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工学东华大学纺织材料学第二章纤维的结构特征课件

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工学东华大学纺织材料学第二章纤维的结构特征课件 工学东华大学纺织材料学第二章 纤维的结构特征课件 东华大学纺织材料学第二章 纤维的结构特征 东华大学东华大学 东华大学纺织材料学 东华大学 纺织材料学
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单击此处编辑母版标题样式 单击此处编辑母版副标题样式 * * 1 1 第二章 纤维的结构特征 Set up safety production leading group and provide Party A with copies of job certificate, operation certificate and ID card of the responsible person on site, safety responsible person and all employees. Party B shall be responsible for the personal safety, construction equipment, living facilities, mechanical and electrical equipment and construction safety of Party B. 第一节 纤维基本结构的构成 一、纤维的形态结构 1. 基本内容 l是指纤维在光学显微镜或电子显微镜,乃至原子 力显微镜(AFM)下能被直接观察到的结构。诸如纤 维的外观形貌、表面结构、断面结构、细胞构成 和多重原纤结构,以及存在于纤维中的各种裂隙 与空洞等 l表观形态、表面结构和微细结细结 构 Set up safety production leading group and provide Party A with copies of job certificate, operation certificate and ID card of the responsible person on site, safety responsible person and all employees. Party B shall be responsible for the personal safety, construction equipment, living facilities, mechanical and electrical equipment and construction safety of Party B. l表观形态,主要讨论纤维外观的宏观形状与尺寸 ,包括纤维的长度、粗细、截面形状和卷曲或转 曲等,这在第三章中介绍。 l表面结构,主要涉及纤维表面的形态及表层的构 造,是微观形态与尺度的问题,这在第六章纤维 的表面性质中表述。 l微细结构,是指纤维内部的有序区(结晶或取向排 列区)和无序区(无定形或非结晶区)的形态、尺寸 和相互间的排列与组合,以及细胞构成与结合方 式。 Set up safety production leading group and provide Party A with copies of job certificate, operation certificate and ID card of the responsible person on site, safety responsible person and all employees. Party B shall be responsible for the personal safety, construction equipment, living facilities, mechanical and electrical equipment and construction safety of Party B. 2. 纤维的原纤结构 – 定义:纤维中的原纤(fibril)是大分子有序排列的结构, 或称结晶结构。严格意义上是带有缺陷并为多层次堆砌 的结构 – 基原纤→微原纤→原纤→巨原纤→细胞 Set up safety production leading group and provide Party A with copies of job certificate, operation certificate and ID card of the responsible person on site, safety responsible person and all employees. Party B shall be responsible for the personal safety, construction equipment, living facilities, mechanical and electrical equipment and construction safety of Party B. l各层次原纤的特征 基原纤(proto-fibril或elementary fibril)是原 纤中最小、最基本的结构单元,亦称晶须,无缺 陷。 微原纤(micro-fibril)是由若干根基原纤平行 排列组合在一起的大分子束,亦称微晶须,带有 在分子头端不连续的结晶缺陷,是结晶结构。 原纤(fibril)是一个统称,有时可代表由若干 基原纤或含若干根微原纤,大致平行组合在一起 的更为粗大的大分子束。 Set up safety production leading group and provide Party A with copies of job certificate, operation certificate and ID card of the responsible person on site, safety responsible person and all employees. Party B shall be responsible for the personal safety, construction equipment, living facilities, mechanical and electrical equipment and construction safety of Party B. 图图2-1 微原纤纤的堆砌形式示意图图 巨原纤(macro-fibril)是由多个微原纤或原纤堆砌而成的结构体。 细胞(cell)是由巨原纤或微原纤直接堆砌而成的,并有明显的细胞 边界。 Set up safety production leading group and provide Party A with copies of job certificate, operation certificate and ID card of the responsible person on site, safety responsible person and all employees. Party B shall be responsible for the personal safety, construction equipment, living facilities, mechanical and electrical equipment and construction safety of Party B. l 定义:指构成该纤维的大分子链之间的 作用形式与堆砌方式,又称为超分子结构 或分子间结构。 l聚集态结构的基础: 大分子间作用力( 次价键力) 二、纤维的聚集态结构 单击此处编辑母版标题样式 单击此处编辑母版副标题样式 * * 8 8 纤维大分子的次价键力包括范 得华力、氢键、盐式键、化学 键、其产生的原因及特点如下 Set up safety production leading group and provide Party A with copies of job certificate, operation certificate and ID card of the responsible person on site, safety responsible person and all employees. Party B shall be responsible for the personal safety, construction equipment, living facilities, mechanical and electrical equipment and construction safety of Party B. ￿￿ 名称产生原因特点 范 得 华 力 定向力产生于极性分子间,是由它们的永 久偶极矩作用而产生的 作用能量3~5千卡/克分 子 与温度有关 诱导力由相邻分子间的诱导电动势产生的 ,产生于极性分子与非极性分子之 间 1.5~3千卡/克分子 与温度有关 色散力由相邻原子上的电子云旋转引起瞬 时的偶极矩而产生的。产生一切非 极性分子中。 0.2~2千卡/克分子 与温度无关 氢键大分子侧基(或部分主链上)极性 基团之间的静电吸引力(如-NH, -COOH,-OH,-CONH等) 能量1.3~10.2千卡/克分 子距离2.3~3.2A 与温 度有关 盐式键在部分大分子侧基上,某些成对基 团之间接近时,产生能级跃迁的原 子转移,从而基团间形成相互结合 的化学键 是化学键中作用力较弱 的一种,能量30~50千 卡/克分子 化学键少数纤维的大分子之间存在这桥式 侧基。化学键键主要包括共价键键、离 子键键和金属键键 能量50~200千卡/克分 子 Set up safety production leading group and provide Party A with copies of job certificate, operation certificate and ID card of the responsible person on site, safety responsible person and all employees. Party B shall be responsible for the personal safety, construction equipment, living facilities, mechanical and electrical equipment and construction safety of Party B. l四种结合力的能量大小: – 化学键>盐式键>氢键>范得华力 l四种结合力的作用距离: – 化学键<盐式键<氢键<范得华力 Set up safety production leading group and provide Party A with copies of job certificate, operation certificate and ID card of the responsible person on site, safety responsible person and all employees. Party B shall be responsible for the personal safety, construction equipment, living facilities, mechanical and electrical equipment and construction safety of Party B. 总结: 纤维大分子链间的作用力 l范德华力 存在于一切分子之间的一种吸引力。 包括定向力、诱导力、色散力。 作用范围小于1纳米,作用能比化学键小1-2个数 量级。 Set up safety production leading group and provide Party A with copies of job certificate, operation certificate and ID card of the responsible person on site, safety responsible person and all employees. Party B shall be responsible for the personal safety, construction equipment, living facilities, mechanical and electrical equipment and construction safety of Party B. l 氢键 极性很强的X-H键上的氢原子,与另一个 键上电负性很大的原子Y上的孤对电子相互 吸引而形成的一种键(X—H···Y)。 发生在分子极性基团之间的作用力。 键能与范德华力的数量级相同 Set up safety production leading group and provide Party A with copies of job certificate, operation certificate and ID card of the responsible person on site, safety responsible person and all employees. Party B shall be responsible for the personal safety, construction equipment, living facilities, mechanical and electrical equipment and construction safety of Party B. 纺织纤维中常见的氢键: O—H···O N—H ··· O N—H ··· N C—H ··· N Set up safety production leading group and provide Party A with copies of job certificate, operation certificate and ID card of the responsible person on site, safety responsible person and all employees. Party B shall be responsible for the personal safety, construction equipment, living facilities, mechanical and electrical equipment and construction safety of Party B. l盐式键 存在于部分纤维大分子间。 如羊毛、蚕丝大分子侧基上的羧基(— COOH)和氨基(—NH 2 )可形成盐式 键 —COO¯ ···+ H 3 N— 盐式键键能大于氢键,小于化学键 Set up safety production leading group and provide Party A with copies of job certificate, operation certificate and ID card of the responsible person on site, safety responsible person and all employees. Party B shall be responsible for the personal safety, construction equipment, living facilities, mechanical and electrical equipment and construction safety of Party B. l 化学键 网状构造的大分子可由化学键构成交联 。 部分纤维,如羊毛和蚕丝的桥式侧基中 存在二硫键和(—S—S—)酯键(—C —O—) O Set up safety production leading group and provide Party A with copies of job certificate, operation certificate and ID card of the responsible person on site, safety responsible person and all employees. Party B shall be responsible for the personal safety, construction equipment, living facilities, mechanical and electrical equipment and construction safety of Party B. Ø纤维大分子主要是通过范德华力和氢键 聚集在一起。 Ø分子间力的大小取决于: 1.单基化学组成(原子团多少、极性集 团数目、极性强弱) 2.聚合度 3.分子间距离 Set up safety production leading group and provide Party A with copies of job certificate, operation certificate and ID card of the responsible person on site, safety responsible person and all employees. Party B shall be responsible for the personal safety, construction equipment, living facilities, mechanical and electrical equipment and construction safety of Party B. l1. 纤维的结晶结构 l将纤维大分子以三维有序方式排列,形成稳定点阵 ,形成有较大内聚能和密度并有明显转变温度的稳 定点阵结构,称为结晶结构。 l将具有结晶结构的区域称作结晶区 l对纤维甚至原纤来说,很少存在完善的结晶区,往 往是结晶与非晶区的混合体,以及与某些结构缺陷 区或其他掺杂成份组合的结构 Set up safety production leading group and provide Party A with copies of job certificate, operation certificate and ID card of the responsible person on site, safety responsible person and all employees. Party B shall be responsible for the personal safety, construction equipment, living facilities, mechanical and electrical equipment and construction safety of Party B. 聚集态结构发展的过程 l缨状微胞模型 l缨状原纤结构模型 l折叠链片晶结构 图图2-2 取向和无序排列的缨缨状微胞结结构 图图2-3 缨缨状原纤结纤结 构 图图2-4 折叠链链片晶 Set up safety production leading group and provide Party A with copies of job certificate, operation certificate and ID card of the responsible person on site, safety responsible person and all employees. Party B shall be responsible for the personal safety, construction equipment, living facilities, mechanical and electrical equipment and construction safety of Party B. 这种模型称为缨状微胞模型。缨状是指无序区中分子 排列的状态;微胞是指分子有序排的结构块。对从晶区到 非晶区是否存在逐步转化的过渡区,尚有不同解释。 图图2-2 取向和无序排 列的缨缨状微胞结结构 Hearle教授提出的缨状原纤 结构模型对此作了很好的解释, 并与纤维的原纤结构形成很好的 对应。 图图2-3 缨缨状原纤结纤结 构 Set up safety production leading group and provide Party A with copies of job certificate, operation certificate and ID card of the responsible person on site, safety responsible person and all employees. Party B shall be responsible for the personal safety, construction equipment, living facilities, mechanical and electrical equipment and construction safety of Party B. 图图2-4 折 叠链链片晶 Kellel等人于1957年用透射电镜观察得 到聚乙烯高分子单晶薄片的厚度约为12nm, 其厚度与分子量无关,并测得分子链垂直于 晶片平面,见图2-4。依此提出了著名的折叠 链片晶结构假说,并认为,线形高分子链长 可达几百到几千纳米,具有很大的表面能, 极易在一定条件下自发地折叠,而形成片状 晶体(片晶)。 Set up safety production leading group and provide Party A with copies of job certificate, operation certificate and ID card of the responsible person on site, safety responsible person and all employees. Party B shall be responsible for the personal safety, construction equipment, living facilities, mechanical and electrical equipment and construction safety of Party B. 图图2-5 取向和非取向折 叠链链片晶结结构模型 根据片晶理论及事实,人们认为片 晶就如同缨状微胞结构中的微胞;伸出 的分子就像缨状分子,再进入其它片晶 的为“缚结分子”,是纤维产生强度的主 机制,如图2-5所示。该结果已在化学纤 维中得到证实,并被称为缨状,折叠链 片晶模型也是典型的两相结构模型。 Set up safety production leading group and provide Party A with copies of job certificate, operation certificate and ID card of the responsible person on site, safety responsible person and all employees. Party B shall be responsible for the personal safety, construction equipment, living facilities, mechanical and electrical equipment and construction safety of Party B. l2、纤维的非晶结构 l纤维大分子高聚物呈不规则聚集排列的区域称为非 晶区,或无定形区。 Set up safety production leading group and provide Party A with copies of job certificate, operation certificate and ID card of the responsible person on site, safety responsible person and all employees. Party B shall be responsible for the personal safety, construction equipment, living facilities, mechanical and electrical equipment and construction safety of Party B. 晶区特点 1)大分子链段排列规整 2)结构紧密,缝隙,孔洞较少 3)相互间结合力强,互相接近的基团结合力饱和 结晶度↑ →纤维的拉伸强度、初始模量、 硬度、 尺寸稳定性、密度↑,纤维的吸湿性、染料吸着性 、润胀性、、柔软性、化学活泼性↓。 Set up safety production leading group and provide Party A with copies of job certificate, operation certificate and ID card of the responsible person on site, safety responsible person and all employees. Party B shall be responsible for the personal safety, construction equipment, living facilities, mechanical and electrical equipment and construction safety of Party B. 非晶区特点: 1)大分子链段排列混乱,无规律; 2)结构松散,有较多的缝隙,孔洞; 3)相互间结合力小,互相接近的基团结合力没 饱和。 结晶度↓→纤维吸湿性↑;容易染色;拉伸强度较小 ,变形较大,纤维较柔软,耐冲击性,弹性有所 改善,密度较小,化学反应性比较活泼 。 Set up safety production leading group and provide Party A with copies of job certificate, operation certificate and ID card of the responsible person on site, safety responsible person and all employees. Party B shall be responsible for the personal safety, construction equipment, living facilities, mechanical and electrical equipment and construction safety of Party B. 3. 纤维的取向结构 l大分子排列方向与纤维轴向吻合的程度称作取向度 l力学性能,强度、模量在纤维轴向上提高,而伸长 性降低 l光泽较好,各向异性明显 Set up safety production leading group and provide Party A with copies of job certificate, operation certificate and ID card of the responsible person on site, safety responsible person and all employees. Party B shall be responsible for the personal safety, construction equipment, living facilities, mechanical and electrical equipment and construction safety of Party B. 单基(链节) – 定义: 构成纤维大分子的基本化学结构单元。 A′-A-A……A-A-A〞或 A′-(A)n-A〞 A ——单基; A′、A〞——端基; n ——聚合度; 三、纤维的分子结构 Set up safety production leading group and provide Party A with copies of job certificate, operation certificate and ID card of the responsible person on site, safety responsible person and all employees. Party B shall be responsible for the personal safety, construction equipment, living facilities, mechanical and electrical equipment and construction safety of Party B. 常用纺织纤维单基的化学组成: Set up safety production leading group and provide Party A with copies of job certificate, operation certificate and ID card of the responsible person on site, safety responsible person and all employees. Party B shall be responsible for the personal safety, construction equipment, living facilities, mechanical and electrical equipment and construction safety of Party B. Set up safety production leading group and provide Party A with copies of job certificate, operation certificate and ID card of the responsible person on site, safety responsible person and all employees. Party B shall be responsible for the personal safety, construction equipment, living facilities, mechanical and electrical equipment and construction safety of Party B. 二.聚合度 1)定义: 构成纤维大分子的单基的数目,或一个 大分子中的单基重复的次数(n)。 大分子的分子量=单基的分子量×聚合度 Set up safety production leading group and provide Party A with copies of job certificate, operation certificate and ID card of the responsible person on site, safety responsible person and all employees. Party B shall be responsible for the personal safety, construction equipment, living facilities, mechanical and electrical equipment and construction safety of Party B. 常用纤维的n: 棉麻的聚合度很高 ,成千→上万; 羊毛 n=576; 蚕丝 n=400 再生纤维素纤维 300-600 涤纶 130 晴纶 1000-1500 维纶 n=1700 丙纶 n=310-430 一根纤维中各个大分子的n不尽相同,具有 一定的分布 → 高聚物大分子的多分散性。 Set up safety production leading group and provide Party A with copies of job certificate, operation certificate and ID card of the responsible person on site, safety responsible person and all employees. Party B shall be responsible for the personal safety, construction equipment, living facilities, mechanical and electrical equipment and construction safety of Party B. 三、纤维大分子链的支化、构型 纤维大分子的形状由于单基的键接方式的不 同,可以分为三种构造形式: l线型linear l枝型branched l网型network(crosslinked) Set up safety production leading group and provide Party A with copies of job certificate, operation certificate and ID card of the responsible person on site, safety responsible person and all employees. Party B shall be responsible for the personal safety, construction equipment, living facilities, mechanical and electrical equipment and construction safety of Party B. Set up safety production leading group and provide Party A with copies of job certificate, operation certificate and ID card of the responsible person on site, safety responsible person and all employees. Party B shall be responsible for the personal safety, construction equipment, living facilities, mechanical and electrical equipment
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