Influence of processing on ethylene propylene block copolymers (II): Fracture behavior

The present work investigates the relationships between the microstructural state and fracture properties in commercial polypropylene‐based materials. In this case an isopolypropylene homopolymer and three ethylene propylene block copolymers (EPBC) with different ethylene content (EC) have been studied. A variety of morphologies were obtained by a combination of several processing methods (injection molding, injection molding‐annealing, and compression molding) and thickness. Fracture behavior of deeply double‐edged notched specimens was evaluated by scanning electron microscopy (SEM) and by the essential work of fracture (EWF) method, analyzing the influence of processing, thickness (t), EC, and orientation respect to melt flow direction (MD and TD). The testing direction and EC are the most relevant variables that affect the ability of the crack tip to deform plastically during the crack propagation, determining the final fracture behavior. The fracture parameters obtained with the EWF method, specific EWF, w_e, and plastic item, βw_p, have proved to be very sensitive to the processing induced morphology, finding interesting relationships between such morphologies (characterized by crystallinity index, orientation level, and skin/core ratio) and the fracture parameters of the plaques. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 2714–2724, 2006     

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     

Injection moldability and properties of compatibilized PA6/LDPE blends

An ethylene‐acrylic acid copolymer (EAA), either alone or combined with a low molar mass bis‐oxazoline compound (PBO), has been used as a compatibilization promoter for blends of polyamide‐6 (PA6) with low‐density polyethylene (LDPE). The effect of compatibilization on blend processability in injection molding operations and on the properties of the molded specimens has been studied. In the absence of compatibilization, the injection molded articles were shown to have low‐quality surface appearance and poor mechanical properties. Both these characteristics were appreciably improved as a result of reactive compatibilization of the blends with EAA and, even more, with the EAA‐PBO couple. In fact, the finished articles prepared by injection molding of the quaternary blends were shown to possess good surface appearance, fine and stable morphology and satisfactory mechanical properties. The results confirm the conclusion of a previous study, i.e., that the PBO fourth component may promote the in situ formation of PA6‐g‐EAA copolymers, by reaction with both the functional groups of PA6 and the carboxyl groups of EAA. Polym. Eng. Sci. 44:1732–1737, 2004. © 2004 Society of Plastics Engineers.     

In situ composites from blends of polycarbonate and a thermotropic liquid‐crystalline polymer: The influence of the processing temperature on the rheology,morphology, and mechanical properties of injection‐molded microcomposites

This work was aimed at understanding how the injection‐molding temperature affected the final mechanical properties of in situ composite materials based on polycarbonate (PC) reinforced with a liquid‐crystalline polymer (LCP). To that end, the LCP was a copolyester, called Vectra A950 (VA), made of 73 mol % 4‐hydroxybenzoic acid and 27 mol % 6‐hydroxy‐2 naphthoic acid. The injection‐molded PC/VA composites were produced with loadings of 5, 10, and 20 wt % VA at three different processing barrel temperatures (280, 290, and 300°C). When the composite was processed at barrel temperatures of 280 and 290°C, VA provided reinforcement to PC. The resulting injection‐molded structure had a distinct skin–core morphology with unoriented VA in the core. At these barrel temperatures, the viscosity of VA was lower than that of PC. However, when they were processed at 300°C, the VA domains were dispersed mainly in spherical droplets in the PC/VA composites and thus were unable to reinforce the material. The rheological measurements showed that now the viscosity of VA was higher than that of PC at 300°C. This structure development during the injection molding of these composites was manifested in the mechanical properties. The tensile modulus and tensile strength of the PC/VA composites were dependent on the processing temperature and on the VA concentrations. The modulus was maximum in the PC/VA blend with 20 wt % VA processed at 290°C. The Izod impact strength of the composites tended to markedly decrease with increasing VA content. The magnitude of the loss modulus decreased with increasing VA content at a given processing temperature. This was attributed to the anisotropic reinforcement of VA. Similarly, as the VA content increased, the modulus and thus the reinforcing effect were improved comparatively with the processing temperature increasing from 280 to 290°C; this, however, dropped in the case of composites processed at 300°C, at which the modulus anisotropy was reduced. Dynamic oscillatory shear measurements revealed that the viscoelastic properties, that is, the shear storage modulus and shear loss modulus, improved with decreasing processing temperatures and increasing VA contents in the composites. Also, the viscoelastic melt behavior (shear storage modulus and shear loss modulus) indicated that the addition of VA changed the distribution of the longer relaxation times of PC in the PC/VA composites. Thus, the injection‐molding processing temperature played a vital role in optimizing the morphology‐dependent mechanical properties of the polymer/LCP composites. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007     

Linear viscoelastic and morphological description of multiphase systems affected by processing parameters

Influence of processing methods, in terms of comparing compression and injection moldings, on the rheological behavior of polycarbonate (PC)/acrylonitrile‐butadiene‐styrene (ABS) blends and PC/ABS/glass fibers composites is presented. Blend compositions and fiber content are considered as material variables. For blends, the effect of the processing route on the viscoelastic functions is evident only for low shearing frequencies. Injection molding created morphology with cocontinuous character, while compression molded blends have “relaxed” structure, where dispersed phase domains are several times larger than in injection molded ones. The glass fiber reinforcement led to the significant differences in viscoelastic properties of composites processed by injection and compression molding. Injected composites have both moduli always higher than compression molded. Also, fiber lengths are reduced more for compressing molding. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Effects of moisture content and heat treatment on the physical properties of starch and poly(lactic acid) blends

Starch, a hydrophilic renewable polymer, has been used as a filler for environmentally friendly plastics for about 2 decades. Starch granules become swollen and gelatinized when water is added or when they are heated, and water is often used as a plasticizer to obtain desirable product properties. The objective of this research was to characterize blends from starch and poly(lactic acid) (PLA) in the presence of various water contents. The effects of processing procedures on the properties of the blends were also studied. Blends were prepared with a lab‐scale twin‐screw extruder, and tensile bars for mechanical testing were prepared with both compression and injection molding. Thermal and mechanical properties of the blends were analyzed, and the morphology and water absorption of the blends were evaluated. The initial moisture content (MC) of the starch had no significant effects on its mechanical properties but had a significant effect on the water absorption of the blends. The thermal and crystallization properties of PLA in the blend were not affected by MC. The blends prepared by compression molding had higher crystallinities than those prepared by injection molding. However, the blends prepared by injection molding had higher tensile strengths and elongations and lower water absorption values than those made by compression molding. The crystallinities of the blends increased greatly with annealing treatment at the PLA second crystallization temperature (155°C). The decomposition of PLA indicated that PLA was slightly degraded in the presence of water under the processing temperatures used. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 81: 3069–3082, 2001     

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.     

Processing and mechanical properties of thermoplastic composites based on cellulose fibers and ethylene—acrylic acid copolymer

The melt processing and the tensile mechanical properties of composites consisting of 30 wt% softwood kraft pulp cellulose fibers and ethylene‐acrylic acid copolymer (EAA) with 7% acrylic acid content were studied. The compounding techniques used were extrusion mixing performed with a single screw extruder and elongation dispersive mixing performed with the injection‐molding machine. All blends were injection‐molded in a final step. Fiber length, fiber content, and mechanical properties were measured and the number and the size of the fiber aggregates were determined by microscopy analysis. It was concluded that two passes of elongation dispersive mixing had a beneficial effect on the mechanical properties, which could be related to the fewer and smaller amounts of aggregates. The different types of processing performed had a small or insignificant effect on the fiber length since the fiber lengths measured were within the same range as that of the starting material. POLYM. ENG. SCI., 52:1951–1957, 2012. © 2012 Society of Plastics Engineers     

Morphology and mechanical properties of injection molded poly(ethylene terephthalate)

This work reports on the relationships between processing, the morphology and the mechanical properties of an injection molded poly(ethylene terephthalate), PET. Specimens were injection molded with different mold temperatures of 30°C, 50°C, 80°C, 100°C, 120°C, 150°C, while maintaining constant the other operative processing parameters. The thermomechanical environment imposed during processing was estimated by computer simulations of the mold‐filling phase, which allow the calculation of two thermomechanical indices indicative of morphological development (degree of crystallinity and level of molecular orientation). The morphology of the moldings was characterized by differential scanning calorimetry (DSC) and by hot recoverable strain tests. The mechanical behavior was assessed in tensile testing at 5 mm/min and 23°C. A strong thermal and mechanical coupling is evidenced in the injection molding process, significantly influencing morphology development. An increase in the mold temperature induces a decrease of the level of molecular orientation (decrement in the hot recoverable strain) and an increment in the initial crystallinity of the moldings (decrement in the enthalpy of cold crystallization), also reflected in the variations of the computed thermomechanical indices. The initial modulus is mainly dependent upon the level of molecular orientation. The yield stress is influenced by both the degree of crystallinity and the level of molecular orientation of the moldings, but more significantly by the former. The strain at break was not satisfactorily linked directly to the initial morphological state because of the expected morphology changes occurring during deformation. Polym. Eng. Sci. 44:2174–2184, 2004. © 2004 Society of Plastics Engineers.     

Characterization and mechanical properties of exfoliated graphite nanoplatelets reinforced polyethylene terephthalate/polypropylene composites

Recently, graphene and its derivatives have been used to develop polymer composites with improved or multifunctional properties. Exfoliated graphite nanoplatelets (GNP) reinforced composite materials based on blend of polyethylene terephthalate (PET), and polypropylene (PP) compatibilized with styrene–ethylene–butylene–styrene‐g‐maleic anhydride is prepared by melt extrusion followed by injection molding. Characterization of the composites' microstructure and morphology was conducted using field emission scanning electron microscopy, transmission electron microscopy (TEM), X‐ray diffraction analysis (XRD), and Fourier transform infrared spectroscopy (FTIR). Tensile and impact strengths of test specimens were evaluated and the results showed maximum values at 3phr GNP in both the cases. Morphological studies showed that the GNPs were uniformly dispersed within the matrix. Results from XRD analysis showed uniformly dispersed GNPs, which may not have been substantially exfoliated. FTIR spectroscopy did not show any significant change in the peak positions to suggest definitive chemical interaction between GNP and the matrix. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40582.     

Effect of dynamic cross‐linking on melt rheological properties of polypropylene/ethylene‐propylene‐diene rubber blends

Study of melts rheological properties of unvulcanized and dynamically vulcanized polypropylene (PP)/ethylene‐propylene‐diene rubber (EPDM) blends, at blending ratios 10–40 wt %, EPDM, are reported. Blends were prepared by melt mixing in an internal mixer at 190°C and rheological parameters have been evaluated at 220°C by single screw capillary rheometer. Vulcanization was performed with dimethylol phenolic resin. The effects of (i) blend composition; (ii) shear rate or shear stress on melt viscosity; (iii) shear sensitivity and flow characteristics at processing shear; (iv) melt elasticity of the extrudate; and (v) dynamic cross‐linking effect on the processing characteristics of the blends were studied. The melt viscosity increases with increasing EPDM concentration and decreased with increasing intensity of the shear mixing for all compositions. In comparison to the unvulcanized blends, dynamically vulcanized blends display highly pseudoplastic behavior provides unique processing characteristics that enable to perform well in both injection molding and extusion. The high viscosity at low shear rate provides the integrity of the extrudate during extrusion, and the low viscosity at high shear rate enables low injection pressure and less injection time. The low die‐swell characteristics of vulcanizate blends also give high precision for dimensional control during extrusion. The property differences for vulcanizate blends have also been explained in the light of differences in the morphology developed. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 77: 1488–1505, 2000     

Processing‐improved properties and morphology of PP/COC blends

The aim of this study was to improve mechanical properties of polypropylene/cycloolefin copolymer (PP/COC) blends by processing‐induced formation of long COC fibers. According to the available literature, the fibrous morphology in PP/COC blends was observed just once by coincidence. For this reason, we focused our attention on finding processing conditions yielding PP/COC fibrous morphology in a well‐defined, reproducible way. A number of PP/COC blends were prepared by both compression molding and injection molding (IM). Neat polymers were characterized by rheological measurements, whereas phase morphology of the resulting PP/COC blends was characterized by means of scanning electron microscopy (SEM). The longest COC fibers were achieved in the injection molded PP/COC blends with compositions 75/25 and 70/30 wt %. Elastic modulus and yield strength of all blends were measured as functions of the blend composition using an Instron tensile tester; statistically significant improvement of the yield strength due to fibrous morphology was proved. Moreover, two different models were applied in the analysis of mechanical properties: (i) the equivalent box model for isotropic blends and (ii) the Halpin‐Tsai model for long fiber composites. In all PP/COC blends prepared by IM, the COC fibers were oriented in the processing direction, as documented by SEM micrographs, and acted as a reinforcing component, as evidenced by stress–strain measurements. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Partial replacement of EPR by GTR in highly flowable PP/EPR blends: Effects on morphology and mechanical properties

This research analyzes the effect of ground tire rubber (GTR) and a novel metallocene‐based ethylene–propylene copolymer (EPR), with high propylene content, on the morphology and mechanical behavior of ternary polymer blends based on a highly flowable polypropylene homopolymer (PP). The PP/EPR blends morphology, with very small domains of EPR dispersed in the PP matrix, indicates a good compatibility among these materials, which leads to a significant improvement on elongation at break and impact strength. The incorporation of EPR on the rubber phase of thermoplastic elastomeric blends (TPE) based on GTR and PP (TPE^GTR) has a positive effect on their mechanical performance, attributed to the toughness enhancement of the PP matrix and to the establishment of shell‐core morphology between the rubber phases. The mechanical properties of the ternary blends reveal that TPE^GTR blends allow the upcycling of this GTR material by injection molding technologies. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42011.     

Improving mechanical performance of injection molded PLA by controlling crystallinity

Currently, use of poly(lactic acid) (PLA) for injection molded articles is limited for commercial applications because PLA has a slow crystallization rate when compared with many other thermoplastics as well as standard injection molding cycle times. The overall crystallization rate and final crystallinity of PLA were controlled by the addition of physical nucleating agents as well as optimization of injection molding processing conditions. Talc and ethylene bis‐stearamide (EBS) nucleating agents both showed dramatic increases in crystallization rate and final crystalline content as indicated by isothermal and nonisothermal crystallization measurements. Isothermal crystallization half‐times were found to decrease nearly 65‐fold by the addition of only 2% talc. Process changes also had a significant effect on the final crystallinity of molded neat PLA, which was shown to increase from 5 to 42%. The combination of nucleating agents and process optimization not only resulted in an increase in final injection molded crystallinity level, but also allowed for a decreased processing time. An increase of over 30°C in the heat distortion temperature and improved strength and modulus by upwards of 25% were achieved through these material and process changes. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

The effect of annealing on tensile properties of injection molded biopolyesters based on 2,5-furandicarboxylic acid

In this study, we investigate four polyesters based on 2,5-furandicarboxylic acid and different diols including 1,2-ethylene glycol, 1,3-propylene glycol, 1,4-butylene glycol, and 1,6-hexylene glycol. Poly(ethylene 2,5-furanoate), poly(propylene 2,5-furanoate), poly(butylene 2,5-furanoate), and poly(hexylene 2,5-furanoate) (PHF) were characterized by thermogravimetric analysis, X-ray diffraction, differential scanning calorimeter, and tensile tests. In addition, the influence of annealing polyesters on their thermal and mechanical properties was investigated. For these reasons samples for the tensile test were prepared by injection molding. The tensile properties of injection molded samples were compared with samples that were additionally annealed after injection molding. All studied polyesters after heating treatment showed multiple melting behavior. The increase in the degree of crystallinity significantly influenced also the mechanical properties of the samples. It was found that the length of the aliphatic chain and degree of crystallinity plays a major role in the final properties of furan-based polyesters.     

Processing characteristics and mechanical properties of metallocene catalyzed linear low‐density polyethylene foams for rotational molding

The object of this work is to assess the suitability of metallocene catalyzed linear low‐density polyethylenes for the rotational molding of foams and to link the material and processing conditions to cell morphology and part mechanical properties (flexural and compressive strength). Through adjustments to molding conditions, the significant processing and physical material parameters that optimize metallocene catalyzed linear low‐density polyethylene foam structure have been identified. The results obtained from an equivalent conventional grade of Ziegler‐Natta catalyzed linear low‐density polyethylene are used as a basis for comparison. The key findings of this study are that metallocene catalyzed LLDPE can be used in rotational foam molding to produce a foam that will perform as well as a Ziegler‐Natta catalyzed foam and that foam density is by far the most influential factor over mechanical properties of foam. Polym. Eng. Sci. 44:638–647, 2004. © 2004 Society of Plastics Engineers.     

Morphology and mechanical properties of liquid crystalline copolyester and polyester elastomer blends

Blends of a polyester elastomer (PEL) having a hard segment of polyester (PBT) and soft segment of polyether (PTMG) and a liquid crystalline copolyester (LCP), poly(benzoate-naphthoate), were prepared in a twin-screw extruder. Specimens for mechanical testing were prepared by injection molding. The morphology of the LCP/PEL blends was characterized under different processing conditions. To determine what conditions were necessary for the development of a fibrillar morphology of LCP, we have studied the effect of processing method (extrusion and injection molding), injection molding temperature (below and above the melting point of LCP), and gate position in the mold (direct gate and side gate). SEM studies revealed that some extensional flow was required for the fibrillar formation of LCP and the fibrillar structure of LCP was controlled by the processing method. The morphology of the blends was found to be affected by their compositions and processing conditions. SEM studies revealed that finely dispersed spherical domains of LCP were formed in the PEL matrix and the inclusions were deformed in fibrils from the spherical droplets with increasing LCP content and injection temperature. The mechanical properties of the LCP/PEL blends were also found to be affected by their compositions and processing conditions. The mechanical properties of LCP/PEL blends were very similar to those of polymeric composite. An attempt was made to correlate the structure of the blends from the scanning electron microscope with the measured mechanical properties. All of the aspects of the morphology were possible to explain in terms of the mechanical properties of the blends. A DSC study revealed that the crystallization of PEL was accelerated by the addition of LCP in the matrix and a partial compatibility between LCP and PEL was predicted. The rheological behavior of the LCP/PEL blends was found to be very different from that of the parent polymers, and significant viscosity reductions were observed in the blend consisting of only 5 wt% of LCP.     

Aspects of foaming a glass‐reinforced polypropylene with chemical blowing agents

This work explores the influence of a chemical blowing agent on different aspects of producing a short glass‐fiber‐reinforced polypropylene foam, examining the rheology of the system, the developed morphology of the part, and the resulting mechanical properties. Two different forms of an endothermic blowing agent, namely powder versus masterbatch, were compared to determine their effects on the process history and properties of an injection molded part. Samples were produced on an injection molding machine between 230 and 270°C using the low‐pressure foaming technique. Rheology of the resulting plasticized melt by the two different blowing agents was measured on an in‐line rheometer, showing a greater reduction in shear viscosity for the masterbatch additive, which correspondingly reduced the extent of fiber breakage observed. The final molded samples were analyzed for their foam structure (i.e., cell size, cell density, and skin thickness) as well as the properties of the glass fibers incorporated (namely, fiber length distribution). Tensile properties were found to diminish with increasing blowing agent content, though differences were observed based on the type of CBA used despite the similarities in foam structure produced. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 4696–4706, 2006     

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     

Effects of the blending sequence in polyolefin ternary blends

Ternary blends of isotactic polypropylene (PP), ethylene–octene copolymer (mPE), and high‐density polyethylene (HDPE) were prepared by melt mixing in a twin‐screw extruder with two different sequences of mixing: the simultaneous mixing of the three components (method I) and the premixing of mPE and HDPE followed by mixing with PP (method II). Regardless of the mixing sequence, mPE encapsulated HDPE in the PP matrix, although better mechanical properties were generally obtained with method II. The domain size was mainly determined by the viscosity ratio of mPE to PP in method I and by the viscosity ratio of the binary blend (mPE/HDPE) to PP in method II. Specimens prepared by injection molding gave much finer dispersions than compression‐molded specimens. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 804–811, 2004