纤维素/丝素复合膜的制备与性能

通过共混法制备了纤维素/丝素复合膜,复合膜的最佳配比为纤维素占共混膜的90%,丝素占10%。在此条件下形成的复合膜的力学性能、水溶液稳定性、水蒸汽透过系数较单一成分的膜有明显改善,纤维素与丝素之间存在着氢键等强烈的相互作用和良好的相容性。X射线衍射分析进一步验证了复合膜的结晶性能。     

丝素蛋白-纳米银复合材料在抗菌领域的研究进展

重点总结归纳了丝素蛋白-纳米银复合膜、水凝胶、纤维等多种应用形态在抗菌领域的最新研究进展,阐述了丝素蛋白与纳米银结合的抗菌优势、复合材料目前尚待解决的稳定性与安全性问题,展望了丝素蛋白-纳米银复合材料发展方向。     

紫外光固化腰果酚/ZnO复合膜的性能研究

将紫外光固化技术与溶胶-凝胶法相结合,制备了紫外光固化腰果酚/ZnO复合涂料;研究了ZnO在复合膜中的分散状态,以及ZnO含量对复合膜的热稳定性、抗紫外线性能、常规物理机械性能、抗溶剂性和耐化学介质性能的影响。结果表明,当ZnO含量不超过3%时,其以纳米尺寸均匀分布于复合膜中;随着ZnO纳米粒子含量的增加,复合膜的热稳定性、抗紫外线性能、抗溶剂性、硬度和抗冲击强度逐渐增大,光泽度、附着力、柔韧性和耐化学介质性能受ZnO含量的影响不大。     

聚乳酸基纳米纤维素/石墨烯导电复合膜的制备与表征

利用真空抽滤方法,制备了纳米纤维素/石墨烯导电膜,将其嵌在聚乳酸表面得到聚乳酸基纳米纤维素/石墨烯导电复合膜。傅里叶红外(FT-IR)表征结果表明石墨烯与纳米纤维素之间存在一定的相互作用;当纳米纤维素与石墨烯质量比为1:2时,导电复合膜的电导率为12 S·cm-1,抗张强度达到13.62 MPa,水接触角为80.6°。热重分析(TGA)表征结果表明导电复合膜有良好的热稳定性,300℃时不同质量比的导电复合膜的失重量低于10%,相比纳米纤维素,在相同温度下失重量减少了20%。以聚乳酸材料为基体的导电复合膜,其抗张强度比未被嵌聚乳酸基体的纳米纤维素/石墨烯导电膜提高15~23倍,将聚乳酸基纳米纤维素/石墨烯导电复合膜埋在土壤中5周后,质量损失了3.7%。聚乳酸材料优异的力学性能和可降解性,扩展了纳米纤维素/石墨烯导电复合膜的应用范围。制备的导电复合膜在柔性导电材料领域有潜在的应用前景。     

聚乳酸基纳米纤维素/石墨烯导电复合膜的制备与表征

利用真空抽滤方法,制备了纳米纤维素/石墨烯导电膜,将其嵌在聚乳酸表面得到聚乳酸基纳米纤维素/石墨烯导电复合膜。傅里叶红外（FT-IR）表征结果表明石墨烯与纳米纤维素之间存在一定的相互作用;当纳米纤维素与石墨烯质量比为1：2时,导电复合膜的电导率为12 S·cm^-1,抗张强度达到13.62 MPa,水接触角为80.6°。热重分析（TGA）表征结果表明导电复合膜有良好的热稳定性,300℃时不同质量比的导电复合膜的失重量低于10%,相比纳米纤维素,在相同温度下失重量减少了20%。以聚乳酸材料为基体的导电复合膜,其抗张强度比未被嵌聚乳酸基体的纳米纤维素/石墨烯导电膜提高15～23倍,将聚乳酸基纳米纤维素/石墨烯导电复合膜埋在土壤中5周后,质量损失了3.7%。聚乳酸材料优异的力学性能和可降解性,扩展了纳米纤维素/石墨烯导电复合膜的应用范围。制备的导电复合膜在柔性导电材料领域有潜在的应用前景。     

不同粒径氧化锌以及改性纳米氧化锌对多功能PBAT复合膜的影响

采用溶剂铸膜法制备了聚己二酸/对苯二甲酸丁二酯（PBAT）/聚乳酸（PLA）/对苯二甲酸二辛酯（DOTP）/氧化锌（ZnO）复合膜材料,并通过硬脂酸改性纳米ZnO,探讨了不同粒径ZnO以及改性纳米ZnO对复合薄膜力学性能、热性能、疏水性能、耐抽出性能以及抗菌性能的影响。结果表明,通过硬脂酸代替纳米ZnO表面的羟基极性基团,复合膜的耐抽出性能提高。硬脂酸的长链烷基与高分子链的链纠缠改善了改性纳米ZnO与PBAT的相容性。随着ZnO粒径的减小以及改性纳米ZnO含量的增大,复合薄膜的热性能有所下降,但耐抽出性能提高。拉伸强度提高,最高达到13.8 MPa。复合膜的疏水性能得到改善,接触角最高达到110°,复合膜材料的抑菌区域增大,抗菌性能有所增强。     

静电纺PLA/丝素-明胶复合纤维膜的性能研究

通过静电纺丝先制备聚乳酸(PLA)纤维膜,在PLA纤维膜上分别喷射不同比例的丝素-明胶纺丝液制得PLA/丝素-明胶复合纤维膜,对复合纤维膜的溶解性能、尺寸稳定性、力学性能及生物性能进行表征。结果表明:与丝素-明胶纤维膜相比,PLA/丝素-明胶复合纤维膜的溶失率明显下降,尺寸稳定性及柔软性得到改善,且经甲醇处理后,复合纤维膜的力学性能提高。将制备的复合纤维膜进行小鼠胚胎细胞(3T3)培养实验,3T3在PLA/丝素-明胶复合纤维膜上能更好地粘附、伸展和繁殖。     

聚乳酸/乙基纤维素生物降解膜的制备及其性能

将聚乳酸(PLA)和乙基纤维素(EC)的三氯甲烷溶液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(FTIR)表征了复合膜结构,并测试了其力学性能和共混物降解性能.FTIR测试结果显示:复合膜中存在强烈的氢键相互作用.力学测试结果表明:烯基琥珀酸酐(ASA)对该复合膜具有良好的增塑效果.当膜中PLA质量分数w(PLA)≤37%时,PLA对复合膜起增强作用.随着EC含量的增加,共混物的亲水性增加,PLA/EC的降解速度增加.     

两种水溶性甲壳素和丝素共混膜的结构与性能

制备了两种水溶性甲壳素:N-乙酰化壳聚糖(N-ACTS,DS=0.55)和6-O-羟乙基甲壳素(6-O-GC,DS=1.0),将其分别与丝素(SF)混合,制备了水溶性均相混合的复合膜;红外光谱(FT-IR)证明了均相混合的复合膜中两种天然高分子官能团结构的变化,相互之间形成了氢键结合,成为均一的混合体,表明天然高分子之间具有良好的相容性;原子间力显微镜(AFM)表面形貌观察表明:均相混合复合膜的表面比单一丝素蛋白质和多糖螺旋立体构造分布均匀表面光滑;体外细胞培养实验表明:人皮肤纤维芽细胞在两种复合膜上均生长良好,具有良好的生物相容性和医学应用前景.     

PLA热稳定性和降解性能研究及其应用

综述了聚乳酸的种类、性能、热稳定性和降解性能的研究及其应用。聚乳酸具有良好的生物降解性和生物相容性,是一种环境友好型高分子材料。聚乳酸因其热稳定性较差,需要进行改性处理,从共混、共聚、添加剂和加工工艺4个方面进行改性处理都可以改善聚乳酸的热稳定性。     

Analyzing the interactions and miscibility of silk fibroin/mucin blends

Mucin, a glycoprotein with viscoelastic properties, and silk fibroin, a protein excreted from silkworms with properties of thermal and mechanical resistance, have been probed as building blocks in the design of biomaterials. Aiming to evaluate the interaction and miscibility between mucin and fibroin, we synthesized silk fibroin and mucin (SF/MU) blends for biomedical applications. The morphological analysis of the SF/MU blends showed the presence of two phases, suggesting a partial miscibility between the polymers. The degradation temperature of the SF/MU blends increased with an increase in the silk fibroin content, indicating that silk fibroin contributed to the thermal stability of the blends. The glass transition temperature of the SF/MU blends lay between the values of the pure polymers. The Fourier-transform infrared spectroscopy results pointed out that the interaction between fibroin and mucin occurred between the amine group of silk fibroin and mucin carboxyl and hydroxyl groups. The outcomes of this work provided essential information on the miscibility of the SF/MU blends. These findings will be critical for further studies with fibroin and mucin-based biomaterials, especially in mucoadhesive systems and wound healing applications.     

The preparation of high performance silk fiber/fibroin composite

An all-silk composite, in which uniaxially-aligned and continuous-typed Bombyx mori silk fibers were embedded in a matrix of silk protein (fibroin), was successfully prepared via a solution casting process. The structure, morphology, mechanical and thermal properties of such silk fiber/fibroin composites were investigated with X-ray diffraction, scanning electron microscopy, tensile and compression tests, dynamic mechanical analysis and thermogravimetric analysis. The results demonstrated that the interface adhesion between silk fiber and the fibroin matrix was enhanced by controlling the fiber dissolution through 6 mol L⁻¹ LiBr aqueous solution. Compare to those of the pure fibroin counterparts, the overall mechanical properties as well as the thermal stability of such silk fiber/fibroin composites were significantly improved. For example, the composite with 25 wt% fibers showed a breaking stress of 151 MPa and a breaking elongation of 27.1% in the direction parallel to the fiber array, and a compression modulus of 1.1 GPa in the perpendicular direction. The pure fibroin matrix (film), on the other hand, typically had a breaking stress of 60 MPa, a breaking elongation of 2.1% and a compression modulus of 0.5 GPa, respectively. This work suggests that such a controllable technique may help in the preparation of animal silk based materials with promising properties for various applications.     

Structure and physical properties of silk fibroin/polyacrylamide blend films

This article deals with the characterization of blend films obtained by mixing silk fibroin (SF) and polyacrylamide (PAAm). The DSC curves of SF/PAAm blend films showed overlapping of the main thermal transitions characteristic of the individual polymers. The exothermic peak at 218°C, assigned to the β‐sheet crystallization of silk fibroin, slightly shifted to a lower temperature by blending. The weight‐retention properties (TG) of the blend films were intermediate between those of the two constituents. The TMA response was indicative of a higher thermal stability of the blend films, even at low PAAm content (≤25%), the final breaking occurring at about 300°C (100°C higher than pure SF film). The peak of dynamic loss modulus of silk fibroin at 193°C gradually shifted to lower temperature in the blend films, suggesting an enhancement of the molecular motion of the fibroin chains induced by the presence of PAAm. Changes in the NH stretching region of silk fibroin were detected by FTIR analysis of blend films. These are attributable to disturbance of the hydrogen bond pattern of silk fibroin and formation of new hydrogen bonds with PAAm. The values of strength and elongation at break of blend films slightly improved at 20–25% PAAm content. A sea–island structure was observed by examining the air surface of the blend films by scanning electron microscopy. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 71: 1563–1571, 1999     

聚乳酸/丝素共混膜的制备及其性能

用分子量为10万的聚乳酸（PLLA）对丝素膜进行改性,研究不同的聚乳酸加入量对丝素膜性能的影响,对聚乳酸/丝素共混膜进行了一系列表征。万能电子试验机的测试结果表明,经聚乳酸改性后,丝素膜的断裂强度,断裂伸长率有了较大的改善,当加入聚乳酸占丝素质量为5%时,丝素膜的强度可达到27.1 MPa,伸长率达4.4%; 改性后的丝素膜的亲水性有一定程度降低,溶失率则明显减小,透汽透湿性也有所提高;红外光谱测试表明,改性后的丝素膜含有较多的β构象成分。     

丝素蛋白/聚丙烯酸共混膜仿生合成羟基磷灰石

将丝素蛋白(SF)与聚丙烯酸(PAA)共混,制备丝素蛋白/聚丙烯酸(SF/PAA)共混膜;然后将此共混膜进行改性及矿化处理后,放置于(37±0.5)℃人体仿生液中24h,诱导合成丝素蛋白/羟基磷灰石(SF/HA)复合材料.利用傅里叶红外(FTIR)、X-射线衍射(XRD)、环境扫描电镜(ESEM)以及X射线能谱(EDX...     

Chemical modification of silk with itaconic anhydride

Bombyx mori silk fibers were chemically modified by acylation with itaconic anhydride. The reactivity of the modifying agent toward silk fibroin was investigated on the basis of the amino acid analysis. We examined the physical properties, the structural characteristics, and the thermal behavior of modified silk fibers as a function of the weight gain. Silk fibers with a weight gain of 9%, corresponding to an acyl content of 68.9 mol/10⁵g, were obtained at the optimum reaction conditions for silk acylation (75°C for 3 h). The amount of basic amino acid residues (Lys, His, and Arg) decreased linearly as the weight gain increased. The alkali solubility increased proportionally with the weight gain, probably due to the dissolution of the modifying agent reacted with silk fibroin, and not to the degradation of the fibers induced by the chemical modification. The birefringence value, related to the molecular orientation, slightly decreased when the weight gain increased. The isotropic refractive index, associated with the crystallinity, increased when the weight gain ranged from about 5 to 7% and then remained unchanged. The moisture regain did not change regardless of the chemical modification, and the crease recovery behavior of modified silk fabrics did not show significant improvement. The thermal behavior of silk fibers was affected by the modification with itaconic anhydride. The decomposition temperature shifted up to 322°C, 10°C higher than the control silk fibers, suggesting a higher thermal stability induced by chemical modification.     

Structural characteristics of silk fibers treated with epoxides

Structural characteristics of the silk fibroin fiber-modified with epoxide treatment were elucidated by refractive index measurement, differential scanning calorimetry, and thermomechanical analysis and on the basis of strength–elongation measurements. The four epoxides used were glycidol (G), ethylene glycol diglycidyl ether (E), tolyl glycidyl ether (T), and resorcinol diglycidyl ether (R). The values of the isotropic refractive index of the silk fiber increased by the action of T or R. The position of the endothermic peak attributed to the thermal decomposition and the position of the onset of the contraction of each of the samples treated with epoxides shifted to higher temperature, suggesting the more thermal stability. However, the values of the molecular orientation and the crystallinity of the specimen evaluated from X-ray diffraction analysis remained unchanged regardless of the epoxide treatment. These experimental results have been interpreted in terms of the cross-links between the adjacent silk fibroin molecules and of the hydrogen bonds between the hydroxyl groups of the epoxide molecules attached to the side chains of the silk fibroin.     

A novel strategy for the construction of silk fibroin–SiO2 composite aerogel with enhanced mechanical property and thermal insulation performance

The practical application of silica aerogels is an enormous challenge due to the difficulties in improving both mechanical property and thermal insulation performance. In this work, silk fibroin was used as scaffold to improve the mechanical property and thermal insulation performance of silica aerogels. The ungelled SiO₂ precursor solution was impregnated into silk fibroin to prepare silk fibroin–SiO₂ composite aerogels via sol−gel method followed by freeze-drying. By virtue of the interfacial hydrogen-bonding interactions and chemical reactions between silk fibroin and silica nanoparticles, SiO₂ was well-dispersed in the silk fibroin aerogel and composite aerogels exhibited enhanced mechanical property. By increasing the loading of silk fibroin from 15 wt % to 21 wt %, the maximum compressive stress was enhanced from 0.266 to 0.508 MPa when the strain reached 50%. The thermal insulation performance of the composite aerogels was improved compared with pure silica aerogel, as evidenced that the thermal conductivity was decreased from 0.0668 to 0.0341 W∙m^‒1∙K^‒1. Moreover, the composite aerogels exhibited better hydrophobicity and fire retardancy compared to pure silica aerogel. Our work provides a novel approach to preparing silk fibroin–SiO₂ composite aerogels with enhanced mechanical property and thermal insulation performance, which has potential application as thermal insulation material.     

Fabrication and characterization of silk fibroin/poly(ethylene glycol)/cellulose nanowhisker composite films

The flexible and transparent composite films were fabricated by a mixture of silk fibroin (SF), poly(ethylene glycol), and mulberry cellulose nanowhiskers (CNWs). The CNWs were uniformly dispersed in the matrix when its content was as high as 12 w/w%. The tensile properties of composite films generally depended on the nanowhisker content, but significantly improved when compared to the pure SF film. DMA analysis revealed that the alpha transition temperature increased gradually with the increase of nanowhisker content, probably due to the formation of interactions between the nanowhiskers and the SF molecular chains, leading to the mobility reduction of the amorphous SF. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

纤维素-丝素复合膜的制备与表征

通过NaOH/尿素/硫脲/水新型溶剂溶解原生木浆纤维素得到纤维素溶液,并与丝素溶液混合制备纤维素-丝素复合膜.利用扫描电镜、红外光谱、X-射线衍射对复合材料的结构进行表征.SEM结果表明复合材料表面粗糙,比表面积较大,可以作为潜在的生物医用材料.IR和X-衍射结果表明再生纤维素与丝素分子之间存在着强烈的氢键作用,且二者相容性较好.