Melt fracture of HDPEs: Metallocene versus Ziegler–Natta and broad MWD effects

The melt fracture of high-density polyethylenes (HDPEs) is studied primarily as a function of molecular weight and its distribution for broad molecular weight distribution metallocene and Ziegler–Natta catalyst resins. It is found that sharkskin and other melt fracture phenomena are very different for these two classes of polymers, although their rheological behaviors are nearly the same for many of these. Moreover, the metallocene HDPE shows significant slip at the die wall without exhibiting stick-slip transition. Important correlations are derived between the critical conditions for the onset of melt fracture and molecular characteristics.     

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     

The effect of teflon™ coatings in polyethylene capillary extrusion

Two LLDPE resins were used in this work to determine the critical conditions for the occurrence of wall slip and melt fracture in capillary extrusion. It was found that the polymer-metal interface fails at a critical value of the wall shear stress of about 0.1 MPa and, as a result, slip occurs. At values of wall shear strees of about 0.18 MPa the extrudate surface appears to be matte, while small amplitude periodic distortions (sharkskin) appear on the surface of extrudates at wall shear stresses above 0.25 MPa. Using a special slit die, the polymer–wall interface was coated with Teflon? in order to examine the effect of this coating on the processability of polyethylenes. It was found that use of Teflon? promotes slip, thus reducing the power requirement in extrusion and, most importantly, eliminates sharkskin at high extrusion rates. © 1995 John Wiley & Sons, Inc.     

Wall slip heating

When molten plastic is extruded, the upper limiting throughput is often dictated by fine irregular distortions of the extrudate surface. Called sharkskin melt fracture, plastics engineers spike plastics formulations with processing aids to suppress these distortions. Sharkskin melt fracture is not to be confused with gross melt fracture, a larger scale distortion arising at throughputs higher than the critical throughput for sharkskin melt fracture. Sharkskin melt fracture has been attributed to a breakdown of the no slip boundary condition in the extrusion die, that is, adhesive failure at the die walls, where the fluid moves with respect to the wall. In this article, we account for the frictional heating at the wall, which we call slip heating. We focus on slit flow, which is used in film casting, sheet extrusion, curtain coating, and when curvature can be neglected, slit flow is easily extended to pipe extrusion and film blowing. In slit flow, the magnitude of the heat flux from the slipping interface is the product of the shear stress and the slip speed. We present the solutions for the temperature rise in pressure‐driven slit flow and simple shearing flow, each subject to constant heat generation at the adhesive slip interface, with and without viscous dissipation in the bulk fluid. We solve the energy equation in Cartesian coordinates for the temperature rise, for steady temperature profiles. For this simplest relevant nonisothermal model, we neglect convective heat transfer in the melt and use a constant viscosity. We arrive at a necessary dimensionless condition for the accurate use of our results: Pé?1. We find that slip heating can raise the melt temperature significantly, as can viscous dissipation in the bulk. We conclude with two worked examples showing the relevance of slip heating in determining wall temperature rise, and we show how to correct wall slip data for this temperature rise. POLYM. ENG. SCI., 55:2042–2049, 2015. © 2014 Society of Plastics Engineers     

The effect of nanoclays on the processibility of polyolefins

The influence of a new processing additive (particles of organically modified nanoclays) on the processibility of polyolefins in extrusion is studied. The equipment used includes an Instron capillary rheometer with two types of dies, namely capillary dies and special annular dies (Nokia Maillefer wire coating crosshead) attached to the rheometer. Ziegler Natta and metallocene polyethylenes and one polypropylene were tested using these two pieces of equipment. It was found that the nanoclay additive had a significant effect on the extrudate appearance of polyethylene. It eliminates surface melt fracture and postpones the critical shear rate for the onset of gross melt fracture to significantly higher values depending on resin type, temperature, and additive concentration (typically 0.05 to 0.5 wt%). To explain the possible mechanism for the effect of the additive on the processibility of the resins, shear and extensional rheological measurements were carried out for the pure resins as well those loaded with the nanoclay additives. It seems that the presence of nanoclays suppresses the development of extensional stresses to such high levels that can cause melt fracture phenomena. Finally, it was found that the combination of nanoclays with traditional processing aids such as fluoropolymers produce an enhanced processing aid that can increase the critical shear rates for the onset of melt fracture to levels much higher than the individual constituents when they are used independently. POLYM. ENG. SCI., 45:1098–1107, 2005. © 2005 Society of Plastics Engineers     

Rheological evaluation of metallocene polyethylenes with processing aids by multi‐wave oscillations

During the die flow of metallocene polyethylenes, flow instabilities may occur. Namely, wall slip, “sharkskin,” and stick‐slip (pressure oscillations) and gross fracture may be obtained depending on the volume flow rate and die geometry. It was reported that fluoroelastomers and boron nitride powders with hexagonal crystal structure can be used as suitable processing aids in melt extrusion processes. Fluoroelastomers at low concentrations act as die lubricants and may eliminate flow instabilities such as surface and stick‐slip melt fracture. On the other hand, specific boron nitride powders may not only eliminate surface and stick‐slip melt fracture, but also postpone gross melt fracture to higher volume flow rates. In this paper, a way for quantitative differentiation of the influence of polymer processing additives on rheological behavior is shown. Standard material functions show no clear‐cut differences. However, using multi‐wave oscillations with higher strain amplitudes make a quantitative assessment possible. Polym. Eng. Sci. 44:2047–2051, 2004. © 2004 Society of Plastics Engineers.     

Effects of type of polymerization catalyst system on the degradation of polyethylenes in the melt state. Part 1: Unstabilized polyethylenes (including metallocene types)

Several polyethylene resins namely, high‐density polyethylene (HDPE) (Phillips metal oxide catalyst) and linear low‐density polyethylenes (LLDPE) (formed by using Ziegler‐Natta and metallocene catalyst technologies), were used in order to acquire insight into the effect of different polymerization catalyst systems on the production of degradation products during melt processing. Infrared spectroscopy, color measurement, hydroperoxide determination, and melt flow rate measurement were used to monitor the degradation as a function of the number of passes through a twin‐screw extruder. The metallocene PEs were shown to exhibit superior melt stability relative to Phillips HDPE. The latter showed high levels of hydroperoxide formation. The superior thermo‐oxidative stability of the metallocene PEs was attributed to low levels of metallic catalyst residues, together with low vinyl unsaturation content. In all of the PEs examined, the rate of crosslinking was greater than that of chain scission. IR spectroscopy indicated that crosslinking (most prevalent in the Phillips HDPE) proceeded via the addition of macroradicals to vinyl unsaturation. The Ziegler‐Natta LLDPE showed an intermediate tendency for crosslinking but notable formation of trans‐vinylidene and the most noticeable color development. J. VINYL ADDIT. TECHNOL., 2011. © 2011 Society of Plastics Engineers     

Melt fracture behavior of polypropylene‐type resins with narrow molecular weight distribution. II. Suppression of sharkskin by addition of adhesive resins

Standing on a hypothesis that the sharkskin of a polymer with a narrow molecular weight distribution at extrusion processing originates from a stick‐slip of the polymer at the die wall, the suppression of the sharkskin was tried by means of suppressing the slip by the addition of adhesives. To polypropylene (PP)‐type resins with narrow molecular weight distributions such as a PP‐type thermoplastic elastomer, PER and a controlled rheology PP were added small amounts of adhesives such as maleated PP, maleated PER, reactive polyolefin oligomers, ethylene/ethylacrylate/maleic anhydride (MAH) copolymer, ethylene/vinyl acetate copolymer, and styrene/MAH copolymer, and their melt fracture behaviors at capillary extrusion were observed. It was found that the sharkskin of the PP‐type resins with narrow molecular weight distributions was suppressed by the addition of the adhesive resins with good adhesion to metal. The suppressive effect of the sharkskin was generally the more remarkable by the higher loading of the adhesives with the higher MAH content. This is the direction of increasing adhesion. From this fact, it was assumed that the sharkskin of the PP‐type resins with narrow molecular weight distribution does not originate from a periodic growth and relaxation of tensile stress at the extrudate surface but from a stick‐slip at the die wall. Based on this mechanism, it may be said that the sharkskin can be suppressed by both ways of directions of promoting and suppressing the slip at the die wall. The former way is the previously known method, and the latter way is the method proposed in the present study. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 84: 2120–2127, 2002     

用双毛细管流变仪对 HDPE与LLDPE挤出压力振荡的研究

用RH2000恒速型双毛细管流变仪研究了3种HDPE和3种LLDPE的挤出压力振荡现象。通过压力振荡图、流动曲线和挤出物表观3方面,对两种类型聚乙烯压力振荡的差异进行了分析。发现HDPE的压力振荡很明显,振幅在2~3MPa,而LLDPE的振幅很小,甚至在压力-时间图上看不出来。6种聚合物的流动曲线都发生了断裂。在柱塞下降速度恒定下发生压力振荡时,流速并不恒定,粘界面条件下流速较小,滑界面条件下流速较大,并通过计算获得了3种HDPE发生压力振荡时对应于粘界面与滑界面的流速。HDPE和LLDPE在粘界面条件下挤出物都是鲨鱼皮,而滑界面条件下HDPE的挤出物类似于无规破裂,LLDPE挤出物表观较光滑,且没有鲨鱼皮。     

Improvement in processability of metallocene polyethylene by ultrasound and binary processing aid

The effect of ultrasonic vibration and binary processing aid in improving the processability of metallocene linear low‐density polyethylene (mLLDPE) was investigated. During extrusion, ultrasonic vibration clearly reduced the die pressure and apparent viscosity of mLLDPE but had only a slight effect on its melt fracture. The effect of diatomite/PEG binary processing aid (BPA) was excellent in reducing the viscosity and eliminating the sharkskin fracture of mLLDPE. The effect of ultrasonic vibration and binary processing aid in improving the processability of mLLDPE was synergetic. With a combination of ultrasonic vibration and a small amount of processing aid, the flowability of mLLDPE was further improved, and the critical shear rate for the onset of sharkskin fracture was increased. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 1927–1935, 2007     

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。     

The synergistic effect of boron nitride particle and die on the capillary extrusion processability of mLDPE

The synergistic effects of boron nitride (BN) powder and die on the rheology and processability of metallocene‐catalyzed low density polyethylene (mLDPE) were investigated. The processability in the extrusion process is closely related to the interfacial properties between the polymer melts and the die wall. BN powder was added to mLDPE to reduce the friction coefficient and surface energy. Adding 0.5 wt% BN powder to mLDPE was very effective in improving the processability and the extrudate appearance. To study the effect of die surface property, three different dies were applied in capillary extrusion. One was conventional tungsten carbide (TC) die, and the others were hot‐pressed BN (hpBN) die and hot‐pressed BN composite (hpBNC) die. The applications of these BN dies were quite effective in delaying surface melt fracture (sharkskin) and postponing gross melt fracture to higher shear rate compared to the TC die. These improvements result from the fact that BN dies reduce the wall shear stress significantly and promote slip. The synergistic effect of processability could be obtained when both BN powder and hpBN die were used together.     

The onset of wall slip and sharkskin melt fracture in capillary flow

The capillary die flow of high density and linear low density polyethylenes is simulated under slip conditions to investigate the origin of sharkskin melt fracture. As suggested in the literature, it is shown that sharkskin originates at the exit of the die and is due to the acceleration (high stretching rate) of the melt as it exits the die. It is also shown that both adhesion and slip promoters eliminate surface defects by decreasing the stretching rate of the polymer melt at the exit region of the die. The effect of length-to-diameter ratio of the die on the sharkskin melt fracture is also examined. It is found that sharkskin is more pronounced in short dies which is in accord with experimental observations. Finally, it is suggested that applied pressure at the capillary exit suppresses surface defects.     

Effects of ultrasonic oscillations on processing behavior and mechanical properties of metallocene‐catalyzed linear low‐density polyethylene/low‐density polyethylene blends

The influences of ultrasonic oscillations on rheological behavior and mechanical properties of metallocene‐catalyzed linear low‐density polyethylene (mLLDPE)/low‐density polyethylene (LDPE) blends were investigated. The experimental results showed that the presence of ultrasonic oscillations can increase the extrusion productivity of mLLDPE/LDPE blends and decrease their die pressure and melt viscosity during extrusion. Incorporation of LDPE increases the critical shear rate for sharkskin formation of extrudate, crystallinity, and mechanical properties of mLLDPE. The processing behavior and mechanical properties of mLLDPE/LDPE blends were further improved in the presence of ultrasonic oscillations during extrusion. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 94: 2522–2527, 2004     

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     

Comparative effect of metallocene and Ziegler‐Natta polypropylene on the exfoliation of montmorillonite and hectorite clays to obtain nanocomposites

The present study was carried out on the effect of molecular weight and polydispersity of polypropylene (PP) obtained via Ziegler‐Natta or metallocene catalysis on the formation of nanocomposites with montmorillonite and mineral and synthetic hectorite. The formation of the nanocomposites was achieved by the melt‐mix method. X‐ray diffraction, transmission electron microscopy, and analysis of mechanical properties showed that, using PP obtained via metallocene catalysis (polydispersity ～ 2), it is possible to achieve improved formation of nanocomposites compared with PP obtained via Ziegler‐Natta catalysis (polydispersity ～ 4). It was also found that the molecular weight of the PP affects the tendency toward clay exfoliation and consequently the properties of the nanocomposites. Montmorillonite type clay was evaluated at 1%, 3%, and 5% by weight in the nanocomposite. The nanocomposite with 1 wt % clay was found to have better mechanical properties compared with the nanocomposite containing 3 wt % and 5 wt %. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 698–706, 2007     

Dynamic slip and nonlinear viscoelasticity

Several significant problems arise when film is fabricated on a large scale. One of these is the appearance of irregularities on the extrudate surfaces when the polymer melt is extruded at high rates. These irregularities vary in intensity and form and are generally known as sharkskin melt fracture. This phenomenon, which occurs when the wall shear stress exceeds a critical value, is a limiting factor for production rates in many industrial extrusion operations such as film blowing of polyethylene. We used a sliding plate rheometer incorporating a shear stress transducer to study slip in both steady and unsteady flows. By combining a dynamic slip model with a nonlinear viscoelastic constitutive model, we determined the slip model parameters for LLDPE film resin with and without a fluoropolymer sharkskin suppressant. The models give good prediction of our slip data in steady shear but show insufficient gap dependence in exponential shear. Our own film blowing studies demonstrated the efficiency of the sharkskin suppressant; it has more than doubled the throughput in our laboratory setup. The fluoropolymer additive was found to profoundly affect both the steady and dynamic slip parameters. Hence, the sharkskin suppressant alters how the LLDPE remembers its past slipping motions.     

Rheological properties of metallocene isotactic polypropylenes

Rheological properties of metallocene‐catalyzed isotactic polypropylenes (MET‐PP) were evaluated in comparison with those of Ziegler–Natta‐catalyzed isotactic polypropylenes (ZN‐PP) and MET‐PP was generally characterized in a rheological aspect. Based on the characterization, various flow processibilities and their effect on the higher order structure and product properties of the processed article were estimated. The capillary flow properties at various temperatures, elongational flow properties, and dynamic viscoelasticities of MET‐PPs and ZN‐PPs with various melt flow indexes (MFIs) were measured. Furthermore, as an example of application of rheological analysis, the selection of proper raw resin and processing conditions in the sheet‐extrusion of MET‐PP was studied. MET‐PP shows the following rheological features due mainly to the narrow molecular weight distribution in comparison with ZN‐PP with equivalent MFI to that of MET‐PP: while the viscosities at low shear rates are lower, those at high shear rates are higher. Although there is little difference in the loss modulus G″ (viscosity), the storage modulus G′ (elasticity) is very (about one decade) lower. The die swell is much smaller. The entrance pressure loss and end correction coefficient are lower. The critical shear rate at which a melt fracture begins to occur is lower. The melt tension, elongational viscosity, and melt flow index ratio are lower. The flow activation energy is slightly lower. The zero‐shear viscosity obeys the 3.4th‐power law independent of catalyst. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 84: 2157–2170, 2002     

Melt spinning of metallocene catalyzed polypropylenes. I. On‐line measurements and their interpretation

The melt spinning of metallocene catalyzed isotactic polypropylene resins was investigated. The details are presented for on‐line studies performed on six miPP resins with melt flow rates (MFRs) between 10 and 100 and a Ziegler–Natta catalyzed isotactic polypropylene resin with a MFR of 35 for comparison. The on‐line studies indicated that, as the molecular weight and polydispersity increased, crystallization occurred closer to the spinneret at higher crystallization temperatures and under lower spin line stresses. Further, as the spinning speed increased, crystallization occurred closer to the spinneret at higher crystallization temperatures because of increased stress in the spin line. These observations were interpreted in terms of an increased rate of crystallization caused by increased molecular orientation in the spin line with increasing molecular weight and increasing spinning speed. This “stress‐enhanced” crystallization was further interpreted in terms of an increased rate of crystal nucleation. It was further concluded that the narrower molecular weight distribution of metallocene resins was the primary factor that produced differences in the structure and properties of fibers spun from these resins compared to those of Ziegler–Natta catalyzed resins of similar weight‐average molecular weight or MFR. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 82: 3223–3236, 2001     

Processability of LLDPE/LDPE blends: Capillary extrusion studies

The processing behavior of a number of linear low‐density polyethylenes/low density polyethylene (LLDPE/ LDPE) blends with emphasis on the effects of long chain branches is presented. A Ziegler‐Natta linear low‐density polyethylene was blended with four low‐density polyethylene LDPE's having distinctly different molecular weights. The weight fractions of the LDPEs used in the blends were 1, 5, 10, 20, 50, and 75 wt%. Capillary extrusion reveals that the onset of sharkskin and gross melt fracture are slightly influenced with the addition of LDPE into LLDPE. However, the amplitude of the oscillations in the stick‐slip flow regime was found to scale well with the weight fraction of LDPE. Amounts as low as 1 wt% LDPE have a significant effect on the amplitude of pressure oscillations. These effects are clearly due to the presence of long chain branching (LCB); furthermore, it was observed that the onset of this flow regime was shifted to higher shear rates with increase of LDPE content. On the other hand, shear rheology is not sensitive to detect addition of small levels of LDPE up to 20 wt%. Extensional rheology can detect levels of LDPE as small as 1 wt% only at high Hencky strain rates (typically greater than 5s^?1) and only for certain blends, typically those that contain LDPE of high molecular weight. It is suggested that the magnitude of oscillations in the oscillating melt fracture flow regime is a sensitive method capable of detecting low levels of LCB. POLYM. ENG. SCI., 47:1317–1326, 2007. © 2007 Society of Plastics Engineers