Compounding and injection molding of polybutene‐1/polypropylene blends

The effect of shear‐controlled orientation injection molding (SCORIM) was investigated for polybutene‐1/polypropylene blends. This article reports on the methods and processing conditions used for blending and injection molding. The properties of SCORIM moldings are compared with those of conventional moldings. SCORIM is based on the application of specific macroscopic shears to a solidifying melt. The multiple shear action enhances molecular alignment. The moldings were investigated with mechanical tests, differential scanning calorimetry studies, and polarized light microscopy. The application of SCORIM improved Young's modulus and the ultimate tensile strength. The gain in stiffness was greater for higher polybutene‐1 content blends. A drastic decrease in the strain at break and toughness was observed in SCORIM moldings. The enhanced molecular orientation of SCORIM moldings resulted in a featureless appearance of the morphology. Interfacial features due to segregation were visible in the micrographs of SCORIM moldings. Both conventional and SCORIM moldings exhibited form I′ in polybutene‐1. This article explains the relationship between the mechanical properties and micromorphologies. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 88: 806–813, 2003     

Structure development and interfacial interactions in high‐density polyethylene/hydroxyapatite (HDPE/HA) composites molded with preferred orientation

Composites of high‐density polyethylene (HDPE) filled with sintered and nonsintered hydroxyapatite (HA) powders, designated as HAs and HAns, respectively, were compounded by twin screw extrusion. Compounds with neoalkoxy titanate or zirconate coupling agents were also produced to improve interfacial interaction and filler dispersion in the composites. The composites were molded into tensile test bars using (i) conventional injection molding and (ii) shear‐controlled orientation in injection molding (SCORIM). This latter molding technique was used to deliberately induce a strong anisotropic character to the composites. The mechanical characterization included tensile testing and microhardness measurements. The morphology of the moldings was studied by both polarized light microscopy and scanning electron microscopy, and the structure developed was assessed by wide‐angle X‐ray diffraction. The reinforcing effect of HA particles was found to depend on the molding technique employed. The higher mechanical performance of SCORIM processed composites results from the much higher orientation of the matrix and, to a lesser extent, from the superior degree of filler dispersion compared with conventional moldings. The strong anisotropy of the SCORIM moldings is associated with a clear laminated morphology developed during shear application stage. The titanate and the zirconate coupling agents caused significant variations in the tensile test behavior, but their influence was strongly dependent on the molding technique employed. The application of shear associated with the use of coupling agents promotes the disruption of the HA agglomerates and improves mechanical performance. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 86: 2873–2886, 2002     

Injection molding of a starch/EVOH blend aimed as an alternative biomaterial for temporary applications

Biodegradable polymers show great potential to be used as materials for temporary implants and bone replacement applications in orthopedics. However, its use in high load‐bearing applications will depend on the successful development of biodegradable implants with a mechanical performance matching that of human bone. This article describes the optimization of the injection molding process of an alternative biodegradable starch‐based polymer aimed at biomedical applications. A blend of starch with a copolymer of ethylene–vinyl alcohol (SEVA‐C) was studied. Both conventional injection molding and shear controlled orientation (SCORIM) were optimized with the support of design of experiments and analysis of variance techniques. The mechanical characterization was performed by tensile testing. The structure developed within the moldings was assessed by wide‐angle X‐ray diffraction and differential scanning calorimetry. Increases up to 30% in the tangent modulus and 20% in the ultimate tensile strength compared with conventional molding were achieved with the application of SCORIM. The holding pressure and the frequency of the shear applied have the strongest influence on the morphology development and consequently on the mechanical performance. The solidification of SEVA‐C at high cavity pressures enhances stiffness for long durations of the shearing stage in SCORIM. However, the effect of viscous heating of SEVA‐C is important and ought to be considered. A decrease of the material phase miscibility in SEVA‐C occurs as result of the shear fields imposed. The microstructure evaluation suggests that the mechanical properties enhancement in SCORIM molded SEVA‐C is attributable to preferred orientation developed during processing. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 77: 1303–1315, 2000     

Structure and physical property relationships in processed polybutene‐1

The effect of SCORIM was investigated on three grades of polybutene‐1 and one grade of ethylene–butene‐1 copolymer. The methods and processing conditions used for injection molding and the properties of the moldings are reported. Phase transformations and their relationship with mechanical properties are discussed in detail. Both, conventional and shear‐controlled orientation injection molding (SCORIM) were employed to produce moldings. SCORIM is based on the application of specific macroscopic shears to a solidifying melt. The multiple shear action enhances molecular alignment. The moldings were investigated by performing mechanical tests, fractographic analysis, differential scanning calorimetry studies, wide‐angle X‐ray diffraction, polarized light microscopy, and atomic force microscopy. The application of SCORIM improves the mechanical performance. Molecular orientation results in the formation of shish‐kebab morphology. One grade of polybutene‐1 exhibited a greater than fivefold increase in Young's modulus. The application of high cavity pressures favored the formation of the stable Form I' in polybutene‐1. The formation of Form I' led to a decrease in crystallinity and mechanical properties. However, this loss was by far smaller than the gain obtained via the formation of shish‐kebab morphology. The relationship between mechanical properties and micromorphologies of the investigated materials is explained. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 88: 814–824, 2003     

Biaxially self‐reinforced high‐density polyethylene prepared by dynamic packing injection molding. I. Processing parameters and mechanical properties

Uniaxial oscillating stress field by dynamic packing injection molding (DPIM) is well established as a means of producing uniaxially self‐reinforced polyethylene and polypropylene. Here, the effects on the mechanical properties of high‐density polyethylene (HDPE) in both flow direction (MD) and transverse direction (TD) of packing modules and processing parameters in DPIM are described. Both biaxially and uniaxially self‐reinforced HDPE samples are obtained by uniaxial shear injection molding. The most remarkable biaxially self‐reinforced HDPE specimens show a 42% increase of the tensile strength in both MD and TD. The difference of stress–strain behavior and impact strength between MD and TD for the DPIM moldings indicates the asymmetry of microstructure in the two directions. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 93: 1584–1590, 2004     

Bi‐axial self‐reinforcement of high‐density polyethylene induced by high‐molecular weight polyethylene through dynamic packing injection molding

Previously, bi‐axial self‐reinforcement of high‐density polyethylene (HDPE) was achieved through a uni‐axial shear stress field introduced by dynamic packing injection molding technology. Here, further improvement of tensile strength along the flow direction (MD) was achieved by blending a small amount of high‐molecular‐weight polyethylene (HMWPE) with HDPE, while the tensile strength along the transverse direction (TD) still substantially exceeded that of conventional moldings. Tensile strengths in both flow and transverse directions were considerably enhanced, with improvements from 23 MPa to 76 MPa in MD and from 23 MPa to 31 MPa in TD. The effect of HMWPE content and molding parameters on tensile properties was also investigated. The tensile strength along MD was highly dependent on HMWPE content, oscillating cycle, mold temperature, melt temperature and packing pressure, while that along TD was insensitive to composition and processing parameters within the selected design space. According to the stress–strain curves, samples with HMWPE produced by dynamic packing injection molding had a special tensile failure mode in MD, different from both typical plastic and brittle failure modes. There were no yielding and necking phenomena, which are characteristic during tensile testing of plastic materials, but there was still a considerably higher elongation compared to those of brittle materials. However, in TD, all dynamic injection molding samples exhibited plastic failure as did typical conventional injection molding samples. Copyright © 2006 Society of Chemical Industry     

Structural development of HDPE in injection molding

This study investigated some relevant structure/properties relationships in shear‐controlled orientation in injection molding (SCORIM) of high‐density polyethylene (HDPE). SCORIM was used to deliberately induce a strong anisotropic character in the HDPE microstructure. Three grades with different molecular weight characteristics were molded into tensile test bars, which were subsequently characterized in terms of the mechanical behavior by tensile tests and microhardness measurements. The structure developed upon processing was also characterized by polarized light microscopy (PLM), scanning electron microscopy (SEM), differential scanning calorimetry (DSC), and wide‐angle X‐ray diffraction (WAXD). SCORIM allows the production of very stiff molded parts, exhibiting a very well‐defined laminated morphology. This morphology is associated with both an M‐shaped microhardness profile and a pronounced mechanical anisotropy. These characteristics are supported by an analogous variation in the crystallinity and a high level of molecular orientation, as indicated, respectively, by calorimetric measurements and X‐ray diffraction results. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 2079–2087, 2003     

Self‐reinforcement of high‐density polyethylene/low‐density polyethylene prepared by oscillating packing injection molding under low pressure

This article reports the toughness improvement of high‐density polyethylene (HDPE) by low‐density polyethylene (LDPE) in oscillating packing injection molding, whereas tensile strength and modulus are greatly enhanced by oscillating packing at the same time. Compared with self‐reinforced pure HDPE, the tensile strength of HDPE/LDPE (80/20 wt %) keeps at the same level, and toughness increases. Multilayer structure on the fracture surface of self‐reinforced HDPE/LDPE specimens can be observed by scanning electron microscope. The central layer of the fracture surface breaks in a ductile manner, whereas the break of shear layer is somewhat brittle. The strength and modulus increase is due to the high orientation of macromolecules along the flow direction, refined crystallization, and shish‐kebab crystals. Differential scanning calorimetry and wide‐angle X‐ray diffraction find cocrystallization occurs between HDPE and LDPE. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 71: 799–804, 1999     

Effect of low‐frequency melt vibration on HDPE morphology

BACKGROUND: A low‐frequency vibration‐assisted injection‐molding (VAIM) device was developed to explore the morphology of high‐density polyethylene (HDPE) injection moldings. Scanning electron microscopy, wide‐angle X‐ray diffraction and differential scanning calorimetry were used to characterize structure‐property relationships of final products prepared under different VAIM processing conditions (vibration frequency and vibration pressure amplitude) with conventional injection molding for comparison. RESULTS: It was found that increasing the vibration frequency at constant vibration pressure amplitude was beneficial for obtaining ‘shish‐kebab’ structures in the core region of VAIM specimens, and increasing the vibration pressure amplitude at constant vibration frequency was a prerequisite for achieving HDPE specimens with large‐scale lamellas, more pronounced orientation and high crystallinity. CONCLUSION: Both preferred orientation lamellas and increased crystallinity allow one to obtain strong injection moldings with the application of the melt vibration technique. Copyright © 2009 Society of Chemical Industry     

Processing–mechanical property relationships in injection moldings of polybutylene

Two unfilled nonpigmented extrusion grades of polybutylene have been injection-molded into a tensile bar mold under a wide range of barrel and mold temperatures. The overall structure of the moldings has been determined and correlated with processing conditions. The short term tensile mechanical properties of the moldings have been ascertained and correlated with molding structure. For low mold temperatures, the Young's modulus and tensile strength of injection moldings of polybutylene are controlled by the extent of and structure within the highly oriented skin. Low barrel temperatures can give rise to highly crystalline thick skins that treble the Young's modulus and fracture stress, when compared to high barrel temperature moldings. Increasing the mold temperature introduces a brittle response in polybutylene injection moldings. Modulus is controlled, at the high mold temperatures, by the skin thickness and by the crystallinity of the material comprising the core of the molding.     

Morphologies and mechanical properties of HDPE induced by small amount of high‐molecular‐weight polyolefin and shear stress produced by dynamic packing injection molding

To better understand the effect of a small amount of high‐molecular‐weight polyethylene (HMWPE) on the mechanical properties and crystal morphology under the shear stress field, the dynamic packing injection molding (DPIM) was used to prepare the oriented pure polyethylene and its blends with 4% HMWPE. The experiment substantiated that the further improvement of tensile strength along the flow direction (MD) of high‐density polyethylene (HDPE)/HMWPE samples was achieved, whereas the tensile strength along the transverse direction (TD) still substantially exceeded that of conventional molding. Tensile strength in both flow and TDs were highly enhanced, with improvements from 23 to 76 MPa in MD and from 23 to 31 MPa in TD, besides the toughness was highly improved. So, the samples of HDPE/HMWPE transformed from high strength and brittleness to high strength and toughness. The obtained samples were characterized via SEM and TEM. For HDPE/HMWPE, the lamellae of the one shish‐kebab in the oriented region may be stretched into other shish‐kebab structures, and one lamella enjoys two shish or even more. This unique crystal morphology could lead to no yielding and necking phenomena in the stress–strain curves of HDPE/HMWPE samples by DPIM. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Processing,tensile, and fracture properties of injection molded Hdpe‐Al2O3‐HAp hybrid composites

The aim of this study is to characterize the physical and mechanical properties of HDPE‐alumina‐HAp composites prepared by injection molding techniques and to demonstrate their superiority over unreinforced HDPE. Composites with up to 30 vol. % of filler, composed of equal volumes of HAp and alumina, were successfully processed by injection molding. On the basis of the analysis of processing results, i.e., melt viscosity, volume flow rate, shear rate, mixing torque, the critical ceramic loading was determined. Tensile tests done at varying crosshead speeds confirm that an increase in ceramic loading results in an increase in strength, as well as a simultaneous decrease in the total elongation at failure. A maximum strength of 20 MPa and a maximum tensile modulus of around 1 GPa was achieved with 30 vol % ceramic loading in semicrystalline HDPE matrix. SEVNB test results demonstrate an improvement in toughness at 20 vol %. The fracture properties are discussed in terms of interfacial bonding between ceramic fillers and the semicrystalline HDPE matrix. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Real‐time diagnosing polymer processing in injection molding using ultrasound

Ultrasonic diagnosing technique with a new high‐temperature ultrasonic transducer is developed to real‐time diagnose polymer processing and its morphology changes in injection molding processing. Compared with the previous researches, the new technique can provide more and accurate information. In this study, ultrasound diagnosis shows that longitudinal wave can real‐time characterize the data of the injection process and polymer morphology changes, including melt flow arrival time, the part ejection time, filling and packing stages, polymer solidification process, and the morphology changes during polymer crystallization. Shear waves can real‐time diagnose Young's and shear storage modulus, anisotropy property of polymer in injection molding. During our research, real‐time ultrasonic diagnosis shows that the storage modulus along the vertical direction is larger than that of the parallel to the melt flow direction under our setup injection conditions. Scanning electron microscopy and dynamic mechanical analysis measurements present that it is because the crystalline lamellas of HDPE are parallel arrangement and grow in a vertical to melt flow direction owing to injection shear force under a certain injection conditions. © 2012 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Study of the effect of organic clay on the shear‐induced crystallization of high‐density polyethylene through dynamic‐packing injection molding

Organic nanoparticles as heterogeneous nucleators have a great effect on the crystallization of polymer matrices in nanocomposite systems, and the effect will be enhanced under shear flow. A home‐made dynamic‐packing injection molding (DPIM) device was developed to explore the effect of organic clay on the shear‐induced crystallization of high‐density polyethylene (HDPE). Differential scanning calorimetry (DSC), wide‐angle X‐ray diffraction (WAXD) and scanning electron microscopy (SEM) were used to characterize the flow‐induced crystalline structure of HDPE/clay nanocomposite injection moldings. It was found that higher crystallinity and thicker crystal planes which contribute to the improvement of mechanical properties were achieved in HDPE/clay nanocomposite samples prepared by DPIM. DSC results clearly showed that an increase of about 16% in crystallinity was achieved in dynamic HDPE/clay nanocomposite samples compared with traditional unfilled HDPE samples. WAXD confirmed that dynamic HDPE/clay nanocomposite samples had maximum crystal sizes at the (110) and (200) planes of 335 and 305 Å, respectively. SEM images indicated that the arrangement of crystalline structures in dynamic HDPE/clay samples was altered slightly compared with unfilled HDPE samples prepared using the same processing parameters. The results showed that organic clay was beneficial for increasing crystallinity and crystal size in the HDPE/clay nanocomposite system under shear flow. Meanwhile the arrangement of crystalline structures was insignificantly affected by the organic clay, and the preferred regular arrangement of lamellae could still be formed in the dynamic HDPE/clay nanocomposite system. Copyright © 2010 Society of Chemical Industry     

Improving the mechanical properties of polypropylene via melt vibration

The effect of melt vibration on the mechanical properties of polypropylene prepared by low-frequency vibration-assisted injection molding (VAIM) has been investigated. With the application of melt vibration technology, the mechanical properties of polypropylene are improved. The yield strength increases with the increment of the vibration frequency, and a peak stands at a special frequency for VAIM; the elongation at break decreases first and then increases with increasing vibration frequency, and a valley stands at a special frequency. The tensile properties increase sharply at an enlarged vibration pressure amplitude with sharply decreased elongation at break. The Young's modulus and impact strength also increase with the vibration frequency and pressure vibration amplitude. When it is prepared at 59.4 MPa and 0.7 Hz, the maximal yield strength is approximately 40 MPa versus 33.7 MPa for a conventional sample; an 18.7% increase in the tensile strength is produced. Self-reinforcing and self-toughening polypropylene molded parts have been found to be prepared at a high vibration frequency or at a large pressure vibration amplitude. Scanning electron micrographs have shown that, in the vibration field, the enhancement of the mechanical properties is attributable to more pronounced spherulite orientation and increased crystallinity in comparison with conventional injection moldings. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Biaxial self‐reinforcement of isotactic polypropylene prepared in uniaxial oscillating stress field by injection molding. I. Processing conditions and mechanical properties

This research explores the longitudinal and latitudinal mechanical properties of injection‐molded isotactic polypropylene (iPP) prepared in a uniaxial oscillating stress field by oscillating packing injection molding (OPIM). The methods, processing conditions, and mechanical test results for iPP by conventional injection molding (CIM) and OPIM are described. The mechanical properties in the flow direction (MD) and transverse direction (TD) of the OPIM moldings indicate three types of self‐reinforced iPP moldings. The pronounced biaxially self‐reinforced iPP specimens exhibit a 55–70% increase of the tensile strength and more than a fourfold increase of the impact strength in the MD, together with more than a 40% increase of the tensile strength and a 30–40% increase of the impact strength in the TD. The OPIM moldings show different stress–strain behavior in the MD and TD. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 78: 1906–1910, 2000     

The morphology and property of HDPE in the presence of oscillation pressure and poly(ethylene terephthalate)

The injection‐molded specimens of neat HDPE and the PET/HDPE blends were prepared by conventional injection molding (CIM) and by pressure vibration injection molding (PVIM), respectively. The effect of oscillation pressure and PET phase with different shapes on superstructure and its crystal orientation distribution of injection molded samples were characterized by differential scanning calorimetry (DSC), scanning electron microscopy (SEM), and two‐dimension wide‐angle X‐ray diffraction techniques (2D‐WAXD). Hermans' orientation functions were determined from the wide‐angle X‐ray diffraction patterns. With the PET particles added, the shear viscosity of blend increase and crystallization rate of HDPE phase is enhanced. For the neat HDPE samples, with the promotion from oscillation shear, the orientation parameter experienced a large increase, moreover, the PVIM can induce transverse lamellae (kebabs) twisting in growth direction. Because of the redefined flow field and nucleation effect of PET particles, the crystal orientation of blend is also increased. So the tensile strength of vibration samples enhanced and elongation at break declined. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Mechanical performance of starch based bioactive composite biomaterials molded with preferred orientation

Composites of blends of starch with ethylene vinyl alcohol copolymer (SEVA‐C) filled with 10, 30 and 50% by weight (wt.) of hydroxyapatite (HA–the major inorganic constituent of human bone) were produced by twin‐screw extrusion (TSE) compounding. These composites were molded into tensile test bars using two molding techniques: (i) conventional injection molding and (ii) shear controlled orientation in injection molding (SCORIM). The bars produced were mechanically characterized by means of tensile testing and dynamical mechanical analysis (DMA). The structure of the moldings was assessed by wide‐angle X‐ray diffraction (WAXD) and the failure surfaces of the moldings analyzed by scanning electron microscopy (SEM). The enhancement of stiffness observed with HA reinforcement results partially from the stiffening effect of the blend associated with the decrease in plasticizer content during the compounding stage. SCORIM was able to further increase the stiffness of SEVA‐C/HA composites, allowing a maximum improvement of 12% for 30% wt. HA as compared to conventional molding. DMA results showed that the reinforcement of SEVA‐C causes the broadening of the relaxation peak of the polymer, suggesting a structural change within the starch fraction that may be related with thermal degradation of the polymer. The addition of HA particles reduces the preferred orientation exhibited by the SEVA‐C matrix, which is believed to limit the maximum mechanical performance that can be attained. Nevertheless, composites based on a biodegradable matrix with modulus above 7 GPa (in the bounds of the lower limit for human cortical bone) could be successfully produced.     

Morphology of gas‐assisted and conventional injection molded polycarbonate/polyethylene blend

The skin‐core structure of the gas‐assisted and conventional injection molded polycarbonate (PC)/polyethylene (PE) blend was investigated. The results indicated that both the size and the shape of the dispersed PC phase depended not only on the nature of PC/PE blend and molding parameters, but also on its location in the parts. Although the gas‐assisted injection molding (GAIM) parts and conventional injection molding (CIM) part have the similar skin‐core structure, the morphology evolution of PC phase in the GAIM moldings and the CIM moldings showed completely different characteristics. In the section perpendicular to the melt flow direction, the morphology of the GAIM moldings included five layers, skin intermediate layer, subskin, core layer, core intermediate layer as well as gas channel intermediate layer, according to the degree of deformation. PC phase changed severely in the core layer of GAIM moldings, as well as in the subskin of CIM moldings. In GAIM parts, PC phase in the core layer of the nongate end changed far more intensely and aligned much orderly than that in the gate end. The morphology of PC phase in the GAIM part molded with higher gas pressure changed more severe than that in the GAIM part molded with lower gas pressure. In a word, PC phase showed more obvious fibrillation in the GAIM moldings than that in the CIM moldings. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 3069–3077, 2006     

Processing–Nanostructure–Property Relationships of All‐Polyethylene Composites Reinforced by Flow‐Induced Oriented Crystallization of UHMWPE

All‐polyethylene composites exhibiting substantially improved toughness/stiffness balance are readily produced during conventional injection molding of high density polyethylene (HDPE) in the presence of bimodal polyethylene reactor blends (RB40) containing 40 wt% ultrahigh molar mass polyethylene (UHMWPE) dispersed in HDPE wax. Scanning electron microscopy (SEM) and differential scanning calorimetry (DSC) analyses shows that flow‐induced crystallization affords extended‐chain UHMWPE nanofibers forming shish which nucleates HDPE crystallization producing shish‐kebab structures as reinforcing phases. This is unparalleled by melt compounding micron‐sized UHMWPE. Injection molding of HDPE with 30 wt% RB40 at 165 °C affords thermoplastic all‐PE composites (12 wt% UHMWPE), improved Young's modulus of 3400 MPa, tensile strength of 140 MPa, and impact resistance of 22.0 kJ/m². According to fracture surface analysis, the formation of skin‐intermediate‐core structures accounts for significantly improved impact resistance. At constant RB40 content both morphology and mechanical properties strongly depend upon processing temperature. Upon increasing processing temperature from 165 °C to 250 °C the average shish‐kebab diameter increases from the nanometer to micron range, paralleled by massive loss of self‐reinforcement above 200 °C. The absence of shish‐kebab structure at 250 °C is attributed to relaxation of polymer chains and stretch‐coil transition impairing shish formation.