纳米纤维素增强聚乙烯醇/水性聚氨酯静电纺膜的研究

采用TEMPO(2,2,6,6-四甲基哌啶氧化物自由基)氧化纤维素纳米纤维(TOCNs)作为聚乙烯醇(PVA)/水性聚氨酯(WPU)静电纺膜的增强剂。研究中使用拉伸实验研究TOCNs的增强作用,此外还使用扫描电子显微镜、红外光谱仪、热重分析仪及差示扫描量热仪等对静电纺膜进行结构性能表征。扫描电镜观察发现当纳米纤维素加入量为5%(质量分数)时,其在聚合物基质中分散良好,所得静电纺纳米纤维保持了良好的形态。此外,加入5%(质量分数)的纳米纤维素能够将材料的抗张强度提高44%,且纳米纤维素的加入对材料的热稳定性也有一定的改善,纳米纤维素起到一种纳米填料的效果。鉴于PVA、WPU、TOCNs均为亲水性,无毒且具有生物相容性的物质,所得静电纺膜在组织支架及伤口护理材料等方面具有潜在应用。     

油茶果壳氧化纳米纤维素-海藻酸钠复合薄膜的 制备及性能

以油茶果壳为研究对象,利用碱煮漂白法提取纤维素,并利用2, 2, 6, 6-四甲基哌啶-1-氧自由基（TEMPO）氧化法,制备TEMPO氧化纳米纤维素（TOCNs）,经离子交联法建立TEMPO氧化纳米纤维素与海藻酸钠（SA）的半互穿交联网络,制得综合性能优异的复合薄膜。对复合薄膜进行了结构表征,力学性能测试,热稳定性和阻氧性能测试。实验结果表明： TOCN/SA薄膜表面平整,有致密的内部层状结构,适量SA和TOCNs具有较好的相容性。当SA的掺杂质量分数达到42%时,TOCN/SA薄膜的断后伸长率较TOCN薄膜增长138.6%,氧气透过率降低15.55%,碳残余量较TOCN薄膜提高21.4%。因此,油茶果壳氧化纳米纤维素TOCN/SA复合薄膜,具有良好的力学性能和热稳定性,同时保持了较好的阻氧性能。     

氧化纳米纤维素增强再生纤维素全纤维素复合薄膜的制备及性能

以2,2,6,6-四甲基哌啶-氮-氧化物(TEMPO)氧化松木粉纳米纤维素(TOCNs)为增强相、α-纤维素粉制备再生纤维素(RC)为基体,采用溶胶-凝胶法制备氧化纳米纤维素增强再生纤维素(TOCNs/RC)全纤维素复合薄膜。对不同TOCNs添加量下TOCNs/RC全纤维素复合薄膜的力学性能、光学性能、氧气阻隔性能和热稳定性能进行研究,并通过FTIR、SEM、TEM、XRD和流变仪对TOCNs和TOCNs/RC全纤维素复合薄膜的结构、形貌及纤维素溶液流变性能进行表征。结果表明,TOCNs添加量对TOCNs/RC全纤维素复合薄膜的力学性能有显著影响,当TOCNs添加量(与纤维素基体的质量比)为1.0%时,TOCNs/RC全纤维素复合薄膜的拉伸强度和断裂能分别可达134.3 MPa和21.51 MJ·m?3,具有最佳的综合力学性能;TOCNs/RC全纤维素复合薄膜的透光率随TOCNs添加量的增加而下降,雾度随TOCNs添加量的增加而增大,但仍保持较高的透光率(>85%)和较低的雾度(<14%);TOCNs/RC全纤维素复合薄膜还具有优异的氧气阻隔性,TOCNs添加量为1.6%时,其透氧系数仅为1.47×10?17cm3·cm/cm2·s·Pa。TOCNs/RC全纤维素复合薄膜有优于一般塑料薄膜的拉伸强度和氧气阻隔性,并有可媲美于塑料薄膜的透明度,可作软包装复合材料的强度层和阻隔层,在绿色高性能包装材料领域具有广阔的应用前景。      

TEMPO氧化修饰的天然多糖纳米纤维增强复合材料及其功能化研究进展

纤维素和几丁质具有相似的结构，是自然界中储量丰富的两类天然多糖。经2, 2, 6, 6-四甲基哌啶氮氧化物(TEMPO)氧化修饰制备的纤维素和几丁质纳米纤维，不仅具有多糖类物质的良好亲水性、生物可降解性、生物相容性及丰富的官能团(羟基、羧基、乙酰氨基和氨基等)所带来的特定化学性质，而且还具有纳米纤维的纳米尺寸效应、大比表面积、高表面活性、高结晶度和手性液晶相结构等特点，已成为生物质纳米材料领域的研究重点之一。本文对TEMPO氧化修饰制备天然多糖纳米纤维的方法及剥离机制进行了总结，同时重点综述了TEMPO氧化修饰的天然多糖纳米纤维在薄膜、凝胶、导电、医用、电磁屏蔽及环境等复合材料的增强和功能升级等方面的研究进展，强调了纤维素和几丁质纳米纤维的官能团及纳米尺寸在复合材料中的增效机制。最后，对天然多糖纳米纤维的发展方向及其在各领域应用的机遇与挑战进行了展望。     

纳米纤维素在功能纳米材料中的应用进展

纳米纤维素分为纤维素纳米纤维(CNF)、纤维素纳米晶体(CNC)、细菌纳米纤维素(BNC)。CNF主要由机械法和2,2,6,6-四甲基哌啶-1-氧基(TEMPO)介导氧化法制备,呈微纤丝状。CNC主要由酸水解法制备,呈棒状或针状颗粒。BNC由细菌合成,呈纳米纤维网络状。文中综述了纳米纤维素在凝胶、仿生复合材料、导电材料、电极材料、导热材料、电磁屏蔽材料、压电材料及传感器材料领域的应用现状,并对其功能纳米材料未来发展的方向进行了展望。     

C6位氧化细菌纤维素的制备及结构表征EI北大核心CSCD

为了改善细菌纤维素的生物降解性,采用2,2,6,6-四甲基-1-哌啶酮(TEMPO)/Na Br/Na Cl O体系对细菌纤维素进行氧化,探讨了Na Cl O和TEMPO用量及反应时间对反应的影响,利用电导滴定、红外光谱、13C-核磁共振、X射线衍射和透射电子显微镜对固体产物进行了表征。结果显示,细菌纤维素取1 g,0.6 mol/L Na Cl O 8 m L,TEMPO 0.016 g,Na Br0.1 g,反应8 h可以获得羧基含量较高的氧化细菌纤维素(羧基含量为1.04 mol/kg)。红外光谱和13C-核磁共振波谱共同证明细菌纤维素C6位伯醇羟基被选择性催化氧化成了羧基,X射线衍射结果表明氧化后细菌纤维素的结晶结构没有发生明显改变,TEM结果显示氧化后细菌纤维素的纳米网状结构得到保留。利用TEMPO/Na Br/Na Cl O体系可以获得氧化度较高的微观结构无损伤的氧化型细菌纤维素。     

纤维素的选择性氧化及发展趋势

纤维素是自然界取之不尽用之不竭的可再生资源,改变纤维素的结构,便赋予其许多新的功能。选择性氧化纤维素成为纤维素科学与纤维素基新材料研究领域中的热点。综述了纤维素的各种选择性氧化体系,重点介绍了TEMPO/NaClO/NaBr选择性氧化体系的反应条件、反应机理及最新的研究进展,并分析了氧化纤维素应用及发展前景。     

醋酸纤维素纳米纤维的制备及应用进展

静电纺丝技术可制备聚合物纳米纤维。由于纳米纤维特有的表面效应、小尺寸效应及量子尺寸效应等特点,在各领域的应用受到广泛重视。醋酸纤维素作为一种重要的纤维素衍生物,在塑料、化纤工业中应用比较普遍,近年来采用静电纺丝技术制备醋酸纤维素纳米纤维的研究成果逐渐增多。笔者综述了采用静电纺丝方法制备醋酸纤维素纳米纤维的技术进展情况,以及醋酸纤维素纳米纤维的应用进展,同时对纤维素衍生物纳米纤维的制备方法与应用进行了展望,以期进一步扩大醋酸纤维素的应用领域。     

TEMPO氧化体系对废纸浆纤维的氧化改性

目的利用2,2,6,6-四甲基哌啶氧化物自由基(TEMPO)/NaClO/NaBr氧化体系改善废纸浆纤维成纸的性能。方法以废纸浆为原料,在碱性条件下采用TEMPO/NaClO/NaBr氧化体系对纤维进行选择性氧化,得到不同羧基含量的氧化废纸浆,通过纤维形态分析仪及化学分析法对纤维形态和羧基含量进行分析和测定;将氧化废纸浆、氧化废纸浆与原浆进行抄片和配抄,对手抄片的强度性能进行检测和分析;从经济效益出发,研究氧化体系中TEMPO及NaBr的循环使用次数对纸张强度性能的影响。结果随着NaClO用量的增加,废纸浆纤维的羧基含量增加;纤维长度、宽度和粗度有所降低;纸张抗张强度和环压强度增长较为明显;NaClO和NaBr循环使用2次后纸张的强度性能有所降低,但降低幅度不大。结论TEMPO氧化体系可用于废纸浆的氧化,改善废纸浆的性能。NaClO和NaBr的循环使用能够降低生产成本。     

利用原子力显微镜研究预处理对木棉纤维/CdS纳米复合材料形貌结构的影响

对木棉纤维进行预处理,然后用预处理后木棉纤维与CdS进行原位复合制备木棉纤维/CdS纳米复合材料。利用扫描电镜(SEM)和原子力显微镜(AFM)对复合材料表面形貌结构进行了观察。用AFM定量地分析了预处理方法对木棉纤维/CdS纳米复合材料表面超微三维结构的影响。研究表明,相比未处理木棉纤维,预处理后木棉纤维/CdS纳米复合材料上CdS粒子的吸附量增大,且经过TEMPO氧化处理的木棉纤维所复合的CdS粒子的分布最均匀,粒径最均一。对于基于植物质纤维素资源为原料的纤维素/无机纳米复合材料的制备及其结构表征具有重要的参考价值。     

Diverse nanocelluloses prepared from TEMPO-oxidized wood cellulose fibers: Nanonetworks,nanofibers, and nanocrystals

When wood cellulose fibers are oxidized with NaClO and catalytic amounts of 2,2,6,6-tetramethylpiperidine-1-oxyl (TEMPO) and NaBr in water at pH 10, significant amounts of sodium carboxylate groups (≤1.7 mmol/g) are introduced into the oxidized celluloses. The original fibrous morphologies and cellulose I crystal structures are unchanged by oxidation. The TEMPO-oxidized cellulose fibers can be converted to partially fibrillated nanonetworks, completely individualized cellulose nanofibers with high aspect ratios, and needle-like cellulose nanocrystals with low aspect ratios by controlling the conditions of mechanical disintegration in water. It is therefore possible to prepare diverse nanocelluloses with different morphologies and properties from the same TEMPO-oxidized cellulose fibers, for various end uses and applications. All TEMPO-oxidized nanocelluloses contain large amounts of carboxylate groups. These provide scaffolds for versatile surface modification of nanocelluloses by simple ion exchange of sodium for other metal ions and alkylammonium ions.     

Nanocellulose for Energy Storage Systems: Beyond the Limits of Synthetic Materials

The ongoing surge in demand for high‐performance energy storage systems inspires the relentless pursuit of advanced materials and structures. Components of energy storage systems are generally based on inorganic/metal compounds, carbonaceous substances, and petroleum‐derived hydrocarbon chemicals. These traditional materials, however, may have difficulties fulfilling the ever‐increasing requirements of energy storage systems. Recently, nanocellulose has garnered considerable attention as an exceptional 1D element due to its natural abundance, environmental friendliness, recyclability, structural uniqueness, facile modification, and dimensional stability. Recent advances and future outlooks of nanocellulose as a green material for energy storage systems are described, with a focus on its application in supercapacitors, lithium‐ion batteries (LIBs), and post‐LIBs. Nanocellulose is typically classified as cellulose nanofibril (CNF), cellulose nanocrystal (CNC), and bacterial cellulose (BC). The unusual 1D structure and chemical functionalities of nanocellulose bring unprecedented benefits to the fabrication and performance of energy storage materials and systems, which lie far beyond those achievable with conventional synthetic materials. It is believed that this progress report can stimulate research interests in nanocellulose as a promising material, eventually widening material horizons for the development of next‐generation energy storage systems, that will lead us closer to so‐called Battery‐of‐Things (BoT) era.     

绿色高吸水性树脂的研究进展

综述了可生物降解的绿色高吸水性树脂的研究发展,讨论了该类高分子树脂的结构要求。主要介绍了近年来淀粉、纤维素、海藻酸钠、甲壳类和蛋白质等天然高分子改性吸水性材料,聚氨基酸类吸水性树脂及丙烯酸合成类高吸水性树脂等的吸水性能和生物降解特性,并对绿色高吸水性树脂的研究发展方向和应用前景进行了展望。     

纳米纤维素基材料在柔性电子器件中的应用

目的 由于纳米纤维素基材料良好的柔韧性、热力学性能和高透明度,近年来在柔性电子产品中引起越来越多的关注。通过综述该领域的研究进展,将有助于研究人员更高效地开展研究。方法 综述3类纳米纤维素的制备方法及将纳米纤维素基材料应用在柔性电子产品中的研究进展。分别阐述纳米纤维素基材料应用于器件柔性衬底及绝缘材料的研究实例,并讨论纳米纤维素在各种应用方向中的优势以及存在的问题,最后对材料的未来应用前景进行展望。结论 纳米纤维素是天然纤维素与纳米技术结合的产物,可主要划分为纤维素纳米纤丝、纤维素纳米晶以及细菌纤维素3类。近年来,纳米纤维素基材料作为电子器件柔性衬底、绝缘材料等研究均有许多成果问世。虽然纳米纤维素基电子器件的开发还主要停留在实验室阶段,但是与传统的石油化工产品相比,纳米纤维素具有原材料丰富、环保可降解等优点。对纳米纤维素基新型材料的开发利用,有助于解决人类社会中日益严重的电子垃圾问题。     

Hierarchical Assembly of Nanocellulose‐Based Filaments by Interfacial Complexation

In the present study, interfacial complexation spinning of oppositely charged cellulose‐materials is applied to fabricate hierarchical and continuous nanocellulose based filaments under aqueous conditions by using cationic cellulose nanocrystals with different anionic celluloses including soluble sodium carboxymethyl cellulose and insoluble 2,2,6,6‐tetramethylpiperidinyl‐1‐oxy radical‐oxidized cellulose nanofibers and dicarboxylated cellulose nanocrystals (DC‐CNC). The morphologies of the wet and dry nanocellulose based filaments are further investigated by optical and electron microscopy. All fabricated continuous nanocellulose based filaments display a hierarchical structure similar to the natural cellulose fibers in plant cells. As far as it is known, this is not only the first report about the fabrication of nanocellulose based filaments by interfacial complexation of cationic CNCs with anionic celluloses but also the first demonstration of fabricating continuous fibers directly from oppositely charged nanoparticles by interfacial nanoparticle complexation (INC). This INC approach may provide a new route to design continuous filaments from many other oppositely charged nanoparticles with tailored characteristics.     

Cellulose‐Based Nanomaterials for Energy Applications

Cellulose is the most abundant natural polymer on earth, providing a sustainable green resource that is renewable, degradable, biocompatible, and cost effective. Recently, nanocellulose‐based mesoporous structures, flexible thin films, fibers, and networks are increasingly developed and used in photovoltaic devices, energy storage systems, mechanical energy harvesters, and catalysts components, showing tremendous materials science value and application potential in many energy‐related fields. In this Review, the most recent advancements of processing, integration, and application of cellulose nanomaterials in the areas of solar energy harvesting, energy storage, and mechanical energy harvesting are reviewed. For solar energy harvesting, promising applications of cellulose‐based nanostructures for both solar cells and photoelectrochemical electrodes development are reviewed, and their morphology‐related merits are discussed. For energy storage, the discussion is primarily focused on the applications of cellulose‐based nanomaterials in lithium‐ion batteries, including electrodes (e.g., active materials, binders, and structural support), electrolytes, and separators. Applications of cellulose nanomaterials in supercapacitors are also reviewed briefly. For mechanical energy harvesting, the most recent technology evolution in cellulose‐based triboelectric nanogenerators is reviewed, from fundamental property tuning to practical implementations. At last, the future research potential and opportunities of cellulose nanomaterials as a new energy material are discussed.