Solid state coextrusion: A new technique for ultradrawing thermoplastics illustrated with high density polyethylene

Ultraoriented films of high density polyethylene (HDPE) have been prepared in continuous lengths by a new method, solid state coextrusion, through conical dies of extrusion draw ratios up to 36. Preformed HDPE billets ∽7 cm long and ∽1 cm in diameter of duPont Alathon 7050R, M_w = 59,000, M_n = 19,900, were split longitudinally into halves and then one or more wafers of the same polymer were inserted between the two sheath halves. Thereafter, the whole assembly was extruded through a conical die of 20° included entrance angle in the absence of lubricant and at temperatures substantially below the melting range yielding continuous and transparent films. The physical and mechanical properties of the HDPE films so produced were evaluated and compared with the properties of the same polymer extruded through a slit die. The high melt transition, tensile modulus and transparency confirm the effectiveness of the new method in continuously attaining ultradrawn films.     

Pressure–volume–temperature behavior of high density polyethylene

Equilibrium pressure-volume-temperature behavior in both the solid and molten regtions was determined for a high density (ρ = 0.958 g./cm.³) polyethylene. Data were measured with a recently developed compressibility device capable of obtaining precise and accurate data. Residual curve treatment showed that the data were true equilibrium data. Compressibilities calculated from the data of this Work compared favorably to existing data which were limited to 205°C. The presented work extended the compressibility behavior to 250°C. It was also found that differences in compressibility of low and high density polyethylenes were not eliminated. in the molten region, indicating that the effect of differences in morphology was not eliminated. The Spencer-Gilmore equation was fitted to the data of the present work. The internal pressure (π) term of the equation showed a definite relation to polymer morphology.     

Ultradrawing of thermoplastics by solid state coextrusion illustrated with high density polyethylene

Ultra-thin films of high density polyethylene of high orientation have been produced by the recently developed technique of solid state coextrusion. The films were prepared under moderate conditions, without lubricant in continuous lengths by extruding through conical dies of extrusion draw ratio up to 36. This is a draw ratio higher than achievable by conventional solid state extrusion at comparable processing conditions through slit dies. The ultra-thin films of high orientation were transparent and exhibited dead bend. The physical and mechanical properties were evaluated and compared with the properties of the same high density polyethylene extruded through a slit die. The increase in the melt point, crystallinity, tensile modulus, and birefringence indicates that the method is very efficient for the production of ultra-thin and highly oriented films. An experimental technique is also presented for preparing billets of controlled and uniform initial morphology and free of voids.     

Die–swell behavior of glass bead‐filled low‐density polyethylene composite melts at high extrusion rates

The extrudate swell behavior of glass bead‐filled low‐density polyethylene (LDPE) composite melts was investigated using a constant rate type of capillary rheometer at high extrusion rates and test temperatures varied from 140 to 170°C. The results show that the die swell ratio (B) of the melts increases nonlinearly with increasing apparent shear rates for the system filled with the surface of glass beads pretreated with a silane coupling agent, while the B for the system filled with uncoated particles remains almost constant when the true wall shear rate is greater than 2000 s⁻¹ at a constant temperature. The values of B for both the pure LDPE and the filled systems decreases linearly with an increase of the temperature and an increase of the die diameter at fixed shear rates, and the sensitivity of B on the die diameter and temperature for the former is higher than that of the latter. Furthermore, the effect of the filler content on B is insignificant, while the values of B decreases, obviously, with an increasing glass bead diameter (d) when d is smaller than 50 μm; then B varies slightly with d. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 76: 419–424, 2000     

Prediction of processability at extrusion coating for low‐density polyethylene

The neck‐in level and the maximum drawdown speed at extrusion coating for low‐density polyethylene are studied with the evaluation of the rheological properties in the molten state and the dilute solution properties. It is found that the viscous properties in the molten state and the dilute solution properties are not sensitive to the processability, whereas the elastic nature has a great impact. In particular, the elastic response in the nonlinear region, such as drawdown force and strain‐hardening behavior in elongational viscosity, can be employed for the prediction of the processability at extrusion coating. POLYM. ENG. SCI., 2008. © 2008 Society of Plastics Engineers     

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     

Foam extrusion of high density polyethylene/wood‐flour composites using chemical foaming agents

A one‐way analysis of variance and thermal analysis were performed in this study to examine the influences of the contents, types (exothermic vs. endothermic), and forms (pure vs. masterbatch) of chemical foaming agents (CFAs), as well as the use of coupling agents, on the density reduction (or void fraction) and cell morphology of extrusion‐foamed neat high density polyethylene (HDPE) and HDPE/wood‐flour composites. The CFA types and forms did not affect the void fractions of both the neat HDPE and HDPE/wood‐flour composites. However, a gas containment limit was observed for neat HDPE foams whereas the average cell size achieved in the HDPE/wood‐flour composite foams remained insensitive to the CFA contents, irrespective of the foaming agent types. The experimental results indicated that the use of coupling agent in the formulation was required to achieve HDPE/wood‐flour composite foams with high void fraction. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 88: 3139–3150, 2003     

A crack layer approach to fatigue crack propagation in high density polyethylene

Fatigue crack propagation (FCP) in high density polyethylene (HDPE) is observed to occur with an accompanying layer of damage ahead of the crack tip. The crack layer theory, which accounts for the presence of both the damage and the main crack, is applied to the problem. It is observed that the kinetic behavior of HDPE under fatigue consists of three regions: initial acceleration, constant crack speed (“deceleration”), and reacceleration to failure. Within the first two regions, crack propagation appears “brittle,” while in the third region “ductile” behavior is manifested. Ultimate failure occurs via massive yielding of the unbroken ligament. Two damage mechanisms are found to be responsible for HDPE failure: formation of fibrillated voids and yielding. Both mechanisms are present throughout the entire lifetime of the crack, but the former dominates the “brittle” crack propagation region, while the latter is more prominent in the “ductile.” Throughout the analysis the resistance moment R_t is approximated as the total volume of transformed material associated with crack advance. Crack layer analysis produces a satisfactory fit of the experimental data and yields a specific enthalpy of damage, γ^*, value in the 1–2 cal/g range.     

Influence of post‐extrusion parameters on the final morphology of polystyrene/high density polyethylene blends

The deformation of the dispersed phase in polystyrene/high density polyethylene (PS/HDPE) blends produced by ribbon extrusion was studied numerically and experimentally. A mathematical model for the deformation of the dispersed phase in ribbon extrusion processing of polymer blends was developed assuming uniaxial deformation of the ribbon and the equilibrium shapes of the dispersed particles with a pressure balance over a drop. Simulated morphologies as function of the post‐extrusion parameters were obtained and compared with experiments. The analysis of the ribbon extrusion process showed that parameters such as draw ratio (DR) and ribbon‐water contact length (X) significantly influence the ribbon dimensions, the extensional stress, and the stretching force. The results also showed that deformation and coalescence of the dispersed phase in the ribbon extrusion processing of polymer blends increase at higher DR and/or lower X values. The comparison between the model and the experimental morphologies of PS/HDPE produced a good agreement.     

Thermal degradation of rice-bran with high density polyethylene: A kinetic study

Thermal degradation behavior of mixtures of rice bran (RB) and high density polyethylene (HDPE) was investigated by thermo-gravimetric analyses (TGA) under dynamic conditions in nitrogen atmosphere and was compared with that of individual materials. Experiments were carried out in the range of ambient temperature to 900 °C at two heating rates (5 and 20 °C per minute). Kinetic analysis indicated that activation energy for pyrolysis of RB, HDPE and those for RB-HDPE mixtures varied with rate of heating as well as with the three temperature ranges. This variation has been explained on the materials’ decomposition behavior. Maximum difference between experimental and theoretical mass loss (Δm) was 26% at 475 °C and 34% at 489 °C at the heating rates of 5 and 20 °C per minute, respectively. These maxima indicate stronger interactions at corresponding temperature between RB and HDPE during copyrolysis. Reduction in activation energy for pyrolysis, lower temperatures at which rate of decomposition is highest, and negligible quantity of the residue suggest a synergism between thermal degradation of RB and HDPE.     

Parison swell—A new measurement method and the effect of molecular weight distribution for a high density polyethylene

The measurement of parison swell is difficult because swell is a time-dependent phenomenon and because, for a parison, two independent swell ratios must be determined. A new technique has been developed that makes use of a video camera focused on the end of the parison. Unlike previous techniques designed to measure time-dependent swell, no oil bath is required. The new technique was used to study the effect of molecular weight parameters on the parison swell of high density polyethylene. For a series of blends of two resins having significantly different weight-average molecular weights, the blends exhibited larger swell ratios than the base resins.     

Preparation of low‐density polyethylene foams with high rebound resilience by blending with polyethylene–octylene elastomer

Low‐density polyethylene (LDPE)/polyethylene–octylene elastomer (POE) foams with different composition ratios (POE, cross‐linking agent, and blowing agent) were produced by using the continuous cross‐linking and foaming process to improve the rebound resilience of chemical cross‐linked LDPE foams. The effects of POE, cross‐linking agent, and foaming agent on rebound resilience of LDPE/POE foams were investigated by using a rebound test, cross‐linking degree experiment, differential scanning calorimetry, and scanning electron microscopy. Results show that the rebound resilience of LDPE was improved by increasing the flexibility of cell walls and the cell density and decreasing the foam density. Compared with the rebound resilience of pure LDPE (33%), the proposed LDPE/POE foams could meet the requirements of gymnastics mats for high rebound resilience (55%). POLYM. ENG. SCI., 53:2527–2534, 2013. © 2013 Society of Plastics Engineers     

Reactive extrusion process for the grafting of maleic anhydride onto linear low‐density polyethylene with ultraviolet radiation

In this work, we chemically modified linear low‐density polyethylene with maleic anhydride in the molten state using, in a first step, different doses of ultraviolet irradiation to generate hydroperoxide groups, which were highly reactive at the processing temperature. Then, in a second reactive extrusion step, maleic anhydride was grafted to the linear low‐density polyethylene under different processing conditions. Characterization of the modified and unmodified linear low‐density polyethylene material was performed with Fourier transform infrared spectroscopy, differential scanning calorimetry, and nuclear magnetic resonance. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

A new method for producing high melt strength polypropylene with reactive extrusion

A high‐melt‐strength polypropylene (HMSPP) was prepared using a twin‐screw reactive extruder from a commercial isotactic polypropylene through two stages, first, maleic anhydride is grafted to polypropylene to obtain a maleic anhydride‐grafted polypropylene (PP‐g‐MA), and then the grafted polymer is reacted with epoxy to extend the branched chain. Fourier transformed infrared spectroscopy indicated that maleic anhydride was grafted on polypropylene and reacted with epoxy. Melt flow rate and sag resistance test showed that the melt strength of the HMSPP improved considerably. Differential scanning calorimetry test showed that the long chain branches (LCBs) act as a nucleating agent in the crystallization of the HMSPP, which leads to a high crystallization temperature and crystallinity. Furthermore, the LCB efficiency of the HMSPP can also be calculated by analyzing its rheological property. POLYM. ENG. SCI., 2008. © 2008 Society of Plastics Engineers     

Ultraviolet preirradiation of high‐density polyethylene for the grafting of maleic anhydride during reactive extrusion

High‐density polyethylene was irradiated with ultraviolet light for various exposure times, as a prestep for hydroperoxide production, before a bulk grafting reaction with maleic anhydride in the melt phase by reactive extrusion. This method was compared with a traditional grafting procedure using peroxides optimized by an evaluation of the grafting level versus the screw speed; the highest speed showed the greatest grafting value. The reaction was followed by Fourier transform infrared, the gel percentage, and the grafting degree, which was evaluated by titration. The effect of grafting for both methods under the established processing conditions on the thermal properties was observed with differential scanning calorimetry via their heating and cooling thermograms; there were notorious changes in the fusion peak temperatures, indicating differences in the crystallization process after the grafting reaction. The latter was confirmed by NMR spectroscopy, which showed succinic anhydride rings attached to the polyethylene chains. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 2882–2888, 2006     

In-line annealing—a new approach to the extrusion of high quality rigid vinyl products

Most polymers exhibit a very fluid melt rheology during extrusion and can be distorted, drawn down, and cooled without building excessive residual stresses into the product. In contrast, rigid vinyl is usually extruded as a stiff, almost selfsupporting mass. Care must be taken to prevent the formation ot oriented stresses in the product which will be relieved during long periods of exposure resulting in dimensional instability and related loss of physical properties. A newly developed method of in-line annealing has shown to be an effective means of relieving oriented stresses developed during extrusion. By use of this instrumented technique, rigid vinyl products can be controlled to much tighter shrinkage specifications in a single step process, thereby eliminating post-annealing treatments.     

Processing characteristics and structure development in solid-state extrusion of a new semicrystalline polyimide (BTDA–DMDA)

In this article, we present detailed processing characteristics and structure development in a thermoplastic polyimide BTDA–DMDA in the solid-state extrusion process. This fully imidized polyimide polymer is known to crosslink at fast rates when it is brought to a molten phase even for short periods of time. This characteristic makes it difficult to process it in the molten phase and attempts at melt processing result in melt fracture and highly distorted extrudates. However, this polymer can be shaped into high-quality extrudates when it is processed below its melting temperature directly from its postpolymerization powdered state. The solid-state extrusion of precompacted BTDA–DMDA powder was studied in the temperature range from 250 to 320°C. At the temperatures from 290 to 320°C, high-quality extrudates were obtained. Below 290°C, solid-state extrusion was not possible due to the limitation of the load cell capacity of the capillary rheometer used in this research. Above 320°C, the extrudates were found to be of poor quality as a result of degradation and crosslinking in the molten phase. Structural characteristics of the samples produced by solid-state extrusion was investigated by the microbeam X-ray diffraction technique. The thermal behavior of the extrudates was also characterized by differential scanning calorimetry (DSC). The DSC results show that at low extrusion temperatures the samples exhibit dual endothermic peaks and are highly crystalline in an extruded state. The higher melting peak located at about 350°C is due to the melting of the new crystalline phase that has developed partially during the solid-state extrusion process and partially during the recrystallization process that takes place at temperatures at and slightly above the primary melting process during the DSC heating scan. This has been confirmed by DSC, depolarized light hot-stage video microscopy, and wide-angle X-ray diffraction studies. The long spacing of the higher melting crystals was found to be much larger than that of the lower melting crystals, as evidenced by the small angle X-ray scattering studies. © 1995 John Wiley & Sons, Inc.     

Studies on high density polyethylene/polycarbonate blend system compatibilized with low density polyethylene grafted diallyl bisphenol A ether

Blends of a high density polyethylene (HDPE) matrix and a polycarbonate (PC) minor phase were investigated through their morphology, heat resistance, mechanical properties, crystallizing behavior, rheological measurement and especially the compatible effect of a compatibilizer: low density polyethylene grafted diallyl bisphenol A ether (LDPE-g-DBAE). The blends without compatibilizer exhibited a phase growth and no adhesive between the HDPE matrix and the dispersed phase. In the presence of 10% by weight of LDPE-g-DBAE as a compatibilizer, more fine particles and a dim phase interface were observed, and the blends showed a remarkable increase in heat distortion temperature and mechanical properties. The compatibilized blends possessed a high apparent viscosity as compared with the noncompatibilized ones. However, the apparent viscosity of the blends, with or without the compatibilizer, was lower than that of the neat HDPE and PC. Exploration by DSC found that the melting point and the crystallinity of HDPE in the blends decreased, and especially for the blends with the compatibilizer. These facts could be interpreted in terms of the efficient compatible effect of the LDPE-g-DBAE, which resulted from the interaction between the diallyl bisphenol A ether unit of LDPE-g-DBAE and polycarbonate, and the miscibility of the LDPE unit and HDPE.     

Small‐angle X‐ray scattering investigation of the deformation processes in the amorphous phase of high density polyethylene

In situ small‐angle X‐ray scattering of high density polyethylene under uni‐axial tensile test was used for investigating the deformation at the scale of the periodic crystalline–amorphous nano‐structure. The more or less uniform elastic straining of the rubbery amorphous layers is discussed in terms of mechanically active intercrystalline tie chains. Correlation is made with the long‐term use properties. It is concluded that this approach is a powerful means to assess the mechanical efficiency of tie molecules. Copyright © 2004 Society of Chemical Industry