玉米秸秆微晶纤维素/聚乳酸复合膜的制备与性能

采用玉米秸秆微晶纤维素(CSCMC)作为增强材料, 生物可降解材料聚乳酸(PLA)作为基体, 制备了CSCMC/PLA复合膜材料, 并对复合膜的结晶度、热稳定性能、力学性能进行了测试。结果表明, 复合膜材料的热稳定性能和力学性能优于纯聚乳酸膜。当CSCMC的质量分数为10%时, 复合膜的热稳定性能和力学性能达到最佳, 与纯PLA膜相比, 起始分解温度提高了34.38 ℃, 拉伸强度提高了58.3%, 断裂伸长率提高了31.1%。      

乙二醛交联对明胶/PVA可生物降解复合膜性能的影响

采用流延成型法制备明胶/聚乙烯醇(Gel/PVA)复合膜,并以乙二醛为交联剂通过溶液交联法制备乙二醛交联的Gel/PVA复合膜,采用红外光谱(FTIR)、X-射线衍射(XRD)、差示扫描量热(DSC)、热重(TG)等表征交联前后复合膜的结构与性能,研究了交联剂用量对Gel/PVA复合膜力学性能及溶解性能的影响。结果表明,随着乙二醛用量的增加,Gel/PVA复合膜的拉伸强度呈先增加后逐渐降低的趋势,而断裂伸长率和溶解率则逐渐降低;乙二醛交联可提高复合膜的熔融温度及热稳定性;乙二醛交联显著影响Gel/PVA复合膜中分子间的氢键和化学结构。     

交联改性阴离子聚氨酯水分散体的制备与性能研究

由甲苯二异氰酸酯（TDI）、聚己内酯二醇（PCL）和二羟甲基丙酸（DMPA）反应,再与高醚化度甲醇醚化三聚氰胺甲醛树脂（HMMM）反应,制备了一种交联型阴离子水性聚氨酯。采用红外光谱对样品进行表征,并讨论了交联改性对聚氨酯乳液粒径分布、胶膜耐水性、力学性能、热稳定性及结晶度的影响。红外分析证实HMMM与聚氨酯发生了交联反应。当m（HMMM）∶m（—COOH）=2.25时,胶膜拉伸强度达到30.3MPa,吸水率为17.2%,吸乙醇率为10.9%,与水接触角为69.6°,Tmax（最快分解温度）为301.5℃,结晶度为1.10%。     

菠萝蜜种子淀粉可生物降解复合膜的制备及性能

针对传统塑料制品难降解、污染环境等问题,选用环境友好、可降解菠萝蜜种子淀粉(JFss)、羧甲基纤维素钠(CMC)和海藻酸钠(SA)为原料,采用涂膜工艺制备了一种可生物降解复合膜。研究JFss的用量对复合膜力学性能、耐水性、水溶性、透湿性的影响及复合膜润湿性随着时间变化规律,并对复合膜进行土埋降解性测试。采用SEM、FITR、XRD和TGA对复合膜形貌、结构和热稳定性表征。结果表明,JFss的添加使复合膜拉伸强度提高35.8%,耐水性提高4.16%,水溶性提高7.8%,水蒸汽阻隔性提高153.7%,且具有良好的润湿性、保湿性和生物降解性。另外,复合膜中CMC、SA、JFss各组分形成分子间氢键,具有良好的相容性和热稳定性。本方法复合膜制备的原料廉价、制备简单,可大规模生产,在生物降解材料领域具有潜在的应用价值。     

微米六方BN-KH550/聚丁二酸丁二醇酯耐热性复合膜的制备及性能

为进一步改善聚丁二酸丁二醇酯(PBS)的力学性能和耐热性能,采用硅烷偶联剂KH550改性微米六方氮化硼(h-BN),对PBS进行共混改性,通过熔融共混与开炼压延工艺制备了具有较高耐热性的h-BN-KH550/PBS复合膜。对h-BN-KH550粒子结构和复合膜的力学性能、聚集态结构、断面形貌、结晶性能及热稳定性进行了测试和表征。结果表明:与PBS相比,h-BN-KH550/PBS复合膜的力学性能得到改善,当KH550与h-BN质量比为2∶50、h-BN-KH550与PBS质量比为3∶50时,综合力学性能最优;h-BN-KH550粒子可在PBS中均匀分散;在PBS结晶过程中,h-BN-KH550作为成核剂,使PBS的结晶速率加快,结晶度增大;h-BN-KH550/PBS复合膜的热稳定性显著提高,当h-BN-KH550与PBS质量比为3∶50时,复合膜热分解过程中质量损失为5%、10%、50%时的温度(T5d、T10d、T50d)和热分解峰值温度(Tp)分别提高了30.0、22.6、9.5和10.0℃。     

木质素/PVA复合膜成膜基础研究

以可再生资源木质素磺酸钙和聚乙烯醇(PVA)为基料制备力学性能良好的木质素/PVA复合膜.采用单因素试验,研究了各因素对木质素/PVA复合膜力学性能及耐水性的影响.研究结果表明:甲醛、尿素和硼砂对复合膜力学性能和吸水率有显著影响.甲醛用量10g、尿素用量7g、硼砂用量2.5g时,复合膜的综合性能较好.     

超支化聚氨酯共混改性聚丁二酸丁二醇酯的性能

采用熔融共混与开炼压延制备聚丁二酸丁二醇酯(PBS)和羟基封端超支化聚氨酯(HBPU)的复合膜。使用X射线衍射(XRD)、差示扫描量热(DSC)、热重分析(TG)和万能试验机对其结晶性、热性能和力学性能进行了研究;采用土埋法在陕西花园土中对复合膜进行降解。结果表明,随着HBPU的增加,复合膜结晶度均有所降低,当HBPU的质量分数为6%时达到25.7%;DSC结果表明,HBPU提高了PBS的结晶温度;随着HBPU的增加,复合材料的热稳定性有所下降;在拉力测试中,复合材料的断裂伸长率得到了显著提高,6%时复合材料的断裂伸长率达到75%;复合膜降解后表面出现明显裂纹。HBPU对PBS改性,降低了PBS的结晶度,提高了复合材料的韧性。     

聚乙烯醇/海藻酸钠复合纳米纤维膜的制备和交联改性

采用静电纺丝技术制备聚乙烯醇/海藻酸钠复合纳米纤维膜,利用氯化钙乙醇溶液进行交联改性。研究复合纳米纤维制备、交联工艺对材料表面形貌、耐水性、热性能等的影响。结果表明:纳米纤维直径在200~500nm之间,纤维平均直径随海藻酸钠含量的增大而增大,复合纳米纤维结晶度随海藻酸钠含量的增大而降低,热稳定性随海藻酸钠含量的增大而下降。交联改性后复合纳米纤维材料耐水性提高,纤维形貌保持,纤维之间粘结增多,材料不发生熔融相转变,热稳定性下降。     

埃洛石纳米管/聚乙烯醇-淀粉复合膜的结构与性能

采用溶液流延法制备了埃洛石纳米管(HNTs)/聚乙烯醇(PVA)-淀粉复合膜,并利用SEM、XRD、DMA、TGA等分析测试手段研究了该复合膜的结构与性能。结果表明:随着HNTs含量增加,HNTs/PVA-淀粉复合膜的力学性能、热稳定性、耐水性能和紫外屏蔽性能均有提高。当HNTs与PVA-淀粉质量比为10%时,力学性能达到最佳,拉伸强度提高了22%。扫描电镜分析表明:HNTs能够以纳米尺度均匀分散于HNTs/PVA-淀粉复合膜中,且以单管状分布,与PVA-淀粉基体界面结合较好。动态力学性能分析表明:HNTs的加入对HNTs/PVA-淀粉复合膜的玻璃化转变温度影响不大,复合膜的储能模量升高,力学损耗下降。透光率测试结果表明:HNTs对HNTs/PVA-淀粉复合膜的透明性影响不大,而在紫外光区域(200~400nm),透光率随HNTs量的增加而下降。     

表面沉积铜纳米颗粒的细菌纤维素/壳聚糖交联复合膜的制备及其抗菌性能研究

通过戊二醛交联制备了细菌纤维素/壳聚糖复合材料,并采用磁控溅射技术在交联复合膜表面沉积铜(Cu)纳米颗粒。利用扫描电子显微镜观察纳米纤维膜表面形貌,采用傅里叶红外光谱仪、热重分析仪和X射线衍射仪比较交联复合前后以及镀铜前后复合膜基本化学结构、热稳定性和晶面结构的变化。通过能量色散X射线光谱对壳聚糖和铜在复合膜表面的分布情况进行表征。同时借助抗菌实验探究复合膜对金黄色葡萄球菌和大肠杆菌的抗菌能力。结果表明:壳聚糖与细菌纤维素发生了有效交联,改变了细菌纤维素的基本形貌、化学结构、晶体形态以及热学性能,并且镀铜后交联复合膜的抗菌性能得到了明显的提升(膜与细菌接触20min,对金黄色葡萄球菌和大肠杆菌的抗菌效果均达到了99.999%)。     

玉米淀粉醋酸酯的制备及成膜性能

以冰醋酸和醋酸酐为改性剂,浓硫酸作催化剂,合成了玉米淀粉醋酸酯,用傅立叶红外(FT-IR)、扫描电镜(SEM)、差示扫描量热法(DSC)、X射线衍射(XRD)分别对淀粉醋酸酯的结构、形貌、玻璃化转变温度和结晶度等进行测试和表征,分析了不同酯化度对淀粉的微观结构和热性能的影响。结果表明,淀粉经酯化后,结晶度降低,热性能提高,制备的酯化淀粉/聚乙烯醇的复合膜具有较好的力学性能和疏水性。     

EDC/NHS交联改性再生桑蚕丝素纳米纤维

用静电纺丝技术制备了再生桑蚕丝素纳米纤维,并用1-(3-二甲基氨基丙基)-3-乙基碳化二亚胺(EDC)和N-羟基丁二酰亚胺(NHS)进行交联改性,考察了交联改性前后,桑蚕丝素纳米纤维微观形貌及聚集态结构等的变化,采用扫描电镜(SEM)、X射线衍射(XRD)及红外光谱(FT-IR)等测试方法对纳米纤维进行表征。研究结果表明,经EDC/NHS交联改性后,纤维直径由250 nm增加到320 nm,纤维表面变粗糙,且纤维发生弯曲变形;丝素的结构以Silk II为主,并含有部分无规卷曲或Silk I构象;桑蚕丝纳米纤维的力学性能和亲水性有所提高,且交联改性后的纳米纤维具有良好的细胞相容性。     

Crosslinked hydroxypropyl cellulose films retaining cholesteric liquid crystalline order Part III Tensile creep behaviour in vacuo

The crosslinked and uncrosslinked hydroxypropyl cellulose solid films retaining the cholesteric liquid crystalline order were cast from the liquid crystalline solutions in methanol. The tensile creep behaviour of the films was determined and the deformability of the films and the size of the liquid crystalline domains in the films were discussed. There was a great difference in the creep behaviour between the crosslinked and uncrosslinked films; both kinds of the films exhibited a linear increase in strain with time, however, only the crosslinked films exhibited a constant region of strain after a given time. The constant strain depended on the crosslinking conditions: The strain decreased with increasing crosslinking agent concentration. The Eyring activation volume (V) could be evaluated. V for the crosslinked films was smaller than that for the uncrosslinked films; V decreased exponentially with increasing crosslinking agent concentration. Our data suggested that the inter-domain crosslinking occurred more or less. There was a critical stress where V changed; V in the lower stress region was greater than that in the higher stress region.     

Fabrication and characterization of biodegradable composites based on microfibrillated cellulose and polyvinyl alcohol

Microfibrillated cellulose (MFC) based thin membrane-like fully biodegradable composites were produced by blending MFC suspension with polyvinyl alcohol (PVA). Desired MFC content in the composites could be easily obtained by varying the PVA solution concentration. Chemical crosslinking of PVA was carried out using glyoxal to increase the mechanical and thermal properties of the composites as well as to make the PVA partially water-insoluble. Examination of composite surfaces and fracture topographies indicated that the MFC fibrils were well bonded to PVA and uniformly distributed. Infrared spectroscopy showed that acetal linkages could be formed in the MFC–PVA composites by a glyoxal crosslinking reaction. Sol–gel and swelling results indicated that crosslinking reaction made PVA partially insoluble and reduced its swelling ability. The MFC–PVA composites had excellent tensile properties which were further enhanced by crosslinking. Thermogravimetric analysis (TGA) showed higher thermal stability for MFC–PVA composites compared to PVA. The crosslinked MFC–PVA composites showed even higher thermal stability. Differential scanning calorimetry (DSC) indicated that crosslinking increased the glass transition temperature and reduced melting temperature and crystallinity of PVA in MFC–PVA composites. Results also indicated that nano- and micro-fibrils in MFC inhibit the crystallization of PVA. These composites could be good candidates for replacing today’s traditional non-biodegradable plastics.     

Collagen- and gelatine-based films sealing vascular prostheses: evaluation of the degree of crosslinking for optimal blood impermeability

The stiffness as well as the biodegradation rate of collagen and gelatine products can be modulated by performing a number of crosslinking treatments. In many biomedical applications, an optimal degree of crosslinking seems to exist, depending on the mechanical and/or biosynthesis properties of the host site. The aim of this study was to evaluate the optimal degree of crosslinking of collagen and gelatine films, to be used as sealants for vascular prostheses. Various crosslinking treatments, including exposure to aldehydes, dehydrothemal treatment, carbodiimide crosslinking and combinations of them, were performed on collagen and gelatine films, and the resulting increases in stiffness, degree of crosslinking and denaturation temperature were evaluated. Analogue crosslinking treatments were also performed on sealed prostheses, which were then tested for blood leakage. The experimental results showed that a good blood impermeability of both collagen and gelatine films was obtained for crosslinking density of about 1.2–1.3 × 10⁻⁵ mol/cm³, which could be yielded by a dehydrothermal crosslinking treatment (DHT). In particular, dehydrothermally treated gelatine-coated prostheses were found to perform better than analogue collagen-coated ones. The presence of glycerol in crosslinked collagen films was found to have plasticizing effects, which are likely to facilitate blood impermeability, and to increase the thermal stability of collagen.     

Silane-crosslinking of recycled low-density polyethylene/wood composites

The aim of this work was to study silane-crosslinking of recycled low-density polyethylene wood composites and its effect on composites properties. The composites were produced in a one-step twin-screw extrusion process and the silane–peroxide solution was pumped into the extruder. Degree of crosslinking, mechanical properties, short-term creep, fractured surfaces and nature of crosslinking were studied to understand the relationship between composite structure and properties. The results showed that crosslinked composite strength, toughness and creep resistance were improved compared to uncrosslinked composites. The flexural strength was doubled compared to uncrosslinked samples and the creep strain was reduced. The crosslinked composites stored under room conditions showed the highest strength, whereas storage in a sauna resulted in a higher degree of crosslinking. The Fourier transform infrared spectroscopy indicated formation of silane-bridges between wood and polyethylene, accordingly improving the interfacial adhesion between the wood and LDPE. The low concentration of peroxide in the silane-solution was shown to be a preferred composition to limit unintentional crosslinking during the process.     

氧化淀粉胶黏剂的交联改性及其性能研究

用玉米淀粉与过硫酸铵反应制备了氧化淀粉胶黏剂,再与二羟甲基双氰胺(DMDCD)进行交联反应,制备了一种交联改性氧化淀粉胶黏剂。采用红外光谱对样品进行了表征,并讨论了交联改性对氧化淀粉胶黏剂耐水性和贮存稳定性的影响。实验结果表明:DMDCD改性提高了淀粉胶黏剂的耐水性与贮存稳定性;当过硫酸铵质量分数为淀粉质量的1.5%,DMDCD质量分数为淀粉质量的3%时,交联改性氧化淀粉胶黏剂的贮存稳定性在45 d以上,其耐水时间、黏度分别为102 h和1680 mPa.s;红外分析证实了DMDCD与氧化淀粉发生了交联反应。     

MAH对干法酯化淀粉/PLA复合材料性能的影响

以玉米淀粉和马来酸酐(MAH)为原料,通过干法合成MAH酯化淀粉,通过熔融挤出法制备酯化淀粉/聚乳酸(PLA)复合材料.研究了MAH用量对复合材料结晶度和相容性的影响,同时考察了相容性和结晶度的变化对复合材料热性能、熔融流动性能、力学性能、耐水性能和流变性能的影响.FTIR结果证明通过干法成功合成了MAH酯化淀粉.酯化淀粉的取代度随MAH用量增多逐渐增大,反应效率高达90%.XRD和DSC结果表明:随着MAH用量增多,酯化淀粉/PLA复合材料的结晶度逐渐降低,淀粉和PLA的相容性逐渐提高.结晶度的降低和相容性的提高使复合材料的玻璃化转变温度逐渐降低,熔融流动性提高,耐水性提高.在力学性能和流变性能受相容性和结晶度的共同影响下,酯化淀粉中MAH用量从0增加到1.0wt%时,复合材料拉伸强度、弯曲强度、储能模量和复数黏度都逐渐增大,MAH用量超过1.0wt%后,性能逐渐降低.     

纳米纤维素晶体和柠檬酸改性聚乙烯醇薄膜的制备及性能

以球形纳米纤维素晶体(NCC)作增强相、柠檬酸作交联剂对聚乙烯醇(PVA)进行改性,制备了PVA/NCC纳米复合薄膜和柠檬酸交联PVA/NCC纳米复合薄膜。通过热重分析、差热分析、吸水实验和拉伸实验考察了NCC的添加和柠檬酸的交联对薄膜热性能、耐水性和力学性能的影响。结果表明,与纯PVA薄膜相比,改性PVA薄膜的起始分解温度升高、熔融/结晶峰向高温方向移动、吸水率降低;只用NCC或柠檬酸对PVA改性时,所得PVA/NCC纳米复合薄膜、柠檬酸交联PVA薄膜的力学性能均对环境湿度敏感;同时用NCC(m(NCC)/m(PVA)=6/100)和柠檬酸(m(柠檬酸)/m(PVA)=3/100或m(柠檬酸)/m(PVA)=4.5/100)对PVA改性时,所得柠檬酸交联PVA/NCC纳米复合薄膜的力学性能不随环境湿度变化。