制备竹LYOCELL纤维对原料竹浆的要求

简要介绍了竹Lyocell纤维的制备原理和工艺,阐述了原料竹纤维素的聚合度对其在氧化甲基吗啉溶剂中溶解性能的影响,介绍了制取竹Lyocell纤维的竹浆原料的精制纯化方法,并提出制备竹Lyocell纤维对竹浆原料--竹纤维素的要求.     

竹Lyocell纤维研制工艺探讨

该文叙述了竹Lyocell纤维研制过程中碰到的几个技术问题,包括原料纤维素浆的选择、溶剂氧化甲基吗啉的合成、纤维素浆的溶解和纺丝工艺、溶剂回用与纯化、制胶和纺丝设备等,探索了制造竹Lyocell纤维的技术可行性,为竹纤维产品的开发和生产提供科学依据.     

制竹Lyocell纤维的竹浆纯化与溶解工艺研究

该研究选择用溶剂纺丝法制备竹Lyocell纤维的合适竹浆原料,并摸索其纯化和溶解的工艺条件,为利用竹子开发纺织纤维积累有关的基础数据。分别用氢氧化钠溶液和乙二胺四乙酸钠溶液处理竹浆原料,以去除其中的木质素、半纤维素和钙、镁、铁等离子类杂质;研究了用氧化甲基吗啉作溶剂溶解竹纤维素的工艺条件。阐述了如何选择纺制竹Lyocell纤维的竹浆原料,提出以纤维素的"平均聚合度"和"α-纤维素含量"这两个指标作为判断的依据。试验表明:适宜的竹纤维素平均聚合度为800~900左右,其α-纤维素含量应在94%以上。可用含水13%的氧化甲基吗啉单水化合物NMMO.H2O,在100~110℃下溶解竹纤维素;也可用含水50%左右的NMMO溶液,用减压工艺溶解竹纤维素。     

制浆造纸用竹——料慈竹

目前,我国用于制浆造纸的竹种约有30种,其中80％以上的原料为钓鱼慈竹、料慈竹和硬头黄竹等3个竹种。其中,以料慈竹最为优良。料慈竹一般胸径4～8厘米、高可达10～15米,单株鲜重7～8公斤,纤维素含量为50.82％、纤维长2.33毫米,制浆得率可达43％～48％。料慈竹作为制浆造纸的原料,有以下优点：①适应性强。料慈竹在云南、贵州、四川、重庆、广东、广西、海南、江西、湖南等省市区均可栽种,生长良好。②繁殖容易,造林成本低,竹林寿命长。近     

优秀的制浆造纸用竹——料慈竹

我国是竹材资源最为丰富,宜竹地域最广泛的国家。竹子生长快,产量高,竹子是中高档造纸原料。以竹代木,竹浆纸一体化,是缓解我国木材供需矛盾的有效途径之一。目前,我国用于制浆造纸的竹种约有30种,其中80%以上的原料为钓鱼慈竹、料慈竹和硬头黄竹等3个竹种。其中,以料慈竹最为优良。料慈竹一般胸径4～8cm、高可达10～15m,单株鲜重7～8kg,为纤维素含量为50.82%、纤维长2.33mm,制浆得率可达43%～48%。料慈竹作为制浆造纸的原料,有以下优点:①适应性强。料慈竹在云南、贵州、四川、重庆、广东、广西、海南、江西、湖南等省市区均可栽种:云南省…     

碱性亚硫酸盐耦合低压蒸汽预处理对慈竹转化乙醇得率的影响

慈竹是转化生物质燃料及化学品的理想原料之一。笔者采用优化的碱性亚硫酸盐耦合低压蒸汽爆破(ALS-SE)“一步法”对原料慈竹进行预处理,在脱除木质素的同时,降低碳水化合物的降解,提高转化乙醇的效率。红外光谱分析表明,ALS-SE预处理液体中含有木素磺酸盐,将其回收用作表面活性剂加入同步糖化发酵试验中,能有效降低木质素对酶的无效吸附,改善发酵效率。试验分别研究对比了底物质量分数5%和10%,纤维素酶用量18 U/g-纤维素和24 U/g-纤维素以及ALS-SE预处理液对慈竹转化乙醇的影响。结果表明,“一步法”预处理慈竹可以显著地提高乙醇得率:底物质量分数5%、纤维素酶用量18 U/g-纤维素时“一步法”预处理慈竹乙醇得率达到其理论得率的6322%,相比原料慈竹和低压蒸汽爆破,慈竹的乙醇得率分别提高了118倍和062倍;提高底物质量分数为10%,纤维素酶用量为24 U/g-纤维素,其乙醇得率提高到8214%,加入ALS-SE预处理液体时乙醇得率进一步提高到8529%,同时降低了发酵副反应的发生。     

慈竹生长过程纤维素、木质素及灰分动态积累

以当年生不同生长高度的慈竹为研究对象,探讨慈竹生长过程中纤维素、木质素和灰分含量的积累规律。结果表明:慈竹不同生长高度纤维素含量顶、中部变化趋势均以对数方式增长;基部纤维素含量和茎秆纤维素总含量变化趋势都呈"S型"曲线;各部位木质素含量变化趋势总体呈倒"S型"曲线,且不同高度间的木质素含量的差异达显著水平;随着生长高度的增高,茎秆顶部、基部灰分含量以及茎秆灰分总含量总体呈倒"S型"曲线变化,中部灰分含量总体呈"S型"曲线变化。纤维素总含量、木质素总含量的积累分别集中在茎秆高度为150~800、30~800 cm这个生长时期;灰分总量在300~800 cm保持较高的水平。     

慈竹生态环境及培育技术初步研究：（Ⅰ）生态环境

本文采用主分量分析和逐步回归分析方法,研究了四川盆地气候、地形、土壤条件与慈竹生长繁殖及纤维素含量之间的生态关系.结果显示:(1)年均温、干燥度等9个指标是制约慈竹生长繁殖的主导因子;(2)低海拔、阴坡生境是慈竹生长的理想环境,沟槽地、台地较坡地生长更好;(3)土层深厚、质地中壤的土壤有利于慈竹生长;(4)母竹径与新竹径成正相关而与新竹率成反相关,2年竹比例大的竹丛,其新竹率高;(5)高海拔、紫色土或台地上生长的慈竹较低海拔处、黄壤或坡地上的纤维素含量低.     

四川两种竹材理化性质及纤维形态分析

为有效利用四川的乡土竹种慈竹和绵竹,测定分析了2个竹种的理化性质和纤维形态,并与毛竹及常见的阔叶材和针叶材做了对比。结果表明：1）在化学成分上,2个竹种的抽提物含量均小于毛竹,而介于针叶材和阔叶材之间,2个竹种的综纤维素含量和纤维素含量均高于毛竹,木质素含量与毛竹接近,但灰分含量远高于毛竹、阔叶材和针叶材;2）在物理力学特性上,2个竹种竹材密度略低于毛竹,顺纹抗压强度均明显高于毛竹,且优于强度较高的阔叶材马占相思木,2个竹种的抗弯弹性模量和抗弯强度均明显高于毛竹,抗剪强度与毛竹接近,表明2个竹种力学强度均较大,可以用作结构用竹或建筑用竹;3）在纤维形态上,慈竹和绵竹的平均纤维长度分别为0.63和0.67 mm,均小于毛竹,且纤维长度多为500~1 000和1 000~1 500 μm,2个竹种的纤维长宽比均在45以下,表明慈竹和绵竹均不适于作为造纸原料。     

IAA对慈竹木质素和综纤维动态积累的调控效应

以慈竹为材料，通过叶面喷施不同浓度的IAA，研究其对慈竹木质素和综纤维积累的动态调控效应，以期为慈竹的优质栽培提供理论依据。结果表明，喷施IAA可以改变木质素含量的动态积累趋势，较低浓度的IAA对慈竹木质素的积累具有抑制作用，而较高浓度的IAA对木质素含量的积累具有促进作用。经IAA处理后，慈竹综纤维动态积累呈上升的趋势，IAA对慈竹综纤维含量具有明显的促进作用，其浓度与综纤维含量呈明显的正相关关系。     

超疏水纤维素复合气凝胶的制备及其油水分离

纤维素气凝胶因具有强亲水性和低油水选择性,且目前纤维素气凝胶表面的疏水化处理过程较冗长,限制了其在油水分离领域的应用。为了解决上述问题,笔者以硫酸水解微晶纤维素制备得到的纳米纤维素(CNC)为原料,利用甲基三甲氧基硅烷(MTMS)在水相中对其进行硅烷化改性,通过冷冻干燥得到了硅烷化纤维素复合气凝胶。结果表明:所制备的纤维素复合气凝胶具有轻质、多孔特性,随着MTMS添加量的增加,密度逐渐升高(≤0.012 0 g/cm^3),孔隙率略有下降; MTMS的加入对纤维素复合气凝胶的微观形貌影响不大,其骨架结构以二维片层形貌为主,聚甲基硅氧烷均匀地包覆在纤维素片层表面; MTMS的加入使纤维素复合气凝胶的热稳定性明显提高,且未改变纤维素气凝胶的晶型结构,但导致其结晶度逐渐下降。纤维素复合气凝胶的表面接触角随着MTMS添加量的增加而升高,最高达到153.7°,表现出优异的超亲油/超疏水性能。作为吸油材料,超疏水纤维素复合气凝胶不仅可以吸附多种油类和有机溶剂(吸附容量达到52～121 g/g),而且表现出很好的循环使用性能。     

纤维素溶解机理研究述评

纤维素是植物细胞壁的主要组分之一,是由葡萄糖通过1,4-β糖苷键连接而成的均一聚糖,广泛应用于生产酯类、醚类等纤维素基化工产品。纤维素基产品的制备及应用与其溶解程度密切相关,探究纤维素溶解机理,寻找一种绿色高效的纤维素溶剂至关重要。综述了当前国内外学者们对纤维素溶解机理的解释(氢键破坏理论)以及可能影响溶解的因素(化学热力学、化学动力学、结晶度、纤维素两亲性、电荷数和温度),在此基础上探讨了导致纤维素水溶性差的原因,提出了在复杂体系中除了氢键作用以外,还需要综合考虑范德华力、疏水性相互作用的影响。同时,总结了纤维素在离子液体中溶解机理方面存在的争议,其中关于氢键理论还存在一定问题,动力学控制理论尚不明确,阳离子在溶解过程所起的作用被忽视,指出离子液体阳离子的两亲性是纤维素溶解的关键因素。基于纤维素的两亲性及两亲性溶剂促进纤维素溶解的重要理论,提出了应重点寻找新型两亲性溶剂的观点,为未来寻求高效、环境友好、成本低廉的纤维素溶剂指明了方向。     

Preparation and characterization of electroless nickel-coated cellulose fibres

The aim of this project was to fabricate electroless nickel-coated cellulose fibres. Ultimately, these nickel-coated cellulose fibres will be used to develop a cost-effective polymer composite for electromagnetic interference (EMI) shielding and/or electrostatic discharge (ESD) applications. An attempt has been made to impart electrical conductivity onto cellulose fibres via an electroless nickel plating process. The aim was to achieve a homogeneous, continuous layer of Ni on the cellulose fibres, and the plating conditions were optimized to achieve this. The relationship between the coating morphology and the performance of the coated fibre was also of interest. Testing was carried out using cellulose filter paper and then loose cellulose fibres. Scanning electron microscopic (SEM) images of nickel-coated filter paper showed that nickel particles are bonded to the cellulose fibres. The coating appeared more compacted and continuous as plating time increased, corresponding to lower surface resistivity. This observation suggested a correlation between morphology and electrical conductivity of the coating. For nickel-coated cellulose fibres, after optimization of plating conditions, a uniform deposition of nickel particles around the cellulose surfaces was confirmed by SEM images. EDS and XRD results confirmed similar coating could be produced on filter paper and cellulose fibres. SEM images of cross-sectioned nickel-coated cellulose fibres illustrated nickel particles had penetrated into the inner walls of the cellulose fibres. This impregnation of the fibres should act to increase the bonding between nickel coating and cellulose fibres. These nickel-impregnated cellulose fibres could now be incorporated into a polymer matrix to create an electrically conducting composite with the right processing parameters.     

纤维素基吸附剂的研究进展

纤维素作为自然界中储量最大的天然高分子材料，具有价廉易得、易被微生物降解、不会给环境带来第二次污染等特点，长期以来对其开发利用一直是科技工作者研究的热点。本文主要综述了近年来纤维素基吸附剂的研究进展，并简要介绍了其作为金属离子吸附剂、特殊用途吸附剂等的结构性能特点，展望了其发展前景。     

NaClO添加量对TEMPO氧化纳米微纤丝结构与性能的影响

以毛竹粉为原料,采用TEMPO催化氧化联合超声处理制备纳米微纤丝,通过改变Na Cl O与纤维素的质量比,研究了Na Cl O添加量对纳米纤维素的长径比、纤维形态以及羧基含量等特性的影响。结果表明:随着Na Cl O添加量的增加,纳米纤维素羧基含量逐渐提高,长径比增大;当Na Cl O添加量为15 mmol/g时,纳米纤维素羧基含量可高达1.646 mmol/g,横截面直径可达6～10 nm,长径比为273～455;随着纳米纤维素羧基含量的增加,纳米纤维素悬浮液的透光率和剪切黏度不断增大。虽然TEMPO催化氧化程度不断加深,但纳米纤维素的晶型并未遭到破坏,仍然呈现出典型的纤维素I晶体结构,而随着羧基含量的增加,纳米纤维素的结晶度和热稳定性有一定程度的下降。     

纤维素合成酶及其在基因工程中的应用

纤维素是地球上最丰富的生物大分子和最重要的可再生资源,广泛存在于植物和部分细菌中.近年来,关于植物纤维素分子乍物学的研究一直是国际相关研究的热点.从几种典型植物的纤维素合成酶基因人手,综述了植物纤维素合成酶的特性、纤维素合成酶基因的克隆与序列特征及其蛋白结构特征.     

Changes of crystallinity in wood cellulose by heat treatment under dried and moist conditions

The different effects of heat treatment on wood, especially on the cellulose crystallites of wood under ovendried and highly moist conditions, were investigated by X-ray diffractometer. Heat was found to increase significantly the crystallinity of wood cellulose; moreover, almost twice as much crystallization was observed after heat treatment of spruce and buna under a highly moist condition than under the oven-dried condition. In pure cellulose almost the same crystallization was observed under both the conditions, whereas more crystallization occurred in wood cellulose than in pure cellulose. Absolute crystallization was observed for the wood species and pure cellulose under both conditions, considering the thermal decomposition of the amorphous region in addition to crystallization. Our results suggested that other components accomparying wood cellulose were involved in the increase of crystallinity by heat treatment, and that wood cellulose contained more quasicrystalline regions than pure cellulose. Moreover, calculated apparent activation energies revealed that crystallization and decrystallization in pure and wood cellulose under heat treatment of highly moist condition were some-what easier than those under the oven-dried condition. The behavior of the piezoelectric modulusd ₂₅ almost paralleled that of crystallinity.     

Influence of carboxyl group on the acid hydrolysis of cellulose

Cellulose isolated from wood is more susceptible than cotton cellulose to homogeneous hydrolysis in phosphoric acid. The influence of carboxyl group introduction at the C6 position on the hydrolysis rate of cellulose in 82.5% phosphoric acid was studied as a model of the oxidation of cellulose during pulping. The rate constant of hydrolysis for dissolving pulp was larger than that of cotton cellulose at temperatures of 25°–35°C. Mercerized cotton cellulose was partially oxidized regioselectively at the C6 position by a free radical system using 2,2,6,6-tetramethylpiperidine 1-oxyl (TEMPO). The oxidized cellulose was obtained at a range of 1.7–12.7 mEq carboxyl content per 100 g of cellulose. The hydrolysis rate of the oxidized cellulose samples accelerated with increasing carboxyl content in the samples.Part of this work was presented at the 5th Annual Meeting of the Cellulose Society of Japan, Kyoto, July 1998     

Mechanism of mercerization revealed by X-ray diffraction

We studied the crystalline conversion of cellulose fiber from cellulose I to cellulose II (mercerization) by X-ray diffraction, focusing on the putative chain-polarity conversion from parallel to antiparallel. The structural change of Na-cellulose was examined during stepwise changes in NaOH concentration. Either Na-cellulose I or Na-cellulose II was formed depending on the initial NaOH concentration. Once formed, both structures were stable and did not inter-convert to each other when the NaOH concentration was changed. Such stability indicates that the parallel-to-antiparallel conversion is not likely to take place in the crystalline region of Na-cellulose. Regeneration of cellulose II from both forms of alkali cellulose proceeded with the formation of 0.44 nm lattice plane corresponding to the sheet of (1 ¯1 0) plane of cellulose II, showing that the molecular stacking due to van der Waals' interaction is the driving force of the formation of cellulose II. A mechanism was proposed whereby the geometry of the cellulose molecule allows close fitting of the hydrophobic faces only in the antiparallel arrangement, thus driving formation of the antiparallel structure of cellulose II.This study was presented in part at the 47th Annual Meeting of the Japan Wood Research Society, Kochi, April 1997; and at the 6th Annual Meeting of the Cellulose Society of Japan, Tokyo, June 1999     

An investigation of mercerization in decayed oak wood by a white rot fungus (Lentinula edodes)

The crystal transformation of cellulose I to cellulose II during alkali swelling was investigated in decayed oak wood that was used for shiitake mushroom cultivation and the results were compared with those of sound wood using X-ray diffraction analysis and ultraviolet microscopy. During mercerization, the sapwood cellulose of decayed wood was easily transformed into Na-cellulose I and then Na-cellulose I was easily converted into cellulose II after washing and drying. The sapwood cellulose of sound wood was converted more slowly to Na-cellulose I and very little Na-cellulose was converted to cellulose II. Na-cellulose I of sound wood can be reconverted to cellulose I during washing and drying. Therefore, it could be concluded that lignin prevented the alkali swelling of wood cellulose and the transformation from cellulose I to cellulose II. The decay of crystalline cellulose might cause an increase in the susceptibility of alkali swelling, so that the degree of mercerization may be also affected.