Structural development of gel-spinning UHMWPE fibers through industrial hot-drawing process analyzed by small/wide-angle X-ray scattering

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.     

Quantification of shish–kebab and β‐crystal on the mechanical properties of polypropylene

The oriented “shish–kebab” structure and β‐crystal can enhance the mechanical properties of polypropylene products. In this regard, equipment and β‐nucleation agents have been developed or modified to form shish–kebab and β‐crystal. However, the effect of shish–kebab/β‐crystal proportion on the mechanical properties of polypropylene remains unclear. The answer is crucial but remains a challenge because of the difficulty in manipulating the shish–kebab proportion. In this work, we used a self‐made multiflow vibrate‐injection molding, which can provide a controllable shear flow, to produce samples with different shear‐layer thicknesses. The shish–kebab proportion was represented by R, which is the thickness ratio of the shear layer to that of the whole sample. Results showed that the tensile strength exponentially increased, whereas the elongation at break exponentially decreased, with R. The impact strength remained constant with R, indicating that the shish–kebab and β‐crystal possessed similar toughening effects. This work proposes a schematic to interpret the strengthening mechanism involved and presents a method of establishing and controlling the mechanical properties of polypropylene samples by using shish–kebab structures and β‐crystals. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 45052.     

Morphologies and mechanical properties of HDPE induced by small amount of high‐molecular‐weight polyolefin and shear stress produced by dynamic packing injection molding

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     

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     

Processing–Nanostructure–Property Relationships of All‐Polyethylene Composites Reinforced by Flow‐Induced Oriented Crystallization of UHMWPE

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.     

Nanostructure of potato starch. II. Structure of a highly crystalline gel obtained by retrogradation using X‐ray diffraction techniques

A highly crystalline gel (65% crystal portions) was prepared by retrogradation of injection‐molded potato starch in humid atmosphere. The different components of the nanostructure were identified by means of successive melting processes using “in situ” simultaneous wide and low angle X‐ray diffractions. At low temperatures, structural changes such as annealing phenomena or evaporation of water, giving rise to a thickening of the gel, are observed. In the range of 55–75°C, a first transition due to melting of a layered structure of concentric sphere‐like alternating crystalline and amorphous lamellar shells (amylopectine, AP, being the crystalline component) is detected. Analysis of results reveals that the AP crystallization contributes 25% to the overall crystal fraction. A spherulitic structure of alternating radial lamellae from amylose (AM) or AP melts in a higher temperature region between 75 and 86°C. This modification represents the major contribution to crystallinity of about 40%. Unexpectedly, the crystalline blocks of such a structure are abnormally anisometric; i.e., they are thicker than their width. This has been related to a contraction of the AMAP‐co‐spherulite due to an excessive growth of the AP‐shell crystals. The anisometry of the blocks of the AMAP lamellae vanishes at the beginning of the melting of the AP shell crystals, just when the total crystallinity decreases below 50% at 60°C. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 104: 689–696, 2007     

High strength poly(vinyl alcohol) films obtained by drying and then stretching freeze/thaw cycled gel

The mechanical properties of stretched poly(vinyl alcohol) (PVA), which is formed by stretching a film prepared from a freeze/thaw cycled gel, were investigated as a function of the stretching ratio. The tensile strength and Young's modulus of 800% stretched PVA annealed at 130°C were 3.4 and 119 GPa, respectively. These values were much higher than those for a PVA film prepared without freeze/thaw cycling. For a film stretched more than 600% before annealing, two melting peaks, assignable to folded and extended chain crystals, were observed around 220°C and 230°C, respectively. This indicates that a shish‐kebab structure is formed as the stretching ratio increases. After annealing at 130°C, the folded‐chain crystal transformed to an extended‐chain crystal if an extended‐chain crystal was present in the stretched film before annealing. High tensile strength and Young's modulus after annealing were due to the formation of extended‐chain crystal. Therefore, the presence of extended‐chain crystal for annealing is important to provide good mechanical properties. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41318.     

Extension of the orientation region of high density polyethylene molded by gas‐assisted injection molding: control of the thermal field

Wider zones with close‐knit orientation crystals in high density polyethylene (HDPE) parts prepared via the gas‐assisted injection molding (GAIM) process were obtained under high cooling gas pressure. In this study, compressed nitrogen, as a cooling medium, was introduced to retain a high cooling rate of the polymer melt. The high gas pressure leads to fast cooling of the polymer melt, which contributes to the stability of more oriented and stretched chains during the cooling stage. Then many more oriented structures are formed. SEM shows that many more oriented structures and interlocking shish‐kebab structures are achieved in parts under highest cooling gas pressure (P3). The P3 parts possess a higher degree of orientation than the corresponding regions of parts under lowest cooling gas pressure (P1). Moreover, tensile testing indicates that, compared with P1 parts, although P3 parts have lower crystallinity, the mechanical properties are improved because of the wider orientation zone and many more interlocking shish‐kebab structures. Combining the HDPE molecular parameters with the characteristics of the GAIM flow field and temperature field, the stability of oriented or stretched chains and the formation of orientation structures in various zones of the parts were analyzed. © 2014 Society of Chemical Industry     

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     

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     

Oriented structure in stretched isotactic polypropylene melt and its unexpected recrystallization: optical and X‐ray studies

At an extremely small extrusion rate, an isotactic polypropylene melt was extruded through a slit die of an extruder. Simultaneously, the extruded melt was stretched at various stretching rates (SRs) at the die exit. The oriented structure and its subsequent recrystallization via self‐seeding were investigated using polarized optical microscopy, two‐dimensional wide‐angle X‐ray scattering and small‐angle X‐ray scattering. As expected, much slenderer and denser oriented structures were formed at larger SR, which indicates that orientation is preferably promoted with increasing SR. In the case of the crystalline morphology developed during recrystallization, a shish kebab‐like structure was retrieved via the surviving oriented structure after annealing. Unexpectedly, for the sheet stretched at higher SR, a mainly sparse and short shish kebab structure was observed. For the sheet stretched at lower SR, a dense and long shish kebab structure was observed. This suggests that the oriented structure in the sheet stretched at lower SR has a better thermal stability than that in the sheet stretched at higher SR. This is discussed based on the relaxation of entangled junctions in the stretched networks with respect to varying chain length. Copyright © 2011 Society of Chemical Industry     

Effect of annealing on the microstructure and mechanical properties of polypropylene with oriented shish‐kebab structure

Annealing is thought to be an effective method to promote chain rearrangement in semicrystalline polymers and improve their physical properties. However, little attention has been paid to the annealing of flow‐oriented semicrystalline polymers despite its importance in polymer processing. In this work, the microstructural evolution of injection‐moulded polypropylene with an oriented shish‐kebab structure upon annealing has been explored with differential scanning calorimetry, small‐angle X‐ray scattering and scanning electron microscopy, Fourier transform infrared spectroscopy and dynamic mechanical analysis. The results show that annealing gives rise to a chain rearrangement in both the crystalline and amorphous phases. Accompanied by the growth and perfecting of the kebabs, relaxation of the initially oriented chains in the amorphous phase is observed. Then, the relationship between the structure and the resulting mechanical properties is established. Copyright © 2011 Society of Chemical Industry     

Sequential biaxial drawing of polypropylene films

Polypropylene cast films were drawn successively in two perpendicular directions at temperatures near the melting point. In order to investigate the structure formation along the deformation path the transverse draw ratio λ_TD was varied between 1 and 9. Quantitative X-ray texture analysis, small angle X-ray scattering and atomic force microscopy were used to characterize the structure of the films on a molecular and supermolecular level. Additionally, the melting behavior and the mechanical properties were investigated.The results of the experimental investigations show, that the first deformation step (MDO Process) transforms the initially spherulitic morphology of the cast film into a stacked lamellae morphology (shish kebab) by partial melting. This stacked lamellae morphology is deformed during the transverse drawing (TDO process) into a fibrillar network under the action of crystallographic slip processes ((010)[001] and (110)[001] slip). Further deformation orients the fibrils towards the actual draw direction. The observed structural changes correlate with the melting behavior and the mechanical and thermomechanical properties of the films.     

The massive formation of hybrid shish‐kebab structures in HDPE/PA6 microfibril blend subjected to melt second flow

During the melt second flow process, the synergetic effect of intense shear and polyamide 6 (PA6) microfibrils finally results in the massive formation of highly oriented crystalline structures in the entire thickness of high‐density polyethylene (HDPE)/PA6 microfibril blend. Interestingly, not only does the small microfibril induce HDPE crystallization to form typical hybrid shish–kebab structure, but the large microfibril (about 2 μm in diameter) also induces the formation of local hybrid shish–kebab structure. For the small PA6 microfibril, the oriented HDPE chains caused by the intense shear are absorbed on the whole surface of the microfibril and then a complete polymer underlayer is formed. Subsequently, the crystal nuclei appear on the underlayer, and then the other oriented HDPE chains overgrow from the nuclei in the form of folded chains and grow perpendicular to the microfibril. Finally, the typical hybrid shish–kebab structure is formed. While for the large PA6 microfibril, a few HDPE chains can be still absorbed on the microfibril surface due to the high surface energy of PA6. However, the driving force is insufficient to absorb largely oriented HDPE chains to form complete hybrid shish but only local adsorption layer, so the local hybrid structure is formed. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 45274.     

Mechanical Properties and Crystal Structure of HDPE Induced by Small Amount of High-molecular-weight and Low-molecular-weight Polyethylene under Shear Stress Produced by Dynamic Packing Injection Molding

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.     

Effects of annealing on the hierarchical crystalline structures and mechanical properties of injection‐molded bars of high‐density polyethylene

The effect of annealing on the microstructural evolution and mechanical properties of high‐density polyethylene parts molded via gas‐assisted injection molding was investigated using scanning electron microscopy, differential scanning calorimetry, two‐dimensional wide‐angle X‐ray diffraction and tensile testing. The results indicated that a variety of annealing temperatures could induce considerable variations in the hierarchical structures, crystallinity, lamellar thickness and yield stress of the molded bars. According to these results, the annealing temperatures could be divided into three regions. In the low‐temperature region of annealing at 80 °C, the spatial variation of the superstructure developed along the thickness direction and mechanical properties of the annealed sample were mainly unchanged and similar to those of the original specimen. At 100 and 120 °C, the intermediate temperature region of annealing, the thickness of the crystals, degree of orientation and yield stress of annealed samples were greatly improved. Finally, at 127 °C, the degree of orientation decreased and yield stress slightly improved, an indication of the high‐temperature annealing region being characterized by increasing melting/recrystallization and causing relaxation of oriented molecular chains. A model is proposed to interpret the mechanism of the annealing treatment of the samples at various temperatures. © 2013 Society of Chemical Industry     

Studies on blends of high‐density polyethylene and polypropylene produced by oscillating shear stress field

Tensile strength and morphology of blends of high‐density polyethylene (HDPE) and polypropylene (PP) obtained by oscillating packing injection molding were investigated via Universal Testing Machine, DSC, and SAXS. Tensile strength is greatly enhanced from 24.5 MPa to more than 90 MPa for pure HDPE and for blends with PP content less than 10 wt %. There exists a sharp decrease of tensile strength when PP content is more than 10 wt %. The shear‐induced morphologies with core in the center, oriented zone surrounding the core and skin layer are observed in the cross‐section areas of the samples. Interestingly, a sharp decrease of oriented zone is seen when PP content is more than 10 wt %, associated with the sharp decrease of tensile strength. DSC result shows double melting peaks with a high‐temperature melting peak that is not present in the endotherm obtained from the central core and obtained from the samples by static packing injection molding, which indicates the existence of shish‐kebab structure in the oriented zone. However, there is no difference of crystallinity between the samples by oscillating and by static packing injection molding. SAXS was used to analyze the complicated morphologies induced by shear stress, and results show that the crystal thickness could be greatly increased under shear stress. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 86: 58–63, 2002     

Controllable reinforcement of stiffness and toughness of polypropylene via thermally induced self‐assembly of β‐nucleating agent

An easy approach was reported to achieve the simultaneous reinforcement and toughening of polypropylene (PP) via thermally induced self‐assembly of β‐nucleating agent (TMB‐5). The results showed that the processing temperatures dictated the solubility and self‐assembly of TMB‐5 in the polymer melts to determine the subsequent morphology development of PP. At low processing temperature, TMB‐5 did not dissolve into the polymer melt but remained original shape to induce PP to crystallize into spherulites so that it only promoted the formation of β‐form crystals to enhance the toughness of the samples. At high processing temperature, TMB‐5 gradually dissolved into the polymer melts. On cooling, the dissolved nucleating agent self‐assembled into high aspect ratio fibrils through intermolecular hydrogen‐bonding interactions. Due to a favorable matching between PP and TMB‐5, PP preferred to nucleate and grow orthogonally to the fibril axis and into oriented hybrid shish‐kebab morphology with rich β‐form crystals. Compared with isotropic spherulites, the anisotropic structure exhibited excellent properties of the β‐form crystal and shish‐kebab morphology to simultaneously improve the strength and toughness of TMB‐5‐modified PP samples. With the increasing processing temperature, more dissolved TMB‐5 was involved in the self‐assembly procedure to generate longer fibrils and induce more lamellae to grow on the surface. As a consequence, the anisotropy of the PP samples increased further, bringing out more improvements of the tensile strength. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40605.     

Effects of mechanical drawing on the structure and properties of peek

This study examines the effects of crystallinity and temperature on the mechanical properties of PEEK. Crystallinity in PEEK Increases with annealing temperature up to a maximum of 28 percent with a melting point at 335°C. A minor melting peak also occurs about 10°C above the annealing temperature. In cold drawing the samples exhibited a yield stress and necking followed by homogeneous drawing. The yield stress increases with crystallinity, but there is no change in the modulus. The extension in the necking process also increases with crystallinity, however there is only a slight increase in extension-to-break since necking is compensated by the final amount of homogeneous drawing. The yield stress of PEEK when drawn at T_g (145°C) is significantly lower than at room temperature indicating a reduction in mechanical properties at temperatures approaching T_g. After mechanical drawing the minor melting peak disappears and on heating the material undergoes cold crystallization near the onset of T_g. There is evidence that this minor crystalline component might contribute to the yield stress changes with annealing history. Cold drawing induces crystallization of amorphous PEEK but decreases crystallinity and generates microscopic voids in crystalline PEEK, The various effects of crystallinity on mechanical properties could be important in determining the stress response of PEEK as the matrix in composites.     

Relationship of polymorphic crystalline phase texture to strain recovery and stiffness of a propylene‐based elastomer

A stretching process to enhance the stiffness of an elastomeric propylene‐ethylene copolymer through orientation was examined. The tensile extension was performed at various temperatures within the unusually broad melting range of the copolymer. Stretching transformed the unmelted lamellar crystals into shish‐kebab fibers that acted as a scaffold for an elastomeric matrix of entangled, amorphous chains. Density measurements indicated that the process did not significantly affect the amount of crystallinity, which was about 23%. If the specimen was recrystallized by cooling after it recovered from the stretched state, the amount of orientation decreased with increasing stretching temperature. However, if recrystallization occurred in the stretched state, it led to the formation of a second crystalline network that prevented contraction of the oriented crystalline structure during strain recovery. It was suggested that the second network was anchored by α′‐PP daughter lamellae that crystallized epitaxially on the α‐PP mother crystals of the extended fibrils. Although the manner in which the films were stretched and recrystallized strongly affected the modulus, good elasticity of the stretched films revealed the persistence of an elastomeric network. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009