The effect of surface energy of boron nitride on polymer processability

Flow instabilities manifest themselves as distortions on the extrudate surface (melt fracture). They are usually observed at high production rates in many polymer processing operations. Certain fluoropolymers/fluoroelastomers have long been used as processing aids for surface melt fracture elimination. Recent developments have shown that a small amount of boron nitride (BN) powder may successfully eliminate surface melt fracture and also delay the onset of gross melt fracture to higher rates. It has also been reported that a combination of BN and fluoropolymer/fluoroelastomer enhances the effectiveness of the polymer processing even further. The main objective of the present work was to measure the surface properties of a number BN powders, mainly surface energy, in order to gain a better understanding of its performance as a processing aid. Based on this study, it can be concluded that surface energy plays an important role in deciding the possible interactions between the processing aid, polymer melt and the extruding surface. It is observed that the lubricious nature of BN along with an optimum balance of its polar (non‐dispersive) and non‐polar (dispersive) components of surface energy renders BN a successful processing aid in eliminating both sharkskin and gross melt fracture phenomena. Polym. Eng. Sci. 44:1543–1550, 2004. © 2004 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     

A new processing aid for the extrusion of polyolefins

The influence of a new processing additive (a composition of fine particles of boron nitride) on the rheology and processability of molten polymers is studied. The equipment used includes both an Instron capillary rheometer with special annular dies (Nokia Maillefer wire coating crosshead) attached to the rheometer and a parallelplate rheometer. Two metallocene polyethylenes with several types of boron nitride powders varying in particle size distribution are tested at various concentration levels. The powder having the finest particle size was found to have the greatest influence in the processing of polyolefins using crosshead dies and tips. As a result, its use eliminates surface melt fracture and postpones the critical shear rate for the onset of gross melt fracture to significantly higher values depending on the additive concentration. The performance of the boron nitride in eliminating melt fracture is compared with that of a typical fluoroelastomer. It is shown that boron nitride is a superior processing aid.     

Effect of boron nitride on melt fracture phenomena and processability of lldpe during extrusion

Melt fractures related to processing instabilities limit processing rates in many commercially important polymer processing operations, such as fiber spinning, film blowing, extrusion, and various coating flows. Therefore, melt fracture is responsible for deteriorating the quality and the mechanical properties of final products for rates greater than a critical processing one at which melt fracture occurs. In this study, a commercial linear low-density polyethylene (LLDPE) was modified by adding a small amount of boron nitride (BN) during extrusion in order to improve processability. Capillary rheometry was used to assess processability at various temperatures, levels of applied shear rate, and the length-to-diameter (L/D) ratio for both the pure resin and resins containing boron nitride. Also, parallel-plate rheometry was used to evaluate the dynamic rheological properties of these resins. The relationship between the characteristic relaxation time and the critical shear rate for the onset of melt fracture and slip is discussed.     

Gross melt fracture elimination: The role of surface energy of boron nitride powders

Boron nitride (BN) is an effective processing aid for the extrusion of polyethylenes. It postpones the onset of gross melt fracture to significantly high shear rates not previously attained with conventional fluoropolymers. However, BN particles containing relatively high amounts of boron oxide (B₂O₃) do not perform well as processing aids. A reliable procedure has been developed for measurement of surface energy of powders using the capillary rise technique through the use of Washburn's equation. It is based on finding the contact angle from liquid penetration experiments with polar and non‐polar liquids. Both the dispersive and non‐dispersive components of surface energy are determined. With this technique, the surface energy of a number of different powders has been assessed. These results of the surface energy of BN powders have been found to correlate well with the critical shear rate for the onset of melt fracture, indicating the important role that surface energy plays in gross melt fracture elimination.     

Combining boron nitride with a fluoroelastomer: An enhanced polymer processing additive

The effect of a new processing additive (boron nitride powder in combination with a fluoroelastomer) on the rheology and processability of molten polymers is studied. The equipment used includes an Instron capillary rheometer equipped with a special annular die (Nokia Maillefer wire coating cross‐head) and a parallel‐plate rheometer. Metallocene polyethylenes with and without boron nitride (BN) and fluoroelastomer are tested in extrusion. First, it is demonstrated that BN is a superior processing aid compared to conventional fluoropolymer ones. Second, it is found that the combination of BN powders with a small amount of a fluorelastomer improves even further the processability of molten polymers (melt fracture performance).     

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.     

Experimental study of the melt fracture behavior of filled high‐density polyethylene melts

In this work, the melt fracture behavior of microfilled polymer melts based on a high‐density polyethylene (HDPE) was investigated by means of a capillary rheometer, which operated at constant piston velocity. The microfilled melts examined had the same filler content (10 vol%), but differed for the type of filler (glass beads, discontinuous glass fibers, and talc). The results demonstrated that the presence of rigid fillers influences the melt fracture behavior of the filled melts in a way that is dependent on the type of filler dispersed in the HDPE melt. Opposite effects were induced by lamellar particles of talc and by glass fillers (either beads or fibers): the former promoted flow stability, whereas the latter fostered the occurrence of instabilities of “stick‐slip” type. The effects induced by the presence of the glass fillers on the oscillating flow that takes place when “stick‐slip” instabilities occur were also analyzed and discussed. POLYM. ENG. SCI., 54:364–377, 2014. © 2013 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.     

Effect of combining boron nitride with fluoroelastomer on the melt fracture of HDPE in extrusion blow molding

Boron nitride (BN) is a new polymer processing aid which not only eliminates surface melt fracture in the extrusion of molten polymers, but also postpones the critical shear rate for the onset of gross melt fracture to significantly higher values that depend on resin type and additive concentration. In this work, the influence of BN as a polymer processing additive is first examined in the extrusion blow molding of high‐density polyethylene (HDPE) resins in order to evaluate its usefulness and performance in operations other than continuous extrusion. The equipment used includes both a Battenfeld/Fisher 50‐mm extrusion blow molding machine and a parallel‐plate rheometer. Two types of HDPE, which are blended with boron nitride at various concentration levels, are tested accordingly. It is found that the degree of BN dispersion, characteristics of the HDPE resins, extrusion temperature, and induction time play an important role in eliminating melt fracture. Finally, the influence of combining BN with fluoroelastomer, as an enhanced and potentially better processing aid on the melt fracture of a third HDPE is examined. It is found that such a combination is a superior processing aid that allows extrusion blow molding at very high shear rates.     

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     

Boron nitride as a processing aid for the extrusion of polyolefins and fluoropolymers

The influence of a new processing additive (fine particles of boron nitride) on the processability of polyolefins and fluoropolymers 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, and an extruder. Two metallocene polyethylenes and several Teflon® fluoropolymers were tested using these two pieces of equipment. The additive had a significant effect on the extrudate appearance of polyethylene and fluoropolymer particularly in the crosshead dies. It was found to eliminate surface melt fracture and to postpone the critical shear rate for the onset of gross melt fracture to significantly higher values depending on resin type, temperature, and additive concentration (typically 0.005% to 0.5%). To explain the possible mechanism for the effect of the additive on the processability of the resins, rheological measurements using both parallel‐plate and sliding‐plate rheometers were carried out. The rheology of the resins did not seem to change significantly with the addition of boron nitride except for the low‐shear‐rate (low‐frequency) range, where the behavior of the filled resin was found to be similar to that of a crosslinked polymer or a phase‐separated entangled blend. Practical wire coating and tubing extrusion studies for these resins were also carried out.     

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     

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     

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     

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。     

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     

A study of the stick‐slip phenomenon in single‐screw extrusion of linear polyethylene

We present results of a study on the stick‐slip phenomenon observed for two linear polyethylenes (HDPE and LLDPE). Experiments were carried out in a single screw extruder using dies of different diameters and L/D ratios. The pressure and the mass flow rate have been measured simultaneously and the instant mass flow rate was determined using laser Doppler velocimetry. Our results clearly confirm the hypothesis that the flow jumps from one stable branch to the other during oscillations as suggested in the literature. The role of the melt compressibility in the reservoir is also established. The effect of the average mass flow rate imposed by the extruder Q_IN on the respective compression and decompression phases is in good agreement with effect predicted by the mass balance in the reservoir. We also used different reservoir volumes to confirm that the period of oscillations increases with the compressed melt volume upstream of the die.     

Measurements of slip velocity and frictional heating in the capillary extrusion of linear‐low‐density polyethylene with a fluoropolymer processing aid

The slip velocity and frictional or slip heating of linear‐low density polyethylene with a fluoropolymer processing aid in capillary flow were measured by rheo‐particle image velocimetry and thermal imaging. The pure polymer did not show slip before the stick‐slip regime but exhibited strong slip when blended with the processing additive. However, for shear stresses beyond the stick‐slip regime, the pure polymer and the blend exhibited the same flow behavior with slip. The slip velocity increased with the shear stress at two different rates before and after the stick‐slip and the contribution of slip to the total flow rate exhibited a minimum. Significant rises in temperature were measured under slip and no slip conditions, being these much higher than the values predicted by the adiabatic flow assumption. Clear difference was made between viscous and frictional heating before the stick‐slip regime, even though they could not be distinguished from one another at higher stresses. Overall, in the presence of slip, frictional and viscous heating act synergistically producing higher temperature rises in the melt. Finally, in contrast to predictions by numerical simulations of viscous heating, measured velocity profiles did not evidence the heating effects in the shear stress range analyzed in this work. POLYM. ENG. SCI., 56:837–845, 2016. © 2016 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