Morphological development in water assisted injection molded polyethylene/polyamide‐6 blends

Water assisted injection molding (WAIM) has gradually become one of the most important polymer processing methods for making hollowed parts. This study examined the morphological development in water assisted injection molded high density polyethylene (HDPE)/polyamide‐6 (PA‐6) blends. Samples for microscopic observation were prepared by an 80‐ton injection‐molding machine equipped with a tube cavity and with a water injection unit. A distinct skin layer, core region, and channel layer were observed across the thickness. The shape and size of the dispersed phase depended on the position both across the part thickness and along the flow direction. Small and large particles coexisted in the skin and channel layers, indicating that both coalescence and disintegration of the dispersed phase occurred in these layers. High water pressures were found to mold parts with smaller polyamide particle distributions. Additionally, the morphology of water assisted injection molded parts was compared to that of gas assisted injection molded products. It was found that water molded parts exhibit a smaller polyamide particle distribution than their gas counterparts. Copyright © 2010 John Wiley & Sons, Ltd.     

Hierarchical crystalline structures and dynamic mechanical properties of injection‐molded bars of HDPE: attributes of temperature field

The relationship among the processing parameters, crystalline morphologies and mechanical properties of injected‐molded bar becomes much complicated primarily due to the existence of temperature gradient coupled with the shear gradient along the sample thickness. The effect of thermal gradient field on the microstructural evolution, hierarchical structures and dynamic mechanical properties of high‐density polyethylene parts molded via gas‐assisted injection molding (GAIM) were investigated using scanning electron microscope, differential scanning calorimetry, dynamic mechanical analysis and two‐dimensional wide‐angle X‐ray diffraction. The three‐dimensional temperature profiles during the cooling stage under different melt temperatures of GAIM process were obtained by using a transient heat transfer model of the enthalpy transformation approach, and the phase‐change plateaus were clearly observed in the cooling curves. It was found that a variety of melt temperatures could induce considerable variations of the hierarchical structures, orientation behavior and dynamic mechanical properties of the injection‐molded bars. With reduced melt temperature, GAIM samples with higher molecular orientation and improved dynamic mechanical properties were obtained. Copyright © 2013 John Wiley & Sons, Ltd.     

The effect of shear on mechanical properties and orientation of HDPE/mica composites obtained via dynamic packing injection molding (DPIM)

The interfacial interaction and orientation of filler play important roles in the enhancement of mechanical performances for polymer/inorganic filler composites. Shear has been found to be a very effective way for the enhancement of interfacial interaction and orientation. In this work, we will report our recent efforts on exploring the development of microstructure of high density polyethylene (HDPE)/mica composites in the injection‐molded bars obtained by so‐called dynamic packing injection molding (DPIM), which imposed oscillatory shear on the melt during the solidification stage. The mechanical properties were evaluated by tensile testing and dynamic mechanical analysis (DMA), and the crystal morphology, orientation, and the dispersion of mica were characterized by scanning electron microscopy and two‐dimensional wide‐angle X‐ray scattering. Compared with conventional injection molding, DPIM caused an obvious increase in orientation for both HDPE and mica. More importantly, better dispersion and epitaxial crystallization of HDPE was observed on the edge of the mica in the injection‐molded bar. As a result, increased tensile strength and modulus were obtained, accompanied with a decrease of elongation at break. The obtained data were treated by Halpin–Tsai model, and it turned out that this model could be also used to predict the stiffness of oriented polymer/filler composites. Copyright © 2009 John Wiley & Sons, Ltd.     

Predicting the location of weld line in microinjection‐molded polyethylene via molecular orientation distribution

The microstructure and molecular orientation distribution over both the length and the thickness of microinjection‐molded linear low‐density polyethylene with a weld line were characterized as a function of processing parameters using small‐angle X‐ray scattering and wide‐angle X‐ray diffraction techniques. The weld line was introduced via recombination of two separated melt streams with an angle of 180° to each other in injection molding. The lamellar structure was found to be related to the mold temperature strongly but the injection velocity and the melt temperature slightly. Furthermore, the distributions of molecular orientation at different molding conditions and different positions in the cross section of molded samples were derived from Hermans equation. The degree of orientation of polymeric chains and the thickness of oriented layers decrease considerably with an increase of both mold temperature and melt temperature, which could be explained by the stress relaxation of sheared chains and the reduced melt viscosity, respectively. The level of molecular orientation was found to be lowest in the weld line when varying injection velocity, mold temperature, and melt temperature, thus providing an effective means to identify the position of weld line induced by flow obstacles during injection‐molding process. © 2019 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2019 , 57, 1705–1715     

Role of gas delay time on the hierarchical crystalline structure and mechanical property of HDPE molded by gas-assisted injection molding

The relationship among the processing parameters, crystalline morphology, and macroscopic properties in injected molded bar becomes very complicated due to existence of temperature gradient and shear gradient along the sample thickness. To enhance the shear strength, gas-assisted injection molding (GAIM) was utilized in producing the molded bars. The aim of our research was to explore the relationship between processing conditions and the spatial variation of the hierarchy structure as well as the mechanical properties of high-density polyethylene (HDPE) obtained via GAIM. In our previous work [Wang L, Yang B, Yang W et al (2011) Colloid Polym Sci 289:1661–1671], we found that the enhancement of the gas pressure can remarkably increase the degree of molecular orientation in the HDPE samples, which turns out to improve the mechanical performances of GAIM parts. In this work, the hierarchy structure, orientation behavior, and mechanical properties of molder bars under different gas delay time were investigated using a variety of characterization techniques including rheological experiments, scanning electron microscope, tensile testing, differential scanning calorimetry, and two-dimensional wide-angle X-ray scattering. Moreover, the temperature field during the short shot stage of GAIM process was simulated using an enthalpy transformation approach. Our results indicate that these properties were intimately related to each other, and with prolonged gas delay time, GAIM samples with higher degree of orientation and improved mechanical properties were obtained.     

Properties of fracture surfaces of glassy polymers: Chain scission versus chain pullout

Fresh fracture surfaces formed by tensile failure of craze in molded polystyrene (PS) bars have been compared with the molded surfaces of the same bars, using an atomic force microscope with a thermal probe and operated in local thermal analysis. The results indicate that molecular weight is much higher in the interior of the sample than at the surface. No evidence was found for degradation of the PS chains via chain scission during crazing. Alternative explanations for the low‐molecular weights at the molded surface are discussed. © 2010 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys, 2010     

Measuring and simulating morphology gradients in injection‐molded talc‐reinforced isotactic polypropylene

Injection molded polymer parts are known to exhibit structural gradients of crystallinity, crystallite phases and crystallite orientations. The structural variations depend on the geometry, the material properties, and the processing conditions, and affect the mechanical properties of the molded part. We explore the use of raster‐scanning small‐ and wide‐angle X‐ray scattering (SAXS, WAXS) for mapping the microstructure in dogbone specimens of an isotactic polypropylene (PP) homopolymer and a talc‐reinforced isotactic PP compound. The specimens were injection molded with different mold temperatures and injection speeds, and the mapping approach revealed systematic structural heterogeneities and asymmetries. Accompanying numerical simulations of the injection molding process yielded predictions of the flow pattern, including the shear rate distribution and the resulting orientation of the flake‐shaped talc particles. We found a clear correspondence between the experimentally observed data and the simulations, in particular regarding the asymmetry of the orientation distributions relative to the center of the dogbone cross section, caused by asymmetric flow through the entrance of the mold. Furthermore, the shear rate distribution correlated with the occurrence of α‐ and β‐phases. Subtle differences in the crystallized structures along the long axis of the dogbones suggest an explanation to the observation that the specimens studied always tended to break at the same position in tensile tests. The results clearly demonstrate the potential of mapping experiments which combine lateral resolution on macroscopic length scales with the molecular‐scale resolution from scattering. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2014 , 52, 1157–1167     

Process Induced Micro Structure Evolution in Polyester Polyurethane and Mechanical Properties Relationship

Summary: MDI-HQEE-Capa based thermoplastic polyurethane (TPU) with Shore hardness of 94 A was injection molded. In order to study the influence of melt conditions on the material structure evolution and resulting mechanical properties a systematical variation in processing temperatures in the range between 195 °C and 250 °C was applied. The mold temperature was kept constant at 60 °C. Process induced samples morphologies were investigated by means of light microscope (LM), scanning electron microscope (SEM) and differential scanning calorimeter (DSC). Mechanical visco-elastic properties were determined by means of cyclic tensile experiment and were correlated with results of structural investigations. The evaluation of morphology micrographs of raw TPU material and specimens molded at different temperatures shows a reduction in visual crystalline fraction. This gains a distinct change in the deformation behavior of injection molded TPU with increasing melt processing temperature.     

The mechanism of ultrasonic improvement of weld line strength of injection molded polystyrene and polystyrene/polyethylene blend parts

The effect of ultrasonic oscillations and ultrasonic oscillation‐induced modes on weld line strength of polystyrene(PS) and polystyrene/polyethylene(PS/HDPE) blend was investigated. And the mechanism of ultrasonic improvement of weld line strength of PS and PS/HDPE blend was also studied. The presence of ultrasonic oscillations can enhance the weld line strength of PS and PS/HDPE blend. Compared with mode I(ultrasonic oscillations were induced into mold at the whole process of injection molding), the induced ultrasonic oscillations as mode II(ultrasonic oscillations were induced into mold after injection mold filling) is more effective to increase weld line strength of PS and PS/HDPE blend. The mechanism for ultrasonic improvement of weld line strength of PS and PS/HDPE blend is that the ultrasonic oscillations can improve the molecular diffusion across weld line of the melt at the core, and make against the fusion of melt at the skin. © 2006 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 44: 1520–1530, 2006     

Characterization of deformation in injection molded parts after packing and cooling

Residual stresses which are developed in injection molded parts affect dimensional accuracy and mechanical properties of the final products. To predict the residual stresses in injection molded parts, three stages of injection molding, i. e., filling, packing, and cooling, must be taken into consideration for the thermal and flow analyses. Flow field anaysis for filling and postfilling stages has been carried out by using the control volume based FEM/FDM hybrid method. The generalized Hele-Shaw flow is assumed. Compressibility of the Polymer melt is considered during packing and cooling stages. Modified Cross model is employed to reflect the dependency of the viscosity upon shear rate and temperature. An equation of state proposed by Tait offers an efficient means to describe pvt-relationship of the polymer. Variations in temperature and pressure fields are obtained over all stages by the numerical flow analysis and used as input data for the stress analysis of the part. Plane stress elements, such as shell elements, are used for finite element stress analysis of injection molded parts with appropriate boundary conditions both in the mold and after ejected from the mold. The numerical analysis yields useful information which is relevant to the mechanical properties of the final products, e. g., residual stress distribution, shape of deformation, displacement field, and strain distribution.     

Shear-induced change of phase morphology and tensile property in injection-molded bars of high-density polyethylene/polyoxymethylene blends

It is feasible to control the phase morphology and phase inversion for immiscible polymer blends to manipulate their properties. In this work, the blend of high-density polyethylene (HDPE)/polyoxymethylene (POM) was used as an example, to demonstrate the effect of shear on the phase morphology and resultant mechanical properties in immiscible polymer blends. To do so, a well defined “in-process morphology control” process during injection molding was conducted. That was: after making the blends via melt mixing, the injection-molded bars were prepared via a so-called dynamic packing injection molding equipment to impose a prolonged shearing on the melts during the solidification stage. Phase morphologies and crystal structures of the blends were estimated mainly through scanning electron microscopy, differential scanning calorimetry and 2D wide-angle X-ray scattering, respectively. For in-process morphology controlled samples, co-continuous structures, especially subinclusions inside another continuous phase induced by shear, were observed when the HDPE content was between 30 wt% and 50 wt%, leading to much early occurrence of phase inversion and also the lowest degree of orientation for both HDPE and POM. However, for samples obtained via conventional injection molding, a droplet morphology was always observed with HDPE dispersed in POM as the content of HDPE was up to 30 wt%, but with POM dispersed in HDPE as the content of HDPE was 50 wt%. The performances of injection-molded bars were mainly respect to the phase morphologies for samples obtained via conventional injection molding in which tensile properties continuously decreased with increasing of HDPE content up to 30 wt% and then increased with further increasing of HDPE content. For the in-process morphology controlled samples, the tensile properties depended not only on the phase morphology, but more importantly on the degree of orientation. One observed only a slight decrease of tensile property as the content of HDPE was less than 15 wt%, while an abrupt decrease when the content of HDPE was between 30 wt% and 50 wt%, probably due to the lowest degree of orientation in this composition range.     

Reinforcement of solid‐melt interfaces for semicrystalline polymers in a sequential two‐staged injection molding process

The solid‐melt interfaces between polyethylene (PE) and polyamide 6 (PA6) reinforced by in situ reactive compatibilization in a sequential two‐staged injection molding process has been studied in this work. The effects of the maleic anhydride grafted PE content and processing parameters, such as injection pressure, injection speed, melt temperature, and mold temperature, on the interfacial adhesion were investigated experimentally. The results of the interfacial adhesion characterized by lap shear measurement showed that the interfacial temperature and heat transfer between PE and PA6 interfaces play a very significant role in the bonding process. The fracture surfaces of the specimens prepared at different calculated interfacial temperature were investigated by scanning electron microscopy (SEM) and differential scanning calorimetry (DSC), which suggested that the fracture failure changes from adhesive to cohesive failure with increasing interfacial temperature. The contribution of crystalline parts of the in situ formed copolymers to the enhancement in interfacial adhesion also was determined by DSC analysis. © 2009 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 47: 1112–1124, 2009     

Optimization of tensile properties of injection molded α-nucleated polypropylene using response surface methodology

Tensile properties are among the significant properties of isotactic polypropylene (iPP). The mechanical properties including the tensile properties are fairly dependent on the overall crystallinity and crystallite size and their distribution in molded product, type of crystal structure and testing conditions. In presence of α-nucleating agents, the crystallization rate and onset temperature of isotactic PP increase. In this paper, the role of externally added commercial α-nucleating agent HPN-20E (Milliken Inc.) on tensile properties was investigated with respect to tensile properties of pure iPP. The experimental part includes the use of design of experiment (DoE) - response surface methodology (RSM) with central composite design (CCD) having three factors namely mold temperature, melt temperature and injection rate. Two levels of each factor with six centre points and five numbers of replicates were selected. The nucleating agent, HPN-20E, was added 1.0% by wt. in iPP (mfr 11.0 g/10min) using a lab scale co-rotating twin screw extruder. The compounded pellets were dried at 85 °C in a circulating hot air oven for 24 h. The tensile samples (ASTM-638D, type-I) were molded on a micro-injection molding machine (make BabyPlast, Italy). The samples were tested for tensile properties on a universal testing machine (make Lloyds, USA). The measured responses were tensile strength (MPa), Young's modulus (MPa) and work to break (N.mm). The same experimental procedure was also followed for pure iPP and same responses were measured to set the baseline of experiment. The analysis of variance (ANOVA) tests unearth that mold and melt temperatures are highly interacting in nature. That is why previous attempts based on traditional way of varying one parameter at a time were not so successful to relate tensile properties with injection molding variables. The RSM tests resulted into useful quantitative relationship between the tensile properties and injection molding process variables.     

Effect of PPO‐g‐MA on structures and properties of PPO/PA6/short glass fiber composites

Poly(2,6‐dimethyl‐1,4‐phenylene oxide)/polyamide 6 (PPO/PA6) blends were reactively compatibilized by maleic anhydride (MA) grafted PPO (PPO‐g‐MA) and reinforced by short glass fibers (SGF) via melt extrusion. An observation of the SGF‐polymer interface by scanning electronic microscope (SEM) together with etching techniques indicated that the PPO‐g‐MA played a decisive role in the adhesion of polymers to SGF. The rheological behavior was investigated by capillary rheometer, and the addition of PPO‐g‐MA, and SGF could increase the viscosity of the PPO/PA6 blends. The analysis of fiber orientation and distribution in the PPO/PA6/SGF composites showed PPO‐g‐MA favored to the random dispersion of SGF. The statistic analysis of SGF length showed that PPO‐g‐MA was helpful to maintain the fiber length during melt‐processing. For the composites at a given SGF content of 30 wt %, the addition of PPO‐g‐MA increased the tensile strength from 59.4 MPa to 97.1 MPa and increased SGF efficiency factor from 0.028 to 0.132. The experimental data were consistent with the theoretical predictions of the extension of Kelly‐Tyson model for tensile strength. The fracture toughness of the composites was investigated by single edge notch three‐point bending test. © 2009 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 47: 2188–2197, 2009     

The effect of polyethylene addition on the morphology of polystyrene/polyamide blends

The effect of a small admixture of high‐density polyethylene (HDPE) with a high or low viscosity to polystyrene/polyamide (PS/PA) blends of various compositions was studied. PS/PA blends with composition near 50/50 form sheet‐like or fiber‐like morphology at mixing that passes to the cocontinuous structure during compression molding. Ternary PS/PA/HDPE blends with PS/PA ratio about 50/50 show similar behavior. Generally, neither continuity nor shape of PS and PA phases was changed qualitatively by the addition of a small amount of HDPE. In agreement with existing rules for ternary blends, HDPE particles prefer a contact with PS phase to PA phase. On the other hand, none of these rules explains why a number of small HDPE subinclusions were dispersed into PS particles instead of HDPE‐PS core‐shell structure with a lower Gibbs free energy. Quantitative evaluation of the size of PA particles in blends with PS matrix showed that the previously proposed rule stating, that the addition of a small amount of a third immiscible component leads to a strong decrease in the size of dispersed particles, was not valid for the blends studied in this work. © 2009 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 47: 2158–2170, 2009     

Preparation and nonisothermal crystallization behavior of polyamide 6/montmorillonite nanocomposites

Polyamide 6 (PA6)/montmorillonite (MMT) nanocomposites were prepared via melt intercalation. The structure, mechanical properties, and nonisothermal crystallization kinetics of PA6/MMT nanocomposites were investigated by X‐ray diffraction (XRD), tensile and impact tests, and differential scanning calorimetry (DSC). Before melt compounding, MMT was treated with an organic surfactant agent. XRD traces showed that PA6 crystallizes exclusively in γ‐crystalline structure within the nanocomposites. Tensile measurements showed that the MMT additions are beneficial in improving the strength and the stiffness of PA6, at the expense of tensile ductility. Impact tests revealed that the impact strength of PA6/MMT nanocomposites tended to decrease with increasing MMT content. The nonisothermal crystallization DSC data were analyzed by Avrami, Ozawa, modified Avrami‐Ozawa, and Nedkov methods. The validity of these empirical equations on the nonisothermal crystallization process of PA6/MMT nanocomposites is discussed. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 2878–2891, 2004     

Modification of surface properties of polyethylene by perfluoropolyether blending

The preparation of a stabile blend from thermoplastic polymer and lubricating additive was studied with high density polyethylene (HDPE) and perfluoropolyether (PFPE). PFPE was melt blended within HDPE by injection molding. The chemical composition of the mixtures, the relative amount of PFPE on the surface, and the nature of the surface were studied by three surface sensitive methods: attenuated total reflectance infrared (ATR‐IR) spectroscopy, secondary ion mass spectroscopy (SIMS), and contact angle (CA) measurement. All the blends exhibited improved hydrophobicity. CA and SIMS gave a maximum response when about 2.0 wt % PFPE was added, whereas ATR‐IR spectroscopy gave maximum response for an addition of about 3.0 wt %. No changes in surface properties were observed when samples were reanalyzed about 1–4 months after preparation. © 2005 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 43: 2252–2258, 2005     

Structure and properties of polyamide‐6/vermiculite nanocomposites prepared by direct melt compounding

Polyamide‐6 (PA6)/vermiculite nanocomposites were fabricated through the direct melt compounding of maleic anhydride‐modified vermiculite (MAV) with PA6 in a twin‐screw extruder followed by injection molding. The structure and morphology of the nanocomposites were determined by X‐ray diffraction and scanning and transmission electron microscopy techniques. The results revealed the formation of intercalated and exfoliated vermiculite platelets in the PA6 matrix. Tensile measurement showed that the tensile modulus and strength of the nanocomposites tended to increase with increasing vermiculite content. The thermal properties of the nanocomposites were determined by dynamic mechanical analysis, differential scanning calorimetry, and thermogravimetry measurements. The storage modulus of the PA6–MAV nanocomposites increased to almost twice that of the neat PA6. The thermal stability of the nanocomposites increased dramatically, and this was associated with the addition of vermiculite. The effect of the addition of maleic anhydride on the formation of the PA6–vermiculite nanocomposites was examined. © 2002 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 40: 2860–2870, 2002     

Simultaneously reinforce and toughen polypropylene by in‐situ introducing polylactic acid microfibrils

A petroleum‐based polymer, isotactic polypropylene (iPP), and a biodegradable polymer, poly(lactic acid) (PLA), were compounded and molded into parts through the micro‐injection technique. A systematic structural investigation indicated that the microfibrillation of PLA minor phase depended on the operation parameter of inter‐mixer, ie, rotor speed. The higher rotor speed, the lower viscosity ratio of the PLA/iPP pair was favorable for microfibrillation occurred during micro‐injection process. The PLA microfibrils with high aspect ratio was successfully introduced into iPP matrix, and the tensile strength and strain at break of iPP/PLA blends were simultaneously improved. This study suggests a promising method for designing special microfibrillar morphology in polymer blend by using conventional melt processing techniques.     

Impact fracture toughness of polyamide‐6/montmorillonite nanocomposites toughened with a maleated styrene/ethylene butylene/styrene elastomer

Polyamide‐6 (PA6)/montmorillonite (MMT) nanocomposites toughened with maleated styrene/ethylene butylene/styrene (SEBS‐g‐MA) were prepared via melt compounding. Before melt intercalation, MMT was treated with an organic surfactant agent. Tensile and impact tests revealed that the PA6/4% MMT nanocomposite fractured in a brittle mode. The effects of SEBS‐g‐MA addition on the static tensile and impact properties of PA6/4% MMT were investigated. The results showed that the SEBS‐g‐MA addition improved the tensile ductility and impact strength of the PA6/4% MMT nanocomposite at the expenses of its tensile strength and stiffness. Accordingly, elastomer toughening represents an attractive route to novel characteristics for brittle clay‐reinforced polymer nanocomposites. The essential work of fracture (EWF) approach under impact drop‐weight conditions was used to evaluate the impact fracture toughness of nanocomposites toughened with an elastomer. Impact EWF measurements indicated that the SEBS‐g‐MA addition increased the fracture toughness of the PA6/4% MMT nanocomposite. © 2005 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 43: 585–595, 2005