MORPHOLOGY OF POLYBUTADIENE “SHISH KEBABS”

Shish kebab structure of cis-1 , 4-polybutadiene has been obtained by quiescent solution crystallization at suitable temperature. The morphology and growth mechanism of formation of shish kebab structure have been studied in detail.The higher the molecular weight the faster the sample crystallizes.     

95 ℃水溶液体系中TiCl4溶胶水解法制备纯金红石纳米粉体(英)

Titanium dioxide (TiO2) nanoparticles of rutile phase were synthesized by hydrolysis of TiCl₄ at 95 ℃ in aqueous solution. The samples as prepared and calcined at 500 ℃ were characterized by XRD, TG-DTA and TEM. The sample as prepared was of imperfect rutile structure, and its morphology was rod-like with a diameter of 10～20 nm, a length of 20～80 nm and an aspect ratio of 2～4. The structure of the sample calcined at 500 ℃ was a perfect rutile one, and its morphology was rod-like with a diameter of 15～25 nm, a length of 25～105 nm and an aspect ratio of 2～4. These results indicate that calcination temperature has a positive effect on the structure and the size of rutile nanocrystals, and has no effect on the aspect ratio of rutile nanocrystal. A model for the formation mechnism of rutile nanocrystal in aqueous solution under hydrolysis conditions has been proposed.     

A RAMAN-SPECTROSCOPIC STUDY OF PHASE STRUCTURE OF DRAWN POLYETHYLENE

A drawn high density polyethylene(HDPE)has been measured by Raman spectroscopy and differential scanning calorimetry (DSC). The crystalline structure of drawn HDPE is analysed by the Raman internal modes in terms of mass fractions of the crystalline orthorhombic phase, the liquid- like amorphous phase and the disordered anisotropic phase. The mass fractions depend on draw temperature T_d and draw ratio R_d . The fraction of disordered anisotropic amorphous phase changes very little with, the T_d and increases with increasing R_d. Sum of the mass fractions of crystalline orthorhombic phase and the disordered anisotropic phase increases linearly as the same slope as the crystallinity W_c determined from DSC measurements with increasing T_d or R_d and it is higher than the W_c for all the samples. The results show that the mass fraction of disordered anisotropic phase is partially devoted by the taut tie molecules (TTM s) in the amorphous state. The dependence of the disordered anisotropic phase on T_d and R_d supports the mechanism of plastic deformation of fibre structure.     

Highly reversible lead-carbon battery anode with lead grafting on the carbon surface

A novel C/Pb composite has been successfully prepared by electroless plating to reduce the hydrogen evolution and achieve the high reversibility of the anode of lead-carbon battery(LCB). The deposited lead on the surface of C/Pb composite was found to be uniform and adherent to carbon surface. Because lead has been stuck on the surface of C/Pb composite, the embedded structure suppresses the hydrogen evolution of lead-carbon anode and strengthens the connection between carbon additive and sponge lead.Compared with the blank anode, the lead-carbon anode with C/Pb composite displays excellent charge—discharge reversibility, which is attributed to the good connection between carbon additives and lead that has been stuck on the surface of C/Pb composite during the preparation process. The addition of C/Pb composite maintains a solid anode structure with high specific surface area and power volume, and thereby, it plays a significant role in the highly reversible lead-carbon anode.     

Morphology,Crystallization Behavior and Tensile Properties of β-Nucleated Isotactic Polypropylene Fibrous Membranes Prepared by Melt Electrospinning

β-nucleated isotactic polypropylene(iPP) fibers with diameters less than 5 μm were prepared through melt electrospinning. The effects of electrospinning process and rare earth β-nucleating agent(WBG) on the crystal structure of iPP fibers were investigated. The results indicate that the addition of WBG can improve the fluidity of iPP melt remarkably and help the formation of fine fibers with thinner diameter, while the electrostatic force applied on the iPP melt is not favorable for the formation of β-crystal in iPP fibers. In addition, the morphology and crystalline structure of WBG/iPP electrospun fibers depended on the content of WBG. Both the crystallinity and the percentage of β-crystal form of WBG/iPP electrospun fibers increase with the rise of the content of nucleating agent, which endows the prepared electrospun fibers excellent mechanical properties. The β-nucleated iPP electrospun fibrous membranes prepared in this study can be used for protective clothing material, filtration media, reinforcement for composites and tissue engineering scaffolds.     

Structure and properties of gel-spun ultra-high molecular weight polyethylene fibers with high gel solution concentration

The gel-spun ultra-high molecular weight polyethylene(UHMWPE) fibers were prepared at the industrial production line with different gel solution concentrations of 15 wt%, 18 wt% and 24 wt%. The difference in ultimate structure and mechanical properties of UHMWPE fibers for different gel solution concentrations were analyzed by tensile testing, differential scanning calorimetry(DSC), wide angle X-ray diffraction(WAXD) and small angle X-ray scattering(SAXS). With the increase of gel solution concentration, the ultimate mechanical properties of UHMWPE fibers were decreased and the crystallization and orientation of UHMWPE fibers became inferior. Besides, both the average shish length(〈L _(shish)〉) and shish misorientation(B_φ) of UHMWPE fibers were decreased with the increase of gel solution concentration. In addition, the appropriate increase of spinning temperature led to the further optimization of the ultimate structure and mechanical properties of UHMWPE fibers.     

Electrochemical performance of sulfur composite cathode materials for rechargeable lithium batteries

The structure and characteristic of carbon materials have a direct influence on the electrochemical performance of sulfur-carbon composite electrode materials for lithium-sulfur battery.In this paper,sulfur composite has been synthesized by heating a mixture of elemental sulfur and activated carbon,which is characterized as high specific surface area and microporous structure.The composite,contained 70%sulfur,as cathode in a lithium cell based on organic liquid electrolyte was tested at room temperature....     

Orientation Efforts as Regulatory Factor of Structure Formation in Permeable Porous Poly(vinylidene fluoride) Films

The manufacturing process of poly(vinylidene fluoride) microporous films containing through flow channels and permeable to liquids has been elaborated. The process is based on polymer melt extrusion with subsequent stages of annealing, uniaxial extensions("cold" and "hot" drawing), and thermal stabilization. The effect of orientation parameters(melt draw ratio and extension degrees) on overall porosity, permeability, morphology, and content of polar piezoactive β-phase in crystalline structure of the films was investigated by filtration porosimetry, sorptometry, scanning electron microscopy, X-ray scattering, and mechanical properties measurements. It is shown that the through pores were formed by a percolation mechanism. It is observed that permeability and the β-phase content increased with the growth of extension degree at the pore formation stages but the portion of β-crystallites decreased with increasing melt draw ratio at extrusion, which permitted to regulate the combination of through permeability and piezoactivity values by variation of the preparation process parameters.     

Effect of Draw Ratio on the Morphologies and Properties of BPDA/PMDA/ODA Polyimide Fibers

3,3,4,4-Biphenyltetracarboxylic dianhydride/pyromellitic dianhydride/4,4-oxydianiline（BPDA/PMDA/ODA） polyimide copolymer fibers with different draw ratios were prepared from the imidization of polyacrylic acid（PAA） fibers via a dry-jet wet-spinning process.Their morphologies,microcrystal orientations,thermal stabilities,and mechanical properties were investigated via scanning electron microscopy（SEM）,wide angle X-ray diffraction（WAXD）,thermogravimetric analysis（TGA）,and tensile experiments.In order to acquire fibers with better mechanical performance,we aimed at obtaining the optimal draw ratio.Drawing during thermal imidization resulted in a decreased diameter of fiber from 25.8 μm to 16.9 μm corresponding to draw ratio from 1 to 3.5.WAXD results show that the degree of the orientation of the undrawn sample is 64.1％,whereas that of the drawn sample is up to 82％.The as-spun fiber and those with different draw ratios all exhibit high thermal stabilities,i.e.,the temperature at a mass loss of 5％ can reach as high as 570 ℃.The tensile strengths and tensile modulus of the fibers increase with the draw ratios,and the maximum tensile strength and modulus are 0.90 and 12.61 GPa,respectively.     

THE EFFECT OF EC ON ORIENTATION AND RELAXATION OF PP OBTAINED VIA DYNAMIC PACKING INJECTION MOLDING

As a long term project aiming at engineering plastics based on polypropylene (PP), in this work, we report the effect of ethylene-cellulose (EC) on the orientation and relaxation of PP obtained via dynamic packing injection molding (DPIM). 2d-WAXD results showed that PP with a highly oriented structure and a shish-kebab structure were achieved by DIPM, leading to an increase of tensile strength from 35.0MPa to 48.6MPa. The degree of orientation of PP was increased by adding only 1% of EC, resulting in a further increase of tensile strength from 48.6MPa to 53.8MPa. Shish was found to exist not only in the oriented layer but also in the core of the sample after adding EC, as evidenced by DSC result.This was understood as due to the overall decrease of viscosity by the addition of EC, thus an increasing of shear rate. Higher shear rate can favor the orientation of molecules and continuous growth of shish structure, resulting in a change of shish distribution along the sample thickness. On the other hand, the relaxation mode of shish in the melt recrystallization of PP is also greatly affected by the presence of EC. A retarded relaxation of PP macromolecules was seen.Even more, SEM results showed that EC could form the short fibers in PP matrix along the shear flow direction. Compared with the morphology obtained by conventional injection molding, a much better dispersion and easy break-up of EC in PP matrix were observed for samples obtained by dynamic packing injection molding.     

Formation of a large‐scale shish‐kebab structure of polyoxymethylene in the melt spinning and the crystalline morphology evolution after hot stretching

Polyoxymethylene (POM) fiber was produced by melt spinning with a high take‐up speed, which imposed a strong flow field. An unexpected formation of a shish‐kebab morphology with multiple shish of POM fibers was reported for the first time. This morphology is a large‐scale shish kebab with a diameter of 10.5 µm. Further orientation of the POM fiber was obtained by hot stretching twice at 160°C. Two crystalline morphology evolution processes were also observed: (i) the process from the large‐scale shish‐kebab to the deformed small shish‐kebab and (ii) the process from the deformed small shish‐kebab to the perfect whiskers. Compared with the melt spinning fiber, fiber tensile strength with first and second hot stretching increased by 976% and 1705%, respectively. The crystalline melting behavior of fibers significantly changes after the first and second hot stretching. The flow field induces a large number of extended chain crystals. Copyright © 2014 John Wiley & Sons, Ltd.     

HDPE solution crystallization induced by electrospun PA66 nanofiber

Nanohybrid shish?Ckebab (NHSK), induced by polyamide 66 (PA66) nanofiber, was successfully fabricated in high-density polyethylene (HDPE)/xylene solution via isothermal crystallization. The crystalline morphological features of NHSK were observed by scanning electron microscopy. In the structure of NHSK, PA66 nanofiber serves as shish and HDPE lamellae act as kebabs periodically surrounding the nanofiber. Additionally, it reveals that both HDPE solution concentration and crystallization time have significant effects on the size of HDPE kebab. That is, as the concentration and crystallization time increase, the diameter of the kebab increases. Moreover, when crystallization time further increases, the crystals decorated on PA66 nanofiber exhibit a three-dimensional growth (i.e., aggregate of crystallites) rather than a two-dimensional one (i.e., disk-like lamellae normal to the axis of nanofiber).     

Structural transformation from shish‐kebab crystals to micro‐fibrils through hot stretching process of gel‐spun ultra‐high molecular weight polyethylene fibers with high concentration solution

Structural evolution of gel‐spun ultra‐high molecular weight polyethylene fibers with high concentration solution via hot stretching process was investigated by in situ small‐angle X‐ray scattering, in situ wide‐angle X‐ray diffraction measurements, scanning electron microscopy, and differential scanning calorimetry. With the increase of stretching strain, the long period continuously increases at relative lower stretching temperature, while it first increases and then decreases rapidly at relative higher stretching temperature. The kebab thickness almost keeps constant during the whole hot‐stretching process and the kebab diameter continually decreases for all stretching temperatures. Moreover, the length of shish decreases slightly and the shish quantity increases although there is almost no change in the diameter of shish crystals during the hot stretching process. The degree of crystal orientation at different temperatures is as high as above 0.9 during the whole stretching process. These results indicate that the shish‐kebab crystals in ultra‐high molecular weight polyethylene fibers can transform continuously into the micro‐fibril structure composed mostly of shish crystals through the hot stretching process. © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2018 , 56, 225–238     

The effect of melt drawing ratio on the crystal structural change and performance of polyketone extrusion cast film

In this paper, the polyketone (POK) extrusion cast film is manufactured by melt stretching method, and the evolution process of the crystal morphology and mechanical properties with the increase of melt drawing ratio (MDR) are followed. The results show that the melt stretching process produces many micro shish-kebab crystals in the POK. The length of the shish crystal and the thickness of the kebab crystal hardly increase with MDR, but the lateral length of the kebab crystal shows linear growth when MDR exceeds 40. The crystalline morphology of POK is mainly affected by melt relaxation. The molecular chain has sufficient relaxation during cooling at a low MDR (20–40). At this time, micro shish-kebab crystals are mainly randomly arranged. When MDR exceeds 40, the rapid melt stretching shortens the relaxation time of the tie chain between the neighborhood shish crystal, and the atomic force microscopy image shows a typical shish-kebab structure. This experimental result indicates that the formation of the oriented lamella structure may be related to the relaxation of the molecular chains between the micro-shish. When the length of the shish axis and the thickness of the kebab lamellae are similar, it is difficult to distinguish the two.     

The mobility of PEG chains versus micellar stability towards the formation of PE‐b‐PEG nanohybrid shish‐kebab on carbon nanotubes

A comparative study of the effect of copolymer composition on nanohybrid shish‐kebab (NHSK) architecture on carbon nanotubes (CNTs) is presented. A semi‐crystalline amphiphilic di‐block copolymer, polyethylene‐b‐polyethylene glycol (PE‐b‐PEG) was used in this study. Copolymer composition was varied on the basis of the molecular weight of individual copolymers and the ratio between PE and PEG. NHSK structure was characterized using a combination of scanning and transmission electron microscopy. The mobility of PEG, which is determined by its chain length was found to have a significant impact on the periodic decoration of the copolymer on CNTs. With higher chain length or molecular weight, PEG chains provided better stability to micelles formed by the copolymer. Further, PEG assisted micellar stability to create a foundation for PE chains to interact and orient along the tube axis of CNTs as a function of the copolymer composition. It was found that the stability of NHSK architecture can also be changed over time at the same crystallization temperature. This work offers novel and fundamental insights towards the mobility of PEG in the copolymer and its disk‐shaped crystal's formation and micellar stability during crystallization with CNTs. This study provides a better understanding of a mechanically tunable NHSK where the architecture of copolymer crystals can be modified by adjusting the molecular weight of PEG.     

Morphological evolution and orientation development of stretched iPP films: Influence of draw ratio

Varying the processing conditions of semicrystalline polymers can produce different morphologies of crystallization, which leads to different properties. There have been extensive studies of flow‐induced crystallization on isotactic polypropylene (iPP) using predominantly shear flow. A stretching method, deduced from extrusion, was introduced to study the morphological evolution of elongation‐induced shish‐kebab crystallization. Different morphologies of the resultant samples with different draw ratios (DRs) were carefully investigated and characterized via differential scanning calorimetry, polarizing light microscopy, scanning electron microscopy, atomic force microscopy, and 2D small‐angle X‐ray scattering. In addition, the degree of orientation of the samples with different DRs was also investigated using the 2D wide‐angle X‐ray scattering technique. The results indicate that the elongation‐induced morphology is strongly dependent on the effective stretching flow expressed in terms of the DR, which is defined as the ratio of rates between take‐up and the extrusion. The spherulite is dominant at low DRs, but it starts to deform along the stretching direction with increasing DR. The shish‐kebab structure in the stretched film, composed of stretched chains (shish) and layered crystalline lamellae (kebabs), increases gradually with an increase in the DR, whereas the spherulites gradually decreased. Furthermore, the overall orientation of α‐phase crystals, expressed by the Hermans orientation parameter, is also found to increase dramatically with the DR, and the rate of increase strongly depends on the DR. The different crystal morphologies are attributed to crystallization induced by different elongations of the stretched iPP films. © 2010 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 48: 1223–1234, 2010     

High‐Strain Shape Memory Behavior of PLA–PEG Multiblock Copolymers and Its Microstructural Origin

Shape memory properties of two thermoplastic multiblock copolymers composed of poly(lactic acid) (PLA) and poly(ethylene glycol) (PEG) having different PEG‐segment lengths of 6 and 11 kDa were studied. The performance as a shape memory polymer at high strain level (600%) and its interrelations with shape‐programming conditions, molecular orientation, and microstructural changes are elucidated. A significant contribution of strain‐induced crystallization of PLA segments to the improvement of temporary shape fixation was evidenced upon increasing draw ratio and/or shape‐holding duration as well as programming temperature (within certain range) without largely sacrificing the shape recoverability. Series of microstructural characterizations reveal the occurrence of fibrillar‐to‐lamellar transformation upon shape recovery (at 60 °C) of the samples programmed at 40 °C, generating shish–kebab crystalline morphology. Such phenomenon is responsible for the high‐strain shape memory effect of these materials. The unprecedented formation of shish–kebab structure at such relatively low temperature (instead of the melting temperature range) in solid state observed in these copolymers as well as their high‐strain shape memory functionality would bestow the promising future for their practicability in diverse areas. © 2018 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2019 , 57, 241–256     

A novel hierarchical crystalline structure of injection-molded bars of linear polymer: co-existence of bending and normal shish–kebab structure

The hierarchy structures and orientation behavior of high-density polyethylene (HDPE) molded by conventional injection molding (CIM) and gas-assisted injection molding (GAIM) were intensively examined by using scanning electronic microscopy (SEM) and 2D wide-angle X-ray diffraction (2D-WAXD). Results show that the spatial variation of crystals across the thickness of sample molded by CIM was characterized by a typical skin–core structure as a result of general shear-induced crystallization. Unusually, the crystalline morphologies of the parts prepared by GAIM, primarily due to the penetration of secondary high-compressed gas that was exerted on the polymer melt during gas injection, featured a richer and fascinating supermolecular structure. Besides, the oriented lamellar structure, general shish–kebab structure, and common spherulites existed in the skin, sub-skin, and gas channel region, respectively; a novel morphology of shish–kebab structure was seen in the sub-skin layer of the GAIM parts of HDPE. This special shish–kebab structure (recognized as “bending shish–kebab”) was neither parallel nor perpendicular to the flow direction but at an angle. Furthermore, there was a clear interface between the bending and the normal shish–kebab structures, which may be very significant for our understanding of the melt flow or polymer rheology under the coupling effect of multi-fluid flow and complex temperature profiles in the GAIM process. Based on experimental observations, a schematic illustration was proposed to interpret the formation mechanism of the bending shish–kebab structure during GAIM process.     

The influence of chitin nanocrystals on structural evolution of ultra-high molecular weight polyethylene/chitin nanocrystal fibers in hot-drawing process

Ultra-high molecular weight polyethylene (UHMWPE)/chitin nanocrystal (CNC) fibers were prepared. Compared with the pure UHMWPE fibers, the ultimate tensile strength and Young’s modulus of UHMWPE/CNC fibers are improved by 15.7% and 49.6%, respectively, with the addition of chitin nanocrystals (CNCs) of 1 wt%. The melting temperature (T _m) of UHMWPE/CNC fibers was higher than that of pure UHMWPE fibers. Pure UHMWPE fibers and UHMWPE/CNC fibers were characterized with respect to crystallinity, orientation and kebab structure by wide-angle X-ray diffraction (WAXD), small-angle X-ray scattering (SAXS) and scanning electron microscopy (SEM). It is found that the CNCs act as the shish structure in UHMWPE/CNC fibers and the kebab crystals are grown around the CNCs. There was almost no difference between pure UHMWPE fibers and UHMWPE/CNC fibers in orientation. But the degree of crystallinity of various stages of UHMWPE/CNC fibers was respectively higher than the corresponding stage of pure UHMWPE fibers. Moreover, the addition of 1 wt% CNCs improved the thickness of kebab crystals and accelerated the transformation of kebab to shish.     

Carbon Nanotube‐Directed Polytetrafluoroethylene Crystal Growth via Initiated Chemical Vapor Deposition

Initiated chemical vapor deposition (iCVD) has been shown to be suitable for blanketing surfaces with thin polymer coatings of ≈1–2 nm and greater. In this work, iCVD coatings of polytetrafluoroethylene (PTFE) deposited on carbon nanotube (CNT)‐based surfaces show CNT‐templated PTFE single crystal growth. While the coating forms disoriented agglomerates when deposited on an amorphous carbon background, “shish‐kebab” structures are observed when grown on single‐walled carbon nanotubes (SWCNT) as well as CNT buckypaper. It is shown that the shish‐kebab structure is composed of PTFE lamellae arranged with the chain backbones running parallel to the SWCNT axis. This result allows one to control not only the surface chemistry using PTFE but also the coating surface topology.