高密度聚乙烯/聚氧化乙烯梯度结构注射成型的研究

采用注射成型机,在高密度聚乙烯/聚氧化乙烯(HDPE/PEO)共混物注入型腔时,调控模具型腔的热力学状态,自组织制备了组成在厚度上呈梯度分布的HDPE/PEO复合材料。通过偏光显微镜和红外光谱对试样断面的组成进行了表征。结果表明:在热力学非平衡状态下注射成型时,HDPE富集在能量流出侧,PEO富集在能量流入侧,组成沿能量流方向成梯度分布。     

聚氧化乙烯(PEO)及其与高氯酸锂复合体系的非等温结晶动力学研究

用示差扫描量热法(DSC)研究了PEO及其与高氯酸锂复合体系的非等温结晶过程.分别用Jeziorny方法、一种结合Avrami和Ozawa方程的方法对该体系的非等温结晶过程进行了研究,分别得到PEO进行非等温结晶时的动力学参数.结果表明LiClO4晶粒缩短了PEO的结晶时间,使复合体系中PEO的结晶速率要大于纯PEO;但纯PEO结晶时形成的晶体更完善.为使二者达到相同的相对结晶度,纯PEO体系需要更大的冷却速度.LiClO4微粒能有效地将PEO的结晶相转变成非晶相,也就是说LiClO4可有效地抑制PEO的结晶过程.     

不同分子量的聚氧化乙烯对聚乳酸结晶和力学性能的影响研究

聚乳酸(PLA)和其他可降解高分子材料熔融共混被认为是增韧PLA而不损失其可降解特性的最经济有效的方法。通过熔融共混法制备了PLA与聚氧化乙烯(PEO)的共混物,并采用DSC、XRD、SEM以及万能试验机等方法系统研究了不同分子量以及不同比例PEO对PLA微观结构和力学性能的影响。结果表明:在相同比例条件下,低分子量PEO与PLA的相容性要优于高分子量PEO,且对PLA结晶速率的提高更显著;PEO的加入提高了共混物的断裂伸长率,但伴随着拉伸强度的下降,且随PEO含量的增加,拉伸强度下降越明显。当PEO的分子量超过10万时,对PLA的增韧效果更加显著,且共混物的拉伸强度下降幅度较小。     

PEO/LiClO4复合体系中PEO的等温结晶动力学研究

用差示扫描量热法研究了聚氧化乙烯(PEO)和PEO/LiClO4复合体系中PEO的等温结晶过程.用Avrami方程分析了PEO和复合体系中PEO的等温结晶动力学,得到PEO在不同体系中等温结晶时的动力学参数.PEO的Avrami指数n都趋近2.5,说明PEO晶体以三维方式依热成核生长.动力学参数表明,复合体系中的PEO以异相成核为主.LiClO4对PEO等温结晶过程的影响为:作为PEO结晶的成核剂而加快其结晶过程;增加了复合体系的粘度,缩短了PEO的半结晶时间,使其结晶总速率增大;降低了复合体系中PEO的绝对结晶度.PEO和复合体系中的PEO等温结晶时成核和生长活化能△E分别为59.28kJ/mol、70.85kJ/mol.     

PMGn—PEO—LiCF3SO3复合结构高分子快离子导体

采用共混方法,研究了往PMG_n-LiCF_3SO_3体系中掺入聚氧化乙烯,或聚醋酸乙烯酯,纤维素丙酸酯的影响,结果表明,共混掺入适量高分子量聚氧化乙烯(PEO)可与以上体系形成均匀结构的由PMGn-PEO-LiCF_3SO_3组成的复合型高分子快离子导体。这种复合结构高分子快离子导体的离子导电性和成膜后的抗蠕变性能比原体系都有明显改善.     

不对称聚乙烯醇缩丁醛超滤膜的形成

采用浸没沉淀相转化法在二甲基乙酰胺(DMAC)、N-甲基吡咯烷酮(NMP)、二甲基甲酰胺(DMF)及二甲亚砜(DMSO)等4种溶剂下制备了聚乙烯醇缩丁醛(PVB)超滤膜,铸膜液组成为PVB-溶剂二元体系,水为非溶剂.利用扫描电子显微镜(SEM)观察了PVB膜的表面形貌与断面结构,并对其渗透及分离性能进行了测试,同时着重讨论了PVB膜表面结构的形成机理.结果表明,溶剂种类不仅决定了PVB-溶剂二元体系的热力学稳定性,同时也影响了其成膜过程的动力学效应;PVB膜断面结构受溶剂-非溶剂相互扩散速度的控制,而膜表面形貌则是铸膜液平衡热力学与成膜动力学结合的结果;不同溶剂的PVB超滤膜纯水通量大小的顺序依次为DMSO＞DMAC＞DMF＞NMP,其截留分子量则分别在40 000～50 000道尔顿之间.     

BaTiO3填充PEO基复合聚合物电解质厚膜的制备与性能研究

采用溶液铸膜法制备PEO基复合聚合物电解质(CPE)厚膜,利用XRD、SEM、DSC、FTIR分析等多种结构测量技术对CPE的性能进行了表征和分析.本文研究的是在(PEO)6:NaPO3基导电聚合物电解质中加入质量分数为3～10 wt％ BaTiO3填料,从而分析性能的变化.(PEO)6:NaPO3在加入填料后玻璃化转...     

茶多酚-聚乳酸/聚碳酸丁二醇酯抗菌复合纤维膜的制备及性能

通过静电纺丝法制备了茶多酚(TP)-聚乳酸(PLA)/聚碳酸丁二醇酯(PBC)复合纤维膜。并采用SEM、FTIR、TG、接触角和抑菌测试进行了表征。研究表明,TP与PLA/PBC复合纤维薄膜共混良好,并且通过接触角测试10 s后接触角从105.42°下降到69.41°,TP的加入使TP-PLA/PBC复合纤维膜的热分解稳定性提高。随着TP含量的增加,纤维直径分布逐渐均匀并且趋于减小。TP-PLA/PBC复合纤维膜的抗菌活性远高于PLA/PBC复合纤维膜,对大肠杆菌(E.coli)的抗菌活性也略高于金黄色葡萄球菌(S.aureus)。当TP的添加量(与PLA/PBC的质量比)为20%时,得到了亲水性、热稳定性和抗菌性能优异的TP-PLA/PBC复合纤维膜。      

非溶剂添加剂对聚芳醚砜酮复合膜气体渗透性能的影响

以含二氮杂萘酮结构的聚芳醚砜酮(PPESK)为制膜材料,以硅橡胶为涂层材料,以N,N-二甲基乙酰胺(DMAc)为溶剂,采用干/湿相转化法,选用多种非溶剂添加剂(NSA),制备了中空纤维富氧膜.考察了非溶剂添加剂对纺丝液体系热力学性质及最终膜性能的影响;研究了不同非溶剂添加剂在延长蒸发距离时对膜性能的影响.为了考察膜的耐热性,将膜的测试温度控制在70℃.结果表明,非溶剂添加剂种类对纺丝液体系的热力学相平衡性质和膜性能的影响显著;随非溶剂添加剂含量的增加,膜的气体渗透率增大,氧/氮选择性降低;增大蒸发距离,非挥发性添加剂与挥发性添加剂对膜性能产生相反的影响.该膜耐热性能良好,在70℃下仍具有较好的选择性.     

γ-丁内酯对聚醚酰亚胺膜结构形态的影响

以聚醚酰亚胺(PEI)为制膜材料、N-甲基吡咯烷酮(NMP)为溶剂、γ-丁内酯(GBL)为弱非溶剂以及纯水为凝胶剂,采用浸没沉淀法制备了系列平板膜和厚度梯度膜,考察了GBL的存在对铸膜液黏度、平板膜及厚度梯度膜结构的影响.随着GBL浓度的增加,PEI铸膜液的黏度会增大,当m(GBL):m(NMP)达到69.6:15.4时,PEI聚合物溶液黏度急剧增大,促使PEI聚合物溶液由单一均相溶液向贫/富两相区转化.GBL浓度增加的同时,PEI膜结构形态逐渐由完全的指状结构向海绵结构转化.就PEI厚度梯度膜而言,当膜厚增加到临界结构转化厚度L<,c>时,海绵状结构开始向指状孔结构转变.铸膜液体系中GBL浓度的增加延迟了厚度梯度膜中海绵状结构向指状孔结构的转化,临界结构转化厚度L<,c>随着铸膜液体系中GBL浓度的增加而增加.     

Crystallisation and miscibility of poly(ethylene oxide)/poly(vinyl chloride) blends

Isothermal crystallisation of blends of Poly(ethylene oxide) and Poly(vinyl chloride), PEO/PVC, was analysed by differential scanning calorimetry (DSC). The influence of the amorphous polymer, PVC, on crystallisation rate of PEO was investigated using pure PEO as reference. Pure PEO and PEO/PVC blends were submitted to different crystallisation temperatures (from 40 to 58°C) and crystallisation times (from 1 to 72 h). Using the Hoffman-Weeks plot procedure, the equilibrium melting temperature, T _m°, was determined for pure PEO and for PEO/PVC blends with compositions (in wt%): 90/10, 80/20, 70/30, 60/40, 50/50, 40/60, 30/70 and 20/80. The lamellar thickness factor of PEO crystals for pure PEO and for the blends showed a strong decrease when the PVC content was higher than 60 wt%. A small depression in T _m° was verified as the composition of PVC was increased. From the depression in T _m° the polymer-polymer interaction parameter, ₁₂, was evaluated using the Nishi-Wang equation. The results indicate that the miscibility between PEO and PVC in the molten state depends on the blend composition. The crystallisation rate also depends on the blend composition: the richer in PVC is the blend, the slower the crystallisation process.     

聚乳酸/ 乙基纤维素复合膜的制备及其性能

以烯基琥珀酸酐( ASA) 作为新型增塑剂, 使用三氯甲烷作为聚乳酸( PLA) 和乙基纤维素( EC) 的共溶剂, 采用溶液浇铸法成功制备了聚乳酸/ 乙基纤维素复合膜。用红外光谱( FT IR) 、X 射线衍射(XRD) 表征了复合膜结构, 并测试了其吸水性和力学性能。FTIR 测试结果显示, 复合膜中存在强烈的氢键相互作用。XRD 表明,ASA 显著提高了PLA 和EC 2 种高聚物的界面黏合性。力学测试结果表明, ASA 对该复合膜具有良好的增塑效果。当膜中PLA 质量分数[ 37%时, PLA 对复合膜起增强作用。复合膜的吸水性随ASA 含量的增大而降低, 随PLA 含量的增大而提高。该复合膜作为一种潜在的药物缓释材料, 将具有广阔应用前景。      

Flexible and Tough Poly(lactic acid) Films for Packaging Applications: Property and Processability Improvement by Effective Reactive Blending

This study demonstrates a practical means to overcome inherent brittleness problem of poly(lactic acid) (PLA) and make PLA feasible as packaging material. PLA with suitable processability is utterly required for package manufacturers, where flexible, tough PLA film is essential for packers and end users. Highly flexible PLA films with 60‐fold increase in elongation at break (Eb) over that of the neat PLA were successfully produced by integrating effective reactive blending and economical film blowing process. The ‘two‐step’ blending was used to prepare PLA compound; poly(butylene adipate‐co‐terephthalate) (PBAT – another biodegradable polymer) was first blended with 0.5–1% chain extender (epoxy‐functionalized styrene acrylic copolymer) (ESA), followed by subsequent blending with PLA in twin‐screw extruder. Blown films of reactive blend of PLA/PBAT/ESA (80/20/1) showed impressively high Eb of 250% versus a very low Eb of 4% for the neat PLA. Resulting blown films still possessed high modulus of 2 GPa, yield stress of 50–60 MPa and good toughness of ~100 MPa. Significant enhancement in the film's ductility was attributed to homogeneous blend with developed fine strand‐like structure as a result of effective in situ compatibilization and good interfacial adhesion between the PLA and PBAT. PLA/PBAT/ESA blend also offered improved processability. Resulting films had acceptable haze of ~10% for common packaging, and clearer film close to PLA (≤2%) could be obtained by designing PLA skin layers in multilayer structure. Films of PLA/PBAT/1%ESA exhibit potential as packaging material; their mechanical and optical properties are comparable with or even exceed some existing films used in the market. Copyright © 2015 John Wiley & Sons, Ltd.     

Scaffolds for drug delivery,part I: electrospun porous poly(lactic acid) and poly(lactic acid)/poly(ethylene oxide) hybrid scaffolds

This is the first in a series of papers, focused on the development of a biodegradable, controlled, and potentially targeted drug delivery system. In this paper, we describe the production of highly porous biodegradable fibrous structures suitable for biomedical applications and as a matrix for drug delivery. Two structures are described below. The first structure is composed of electrospun poly(lactic acid) (PLA) fibers and is unique due to (1) the uniformity if its constitute fibers’ diameter, (2) consistent surface pore dimensions of each fiber, (3) the use of only a single solvent, (4) interior nano-size porosity throughout each individual fiber, and (5) the independency of surface pore dimensions on fiber diameter. The produced matrix will be further impregnated with cargo loaded nanoparticles—Red clover necrotic mosaic virus (RCNMV)—to achieve a controlled drug delivery system (described in Part III) for cancer treatments. Such a structure can also be used as tissue engineering scaffolds and filter media. The second electrospun structure has enhanced hydrophilicity compared to PLA matrix and is formed by blending poly(lactic acid)/poly(ethylene oxide) (PEO) polymers. The incorporation of PEO in the matrix introduces preferable sites for aqueous compounds to be attached to while retaining the overall structural integrity and porous morphology. It is hypothesized that the existence of alternative hydrophilic and hydrophobic segments in the structure may reduce post-implantation complications such as platelet adhesion.     

Effect of starch type on miscibility in poly(ethylene oxide) (PEO)/starch blends and cytotoxicity assays

This study reports results on the miscibility of polymer blends based on PEO and different starches (unmodified, cationic, and hydrophobic) and their respective cytotoxicity. Films of PEO/starch blends at different weight ratios (95/05, 90/10, 80/20, 70/30, 65/35, and 60/40), as well as films of pure PEO as control, were prepared by casting methodology. Several techniques, such as SEM, WAXS, FTIR, and FT-Raman spectroscopy were used in this study for evaluating blend miscibility. The results revealed that the miscibility of such blends is dependent on the type of starch used. Regarding the PEO/unmodified starch blends, it was concluded that the system is miscible in the ratio range from 90/10 to 65/35. Although the PEO/hydrophobic starch blends are miscible in all the studied range, blends of PEO and cationic starch are immiscible, regardless the blend ratio. The different samples presented distinct cytotoxic behaviors. PEO and hydrophobic starch presented no relevant toxicity (CC_50/72 > 2.5 mg/mL). Otherwise, the cationic starch was the most harmful for the cells. The blends presented cytotoxicity values between those of PEO and cationic starch.     

大黄素/聚乳酸物复合薄膜的制备及抗凝血研究

药物洗脱支架具有良好的抗增生性能,对血管支架内再狭窄起到很好的抑制作用,但其抗凝血性能仍有待改善.大黄素(emodin)是一类具有抗增生以及抑制血小板黏附聚集等特性的中药提取物,有望成为药物洗脱支架的选用药物.本文以可降解高分子材料聚乳酸(PLA)为载体制备了浓度为3%(质量分数)、5%(质量分数)的大黄素复合薄膜.采用傅立叶变换红外光谱研究了复合薄膜的组成成分,用体外血小板粘附实验和部分凝血活酶时间(APTT)表征复合薄膜的体外抗凝血性能.结果显示大黄素与PLA的特征峰在复合薄膜的红外图谱中均有出现,复合薄膜的血小板粘附和聚集数量减少且APTT长于纯PLA薄膜,这都表明大黄素/聚乳酸复合薄膜的抗凝血性能优于纯PLA薄膜.     

Microcellular extrusion foaming of poly(lactide)/poly(butylene adipate-co-terephthalate) blends

Foamed poly(lactide) (PLA)/poly(butylene adipate-co-terephthalate) (PBAT) blends were processed via the microcellular extrusion process using CO₂ as a blowing agent. Talc has been added to promote heterogeneous nucleation. Two types of PLA/PBAT blend systems were investigated: Ecovio, which is a commercially available compatibilized PLA/PBAT blend; and a non-compatibilized PLA/PBAT blend at the same PLA/PBAT ratio (i.e., 45:55 by weight percent). Six different formulations were investigated: pure PLA, PLA-talc, Ecovio, Ecovio-talc, non-compatibilized PLA/PBAT blend, and non-compatibilized PLA/PBAT-talc. The effects of various processing parameters such as die temperature, talc and compatibilization on various foaming properties such as cell morphology, volume expansion ratio (VER), open cell content (OCC) and crystallinity were investigated. As per the DSC thermograms, it was observed that compatibilization has merged the two distinctive melting peaks of PLA and PBAT into a single peak while lowering the peak temperature. In general, the addition of talc has decreased the average cell size and VER and increased the cell density and crystallinity; however, it has varying effects on the open cell content. Compatibilization has reduced the average cell size and volume expansion but increased the cell density and had varying and no effects on the OCC and crystallinity, respectively. Similar to compatibilization, the die temperature was found to have varying and no effects on the OCC and crystallinity, respectively. Except for PLA and non-compatibilized PLA/PBAT blend, the cell size and VER of all other formulations did not vary much throughout the entire temperature range (130–150 °C). The cell density was found to be insensitive to die temperatures except for Ecovio and Ecovio-talc.     

MFC-structured biodegradable poly(l-lactide)/poly(butylene adipate-co-terephatalate) blends with improved mechanical and barrier properties

Both polylactide (PLA) and poly(butylene adipate-co-terephthalate) (PBAT) are biodegradable polymers. They are thermoplastics which can be processed using conventional polymer processing methods. In this study, microfibrillar-reinforced composites (MFC) based on PLA/PBAT (PLA/Ecoflex^®) blends in different weight ratios were prepared under industry-relevant conditions by melt extrusion followed by continuous cold drawing of the extrudates. Strip-like specimens (films) and plates (laminates) of the drawn blends were prepared by compression molding (CM) at processing temperature above the melting temperature (T _m) of PBAT, but below T _m of PLA. SEM and WAXS observations show that the extruded blend components are isotropic, but become highly oriented after drawing, and they are converted into MFC-structured polymer–polymer composites after CM. An effect of PLA microfibrils on the non-isothermal crystallization of the Ecoflex during cooling from the melt, associated with the formation of crystalline regions of the matrix around the fibrils, was observed. Depending on the blend composition, the compression-molded samples possess a 3- to 7-time higher tensile strength as well as a 15–30 higher modulus than the neat Ecoflex. In addition, the MFC-structured plates exhibited superior barrier properties compared to the neat Ecoflex, e.g., the oxygen permeability decreased by up to 5 times.     

Phase behaviour, mechanical properties and thermal stability of thermosetting polymer blends of unsaturated polyester resin and poly(ethylene oxide)

The results of dynamic mechanical analysis reveal that crosslinked polyester resin (PER)/poly(ethylene oxide) (PEO) blends show a composition dependent glass transition temperature, Tg, which suggests that the blends studied are homogeneous in the amorphous state. The initial dynamic storage modulus, E', decreases with increasing PEO content up to 30 wt% in the blends, whereas E for both the 60/40 and 40/60 PER/PEO blends is close to that for the 80/20 PER/PEO blend and much larger than that for the 70/30 PER/PEO blend. The addition of crystalline PEO has a remarkable effect on the mechanical properties of crosslinked PER. Tensile testing shows that the elongation at break first increases greatly and then decreases slightly, whereas the Young's modulus and the tensile strength first decrease and then increase slightly with increasing PEO content in the blends. The variation of tensile properties was considered to be due to both the plasticization effect and the crystallization effect of PEO in the blends. The impact strength remains almost unchanged with increasing PEO content in the blends studied. No dramatic decrease of thermal stability for PER/PEO blends was observed for the blends with PEO content up to 30 wt%.     

Microstructure, mechanical and tribological properties of Ti(C, N)/a-C gradient composite films

Ti(C, N)/a-C composite films with compositional gradient from Ti-TiN-Ti(C, N) to Ti-containing a-C layers have been prepared by closed-field unbalanced magnetron sputtering. Within the composite films, the carbon contents gradually increase and achieve maximum in the a-C layer by increasing the power applied to the graphite targets, the nitrogen contents gradually decrease to zero from Ti(C, N) layer of the interface to a-C layer of the films. In order to achieve a good combination of the mechanical and tribological properties in the composite films, a designed experimental parameter basing on various substrate rotation speeds is also selected. Results show that the compositional gradient result in the microstructure change of composite films where the Ti(C, N) layers consist of fine nanocolumnar Ti(C, N) grains and the a-C layers consist of 2-7 nm TiC nanocrystallites embedded in an amorphous C matrix. The Ti(C, N) layers also exhibit clear multilayer structure where the period thickness gradually decreases as substrate rotation speed increases. Under higher rotation speed, disappearance of the multilayer structure is accompanied with simultaneous increase in the crystallinity of Ti(C, N) layer and also the Ti(C, N) grain size. In the a-C layer, the TiC nanocrystallites embedded in the a-C matrix is produced by the high rotation speeds. The Ti(C, N)/a-C gradient composite films exhibit high microhardness values (~5000 H_V) and low friction coefficient (~ 0.15), which is related to the hard Ti(C, N) layer and self-lubricate a-C layer, respectively. The combination of the Ti(C, N) layer with a-C layer increases the load and the wear resistance capacity of the composite films, which gives satisfactory friction performance in the pin-on-disk tests with a wear rate of 3.7 × 10^− 17 m³/mN.