On the origin of the “core‐free” morphology in microinjection‐molded HDPE

This study investigates the morphology of a high‐density polyethylene processed with microinjection molding. Previous work pointed out that a “core‐free” morphology exists for a micropart (150‐μm thick), contrasting with the well‐known “skin‐core” morphology of a conventional part (1.5‐mm thick). Local analyses are now conducted in every structural layer of these samples. Transmission electron microscopy observations reveal highly oriented crystalline lamellae perpendicular to the flow direction in the micropart. Image analysis also shows that lamellae are thinner. Wide‐angle X‐ray diffraction measurements using a microfocused beam highlight that highly oriented shish–kebab morphologies are found through the micropart thickness, with corresponding orientation function close to 0.8. For the macropart, quiescent crystallized morphologies are found with few oriented structures. Finally, the morphology within the micropart is more homogeneous, but the crystalline structures created are disturbed due to the combined effects of flow‐induced crystallization and thermal crystallization during processing. © 2011 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 49: 1470–1478, 2011     

Morphology evolution and crystalline structure of controlled‐rheology polypropylene in micro‐injection molding

In this paper, the microstructural evolution of controlled‐rheology polypropylene (CRPP) with different melt viscoelasticities was investigated by polarized optical microscopy, scanning electronic microscopy, differential scanning calorimeter, and wide‐angle X‐ray diffraction. It is found that a typical “skin‐core” structure formed in CRPP microparts and the thickness of oriented layer of CRPP microparts decreases notably with the addition of peroxide. The thickness of oriented layer and the distribution of different layers strongly depend on the melt flow properties and the corresponding relaxation time (λ). Furthermore, the mechanisms of the suppressed formation of oriented layers during the micro‐injection molding process are discussed mainly from the viewpoint of rheology and thermodynamics. It is revealed that the shear‐induced orientation is one of the key factors for the formation of oriented molecular structure (row nuclei). The final thickness of the oriented layer is the result of the competition between the orientation behavior and the disorientation behavior. Copyright © 2015 John Wiley & Sons, Ltd.     

Effect of in situ poly(ethylene terephthalate) (PET) microfibrils on the morphological structure and crystallization behavior of isotactic polypropylene (iPP) under an intensive shear rate

The morphological structure and crystallization behavior of in situ poly(ethylene terephthalate) (PET)/isotactic polypropylene (iPP) microparts prepared through micro‐injection molding are investigated using a polarized light microscope, differential scanning calorimeter, scanning electron microscope, and two‐dimensional wide‐angle X‐ray. Results indicate that both the shear effect and addition of PET fibers greatly influence the morphologies of the iPP matrix. Typical “skin‐core” and oriented crystalline structures (shish‐kebab) may simultaneously be observed in neat iPP and iPP/PET microparts. The presence of PET phases reveals significant nucleation ability for iPP crystallization. High concentrations of PET phases, especially long PET fibers, correspond to rapid crystallization of the iPP matrix. The occurrence of PET microfibrils decreases the content and size of β‐crystals; by contrast, the orientation degree of β‐crystals increases with increasing PET content in the microparts. This result suggests that the existence of the microfibrillar network can retain the ordered clusters and promote the development of oriented crystalline structures to some extent. Copyright © 2015 John Wiley & Sons, Ltd.     

Role of dicumyl peroxide on the morphology and mechanical performance of polypropylene random copolymer in microinjection molding

The purpose of this work is to systematically investigate the effects of dicumyl peroxide (DCP) on the microstructural evolution and mechanical properties of polypropylene random copolymers (PPRs) during the microinjection process. Polarized light microscopy, differential scanning calorimetry, X‐ray diffraction, and scanning electronic microscopy measurements were employed to characterize the morphology evolution of the PPR microparts with DCP. A hierarchical structure was found in the PPR microparts with DCP. Specifically, with the individual addition of organic peroxide, the orientation parameter of the PPR microparts decreased pronouncedly and the formation of skin layer was suppressed, while the formation of core layer was promoted. This was ascribed to the distribution of shear rate in the microchannel, which was determined by the wall ship effect in the filling stage and the relaxation behavior in the cooling stage. A mechanism was proposed to explain the distinctive filling behavior and molding characteristics of PPR with DCP in microinjection molding.     

Altering the hierarchical morphology distribution of injection molded polyethylene by the introduction of crosslink network and periodical shear

High density polyethylene (HDPE) with moderate content of crosslink network (CPE) was successfully prepared through chemical method. Specimens for structural characterization have been molded by conventional injection molding (CIM) and pressure vibration injection molding (PVIM). Influence of crosslink network on hierarchical morphology distribution and mechanical properties was systematically studied. Polarized light microscopy (PLM) revealed that both CIM and PVIM PE samples have a typical “skin-core” structure and the thickness of shear layer of CIM PE and PVIM CPE samples obviously increase. Scanning electron microscopy (SEM) showed that shish-kebab structures are clearly observed in shear layer of CIM CPE sample, indicating that the crosslink network can surely improve the formation of shish-kebab structures. Moreover, we suppose that shish-kebab structures emerged in shear and core layer of PVIM CPE sample. Wideangle X-ray diffraction (WAXD) and small-angle X-ray scattering (SAXS) confirmed that more orientation and shish-kebab structures form even in core layer of PVIM CPE sample, which demonstrated that the hierarchical morphology was apparently altered by periodical shear and crosslink network. Finally, the mechanical properties revealed that this oriented structure increase the tensile strength from 31 MPa of CIM PE sample to 46 MPa of PVIM CPE sample. However, the tensile behavior tended to change from ductile fracture to brittle fracture.     

Morphology and mechanical behavior of isotactic polypropylene with different stereo‐defect distribution in injection molding

Large amount of work has been published on the isotacticity–properties relationship of isotactic polypropylene (iPP). However, the stereo‐defect distribution dependence of morphology and mechanical properties of iPP injection molding samples is still not clear. In this study, two different isotactic polypropylene (iPP) resins (PP‐A and PP‐B) with similar average isotacticity but different stereo‐defect distribution were selected to investigate the morphology evolution and mechanical properties (tensile and notching) of their injection molding samples using differential scanning calorimetry (DSC), dynamic mechanical analysis (DMA), 2D wide angle X‐ray diffraction (2D‐WAXD), and scanning electron microscope (SEM). The results of DMA showed that the molecular movement ability of PP‐A (with less uniform distribution of stereo‐defect) was stronger than that of PP‐B, meanwhile the analysis of DSC and SEM suggested that after injection molding, smaller spherullites, and crystals with higher perfection had formed in the specimens of PP‐A. The resulting of tensile properties of PP‐A were found to be better than that of PP‐B. The results of morphology evolution by SEM observation and 2D‐WAXD showed that PP‐A is more likely to occur interspherulite deformation and can disperse the tensile stress more efficiently, and therefore, its crystal structure can withstand a greater force when tensile stress is applied. On the other hand, PP‐B has larger spherulites and boundaries, and low perfection of lamellaes, and the intraspherulte deformation tend to take place. It is easier for the crystal of PP‐B to be broken up and reoriented along the tensile direction. Copyright © 2014 John Wiley & Sons, Ltd.     

Insight into understanding the evolution of the epitaxy crystallization in isotactic polypropylene and polyethylene blends

In this article, epitaxial structures have been successfully obtained in the isotactic polypropylene (iPP)/polyethylene (PE) blends by an accessible injection molding methods. By studying a series of iPP/PE blends, the evolution of the epitaxial growth of PE lamellae on the oriented iPP lamellae has been detailedly discussed via wide‐angle X‐ray diffraction, small‐angle X‐ray scattering, scanning electron microscopy and differential scanning calorimetry. Unexpectedly, the exactly epitaxial angles between peculiarly arranged PE lamellae and oriented PP lamellae are all larger than the classical epitaxy theory value of 50°, and it even increases gradually with increasing PP content. It is inferred that the special crystallization of PE is the consequence of joint construction of the oriented PP crystals and the continuous intense shear field provided by pressure vibration injection molding. The epitaxial structures play a positive role in the interfacial connection between two components; thus, the mechanical properties of the blends are improved. This work provides an insight understanding on the formation mechanism of the epitaxy crystallization under shear field. Copyright © 2017 John Wiley & Sons, Ltd.     

Microinjection molding of polyamide 6

Processing polymers by microinjection molding (μIM) generate specific constraints upon the polymer melt such as high shear stress and rapid cooling, leaving a mark upon the microstructure of the micropart. The present work compares the morphology and structure of polyamide 6 samples produced by melt extrusion and μIM. The specimens obtained were analyzed by polarized light microscopy, differential scanning calorimetry, and wide‐angle X‐ray diffraction. α and γ crystalline forms were formed in polyamide 6 samples prepared by both methods. The γ form was dominant in the skin of the microinjection molded part, with larger contribution for these samples compared with extruded samples. The conditions used in μIM lead to considerable orientation at the skin region, decreasing toward the core, while the extruded samples showed almost no orientation. The overall degree of crystallinity of the microinjection molded part was lower compared with the extruded sample. Copyright © 2014 John Wiley & Sons, Ltd.     

A study on the micro‐injection molding of multi‐cavity ultra‐thin parts

In this study, we report the micro‐injection molding of ultra‐thin parts (100, 250, and 500 µm). The results show that the flow resistance increases as the cavity becomes thinner. The melt front is not symmetric when filling a four‐cavity ultra‐thin part and filling the eight‐cavity mold under a low temperature. If we increase the mold temperature or cavity thickness, the melt front becomes symmetric. Finally, we construct the operation windows of molding for three kinds of plastics (PS, PMMA, PC) and provide a molding range based on mold temperature and injections speed. Meanwhile, the relationship between the thickness and the operation windows are also investigated. The thinner the cavity is, the smaller the operation window is. We need to increase the injection speed significantly for molding the ultra‐thin parts with micro‐features on both surfaces which are 60 µm in thickness. Furthermore, we succeed in molding 30 µm ultra‐thin parts in this experiment. Copyright © 2009 John Wiley & Sons, Ltd.     

Microinjection molding of multiwalled carbon nanotubes (CNT)–filled polycarbonate nanocomposites and comparison with electrical and morphological properties of various other CNT‐filled thermoplastic micromoldings

A series of polycarbonate (PC)/multiwalled carbon nanotubes (CNT) nanocomposites were prepared by diluting a commercially available masterbatch using a neat PC resin in a lab‐scale batch mixer. The obtained nanocomposites were subjected to microinjection molding to fabricate microparts, which have a 3‐step decrease in thickness along the flow direction, under a defined set of processing conditions. The obtained microparts were mechanically divided into 3 different sections, namely, thick, middle, and thin sections, based on thickness. Morphology observations and electrical conductivity measurements were conducted to explore the evolution of microstructure within subsequent microparts. Additionally, a comparison of the electrical and morphological properties of stepped microparts of various thermoplastic polymers filled with CNT was studied. Results suggested that the selection of host polymers influences the dispersion of nanotubes within subsequent moldings, thereby affecting the electrical properties. The thermal stability of subsequent moldings deteriorated upon the addition of CNT, suggesting that the addition of CNT and the thermomechanical history experienced by the polymer melts in microinjection molding might cause a chain scission effect on PC. Raman spectroscopy analysis was used to study the orientation and properties of CNT in microparts.     

Influence of scale effect and injection speed on morphology and structure of the microinjection molded isotactic polypropylene parts

The morphology and microstructure as well as their forming mechanism of the parts in microinjection molding process are critical. In this work, the coupling effect of scale factor and injection speed on the morphology of the microparts was systematically investigated. Neat isotactic polypropylene parts with thicknesses of 1 mm, 200 μm, and 100 μm were molded at different injection speeds. Polarized light microscope and wide‐angle X‐ray diffraction were used to inspect the microstructures along the sample thickness. In this way, three kinds of typical morphology were observed in the parts, including typical skin‐core structure for the parts with the thickness of 1 mm, noncore shear layer structure for the parts with the thickness of 200 μm, and special skin‐core structure with large fraction of columnar crystal for the parts with the thickness of 100 μm. Most interestingly, it was intuitively and straightforward found that the wall slip occurs when the injection speed exceeds a certain value. Specifically, opposite morphological change trend can be obtained when the parts were molded at different levels of injection speeds. Based on these experimental observations, the formation mechanism was proposed to interpret the morphological evolution. Our work provides a new insight for better understanding the morphology evolution mechanism for microinjection molding parts.     

Study on the improvement of crystallization of high density polyethylene through dynamic packing injection molding

To better understand the effect of high‐density polyethylene on crystal morphology under the shear stress field, the dynamic packing injection molding was used to prepare the oriented pure polyethylene. In this present work, dynamic packing injection molding can exert a successive shear field on the melt in the mold cavity during packing stage. The structure of the samples was characterized through differential scanning calorimetry, wide‐angle X‐ray diffraction, and scanning electron microscopy. The oriented lamellae perpendicular to the flow direction can be formed. Oscillating stress between the lower and upper critical values can induce shish forming. The shish kebabs can be generated through sufficient relaxation led by slow cooling and suitable shear. We roughly discuss the relationship between the shear rate and crystal shape. Our results set up a method to reinforce polymer parts by regulating morphology and structure which can be used to do practical processing condition. Copyright © 2016 John Wiley & Sons, Ltd.     

Study on mechanical properties of co-injection self-reinforced single polymer composites based on micro-morphology under different molding parameters

Self-reinforced single polymer composites (SRCs), which are fabricated by combining the same type of polymer with different properties into one body, have high specific strength, no interfacial heterogeneity, and ease of recycling. To better understand the relationship between the micro-morphology and mechanical properties of SRCs, the co-injection molding process was used in this study to process SRCs parts with different molding parameters and obtain the co-injection self-reinforced single polymer composites parts(CI-SRCs parts). Further, the micro-morphology of CI-SRCs parts were observed by polarizing microscope (PLM), scanning electron microscope (SEM), differential scanning calorimetry (DSC) and wide Angle X-ray diffraction (WAXD). From the results, it was found that the tensile properties of CI-SRCs parts with different molding parameters were improved by up to 23.94% compared with the conventional parts. Through PLM observation, it is found that the section shape of CI-SRCs parts perpendicular to the flow direction shows a double ‘skin-core’ structure, and the area ratio of skin layer was higher than that of conventional parts, with a maximum increase of 68%. The low-temperature and low-speed environment were conducive to the formation of skin layer, and the tensile property of CI-SRCs parts were positively correlated with the area ratio of skin layer. SEM was carried out on the skin layer near the fusion position of the interface, and the highly oriented ‘shish-kebab’ structure was observed. The 1D-WAXD pattern analysis shows that the crystallinity of CI-SRCs parts were lower than that of conventional parts, with a maximum reduction of 19.32%. The crystallinity of CI-SRCs parts were positively correlated with melt temperature gradient, and its tensile properties were negatively correlated with the change of crystallinity. The 2D-WAXD pattern analysis shows that the molecular orientation of CI-SRCs parts were higher than conventional parts, with the maximum increase of 37.44%. Low temperature and low speed can improve the molecular orientation of CI-SRCs parts, and the change of molecular orientations were positively correlated with the tensile properties of CI-SRCs parts. By means of response surface method, the molecular orientation obtained was the decisive factor affecting the performance of CI-SRCs parts. Furthermore, by means of the least squares minimization program, the dimensionless equations among molding parameters, micro-morphologies and mechanical properties were established. The prediction of mechanical properties of CI-SRCs parts based on micro-morphologies were realized, providing theoretical support for the ‘adjustability’ of CI-SRCs parts properties.     

Crystallization and phase morphology of injection‐molded isotactic polypropylene (iPP)/syndiotactic polypropylene (sPP) blends

The crystallization and phase morphology of the injection‐molded isotactic polypropylene (iPP)/syndiotactic polypylenen (sPP) blends were studied, focusing on the difference between the skin layer and core layer. The distribution of crystallinity of PPs in the blends calculated based upon the DSC results shows an adverse situation when compared with that in the neat polymer samples. For 50/50 wt % iPP/sPP blend, the SEM results indicated that a dispersed structure in the skin layer and a cocontinuous structure in the core layer were observed. A migration phenomenon that the sPP component with lower crystallization temperature and viscosity move to the core layer, whereas the iPP component with higher crystallization temperature and viscosity move to the skin layer, occurred in the iPP/sPP blend during injection molding process. The phenomenon of low viscosity content migrate to the low shear zone may be due to the crystallization‐induced demixing based upon the significant difference of crystallization temperature in the sPP and iPP. This migration caused the composition inhomogeneity in the blend and influenced the accuracy of crystallinity calculated based upon the initial composition. © 2007 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 45: 2948–2955, 2007     

Microstructure and mechanical properties of isotactic polypropylene composite with two‐scale reinforcement

Isotactic polypropylene (iPP) composite with two‐scale reinforcement structure, i.e. nanoscale shish–kebab structure and micron‐scale glass fiber (GF) with orientation, was fabricated by an oscillatory shear injection molding (OSIM) technology. The oscillatory shear flow provided by the OSIM gave rise to a high fraction of shish–kebab structures in the iPP composite, characterized by X‐ray scattering technique. On the other hand, the oscillatory shear flow oriented GFs in the iPP composite, which was revealed by scanning electron microscopy measurement. The iPP composite with this two‐scale reinforcement structure exhibited simultaneously remarkably enhanced tensile strength and impact strength. Fracture mechanism of this iPP composite was also proposed. Copyright © 2012 John Wiley & Sons, Ltd.     

Epitaxial crystallization and oriented structure of linear low‐density polyethylene/isotactic polypropylene blends obtained via dynamic packing injection molding

In this work, as a part of a long‐term project aimed at controlling of crystal structure and phase morphology for a injection molded product, we investigated the oriented structure and possible epitaxial growth of polyolefin blend (low‐density polyethylene (LLDPE)/isotatic polypropylene (iPP)), achieved by dynamic packing injection molding, which introduced strong oscillatory shear on the gradually‐cooled melt during the packing process. The crystalline and oriented structures of the prepared blends with different compositions were estimated in detail through 2D X‐ray diffraction, calorimetry, and optical microscopy. As iPP was the dominant phase (its content was more than 50 wt%), our results indicated that it could be highly oriented in the blends. In such case, it was interesting to find that LLDPE epitaxially crystallized on the oriented iPP through a crystallographic matching between (100)_LLDPE and (010)_iPP, resulting in an inclination of LLDPE chains, about 50° to the iPP chain axis. On the other hand, as iPP was the minor phase, iPP was less oriented and no epitaxial growth between iPP and LLDPE was observed; even LLDPE remained oriented. The composition‐dependent epitaxial growth of LLDPE on oriented iPP could be understood as due to: (1) the effect of crystallization sequence, it was found that iPP always crystallized before LLDPE for all compositions; (2) the dependence of oriented iPP structure on the blend composition; (3) the “mutual nucleation” between LLDPE and iPP due to their partial miscibility. Copyright © 2009 John Wiley & Sons, Ltd.     

The banded spherulites of iPP induced by pressure vibration injection molding

Isotactic polypropylene(i PP) samples obtained by pressure vibration injection molding(PVIM) and conventional injection molding(CIM) were studied by polarized-light microscopy(PLM), respectively. It was found that the alternating bright and dark banded spherulites were generated in the transitional region of PVIM parts. It is the first time that the banded spherulites of isotactic polypropylene were observed in polymer processing. What's more, the banded spherulites were proved to be constituted of ?-form crystal by hot stage polarized-light microscopy(HT-PLM) and wide angle X-ray diffraction(WAXD). Morphology of the banded spherulites was also studied by scaning electronical microscopy(SEM).     

Conductive polyethylene-carbon black composites by elongational-flow injection molding Part 3. Study of the structure and morphology

The morphology and structure of high molecular weight linear polyethylene (M _w 450000) filled with carbon black and processed using molds that introduce an elongational flow component during injection molding has been examined using electron microscopy and x-ray diffraction techniques. The study of fracture surfaces reveals the display of shish-kebabs oriented along the injection direction with segregated longitudinal channels of carbon black particles. Molecular and lamellar changes in orientation are, furthermore, studied across the thickness of the moldings. It is shown that addition of carbon black particles to injection-molded polyethylene induces significant changes in lamellar orientation. Thus, while lamellar overgrowth proceeds perpendicular to the fiber axes within carbon free channels, lamellae grow randomly within carbon-enriched regions where flow is less pronounced.     

The influence of thermoelastomers on the crystallization behavior of isotactic polypropylene under shear

The crystallization behaviors of isotactic polypropylene (iPP) and its blends with thermoelastomers have been investigated with in situ X‐ray scattering and optic microscopy. At quiescent condition, the crystallization kinetics of iPP is not affected by the presence of elastomers; while determined by the viscosity, the differences are observed on sheared samples. With a fixed shear strain, the crystallization rate increases with increasing the shear rate. The fraction of oriented lamellar crystals in blends is higher than that in pure iPP sample, while the percentage of β phase is reduced by the presence of the elastomers. On the basis of experimental results, no direct correlation among the fraction of oriented lamellae, the percentage of β phase, and growth rate can be deduced. The evolution of the fraction of oriented lamellae supports that shear field promotes nucleation rather than growth process. Shear flow induces the formation of nuclei not only with preferring orientation but also with random orientation. The total density of nuclei, which determines the crystallization kinetics, does not control the ratio between nuclei with and without preferring orientation, which determines the fraction of oriented lamellae. © 2006 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 44: 1188–1198, 2006