time constants revealed that with increasing strain rate the molecular field of the melt asymptotically gained orientation in approaching a limit. As a result of this behavior, molecular uniqueness became much less distinct at high process strain rates, apparently yielding to orientation development and the associated restructuring of the melt's molecular morphology. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 79: 2170–2184, 2001     

Influence of polyfunctional monomer on melt strength and rheology of long‐chain branched polypropylene by reactive extrusion

Long chain branching (LCB) were added to linear polypropylene (PP) using reactive extrusion in the presence of selected polyfunctional monomers (PFMs) and a peroxide of dibenzoyl peroxide (BPO). Fourier Transformed Infrared spectra (FTIR) directly confirmed the grafting reaction occurred during the reactive extrusion process. Various rheological plots including viscosity curve, storage modulus, Cole‐Cole plot, and Van‐Gurp plots, confirmed that the LCB structure were introduced into modified PPs skeleton after modification. In comparison with linear PP, the branched samples exhibited higher melt strength, lower melt flow index, and the enhancement of crystallization temperature. The LCB level in modified PPs and their melt strength were affected by the type of PFM used and could be controlled by the PFM properties and structure. PFMs with lower boiling points, such as 1, 4‐butanediol diacrylate (BDDA), could not produce LCB structure in modified PP skeleton. The shorter molecular chain bifunctional monomers, such as 1,6‐hexanediol diacrylate (HDDA), favored the branching reaction if their boiling points were above the highest extrusion temperature. And some polar groups, such as hydroxyl, in the molecule of PFM were harmful to the branching reaction, which might be attributed to the harm of the polarity of groups to the dispersion of PFM in PP matrix. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Effect of diatomite/polyethylene glycol binary processing aid on the melt fracture and the rheology of polyethylenes

The influence of polyethylene (PE) glycol (PEG), diatomite, and diatomite/PEG binary processing aid (BPA) on the rheological properties and the sharkskin melt fracture of three PEs was studied using a capillary rheometer. When diatomite or PEG is added to the PE matrix, they have little effect on the viscosity reduction of PEs, while the diatomite/PEG BPA shows a synergetic effect on the viscosity reduction of PEs. The incorporation of small amount of BPA was found to increase the shear‐thinning behavior and decrease the melt viscosity significantly. Meanwhile, the critical apparent shear rate for the onset of sharkskin melt fracture of PEs is increased. The mechanism for BPA to improve the rheological properties and the melt flow instability of PEs was discussed. POLYM. ENG. SCI., 45:898–903, 2005. © 2005 Society of Plastics Engineers     

Melt rheology of high-density polyethylene

The melt rheology of high density polyethylene was investigated. Linear viscoelasticity, capillary flow properties, and molecular weight parameter were measured with a plate relaxometer, capillary rheometer, and gel permeation chromatography, respectively. Intimate correlations among the slope of relaxation modulus curve, non-Newtonian flow behavior, Barus effect, and molecular weight parameter, M_z(M_z+1)/M_w, respectively, were found.     

High density polyethylene/polystyrene blends: Phase distribution morphology,rheological measurements,extrusion, and melt spinning behavior

An experimental study of the development of phase morphology, rheological properties, and processing behavior of mechanical blends of a polystyrene (PS) and a high density polyethylene (PE) is presented. Phase morphologies were determined by scanning electron microscopy for (i) products prepared in a screw extruder/static mixer system, (ii) samples removed from a cone-plate viscometer, (iii) extrudates, and (iv) melt spun fibers. Disperse phase dimensions were measured. The values varied from 1–5 μm in the products from static mixers. The dimensions of the dispersed phase in the blend products from the cone plate and capillary die were of the same order. The melt-spun fibers exhibited disperse phase dimensions as low as 0.35 μm. Polystyrene was extracted from the blend fibers producing small diameter, PE fibrils, or minifibers. Both the initial melts and the blends were rheologically characterized. The shear viscosity and principal normal stress difference N₁ exhibit maxima and minima when plotted as a function of composition. The characteristics of extrudates and melt spinning behavior of the blends were investigated. The shrinkage of extrudates of PE is much greater than PS. Additional small amounts of PE to PS greatly increase its shrinkage. Addition of PE to PS initially increases extrudate swell, though the swell shows maxima and minima when considered as a function of composition. The positions of the maxima and minima correspond to those of N₁. The onset of draw resonance has been investigated in isothermal melt spinning. Wide angle X-ray diffraction studies have been carried out on blend fibers and the orientation of the crystalline polyethylene regions has been determined as a function of process conditions. This orientation decreases rapidly with the addition of polystyrene when the melt-spun filaments are compared at the same spinline stress or drawdown ratio.     

控制聚乙烯熔融接枝马来酸酐副反应的研究进展

介绍了聚乙烯熔融接枝马来酸酐的反应机理,引发剂用量、单体用量、螺杆转速、反应温度等对反应的影响。综述了熔融接枝过程中控制副反应发生的方法,包括加入给电子体、共聚单体、新型引发剂或复配引发剂以及加入其他有机物添加剂,同时比较了加入这些物质的有效性。展望了聚乙烯熔融接枝马来酸酐的发展趋势。     

Anomalous rheological behavior of polyethylene melts in the gross melt fracture regime in the capillary extrusion

During the capillary extrusion with several different polyethylenes, we observe an abnormal rheological behavior. The nominal viscosity of polyethylene melt in the gross melt fracture regime does not change with a temperature. All polyethylenes tested show same behaviors. More interestingly, the nominal viscosity in the gross melt fracture regime shows even no molecular weight dependency when PEs have similar molecular structures (degree of branching and co-monomer content). From various experiments, we conclude that this abnormal phenomenon is relevant to the structural change with the melt temperature.     

The melt rheology of chloro-polyether and polyepichlorohydrin blends

The melt rheological behavior of chloro-polyether and polyepichlorohydrin blends was studied. It was found that both the coupled and uncoupled blends at different blending ratios are pseudoplastic, but there was a great difference in pseudoplastic behavior between them. All the blends obeyed the principles of temperature superposition and composition superposition for plots of shear stress vs. shear rate. A model is proposed to describe and predict the rheological behavior of the blends.     

Warm hydrostatic extrusion of polyethylene

Hydrostatic extrusion of high density polyethylene at an extrusion ratio of 15:1 was investigated in the temperature range between 100 and 134°C. A thin-walled tube was extruded having a tensile strength of 370 MPa and a tensile modulus of 10 GPa. The extrusion rate was limited by severe extrudate distortion which occurs at a limiting shear stress under stick-slip conditions. Even during steady extrusion wall slip was evident. At a constant extrusion speed, the extrusion pressure was found to be very sensitive to the extrusion temperature. An increase from 120 to 125°C reduced the extrusion pressure by half. Various thermal pretreatments of the starting billets were found to have little effect on the extrusion behavior and physical properties of the extrudate.     

The use of melt strength of low density polyethylene as a processability measure in film blowing extrusion

The melt strength method is analyzed in terms of its ability to predict the axial stress levels found in tubular film extrusion of low density polyethylene. For certain values of the capillary L/D, the level of axial stresses and average Newtonian viscosity found in the filament stretching and film blowing are comparable at the same draw ratio. The elongation to break of the finished film was found to be primarily determined by the axial stress during the film blowing, at constant frost line height.     

Flow properties of polyethylene melt

Flow properties for low-density and high-density polyethylene over a broad range of shear stress are described. Flow equations presented in literatures are tested from the point of view of the extrapolating method for evaluating the zero shear viscosity. It is shown that the method based on the equation of Cross gives relatively good results. The recoverable shear strain calculated from the capillary end correction is practically equal to that determined from the creep experiment at the same shear stress. The effect of shear stress on the elastic property is examined.