马来酸酐接枝共聚物增容聚乳酸/改性淀粉复合材料的制备与性能研究

采用熔融共混方法制备聚乳酸/改性淀粉复合材料。研究了不同含量的马来酸酐接枝共聚物对聚乳酸/改性淀粉复合材料力学性能的影响,并且采用差示扫描量热(DSC)仪和扫描电子显微镜(SEM)对复合材料的微观结构进行分析。结果表明,马来酸酐接枝共聚物的加入改善了聚乳酸与淀粉的相容性,提高了复合材料的力学性能,添加量为0.5份时复合材料的拉伸强度提高了61.6%,断裂伸长率提高了53.1%,弯曲强度提高了104.7%,同时还能提高复合材料的热变形温度和耐水性;改性淀粉与聚乳酸两相紧密连接。     

长链型超支化聚合物对PLA/PPC共混体系的增容改性研究

将“一步法”合成的超支化聚酯进行接枝改性,得到末端带有大量脂肪酸长链的超支化聚合物（长链型超支化聚合物,LCHBP）,并采用红外光谱、核磁共振、羟值滴定等方法对其进行表征。以LCHBP为改性剂,对聚乳酸（PLA）/聚碳酸亚丙酯（PPC）进行不同程度的改性,制备了PLA/PPC/LCHBP熔融共混物,采用差示扫描量热仪、电子万能试验机、扫描电镜等,对其热性能、力学性能、断面形貌等进行表征。结果表明,加入不同含量的LCHBP后,共混体系的ΔTg出现不同程度降低,表明LCHBP的加入改善了PLA与PPC的相容性;与PLA/PPC体系相比,LCHBP的加入可使共混体系在保持拉伸强度基本不变的情况下,大幅提升断裂伸长率和冲击强度,其中当LCHBP的加入量为2.0 %时,冲击强度提高61 %,断裂伸长率提高367 %。     

丝素/聚乳酸静电纺丝的研究

以具有一定生物活性、细胞黏附性能好的丝素蛋白与降解性能优良的聚乳酸复合,以静电纺丝方法形成20%丝素与80%聚乳酸的丝素/聚乳酸共混纤维非织造网。通过扫描电子显微镜研究其形态,X-射线衍射、红外光谱等分析研究其聚集态结构变化。研究表明:丝素/聚乳酸静电纺的纤维直径与电压、接收距离大小和后处理方法有关;不同后处理方法对丝素/聚乳酸静电纺纤维的结晶结构有较大影响。     

淀粉对水转印用PVA膜的改性研究

以聚乙烯醇1788(PVA)作为原料,以丙三醇为增塑剂,加入0%~2.5%的淀粉,对水转印PVA膜进行了改性研究。结果表明,加入淀粉后,PVA溶液的粘度增大,膜的溶解时间变长,水上伸长率变小,含水率变小,扯断强度增强,形变缩小;通过膜表面观察,发现淀粉在膜中以聚集颗粒状态存在。研究发现,在淀粉加入PVA后使水转印膜的水溶性得到很大改善。     

表面处理剂对聚乳酸/核桃壳粉复合材料性能的影响

研究核桃壳粉(WSP)含量对复合材料力学性能影响,结果发现,WSP的最佳添加量为1%,此时材料的断裂伸长率提高了15.69%。在此最佳用量的基础上,采用钛酸酯、硅烷偶联剂、十八胺和Na OH对WSP进行表面处理,从而研究不同的表面处理对聚乳酸(PLA)/WSP复合材料性能的影响。通过拉伸强度、熔体流动速率(MFR)以及红外光谱检测比较改性效果。结果表明:用钛酸酯改性后,材料的拉伸强度达到67.82 MPa,比未处理材料的拉伸强度提高了9.80 MPa,断裂伸长率提高了18.15%;碱处理后,PLA/WSP复合材料的MFR最多提高了120%,流动性有了很大的改善。     

纳米二氧化硅/淀粉/聚乳酸三元复合材料力学性能研究

主要是对淀粉进行增韧改性,研究共混改性后对力学性能的影响。首先是制备不同含量的淀粉/聚乳酸共混材料,通过双螺杆挤出机进行挤出、造粒,在通过注塑机将共混材料注塑成样条,对注塑的样条进行力学性能测试,检测其拉伸强度、断裂伸长率。选出性能做好的一组材料,得到最佳的加工工艺。研究结果表明:在淀粉/聚乳酸共混体系中,随着偶联剂与纳米二氧化硅的增加,共混体系出现了曲线形的变化,随着聚乳酸含量的增加断裂伸长率升高再降低,由此得到了偶联剂、纳米二氧化硅的最佳配比,淀粉与甘油含量的最佳配比。由力学性能得到淀粉材料通过改性后的力学性能优于没有改性前,有明显的断裂伸长率,缓解了全淀粉断裂伸长率低的特点。     

熔融共混立构复合聚乳酸的制备及其性能研究

采用微型双螺杆挤出机制备了立构复合聚乳酸(scPLA),并添加聚己二酸/对苯二甲酸丁二酯(PBAT)对其进行增韧改性。采用X射线衍射(XRD)、差示扫描量热法(DSC)、维卡软化点分析(VST)、拉伸和冲击试验等对其进行了测试。结果表明当左旋聚乳酸和右旋聚乳酸比例为1∶1时,能够形成完全的立构复合(SC)晶体结构,不含有同质结晶(HC)晶体结构,且结晶度最高;熔点高达230℃,比聚乳酸均聚物提高了50℃;维卡软化温度高达174. 2℃,比聚乳酸均聚物提高了115℃;力学性能也有了一定提升,但是仍然发生脆性断裂。加入PBAT进行增韧后,样品的韧性得到较大改善,发生塑性变形,屈服强度为68. 6 MPa,断裂伸长率达到9. 8%,冲击强度提高到36. 5 k J/m^2,且断裂强度(77. 7 MPa)没有损失。     

生物可降解聚乳酸的无卤阻燃与增韧改性研究

选用次磷酸铝(AHP)与聚乳酸(PLA)熔融挤出共混制备无卤阻燃PLA复合材料,采用氮系阻燃剂(MCA)与次磷酸铝进行复配,并通过添加增韧剂乙烯-甲基丙烯酸酯-甲基丙烯酸缩水甘油酯共聚物(EMA-GMA)改善阻燃PLA的冲击性能。研究结果表明,随着磷系阻燃剂AHP用量的增加,聚乳酸的阻燃性能提高;当AHP添加量为20%时,阻燃PLA复合材料的氧指数为29.0%,UL94测试达到V-0级,AHP与MCA有一定的阻燃协同作用。随增韧剂EMA-GMA用量的增大,阻燃聚乳酸复合材料的韧性较未改性的阻燃聚乳酸材料有明显增加。当EMA-GMA质量分数为15%时,改性聚乳酸复合材料的断裂伸长率比PLA阻燃复合材料提高5倍;缺口冲击强度增加了54.8%,无缺口冲击强度增加了230%。     

静电纺丝PLA/丝素复合纤维膜的结构和性能

以氯仿、丙酮为混合溶剂,制得质量分数为5%的聚乳酸(PLA)纺丝液,经静电纺丝制备PLA纤维膜;以98%的甲酸为溶剂,制得丝素纺丝液,在PLA纤维膜上喷射丝素纺丝液制成PLA/丝素复合纤维膜.采用扫描电镜观察其形貌结构,并测定其微细结构、力学性能、溶失率及生物性能.结果表明:PLA/丝素复合纤维膜呈规整排列的多孔网状结构.与丝素膜相比,PLA/丝素复合纤维膜的丝素蛋白转向β折叠结构,断裂比功提高18倍,水中溶失率降低3倍,更有利于人脐静脉内皮细胞在纤维膜上的生长.     

丝素/羧甲基壳聚糖共混膜的结构性能探讨

将含有甘油和戊二醛的丝素与羧甲基壳聚糖按一定比例混合,制得丝素/羧甲基壳聚糖共混膜,对共混膜的结构与性能进行了探讨。结果表明:随着羧甲基壳聚糖含量的增加,共混膜的透气率增大,加入交联剂戊二醛有效地改善了共混膜的力学性能,但其透气率有所降低;当丝素与羧甲基壳聚糖的质量比为4/1时,共混膜的断裂强度最大,力学性能较好,共混膜相容性较好,其断面光滑、致密。制备丝素/羧甲基壳聚糖共混膜的较佳条件为:丝素中的甘油质量分数为15%,戊二醛质量分数为0.075%,丝素与羧甲基壳聚糖质量比为4/1。     

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...     

Fibroin membrane preparation and stabilization by polyethylene glycol diglycidyl ether

Membranes prepared by drying aqueous Bombyx mori silk fibroin (SF) solution and modified silk fibroin (MSF) solutions, prepared by adding the low molecular weight crosslinking agent, polyethylene glycol diglycidyl ether (PEGDE) MW 526, 0–10% w/w, were investigated by Scanning Electron Microscopy (SEM), Fourier Transform Infrared (FTIR) spectroscopy, and UV–vis spectroscopy. Weight gain in aqueous solutions and their mechanical properties (tensile strength, elongation, and Young's modulus) were then characterized. SEM measurements revealed greater porosity in MSF membranes. IR spectra showed transformation from the largely α‐helical/random coil structures in SF membranes to predominantly β‐sheet in MSF membranes. Results from UV–vis spectroscopy showed that the MSF membranes were largely insoluble within the pH range of 4–10. Water absorbability of the MSF membranes improved with increasing the amounts of cross‐linker, up to 4%. The MSF membranes showed greater pliability and tenacity, but lower tensile strength, with increasing PEGDE concentrations. In the wet condition, PEGDE levels up to 4% can improve both tensile strength and tenacity of the MSF membrane, but higher levels (up to 10%) did not significantly change these properties. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci 2008     

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     

丝素/羧甲基壳聚糖共混膜的结构与性能

利用丝素(SF)与羧甲基壳聚糖(CMCS)共混制取不同比例的SF/CMCS共混膜。研究了CMCS诱导的丝素构象转变行为,测试了共混膜的吸湿性、透湿性和保水性。当CMCS的质量分数为5%时,共混膜中丝素的构象以β-折叠为主;当CMCS的质量分数为10%时,共混膜中丝素的构象由β-折叠向α-螺旋发生转变;当CMCS的质量分数达到15%时,共混膜中丝素的构象向无规卷曲发生转变。当CMCS质量分数小于15%时,共混膜中SF与CMCS具有良好的相容性,溶胀度较小,吸湿性随CMCS含量的增加而迅速降低。     

Biodegradable nanofibrous membrane of zein/silk fibroin by electrospinning

BACKGROUND: Electrospinning of natural polymers offers a promising approach to generate nanofibers with a similar fibrillar structure to that of native extracellular matrix. In the present work, zein/silk fibroin (SF) blends were electrospun with formic acid as solvent to fabricate bicomponent nanofibrous scaffolds for biomedical applications. RESULTS: The zein/SF electrospun nanofibers had a smaller diameter and narrower diameter distribution than pure zein nanofibers, and the average diameter gradually decreased from 265 to 230 nm with increasing SF content in the blend. The predominant presence of α‐helix zein structure and random coil form of silk I in blend fibrous membranes was confirmed from Fourier transform infrared spectral and wide‐angle X‐ray diffraction data, while conversion to the β‐sheet structure of SF was also detected. The tensile strength of the zein/SF fibrous membranes was improved as the content of SF in the blend fibers increased. A preliminary study of in vitro degradation and cytotoxicity evaluated by MTT assay indicated that biodegradable zein/SF fibrous membranes did not induce cytotoxic effects in an L929 mouse fibroblast system. CONCLUSION: Biodegradable zein/SF fibrous membranes with good mechanical properties and cytocompatibility combine the beneficial characteristics of the individual components and may be useful for biomedical applications. Copyright © 2009 Society of Chemical Industry     

聚乙二醇缩水甘油醚改性丝素蛋白研究

采用聚乙二醇400与环氧氯丙烷合成聚乙二醇缩水甘油醚(PEGO)并对丝素蛋白(SF)进行改性,采用红外光谱、X射线衍射、差式量热扫描、扫描电镜和物理性能测试对共混膜的结构和性能进行表征,表明PEGO的加入使得丝素蛋白从silkⅠ结构向silkⅡ构象转变,而当m(PEGO)∶m(SF)>50%的时候,共混膜的二级结构却呈现相反变化。共混膜的含水量由共混膜的表面粗糙度和亲水性决定,在m(PEGO)∶m(SF)<50%时,其含水量随粗糙度增加而减少;在m(PEGO)∶m(SF)>50%时,随着PEGO的增加,SF/PEGO共混膜的含水量增加。当m(PEGO)∶m(SF)=50%时,共混膜SP50具有最好的热稳定性和良好的机械性能。     

Preparation of Porous Poly(vinyl alcohol)‐Silk Fibroin (PVA/SF) Blend Membranes

The relation of PVA/SF blending ratio and freezing temperature with the morphology, fine structure and properties of porous PVA/SF blend membranes prepared by means of freeze drying was investigated. It was indicated that the pore diameter of the blend membranes remarkably decreased and the pore density obviously increased with increasing proportion of PVA or decreasing freezing temperature. With increasing proportion of PVA, the crystallinity of the blend membrane increased. When the blend ratio of PVA/SF was larger than 25/75 or 50/50, the strength, the elongation and the initial tensile modulus of the blend membrane increased somewhat and the compressibility decreased a little with increasing proportion of PVA or decreasing freezing temperature. Therefore, by increasing the proportion of PVA or decreasing the freezing temperature, porous SF/PVA blend membranes could be prepared which had smaller pore diameter, larger pore density, higher crystallinity, strength and elongation.     

Silk fibroin/cellulose blend films: Preparation,structure, and physical properties

This article deals with the preparation and characterization of silk fibroin (Bombyx mori)/cellulose blend films. Following dissolution with a metal complex solution, the average molecular weight of silk fibroin slightly decreased. While cellulose was almost unaffected. After coagulation and washing, transparent films were obtained by blending fibroin and cellulose in all proportions. The crystalline structures of regenerated fibroin and cellulose were β-form and cellulose II, respectively, as shown by the characteristic x-ray diffraction profiles. Density values increased with cellulose content, though less than expected from a pure additive behavior. Moisture regain increased following the addition of a small amount of cellulose to silk fibroin. The mechanical properties showed that both strength and elongation at break of silk fibroin films were improved by blending with cellulose. IR spectra exhibited changes in the skeletal frequences of silk fibroin, suggesting the occurrence of intermolecular interactions between fibroin and cellulose through hydrogen bond formation. © 1995 John Wiley & Sons, Inc.     

Fabrication of Chitosan/Silk Fibroin Composite Nanofibers for Wound-dressing Applications

Chitosan, a naturally occurring polysaccharide with abundant resources, has been extensively exploited for various biomedical applications, typically as wound dressings owing to its unique biocompatibility, good biodegradability and excellent antibacterial properties. In this work, composite nanofibrous membranes of chitosan (CS) and silk fibroin (SF) were successfully fabricated by electrospinning. The morphology of electrospun blend nanofibers was observed by scanning electron microscopy (SEM) and the fiber diameters decreased with the increasing percentage of chitosan. Further, the mechanical test illustrated that the addition of silk fibroin enhanced the mechanical properties of CS/SF nanofibers. The antibacterial activities against Escherichia coli (Gram negative) and Staphylococcus aureus (Gram positive) were evaluated by the turbidity measurement method; and results suggest that the antibacterial effect of composite nanofibers varied on the type of bacteria. Furthermore, the biocompatibility of murine fibroblast on as-prepared nanofibrous membranes was investigated by hematoxylin and eosin (H&E) staining and MTT assays in vitro, and the membranes were found to promote the cell attachment and proliferation. These results suggest that as-prepared chitosan/silk fibroin (CS/SF) composite nanofibrous membranes could be a promising candidate for wound healing applications.     

聚酰胺类热塑性弹性体含量对PLLA/三元聚酰胺共混物形态和性能的影响

以聚酰胺类热塑性弹性体（TPAE）为增容剂增容左旋聚乳酸（PLLA）与三元聚酰胺共混物,采用扫描电子显微镜（SEM）、差热扫描量热仪（DSC）、X射线衍射仪（XRD）等研究了TPAE含量对PLLA/三元聚酰胺（70/30,质量比,下同）共混物的形态、力学性能和热性能的影响。力学性能研究结果表明,添加TPAE后,PLLA/三元聚酰胺共混物的拉伸强度、断裂伸长率、缺口冲击强度显著提高,TPAE含量为5份时,共混物的断裂伸长率为370 %,缺口冲击强度为90 J/m,拉伸强度为39 MPa;SEM分析表明,添加TPAE后,共混物中三元聚酰胺相的粒径显著变小;DSC与XRD分析结果表明,TPAE含量对PLLA/三元聚酰胺共混物的熔融行为和结晶行为无明显影响,而共混物拉伸后,其结晶度显著提高。