Microstructure and crystallography in microcellular injection‐molded polyamide‐6 nanocomposite and neat resin

The effects of adding nanoclay to polyamide‐6 (PA‐6) neat resin, and the effects of processing parameters on cell density and size in microcellular injection‐molded components were investigated. In addition, the crystal sizes, structures, and orientation were analyzed with the use of x‐ray diffraction (XRD) and a polarized optical microscope. The standard ASTM D 638‐02 tensile bars for the analyses were molded according to a fractional four‐factor, three‐level, L9 Taguchi design of experiment (DOE) with varying melt temperature, injection speed, supercritical fluid (SCF) concentration, and shot size. It was found that the presence of montmorillonite (MMT) nanoclay greatly reduced the size of the cells and crystals, but increased their density in comparison with neat resin processed under identical molding conditions. In addition, at the sprue section downstream of the machine nozzle, cell size gradually decreased from the part center toward the skin for both the neat resin and the nanocomposite. It was also found that shot size was the most important processing parameter for both the neat resin and nanocomposite in affecting cell density and size in microcellular injection molding components. Weakly preferred crystal orientations were observed on the surface of microcellular injection‐molded PA‐6/MMT tensile bars. Finally, the addition of nanoclay in PA‐6 neat resin facilitated the formation of γ‐phase crystals in the molded components. Polym. Eng. Sci. 45:52–61, 2005. © 2004 Society of Plastics Engineers.     

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     

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.     

Microcellular injection molding of in situ modified poly(ethylene terephthalate) with supercritical nitrogen

The microcellular injection molding (commercially known as MuCell) of in situ polymerization‐modified PET (m‐PET) was performed using supercritical nitrogen as the physical blowing agent. Based on the design of experiment matrices, the influence of operating conditions on the mechanical properties of molded samples was studied systematically for two kinds of m‐PETs, namely, n‐m‐PET and m‐m‐PET synthesized using pentaerythritol and pyromellitic dianhydride (PMDA) as modifying monomers, respectively. Optimal conditions for injection molding were obtained by analyzing the signal‐to‐noise (S/N) ratio of the tensile strength of the molded samples. The specific mechanical properties, especially the impact strength, of the microcellular samples under those optimal conditions increased significantly. Scanning electron microscope analyses showed a uniform cell structure in the molded specimens with an average cell size of around 35 µm. The m‐m‐PET modified with PMDA generated a slightly finer cell structure and a higher cell density than the n‐m‐PET. POLYM. ENG. SCI., 54:2739–2745, 2014. © 2013 Society of Plastics Engineers     

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.     

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.     

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.     

Cell morphology and mechanical properties of microcellular mucell® injection molded polyetherimide and polyetherimide/fillers composite foams

Microcellular polyetherimide (PEI) foams were prepared by microcellular injection molding using supercritical nitrogen (SC‐N₂) as foaming agent. The effects of four different processing parameters including shot size, injection speed, SC‐N₂ content, and mold temperature on cell morphology and material properties were studied. Meanwhile, multiwalled carbon nanotube (MWCNT), nano‐montmorillonoid (NMMT), and talcum powder (Talc) were introduced into PEI matrix as heterogeneous nucleation agents in order to further improve the cell morphology and mechanical properties of microcellular PEI foams. The results showed that the processing parameters had great influence on cell morphology. The lowest cell size can reach to 18.2 μm by optimizing the parameters of microcellular injection molding. Moreover, MWCNT can remarkably improve the cell morphology of microcellular PEI foams. It was worth mentioning that when the MWCNT content was 1 wt %, the microcellular PEI/MWCNT foams displayed optimum mechanical properties and the cell size decreased by 28.3% compared with microcellular PEI foams prepared by the same processing parameters. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 130: 4171–4181, 2013     

Relationship between cell morphology and impact strength of microcellular foamed high‐density polyethylene/polypropylene blends

Polymer blends, such as those resulting from recycling postconsumer plastics, often have poor mechanical properties. Microcellular foams have been shown to have the potential to improve properties, and permit higher‐value uses of mixed polymer streams. In this study, the effects of microcellular batch processing conditions (foaming time and temperature) and HDPE/PP blend compositions on the cell morphology (the average cell size and cell‐population density) and impact strength were studied. Optical microscopy was used to investigate the miscibility and crystalline morphology of the HDPE/PP blends. Pure HDPE and PP did not foam well at any processing conditions. Blending facilitated the formation of microcellular structures in polyolefins because of the poorly bonded interfaces of immiscible HDPE/PP blends, which favored cell nucleation. The experimental results indicated that well‐developed microcellular structures are produced in HDPE/PP blends at ratios of 50:50 and 30:70. The cell morphology had a strong relationship with the impact strength of foamed samples. Improvement in impact strength was associated with well‐developed microcellular morphology. Polym. Eng. Sci. 44:1551–1560, 2004. © 2004 Society of Plastics Engineers.     

Microstructure and Properties of Microcellular Poly (phenylene sulfide) Foams by Mucell Injection Molding

A series of microcellular poly (phenylene sulfide) (PPS) foams were prepared by Mucell injection molding. The cell structure, mechanical properties, crystallization behavior and dielectric property of microcellular PPS foams were systemically investigated. The results showed that the longer the length of flow passage of injection mold, the larger cell size of microcellular PPS foams. The injection parameter of shot size played an important role in relative density of microcellular PPS foams. When the relative density of microcellular PPS foam reached to 0.658, the tensile strength, flexural strength and impact strength of PPS foam materials achieved 10.82 MPa, 52.99 MPa and 0.305 J/cm², respectively. Meanwhile, with the relative density decreasing, the dielectric constant of PPS foam materials reduced, while the volume resistivity of its uprated.     

Effect of vibration parameters of electromagnetic dynamic plastics injection molding machine on mechanical properties of polypropylene samples

Dynamic injection processing experiments have been carried out on polypropylene using the self‐made electromagnetic dynamic plastics injection molding machine, and the effects of the vibration force field on mechanical properties of molding samples are studied, namely, the influence of vibration frequency and vibration amplitude on the mechanical properties of samples are researched by using tensile testing, impact testing, differential scanning calorimeter (DSC) and scanning electronic micrograph (SEM) techniques. The results show that the tensile strength and impact strength are both enhanced and the melting point shifts toward the higher temperature, which facilitates the perfection of crystal. The best vibration parameters for processing polypropylene using electromagnetic dynamic plastics injection molding machine are that frequency is from 3 to 9 Hz and amplitude is from 0.1 to 0.4 mm. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 972–976, 2006     

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     

Influence of the injection molding process on the mechanical properties of (PA6/GF/MMT) nanocomposite

This work describes the first part of a series of studies on the effect of injection molding conditions on the mechanical properties of polyamide 6/glass fiber/montmorillonite (PA6/GF/MMT) composites, wherein the effect of the injection molding mass temperature on the mechanical properties of the composite is investigated. The results demonstrate that composites processed at lower mass temperatures exhibited higher tensile strength and flexural strength. These findings are explained by the fact that the use of different mass temperatures leads to PA6 matrices with different degrees of crystallinity. In addition, changes in the mass temperature affect the fiber–matrix adhesion of the composite and the intercalation between the matrix and the various components in the nanocomposite. POLYM. COMPOS., 36:237–244, 2015. © 2014 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.     

Solid‐state microcellular polycarbonate foams. II. The effect of cell size on tensile properties

The effect of cell size on the tensile behavior of high‐relative‐density microcellular polycarbonate foams is investigated. Microcellular PC foams were produced in a way that allowed the average cell size to be varied, while the foam density was held constant. The polycarbonate‐CO₂ system offers an order of magnitude variation in the average cell size at a given density, allowing the tensile properties of microcellular polycarbonate to be investigated as a function of cell size. It was found that the tensile modulus, tensile strength, elongation to break, and toughness are not significantly affected when the average cell size is varied from 2.8 to 37.1 μm, and the nominal relative density is held constant at 0.5. This result is significant for solid‐state processing of microcellular polycarbonate foams of the type produced here, for it shows that regardless of the processing conditions and regardless of the average cell size, if two foams have the same density then they will also have the same tensile properties. POLYM. ENG. SCI., 2010. © 2010 Society of Plastics Engineers     

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     

Quantitative study of shrinkage and warpage behavior for microcellular and conventional injection molding

This research investigated the effects of processing conditions on the shrinkage and warpage (S&W) behavior of a box‐shaped, polypropylene part using conventional and microcellular injection molding. Two sets of 2^6‐1 fractional factorial design of experiments (DOE) were employed to perform the experiments and proper statistical theory was used to analyze the data. After the injection molding process reached steady state, molded samples were collected and measured using an optical coordinate measuring machine (OCMM), which had been evaluated using a proper R&R (repeatability and reproducibility) measurement study. By analyzing the statistically significant main and two‐factor interaction effects, the results show that the supercritical fluid (SCF) content (nitrogen in this case, in terms of SCF dosage time) and the injection speed affect the S&W of microcellular injection molded parts the most, whereas pack/hold pressure and pack/hold time have the most significant effect on the S&W of conventional injection molded parts. Also, this study quantitatively showed that, within the processing range studied, a reduction in the S&W could be achieved with the microcellular injection molding process. POLYM. ENG. SCI., 45:1408–1418, 2005. © 2005 Society of Plastics Engineers     

Effect of Compatibilizer Type on Properties of 70:30 Polyamide 6/Polypropylene/MMT Nanocomposites

PA6/PP nanocomposites with either polyethylene octene elastomer grafted maleic anhydride (POEgMAH) or PP grafted maleic anhydride (PPgMAH) as compatibilizer were prepared using co-rotating twin-screw extruder followed by injection molding. The mechanical and microstructural properties of the composites were investigated by means of tensile, flexural, and impact testing and by scanning electron microscopy (SEM). X-ray diffraction (XRD) was used to characterize the formation of nanocomposites. The result indicated that the miscibility of PA6/PP nanocomposites was improved with the addition of POEgMAH and PPgMAH. The impact strength of PA6/PP nanocomposite with POEgMAH increased about 5 times higher than uncompatibilized composite. Increment in tensile properties was observed when PPgMAH was used as compatibilizer. XRD results revealed that PA6/PP nanocomposites were successfully formed. Uniform dispersion of PP in matrix were observed through SEM, which showed the improvement of the compatibility between polymers.     

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     

Microcellular thin PET sheet foam preparation by compression molding

This study has created a new way of microcellullar processing PET thin sheet foam using a conventional hydraulic press by compression molding and by setting the temperature of press plates differently. Comparing this study with our previous work, the emphasis is on the difference of plate temperature. The nonisothermal condition is used to control the foaming agent decomposition to lead to more uniform cell size microcellular foam. A variety of cell sizes, cell densities, and relative densities are obtained as a consequence of the different foaming temperature, time, pressure, and foaming agent content via isothermal and nonisothermal conditions. The effect of isothermal and nonisothermal foaming on the cell size, cells density, and relative density has been discussed. The electrical properties of the microcellular poly(ethylene terephthalate) (PET) samples prepared in nonisothermal foaming have been investigated. The experimental results show that the microcellular PET foam has lower dielectric constant and dielectric loss and higher electric resistivity than unfoamed PET. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 93: 1698–1704, 2004