Effects of nano‐ and micro‐fillers and processing parameters on injection‐molded microcellular composites

The effects of submicron core‐shell rubber (CSR) particles, nanoclay fillers, and molding parameters on the mechanical properties and cell structure of injection‐molded microcellular polyamide‐6 (PA6) composites were studied. The experimental results of PA6 nanocomposites with 5.0 and 7.5 wt% nanoclay loadings and of CSR‐modified PA6 composites with 0.5 and 3.1 wt% CSR loadings were compared to their neat resin counterparts. This study found that nanoclay was more efficient in promoting a smaller cell size, larger cell density, and higher tensile strength for microcellular injection molding parts. A higher nanoclay loading led to more brittle behavior for microcellular parts. It was found that a proper amount of CSR particles could be added to the microcellular injection‐molded PA6 to reduce the cell size, increase the cell density, and enhance the toughness of the molded part. However, CSR particles were less effective cell nucleation agents as compared to nanoclay for producing desirable cell structures, and a higher CSR loading was found to have diminishing effects on the process and on the properties of the parts. POLYM. ENG. SCI., 45:773–788, 2005. © 2005 Society of Plastics Engineers     

Study of injection molded microcellular polyamide‐6 nanocomposites

This study aims to explore the processing benefits and property improvements of combining nanocomposites with microcellular injection molding. The microcellular nanocomposite processing was performed on an injection‐molding machine equipped with a commercially available supercritical fluid (SCF) system. The molded samples produced based on the Design of Experiments (DOE) matrices were subjected to tensile testing, impact testing, Dynamic Mechanical Analysis (DMA), and Scanning Electron Microscope (SEM) analyses. Molding conditions and nano‐clays have been found to have profound effects on the cell structures and mechanical properties of polyamide‐6 (PA‐6) base resin and nanocomposite samples. The results show that microcellular nanocomposite samples exhibit smaller cell size and uniform cell distribution as well as higher tensile strength compared to the corresponding base PA‐6 microcellular samples. Among the molding parameters studied, shot size has the most significant effect on cell size, cell density, and tensile strength. Fractographic study reveals evidence of different modes of failure and different regions of fractured structure depending on the molding conditions. Polym. Eng. Sci. 44:673–686, 2004. © 2004 Society of Plastics Engineers.     

Effects of nano‐fillers and process conditions on the microstructure and mechanical properties of microcellular injection molded polyamide nanocomposites

This paper presents the effects of process conditions and nano‐clay fillers on the microstructure (namely, size, density, and distribution of microcells within samples) and the resulting mechanical properties of microcellular injection molded polyamide‐6 (PA‐6) nanocomposite and its neat‐resin counterpart. Based on the design of experiments (DOE) matrices, samples were molded at various supercritical fluid (SCF) levels, melt temperatures, shot sizes, melt plastication pressures (MPP), and injection speeds. These samples were then subjected to scanning electron microscope (SEM) analysis, tensile testing, and impact testing. For both materials, the microstructure and the mechanical properties of the molded samples were found to be dependent on the process conditions and presence of nano‐clay, which could serve as microcell nucleating agent. At higher weight reductions, the nanocomposite samples exhibit much smaller microcells and higher cell densities than those obtained in the neat‐resin samples. The SEM micrographs reveal noticeable differences in microcell surface roughness between the nanocomposite and the neat resin. A statistical design analysis was used to identify the optimal process conditions that would result in desirable cell size and density and, thus, better mechanical properties. For example, the highest tensile strengths have been observed at the highest levels of shot size, MPP, injection speed, and SCF level, and at the lowest level of melt temperature.     

Spatial orientation of nanoclay and crystallite in microcellular injection molded polyamide‐6 nanocomposites

Three different types of characteristic structures‐microcells, nanoclay, and crystallite lamella‐exist in injection molded polyamide‐6 microcellular nanocomposites. These structures are in completely different scales. The spatial orientation of these microscale structures crucially determines the material's bulk properties. Based on scanning electron microscopy, transmission electron microscopy, and two‐dimensional X‐ray diffractometry measurements, it was found that the nanoclay and the crystallite formed special geometric structures around the microcells and near the part skins. The nanoclay platelets lay almost parallel to the surfaces of the molded parts. Preferred orientation of the crystallites was induced by the presence of the nanoclay. A molecular‐based model is proposed to describe the structural hierarchy and correlations among the microcells, nanoclay, and crystallite lamella. From the small‐angle X‐ray scattering experiments, it was found that microcellular injection molding produces relatively smaller crystallite lamella than that of conventional injection molding, and that for both solid and microcellular neat resin parts the crystallite lamella thickness at the part skin is smaller than that at the core. Polarized optical microscopy results also indicated that the size of crystallites in the microcellular neat resin and nanocomposite parts is smaller than that in the corresponding solid parts. POLYM. ENG. SCI., 47:765–779, 2007. © 2007 Society of Plastics Engineers     

Crystallization and thermal behavior of microcellular injection‐molded polyamide‐6 nanocomposites

This article presents the effects of nanoclay and supercritical nitrogen on the crystallization and thermal behavior of microcellular injection‐molded polyamide‐6 (PA6) nanocomposites with 5 and 7.5 wt% nanoclay. Differential scanning calorimetry (DSC), X‐ray diffractometry (XRD), and polarized optical microscopy (POM) were used to characterize the thermal behavior and crystalline structure. The isothermal and nonisothermal crystallization kinetics of neat resin and its corresponding nanocomposite samples were analyzed using the Avrami and Ozawa equations, respectively. The activation energies determined using the Arrhenius equation for isothermal crystallization and the Kissinger equation for nonisothermal crystallization were comparable. The specimen thickness had a significant influence on the nonisothermal crystallization especially at high scanning rates. Nanocomposites with an optimal amount of nanoclay possessed the highest crystallization rate and a higher level of nucleation activity. The nanoclay increased the magnitude of the activation energy but decreased the overall crystallinity. The dissolved SCF did not alter the crystalline structure significantly. In contrast with conventionally injection‐molded solid counterparts, microcellular neat resin parts and microcellular nanocomposite parts were found to have lower crystallinity in the core and higher crystallinity near the skin. POLYM. ENG. SCI., 46:904–918, 2006. © 2006 Society of Plastics Engineers     

Microcellular poly(hydroxybutyrate‐co‐hydroxyvalerate)‐hyperbranched polymer–nanoclay nanocomposites

The effects of incorporating hyperbranched polymers (HBPs) and different nanoclays [Cloisite® 30B and halloysite nanotubes (HNT)] on the mechanical, morphological, and thermal properties of solid and microcellular poly(hydroxybutyrate‐co‐hydroxyvalerate) (PHBV) were investigated. According to the X‐ray diffraction (XRD) and transmission electron microscopy (TEM) analyses, Cloisite 30B exhibited a combination of exfoliation and heterogeneous intercalation structure for both solid and microcellular PHBV–12% HBP–2% Cloisite 30B nanocomposites. TEM images indicated that HNTs were uniformly dispersed throughout the PHBV matrix. The addition of 2% nanoclays improved the thermal stability of the resulting nanocomposites. The addition of HBP+poly(maleic anhydride‐alt‐1‐octadecene) (PA), Cloisite 30B, and HNT reduced the average cell size and increased the cell density of the microcellular components. The addition of (HBP+PA), Cloisite 30B, and HNT also increased the degree of crystallinity for both solid and microcellular components in comparison with neat PHBV. Also, with the addition of 12% (HBP+PA), the area under the tan‐δ curve, specific toughness, and strain‐at‐break of the PHBV–HBP nanocomposite increased significantly for both solid and microcellular specimens, whereas the storage modulus, specific Young's modulus, and specific tensile strength decreased. The addition of 2% nanoclays into the PHBV–HBP nanocomposites improved the storage modulus, specific Young's modulus, and specific tensile strength of the PHBV–HBP–nanoclay‐based nanocomposites, but they were still lower than those of the neat PHBV. POLYM. ENG. SCI., 2011. © 2011 Society of Plastics Engineers     

Effect of process conditions on the weld‐line strength and microstructure of microcellular injection molded parts

This study was aimed at understanding how the process conditions affect the weld‐line strength and microstructure of injection molded microcellular parts. A design of experiments (DOE) was performed and polycarbonate tensile test specimens were produced for tensile tests and microscopic analysis. Injection molding trials were performed by systematically adjusting four process parameters (i.e., melt temperature, shot size, supercritical fluid (SCF) level, and injection speed). For comparison, conventional solid specimens were also produced. The tensile strength was measured at the weld line and away from the weld line. The weld‐line strength of injecton molded microcellular parts was lower than that of its solid counterparts. It increased with increasing shot size, melt temperature, and injection speed, and was weakly dependent on the supercritical fluid level. The microstructure of the molded specimens at various cross sections were examined using scanning electron microscope (SEM) and a light microscope to study the variation of cell size and density with different process conditions.     

Microstructure and mechanical properties of microcellular injection molded polyamide-6 nanocomposites

The microstructure and mechanical properties of microcellular injection molded polyamide-6 (PA6) nanocomposites were studied. Cell wall structure and smoothness were determined by the size of the crystalline structure, which, in turn, were based on the material system and molding conditions. The correlation between cell density and cell size of the materials studied followed an exponential relationship. Supercritical fluid (SCF) facilitated the intercalation and exfoliation of nanoclays in the microcellular injection molding process. The orientation of nanoclays near the surface of microcells and between microcells was examined and a preferential orientation around the microcells was observed. Nanoclays in the microcellular injection molding process promoted the γ-form and suppressed the α-form crystalline structure of PA6. Both nanoclays and SCF lowered the crystallinity of the parts. Microcells improved the normalized toughness of the nanocomposites. Both microcells and nanoclay had a significant influence on the mechanical properties of parts depending on the molding conditions.     

The effect of nanoclay on the crystallization behavior,microcellular structure,and mechanical properties of thermoplastic polyurethane nanocomposite foams

The effects of nanoclay on the crystallization behavior, microcellular structure, and mechanical properties of thermoplastic polyurethane (TPU)/clay nanocomposite (TPUCN) foams were investigated using differential scanning calorimetry, rheometry, scanning electron microscope, transmission electron microscopy, and X‐ray diffraction. It was found that the nanoclay acted as an effective nucleating agent for both crystal nucleation and cell nucleation. As a result, it significantly enhanced the crystallization behavior of the hard segment (HS) domains in TPU while refining the foamed structure of the microcellular injection molded parts. In particular, the average cell diameter of TPUCN foams decreased from 45 µm for neat TPU to 27 µm for TPUCN5 (5 wt% clay) and 18 µm for TPUCN10 (10 wt% clay). Furthermore, the cell density increased from 0.7 × 10⁷ cell/cm³ for neat TPU to 1.4 × 10⁷ cell/cm³ and 3.1 × 10⁷ cell/cm³ for TPUCN5 and TPUCN10, respectively. In addition, the tensile strength also increased by 56.3% and 89.2% with 5 and 10 wt% clay content, respectively. By controlling the cell nucleation behavior through uniformly dispersed nanoclay, this study demonstrates that it is feasible to produce TPUCN foams via microcellular injection molding with desirable microcellular structures and improved mechanical properties. POLYM. ENG. SCI., 56:319–327, 2016. © 2015 Society of Plastics Engineers     

A new microcellular injection molding process for polycarbonate using water as the physical blowing agent

This article presents a new process for producing microcellular injection molded plastic parts using water as the physical blowing agent and micro‐scaled particles as the cell nucleating agents. Distilled water with dissolved salt were fed through the hopper of an injection molding machine at a preset rate and mixed with polycarbonate (PC) in the machine barrel. Microcellular PC tensile bars were then injection molded with different shot volumes, water/salt solution feed rates, and salt concentrations. Tiny salt crystals of 10–20 μm recrystallized during molding acted as nucleating agents in the PC foamed parts. The surface roughness, mechanical properties, and microstructure of the solid and foamed parts were measured and compared with microcellular injection molded parts using supercritical fluid (SCF) nitrogen as the physical blowing agent. At a similar weight reduction of about 10%, the water foamed PC parts have a smooth surface comparable to that of solid injection molded parts. They also possess similar, if not better, mechanical properties compared to SCF nitrogen foamed PC parts. Without the nucleating agent, PC/water foamed parts exhibit much larger and fewer bubbles within the molded parts. POLYM. ENG. SCI., 2012. © 2012 Society of Plastics Engineers     

Uni‐ and biaxial impact behavior of double‐gated nanoclay‐reinforced polypropylene injection moldings

Polypopylene/nanoclay three‐dimensional parts were produced without intermediate steps by direct injection molding to explore the influence of flow features and nanoclay incorporation in their impact performance. The nanocomposite was obtained by direct compounding of commercial PP with nanoclay masterbatch. The as‐molded morphology was analyzed by X‐ray and TEM analyses in terms of skin‐core structure and nanoclay particle dispersion. The nanoclay particles induced the reduction of β‐form spherulites, a known toughener. The impact behavior was assessed in tensile and biaxial modes. The PP nanocomposite molding toughness was practically unaffected by the processing melt temperature and flow rate. Conversely the nanoclay presence is influent in the impact performance. Under biaxial stress impact, the regions close to weld lines are tougher than the bulk and the fracture develops with main crack paths along the flow direction and the weld line. Cracking along the weld line results from less macromolecular interpenetration and chain entanglement, and unfavorable nanoparticle orientation. It seems that a failure mechanism which involves nanoclay delamination and multiple matrix crazing explains the toughening of PP in the directions where the nanoparticle orientation with respect to loading is adequate. POLYM. ENG. SCI. 2013. © 2012 Society of Plastics Engineers     

The mechanical/thermal properties of microcellular injection‐molded poly‐lactic‐acid nanocomposites

This study investigated the influence of montmorillonite (MMT) content on the mechanical/thermal properties of microcellular injection‐molded polylactide (PLA)/clay nanocomposites. Carbon dioxide was the blowing agent. The PLA/MMT nanocomposites were prepared by twin screw extrusion. The results showed that as MMT content is increased, tensile strength, impact strength, and cell density decrease. This is caused by the speed degradation of PLA due to the addition of MMT. MMT decreases the crystallization temperature but increases the decomposition temperature of the nanocomposites. The XRD results showed that the layer spacing of the clay increases as MMT content increases. TEM pictures showed that the MMT is well dispersed within the PLA matrix. POLYM. COMPOS., 2009. © 2008 Society of Plastics Engineers.     

Reducing water sorption of injection‐molded polyamide 6 bars by polymerization‐induced diffusion of styrene and grafting with polystyrene

An innovative method for reducing water sorption of injection‐molded polyamide 6 (PA6) bars by polymerization‐induced diffusion of styrene and grafting with polystyrene (PS) is reported. The process involves diffusion of styrene into PA6 bar in aqueous medium, addition of benzoyl peroxide to initiate polymerization of styrene, and further diffusion of styrene into the bar during polymerization. A hydrophobic PS‐rich shell consisting mainly of PS‐g‐PA6 can be formed in the surface layer of the PA6 bar, and as a result, the water sorption and dimensional change of PS‐modified PA6 bars reduce significantly. An incorporation of only 1.2% PS is sufficient, showing the advantage of this method over conventional melt mixing. The tensile modulus and strength of 1.2% PS‐modified PA6 bar increase slightly compared to those of neat PA6 bar due to reinforcement effect of rigid PS and reduced level of water‐caused plasticization, while maintaining the good ductility. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46243.     

Thermal–oxidative degradation and accelerated aging behavior of polyamide 6/epoxy resin‐modified montmorillonite nanocomposites

Polyamide 6 (PA6) nanocomposites based on epoxy resin‐modified montmorillonite (EP‐MMT) were prepared by melt processing using a typical twin‐screw extruder. X‐ray diffraction combined with transmission electron microscopy was applied to elucidate the structure and morphology of PA6/EP‐MMT nanocomposites, suggesting a nearly exfoliated structure in the nanocomposite with 2 wt % EP‐MMT (PA6/2EP‐MMT) and a partial exfoliated‐partial intercalated structure in PA6/4 wt %EP‐MMT nanocomposite (PA6/4EP‐MMT). The thermogravimetric analysis under air atmosphere was conducted to characterize the thermal–oxidative degradation behavior of the material, and the result indicated that the presence of EP‐MMT could inhibit the thermal‐oxidative degradation of PA6 effectively. Accelerated heat aging in an air circulating oven at 150°C was applied to assess the thermal–oxidative stability of PA6 nanocomposites through investigation of reduced viscosity, tensile properties, and chemical structure at various time intervals. The results indicated that the incorporation of EP‐MMT effectively enhanced the thermal–oxidative stability of PA6, resulting in the high retention of reduced viscosity and tensile strength, and the low ratio of terminal carboxyl group to amino group. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40825.     

Mathematical modeling and numerical simulation of cell growth in injection molding of microcellular plastics

A mathematical formulation and numerical simulation for non‐isothermal cell growth during the post‐filling stage of microcellular injection molding have been developed. The numerical implementation solves the energy equation, the continuity equation, and a group of equations that describe the mass diffusion of dissolved gas and growth of micro‐cells in a microcellular injection molded part. The “unit‐cell” model employed in this study takes into account the effects of injection and packing pressures, melt and mold temperatures, and super‐critical fluid content on the material properties of the polymer‐gas solution and the cell growth. The material system studied is a microcellular injection molded polyamide 6 (PA‐6) resin. Two Arrhenius‐type equations are used to estimate the coefficients of mass diffusion and solubility for the polymer‐gas solution as functions of temperature. The dependence of the surface tension on the temperature is also included in this study. The numerical results in terms of cell size across the sprue diameter agree fairly well with the experimental observation. The predicted pressure profile at the sprue location has also been found to be in good agreement with the dynamics of the cell growth. Whereas for conventional injection molding the pressure of the system tends to decay monotonously, the pressure profile in microcellular injection molding exhibits an initial decay resulting from cooling and the absence of packing followed by an increase due to cell growth that expands the polymer‐gas solution and helps to pack out the mold uniformly. Polym. Eng. Sci. 44:2274–2287, 2004. © 2004 Society of Plastics Engineers.     

Experiment and simulation of foaming injection molding of polypropylene/nano-calcium carbonate composites by supercritical carbon dioxide

Microcellular injection molding of neat isotactic polypropylene (iPP) and isotactic polypropylene/nano-calcium carbonate composites (iPP/nano-CaCO₃H) was performed using supercritical carbon dioxide as the physical blowing agent. The influences of filler content and operating conditions on microstructure morphology of iPP and iPP/nano-CaCO₃H microcellular samples were studied systematically. The results showed the bubble size of the microcellular samples could be effectively decreased while the cell density increased for iPP/nano-CaCO₃H composites, especially at high CO₂ concentration and back pressure, low mold temperature and injection speed, and high filler content. Then Moldex 3D was applied to simulate the microcellular injection molding process, with the application of the measured ScCO₂ solubility and diffusion data for iPP and iPP/nano-CaCO₃H composites respectively. For neat iPP, the simulated bubble size and density distribution in the center section of tensile bars showed a good agreement with the experimental values. However, for iPP/nano-CaCO₃H composites, the correction factor for nucleation activation energy F and the pre-exponential factor of nucleation rate f0 were obtained by nonlinear regression on the experimental bubble size and density distribution. The parameters F and f0 can be used to predict the microcellular injection molding process for iPP/nano-CaCO₃H composites by Moldex 3D.     

The cell forming process of microcellular injection‐molded parts

In this article, we studied the cell forming process of microcellular injection‐molded parts. Using a modified injection molding machine equipped with a Mucell^® SCF delivery system, microcellular‐foamed acrylonitrile–butadiene–styrene parts with different shot sizes were molded. The cell structure on the fractured surfaces along the direction both vertical and parallel to melt flow in the molded parts was examined. The results showed that a regular spherical cells region and a distorted ellipsoidal cells region exist in the molded parts simultaneously. The length of the distorted cells region along the melt flow direction in the molded parts remained basically unchanged for different shot sizes and it is about 195 mm away from the flow front in this study's conditions. The cell formation mechanism was analyzed, two cell forming processes in microcellular injection molding, the “foam during filling” process and the “foam after filling” process, were proposed. It was also found that the melt pressure in the filling stage is the dominant factor affecting the cell forming process, and there is a critical melt pressure value in the filling stage, 20.9 MPa, as the dividing line of the two cell forming processes in this study. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40365.     

Crystallization and melting behavior of multi‐walled carbon nanotube‐reinforced nylon‐6 composites

The crystallization and melting behavior of neat nylon‐6 (PA6) and multi‐walled carbon nanotubes (MWNTs)/PA6 composites prepared by simple melt‐compounding was comparatively studied. Differential scanning calorimetry (DSC) results show two crystallization exotherms (T_{CC, 1} and T_{CC, 2}) for PA6/MWNTs composites instead of a single exotherm (T_{CC, 1}) for the neat matrix. The formation of the higher‐temperature exotherm T_{CC, 2} is closely related to the addition of MWNTs. X‐ray diffraction (XRD) results indicate that only the α‐phase crystalline structure is formed upon incorporating MWNTs into PA6 matrix, independently of the cooling rate and annealing conditions. These observations are significantly different from those for PA6 matrix, where the increase in cooling rate or decrease in annealing temperature results in the crystal transformation from α‐phase to γ‐phase. The crystallization behavior of PA6/MWNTs composites is also significantly different from those reported in PA6/nanoclay systems, probably due to the difference in nanofiller geometry between one‐dimensional MWNTs and two‐dimensional nanoclay platelets. The nucleation sites provided by carbon nanotubes seem to be favorable to the formation of thermodynamically stable α‐phase crystals of PA6. The dominant α‐phase crystals in PA6/MWNTs composites may play an important role in the remarkable enhancement of mechanical properties. Copyright © 2005 Society of Chemical Industry     

Combined effect of shear and nucleating agent on the multilayered structure of injection‐molded bar of isotactic polypropylene

Molten polymers are usually exposed to varying levels of shear flow and temperature gradient in most processing operations. Many studies have revealed that the crystallization and morphology are significantly affected under shear. A so‐called “skin‐core” structure is usually formed in injection‐molded semicrystalline polymers such as isotactic polypropylene (iPP) or polyethylene (PE). In addition, the presence of nucleating agent has great effect on the multilayered structure formed during injection molding. To further understand the morphological development in injection‐molded products with nucleating agent, iPP with and without dibenzylidene sorbitol (DBS) were molded via both dynamic packing injection molding (DPIM) and conventional injection molding. The structure of these injection‐molded bars was investigated layer by layer via SEM, DSC, and 2 days‐WAXD. The results indicated that the addition of DBS had similar effect on the crystal size and its distribution as shear, although the later decreased the crystal size more obviously. The combination of shear and DBS lead to the formation of smaller spherulites with more uniform size distribution in the injection‐molded bars of iPP. A high value of c‐axis orientation degree in the whole range from the skin to the area near the core center was obtained in the samples molded via DPIM with or without DBS, while in samples obtained via conventional injection molding, the orientation degree decreased gradually from the skin to the core and the decreasing trend became more obvious as the concentration of DBS increased. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Studies of microcellular nanocomposites with supercritical fluid assisted injection moulding process

Abstract

In this study, the microstructure, thermal behaviour and mechanical properties of microcellular nanocomposites were studied. Microcell wall structure and smoothness were determined by the size of the crystalline structure, which, in turn, was based on the material system and moulding conditions. Nanoclay in the microcellular, supercrtitical fluid assisted injection moulding process promoted the γ form and suppressed the α form crystalline structure of polyamide 6 (PA6). In the crystallisation kinetics studies, the Avrami equation and the modified Ozawa equation with the Mo method were used to model and analyse isothermal and non-isothermal crystallisation processes respectively. The existence of nanoclay increased the magnitude of the activation energy for both isothermal and non-isothermal crystallisation processes. This suggests the fast crystallisation process and the small crystalline size for microcellular nanocomposite processing. Interestingly, the dissolved gas lowered the crystallinity of the cores of moulded microcellular parts, but the addition of nanoclay reduced the crystallinity of both the cores and the skins of parts. The collective effect of the dissolved gas and nanoclay acted to shorten the moulding cycle time greatly with a reduction in the overall crystallinity of microcellular nanocomposite parts.