木质素碳纤维研究进展

由于不可再生石油资源的日益消耗,生物质可再生资源的开发与利用成为全球的研究热点。木质素来源广泛,属于可再生低成本资源,并且含碳量高于60%,备受碳纤维研发工作者的广泛关注,近年来在研究开发方面取得了许多突破。本文从归纳总结木质素纺丝前处理出发,综述了纯木质素碳纤维、共混和接枝木质素碳纤维改性制备的发展历程、工艺性能比较和最新研究进展,并对木质素碳纤维研究前景进行了展望。     

木质素灰分含量控制及其影响研究

木质素是自然界中含量最丰富的天然芳香族高分子,含有丰富的碳元素,是制备碳纤维的理想原料。但是,工业木质素的杂质含量普遍较高,不能满足碳纤维制备要求。为此,本文采用盐酸沉析、离心分离和酸洗的方式对某种国产工业木质素进行纯化处理,考察了盐酸用量及纯化次数对木质素灰分含量的影响,并采用GPC、FT-IR和DSC研究了木质素的分子量、化学结构和反应活性随纯化处理次数的变化规律。结果表明:随着纯化次数的增加,木质素的灰分含量大幅降低,反应活性显著提高;随着盐酸用量的增加,在一次提纯时,木质素的灰分含量先大幅降低,当浓盐酸与木质素的质量比大于0.6:1时,木质素的灰分含量趋于稳定;经四次纯化处理后,木质素的灰分含量降低至0.77%。     

木质素:一种有潜力的生物质基催化剂来源

木质素是自然界中储量丰富的唯一含芳环生物质可再生资源,但复杂的结构使其难以高效利用,目前大部分被废弃。除通过氧化还原等过程可将其转化为石油化工产品的替代品外,木质素结构中丰富的含氧官能团及制浆过程引入的硫元素等均可提供有效位点,为其作为催化剂基质提供了丰富的可行性。本文从木质素资源的来源和结构分析出发,根据不同催化反应的机理和制备催化剂过程中的结构改性类型,综述了具有不同结构特征的木质素基催化剂分别在生物质平台化合物水解等酸碱催化反应、电催化反应和负载金属纳米粒子催化氧化还原反应等过程中的应用,讨论了木质素类型、制备或活化改性条件对催化材料性能的影响,也指出了当前木质素基催化剂的开发研究难点和未来发展方向。     

木质素多孔碳材料在电化学储能中的应用

木质素可再生资源成本低、含碳量高、芳香度高和易集中收集,被认为是具备潜力大规模工业化制备新型多孔碳材料的重要碳质原料之一,对缓解化石资源消耗及可持续发展具有重大的意义。多孔碳材料具有较高的电导率、较高的比表面积、丰富的孔道结构及良好的稳定性等特点,作为储能材料有广阔的应用前景。本文介绍了模板法、活化法及水热法制备木质素多孔碳材料的国内外最新研究进展,详细总结了不同热解工艺参数对木质素多孔碳材料微观结构的影响规律,重点阐述了其作为锂离子电池、钠离子电池和超级电容器电极材料的研究进展。针对功能化木质素多孔碳材料制备工艺复杂及储能性能差等瓶颈问题,提出离子/电子扩散动力学的优化、多种储能机制的协同作用和绿色、简便制备工艺的开发等研究策略,指出研发先进炭化技术构筑合理分级孔径结构,精准调控适宜层间距且高度有序排列碳层、功能化改性表面微环境及直接构建炭化工艺参数与电化学性能之间的因效关系是制备高储能性能木质素多孔碳材料的未来研究方向。     

NiSO_4改性对聚丙烯腈原丝及其碳纤维结构与性能的影响

碳纤维具有高比强度、高比模量、导电、耐热、自润滑等优异的综合性能,在纤维增强复合材料中得到了广泛的应用.可制备碳纤维的前驱体有人造丝、沥青、聚丙烯腈纤维、木质素、聚乙烯纤维、聚苯并噻唑(PBO)纤维等.但大多数高强碳纤维目前仍然是由聚丙烯腈纤维制备的,同时,许多工作都集中在更进一步提高碳纤维的机械性能.特别是在我国, 碳纤维质量与某些发达国家相比,还有较大的差距,急需解决的问题就是如何尽快研制出高力学性能的碳纤维.采用氨基硅氧烷、脂肪族羧酸[1]、CuCl[2]、KMnO 4[3]、CoCl2[4]等有机或无机化学试剂对聚丙烯腈原丝进行化学处理, 以改进最终碳纤维的结构与性能是一种有效的方法.国内在这方面的研究还很少.文献[1 ～4]中所采用的方法都是利用商业聚丙烯腈原丝在碳化前进行洗油、浸渍、洗涤烘干处理 ,增加了碳纤维制备的工序,同时,原丝损伤较大,在连续生产中难以适用.我们在原丝连续制备的同时采用NiSO4溶液浸渍处理聚丙烯腈纤维,本文主要研究了采用NiSO4浸渍改性后聚丙烯腈原丝及其碳纤维的结构与性能.研究表明,采用NiSO4在线浸渍改性聚丙烯腈原丝,生产工艺简单,且能有效地改进最终碳纤维的结构与性能.     

木质素活化改性制备酚醛树脂胶黏剂研究进展

木质素由于化学结构与苯酚相似,通过活化改性可部分替代苯酚制备木质素改性酚醛树脂胶黏剂。既可降低成本、达到生物质资源高效利用的目的,并且制备的木质素改性酚醛树脂胶黏剂有毒残余较低,具有环保意义,是合成制备生物质高分子材料的重要途径。本文综述了国内外研究人员在木质素活化改性制备酚醛树脂胶黏剂研究领域的最新进展,重点介绍了化学改性、物理改性、生物改性等木质素活化改性方法,比较了不同改性产物制备酚醛树脂胶黏剂的性能,并对影响木质素活化改性制备酚醛树脂胶黏剂实现工业化应用的主要因素进行了分析。     

高取向度碳纤维原丝制备工艺研究进展

碳纤维原丝的性能好坏在很大程度上决定着碳纤维的最终性能。缺陷少、细旦化、高取向、高纯化等是高性能原丝的基本要求。其中原丝的取向度在很大程度上决定了碳纤维在预氧化、碳化过程中形成的类石墨片层的取向结构，这会影响碳纤维最终的强度和模量，所以制备出高取向的碳纤维原丝具有重大意义。本文聚焦于高取向碳纤维原丝制备工艺，首先分析了高取向原丝的重要性，然后在原丝制备工艺上将纺丝方法以及牵伸工艺对取向度的影响进行总结分析，同时介绍了微积分纳米层叠法和高取向复合纤维原丝的制备工艺，指出优质的初生纤维以及具有稳定化取向排列的原丝是制备高取向碳纤维原丝的关键，以期对提升原丝的取向度进而提升碳纤维性能的研究有所贡献。     

高性能聚丙烯腈碳纤维中纳米级微孔分析表征研究

高性能碳纤维由于其优异的性能,在各行各业中具有广泛应用。为深入研究碳纤维内结构与其性能之间的相关性,本文应用小角X射线散射研究了一系列典型的聚丙烯腈碳纤维样品,分析了样品内微孔的尺寸及取向,讨论了强度和模量与微孔的相关性,研究结果表明:高性能碳纤维的力学强度和模量与碳纤维内微孔缺陷的长度和长径比有关,控制碳纤维内微孔缺陷的长度有望实现高强碳纤维的制备,控制牵伸倍率从而控制碳纤维内微孔的长径比有望实现高模碳纤维的制备。     

木质素资源利用的研究进展

木质素作为一种大量存在的可再生资源,具有巨大的应用潜力。近年来,木质素资源的高效利用问题引起了人们的广泛关注。本文综述了近几年来国内外木质素资源利用的研究状况,简要介绍了木质素利用的两种方式:大分子形式利用以及液化降解利用。重点介绍了木质素液化降解制备生物油及酚类化合物的国内外研究现状,并对液化降解机理进行了阐述。最后,总结了当前木质素资源利用存在的问题,提出了未来木质素利用的研究方向,展望了木质素的发展前景。     

螺旋纳米碳纤维的制备与表征

利用氢电弧等离子体法制备了纳米铜-镍合金作为催化剂,通过乙炔的催化热解制备了对称生长的螺旋纳米碳纤维.并用扫描电子显微镜(SEM)、透射电子显微镜(TEM)和红外(IR)对其进行表征,发现在单个纳米铜-镍合金粒子上对称生长出两根螺旋纳米碳纤维,它们的旋向相反,但是具有相同的螺旋直径、螺旋长度和碳纤维直径,而且纳米铜-镍合金粒子也有各种不同的形状.此外,这两根对称生长的螺旋纳米碳纤维之间的夹角也不同,分别为60°,90°,110°和160°.IR结果表明,螺旋纳米碳纤维分子结构中既含有不饱和的CC双键,又含有饱和的-CH₂-和-CH₃-基团.然而,利用氢电弧等离子体法制备的纳米铜和纳米镍作为催化剂,催化热解乙炔,得到的产物均是直线型碳纤维.     

Preparation of Oxidized Organosolv Lignin⁃based Hydrophilic Sizing Agent and Its Application in Polypropylene北大核心CSCD

The interfacial compatibility of carbon fiber （CF） reinforced composites is the key factor to determine the comprehensive properties of the composites. The sizing agent plays an indispensable role between carbon fibers and matrix resins. Environmentally friendly hydrophilic sizing agent is is a hot research issue to be solved. In this work,the hydrophilic lignin-based sizing agent and carbon fiber reinforced polypropylene （PP） composites are prepared and studied. The lignin is ozonized to increase the reactive group. The obtained lignin reacts with epoxy group to prepare the oxidized organic solvent lignin based epoxy resin（OLBE）. OLBE reacts with alcohol amine and carboxylic acid to obtain the hydrophilic lignin-based sizing agent. KH550 is further added to balance the hygroscopicity of sizing agent. Finally,an oxidized organic solvent lignin-based hydrophilic sizing agent（OLBEDK）with excellent stability was prepared. The CF treated with 2. 5% solid content OLBEDK was only 3. 0 mg. The ILSS,Flexural strength,Flexural modulus and Impact strength of CF/PP composites are increased by 50. 8%,34. 2%,53. 7% and 127. 8%, respectively,compared with those of CF/PP composites without sizing. This is attributed to the π-π conjugation between the benzene ring of lignin and the carbon six-membered ring of CF,and the physical entanglement between the alkyl chain of KH550 and the molecular chain of PP,which enhances the interfacial interaction between CF and PP effectively. © 2022, Science Press (China). All rights reserved.     

Preparation of Lignin-Based High-Ortho Thermoplastic Phenolic Resins and Fibers

Surplus lignin, which is inefficiently used, is generated in the forestry industry. Currently, most studies use lignin instead of phenol to synthesize thermosetting resins which cannot be reprocessed, thus affecting its application field. Thermoplastic phenolic resin has an orderly structure and excellent molding performance, which can greatly improve its application field and economic value. Herein, phenol was partially replaced with enzymolysis lignin (without treatment), generating lignin-based high-ortho thermoplastic phenolic resins (LPRs), and then lignin-based phenolic fibers (LPFs) were prepared by melt spinning. FTIR, ¹³C-NMR and GPC were used to characterize the ortho–para position ratio (O/P value), molecular weight and its distribution (PDI), and rheological properties of the resin. TG, XRD, SEM and tensile property studies were used to determine the thermal stability, orientation, and surface morphology of the fiber. Lignin addition resulted in the decline of the O/P value and molecular weight of the resin. For the 10% LPR, the O/P value, Mw, and PDI were 1.28, 4263, and 2.74, respectively, with the fiber exhibiting relatively good spinnability. The tensile strength and elongation at break of the 10% LPF were 160.9 MPa and 1.9%, respectively. The addition of lignin effectively improved the thermal properties of the fiber, and the carbon yields of 20% LPF before and after curing were 39.7% and 53.6%, respectively, which were 22.2% and 13.7% higher than that of the unmodified fiber, respectively.     

Fabrication of polyacrylonitrile/lignin-based carbon nanofibers for high-power lithium ion battery anodes

Low-cost carbon nanofibers are fabricated from lignin, the second most abundant raw material in wood after cellulose and polyacrylonitrile mixture as a carbon precursor by electrospinning, followed by suitable heat treatments. As the lignin content in the precursor increases, the carbon nanofibers become thinner, as seen from scanning electron microscopy images. However, their carbon structure and electrochemical performance are found to be very similar, even though surface functional groups on carbon nanofibers are slightly different from each other. For example, in the initial charge (lithium insertion) and discharge (lithium deinsertion) process, the reversible specific capacities of the various carbon nanofibers come from different precursor ratios of lignin and polyacrylonitrile are similar. Even at a fast (7 min) charge and discharge condition, the carbon nanofibers prepared from the lignin-containing precursors show a discharge capacity of 150 mAh g^?1. The lignin-based carbon nanofibers thus show promise for use in high-power lithium ion battery anodes with low price.     

Local Structure Analysis and Modelling of Lignin-Based Carbon Composites through the Hierarchical Decomposition of the Radial Distribution Function

Carbonized lignin has been proposed as a sustainable and domestic source of activated, amorphous, graphitic, and nanostructured carbon for many industrial applications as the structure can be tuned through processing conditions. However, the inherent variability of lignin and its complex physicochemical structure resulting from feedstock and pulping selection make the Process-Structure-Property-Performance (PSPP) relationships hard to define. In this work, radial distribution functions (RDFs) from synchrotron X-ray and neutron scattering of lignin-based carbon composites (LBCCs) are investigated using the Hierarchical Decomposition of the Radial Distribution Function (HDRDF) modelling method to characterize the local atomic environment and develop quantitative PSPP relationships. PSPP relationships for LBCCs defined by this work include crystallite size dependence on lignin feedstock as well as increasing crystalline volume fraction, nanoscale composite density, and crystallite size with increasing reduction temperature.     

Lignin bio-oil-based electrospun nanofibers with high substitution ratio property for potential carbon nanofibers applications

We reported a new approach for development of lignin bio-oil-based electrospun nanofibers (LENFs) that had high substitution ratio (up to 80 wt%) and good morphology. This approach was particularly unique and translatable as it used small molecule lignin bio-oil with high reactivity and low heterogeneity obtained via lignin depolymerization reaction to produce well-oriented LENFs. Firstly, effects of various blends solutions ratios and electrospinning parameters on the characteristics of the obtained LENFs were analyzed. The results showed that the optimal parameters that resulted in the best electrospun nanofibers were as follows: blend solution ratio, the 20 wt% blend solution containing 80 wt% straw lignin bio-oil (SLB) and 20 wt% polyacrylonitrile (PAN), flow rate, 1 mL/h, voltage, 20 kV, rotational speed, 500 r/min and the distance between needle and collection screen, 20 cm. Secondly, used the best LENFs, we also applied to prepare lignin bio-oil-based carbon nanofibers (LCNFs) and estimated its properties by scanning electron microscope (SEM), X-ray diffraction (XRD) patterns, Raman spectroscopy and tension testing. Our results demonstrated that compared with pure PAN carbon nanofibers (PCNFs), the as-prepared LCNFs had similar smooth surfaces, similar crystallinity and similar mechanical properties. This work can promote the utilization of lignin depolymerization main-products to produce lignin-based materials, while also help to reduce use of high-cost PAN.     

Isoconversional kinetic analysis of novolac-type lignophenolic resins cure

Several phenomenological models (including simple models by Ozawa and Kissinger and the Kissinger–Akahira–Sunose isoconversional method) have been used to compare the cure kinetics of two lignin-based novolac-type phenolic resins with those from a commercial novolac system. When 45 wt% phenol is substituted by a sulfonated kraft lignin, an important reduction in the activation energy is obtained. This behaviour has been attributed to the incorporation of an extra amount of hydroxymethyl groups in the formulation, as they are present in important quantities in the original lignin structure. KAS isoconversional model shows that the rise in viscosity derived from lignin introduction leads to a moderate change in the limiting stage from a kinetic to a diffusion regime, while condensation reactions, which are favoured by the abundance of lignin hydroxymethyl groups, acquire high relevance in LPF-45 system cure. Finally, competition with other mechanisms initiated at high temperature is reported at high conversion grades for all cases.     

氯化钠模板诱导木质素基多孔炭的制备及其超级电容器性能

以木质素为碳源,氯化钠为模板,通过低温回流使木质素包覆在氯化钠外层,高温煅烧获得木质素基多孔炭,研究了其作为电极材料在超级电容器中的应用。 结果表明,改变煅烧温度可调控所得样品的孔结构,其比表面积在548~600 m²/g之间可变,且随着煅烧温度升高,比表面积和孔体积先增大后减少。 700 ℃煅烧所得样品具有最大的比表面积,并表现出最高的电容性能,其在6 mol/L KOH电解液中比电容可达252 F/g,有效面积电容高达31.2 μF/cm²,模板氯化钠可清洗分离并可循环利用。 提出了一种废弃物高附加值制备超级电容器用多孔炭的绿色方法。     

木质素改性高分子材料研究进展

木质素改性高分子材料的基础研究和应用开发极为活跃.在材料中引入木质素,不仅可提高材料的性能,还能降低成本,产生可观的经济效益.本文综述了木质素改性高分子材料的最新研究成果,并由此归纳出木质素结构与材料性能之间的关系,提出了基于控制木质素多级结构的材料设计和性能优化的思路.     

Recent advances in epoxy resins and composites derived from lignin and related bio-oils

This short critical review gives an insight on the potential that lignin and its bio-oils present towards the production of thermosetting epoxy polymers and composites. Green and sustainable ways of producing monomers and polymers from renewable sources are critical and lignin, as an underutilized bio-based waste material, presents a high exploitation potential. Due to its versatile and highly functional phenolic structure, the utilization of lignin or its depolymerized fractions (bio-oils) has been investigated in the last years as alternative for fossil-based epoxy resin pre-polymers and crosslinkers. Lignin can in fact be considered as a crosslinker for epoxy resins, especially after appropriate functionalization with amine groups or with additional hydroxyl groups, or it can be modified with epoxide groups towards the replacement of toxic BPA-based epoxy prepolymers. Furthermore, lignin derived pyrolysis or hydrogenolysis bio-oils may offer highly reactive soluble oligomers that after appropriate functionalization could be utilized as bio-based epoxy prepolymers. The lignin-based epoxy resins and composites exhibit similar or even better and novel properties, compared to those of pristine epoxy polymers, thus rendering lignin a highly valuable feedstock for further utilization in the thermoset polymer industry.