不同厚度聚氯代对二甲苯膜的结晶与性能研究

在真空气相沉积条件下制备厚度分别为0.32μm、2.39μm、7.98μm和17.11μm的聚氯代对二甲苯膜(PC膜),采用X射线衍射仪(XRD)、原子力显微镜(AFM)和纳米压痕仪对不同厚度PC膜的结晶度、表面形貌以及力学性能进行了表征与测试。结果表明,随着成膜厚度的增加,聚氯代对二甲苯薄膜的结晶度提高,表面晶粒尺寸增大,结晶形态更加完整,其表面粗糙度、压入模量和压入硬度呈逐渐增大的趋势。而PC膜表面形貌、力学性能的差异又与结晶度密切相关。     

聚己内酯/纳米Si3N4复合材料的非等温结晶研究

采用溶液成膜法制备纳米Si3N4/聚己内酯(PCL)复合材料,并通过DSC、偏光显微镜及透射电镜等研究手段分析了纳米Si3N4颗粒对PCL的非等温结晶行为和微观形态的影响。结果表明:改性后的纳米Si3N4粒子在PCL基质中的分散性好于未改性纳米Si3N4;纳米Si3N4具有明显的成核效应,加快了PCL的前期结晶速率,对由成核控制的聚合物结晶前期阶段具有积极作用,而对晶体的生长则具有限制作用,导致聚合物结晶后期速率缓慢,晶体尺寸变小,结晶度下降;当纳米Si3N4的含量为5%时,聚合物结晶温度出现最大值;加快降温速率与添加纳米粒子对聚合物结晶行为的影响具有相似的效果。     

聚乳酸/聚己内酯共混膜的结晶机理

将消旋聚乳酸(D,L-PLA)和聚己内酯(PCL)按一定比例共混,在精制的二氯甲烷中溶解,通过流延法成膜。以结晶性高的聚己内酯为成核剂,诱导无定形消旋聚乳酸结晶。利用傅里叶变换红外光谱法、差示扫描量热法、X射线衍射法、偏光显微镜研究其结晶度和结晶行为的变化,并探讨共混流延膜的结晶机理。实验结果表明,共混膜中聚己内酯的质量分数越大,薄膜表面的结晶度越低。成膜过程中聚乳酸和聚己内酯是互不相容的。聚己内酯可以诱导消旋聚乳酸形成α晶型,且结晶度与聚己内酯的质量分数密切相关。其中加入聚己内酯的质量分数为1%时,共混膜的结晶度最高,聚己内酯的质量分数越大,共混膜的结晶度越低,但均大于纯消旋聚乳酸薄膜的结晶度。     

尿素对聚己内酯二醇结晶性能的影响研究

通过添加小分子尿素制备了聚己内酯(PCL)/尿素复合物,以期改变PCL的结晶性能。利用显微熔点、X射线衍射(XRD)、差示扫描量热法(DSC)、偏光显微镜(POM)等手段研究了PCL/尿素复合物的熔程、结晶度、结晶形态以及结晶过程,通过傅里叶变换红外光谱仪分析了PCL/尿素复合物的结构。结果表明:PCL及其复合物的结晶形态均为球晶,复合物球晶的密集程度较纯PCL明显增加,随着尿素含量增加,球晶尺寸变小;PCL/尿素复合物的结晶度相比纯PCL略有降低;尿素的加入使PCL熔程变窄。这是由于尿素与PCL间产生了氢键,并起到了成核剂的作用。     

聚丁二酸丁二醇酯/聚ε-己内酯共混物的性能研究

将不同比例的聚丁二酸丁二醇酯(PBS)和聚ε-己内酯(PCL)经过混炼、压膜成型制成PBS/PCL共混聚酯。通过红外(FT-IR)、热失重(TG)、X-射线衍射(XRD)、偏光显微镜、拉力测试对聚酯的化学结构、热性能、结晶度、表面形貌、拉伸性能等进行了研究。结果表明:共混聚酯的热稳定性随着PBS含量的增加而增强;结晶度随着共混比例的变化呈现减少、增加、又减少的趋势,PBS/PCL60结晶度最大达到58%,聚酯结晶均以球晶为主;延展性随着PCL比例的增加而增强。     

水蒸汽辅助法聚乳酸多孔膜的制备及性能研究

首先以聚乳酸(PLA)为成膜材料,采用水蒸汽辅助法制备了PLA多孔薄膜。利用电子显微镜(EM)和扫描电子显微镜(SEM)研究了有机溶剂、铸膜液浓度、环境湿度和表面活性剂等因素对多孔膜结构和形貌的影响;然后在铸膜液中添加TiO_2制备了PLA/TiO_2复合膜,采用SEM和X-射线衍射仪(XRD)对其表面形貌和结构进行表征,采用分光光度计评价了PLA/TiO_2复合多孔膜对亚甲基蓝染料的光催化降解性能。结果表明:水蒸汽辅助法制备PLA多孔膜的最佳条件为以CH_2Cl_2为溶剂、PLA质量浓度3%、环境湿度为83%、不添加表面活性剂;TiO_2的加入降低了多孔膜的有序性,使得PLA的结晶度略有降低,晶粒尺寸略有减小,复合膜对亚甲基蓝的光催化降解效果较好。     

铸膜液溶剂对醋酸酯型改性淀粉膜结构及性能的影响

以醋酸酯型改性淀粉(简称醋酸酯淀粉)为原料,分别以二氯甲烷、三氯甲烷、丙酮和1,4-二氧六环为铸膜液溶剂,用浇铸法制备醋酸酯淀粉膜,并研究了铸膜液溶剂对膜致密性、膜结晶度、膜耐水性及膜在土壤中降解速率的影响.实验结果表明:铸膜液溶剂的挥发速度越慢,则膜的致密性越好,结晶度越高;醋酸酯淀粉膜在土壤中能降解,致密性好的膜耐水性能较好并且土壤降解速率较低.     

高分子富氧膜的研究——(Ⅰ)几种聚烯烃及其改性聚合物的成膜与氧氮透过性能

研究了TPX、乙丙共聚物、中1,2-聚丁二烯和3,4-聚异戊二烯及其共混改性聚合物的均质膜的成膜规律和工艺方法,提出了“液面框架成膜法,成功地解决了强度低,、室温处于高弹态聚合物均质膜的制膜困难。用SEM.DSC.WAXD和POM分析了膜的形貌和形态结构、以压力法和体积法测定了膜的氧氮选择透过性,发现溶剂蒸发温度和后处理条件对膜的表面形貌,形态结构及气体透过性产生深刻影响;大分子共混改性TPX膜的结晶度降低;除等规聚丙烯和3,4-聚异戊二烯外、其余所研究的聚合物膜的P_(O_2)达10~(-9)(cm~3(STP)cm/cm~2.s.cmHg],α-(O_2)/N_2为2.8—5.0,改性TPX的气体透过性及透过稳定性较改性前有所改善。     

水性聚氨酯膜的制备及在超纤革中的应用

以水性聚氨酯(WPU)为聚合物,采用物理机械发泡的方法制备WPU膜,系统研究了成膜温度对WPU膜形态结构和性能的影响规律。结果表明,当成膜温度低于100℃时,所制备WPU膜的泡孔密度、表面孔孔径、平均孔径、结晶度、透气量、透湿率、断裂强度和断裂伸长率等均随成膜温度的升高而增大。其中,当成膜温度为80℃时,膜具有最佳的性能。随着成膜温度进一步升高,膜的表面出现裂纹,透气量和透湿率增加,而断裂强度和断裂伸长率显著减小。在此基础上,经干法移膜技术制备的WPU超纤革达到了成品等级的A类产品。     

新型两亲性生物降解接枝共聚物的性能

对新型的两亲性生物降解接枝共聚物羟丙基纤维素接枝聚己内酯(HPC-g-PCL)的综合性能进行了测试。X射线衍射结果表明,接枝共聚有效地降低了PCL的结晶度,且随着PCL链段含量的降低,接枝共聚物的结晶度相应下降。DSC结果表明,与PCL均聚物相比,所得接枝共聚物的Tm、Tc和Xc均明显降低,且随着PCL链段含量的降低而不断下降;同时,与先熔融后冷却相比,室温下的共聚物溶液浇注膜,其结晶程度更完善。水解降解实验结合GPC曲线和SEM照片结果表明,与均聚物PCL相比,接枝共聚物更易发生降解。     

Crystallization, mechanical properties, and controlled enzymatic degradation of biodegradable poly(epsilon-caprolactone)/multi-walled carbon nanotubes nanocomposites

Biodegradable poly(epsilon-caprolactone) (PCL)/multi-walled carbon nanotubes containing carboxylic groups (f-MWNTs) nanocomposites were prepared via simple melt compounding at low f-MWNTs loading in this work. Scanning and transmission electron microscopy observations indicate a homogeneous and fine distribution of f-MWNTs throughout the PCL matrix. The effect of low f-MWNTs loading on the crystallization, mechanical properties, and controlled enzymatic degradation of PCL in the nanocomposites were studied in detail with various techniques. The experimental results indicate that the incorporation of f-MWNTs enhances both the nonisothermal crystallization peak temperature and the overall isothermal crystallization rate of PCL in the PCL/f-MWNTs nanocomposites relative to neat PCL; moreover, the incorporation of a small quantity of f-MWNTs has improved apparently the mechanical properties of the PCL/MWNTs nanocomposites compared to neat PCL. The enzymatic degradation of neat PCL and the PCL/f-MWNTs nanocomposites at low f-MWNTs loading was studied in detail. The variation of weight loss with enzymatic degradation time, the surface morphology change, the reduced film thickness, the appearance of f-MWNTs on the surface of the films, and the almost unchanged molecular weight after enzymatic degradation suggest that the enzymatic degradation of neat PCL and the PCL/f-MWNTs nanocomposites may proceed via surface erosion mechanism. The presence of f-MWNTs reduces the enzymatic degradation rate of the PCL matrix in the nanocomposites compared with that of the pure PCL film.     

准分子激光引起的非晶硅薄膜晶化行为的研究

利用KrF准分子激光对非晶硅薄膜的表层进行了晶化.研究了激光能量密度和照射脉冲数对薄膜结晶度的影响,并对晶化后薄膜的形貌和结构进行了表征.结果表明:该非晶硅薄膜晶化阈值约为110 mJ/cm2,且不受照射脉冲数的影响;激光能量密度是影响薄膜结晶度的首要因素,但在较低的能量密度时,增加照射脉冲数也会显著的提高薄膜结晶度;结构及形貌表征发现,薄膜晶化层厚度约为400～500 nm,平均晶粒尺寸为30～50 nm.     

Photochemically promoted degradation of poly(ɛ-caprolactone) film

Poly(?-caprolactone) (PCL) films were doped with photoactive 1,2-diphenylethane-1,2-dione (benzil, BZ), and the effect of the photochemical transformation of benzil on the molecular characteristics of the PCL films and the rate of PCL hydrolysis was studied. Both crosslinking and degradation of the PCL film were observed during irradiation of the PCL/BZ films. Irradiation of a PCL/BZ film at λ > 400 nm under an air atmosphere resulted in a decrease of the average molecular weight (M_n) of PCL to approximately one half, while formation of polar groups and an increase in the hydrophilicity of the PCL film were observed. Moreover, a subsequent hydrolytic test showed a significant increase in the hydrolytic degradation rate of the PCL/BZ film in comparison with non-irradiated or irradiated PCL films without doped benzil. Using benzil as a dopant in the PCL matrix can allow adjusting the degradation rate of PCL, what can be very important from both environmental and biomedical perspectives.     

Preparation and characterization of hydroxyapatite/polycaprolactone–chitosan composites

Hydroxyapatite (HA)/polycaprolactone (PCL)–chitosan (CS) composites were prepared by melt-blending. For the composites, the amount of HA was varied from 0% to 30% by weight. The morphology, structure and component of the composites were evaluated using environmental scanning electron microscope, X-ray diffraction and Fourier transform infrared spectroscope. The tensile properties were evaluated by tensile test. The bioactivity and degradation property were investigated after immersing in simulated body fluid (SBF) and physiological saline, respectively. The results show that the addition of HA to PCL–CS matrix tends to suppress the crystallization of PCL but improves the hydrophilicity. Adding HA to the composites decreases the tensile strength and elongation at break but increases the tensile modulus. After immersing in SBF for 14 days, the surface of HA/PCL–CS composites are covered by a coating of carbonated hydroxyapatite with low crystallinity, indicating the excellent bioactivity of the composites. Soaking in the physiological saline for 28 days, the molecular weight of PCL decreases while the mass loss of the composites and pH of physiological saline increase to 5.86% and 9.54, respectively, implying a good degradation property of the composites.     

Crystalline structure and morphology of biaxially oriented polypropylene film under the coexistence of organic silica particles and its influence on the adsorption diffusion of polar solvent molecules

In this article, a silica/EVA/PP composite was prepared by melt‐blending nanosilica with polypropylene, and a surface‐modified BOPP film was prepared by using this as raw material. SEM studies have shown the special microscopic morphology of the surface and its cross section. X‐ray diffraction (XRD) characterized and analysed crystallinity, molecular orientation, and grain size in the modified film. Furthermore, the presence of microholes in the modified film was verified by positron annihilation spectroscopy. The results show that compared with the unmodified films, the modified BOPP films have higher crystallinity and smaller grain size. Its dense surface structure and reticular fibre bundle structure make the diffusion coefficient and solubility of ethyl acetate small in the film. The mechanical properties, barrier properties, heat resistance, and ink adhesion of this film have been significantly improved. Modified film can be used as the food packaging film which has high performance and low residue.     

基于PEG-PCL-PLLA杂臂星形高分子胶束的合成与性能

聚己内酯(PCL)和聚L-乳酸(PLLA)是胶束中常用的生物可降解高分子材料,将PCL和PLLA共聚或共混能改善PCL降解缓慢的缺陷,但PCL和PLLA同时作为杂臂星形高分子胶束的疏水部分却鲜少研究。文中合成了基于PEGPCL-PLLA的ABC杂臂星形高分子胶束与对应的线型三嵌段高分子胶束,研究了聚合物的不同结构对高分子胶束的结晶和粒径的影响。二者的化学结构、相对分子质量及其分布、结晶行为和粒径由核磁共振、差示扫描量热和动态光散射等测试来表征,其结果表明杂臂星形高分子胶束具有比线型嵌段高分子胶束有更强的结晶能力和更小的粒径。     

In vitro degradation and drug release from polymer blends based on poly(<Emphasis Type="SmallCaps">dl</Emphasis>-lactide), poly(<Emphasis Type="SmallCaps">l</Emphasis>-lactide-glycolide) and poly(ε-caprolactone)

Bioresorbable materials are extensively used for a wide range of biomedical applications. Accurately modifying and evaluating the degradation rate of these materials is critical to their performance and the controlled release of bioactive agents. The aim of this work was to modify the physical properties, degradation rate and drug delivery characteristics of thin films for medical applications by blending poly(dl-lactic acid) (PDLLA), poly(l-lactide-co-glycolide) (PLGA) and poly(ε-caprolactone) (PCL). The thin films were prepared using solvent casting and compression moulding and the in vitro degradation study was performed by immersing the films in a phosphate-buffered saline at elevated temperature for a period of 4 weeks. The degradation rate of the materials was analysed by differential scanning calorimetry, tensile testing and weight loss studies. The thermal analysis of the blends indicated that the presence of PLGA or PDLLA in the film resulted in increased degradation of the amorphous regions of PCL. It was observed that the samples consisting of PDLLA with PCL demonstrated the greatest weight loss. The decrease in mechanical properties observed for both sets of polymer blends proved to be similar. The solvent cast technique was selected as the most appropriate for the formation of the polymer/drug matrices, due to the potentially adverse thermal processing effects associated with compression moulding. It was found that modulation of drug release was achievable by altering the ratio of PCL to PDLLA or PLGA in the thin film blends.     

多晶硅薄膜的铝诱导晶化法制备及其晶粒的择优取向特性

采用铝诱导非晶硅薄膜晶化技术制备了多晶硅薄膜,并研究了多晶硅的成核和生长特性。非晶硅薄膜采用等离子体增强化学气相沉积法制备,其表面沉积铝薄膜后经不同温度的氮氛围退火处理。结果表明,退火后的硅薄膜层与铝层发生置换,所生长的多晶硅颗粒的平均尺寸约为150nm。X射线衍射分析结果揭示,薄膜的晶向显著依赖于退火温度,较低温度下,铝诱导晶化速率较慢,薄膜的优化晶向与非晶硅薄膜中团簇的初始原子排列趋势紧密相关。而较高温度下,铝诱导晶化促使多晶硅(111)择优成核及随后的固相生长。     

Microstructural evolution of a TiO2 mesoporous single layer film under calcination: Effect of stabilization and repeated thermal treatments on the film crystallization and surface area

This study quantifies the highest perturbation encountered by the first layer of a TiO₂ 12 layers-mesoporous coating, which is submitted to a multistep calcination process. Besides, we propose an alternative thermal treatment in order to limit the degradation induced by repeated calcinations. This paper reports and compares the modifications in film thickness, surface area, anatase crystallite size and global crystallinity of films obtained from different thermal treatments. It defines the maximum crystal size compatible with the preservation of the mesoarchitecture initially induced by templating. Differences in microporosity and rate of crystallization are also discussed.     

PLA/PCL共混膜的制备及性能研究

目的研究PCL含量对PLA/PCL共混包装膜性能的影响,以改善PLA的韧性。方法将不同质量比的PLA和PCL树脂均匀混合,而后熔融挤出吹膜制得PLA/PCL共混膜。对制得的共混膜进行力学性能测试,获得拉伸强度和断裂伸长率,再通过扫描电镜分析观察其微观断面,采用DSC测试分析其熔融结晶行为,通过氧气透过性能和透湿性能的测试获得其阻隔性能。结果通过扫描电镜与红外光谱发现,PLA与PCL为两相结构,界面不相容;力学性能显示当PCL的质量少于20%时,对PLA的增韧效果不明显;当PCL的质量为50%时,PLA的断裂伸长率从2.9%提高到290%;DSC结果发现,PCL的加入有助于降低PLA的玻璃化转变温度,提高结晶度;阻隔性能结果表明,随着PCL质量比的增大,共混膜的氧气透过系数和透湿系数下降,阻隔性得到提高。结论 PCL的加入能提高PLA的韧性,当PCL与PLA质量比为3∶7时,共混膜具有最佳的性能。