UHMWPE/HDPE/纳米SiO2共混体系的毛细管挤出流变行为

采用毛细管流变仪,研究了超高分子量聚乙烯(UHMWPE)/高密度聚乙烯(HDPE)/纳米二氧化硅(SiO2)共混体系,及其对照组的流变行为和挤出过程中的不稳定流动现象,分析了共混物发生鲨鱼皮畸变和整体破裂的临界剪切应力和临界剪切速率的变化情况。结果表明,经过偶联剂改性的纳米SiO2粒子,在PE基质的共混体系中存在一定的界面黏附作用,降低了纳米共混体系的挤出胀大比,弹性特征减轻。这种界面相互作用限制了纳米共混材料在口模区域的黏性流动以及分子链离开口模后的构象恢复,降低了发生流动不稳定现象的临界剪切速率,发生鲨鱼皮畸变的临界剪切应力增大,整体破裂后,形成交替出现"鲨鱼皮-破裂"的振荡性变化外观。     

Characterization of melt flow instabilities in polyethylene/carbon nanotube composites

The effect of single (SWCNT) and multi- (MWCNT) walled carbon nanotubes on the melt flow instabilities of polyethylenes with different topologies was characterized by means of a novel capillary rheometer allowing in-situ measurements of the pressure fluctuations inside the die and by scanning electron microscopy (SEM) analysis. Our results show that carbon nanotubes modify the main characteristics of the spurt instability developed by the linear polyethylene. Furthermore, the sharkskin instability, developed in short chain branched polyethylene, is reduced at low amounts of MWCNT and SWCNT. Noteworthy, the critical shear rate for the on-set of the spurt and the sharkskin instabilities decreases in the nanocomposites due to the physical interactions between the polymer and the nanofiller.At high shear rates, the gross melt fracture instability is completely erased in the nanocomposites based on the linear polymer whereas in short chain branched polyethylene the amplitude of this bulk distortion is rather moderated. These changes were confirmed by on-line pressure measurements using the novel capillary rheometer set-up. Based on our results, it is concluded that carbon nanotubes drastically affect the non-linear molecular dynamic leading to polyethylene melt flow instabilities.     

Novel processing aids for extrusion of polyethylene

Commercially available thermoplastic elastomers (TPEs) based on block copolymers of diisocyanates and polyols (i.e., TPUEs) were used to delay sharkskin and stick‐slip instabilities in the extrusion of linear low density polyethylene (LLDPE). When TPUE is added in a small mass fraction to LLDPE, it deposits at the die surface during extrusion and may postpone the onset of sharkskin instability to a 12–20 times higher rate of extrusion. Substantial delay of sharkskin was also achieved under conditions without slip of molten PE inside the die coated by TPUEs. Efficiency to delay the instabilities depends on elasticity of TPUE at processing temperature. The TPUEs could be a cost‐effective substitution of fluorinated polymers such as processing aid, lubricant and release agent in the processing of polyethylene by extrusion, blow molding, and injection molding. J. VINYL ADDIT. TECHNOL., 11:127–131, 2005. © 2005 Society of Plastics Engineers     

Correlation between polyethylene topology and melt flow instabilities by determining in-situ pressure fluctuations and applying advanced data analysis

Using three high sensitive pressure transducers located inside a slit-die of a capillary rheometer and applying a set of advanced mathematical tools to process the acquired time dependent pressure signals, we are able to detect in-situ pressure fluctuations associated with sharkskin instabilities. Other distortions, as spurt and gross melt fracture, can also be in-situ detected. This originates from a factor of 10³ and 10² improvement in terms of time and pressure resolution achieved using the new set-up and data analysis that it will be described in detail in this article. Our approach quantifies the effect of polymer topology and shear rate on the characteristic frequency and amplitude of these pressure fluctuations inside the die. Depending on the polymer structure and the shear rate, different instabilities with large deviation in their main properties at melt-state, can be determined. Based on our results, a polymer-independent power law relationship between the characteristic frequency of the instability and the apparent shear stress has been found. Combining this new technique with the advanced mathematical analysis used, clear evidences concerning the origin and location of these instabilities, could be established. According to our analysis, the spurt instability starts in the entrance of the die and it propagates downstream while increasing its velocity along the die. This was confirmed by non-zero-time-lags in the cross-correlation function between the transducers located inside the slit-die. In case of sharkskin instability, pressure fluctuations inside the die indicate that its origin could also be already inside the die instead of being exclusively located at the die-exit region, as stated in earlier investigations.     

A study of melt density of flowing linear polyethylene

Linear polyethylene was extruded from a capillary rheometer with the driving piston operated at fixed speed and at fixed pressure. Apparent viscosity and melt density were measured in both extrusion modes. Apparent density decreased at shear rates approaching the melt fracture region in fixed piston-speed operation. Flow of other polymer melts was essentially incompressible in fixed piston-speed operation, and all polymers exhibited incompressible flow in fixed-pressure extrusion. The oscillating portion of the flow curve of linear polyethylene reflects alternating periods in which the polymer exits faster and slower than the rate at which the advancing piston clears the rheometer reservoir. Linear polyethylene behaves differently from most other polymers in fixed piston-speed extrusion and during melt fracture because of the existence of a more extensive entanglement network in the melt. It is suggested that melt fracture in general results from a tensile failure of the entanglement network, which may occur at the die inlet and in the orifice.     

Processing history in extrusion dies and its influence on the state of the polymer extrudate at the die exit

A method is proposed to describe the processing history in extrusion dies and its influence on the state of the polymer after processing. The approach differs from conventional processing analysis, which uses the shear viscosity function to calculate pressure drop vs flow rate relations. The approach also differs from heuristic analysis which tries to find empirical correlations between rheological observations and processing behavior. The method is applied to the flow in annular extrusion dies. An integral constitutive equation is chosen to calculate the flow and to describe the flow history at the die exit as memorized. In the analysis, the kinematics are locally approximated by isothermal steady shear flow. The velocity and the velocity gradient are used to determine the Finger strain tensor, the path lines, and the residence times of the deforming material elements. Measures of the state of the polymer at the die exit are chosen to be the stress ratio N₁/2τ₁₂ and the free recovery. The free recovery calculations presume that the extrudate is chopped into small volumes of homogeneous flow history. The results of the calculations show the polymer very sensitively reacts to small changes of the die geometry. Important applications of this analysis are film blowing and blow molding, where the extensional behavior during the blowing process outside the die depends greatly on the preceding shaping process inside the die.     

Triple-detector GPC characterization and processing behavior of long-chain-branched polyethylene prepared by solution polymerization with constrained geometry catalyst

Fourteen long-chain branched (LCB) polyethylene (PE) samples were prepared by a constrained geometry catalyst. The PE samples had average branching frequencies of 0.06-0.98 branches per polymer chain, as determined by the nuclear magnetic resonance spectroscopy (¹³C NMR). These samples, as well as five linear PEs were characterized using a gel permeation chromatography (GPC) coupled with online three-angle laser light scattering (LS), differential refractive index (DRI), and viscosity (CV) detectors. The root mean-square radius of gyration intrinsic viscosity ([η]), and molecular mass (M) of the PEs were measured for each elution fraction. Based on the comparison of the long-chain branching (LCB) PEs with their linear counterparts and the Zimm-Stockmayer equation, the distributions of long-chain branch frequency (LCBF) and density (LCBD) as function of molecular mass were estimated. It was found that although the LCBF increased with the increase of molecular mass, the LCBD showed a maximum value in the medium molecular mass range for most of the PE samples. The average LCBD data from the GPC analysis were in good agreement with the ¹³C NMR measurements. The rheological properties and processing behavior of these samples were also assessed. While the long chain branching showed significant effects on the modulus and viscosity, it did not improve the processing. Compared to linear PE, polymer melt flow instabilities such as sharkskin, stick-slip and gross melt fracture developed in extrusion of LCB PEs occurred at lower wall shear stresses and apparent shear rates.     

A study of “worms” melt fracture in polyethylene extrusion blow molding process using capillary rheometry

During the polyethylene (PE) blow molding process of large size drums, string‐like defects, which are referred to here as worm melt fracture, can sometimes be observed on the extrudate surface. Such string‐like defects, in various shapes and sizes, are also observed in the capillary extrusion at high shear rates after the slip‐stick transition. The PE resin with broader molecular weight distribution (MWD) exhibits a greater degree of worm melt fracture while narrow MWD PE resin, which has higher slip velocity and a uniform slip layer, shows a lesser degree of worm melt fracture. It is hypothesized that the worm melt fracture is related to the die build‐up. Based on the mechanism of the fast die build‐up, it is proposed that the cohesive slip layer, which is a failure within the polymer melts at an internal surface, could emerge out from the die as these string‐like materials attached on the extrudates. The broader MWD resin, which has more small polymer chains and a lower plateau modulus, is postulated to have a weaker polymer melt, which then makes it easier to have such an internal failure and consequently have more string‐like defects at high shear rates. POLYM. ENG. SCI., 56:650–656, 2016. © 2016 Society of Plastics Engineers     

The application of an extrusion slit die in the rheological measurements of polyethylene composites with calcium carbonate using an in‐line rheometer

This article has reported the results of rheological testing of low‐density polyethylene (LDPE) and its calcium carbonate composites containing 7, 14, 21, and 28 wt% filler, respectively. The polymer composites were produced in a twin‐screw extrusion process. The assessment of the rheological properties of the polymeric materials was made under extrusion process conditions, using an in‐line rheometer with an extrusion slit die (W = 20, H = 2, L = 150 mm), at temperatures of 170°C, 180°C, and 190°C, respectively. The rheological parameters were determined based on the Ostwald‐de‐Waele power law model. The employed testing stand enabled the assessment of the effect of filler addition and slit die temperature on the variations in viscosity, power law index (n), consistency index (K), maximum flow velocity (V_max), and maximum flow profiles (V_z), under the conditions of technological processing (extrusion) of plastics. POLYM. ENG. SCI., 59:E16–E24, 2019. © 2018 Society of Plastics Engineers     

黏结磁性材料复合体系流动缺陷的研究

利用双料简毛细管流变仪，讨论了在高磁性粉末装载量下黏结磁性材料复合熔体流动缺陷问题。实验表明，黏结磁性材料复合熔体具有超高的流动黏度，在毛细管内受压流动时流动行为与管径尺寸相关。在小管径时容易产生“时黏时滑”、“压力振荡”等流动不稳定现象。分析认为，黏结磁性材料复合熔体体系是低量黏结剂和超高量的磁性粉末共混合体系，在小管径毛细管内受压流动时由于粉末粒子自由转动空间较小，产生剪切迁移行为不均匀，集聚在管壁处的低黏度物料量不稳定而引起管壁滑移等不稳定流动缺陷。     

Linear low-density polyethylene/high-density polyethylene blends: Effect of high-density polyethylene content on die swell and flow instability

This work aimed to evaluate the effect of high-density polyethylene (HDPE) content and of shear rate on the die swell and flow instability of linear low-density polyethylene (LLDPE)/HDPE blends. The results showed that the die swell of the LLDPE/HDPE blends increased with the increase in the shear rate. At high shear rates, the increase in the HDPE content led to an increase in the die swell of LLDPE/HDPE blends. The surface morphology analysis of the extrudates by optical and scanning electron microscopy revealed the presence of sharkskin and stick–slip flow instabilities in LLDPE and LLDPE/HDPE blends at the shear rates investigated. These instabilities were attenuated with the addition of HDPE and almost disappeared in the LLDPE/HDPE blend containing 50 wt% of HDPE.     

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     

Sharkskin and oscillating melt fracture: Why in slit and capillary dies and not in annular dies?

The sharkskin and stick‐slip polymer extrusion instabilities are studied primarily as functions of the type of die geometry. Experimental observations concerning the flow curves, the critical wall shear stress for the onset of the instabilities, the pressure and flow rate oscillations, and the effects of geometry and operating conditions are presented for linear low‐density polyethylenes. It is found that sharkskin and stick‐slip instabilities are present in the capillary and slit extrusion. However, annular extrusion stick‐slip and sharkskin are absent at high ratios of the inside‐to‐outside diameter of the annular die. This observation also explains the absence of these phenomena in other polymer processing operations such as film blowing. These phenomena are explained in terms of the surface‐to‐volume ratio of the extrudates, that is, if this ratio is high, sharkskin and stick‐slip are absent. POLYM. ENG. SCI., 2008. © 2007 Society of Plastics Engineers     

Oscillating flow behavior of high-density polyethylene melts

The oscillating flow behavior of a variety of high-density polyethylene and copolymer samples was studied in a constant displacement rate rheometer. At any plunger velocity, the period of the oscillations decreases linearly with melt depth, suggesting a resonance phenomenon. As plunger velocity is increased, the load waveform changes in a regular manner that indicates a progressive increases in the proportion of each cycle spent on the right-hand branch of the flow curve. Little difference was found in the shear stress at which oscillating flow began for samples differing in molecular weight, molecular weight distribution, and manufacturing process. However, the shear rate at which oscillating flow begins depends, strongly on both molecular weight and distribution. Oscillating flow is shifted to higher shear rates by broadening distribution, reducing molecular weight, increasing temperature, or decreasing the L/D ratio of the capillary.     

Rheological properties of glass bead-filled low-density polyethylene composite melts in capillary extrusion

The melt flow of glass bead-filled low-density polyethylene composites in extrusion have been observed by using a capillary rheometer to investigate the effects of temperature, shear rate, and filler content on the rheological properties of the melts. The results show that the melt shear flow obeys a power law, and the dependence of the apparent shear viscosity, η_app, on temperature is in accord with an Arrhenius equation. At the same temperature and shear rate, η_app increases slightly with increasing the volume fraction of glass beads, but the flow behavior index decreases with increasing filler content. In addition, the first normal stress difference of the melts linearly increases with increasing wall shear stress. Good agreement is shown with the N₁ calculated with the equation presented in this article and the pressured data from the sample melts. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 73: 1451–1456, 1999     

Effect of degree of polymerization on gelation and flow processability of poly(vinyl chloride)

The effect of degree of polymerization (DP) on the gelation and flow processability of poly(vinyl chloride) (PVC) was studied. Sheets with adjusted degree of gelation were prepared by rolling rigid pipe formulation suspension PVC compounds with DPs of 800, 1050 and 1300 by changing the milling temperature. Their degrees of gelation were measured with DSC and their capillary flow properties were measured with a capillary rheometer at 150, 170 and 190°C and the effect of DP on the relation between gelation and flow processabilities was studied. Because of the higher shearing heat during milling, the sample with the higher DP had a higher history temperature and thus tended to show a higher degree of gelation. The viscosity increased as the gelation increased. The dependency of viscosity on DP was higher at higher milling and extrusion temperatures and thus at a higher degree of gelation and a lower shear rate. This was assumed to be attributed to the more prominent uniform molecular flow as against the particle flow. The die swell increased with increasing the milling and extrusion temperatures and hence with increasing the gelation. A sample with a lower DP tended to show a larger die swell and this tendency was even more pronounced at the higher extrusion temperature. The melt fracture easily occurred when a sample with advanced gelation was extruded at low temperature. Whereas at low milling temperatures a sample with the lower DP showed a lower critical shear rate at onset of melt fracture, and thus easily generating melt fracture, at high milling temperatures it showed a higher critical shear rate and hence scarcely generated melt fracture. These experimental results were explained by the fact and concept that a sample with a lower DP shows a higher increase in the gelation during extrusion and/or the slighter feature of particle flow as against the uniform molecular flow at the same gelation level. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 1915–1938, 2004     

Rheological properties of branched low-density polyethylene

The shear flow properties of six commercially available long-chain branching low-density polyethylene resins were determined, using a cone-and-plate rheometer at low shear rates and a capillary rheometer at high shear rates. Also determined were the elongational viscosities of the resins, using an apparatus developed by Ide and White. Interpretation of the rheological measurements is given with the aid of the molecular parameters, namely, molecular weight and molecular weight distribution.     

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     

Melt fracture of two broad molecular weight distribution high‐density polyethylenes

The melt fracture instabilities of two broad molecular weight distribution (MWD) high‐density polyethylenes (one Ziegler–Natta and one metallocene HDPEs) are studied as functions of the temperature and geometrical details and type of die (cylindrical, slit, and annular). It is found that sharkskin and other melt fracture phenomena are distinctly different for these resins, despite their almost identical rheology. It is also found that the critical conditions for the onset of various melt fracture phenomena depend significantly on the type of die used for their study. For example, sharkskin melt fracture in slit and capillary extrusion was obtained at much small critical shear stress values compared with those found in annular extrusion. Moreover, the metallocene HDPE shows significant slip at the die wall in the sharkskin flow regime. On the other hand, the Ziegler–Natta HDPE has shown no sign of slip. These differences are discussed on the basis of differences in their MWDs that influence their melt elasticity. POLYM. ENG. SCI., 2011. © 2011 Society of Plastics Engineers     

Gross melt fracture mitigation in converging dies: A singular behavior due to polymer wall slip

This work focuses on mitigating the gross melt fracture defect of polymer flowing through axisymmetrical and two‐dimensional dies. The die entrance angle is considered as well as the influence of the converging wall roughness. Singular results are obtained with a random styrene butadiene rubber (SBR) copolymer, as the gross melt fracture defect cannot be eliminated or mitigated by reducing the die entrance angle. Other experiments carried out with rough converging dies do not give better results. Indeed, the polymer essentially slips along the walls, as shown from capillary rheometer and birefringence experiments. Thus, these results point out the importance of elongational stresses and interfacial conditions in the die entrance region on flow instabilities and the gross melt fracture defect.