Investigation of nonisothermal crystallization of hydroxyapatite/ethylene‐vinyl acetate (HA/EVA) composite

Hydroxyapatite/ethylene‐vinyl acetate (HA/EVA) composites were prepared by injection molding and characterized by X‐ray diffraction (XRD) and attenuated total multiple reflection infrared (ATR‐IR) spectroscopy. The nonisothermal crystallization behavior of HA/EVA composites at different cooling rates and with different HA content were examined by differential scanning calorimetry (DSC). The results exhibit the occurrence of interaction between HA and EVA, and the HA particles in EVA matrix act as effective nucleation agent. The addition of HA influences the mechanism of nucleation and growth of EVA crystallites. HA particles, as nucleus, are efficient to promote EVA crystallization at early stage but prevent EVA crystal growth in the late stage. The EVA crystallization in the composite is mainly through heterogeneous nucleation. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Thermal characteristics of ethylene‐co‐vinyl acetate/cellulose microfibers composites

Cellulose microfibers were obtained from Hibiscus sabadariffa by steam explosion technique. Structural and surface analysis of the microfibers showed a reduction in diameter and changes in surface morphology from that of raw fibers. The chemical composition of fibers showed increase in α‐cellulose content and decrease in lignin and hemicelluloses for the microfibers. These factors were further confirmed by XRD, SEM, and FTIR results. The CMF were introduced to EVA at different loading by melt extrusion. The composites were analyzed for their thermal stability and phase transition using thermogravimetric analysis (TGA) and differential scanning calorimetry (DSC). TGA analysis of the composites showed increased onset temperatures for composites compared with pure EVA indicating the superior thermal stability of the composites with fiber loading. DSC analysis shows increase in melting enthalpy and percentage crystallinity with fiber loading increases. Kinetic parameter for the degradation of the composites was obtained using Broido, Coats–Redfern, and Horowitz‐Metzger methods. POLYM. COMPOS., 2013. © 2013 Society of Plastics Engineers     

Thermal properties and crystallization behavior of bamboo fiber/high‐density polyethylene composites: Nano‐TiO2 effects

In this study, bamboo fiber/high‐density polyethylene (HDPE) composites were prepared, and the effects of nano‐TiO₂ on their thermal properties and crystallization behavior were investigated via thermal gravimetric analysis (TGA), differential scanning calorimetry (DSC), X‐ray diffraction (XRD), and Fourier transform infrared spectroscopy (FTIR). The results show that the addition of nano‐TiO₂ improved the thermal stability and had a dual function in the crystallization behavior of the composites. On one hand, it functioned as a nucleating agent. The addition of 2 wt % nano‐TiO₂ promoted the crystallization, which caused the increase of the crystallization rate and crystallinity degree, as well as the micronization of the crystalline grain. On the other hand, intermolecular hydrogen bonds and covalent bonds were formed between nano‐TiO₂ and the polymer matrix, which hindered the crystallization of the composites. When the content of nano‐TiO₂ was continually increased, the inhibitory effect of the crystallization was gradually enhanced, which resulted in a decrease in the crystallization rate and crystallinity degree of the composites. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 39846.     

Morphology,rheological, crystallization behavior,and mechanical properties of poly(L‐lactide)/ethylene‐co‐vinyl acetate blends with different VA contents

Poly(L‐lactide)/ethylene‐co‐vinyl acetate (PLLA/EVA) blends with different contents of Vinyl Acetate (VA) in EVA phase were prepared through melt blending process. Although the composition of the blends was invariant (70/30), different phase morphologies were observed, namely, sea‐island morphologies for the blends with VA contents of 7.5, 18, and 28 wt %, whereas approximate co‐continuous morphology for the blend with VA content of 40 wt % was observed. The interfacial interaction between PLLA and EVA was visualized by Fourier transform infrared and rheological measurements. The nonisothermal and isothermal crystallization behaviors of the blends were investigated by wide angle X‐ray diffraction, Differential scanning calorimetry, and polarization optical microscope. Post‐thermal treatment was applied to improve the crystalline structure of PLLA. The results show that all the samples are mainly in amorphous state during the injection molding process. However, annealing promotes the second crystallization of PLLA matrix, leading to the improvement of the crystalline structure. Especially, the effect of annealing on crystalline structure of PLLA matrix is greatly dependent on the VA content of EVA. As expected, addition of EVA results in the improvement of the ductility and fracture toughness of the blends. The decreased tensile modulus and tensile strength can be enhanced through annealing process. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Study on viscoelastic,crystallization, and mechanical properties of HDPE/EVA/Mg(OH)2 composites

In this article, elastomer‐toughened high density polyethylene/magnesium hydroxide (HDPE/MH) composites with various contents of ethylene vinyl acetate copolymer (EVA) are prepared in a twin‐screw extruder and then injection‐molded. The effect of EVA on the viscoelastic, crystallization, morphology, and tensile properties of the HDPE/EVA/MH composites is studied. The rheological behaviors show that the complex viscosity, storage, and loss modulus at low frequencies are largely unaffected with various EVA contents; however, the corresponding values decrease with increasing EVA content at high frequencies. The scanning electronic microscopy studies on the HDPE/EVA/MH composites show that the MH particles mainly disperse in the EVA phase, and the interfacial adhesion has been also enhanced due to the addition of EVA. The crystallization of HDPE diminishes because of the surface energy difference resulting in encapsulation structure. The tensile properties of the HDPE/EVA/MH composites are strong influenced by the incorporation of EVA. POLYM. COMPOS., 38:1221–1226, 2017. © 2015 Society of Plastics Engineers     

Fabrication of Hydroxyapatite/Ethylene-Vinyl Acetate/Polyamide 66 Composite Scaffolds by the Injection-Molding Method

This research investigated the injection-molding techniques to produce hydroxyapatite (HA)/ethylene-vinyl acetate (EVA)/polyamide 66 (PA66) composite scaffolds. The effects of HA, EVA, azodicarbonamide (AC) content and shot size on the mechanical properties, pore morphology, porosity and crystallization behavior of the composite scaffolds were analyzed by XRD, DSC, SEM and mechanical test. The compressive modulus and strength of the HA/EVA/PA66 scaffolds with a pore size of 200–600 µm are close to the cancellous bone. Compared with common methods to fabricate scaffolds, this process makes the fabrication of composite scaffolds come true in a rapid and convenient manner.     

碱处理竹纤维对EVA结构和性能的影响

采用NaOH碱液处理竹纤维（BF）,通过双螺杆挤出和注射成型制备了乙烯醋酸乙烯酯共聚物（EVA）/BF复合材料。用红外光谱﹑扫描电子显微镜﹑差示扫描量热仪﹑X射线衍射仪和热失重分析等表征了材料的形貌、组成结构和热性能,测试了力学性能和熔体流动速率。结果表明,BF对EVA结晶有异相成核作用;BF使EVA的压缩强度和模量明显增大,EVA/30 %~40 % BF的拉伸强度接近或超过纯EVA;EVA/BF在熔体加工中保持较高的热稳定性能,源于碱处理去除了BF中的胶质物、EVA与BF较好的界面结合以及EVA较低的熔体加工温度。     

Crystallization,melting behavior,and crystal structure of reactive,intumescent, flame‐retardant polypropylene

Polypropylene (PP)/2‐({9‐[(4,6‐diamino‐1,3,5‐triazin‐2‐yl) amino]‐3,9‐dioxido‐2,4,8,10‐tetraoxa‐3,9‐diphosphaspiro [5.5] undecan‐3‐yl} oxy) ethyl methacrylate (EADP) composites were prepared by the blending of PP with EADP as a new flame‐retardant material. The nonisothermal crystallization and melting behaviors of composites were investigated with differential scanning calorimetry (DSC). Their crystal morphologies and structures were studied by polarized optical microscopy (POM) and X‐ray diffraction (XRD), respectively. The DSC results show that the addition of EADP increased the crystallization onset temperature, crystallization peak temperature, and degree of crystallinity of PP in the PP/EADP composites. The melting onset temperature and melting end temperature of the PP/EADP composites decreased slightly, whereas the melting peak temperature of the PP/EADP composites increased. The POM results show that the addition of EADP greatly reduced the crystal size of PP in the composites. When the content of EADP in the PP/EADP composites was increased, the crystal size of PP became smaller. The XRD results indicate that the addition of EADP changed the crystal structure of PP in the PP/EADP composites, which exhibited both α‐form and β‐form crystal structures. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41374.     

Facile and effective promotion of β crystalline phase in poly(vinylidene fluoride) via the incorporation of imidazolium ionic liquids

In this study, a facile and efficient protocol to enhance the β‐phase content of poly(vinylidene fluoride) (PVDF) is developed, in which the effect of room temperature ionic liquids (RTILs), including [1‐butyl‐3‐methylimidazolium (bmim)][PF₆], [bmim][BF₄], [bmim][FeCl₄] and [bmim][Cl], on the crystallization behavior of PVDF is investigated. The resulting PVDF/RTIL hybrids are characterized by Fourier transform infrared (FTIR) spectroscopy, XRD, polarized optical microscopy (POM) and DSC. The FTIR spectroscopy and XRD results show that the fraction of β‐phase, F(β), is significantly enhanced by the incorporation of RTILs, specifically from 49.2% for neat PVDF to 92.6% for hybrid filled with 15 wt% [bmim][PF₆]. The analysis of the crystallization behavior based on the DSC tests reveals that the degree of crystallinity increases with incorporation of RTILs, implying that RTILs could act as directing agents to facilitate the crystallization process, which is further evidenced by the POM results. In addition, the non‐isothermal crystallization kinetics of PVDF and PVDF/RTIL composites are investigated by means of DSC and the results indicate that the addition of the RTILs significantly influences the mechanism of nucleation and growth of PVDF crystallites. © 2013 Society of Chemical Industry     

Induced crystallization of EVA having various VA contents by compressed CO2

The crystallization induced by compressed CO₂ was investigated for rubbery ethylene‐vinyl acetate copolymer (EVA) containing various amounts of vinyl acetate (VA). The induction of crystallization was demonstrated by appearance of shoulder‐like differential scanning calorimetry (DSC) endotherms at temperatures lower than T_m of polyethylene segments of EVA after CO₂ treatments. The intensity of the endothermic shoulders and the degree of crystallinity increased with increasing VA content, suggesting that the interaction of CO₂‐carbonyl groups governed the induction of crystallization of EVA upon CO₂ treatment. The interaction of CO₂‐carbonyl group was found to decrease with increasing temperature as demonstrated by the decreased crystallization enhancement for 37°C as compared with that for 32°C. The enhancement of crystallization did not monotonically increase with increasing CO₂ pressure, resulting from the interplay of thermodynamic and kinetic driving forces, both being associated with the CO₂ pressure and thus the sorption concentration. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 87: 1144–1151, 2003     

Poly(vinylidene fluoride) with zinc oxide and carbon nanotubes applied to pressure sheath layers in oil and gas pipelines

In this work, PVDF composites containing 0.2% (m/m) of carbon nanotubes (MWCNTs), PVDF with 5.0% (m/m) of zinc oxide (ZnO), and composites containing both particles in the same contents in the matrix were melt processed in a mini-extruder machine with double screws, using the counter-rotation mode. Composites were characterized by scanning electron microscopy (SEM), Fourier-transform infrared spectroscopy (FTIR), thermogravimetric analysis (TGA), differential scanning calorimetry (DSC), X-ray diffraction (XRD), dynamic-mechanical analysis (DMA), and contact angle tests (CA). The samples presented the predominance of the α phase, with an increased degree of crystallinity as well as an increase in dimensional stability by incorporating both fillers, showing a synergistic effect between these particles, as shown on FTIR, DSC, and XRD results. SEM images showed a good dispersion of high aspect ratio particles. In general, DMA and TGA analysis showed that composites had not decreased their thermal and mechanical performance when compared to neat PVDF. Results of CA analysis showed an increase in the hydrophobicity of the sample containing MWCNTs. Permeability tests were also performed using a differential pressure system, combining high temperature and pressure, obtaining permeability measures and time lag. This work presents an alternative of composite materials, suggesting its application in the internal pressure sheath layers of oil and gas flexible pipes.     

Effects of nano‐TiO2 on the properties and structures of starch/poly(ε‐caprolactone) composites

Poor physical properties resulting from low interfacial interactions between hydrophilic biopolymers and hydrophobic thermoplastic matrices have been one of the biggest obstacles in preparing quality biomass materials. This study concentrates on the effects of nano‐TiO₂ on the properties and structure of starch/poly (ε‐caprolactone) (PCL) composites. The molecular and crystal structures of the composites were characterized by using Fourier transform infrared spectroscopy, differential scanning calorimeter (DSC), X‐ray diffraction (XRD), and field emission scanning electron microscope. The results indicated that an interpenetrating network structure formed by adding nano‐TiO₂ into starch/PCL composites. The DSC and XRD analysis indicated that the crystallinity degree and the crystallization rate of the composites reduced, whereas the crystal form and crystal size were unchanged. The results also showed that the mechanical properties and water resistance of the composites were improved significantly with the addition of nano‐TiO₂, whereas their transparency decreased. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 130: 4129–4136, 2013     

Mechanical and thermal properties of wood‐plastic composites reinforced with hexagonal boron nitride

Mechanical, thermal, and morphological properties of injection molded wood‐plastic composites (WPCs) prepared from poplar wood flour (50 wt%), thermoplastics (high density polyethlyne or polypropylene) with coupling agent (3 wt%), and hexagonal boron nitride (h‐BN) (2, 4, or 6 wt%) nanopowder were investigated. The flexural and tensile properties of WPCs significantly improved with increasing content of the h‐BN. Unlike the tensile and flexural properties, the notched izod impact strength of WPCs decreased with increasing content of h‐BN but it was higher than that of WPCs without the h‐BN. The WPCs containing h‐BN were stiffer than those without h‐BN. The tensile elongation at break values of WPCs increased with the addition of h‐BN. The differential scanning calorimetry (DSC) analysis showed that the crystallinity, melting enthalpy, and crystallization enthalpy of the WPCs increased with increasing content of the h‐BN. The increase in the crystallization peak temperature of WPCs indicated that h‐BN was the efficient nucleating agent for the thermoplastic composites to increase the crystallization rate. POLYM. COMPOS., 35:194–200, 2014. © 2013 Society of Plastics Engineers     

Morphology and mechanical properties of polypropylene/organoclay nanocomposites

Polypropylene (PP) nanocomposites were prepared by melt intercalation in an intermeshing corotating twin‐screw extruder. The effect of molecular weight of PP‐MA (maleic anhydride‐ modified polypropylene) on clay dispersion and mechanical properties of nanocomposites was investigated. After injection molding, the tensile properties and impact strength were measured. The best overall mechanical properties were found for composites containing PP‐MA having the highest molecular weight. The basal spacing of clay in the composites was measured by X‐ray diffraction (XRD). Nanoscale morphology of the samples was observed by transmission electron microscopy (TEM). The crystallization kinetics was measured by differential scanning calorimetry (DSC) and optical microscopy at a fixed crystallization temperature. Increasing the clay content in PP‐ MA330k/clay, a well‐dispersed two‐component system, caused the impact strength to decrease while the crystallization kinetics and the spherulite size remained almost the same. On the other hand, PP/PP‐MA330k/clay, an intercalated three‐component system containing some dispersed clay as well as the clay tactoids, showed a much smaller size of spherulites and a slight increase in impact strength with increasing the clay content. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 85: 1562–1570, 2002     

过氧化物交联改性PE-HD/EVA防水材料的研究

用过氧化二异丙苯（DCP）交联法改善高密度聚乙烯/乙烯醋酸乙烯共聚物（PE-HD/EVA）防水材料的尺寸稳定性,研究了交联剂用量对PE-HD/EVA片材热稳定性和力学性能的影响。采用傅里叶变换红外光谱仪、差示扫描量热仪、X射线衍射仪、索氏提取交联度测试法等对片材进行了分析,研究了片材力学性能的影响因素。结果表明,随着交联度的增大,片材的软化温度和结晶度逐渐降低,晶体结构基本不变,晶粒尺寸减小, 拉伸强度提高;当DCP用量为1.2 %（质量分数,下同）时,片材的拉伸强度达到了最大值,其断裂伸长率比未交联片材降低了77 %,尺寸稳定性得到明显改善;交联改性对于PE-HD/EVA解决防水材料尺寸稳定性差等问题具有一定的指导意义。     

Effect of damp‐heat aging on the structures and properties of ethylene‐vinyl acetate copolymers with different vinyl acetate contents

We reported herein the damp‐heat aging of ethylene‐vinyl acetate copolymers (EVA) with different vinyl acetate (VAc) contents simultaneously for weeks. The aging was carried out under temperature of 40°C and relative humidity of 93% in air atmosphere. The changes of copolymers' structures and properties were investigated by means of FTIR, wide angle X‐ray diffraction (WAXD) and differential scanning calorimetry (DSC) and mechanical tests. CI values derived from ATR‐FTIR spectra have a decrease when aging time is 1 week and then increase during damp‐heat aging process which suggests the first loss then incorporation of O?C group. WAXD infer that the narrowing trend of FWHM and increase of crystal sizes may attribute to the melting and re‐crystallization of secondary crystallization, which is also confirmed by DSC results. Mechanical tests including Shore A and Shore D hardness, modulus at 100%, tensile strength and elongation at break, are all depending on the primary crystallization and influenced little by damp‐heat aging. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Preparation and thermal properties of polyethylene terephthalate/huntite–hydromagnesite composites

In this report, it was aimed to the improve thermal stability of polyethylene terephthalate (PET) by adding huntite/hydromagnesite minerale. PET/huntite/hydromagnesite composites were prepared by adding various proportions of huntite/hydromagnesite to PET. The chemical structures of the composites were characterized by Fourier transform infrared spectroscopy (FTIR) and X‐ray diffraction (XRD) analysis. Thermal properties of the composites were determined by thermogravimetric analysis (TGA) and differential scanning calorimetry (DSC). Glass‐transition temperatures and char yields increased with the increase of the huntite/hydromagnesite content in the composites. The surface morphologies of the composites were investigated by a scanning electron microscopy. The obtained results proved that the composite system is more thermally stable than the pure PET itself. POLYM. COMPOS., 37:3275–3279, 2016. © 2015 Society of Plastics Engineers     

Microstructure and properties of polypropylene/glass fiber composites grafted with poly(pentaerythritol triacrylate)

Isotactic polypropylene(PP)/glass fiber(GF) composites were modified by grafting polymerization of polyfunctional monomer, pentaerythritol triacrylate (PETA), in the presence of 2,5-dimethyl-2,5-di(tert-butylperoxy) hexane peroxide (DDHP) via melt extrusion. Fourier transform infrared spectroscopy (FTIR), melt strength test (MS), mechanical property test, differential scanning calorimetry (DSC) and X-ray diffraction (XRD) were used to characterize the microstructure and properties of the modified composites. The crystallization kinetics was investigated by Mo method while apparent activation energy of crystallization of the composites was determined by Kissinger method. The FTIR results showed that the acrylic polymers were grafted onto the polypropylene chains. The grafting made the melt strengths and the mechanical properties of the modified composites, and the interfacial adhesion between PP and glass fiber all enhanced. High melting and crystallization temperatures, high crystallization rate and large activation energy of crystallization were also obtained after grafting. In addition, the grafted acrylic polymers recovered the depressed crystallization of polypropylene and restrained α-β transition in fatigue experiment.     

Effect of kenaf fiber age on PLLA composite properties

A challenge facing engineering with natural fibers is the high standard deviation of mechanical properties of natural fiber compared with synthetic fiber. Plants have a chemical and physical architecture reflective of their age. The region near the apex is more flexible than that near the base. In this paper we investigate the impact of increasing age of plant fiber on the corresponding composite. Bast fibers stems of kenaf (Hibiscus cannabinus, L.), a warm season tropical herbaceous annual plant extracted corresponding to different age, were dispersed into Poly‐l ‐lactide (PLLA) matrix by melt blending followed by compression molding. The resulting bio‐based hybrid composites were characterized by X‐ray diffraction (XRD), attenuated total reflectance‐Fourier transfer infrared spectroscopy (ATR‐FTIR), differential scanning calorimetry (DSC), optical microscopy (OM), scanning electron microscopy (SEM), and thermogravimetric analysis (TGA) were conducted. DSC and XRD indicated that the kenaf was effective in promoting crystallization. TGA indicated that the thermal stability of composites is reduced compared with PLLA, but the older fiber sample based on 120–150 cm from the plant apex improved thermal stability compared with the rest. SEM and OM inferred good fiber dispersion while dynamic mechanical tests revealed increased modulus. POLYM. COMPOS., 35:915–924, 2014. © 2013 Society of Plastics Engineers     

Morphology and thermal properties of maleic anhydride grafted polypropylene/ethylene–vinyl acetate copolymer/wood powder blend composites

Maleic anhydride grafted polypropylene (MAPP) was blended with ethylene–vinyl acetate (EVA) copolymer to form MAPP/EVA polymer blends. Wood powder (WP) was mixed into these blends at different weight fractions to form MAPP/EVA/WP blend composites. Differential scanning calorimetry (DSC) analysis of the blends showed small melting peaks between those of EVA and MAPP, which indicated interaction and cocrystallization of fractions of EVA and MAPP. The presence of MAPP influenced the EVA crystallization behavior, whereas the MAPP crystallization was not affected by the presence of EVA. Scanning electron microscopy, Fourier transform infrared spectroscopy, and DSC results show that the WP particles in the MAPP/EVA blend were in contact with both the MAPP and EVA phases and that there seemed to be chemical interaction between the different functional groups. This influenced the crystallization behavior, especially of the MAPP phase. The thermogravimetric analysis results show that the MAPP/EVA blend had two degradation steps. An increase in the WP content in the blend composite led to an increase in the onset of the second degradation step but a decrease in onset of the first degradation step. The presence of WP in the blend led to an increase in the modulus but had almost no influence on the tensile strength of the blend. The dynamic mechanical analysis results confirm the interaction between EVA and MAPP and show that the presence of WP only slightly influenced the dynamic mechanical properties. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010