【作者】 喻红芹；

【导师】 郁崇文；

【作者基本信息】 东华大学 ， 纺织工程， 2009， 博士

【摘要】 亚麻作为麻类的一种,其织物具有吸湿散湿快、透气性好、纹理自然、色调柔和、风格独特等优点,颇受消费者的喜爱,被广泛应用于服装、服饰等领域。因此,我国亚麻行业生产规模不断扩大,现今的规模仅次于俄罗斯,居世界第二位。但是,我国的种植尚不能满足纺织加工的要求,约有70%左右的原料需要进口。而且,我国亚麻进口量与日剧增。为了对不同国家的亚麻纤维的特点有比较系统的认识,以便可以对不同来源的亚麻制定出更为合理和针对性强的加工工艺,本文中首先对荷兰、比利时、法国、俄罗斯以及中国的亚麻打成麻作了化学成分分析及常规的性能测试,如,细度、强力、长度、伸长等指标,并用扫描电镜、红外、X-射线衍射等测试对这些打成麻进行了分析对比,结果表明荷兰和法国麻的胶质含量较少,中国和俄罗斯麻的胶质含量偏多。而强度方面,荷兰麻的断裂强度最高,其次为俄罗斯麻,中国麻次之,法国和比利时麻的强度相对较小。柔软性则是荷兰、法国、俄罗斯麻较好,中国和比利时麻相对较差,同时,荷兰麻的平均长度也是最长的,离散性也最小,比利时麻、俄罗斯麻次之,而中国打成麻的长度最短。综合起来,荷兰麻的性能相对较优,中国打成麻的果胶和木质素含量较高,细度较大。由于纤维在生长的过程中,既是纤维产量的形成过程、也是纤维品质的形成过程。因此,要改善我国亚麻品质的关键问题是要明确亚麻纤维品质的形成规律,明确收获时间对纤维品质的影响,由此,本文对我国亚麻的两大产地:黑龙江和新疆的亚麻进行了系统的研究,在不同收获时期进行采样,并对各个收获期的亚麻进行性能的测试与分析。实验结果证明,新疆、黑龙江亚麻的强伸性能都是在开花期后一周达到了最佳点,因此,从纺织性能的角度来考虑,开花期后一周是亚麻最佳的收获时期。而在麻纤维中除了纺织中可利用的纤维素外,还含有非纤维素物质,即,胶质,包括果胶、半纤维素、木质素等,这些胶质将纤维胶结在一起呈现坚硬的片状麻束,这样的麻束是不能直接用于纺纱的,因此,在纺纱之前必须将胶质去除掉,这个过程即为脱胶。因此,脱胶程度及脱胶质量的好坏将直接影响到纺织后加工的顺利进行。而在所有的胶质成分中,果胶是很重要的一种物质,在麻的初加工中果胶的去除将会对脱胶及后加工产生很大的影响,而对果胶的研究则会为脱胶奠定十分重要的理论基础。由此,在对果胶位置的研究中,发现果胶分布在细胞交接处,外层和中间薄层的果胶通过钙离子以离子键的方式结合,而靠内层的果胶以共价键结合。钙离子的分布也是在外层和细胞的交接处的很多,内层较少。这样,钙离子与果胶的分布规律是一致的,本课题中也对钙离子的含量进行了定量的分析,并验证了其与果胶的关系。测试结果证明了钙离子存在于果胶中。钙离子的存在使得果胶大分子形成了egg-box结构,使果胶形成了复杂的空间网状结构,这就加大了脱胶的难度。为了更好地处理亚麻,须对麻中的果胶进行系统的研究,因此,本文中用两种不同的方法提取果胶,进行质谱、液相色谱、红外等测试,以便从理论上更深入地掌握果胶的成分。用两种提取方法所得的提取物经红外、质谱、液相色谱、液质联用等现代分析测试技术测定,结果证明了水溶物和去除钙离子后的果胶可认为是同一种物质,即,水溶物的主要成分为可溶性果胶,而普遍所说的果胶即为果胶酸的钙盐。在确定了果胶与钙离子的关系后,选用了EDTA、多聚磷酸钠、草酸和草酸铵等不同的螯合剂对亚麻进行预处理实验,以改进的Fried Test为评定方法,结果发现草酸铵是一种有效的预处理试剂,5g/L的草酸铵在60℃条件下对亚麻处理5小时基本上能够将韧皮与麻秆完全分离。同时,本课题针对亚麻传统处理方法的弊端:不容易人为控制、劳动强度大、污染环境、麻质量不稳定等缺陷,对亚麻生物处理进行了研究,以沤麻水及种麻地的土壤作为原料,并经富集培养后进行菌株的筛选,最终找出了一株有效的脱胶菌株,在不同的pH、温度、碳源、氮源等条件下进行产果胶酶工艺的优化,结果得出其最佳产酶条件为马铃薯作氮源,果胶作碳源,pH6,30℃,培养时间60h,摇床转速200r/min。它产出酶的最适作用pH和温度分别为pH5.5、40℃。在此基础上,以残胶率作为指标,对亚麻粗纱进行了实验,在对比实验中发现,在最佳产酶条件下处理粗纱的效果并没有以残胶率作为衡量指标的效果好,这充分说明了酶活并不是评定脱胶效果的最佳方法。用与亚麻结构相似的红麻来进行实验验证,结果也充分证明了这一点。此外,对筛选出的脱胶菌株的培养发现此菌的菌落形态较大,质地比较疏松,外观干燥,不透明,呈现或紧或松的蛛网状、绒毛状或棉絮状;菌落与培养基的连接紧密,菌落正反面的颜色和边缘与中心的颜色常不一致,具体表现为:菌落表面呈现出黑褐色或炭黑色,培养皿反面有不同程度的黄色,正反面颜色呈现明显差别。置于显微镜下观察,可看到菌株的产孢结构是一顶端膨大成圆形的囊状形状,它的分生孢子梗便是由营养菌丝分化的足细胞长出,在其顶端形成膨大的顶囊,在顶囊表面以辐射状长出一层或二层小梗,小梗顶端产生一串圆形的分生孢子。由《中国真菌志》初步鉴定,此菌株为曲霉属。最后,对经过草酸铵预处理的亚麻原麻进行生物处理,并经过测试表明了亚麻韧皮在较短的时间内就能够与麻秆完全分离。这个结果也经红外、衍射等现代的测试方法得到验证。在此基础上,对亚麻的生物处理机理进行了初步的探讨。结果得出,由于黑曲霉是化能异养型微生物,能够利用环境中的有机物作碳源,并以有机物氧化产生的化学能为能源来进行生长,因此,在菌体生长的快速阶段,亚麻的生物处理已经开始,这是因为菌株首先利用麻中少量的可溶性糖及其他低聚物质作为营养来源进行生长繁殖,这不仅破坏了胶质分子的紧密稳定的结构,更使得菌的营养菌丝体更顺利、快速地伸入到胶质的分子中,使大分子产生劈裂。再加上菌株的数量剧增,分泌的果胶酶量也不断增加,切断了果胶分子中半乳糖醛酸之间的甙键,使得麻中的胶质在结构上发生了较大的变化,胶质复合体的稳定性受到很大的破坏,此时菌更能直接利用这些物质作为其营养来源进行生长繁殖。而在此过程中,脱胶便完成了。因此,在实际的应用中,即对纤维的处理中,效果并不是和酶活能够对应上,这也从一方面证明了酶活与脱胶并不是直接的关系。更多还原

【Abstract】 Flax,as one kind of bast fibers,is preferred by consumers and used widely in clothing and garment because its fabric has many virtues,such as,fast moisture absorption and carry-off,natural grain,bland color,unique style,etc..Therefore,the production scale in China is so expanded constantly that it has been listed the second globally,next only to Russia now.But the yield in China is too deficit to meet textile industry about seventy percents of flax materials are imported.Furthermore,import quantum of flax is increasing.The main properties and components ofscutched flax from Holand,Belgium,Fance,Russia and China are tested in this paper,such as, fineness,strength,length,elongation.In addition,SEM,infrared and x-ray diffraction are also used in comparison,so that more informations about different scutched flax can be obtained and more rational and concrete parameters can be set down in manufacture.The results indicate that scutched flaxes from Holand and France have few gum,while that from Russia and China have more gum.The tenacity of flax from Holand is biggest followed by that of Russia and China,flaxes from France and Belgium have smaller tenacity.As far as softness is concerned,flaxes from Holand, France and Russia have better softness,while flaxes from China and Belgium have worse softness.In addition,the average length and discreteness of flax of Holand is best,followed by that of Belgium and Russia,that of China is worst.In conclusion, the properties of flax from Holand is relatively better,scutched flax from China has more pectin and lignin and is coarse.The quantity and quality of fiber come into being during growing period. Therefore,the key problem of improving fiber quality is to find out the form law of fiber.So fibers in Xinjiang and Heilongjiang,which are the main fields in China,are studied in detail.Fibers with different growing time are harvested and analysed.The datas prove that the optimal strength and elongation of fiber are best when flax is harvested one week after blossom.Therefore,the optimal harvesting time is one week after blossom when textile properties are taken into account.Not only cellulose that can be used in textile industry but also non-cellulose lie in bast fiber,non-cellulose is also named gum including pectin,hemicellulose and lignin, which glues cellulose into stiff sheet bundle fiber,which can not be spinned,therefore, gum must be removed before spinning,this process is retting.Thus,the degree and quality of retting can affect downstream process.As pectin is one important component in gum and its removal can influence postprocessing in textile,so research on pectin is theoretical foundation of retting.The results prove that pectin lies in the junction of cells and its macromolecule is linked by electrovalent bond in outer and lamella,while pectin is connected by covalent bond in inner bast.At the same time, more calcium ion distributes in outer and junction of cell and few lies in inner of cell, so the distribution trends of pectin and calcium ion are same.The quantity of calcium ion is analysed in this paper and the ralation between pectin and calcium ion is also studied,the results indicate that calcium ion lies in pectin of flax.Calcium ion makes macromolecule of pectin turn into egg-box structure,which is meshy and intricate. The structure of pectin makes retting more difficult.Therefore research on pectin is carried in the paper in order to treat flax efficiently.Pectin is extracted with two methods and tested by mass spectrum,liquid chromatogram and infrared.As a result, the hydrotrope and the pectin in which calcium ion is removed are the same matter, that is,hydrotrope is soluble pectin,while pectin is the calcium ion of pectic acid.Since calcium ion chelateds the macromolecule of pectin,chelating agents,such as elhylene diamine tetraacetic acid,sodium salt of triphosphoric acid,oxalic acid and ammonium oxalate,are involved in the pretreatment experiments of flax.The evaluation is based on modified Fried Test.The results manifest that ammonium oxalate is effective,bast and xylem can be separated fully when flax is treated with ammonium oxalate,the conditions are:the concentrationof ammonium oxalate 5g/L, 60℃,5h.Microbe treatment of flax is also studied in the paper in order to conquer the defects of traditional retting,for example,unmanageable,intensity of labor, environmental pollution and unstable quality of fiber.A effective fungus strain is separated and screened from retting water and soil in planting area of flax,pH, temperature,carbon source and nitrogen source are involved in optimization experimnts of pectinase production.The results show that the optimal production conditions ofpectinase are:nitrogen source potato,carbon source pectin,pH6,30℃, culture time 60h,speed of shaker 200r/min,the optimal pH and temperature of pectinase are pH5.5,40℃,respectively.Then flax roving is treated,evaluation is based on residual gum content.Datas indicate that effect of flax roving treated based on residual gum content is better than that treated under optimal pectinase productin conditions,which is proved by treatment of kenaf that is similar to flax in structure. All these show that enzyme activity is not suitable for evaluating retting.In addition, the colony of the strain is big,loose,opaque and arachnoid,connection between strain and substrate is tight,the colors of two sides of colony are different,marginal and central colors are also different,that is,the surface of colony is pitchy or carbonarius,the other side is yellow with different brightness,differences of colors of two sides are obvious,spherical gleba of strain is saccate whose top expands into roundness,its spore results from podocyte differentiated by nutrient hypha,one or two radialized trichidiums come into being at the top of gleba,from which spores are produced.All these are observed with microscope.This strain is aspergillus certificated by certification handbook of China fungus.Last,raw flax is treated with ammonium oxalate followed by microbe retting, thus,bast separate from xylem fastly proved by infrared and diffraction.Mechanism of microbe retting is also studied.The results indicate that aspergillus niger,as one kind of mcirobe whose carbon source and energy come from external organics,can absorb carbon source and energy from organics and its oxidation reaction to grow. Therefore,microbe retting of flax begins at the stage of fast growing period of strain, strain use oligomer in flax as its nutrient to propagate,which damage tight structure of gum and make it easy for mycelium to enter molecule,thus,cleavage appears in molecule of gum.Furthermore,glucosidic bond in macromolecule of pectin breaks due to pectinase excreted by increasing strain,which makes great change and damage occur in macromolecule,at this time,strain can use nutriment from pectin easily, during which retting completes.Therefore,there is not a significant linear correlation between retting effect and enzyme activity in practical flax treatment.更多还原