Cold Crystallization of PLLA Studied by Simultaneous SAXS and WAXS

Summary: The cold crystallization process of initially amorphous poly(L ‐lactic acid), PLLA, with two different molecular weights, during a heating at 2 °C/min, was investigated by DSC and time‐resolved simultaneous SAXS and WAXS, using synchrotron radiation. Equatorial scans of the isotropic 2D‐SAXS patterns showed that the average Bragg long period (L_B) of PLLA samples was approximately constant with the development of cold crystallization up to a temperature that corresponded to a melt/re‐crystallization process that took place before the nominal melting peak seen by DSC. L_B values were found to be higher for the high molecular weight material. This was in accordance with the higher melting temperature observed in the high molecular weight PLLA that implied the existence of thicker lamellae. WAXS results showed that the molecular weight did not apparently affect the crystal form and the final degree of crystallinity of PLLA. The Avrami parameters from WAXS and DSC were consistent, showing that the non‐isothermal cold crystallization of the two PLLA samples corresponded mainly to a three‐dimensional growth, although an imperfect crystallization process was involved at early times. The crystallization rate of PLLA, observed both by WAXS and DSC, decreased with increasing molecular weight.

SAXS profiles of PLLA2 as a function of temperature. The inset shows the 2D‐SAXS pattern obtained at 180 °C.     

Glass transition and mechanical properties of PLLA and PDLLA‐PGA copolymer blends

The change of the glass transition temperatures (T_g) in the blend of poly(L ‐lactic acid) (PLLA) and the copolymers of poly(D,L ‐lactic acid) and poly(glycolic acid) (PDLLA‐PGA) with different D,L ‐lactic acid and glycolic acid composition ratio (50 : 50, 65 : 35, and 75 : 25) was studied by DSC. Dynamic mechanical measurement and tensile testing were performed at various temperatures around T_g of the blend. In the blend of PLLA and PDLLA‐PGA50 (composition ratio of PDLLA and PGA 50 : 50), T_g decreased from that of PLLA (about 58°C) to that of PDLLA‐PGA50 (about 30°C). A single step decrease was observed in the DSC curve around T_g between the weight fraction of PLLA (W(PLLA)) 1.0 and 0.7 (about 52°C) but two‐step changes in the curve are observed between W(PLLA) = 0.6 and 0.3. The T_g change between that of PLLA and that of PDLLA‐PGA and the appearance of two T_gs suggest the existence of PLLA rich amorphous region and PDLLA‐PGA copolymer rich amorphous region in the blend. A single step decrease of E′ occurs at around T_g of the pure PLLA but the two‐step decrease was observed at W(PLLA) = 0.6 and 0.4, supporting the existence of the PLLA rich region and PDLLA‐PGA rich region. Tensile testing for various blends at elevated temperature showed that the extension without yielding occurred above T_g of the blend. Partial miscibility is suggested for PLLA and PDLLA‐PGA copolymer blends. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 93: 2164–2173, 2004     

In Vitro Characterizations of PLLA/β-TCP Porous Matrix Materials and RMSC-PLLA-β-TCP Composite Scaffolds

To develop a novel degradable poly (L-lactic acid)/β-tricalcium phosphate (PLLA/β-TCP) bioactive materials for bone tissue engineering, β-TCP powder was produced by a new wet process. Porous scaffolds were prepared by three steps, I.e. Solvent casting, compression molding and leaching stage. Factors influencing the compressive strength and the degradation behavior of the porous scaffold, e.g. Weight fraction of pore forming agent-sodium chloride (NaCl), weight ratio of PLLA: β-TCP, the particle size ofβ-TCP and the porosity, were discussed in details. Rat marrow stromal cells (RMSC) were incorporated into the composite by tissue engineering approach. Biological and osteogenesis potential of the composite scaffold were determined with MTT assay, alkaline phosphatase (ALP) activity and bone osteocalcin (OCN) content evaluation. Results show that PLLA/β-TCP bioactive porous scaffold has good mechanical and pore structure with adjustable compressive strength needed for surgery. RMSCs seeding on porous PLLA/β-TCP composite behaves good seeding efficacy, biocompatibility and osteoinductive potential. Osteoprogenitor cells could well penetrate into the material matrix and begin cell proliferation and osteogenic differentiation. Osseous matrix could be formed on the surface of the composite after culturing in vitro. It is expected that the PLLA/β-TCP porous composites are promising scaffolds for bone tissue engineering in prosthesis surgery.     

Electroactive phases of poly(vinylidene fluoride): Determination,processing and applications

Poly(vinylidene fluoride), PVDF, and its copolymers are the family of polymers with the highest dielectric constant and electroactive response, including piezoelectric, pyroelectric and ferroelectric effects. The electroactive properties are increasingly important in a wide range of applications such as in biomedicine, energy generation and storage, monitoring and control, and include the development of sensors and actuators, separator and filtration membranes and smart scaffolds, among others. For many of these applications the polymer should be in one of its electroactive phases. This review presents the developments and summarizes the main characteristics of the electroactive phases of PVDF and copolymers, indicates the different processing strategies as well as the way in which the phase content is identified and quantified. Additionally, recent advances in the development of electroactive composites allowing novel effects, such as magnetoelectric responses, and opening new applications areas are presented. Finally, some of the more interesting potential applications and processing challenges are discussed.     

N,N-双十二烷基壳聚糖/聚(L-乳酸)复合膜的氢键及相容性研究

以氯仿为共溶剂,通过溶液共混,制备了不同组成的N,N-双十二烷基化壳聚糖/聚(L–乳酸)(NCS/PLLA)复合膜。利用红外光谱、热分析、WAXD及SEM探讨了复合膜的氢键作用和相容性。红外分析表明,NCS随PLLA的加入,NCS的缔合羟基伸缩振动由3430cm-1红移至3 380 cm-1、谱带变宽、吸收增强;随NCS的加入,PLLA的羰基伸缩振动由1 760 cm-1红移到1 753 cm-1。热重及热重微分分析表明,复合膜的热稳定性高于纯NCS;DSC分析表明,NCS的加入使PLLA的Tm降低,结晶度下降。WAXD分析表明,NCS的加入使PLLA在2θ=16.7°和2θ=19.1°的结晶衍射峰往低角度偏移、峰变宽、峰强逐渐减弱,当NCS为50%和75%时,PLLA的结晶衍射峰消失。SEM观察表明NCS/PLLA复合膜无相分离。实验结果表明NCS与PLLA存在较强的氢键作用,复合膜具有良好的相容性。     

PLLA封孔工艺对微弧氧化镁合金丝材性能的影响

目的提高微弧氧化镁合金丝材的强度和耐腐蚀性能。方法通过硅烷偶联及聚乳酸封孔处理对微弧氧化AZ31B镁合金丝材进行表面改性,采用扫描电子显微镜(SEM)、电子能谱仪(EDS)以及模拟胃液(SGF)浸泡实验、拉伸实验等设备和方法,研究了硅烷偶联工艺、聚乳酸封孔工艺对丝材综合性能的影响。结果微弧氧化镁合金丝材的耐腐蚀性能随偶联处理时间的延长先升高后降低,当处理时间为90 min时,丝材的耐腐蚀性能最佳。随封孔聚乳酸浓度的升高,丝材的耐腐蚀性能先升高后降低,强度增大;随提拉速度的增大,其耐腐蚀性能和强度均逐渐提高;随浸渍提拉次数的增多,丝材的耐腐蚀性能和强度逐渐降低。当聚乳酸质量浓度为0.14 g/m L、提拉速度为0.9 cm/s、浸渍提拉次数为1次时,硅烷偶联处理过的丝材的综合性能最佳。结论微弧氧化镁合金丝材的性能可以通过聚乳酸封孔处理改善,改善效果与聚乳酸浓度、提拉速度和浸渍提拉次数有关。微弧氧化镁合金丝材表面硅烷偶联处理能有效提高聚乳酸封孔效果。     

含生物功能基团磷脂胆碱的聚乳酸的合成反应

用天然甘油磷脂胆碱开环丙交酯,以获得具有仿生功能的生物降解聚乳酸.采用1H-NMR、FT-IR确证在聚合物结构中引入了生物功能基团磷脂胆碱.通过1H-NMR和GPC测定分子量及其分布,研究了反应时间和温度对聚合物分子量扣产率的影响,聚合物产率达80%以上.将磷脂引入聚乳酸链段中得到可全降解的、生物相容性好的磷脂高分子.这一新的思路可以用于合成一系列新型的药物载体和组织工程支架材料.     

Supercritical CO2 precipitation of poly(l-lactic acid) in a wide range of miscibility

Polymer microparticles are useful for numerous applications such as stationary phases in chromatography, adsorbents and catalyst supports, as well as for drug delivery systems. In recent decades the application of supercritical fluids for microparticle precipitation has been developed to a point where it is an ideal alternative to conventional processes. In this work poly(l-lactic acid) (PLLA), a biodegradable and biocompatible thermoplastic aliphatic polyester, has been processed using supercritical fluids, particularly by rapid expansion of supercritical solutions (RESS) and supercritical antisolvent (SAS) processes over a wide miscibility range. Particle morphology was greatly improved from irregular blocks to spherical microparticles on applying the SAS process. The effects of changes in polymer concentration, liquid flow rate, nozzle diameter, solvent, pressure and temperature have also been evaluated on the particle size of PLLA in the SAS precipitation. A higher concentration of the initial solution led to a decrease in particle size. Dichloromethane was the best of the chlorinated solvents investigated. The nozzle diameter had a negligible effect on particle size and the highest liquid flow rate gave the largest particle size. A larger particle size was also obtained on increasing the operating temperature. In contrast, the particle size decreased on increasing the operating pressure.     

Surface wetting phenomena of plasma polymer-coated sheets of poly(l-lactic acid)/poly(butylene succinate)

Water-repellent surfaces were fabricated on blend sheets of poly(l-lactic acid)/poly(butylene succinate) with various blending ratios by the successive processing; (1) plasma etching, followed by (2) the hydrophobic plasma polymer coating. Rough morphology was formed effectively on the mosaic structured surface of blend sheets via the oxidative etching, and advanced water repellency was achieved after the thin membrane coating was synthesized with a hydrophobic plasma polymer coating by use of hexamethyldisiloxane or hexamethyldisilazane. High water repellency is expressed through the columnar hair-like structured model, where the air-water surface interaction in the voids is taken into account.     

镁合金支架材料AZ81表面PLGA(PTX)/PLLA/MAO涂层的研究

在AZ81镁合金表面制备了抗腐蚀和药物释放复合涂层,并对其耐蚀性、药物释放性能及生物相容性进行研究。DSC和红外光谱数据表明,紫杉醇均匀分散在PLGA体系中。药物释放数据表明30 d后,药物释放率在80%左右。SEM、电化学阻抗、极化及镁离子释放数据表明,PLLA涂层通过有效填充微弧氧化膜表面的微孔与裂缝提高了镁合金的耐腐蚀性。血液和细胞实验表明涂层镁合金血液相容性良好,无细胞毒性。