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1.
High density polyethylene (HDPE) was molded by a new polymer processing method, that is, water-assisted injection molding (WAIM), and its hierarchical structure was studied by two-dimensional small angle X-ray scattering (SAXS). For comparison, the hierarchical structure of HDPE molded by conventional injection molding (CIM) was also characterized. The result shows that the WAIM part exhibits a distinct skin-core-water channel structure which is different from the skin-core structure for the CIM part. In the skin layer of both WAIM and CIM parts, the shish-kebab structure was formed due to the shear stress brought by melt filling, but the lamellar orientation parameter of CIM part is smaller than that of WAIM part. The spherulites with random lamellar orientation are dominant at the core of both parts owing to the low cooling rate and feeble shear stress therein. Interestingly, the shish structure and the lamellae with low level of orientation can be found at the water channel layer of WAIM part. They are attributed to the shear stress brought by water penetration. Moreover, the lamellar orientation parameter in water channel layer is smaller than that of skin layer. In addition, the long period of WAIM part first increases and then decreases with the elevating distance from the skin surface, while that of CIM part tends to increase monotonously. In a word, one can conclude that the rapid cooling rate and shear brought by the injected water have significant influence on the structural evolution for the WAIM part. © 2012 Wiley Periodicals, Inc. J Appl Polym Sci, 2012  相似文献   

2.
Jinghui Yang 《Polymer》2010,51(3):774-8092
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.  相似文献   

3.
Three types of ultra-high molecular weight polyethylene (UHMWPE) with different entangled state and molecular weight were blended with high-density polyethylene (HDPE) matrix by melt blending. Rheology, 2D-SAXS, 2D-WAXD, DSC, and mechanical tests were used to study the evolution and difference of microstructure and mechanical properties of the blends. The addition of weakly entangled UHMWPE enhanced the chain diffusion and chain orientation ability under a specific flow field. Thus, the rheological properties and mechanical properties of the blends were improved with the mix of weakly entangled UHMWPE. The mechanical properties enhancement effect of HDPE/UHMWPE blends with weakly entangled UHMWPE was owing to the shish-kebab structure formed in the injection molding process. The molecular chains of UHMWPE with a low degree of entanglement and high molecular weight increased the lamella size and crystallinity of the blends during processing. This leads to the formation of more oriented shish structures and more kebab lamella. Besides, the molecular chains of weakly entangled UHMWPE were better interlocked and intertwined with other polyethylene chains in the amorphous region, acting as the tie molecules, significantly improving the impact resistance.  相似文献   

4.
Yong Wang  Qiang Fu  Yongfeng Men 《Polymer》2004,45(1):207-215
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.  相似文献   

5.
All‐polyethylene composites exhibiting substantially improved toughness/stiffness balance are readily produced during conventional injection molding of high density polyethylene (HDPE) in the presence of bimodal polyethylene reactor blends (RB40) containing 40 wt% ultrahigh molar mass polyethylene (UHMWPE) dispersed in HDPE wax. Scanning electron microscopy (SEM) and differential scanning calorimetry (DSC) analyses shows that flow‐induced crystallization affords extended‐chain UHMWPE nanofibers forming shish which nucleates HDPE crystallization producing shish‐kebab structures as reinforcing phases. This is unparalleled by melt compounding micron‐sized UHMWPE. Injection molding of HDPE with 30 wt% RB40 at 165 °C affords thermoplastic all‐PE composites (12 wt% UHMWPE), improved Young's modulus of 3400 MPa, tensile strength of 140 MPa, and impact resistance of 22.0 kJ/m2. According to fracture surface analysis, the formation of skin‐intermediate‐core structures accounts for significantly improved impact resistance. At constant RB40 content both morphology and mechanical properties strongly depend upon processing temperature. Upon increasing processing temperature from 165 °C to 250 °C the average shish‐kebab diameter increases from the nanometer to micron range, paralleled by massive loss of self‐reinforcement above 200 °C. The absence of shish‐kebab structure at 250 °C is attributed to relaxation of polymer chains and stretch‐coil transition impairing shish formation.  相似文献   

6.
The effect of high–molecular-weight polyethylene (HMWPE) on crystal morphology was investigated for high-density polyethylene (HDPE) through dynamic packing injection molding (DPIM). With the aid of differential scanning calorimetry (DSC), wide-angle x-ray diffraction (WAXD), and scanning electron microscopy (SEM) measurements, a typical web-like shish kebab morphology, which markedly increases stiffness and toughness, was found in HMWPE-induced samples through DPIM. The SEM results show that the much better web-like shish kebab structure, in which most of the lamellae connect different columns, compared with conventional shish kebab, was formed in HDPE blends with 4% HMWPE content (B4) through DPIM. The WAXD studies indicate that orientation degrees of crystallographic planes (110) and (200) in the B4 samples were much higher than those of samples molded by static packing injection molding and B0 samples molded by DPIM. A combination of the higher degree of crystal orientation and the formation of web-like shish kebab led to simultaneous great increments of stiffness and toughness, which overcomes the traditional limitation that stiffness and toughness cannot be greatly enhanced simultaneously. All these results show that HWMPE favored for great improvement of crystal structures in HDPE when its content is appropriate through DPIM.  相似文献   

7.
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  相似文献   

8.
A strong shear flow was imposed on the melt of polycarbonate (PC) microfibril reinforced high density Polyethylene (HDPE) during a secondary melt flow process, i.e. gas assisted injection molding (GAIM). Classic shish-kebabs and typical transcrystallinity were simultaneously observed in the entire thickness of the GAIM HDPE/PC microfibril composites, which were closely related to the strong shear flow that was further amplified and distributed by incorporated PC microfibrils. Interestingly, some nano-sized ultrafine PC microfibril inclined to absorb extended chain bundles to form shish nuclei on its surface first, which subsequently evolved into hybrid shish-kebab superstructures. It was deemed that the induced formation of hybrid shish-kebab superstructures on nano-sized ultrafine PC microfibril was due to the absorbing of extended chain bundles for hybrid shish nuclei with the strong shear flow serving as the driving force. Importantly, large scale formation of these highly oriented crystalline superstructures can bring significant mechanical reinforcement in GAIM HDPE/PC microfibril composite. For GAIM HDPE/PC microfibril composites, its yield strength is increased by 68% and 66%, compared to the GAIM HDPE parts and the common injection molded (CIM) HDPE/PC composites, respectively; meanwhile, the Young's modulus is enhanced by 253% and 17%, compared to the GAIM HDPE parts and the CIM HDPE/PC composites, respectively.  相似文献   

9.
Flow-induced crystallization has long been an important subject in polymer processing. Varying processing conditions can produce different morphologies, which lead to different properties. Recent studies indicated that the final morphology is in fact dictated by the initial formation of crystallization precursor structures (i.e. shish-kebabs) under flow. In this article, factors that affect the shish-kebab formation in entangled polymer melts are systematically reviewed, including the concept of coil-stretch transition, chain dynamics, critical orientation molecular weight, phase transition during shish and kebab formations. In particular, recent experimental results from in situ rheo-X-ray studies and ex situ microscopic examinations have been presented to illustrate several new findings of flow-induced shish-kebab structures in polymer melts. (1) The shish entity consists of stretched chains (or chain segments) that can be in the amorphous, mesomorphic or crystalline state. (2) The kebab entity mainly arises from the crystallization of coiled chains (or chain segments), which seems to follow a diffusion-control growth process. (3) A shish-kebab structure with multiple shish was seen in the ultra-high molecular weight polyethylene (UHMWPE) precursor. Based on the above results and recent simulation work from other laboratories, a modified molecular mechanism for the shish-kebab formation in entangled melt is presented.  相似文献   

10.
The dependence of hierarchy in crystalline structures and molecular orientations of high density polyethylene parts with different molecular weights molded by gas‐assisted injection molding (GAIM) was intensively examined by scanning electron microscopy, two‐dimensional wide‐angle X‐ray scattering as well as dynamic rheological measurements. The non‐isothermal crystallization kinetics of the samples were also analyzed with a differential scanning calorimeter at various scanning rates. It was found that oriented lamellar structure, shish‐kebab and common spherulites were formed in different regions of the GAIM samples. The scanning electron microscope observations were consistent with the two‐dimensional wide‐angle X‐ray scattering results and showed that the molecular chains near the mold wall had strong orientation behavior, revealing the distribution of the shear rate of the GAIM process. The differences in crystal morphologies can be attributed to molecular weight differences as well as their responses to the external fields during the GAIM process. The formation mechanism of the shish‐kebab structure under the flow field of GAIM was also explored. Copyright © 2012 Society of Chemical Industry  相似文献   

11.
A small amount of high molecular weight molecules can have a dramatic influence on the flow‐induced crystallization kinetics and orientation of polymers. To elucidate the effects of the high molecular weight component under a real processing process, we prepared model blends in which high density polyethylene with a high molecular weight and wide molecular weight distribution was blended with a metallocene polyethylene with a low molecular weight and very narrow molecular weight distribution. To enhance the shear strength, gas‐assisted injection molding was utilized in producing the molded bars. The hierarchical structures and orientation behavior of the molded bars were intensively explored by using scanning electron microscopy and two‐dimensional wide‐angle X‐ray diffraction, focusing on effects of the high molecular weight component on the formation of the shish kebab structure. It was found that there exists a critical concentration of high molecular weight component for the formation of a shish kebab structure. The threshold was about 5.5–7.0 times larger than the chain overlap concentration, suggesting an important role of entanglements of the high molecular weight component. Moreover, the rheological properties of molten polyethylene melts were studied by dynamic rheological measurements and a critical characteristic relaxation time for shish kebab formation was obtained under the processing conditions adopted in this research. © 2013 Society of Chemical Industry  相似文献   

12.
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  相似文献   

13.
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).  相似文献   

14.
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  相似文献   

15.
Shish‐kebab, which is endowed with superior strength and modulus, provides the potential to fabricate self‐reinforced polymer products. However, the injection‐molded product usually exhibits a typical skin–core structure, and the shish‐kebab is only located in an extremely thin shear layer. Therefore, the controlling and tailoring of crystal structures in complex flow field to improve the mechanical properties of the injection‐molded sample are still a great challenge. Herein, for the first time, high‐density polyethylene sample with a novel macroscopic alternating skin–core structure is achieved using a melt multi‐injection molding technique. Results show that, with increasing the amount of melt injection, the layers of skin–core structure increase in the form of arithmetic progression, and therefore the tensile strength of the samples progressively increases due to an increase of shish‐kebab content. This study demonstrates a new approach to achieve multilayer homogeneous materials with excellent tensile strength via macroscopic structural design during the practical molding process.  相似文献   

16.
Bing Na 《Polymer》2004,45(18):6245-6260
Shish structure and its relaxation dependence of re-crystallization of isotactic polypropylene (iPP) from an oriented melt, caused by melting of shish kebab in original samples (indicated by 2D SAXS and 2D-wide-angle X-ray scattering experiments (2D WAXS) measurements), has been investigated by differential scanning calorimetry (DSC) and optical microscopy (OM). Shish was obtained by dynamic packing injection molding and its size was controlled by addition of high-density polyethylene (HDPE). An increase in shish size was observed with increasing of HDPE content, as indicated by an increase in the crystallization temperature for iPP during re-crystallization. This is understood as, on one hand, the overall decrease in viscosity by addition of HDPE, thus an increase in shear rate. Higher shear rate can promote larger orientation of molecules and continuous growth of shish structure. On the other hand, the relaxation mode of shish in the melt while re-crystallization is also dominated by its size. Shish with larger size has higher thermal stability and can endure more duration time in the melt. Even more, shish with a larger size cannot be transformed to random coil entirely even subjected to annealing at 200 °C for 60 min, and thus re-crystallization via self-seeding is always observed on primary nuclei originated from shish structure. A permanent ordered structure, most likely with chain helical conformation, is proposed for iPP with large shish size. However, shish with smaller size can only maintain for a short time and then relax into random coil completely, resulting in almost absence of self-seeding in re-crystallization. Re-crystallization of isotactic polypropylene was discussed based on: (1) self-seeding with respect to size of shish structure and (2) relaxation of shish with different size.  相似文献   

17.
To better understand the effect of a small amount of high‐molecular‐weight polyethylene (HMWPE) on the mechanical properties and crystal morphology under the shear stress field, the dynamic packing injection molding (DPIM) was used to prepare the oriented pure polyethylene and its blends with 4% HMWPE. The experiment substantiated that the further improvement of tensile strength along the flow direction (MD) of high‐density polyethylene (HDPE)/HMWPE samples was achieved, whereas the tensile strength along the transverse direction (TD) still substantially exceeded that of conventional molding. Tensile strength in both flow and TDs were highly enhanced, with improvements from 23 to 76 MPa in MD and from 23 to 31 MPa in TD, besides the toughness was highly improved. So, the samples of HDPE/HMWPE transformed from high strength and brittleness to high strength and toughness. The obtained samples were characterized via SEM and TEM. For HDPE/HMWPE, the lamellae of the one shish‐kebab in the oriented region may be stretched into other shish‐kebab structures, and one lamella enjoys two shish or even more. This unique crystal morphology could lead to no yielding and necking phenomena in the stress–strain curves of HDPE/HMWPE samples by DPIM. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008  相似文献   

18.
The ultrahigh molecular weight polyethylene (UHMWPE) fibers were obtained directly from the industrial production line. Two-step industrial hot-drawing-to-specific-drawing ratios were carried out at the temperature of 120 and 130 °C, respectively. Small-angle X-ray scattering (SAXS) measurements using synchrotron radiation were applied to study the evolution of kebab structure and the formation of shish structure. The slight increase of long period and the rapid decrease of lateral sizes indicated the destruction of original lamellae which was accomplished by chain slip resulted in the orientation of lamellae to form shish structure. The decrease of average shish length was explained that the formed new shish structure had shorter shish length than the original shish at the early stage with the high concentration of spinning solution. Wide-angle X-ray diffraction (WAXD) measurements were performed to explore the changes of the degree of orientation of the crystals. It was found that the elevated drawing temperature was benefited to the evolution of the orientational order. The DSC result confirmed the evolution of shish–kebab structure through the melting behavior.  相似文献   

19.
Differential scanning calorimetry, wide‐angle X‐ray diffraction, small‐angle X‐ray scattering, and transmission electron microscope are employed to study the microstructure of biaxially self‐reinforced high‐density polyethylene (HDPE) prepared in uniaxial oscillating stress field by dynamic packing injection molding. The results indicate that the biaxial self‐reinforcement of HDPE is mainly due to the existence of interlocking shish‐kebab morphology (i.e., zip fastener structure), along with the orientation of lamellae and molecular chains and the enhanced crystallinity. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 93: 1591–1596, 2004  相似文献   

20.
In order to better understand the effect of small amount of both high-molecular-weight polyethylene (HMWPE) and low-molecular-weight polyethylene (LMWPE) on the mechanical properties and crystal morphology under the shear stress field, the dynamic packing injection molding (DPIM) was used to prepare the oriented pure polyethylene samples and its blends ones with different contents of HMWPE and LMWPE. The experiment substantiated that the further improvement of tensile strength and impact stength along the flow direction (MD) of HDPE/HMWPE/LMWPE samples was achieved, while the tensile strength along the transverse direction (TD) still substantially exceeded that of conventional molding. When the contents of HMWPE and LMWPE were respectively 8% in blends, the tensile strength in both flow and transverse directions of the samples were highly enhanced, with improvements from 27.75 MPa to 115.43 MPa (about 316%), in MD and from 23MPa to 32.74 MPa (about 42.34%), in TD; besides the impact strength was improved from 21.55 KJ/m2 to 72.6 KJ/m2 (about 236.89%), in MD but decreased from 17 KJ/m2 to 6.92 KJ/m2 in TD. The obtained samples were characterized via DSC, WAXD and SEM. For HDPE/HMWPE/LMWPE, the shish-kebab structure which is composed of stretched chains (shish) and lamellae (kebab) was seen in the oriented region of DPIM samples and the spherulites existed in the oriented region of SPIM samples. Furthermore, the appropriate amount HMWPE and LMWPE (about 8%, respectively) blended into mixture can improve the thickness and the length of lamellae, and the degree of crystallinity in shear region by DPIM which were approved by DSC and SEM, at the same time, it can also enhance the intensity of orientation of lamellae in shear region confirmed by SEM and WAXD. The reason of improvement of mechanical properties is the existence of these thicker, longer and more orientated lamellae in shear region.  相似文献   

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