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     

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     

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     

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.     

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     

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.     

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。     

Rheological characterisation of hydroxyapatite filled polyethylene composites. Part 2 – Isothermal compressibility and wall slip

Abstract

Rheological characterisation of hydroxyapatite–high density polyethylene (HA–HDPE) composites has been performed in terms of isothermal compressibility and wall slip. Addition of HA to the polymer melt decreases the compressibility of the melt. The unfilled HDPE was found to exhibit wall slip at shear stresses as low as 0·10 MPa. The flow curves of the composites showed three distinct regions: a gradient at low shear rates; a plateau region; and a gradient at higher shear rate. An increase in rheometer pressure seems to suppress the slip in composites. The 40 vol.-% HA–HDPE composite exhibited two critical shear stresses, one corresponding to wall slip, which occurs in the lower shear rate region of the flow curve, and the other corresponding to a plateau, which is identified with the stick–slip behaviour of unfilled HDPE reported in the literature. The plateau shear stress increased with filler volume fraction and this effect is attributed to the decreased compressibility of the melt. A good correlation with a negative correlation coefficient was found to exist between compressibility and shear stress in the plateau region. The slip observed in unfilled HDPE and at low shear rates in the 40 vol.-% HA–HDPE systems has been explained in terms of a low molecular weight polymer layer formed at the melt/wall interface. The large interfacial slip observed in the plateau region is attributed to complete disentanglement of adsorbed chains from free chains at the melt/wall interface at and beyond the plateau region.     

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     

高密度聚乙烯的壁面滑移行为

用双筒毛细管流变仪和旋转流变仪研究了两种牌号的高密度聚乙烯(HDPE)熔体的壁滑行为,考察了发生壁滑的临界剪切应力。通过剪切速率扫描的方法发现两种牌号的HDPE熔体在较高的剪切速率下均发生粘滑转变,在150～230℃温度范围内,HDPE发生粘滑转变的临界剪切应力位于0.20～0.38 MPa范围内,与文献报道值一致;而且发生粘滑转变的临界剪切应力随温度线性增加,这与B rochard和de Gennes提出壁滑的解缠机理一致。用壁滑外推长度表征壁滑程度,发现两种牌号的HDPE熔体的壁滑外推长度均处于0.05～0.09 mm范围内。     

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.     

HDPE及其共混物的挤出压力振荡现象

采用恒速型双毛细管流变仪研究高密度聚乙烯及其共混物的压力振荡现象,测量了压力振荡的振幅及频率,计算了熔体在管壁的滑移速率和临界外推滑移长度。结果表明,发生压力振荡时,熔体与毛细管壁的界面出现“时黏时滑”转变。黏界面时,挤出物表面出现“鲨鱼皮”现象;滑界面时,挤出物表面粗糙,类似于无规破裂。随剪切速率的增加,压力振荡的振幅减小,而滑移速率、临界外推滑移长度及振荡频率均有提高。升高挤出温度和采用共混改性都可抑制压力振荡现象。     

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.     

Melt fracture behavior of polypropylene‐type resins with narrow molecular weight distribution. I. Temperature dependence

Polypropylene (PP)‐type resins with narrow molecular weight distribution, such as PP‐type thermoplastic elastomer PER and controlled‐rheology PP (CRPP) made by peroxide degradation of high molecular weight PP, have a problem of easy generation of skin roughness at extrusion. To examine the present state, the occurrence of skin roughness in PER and CRPP at extrusion was investigated with a capillary rheometer in a shear rate range of 12–6100 s^?1 and a temperature range of 180–280°C. A homo‐PP (HPP) and a block‐PP (BPP) with usual molecular weight distributions were used for comparison. HPP and BPP with usual molecular weight distributions show smooth extrudates at low shear rates and abruptly generate severe skin roughness “elastic failure” originating at the die entrance at a higher shear rate. PER and CRPP with narrow molecular weight distributions easily generate “sharkskin” melt fracture originating at the die exit, from a shear rate nearly one decade lower than rates of elastic failure of HPP and BPP. The sharkskin becomes more severe, with increasing shear rate, and attains to the elastic failure. The critical shear rate at which sharkskin occurs increases with increasing extrusion temperature. The critical shear rate is about 20 s^?1 at 180°C and about 120 s^?1 at 280°C, which is in the range encountered by the molten resin at extrusion processing. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 84: 2111–2119, 2002     

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.     

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。     

Novel processing aid based on modified Silly Putty®

A viscoelastic material based on low‐molecular‐weight silanols cured by boric acid, i.e., having a composition similar to that of the well‐known Silly Putty®, was used to delay sharkskin and stick–slip instabilities in the extrusion of linear low‐density polyethylene (LLDPE). The use of sodium hydroxide and phosphoric acid in the composition helped to improve adhesion of the material to metal and to extend its efficiency above 200°C. Adding powders of metal oxides, e.g., borax, silica, and especially silicates, further helped to delay the flow instabilities. A delay of the sharkskin instability to 25–35 times higher extrusion rates was achieved, and about 45% less pressure was observed in a screw extruder at the same throughput when this material was used as an additive to LLDPE (～0.1%) or as a coating of the extrusion die. Tentative explanations of the sharkskin origin and for the delay of the instability are proposed. J. VINYL. ADDIT. TECHNOL., 12:131–142, 2006. © 2006 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.     

Sharkskin mechanism of high‐impact polystyrene (HIPS) and rheological behavior of HIPS/TiO2 composites

The rheological behaviors of high‐impact polystyrene (HIPS) and HIPS/TiO₂ composites were investigated by use of a rheometer in the present article. HIPS exhibited a constant critical stress of the sharkskin in various temperatures, and the analysis indicated that the mechanism of sharkskin of HIPS was wall–slip and its special temperature dependency was determined by weak wall–melt adsorption. The experimental results also showed that the introduction of TiO₂ into HIPS only slightly influenced the apparent viscosity (η_a) of the composites. Moreover, TiO₂ exhibited an unusual effect on the non‐Newtonian index of the composites at high shear rate. Both phenomena indicated the increase of inner free volume induced by TiO₂ in molecularly rigid HIPS. Moreover, it was noteworthy that a featured stress could be used to label the dispersion of TiO₂ in the HIPS matrix, and the numeric affinity of this featured stress and the critical stress of sharkskin revealed that both processes were relevant to the same molecular relaxation. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 96: 802–807, 2005     

挤出过程中NR／CPB混炼胶壁滑移行为研究：Ⅱ.壁滑移速度

应用Ｍｏｎｓａｎｔｏ加工性能试验机，考察了天然胶／顺丁胶胶料在毛细管挤出过程中的壁滑移速度及其影响因素。发现，在较低的剪切速率下，试样的流动曲线出现不连续；壁滑移速度与壁面剪切应力之间大体上呈指数函数关系；发生壁滑移时的临界剪切应力随着温度的升高而下降。