Formation mechanism of crystal morphologies in LLDPE/HDPE blends investigated via water‐assisted and conventional injection molding

The LLDPE/HDPE blends with two different weight ratios as well as pure LLDPE were molded by means of water‐assisted and conventional injection molding (WAIM and CIM) in terms of their different thermal fields. The formation of the crystal morphology in the molded parts was investigated by a scanning electron microscope. The results showed that banded spherulites formed in the WAIM and CIM pure LLDPE parts. Banded spherulites of LLDPE coexisted with the randomly oriented lamellae of HDPE for LLDPE/HDPE blend parts with lower HDPE content at higher cooling rates, whereas a banding to nonbanding morphological transition occurred for LLDPE component (particularly for blend with higher HDPE content) at lower cooling rates. The heterogeneous nucleation effect of HDPE component on LLDPE component was responsible for the banding to nonbanding morphological transition by hindering the twist of LLDPE lamellae. It was interesting to find that the thermal effect, rather than the shear effect, was the main factor for the formation of crystal morphologies in both CIM and WAIM blend parts. POLYM. ENG. SCI., 2012. © 2011 Society of Plastics Engineers     

Hierarchical crystalline structure of HDPE molded by gas-assisted injection molding

To understand the crystalline morphology of the parts molded by gas-assisted injection molding (GAIM), in this work, the hierarchical structures and the crystalline morphology of gas-assisted injection molded high-density polyethylene (HDPE) were investigated. According to the comparison between the results of the GAIM part and those of the conventional injection molded counterpart, it is found that gas penetration can remarkably enhance the shear rate during GAIM process and oriented lamellar structure, shish-kebab structure and common spherulites arise in the skin, subskin and gas channel region, respectively, owing to the different shear rate in these regions. Meanwhile, cooling rate also plays an important role in the formation of the oriented crystalline structure.     

水辅助注塑聚丙烯制品的晶体结构研究

通过偏光显微镜(PLM)观察了水辅助注塑(WAIM)聚丙烯(PP)制品靠近注水喷嘴和远离注水喷嘴两个位置的晶体结构,发现WAIM制品沿壁厚方向都可以分为表层、中芯层和水道层,并且发现两个位置水道层和中芯层的晶体结构比较相似,表层晶体结构出现了较大的差异;靠近注水喷嘴位置表层晶体结构出现明显的取向现象,而在远离注水喷嘴位置没有出现。在晶体结构分析的基础上,初步探讨了水辅助注塑制品晶体结构的形成机理。结果表明:水的穿透对于熔体内部剪切的增加和取向结晶的形成有明显的促进作用。     

The hierarchy structure and orientation of high density polyethylene obtained via dynamic packing injection molding

The evaluation of microstructure and crystal morphology in injected-molded bar becomes much complicated because of the existence of a shear gradient and a temperature gradient from the skin to the core of the samples. To understand the relationship between shear rate-molecular weight and oriented structure of injection molded bar, in this work, the hierarchy structure and the effect of molecular weight on the formation of shish-kebab structure were investigated by examining the lamellar structure of injection molded samples of high density polyethylene (HDPE) with different melt flow index (MFI), layer by layer, along the sample thickness. To enhance the shear effect, so-called dynamic packing injection molding (DPIM), in which the melt is firstly injected into the mold and then forced to move repeatedly in a chamber by two pistons that move reversibly with the same frequency as the solidification progressively occurs from the mold wall to the molding core part, was used to obtain the molded bar. Furthermore, a small amount of ultra-high molecular weight polyethylene (UHMWPE) was added into HDPE to explore the effect of UHMWPE on the crystal morphology and orientation. Our results indicated (1) that the overall orientation in the molded bar increased with decreased MFI, and a small amount of UHMWPE could enhance substantially HDPE orientation; (2) at the skin, there existed intertwined lamellae constituting an interlocked lamellar assembly, a typical shish-kebab structure gradually developed from the subskin-layer to the core, with increased shish content toward the center, but in the core was a spherulite-like superstructure with randomly distributed lamellae; (3) UHMWPE played an important role not only in the formation of shish, but also in the transformation from spherulite to shish-kebab oriented structure for HDPE with a low molecular weight (high MFI).     

水辅注射成型聚丙烯制品的取向结晶

应用小角X射线散射研究了水辅注射成型(WAIM)等规聚丙烯制品中串晶(shish-kebab)结构的形成、分布以及片晶取向行为.结果表明:根据取向度不同,WAIM制品沿壁厚方向可明显分为表层、芯层和水道层.表层和水道层均有shish-kebab结构生成,且在表层生成的数量比水道层多,而芯层则没有这种结构.这种shish...     

Process‐induced phase and crystal morphologies in water‐assisted injection molded polypropylene/polymeric β‐nucleating agent blend parts

By adding a polymeric β‐nucleating agent (acrylonitrile–styrene copolymer, SAN), in situ microfibril reinforced isotactic polypropylene (iPP)/SAN blend parts with high contents of β‐form crystals and transcrystals were molded via water‐assisted injection molding (WAIM). Thanks to the unique stress and temperature fields occurring during the WAIM, SAN microfibers formed across the whole residual wall of iPP/SAN blend parts with relatively large thickness. Numerical simulations on high‐pressure water penetration and cooling stages of the WAIM were carried out to reveal the stress and temperature fields. Comprehensive analysis of both experimental and simulated results showed that not only the shear flow field but also elongational flow field occurring during the WAIM was responsible for the formation of SAN microfibers and unique crystal morphology distribution in the WAIM iPP/SAN blend part. Moreover, during the WAIM, the high cooling rate also played an important role in the formation of both phase and crystal morphologies. The preferential formation of transcrystals in the inner layer of WAIM iPP/SAN blend part could be ascribed to the strong elongation, rather than the strong shear. It was believed that the quantification of stress and temperature fields of the WAIM via numerical simulation could provide a guidence for molding high‐performance products. POLYM. ENG. SCI., 55:1698–1705, 2015. © 2014 Society of Plastics Engineers     

Hierarchical structure of injection-molded bars of HDPE/MWCNTs composites with novel nanohybrid shish-kebab

Injection-molded products usually show hierarchical structure from skin to core due to the existence of shear gradient and temperature gradient. Investigating the hierarchical structure is helpful to better understand the structure-property relationship of injection-molded sample, which is important for design and preparation of polymer products with high performance. In this work, the hierarchical structures of injection-molded bars of high-density polyethylene (HDPE)/multi-walled carbon nanotubes (MWCNTs) composite were explored by examining the microstructure and crystal morphology, layer by layer, along the sample thickness, using SEM, DSC and 2D-WAXS. To enhance the shear effect, a so-called dynamic packing injection molding (DPIM) technique was used to prepare the molded bar with high orientation level. Interestingly, SEM revealed that in the skin and core zones, the lamellae of PE anchored randomly on the surface of MWCNTs, while well-defined nanohybrid shish-kebab (NHSK) entities, in which fibrillous carbon nanotubes (CNTs) act as shish while HDPE lamellae act as kebab, exist in the oriented zone. The changed NHSK crystal structure along the thickness direction of molded bar is considered as due to the shear gradient and thermal gradient in injection molding. And the underlying origin of in situ formation of NHSK under shear effects is discussed based on experimental observations.     

Enhanced orientation of the water‐assisted injection‐molded ipp in the presence of nucleating agent

The nucleated isotactic polypropylene (iPP) was molded by water‐assisted injection molding. The crystalline morphology and orientation distribution were studied. The results show that shear brought by melt filling and pressurized water penetration can separately induce the formation of oriented structures in skin region (i.e., the region near mold cavity wall) and the water channel region. For virgin iPP, slightly oriented lamellae appear exclusively in the above aforementioned regions. However, shish‐kebab structure occurs not only in skin and water channel region of the iPP containing moderate content of nucleator (0.2 wt%) but also in the whole region of the iPP containing a higher content of nucleator (1 wt%). It is well known that nucleator cannot directly induce the development of shish‐kebab in the absence of shear, thus the results indicate: shear flow actually distributes over a much broader range than expected; in shear field, nucleator is significantly helpful for the shear which is not sufficient to solely induce oriented structure to promote the formation of the oriented structure. POLYM. ENG. SCI., 2012. © 2012 Society of Plastics Engineers     

Morphology of gas‐assisted and conventional injection molded polycarbonate/polyethylene blend

The skin‐core structure of the gas‐assisted and conventional injection molded polycarbonate (PC)/polyethylene (PE) blend was investigated. The results indicated that both the size and the shape of the dispersed PC phase depended not only on the nature of PC/PE blend and molding parameters, but also on its location in the parts. Although the gas‐assisted injection molding (GAIM) parts and conventional injection molding (CIM) part have the similar skin‐core structure, the morphology evolution of PC phase in the GAIM moldings and the CIM moldings showed completely different characteristics. In the section perpendicular to the melt flow direction, the morphology of the GAIM moldings included five layers, skin intermediate layer, subskin, core layer, core intermediate layer as well as gas channel intermediate layer, according to the degree of deformation. PC phase changed severely in the core layer of GAIM moldings, as well as in the subskin of CIM moldings. In GAIM parts, PC phase in the core layer of the nongate end changed far more intensely and aligned much orderly than that in the gate end. The morphology of PC phase in the GAIM part molded with higher gas pressure changed more severe than that in the GAIM part molded with lower gas pressure. In a word, PC phase showed more obvious fibrillation in the GAIM moldings than that in the CIM moldings. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 3069–3077, 2006     

Crystalline morphology of isotactic polypropylene (iPP) in injection molded poly(ethylene terephthalate) (PET)/iPP microfibrillar blends

The poly(ethylene terephthalate) (PET)/isotactic polypropylene (iPP) in situ microfibrillar blends have been prepared through a “slit die extrusion-hot stretch-quenching” process, in which PET assumes microfibrils with 0.5-15 μm in diameter depending on the hot stretching ratios (HSR, the area of the transverse section of the die to the area of the transverse section of the extrudate). The injection molded specimens of virgin iPP and the PET/iPP blends were prepared by conventional injection molding (CIM) and by shear controlled orientation injection molding (SCORIM), respectively. The effect of shear stress and PET phase with different shape on superstructures and their distribution of injection molded microfibrillar samples were investigated by means of small angle X-ray scattering (SAXS) and wide angle X-ray scattering (WAXS). The shear (or elongational) flow during CIM and SCORIM can induce oriented lamellae (i.e. kebabs induced by shish). The shish-kebab structure appears not only in the skin and intermediated layers of CIM samples, but also in the whole region of SCORIM samples. For the neat iPP samples, a more “stretched” shish-kebab structure with higher orientation degree can be obtained in the interior region (intermediate and core layers) by the SCORIM method; moreover, the SCORIM can result in the growth of β-form crystal both in intermediate layer and in core layer, which only appears in intermediate layer of the neat iPP samples obtained by CIM. For the PET/iPP blends, interestingly, the addition of microfibrils as well as their aspect ratios can affect the orientation degree of kebabs only in the intermediate layers, and the addition of microfibrils with a low aspect ratio can bring out a considerable increase in the orientation degree of kebabs along the flow direction. However, for the SCORIM, the addition of microfibrils seems to be a minor effect on the orientation degree of kebabs, and it tends to hamper the formation of a more “stretched” shish-kebab structure and suppresses the growth of β-form crystal distinctly. Furthermore, It appears from experiment that γ-form crystals can grow successfully in this oriented iPP melt with the synergistic effect of shear and pressure only when the growth of β crystals can be restrained by some factors, such as the PET dispersed phase and thermal conditions (cooling rate).     

Cylindritic structures of high-density polyethylene molded by multi-melt multi-injection molding

The crystalline morphologies of high-density polyethylene (HDPE) molded by multi-melt multi-injection molding (MMMIM) and conventional injection molding (CIM) were studied by employing polarizing light microscopy (PLM) and scanning electronic microscopy (SEM). It was found that a special double skin-core structure was formed in MMMIM parts. Namely cylindritic structures appeared in both sub-skin layer and core layer, which were attributed to the strong shear flow introduced by the secondary melt penetration process. As the decrease in temperature and injection pressure of the second melt, the number of cylindritic structures in the core layer decreases and the cylindritic structures gradually develop into irregularly-arranged spherulites. Strong shear flow, as compared to CIM, is an important factor which dictates the formation of cylindritic structures in MMMIM. Meanwhile, on going from the interface to the core of MMMIM parts the distance between the centers of banded spherulites which consist of cylindritic structures and the radius of them increased gradually. This phenomenon was primarily caused by the coupling effect of the decreased shear intensity and the cooling rate of melts towards core layer. Based on the above observations, a modified model is proposed to interpret the mechanism of the formation of cylindritic structures during MMMIM process.     

Formation mechanism of high-pressure water penetration induced fiber orientation in overflow water-assisted injection molded short glass fiber-reinforced polypropylene

Recently, there has been growing interest in water-assisted injection molding (WAIM) not only for its advantages over gas-assisted molding (GAIM) and conventional injection molding (CIM), but also for its great potential advantages in industrial applications. To understand the formation mechanism of water penetration induced fiber orientation in overflow water-assisted injection molding (OWAIM) parts of short glass fiber-reinforced polypropylene (SGF/PP), in this work, the external fields and water penetration process within the mold cavity were investigated by experiments and numerical simulations. The results showed that the difference of fiber orientation distribution in thickness direction between WAIM moldings and CIM moldings was mainly ascribed to the great external fields generated by water penetration. Besides, fiber orientation depended on the position both across the part thickness and along the flow direction. Especially in the radial direction, fiber orientation varied considerably. The results also showed that the melt temperature is the principal parameter affecting the fiber orientation along the flow direction, and a higher melt temperature significantly facilitated more fibers to be oriented along the flow direction, which is quite different from the results as previously reported in short-shot water-assisted injection molding (SSWAIM). A higher water pressure, shorter water injection delay time, and higher melt temperature significantly induced more fibers to be orderly oriented in OWAIM moldings, which may improve their mechanical performances and broaden their application scope.     

Morphological evolution of HDPE parts in the microinjection molding: Comparison with conventional injection molding

To compare the difference of morphological evolution of HDPE micropart and macropart, micropart with 200 μm thickness and macropart with 2000 μm thickness were prepared. The PLM images of micropart and macropart exhibited a similar “skin–core” structure, but the micropart showed a much larger fraction of orientation layer. The SEM observation of core layer of micropart featured an unoriented lamellae structure and shear layer of micropart showed a highly oriented shish‐kebab structure. The 2D‐WAXD patterns of shear layer of macropart indicated twisted oriented shish‐kebab (KM‐I) structures, however that of micropart indicated untwisted oriented shish‐kebab (KM‐II) structures which was firstly found in microinjection molding. The diffraction pattern of the micropart exhibited stronger azimuthal dependence than the shear layer of macropart, indicating the most pronounced orientation of HDPE chains within lamellae. © 2012 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Gas‐assisted injection molded polypropylene: The skin‐core structure

In this article, gas penetration‐induced skin‐core structure of isotactic polypropylene(iPP), which is molded by gas‐assisted injection molding at different gas pressures, was investigated. For comparison, the counterpart was also molded by conventional injection molding (CIM) using the same processing parameters but without gas penetration. They were characterized via PLM, DSC, and SEM. And the crystal morphology at different gas pressures was principally concerned. For the GAIM parts, highly oriented structure is formed in the skin zone, and much less oriented structure in the inner zone (near the gas channel surface). Furthermore, it is suggested that the naked shish structure can be developed in the skin zone of GAIM part, which is molded at higher gas pressures, and shish‐kebab structure is mainly formed in the skin zone of that, which is molded at lower gas pressure. However, for the CIM part, from the skin to the core zone, the dominant morphological feature is spherulite. In a word, the presence of gas penetration notably enhances the oriented structure formation and gives rise to the skin‐core structure. POLYM. ENG. SCI., 2008. © 2008 Society of Plastics Engineers     

The morphology and property of HDPE in the presence of oscillation pressure and poly(ethylene terephthalate)

The injection‐molded specimens of neat HDPE and the PET/HDPE blends were prepared by conventional injection molding (CIM) and by pressure vibration injection molding (PVIM), respectively. The effect of oscillation pressure and PET phase with different shapes on superstructure and its crystal orientation distribution of injection molded samples were characterized by differential scanning calorimetry (DSC), scanning electron microscopy (SEM), and two‐dimension wide‐angle X‐ray diffraction techniques (2D‐WAXD). Hermans' orientation functions were determined from the wide‐angle X‐ray diffraction patterns. With the PET particles added, the shear viscosity of blend increase and crystallization rate of HDPE phase is enhanced. For the neat HDPE samples, with the promotion from oscillation shear, the orientation parameter experienced a large increase, moreover, the PVIM can induce transverse lamellae (kebabs) twisting in growth direction. Because of the redefined flow field and nucleation effect of PET particles, the crystal orientation of blend is also increased. So the tensile strength of vibration samples enhanced and elongation at break declined. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

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     

水辅助注塑尼龙6制品的结晶行为研究

利用差示扫描量热法(DSC)对水辅助注塑尼龙6(PA6)制品靠近注水喷嘴(P1)位置和远离注水喷嘴(P2)位置的表层、中芯层和水道层的结晶行为进行了研究,并初步探讨了高压水对PA6制品结晶行为的影响。结果表明:对于P1和P2位置,表层与水道层的结晶度均低于中芯层的结晶度;P1位置表层与水道层结晶度均低于P2位置同层的结晶度;P1位置中芯层结晶度高于P2位置中芯层的结晶度;高压水的冷却作用会降低水道层熔体的结晶度并促使水道层形成较小的晶体。     

Optical properties of high‐density polyethylene in injection press molding for IR system lenses

An experimental investigation of injection press molding (IPM) was conducted to assess high infrared radiation (IR) transmittance with an opaque state (low‐visibility ray (VR) transmittance) necessary for IR system lenses as a target high‐density polyethylene (HDPE) IR transmission material. The changed conditions were the cavity open distance and delay time considering the polymer melt flowability. Other molding conditions were held constant. Mold surface roughnesses of two kinds were used. Data for IR and VR transmittance were evaluated using measurements or observation results obtained for surface roughness, thickness, differential scanning calorimetry (DSC), crystallinity, and the internal structure. Results show that the surface roughness and thickness of molded parts did not influence IR or VR transmittance. For thin skin layers with low orientation of molecular chains, the IR transmittance was higher for longer delay times. For low molecular chain orientation in the shear–core layer, the VR transmittance was also low. The molecular chain orientation differed depending on IPM conditions. Setting a longer delay time produced a uniform distribution of the molded part thickness. Furthermore, thickness became a constant value when a mold with high surface roughness was used. POLYM. ENG. SCI., 2017. © 2017 Society of Plastics Engineers     

Hierarchic structure and mechanical property of glass fiber reinforced isotactic polypropylene composites molded by multiflow vibration injection molding

Maleic anhydride‐grafted polypropylene (Ma‐PP) and β nucleation agents (β‐NA) were used to modify the glass fiber (GF)/isotactic polypropylene (iPP) composite. The interface adhesion, degree of orientation, and crystalline morphologies of the PP/GF composites molded by multiflow vibrate‐injection molding (MFVIM) and conventional injection molding (CIM) were studied by polarized light microscopy (PLM), scanning electronic microscopy (SEM), and X‐ray measurements. Results prove that the interface adhesion was improved by the Ma‐PP; γ crystal was generated by the MFVIM due to the instant high pressure and shear during the multiflow; and a hierarchical structure which has a strengthened skin and a toughened core was formed. As a result, the final PP/GF/β‐NA composite has a 60% increase in tensile strength and 80% improvement in impact strength compare with the CIM pure PP/GF composite. Based on the observations, a modified model is proposed to interpret the strengthening and toughening mechanism. Our work paves the way to obtain high‐performance GF/iPP composites. POLYM. COMPOS., 38:2707–2717, 2017. © 2015 Society of Plastics Engineers     

Shear induced shish-kebab structure in PP and its blends with LLDPE

In order to better understand the effect of shear stress on the crystal morphology and orientation of polyolefins, dynamic packing injection molding was used to prepare oriented pure polypropylene (PP) and its blends with linear low density polyethylene (LLDPE). The obtained samples were characterized via 2d-SAXS, 2d-WAXD and AFM. Macroscopically, shear induced morphology with surface skin, central core and oriented layer between the skin and the core was observed in the cross-section areas of the samples. For pure PP, a highly oriented structure was seen in the sheared layer but much less oriented structure exists in the core. The orientation in the skin lies in between. The shish-kebab structure, composed of stretched chains (shish) and layered crystalline lamellae (kebabs), was found in the sheared layer. Shish structure exists mainly in the skin layer and oriented spherulits dominates in the core. For PP/LLDPE (50/50) blends, a change of phase morphology from less-phase-separated structure (homogeneous) in the skin, to co-continuous structure in the sheared layer and sea-island structure in the core was observed. PP formed a shish-kebab structure in all the three layers. And on the other hand, a very unique crystal morphology and lamellar orientation of LLDPE were obtained, with the lamellar stack oriented either perpendicularly or 45-50° away from the shear flow direction.