HYDROGEN-BONDING INDUCED CHANGE OF CRYSTALLIZATION BEHAVIOR OF POLY（BUTYLENE SUCCINATE） IN ITS MIXTURES WITH BISPHENOL A

In the present work, the blend of poly（butylene succinate） （PBS） and bisphenol A （BPA） was prepared by solution mixing, and the intermolecular interactions between the two components were characterized by a combination of nuclear magnetic resonance （NMR） and Fourier transform infrared spectroscopy （FTIR）. The results showed that intermolecular hydrogen-bonding forms between the carbonyl group of PBS and phenol hydroxyl of BPA. With the increase of BPA content, more hydrogen bonds were formed. The effect of hydrogen bonding on the crystallization behavior of PBS was investigated by differential scanning calorimetry （DSC） and polarized optical microscopy （POM）. The results showed that the overall isothermal crystallization kinetics and the spherulite growth rate of PBS decrease with the increase of BPA content, while the PBS spherulite size increases with BPA content.     

Structure–property relationships of blended polysaccharide and protein biomaterials in ionic liquid

Cellulose and silk blended biomaterial films were regenerated from ionic liquid solution and investigated to characterize and understand the effect of inter- and intra-molecular interactions upon the morphology and thermal properties. The blended films were dissolved in 1-allyl-3-methylimidazolium chloride ionic liquid, coagulated and regenerated with water. Various characterization techniques were implemented to characterize structural, morphological and thermal properties: FTIR, SEM, TGA, DSC and X-ray scattering. The results showed that the cellulose microcrystalline structure and β-sheets from the silk can be disrupted by inter- and intra-molecular hydrogen bonds forming intermediate semicrystalline or amorphous structures. The SEM showed morphological effects of such interactions that cause varying thermal degradation and glass transition temperature. The X-ray scattering confirms such findings at the molecular level, demonstrating that the cellulose microfibril diameter decreases as the silk content increases. It also shows that the β-sheets size increases as the cellulose content increases. These various techniques provide evidence that suggest the hydrogen bonds between the β-sheets and the glucose units in the cellulose chains control the thermal and structural properties of the blended films, changing the morphology and physicochemical properties.     

聚甲醛与热塑性酚醛树脂相容性研究

考察了聚甲醛(POM)与热塑性酚醛树脂(Novolak)的相容性;浊点法研究结果表明,POM/Novolak共混物存在一个低位临界相转变温度.DSC测试表明,POM与Novolak共混后,共混物的熔点下降;通过DSC测试得到数据,采用Hoffman-Weeks平衡熔点外推法和Flory熔点下降方程推算出POM与Novolak的相互作用参数(χ)约为-0.032.FTIR研究表明,Novolak的羟基能够与POM的醚氧基形成氢键,导致共混物中Novolak的羟基峰向高频偏移.研究结果表明,POM与Novolak能够达到热力学相容.     

Crystallization kinetics and the fine morphological evolution of poly(ethylene oxide)/ionic liquid mixtures

The overall crystallization kinetics and spherulite morphologies of miscible poly(ethylene oxide)(PEO)/1-butyl-3-methylimidazolium hexafluorophosphate([BMIM][PF_6]) mixtures were studied by differential scanning calorimetry(DSC),polarized optical microscopy(POM) and rheological measurements. The finer crystal structures were further detected by wide angle X-ray diffraction(WAXD) and small angle X-ray scattering(SAXS). Crystallization of PEO is largely suppressed by [BMIM][PF_6] addition especially at higher ionic liquid(IL) concentrations above 20 wt%. Both the overall crystallization rate and the spherulite growth decrease with the increase of IL content and crystallization temperature; however, the crystallization mechanism keeps unchanged as evidenced by the similar Avrami exponent n and WAXD results. The addition of [BMIM][PF_6] could induce more nuclei to some extent, but the induction time of crystallization is evidently prolonged,and a linear to non-linear transition of the spherulite growth(R ∝ t to R ∝ t~(1/2)) can be observed. At higher IL concentration,the spherulite texture changes apparently from particular serrated to branch surface due to the diffusion-controlled growth and the dilution effect, which also as a main factor contributes to the increasing trend of the long period of crystals.     

Preparation and characterization of biodegradable poly(l-lactide)/chitosan blends

In order to improve the properties of chitosan and obtain new fully biodegradable materials, blends of poly(l-lactide) (PLLA) and chitosan with different compositions were prepared by precipitating out PLLA/chitosan from acetic acid-DMSO mixtures with acetone. The blends were characterized by Fourier transform infrared analysis (FTIR), X-ray photoelectron spectroscopy (XPS), differential scanning calorimetry (DSC), ¹³C solid-state NMR and Wide-angle X-ray diffraction (WAXD). FTIR and XPS results showed that intermolecular hydrogen bonds existed between two components in the blends, and the hydrogen bonds were mainly between carbonyls of PLLA and amino groups of chitosan. The melting temperatures, cold crystallization temperatures and crystallinity of the PLLA component decreased with the increase in chitosan content. Blending chitosan with PLLA suppressed the crystallization of the PLLA component. Although the crystal structure of PLLA component was not changed, the crystallization of the blends was affected because of the existence of hydrogen bonds between two components, which was proved by WAXD results.     

聚左旋乳酸/聚消旋乳酸共混物的结晶行为

非晶态聚消旋乳酸(PDLLA)对PLLA的结晶行为有较大的影响。本文利用差示扫描量热仪(DSC)和偏光显微镜(POM)对不同分子量PLLA、PDLLA按不同比例制得的共混物结晶进行了系统研究。结果表明随PDLLA含量的增大PLLA冷结晶温度升高,且越接近熔融温度。PDLLA分子量较小时PLLA球晶特征被明显破坏,PDLLA分子量较大时PLLA更易形保持球晶特征且易形成环带球晶形貌,这与结晶速率与非晶组分的扩散速率匹配程度有关。低分子量的PDLLA使PLLA的最大生长速率对应的温度出现在较低温度。     

聚乳酸/羧基化聚丙烯共混物的形态与热性能研究

以扫描电子显微镜、热重分析仪、差示扫描量热仪、热台偏光显微镜分别研究了聚乳酸/羧基化聚丙烯共混体系的相形态、热性能和结晶形态.结果显示,共混物熔体冷却时,聚乳酸和羧基化聚丙烯均形成球晶,但羧基化聚丙烯球晶较大而十字消光较暗,聚乳酸球晶尺寸较小而十字消光较亮,且聚乳酸球晶产生规则的、不连续的同心环线——裂纹,裂纹厚度约为1~2μm,且裂纹内部有微纤存在.当聚乳酸含量≤50%时,由于聚丙烯上羧基的存在而使共混体系具有较好的相容性.共混物的热分解过程分为三个阶段,热分解温度的变化是聚丙烯上的羧基、聚乳酸和聚丙烯骨架分解三种机制共同作用的结果,少量聚乳酸能够明显提高共混物中聚丙烯上羧基的热稳定性.共混物中的羧基化聚丙烯组分可以发挥稀释剂的作用,大幅度降低了聚乳酸的冷结晶温度.聚乳酸含量≥50%时,共混熔体降温时DSC谱图中聚乳酸和羧基化聚丙烯分别结晶,而聚乳酸含量<50%时,只观察到羧基化聚丙烯的结晶行为.     

Rheological,thermal and mechanical properties of biodegradable poly(propylene carbonate)/polylactide/Poly(1,2-propylene glycol adipate) blown films

Poly(propylene carbonate)(PPC) was blended with polylactide(PLA) and poly(1,2-propylene glycol adipate)(PPA) using a twin screw extruder. Then the PPC/PLA/PPA films were prepared using the blown film technique. DMA results showed that PPA could act as a plasticizer and improve the miscibility between PPC and PLA. Crystal morphology displayed that blending PLA with the amorphous PPC led to a decrease of the spherulite size of PLA. The results of mechanical tests indicated that PPC-rich films showed high elongation at break and PLA-rich films showed high tear strength and good optical properties. The content of PPC and PLA significantly affected the physical properties of the films. With increasing PPC content, the melt strengths of the PPC/PLA/PPA films were enhanced. These findings contributed to the biodegradable materials application for designing and manufacturing polymer packaging.     

EFFECT OF PROCESSING METHOD ON THE IMPACT STRENGTH OF POM/TPU/CaCO3 TERNARY COMPOSITES

Polyoxymethylene （POM）/elastomer/filler ternary composites were prepared, in which thermoplastic polyurethane （TPU） and inorganic filler, namely, CaCO3, were used to achieve balanced mechanical properties of POM. The dispersion and phase morphology of POM/elastomer/filler composites were found to depend largely on processing method, CaCO3 content in masterbatch and the filler size. Two processing methods were employed to prepare POM/elastomer/filler ternary composites. One is called the one-step method, in which elastomer and the filler directly melt blended with POM matrix. The other is called the two-step method, in which the elastomer and the filler were mixed to get masterbatch first, which was then melt blended with pure POM of different content. The effect of phase morphology and processing method on impact strength was investigated. It was found that the two-step method results in an increase in impact strength but not for the one-step method. Additionally, the impact strength of POM ternary composites decreases with the increase in the size of CaCO3 particles.     

Probing molecular-level surface structures of polyethersulfone/pluronic F127 blends using sum-frequency generation vibrational spectroscopy

We blended Pluronic F127 into polyethersulfone (PES) to improve surface properties of PES, which has been extensively used in biomaterial and other applications. The molecular surface structures of PES/Pluronic F127 blends have been investigated by sum-frequency generation (SFG) vibrational spectroscopy. The molecular orientation of surface functional groups of PES changed significantly when blended with a small amount of Pluornic F127. Pluronic F127 on the blend surface also exhibited different features upon contacting with water. The entanglement of PES chains with Pluronic F127 molecules rendered the blends with long-term surface stability in water in contrast to the situation where a layer of Pluronic F127 adsorbed on the PES surface. Atomic force microscopy (AFM) and quartz crystal microbalance (QCM) measurements were included to determine the relative amount of protein that adsorbed to the blend surfaces. The results showed a decreased protein adsorption amount with increasing Pluronic F127 bulk concentration. The correlations between polymer surface properties and detailed molecular structures obtained by SFG would provide insight into the designing and developing of biomedical polymers and functional membranes with improved fouling-resistant properties.     

Role of hydrogen bonds in controlling the morphology of self-assembling carbamate systems

With a view to understand the role of hydrogen bonding in controlling the morphology of self-assembling carbamate systems, N-octadecylcarbamate dodecyl ester was blended individually with a low molecular weight polyethylene and two commercial clarifiers, namely Kemamide S and Kemamide E 180. The effect of blending on the morphology of this long chain carbamate was investigated using optical microscopy, differential scanning calorimetry, and X-ray diffraction. The crystal structure of the carbamate was not affected by the addition of polyethylene or Kemamide S. The heterogeneous nucleation of the carbamate by the polyethylene or Kemamide S resulted in the reduction of the spherulite size of the carbamate, but it did not improve the transparency of the sample due to phase separation. On the other hand, significant improvement of transparency was achieved when the carbamate was blended with Kemamide E 180. Blending reduced the crystallite and spherulite size, heat of fusion, and crystallinity. An exchange of hydrogen bonds between the carbamate and Kemamide E is indicated in the IR spectra, and this affects the packing of the alkyl chains of the carbamates. This heterogeneous blending shows similar effects on the morphology as was achieved by blending two homologous carbamates in our previous study (J. Phys. Chem. B 2003, 107, 8416).     

Controlled crystallization of poly(vinylidene fluoride) chains from mixed solvents composed of its good solvent and nonsolvent

Poly(vinylidene fluoride) (PVDF) chains with the same expanded state were obtained by dissolving PVDF resin in good solvent. Then, the crystallization of PVDF chains from mixed solvents composed of its good solvent and nonsolvent was investigated. N,N‐dimethylformamide (DMF) and ethanol were used as good solvent and nonsolvent of PVDF, respectively. The crystalline phases of PVDF were characterized by Fourier transform infrared (FTIR) spectroscopy and wide angle X‐ray diffraction (WAXD). For the crystallization of PVDF chains from mixed solvents, low ethanol content favored the formation of β phase, while high ethanol content resulted predominantly in the α phase. Different crystallization morphology was observed from the scanning electron microscopy (SEM) images. The obvious spherulite morphology disappeared with the increase in ethanol content in mixed solvent. According to thermal analyses, the crystallized PVDF from mixed solvents with high ethanol content had lower onset melting temperatures than that from low ethanol content. Smaller lamellar thickness calculated from WAXD data reasoned the low onset melting temperatures. The above results indicated that the crystallization of PVDF chains from mixed solvent was a “controlled” process by ethanol content. © 2010 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 48: 575–581, 2010     

Development of the morphology and crystalline state due to hybridization of reinforced toughened nylon containing a liquid‐crystalline polymer

A hybrid composite consisting of rubber‐toughened nylon‐6,6, short glass fibers, and a thermotropic liquid‐crystalline polymers (LCP) was investigated by the LCP content being varied. The thermal behavior, morphology, and crystallization behavior due to hybridization were studied by differential scanning calorimetry (DSC), dynamic mechanical analysis (DMA), scanning electron microscopy (SEM), Fourier transform infrared (FTIR) spectroscopy, and wide‐angle X‐ray scattering (WAXS). DSC results indicated that the crystallinity of the glass‐fiber‐reinforced toughened nylon‐6,6 was reduced by LCP addition, particularly 5–10 wt % LCP. DMA data showed that the miscibility between the blended components was maximum at the 5 wt % LCP composition, and the miscibility decreased with increasing LCP content. SEM photomicrographs revealed information consistent with the thermal behavior on miscibility. It was also observed that the 10 wt % LCP composition showed predominantly an amorphous character with FTIR and WAXS. WAXS results indicated that LCP hybridization increased the interplanar spacing of the hydrogen‐bonded sheets of the nylon crystals rather than the spacing between the hydrogen‐bonded chains. © 2003 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 41: 549–559, 2003     

Miscibility and Crystallization of PHB/PMA Blends

BacterialPoly(5-hydroxybutyrate)(PHB)isabiodegradableandbioc0mpatiblethermo-plasticswithhighmeltingtemperatureandcrystallinity'.Theintrinsicbrittleness0fPHBpreventSitsdirectuseasac0mmoditypolymermaterial.ItisknownthatPHB,sbrittlenessisassociatedwiththecrackswithinthelargespherulitesofPHB2.Hence,itisconsideredthattopreparemiscibleblendsofPHBwithanamorph0usp0lymershouldbeago0dwaytodecreasethebrittleness0fPHBandproducePHBbasedmaterials3'4.PHBisknowntobendsciblewithPoly(vinylacetate)(P…     

Crystallization kinetics and morphology of binary phenolic/poly(ϵ-caprolactone) blends

For the first time, quantitative analyses of the crystallization kinetics, surface free energy of chain folding, and morphology in phenolic/poly(ϵ-caprolactone) (PCL) binary blends have been studied. The spherulite growth rate and the overall crystallization rate depend on the crystallization temperature and PCL content in the blend. In addition, the crystallization and melting temperatures of the PCL phase decrease with an increase in the phenolic content. An Avrami analysis shows that the addition of phenolic to PCL results in a decrease in the overall crystallization rate of the PCL phase. The presence of an amorphous phenolic phase results in a reduction in the rate of the spherulite growth of PCL. The surface free energy of folding increases with increasing phenolic content, and the crystal thickness of a phenolic/PCL blend, according to small-angle X-ray scattering (SAXS), is greater than that of pure PCL because of the increase in the surface free energy of chain folding and the decrease in the degree of supercooling. The observed domain size of the crystalline/amorphous phase (5.9 nm) from SAXS is also consistent with that from solid-state NMR (3–20 nm). All these results indicate that the crystallization ability of PCL decreases with increasing phenolic content in the blends. © 2003 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 117–128, 2004     

Structure formation of hydrophobically end-capped poly(ethylene oxide) in the solid state

The conformational transition of hydrophobically end-capped poly(ethylene oxide), HP-PEO-HP [hydrophobic-poly(ethylene oxide)-hydrophobic], was studied using X-ray diffraction (XRD), differential scanning calorimetry (DSC), and Fourier transform infrared spectroscopy (FTIR) methods. Conformational transitions of HP-PEO-HP from a planar zigzag to a 7/2 helical conformation were observed as the molecular weight of the PEO main chain increased. HP-PEO-HP 1(18), with a PEO molecular weight of 1000 and 18 hydrocarbons on each end, has mainly an alpha-helical structure in poor solvents, whereas alpha and beta conformations coexist in good solvents. This means that the alpha-helical structure caused by the hydrogen bonds between the urethane linkages was broken by the high chain mobility caused by the melted adjacent chains of PEO, and instead, the beta-sheet was formed by the interaction of multiple hydrogen bonds. Another indication of hydrogen bonds breaking at increasing temperature is the transition of the N-H stretching peak in the FTIR data. HP-PEO-HP 2(18) and 4(18), which have 18 hydrocarbons on each end and PEO molecular weights of 2000 and 4000, respectively, and consist mostly of PEO, showed spherulites. This result also suggests that the PEO molecule has a 7/2 zigzag helical conformation. In contrast, HP-PEO-HP 1(18), which is composed of less PEO than HP-PEO-HP 2(18) and 4(18), did not show a spherulite structure.     

Preparation of biocompatible system based on electrospun CMC/PVA nanofibers as controlled release carrier of diclofenac sodium

Nanofibers of naturally modified polymer such as carboxymethyl cellulose (CMC) blended with poly(vinyl alcohol) (PVA) at different ratios was obtained by electrospinning technique. The blended solutions of CMC and PVA loaded with and without diclofenac sodium (DS) were electrospun using environmentally benign electrospinning technique in the absence of organic solvents. Scanning electron microscopy (SEM), Fourier transform infrared (FTIR), thermogravimetric analysis (TGA) were used to investigate the surface morphology functional groups, as well as the thermal stability of DS loaded CMC/PVA nanofibers mat. The mechanical properties of the as prepared electrospun nanofibers was also evaluated. The entrapment efficiency and the in vitro release of DS loaded CMC/PVA nanofibers were characterized using UV-Vis spectroscopy. The obtained results displayed that the blended nanofibers have shown a smooth morphology, no beads formation when the concentration of CMC was equal or below 5% and beads formation above 5%. FTIR data demonstrated that there were good interactions between CMC and PVA possibly via the formation of hydrogen bonds. The electrospun blended CMC/PVA nanofibers exhibit good mechanical properties. From the in vitro release data, it was found that with the presence of CMC, the release of DS from the nanofibers mats became sustained controlled. Due to the biocompatibility and low cost of the two blended polymers (CMC and PVA), the blended nanofibers system can be considered as one of the promising materials for the preparation of excellent drug carrier.     

聚丙烯/凹凸棒土纳米复合材料结晶形态和形貌研究

采用熔融共混的方法 ,制备聚丙烯 凹凸棒土纳米复合材料 .通过X射线衍射 (XRD)分析凹凸棒土在聚丙烯复合材料中晶面间距的变化以及对聚丙烯晶型的影响 ,结果表明凹凸棒土在复合材料中晶面间距没有变化 ;聚丙烯晶型没有发生变化但晶粒尺寸增加了 .用示差扫描量热法 (DSC)分析聚丙烯复合材料的结晶度的变化 ,发现凹凸棒土的加入使复合材料的结晶温度提高 ,结晶速率增大 ,结晶度增加 .用偏光显微镜(POM)观察凹凸棒土对聚丙烯球晶的影响 ,结果表明凹凸棒土的加入起到了成核剂的作用 ,使得聚丙烯球晶尺寸减小 ,当凹凸棒土的加入量到 10 %左右时 ,观察不到完整的球晶 .利用扫描电子显微镜 (SEM)和原子力显微镜 (AFM)观察凹凸棒土在聚丙烯中的分散 ,发现凹凸棒土在聚丙烯基体中分散比较均匀 ,但呈无序分布 .     

Studies on Rheological,Thermal, and Mechanical Properties of Polylactide/Methyl Methacrylate-Butadiene-Styrene Copolymer/Poly(propylene carbonate) Polyurethane Ternary Blends

Polylactide(PLA), methyl methacrylate-butadiene-styrene copolymer(MBS), and poly(propylene carbonate) polyurethane(PPCU) were blended and subjected to blown film process. The rheological, mechanical, morphological, thermal, and crystalline properties of the PLA/MBS/PPCU ternary blends and the mechanical properties of the resulting films were studied. Results of mechanical test showed that PPCU and MBS could synergistically toughen PLA. The impact strength of 50/10/40 PLA/MBS/PPCU blend(74.7 k J/m~2)was about 7.5 times higher than that of the neat PLA(10.8 k J/m~2), and the elongation at break of 50/10/40 PLA/MBS/PPCU blend(276.5%) was higher by about 45 times that of PLA(6.2%). The tear strength of PLA/MBS/PPCU films was 20 k N/m higher than that of PLA, and the elongation at break(MD/TD) of 50/10/40 PLA/MBS/PPCU films was 271.1%/222.3%, whereas that of PLA was only 2.7%/3.0%. POM observations displayed that the density of spherulite nucleation increased and the size of crystalline particles decreased with the addition of MBS. With increasing PPCU content from 5% to 20%, the density of spherulite nucleation increased and the size of crystalline particles decreased continuously, but the nucleation density of spherulites was slightly lowered with increasing PPCU content from 30% to 40%. The PLA/MBS/PPCU films exhibited excellent mechanical properties, which expanded the application range of these biodegradable films.     

新型热塑性淀粉的制备和性能

以二甲基亚砜(DMSO)为增塑剂, 通过熔融共混法制备了一种新型热塑性淀粉(TPS), 研究不同增塑剂含量对材料结构和性能的影响, 并与甘油及甘油/水复合增塑淀粉体系进行了比较. FTIR结果显示, DMSO能够与淀粉产生强烈而稳定的氢键相互作用. WAXD和SEM的研究结果表明, DMSO的加入破坏了淀粉的有序结构, 实现了淀粉的塑化, 形成均一的非晶连续相. 同甘油及甘油/水增塑体系相比, DMSO与淀粉的羟基形成更为稳定的氢键, 能够有效抑制淀粉的重结晶. 动态力学和拉伸力学性能测试结果表明, 经过DMSO的增塑, 有效降低了淀粉的玻璃化转变温度, 改善了材料的韧性, 增塑效率要好于甘油及甘油/水复合增塑体系.