【作者】 张志奋；

【导师】 朱苏康；

【作者基本信息】 东华大学 ， 纺织工程， 2010， 博士

【摘要】 织造工艺研究中,提高经纱上浆质量一直是作为核心课题受到纺织业界的广泛关注。近年,新型浆料和浆纱助剂研发、上浆工艺优化,特别是纳米、微纳米掺杂浆料的开发和利用,为提高浆纱质量开辟了全新的广阔前景。但是,在浆料研发、上浆工艺优化进程中,如何进行过程质量控制,并对最终结果作出科学、准确的预测和质量评价,长期以来围绕这一命题的研究甚少。本文全面归纳分析了传统的上浆工程质量体系,认为传统的过程质量控制及评估方法虽然在实际生产和研究工作中已经起到了很大的作用,但是其测试方法和手段仍属于表观、与事物本质有所偏离的实验方法范畴,基本上游离于现代材料科学的成就之外。特别是传统的浆膜性能测试通常采用静态的、形式单一的外力作用方式,因此测试结果和浆膜实际的工作状况具有很大差异。本文认为,浆纱表面以及内部部分纤维之间黏附的浆膜对浆纱的可织性起着最为重要的作用。浆纱和浆膜随着织机的运行始终处于动态的变化过程中,这些动态变化不仅包括自身的结构性能渐变,而且包含各种外部条件的变化。为此,应当从动态的角度,从材料科学角度对浆膜进行测试、审视,并以此建立起各种因素间的相互关联,客观而综合地表征浆膜的特点与性能。本文在研究中摈弃了传统的从宏观到宏观的研究路线,按照高分子材料性能的特征,遵循从微观、细观再到宏观的现代材料科学的研究路线及方法,根据织机上浆纱、浆膜的实际工况,建立起相应的、科学的浆膜性能表征和测试新方法。进而,在动态变化条件下,从浆膜拉伸力学性能、耐磨性能、耐疲劳性能、浆膜与浆纱的拉伸模量适配性能、浆膜和浆纱的受热软化性能和再粘性能、浆膜和纤维的亲和性能、浆纱强伸性能等方面客观地描写浆膜乃至浆纱上浆质量的优劣。上浆工程质量体系是一项内涵十分丰富的系统工程,需要一个长期探索,逐步完善的过程,本文仅围绕合理、科学的浆膜性能评价、表征作一些初步的开拓性研究。基于近年来纳米科技取得的成果,以本文所提出的浆膜性能的测试新方法为过程质量控制手段,开展了新型微纳米蒙脱土粉体掺杂PVA/磷酸酯淀粉混合浆料的研发和多方位的性能表征。同时,通过这些研发工作来验证所提出的测试新方法的必要性及科学性。本论文主要进行了下列研究。参考传统的浆膜性能测试方法,嫁接现代材料科学与工程的理论和研究成果,本文选择了几种具有代表性的主浆料：变性淀粉、PVA和聚丙烯酸酯类浆料,从浆膜动态拉伸力学性能、动态的耐疲劳性能、动态耐磨性能、动态过程中浆膜软化和再粘现象等五个方面,提出相应的比较完整的浆膜性能评判方法和测试手段。1.使用动态力学热分析法(DMA)进行浆膜和浆纱的动态拉伸力学性能测试,反映浆膜的动态应力与应变的关系和动态模量变化。通过静态和动态应力作用两种模式,对浆膜和其浆纱进行拉伸力学性能测试、比较,凸显了动态拉伸力学性能分析的重要性和写实性。研究发现,在动态应力条件下,浆膜的动态模量值要远大于静态拉伸测试的浆膜小变形弹性模量值,因此,在实际生产中,必须考虑浆膜与浆纱动态模量的适配问题。2.采用DMA仪进行浆膜拉伸蠕变-回复性能测试和动态拉伸应力测试,两种测试方法均可评价浆膜的动态耐疲劳性能。浆膜拉伸蠕变-回复性能的测试,衡量材料在反复拉伸加载、卸载下的应变回复能力和蠕变特性。本文对传统的浆膜回弹率尺的计算公式加以改进,提出了动态蠕变-回复评估指标。拉伸动态应力测试则是在动态交变载荷作用下,测定材料的时间-动态应力-应变曲线,交变频率及测试温度参考织机运行的转速和织造车间温度选定。测试中,以一定次数交变外力作用之后材料累积的应变量,来表述材料耐疲劳性能。对浆膜及其相应浆纱进行拉伸蠕变-回复性能测试和动态拉伸应力测试,测试结果表明了浆膜与浆纱耐疲劳性能的一致性,可以用浆膜预测它所对应浆纱的耐疲劳性能,与传统的测试方法相比,更贴近浆膜与浆纱的实际工作情况。3.自制了动态拉伸条件下纺织浆膜磨损试验装置,该装置可根据测试的需要设置不同的浆膜变形量、磨损载荷以及浆膜变形速度等参数,能够比较真实地模拟织机上浆膜的实际工作条件。测试得到样品磨断次数,以此评判浆膜在动态拉伸变形状态下的耐磨性能。通过对动态条件下的磨损浆膜的表面形貌观察分析和差示扫描量热分析法DSC对磨损浆膜的热学性能测试,可以获知：浆膜在反复动态拉伸下经受摩擦比无拉伸状态下的摩擦产生更为严重的磨损,前者反映了实际的浆膜摩擦、磨损情况。4.浆膜玻璃化温度Tg,可以作为衡量浆膜受热软化的重要特性参数。采用动态热机械分析法DMA测试浆膜玻璃化温度值,以此来评估和推测在实际织造工况下浆膜软化发生的可能性和程度。在研发新型浆料时,可以控制其浆膜的玻璃化温度,保持织造条件下浆膜适当的强度和刚柔性,保证织造正常进行。5.在织造车间的高温湿度条件下,浆膜乃至浆纱会发生再粘现象。本文首先测量去离子水在浆膜表面的接触角,用以判断水分对于浆膜的浸润性能。接触角小浆膜浸润性能越好,则越容易吸收水分并引起再粘现象。通过差示扫描量热分析法(DSC)进行浆膜和水的混合物热学性能测试,可以定量地确定浆膜开始发生再粘现象的溶胀温度Tn,以及从溶胀温度Tn开始到此后ΔT温度变化范围内,浆膜溶胀所发生的焓变,从而综合地描写材料的形态结构变化和“再粘”现象的明显程度。因此,接触角、溶胀温度和ΔT温度范围内焓变被列为比较各种浆膜再粘性的指标。上述五方面浆膜动态性能的测试,比较完整、真实地刻画了浆膜直至浆纱的特点与性能,为各类浆料研发、上浆工程优化提供可靠的过程质量评估依据。二、本文针对涤棉浆纱上浆研制了微纳米蒙脱土粉体掺杂的PVA-1799/磷酸酯淀粉混合浆料,采用浆膜动态性能的五个方面测试方法,辅以浆膜和纤维亲和性能、浆纱强伸性能测试等,对浆料的微纳米蒙脱土掺杂改性工艺进行过程质量控制、优化以及改性效果评估。首先,采用低温等离子体方法对市购纳米蒙脱土粉体进行表面处理,借助超声粉碎方法调制微纳米蒙脱土分散液,确定了它们的优化工艺条件。经优化工艺所获得的微纳米蒙脱土分散液中,微粒的平均粒径为472nm。选择PVA-1799和磷酸酯淀粉作为主浆料。由于PVA-1799/磷酸酯淀粉混合浆液与配制的微纳米蒙脱土分散液Zeta电位均为负值,两者混合、掺杂后不会因电性相反而造成异质聚沉或微纳米粉体颗粒二次团聚。微纳米蒙脱土掺杂浆膜经过红外光谱的结构分析,证明微纳米材料的掺杂不会引起浆料化学性质的变化。通过微纳米蒙脱土掺杂浆膜XRD分析,说明磷酸酯淀粉和PVA-1799除了作为主粘着剂外,还可作为微纳米蒙脱土的插层剂,混合、掺杂的结果进一步改善了微纳米蒙脱土粉体的分散程度。文章以微纳米蒙脱土改性前后的浆膜动态拉伸力学性能、动态耐疲劳性能、动态耐磨性能、浆膜软化性能和再粘性能、浆膜和涤棉纤维亲和性能、涤棉浆纱强伸性能来优化掺杂工艺(微纳米蒙脱土掺杂比例),并且综合评判其浆料的改性效果。优化及评判结果表明：微纳米蒙脱土掺杂有利于提高PVA-1799／磷酸酯淀粉混合浆膜及其浆纱的性能,其中以微纳米蒙脱土掺杂比例3%的综合效果较好。论文基于浆膜动态拉伸力学性能、动态耐疲劳性能、动态耐磨性能、浆膜软化性能和再粘性能的测试方法,组合传统的浆膜和纤维亲和性能、浆纱强伸性能的测试方法,提出了一个比较完整的、隶属于上浆工程质量体系的子系统,用于浆料研发和浆纱工艺过程改进的过程质量控制、优化以及效果评估,具有较好的科学性和明显的可行性。同时,通过这一子系统的研究,也为今后上浆工程质量体系的逐步完善提供了新的思路和理论基础。更多还原

【Abstract】 It has always been highly concerned by the textile industry to improve the quality of warp sizing in the weaving technology. In recent years, the researches of new size and sizing additives, the optimization of sizing technology, especially the development and utilization of sizing agent doped by micro-nano material, have highly broaden new prospects for the improvement of the sizing quality. However, there’re rarely the researches about the topic for a long time that, in the process of size developing and the optimization, how to control the quality in the process and to dependently brings forward the scientific prediction and accurate quality evaluation.This paper comprehensively summarized and analyzed the traditional sizing engineering quality system, and considered that although the traditional process quality control and evaluation methods are very effective in the actual production and research, these methods are still parts of the apparent, within the scope of experimental methods that deviate things from the essence, basically separated from the achievements of modern materials science. Especially, the static and single external factors modes are widely used in the test of the traditional mechanical performance which have caused that the testing results have significant difference from the actual working conditions of the size film.The paper believed that the sizing surface and film adhered to the fibers play the most important role in the waving efficiency. Sized yarn and its film are always under the motional changes with the running loom. These motional changes include not only a gradual change of their own structural performance, but also variety changes of external conditions. Regarding this, the size film should be tested and analyzed from dynamic perspective according to material science, and thus the linkages between the various factors are established. Accordingly, dynamic characteristics of the film are objectively and comprehensively characterized. This paper, rejecting the idea of traditional research from the macro to the macro-line, undertook much research work according to the performance of polymer materials and on the methodology for contemporary material science from the microscopic to the macro. Thus, new appropriate and scientific methods to test the performance of film were presented. These presented testing methods cover a wide range of sized yarns performance including properties of dynamic mechanical, wear resistance, fatigue resistance, the suitability of tensile modulus of the film and yarn, soften and re-sticky due to heat during the dynamic process, supplemented by affinity between the film and fiber,strength and extension of sizing yarn. The quality of the film and sizing are described objectively. However, the sizing engineering quality system is a system containing rich content which needs a long-term exploration and a process to gradually achieve perfect. This paper only focused on rational and scientific evaluation method of film to made some preliminary exploration and research.Based on the achievement, in nanotechnology, the new type of size mixture of PVA/phosphate starch doped by micro nano-montmorillonite powder is developed. Their various properties were studied adopting the new measuring methods presented by this paper. Meanwhile, the necessity of the scientific testing methods is validated through these researches and developments.The main researches included in this thesis are as following.Ⅰ. Several typical main sizes:modified starch, PVA and polyacrylate sizing were studied referring to the traditional test methods of the properties of film, grafting of the theory and the research findings in the field of modern materials science and engineering. It presented a relatively complete corresponding evaluation methods and test means of sizes performance from five parts, including dynamic tensile mechanical properties, dynamic fatigue resistance, dynamic wear-resistance, soften and re-sticky Properties during the dynamic process.1. The dynamic mechanical thermal analysis (DMA) is used to test dynamic tensile mechanical properties of the film and sizing yarn to test the relationship between the dynamic stress and strain and the dynamic changes of modulus. By means of two testing modes of the static and dynamic, the dynamic tensile mechanical properties of the film and sizing yarn have been tested and compared, and the analysis showed that test of dynamic tensile mechanical properties is important and realistic.The study found out that under the dynamic stress conditions, the value of dynamic modulus of the film is much larger than the elastic modulus of small deformation at the static tensile. Therefore, in actual production, we must consider the adaptation between the dynamic modulus of the film and sizing yarn.2. DMA is applied to test tensile creep-recovery and dynamic tensile stress of the film, both of which can evaluate the dynamic fatigue resistance. The test of tensile creep-recovery is a way that tests the strain recovery ability and creep properties of the film in repeated tensile loading and unloading. The traditional equation of recovery rate R of the film was improved, and the evaluation index of dynamic creep-recovery has been presented.The test of dynamic tensile stress is a way that test time- dynamic stress-strain curve under external alternating loads, frequency and test temperature of which are respectively determined by the speed of looms and the ambient temperature in the weaving workshop. The accumulation of the strain after exposure to a certain number of alternating external force is adopted to indicate the fatigue resistance.The film and its sizing yarn were tested using the methods of the tests of tensile creep-recovery and dynamic tensile stress. The test results show the fatigue-resistance of the film and sizing yarn have consistency, so testing film can be used to predicate the dynamic fatigue resistance of the corresponding yarn. Compared with the traditional test method, the tests of tensile creep-recovery and dynamic tensile stress are closer to the actual working situation.3. The wear tester of the sizing film under the condition of dynamic tensile was self developed. The Instrument can set the different parameters, such as film deformation amount, load for wear and deformation velocity, to simulate the actual working condition of the film in the looms. The wear number of film by friction is used to judge the wear resistance of the film when stretching. With the help of scanning electron microscope (SEM) and differential scanning calorimeter (DSC), the surface morphology and thermal properties of the film by alternately stretching were investigated. The testing results express that the film under stretching causes more serious wear than when the film is not stretched alternately, so testing the film under stretching alternately reflects the actual wear resistance of the film.4. Glass transition temperature (Tg) is used as an important parameter to present softening characteristic of the film due to heat. Dynamic mechanical analyzer(DMA) was applied to measure the value of glass transition temperature to assess and speculate the possibility of happening and extent of softening in real working condition. In the development of new size, the glass transition temperature would be controlled to maintaining the appropriate strength and softness of the film for ensuring normal weaving.5. under the high temperature and high humidity conditions in the weaving workshop, the size film as well as sizing yarn would have re-sticky phenomenon. In this paper, The contact angle on the size film dropped by deionized water has first been tested to judge the wettability of water on the sizing film. The smaller the contact angle can be, the better the wettability has, which make easier to absorb water and cause the phenomenon of re-sticky.Testing the thermal properties of the mixture of sizing and water with differential scanning calorimeter (DSC) can determine quantitatively the swelling temperature Tn,which presents that the size film will begin to appear re-sticky, and the enthalpy in the range from swelling temperature Tn to subsequentΔT temperature due to the swelling of size film, therefore, the swelling temperature Tn and the enthalpy will comprehensively describe structural changes of material and the extent of the phenomenon of re-sticky. So, the contact angle, swelling temperature and the enthalpy during theΔT temperature are listed as parameters comparing the re-sticky performance of various size film.The above five kinds of testing of dynamic properties of size film comparatively and factually describe the properties and functions of size film as well as sizing yarn. And they provide the reliable evaluation reference of process quality for the development of different kinds of sizing and the optimization of sizing engineering.Ⅱ. This paper developed specifically the size mixture, which appropriate to the polyester cotton yarn, of PVA-1799 and phosphate starch doped by micro nano-montmorillonite powder. The five methods for testing dynamic properties of the film were adopted, supplemented by testing of affinity between the film and fiber and strength and extension of sizing yarn, to control and optimize the size mixture and modification technology of doping micro nano-montmorillonite powder. Based on this, the modification effect are evaluatedFirst of all,low temperature plasma treatment has been used to deal with the surface modification for raw nano-montmorillonite powder. Then, the nano-montmorillonite disperse liquid were prepared by using the method of ultrasonic dispersion and their process conditions were determined. The average particle size in the disperse liquid by optimized process was 472 nm.PVA-1799 and phosphate starch were selected as the main sizing agent. As Zeta potential of both the size mixture of the PVA-1799/phosphate starch and the prepared disperse liquid of micro-nano-montmorillonite is negative or have the same phase-electricity, the two kinds of materials will not result in coagulation or agglomeration of the nano-powder when they are mixed. The structural analysis of infrared spectrum showed that micro-nano-montmorillonite is doped into sizing did not cause the change of chemical properties of the sizing agent. Through the XRD analysis of the film doped with nano-montmorillonite, it was indicated the phosphate starch and PVA-1799 act not only as the primary adhesive agent but also as a the assist intercalation agent for micro-nano-montmorillonite to further improve the dispersion extent of the powder.The film modified by micro nano-montmorillonite were studied through testing methods of the dynamic mechanical properties, dynamic fatigue performance, dynamic wear resistance, softening, re-sticky of the film, affinity between the film and polyester cotton fiber,strength and extension of sizing polyester cotton yarn. These studied results were used to optimize doping process and the proportion of the doping micro nano-montmorillonite. The testing and the comprehensive evaluation show that: doping with micro-nano-montmorillonite help to improve the dynamic properties of the film and sizing yarn of size mixture of PVA/phosphate starch. Of which, the proportion of micro nano-montmorillonite doped with 3% has the best effect.Based on the testing methods of the dynamic mechanical properties, dynamic wear resistance, dynamic fatigue performance, softening and re-sticky of the film, by combining the traditional affinity between the film and fiber, strength and extension of sizing yarn, this paper proposed a comparatively completed subsystem which belonged to sizing engineering quality system. This subsystem is more scientific and practical for size developing and it can be applied to the quality control in the process of sizing, the optimization of sizing technology and the evaluation of modification effect. At the same time, the study of this sub-system also provides new ideas and fundamental theories for sizing engineering quality system, which is being gradually improved.更多还原