轮胎帘子线用Lyocell纤维的研制
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摘要
Lyocell纤维是二十世纪九十年代开发出来的一种新型的纤维素纤维,同传统的粘胶纤维相比,其强度和模量更高、生产工艺简单环保,并能直接采用相对分子质量较高的纤维素原料进行溶解纺丝,这是粘胶工艺所无法达到的。因此,Lyocell纤维有望替代现有的粘胶帘子线作为一种轮胎帘子线用纤维素纤维。
迄今为此,国内外尚未见Lyocell纤维应用于轮胎帘子线领域的相关报道。为此,本论文在研究各种纤维素原料溶解特性及其溶液流变性能的基础上,探讨了原料的性质、纺丝条件、氯化铵改性、热处理及交联处理等因素对最终所制得的Lyocell纤维结构和性能的影响,由此探索出了制备轮胎帘子线用Lyocell纤维的几种可行的方法。
本论文首先采用带有CCD和热台的偏光显微镜跟踪观察了纤维素原料在N-甲基吗啉-N-氧化物一水合物(NMMO·H_2O)溶剂中的溶解过程,并利用HAAKE流变仪分析了各种溶液的流变性能。研究发现:纤维素的相对分子质量越高,溶解过程对温度依赖性越强,相应溶液出现切力变稀的临界剪切速率也越小,同时粘流活化能升高,且溶液均匀性下降。因此,采用较高相对分子质量的纤维素原料纺制Lyocell纤维时,应特别注意溶解工艺的合理选择及纺丝温度等纺丝条件的稳定控制。
在上述研究基础上,本论文探讨了纤维素原料性质对所制得的Lyocell纤维性能的影响,结果表明:纤维素原料的相对分子质量(或聚合度)相对于α-纤维素含量而言对纤维力学性能的影响更大一些,原料相对分子质量越高,所得纤维的力学性能越好;当原料的相对分子质量接近时,纤维的力学性能则随原料中α-纤维素含量的增加而改善;并且,较高的α-纤维素含量还有利于纤维耐热性的提高。与此同时,本论文还利用凝胶渗透色谱(GPC)等手段分析了高(或超高)相对分子质量纤维素与中等相对分子质量纤维素的混合原料所形成的纺丝液的纺丝性能,发现通过在中等相对分子质量纤维素原料中混合适量的高相对分子质量纤维素原料可以改善所得Lyocell纤维的力学性能,但若两种原料的相对分子质量相差过大,则易引起纺丝液在流经纺丝组件过滤层时发生分层从而无法有效地提高纤维的力学性能。通过上述研究表明,采用以高相对分子质量纤维素或其与中等相对分子质量纤维素的混合体系为原料是提高Lyocell纤维力学性能和制备轮胎帘子线用Lyocell纤维的一种可行的途径。
除了采用高相对分子质量纤维素为原料的方法外,本论文还探讨了在纺丝液中加入氯化铵添加剂来制备高性能Lyocell纤维的可行性,发现添加氯化铵对纤维素/NMMO·H_2O溶液流变性能的影响规律与提高纤维素相对分子质量十分相似:随着体系中氯化铵添加量的增加,溶液体系表观粘度、零切粘度和结构化程度均呈上升趋势,纤维素分子级溶解均匀性变差。因此,为确保良好的可纺性和纺丝稳定性,在纤维素/NMMO·H_2O纺丝液中氯化铵的添加量不宜过多。对所纺得纤维的分析结果表明:氯化铵的添加有利于纤维素Ⅲ结晶结构的形成,经适量氯化铵改性后的Lyocell纤维具有纤维素Ⅱ和纤维素Ⅲ两种结晶变体的混合结构,并且纤维总的结晶度和取向度均有所增加,力学性能也明显改善。由此可见,氯化铵改性也不失为制备高力学性能Lyocell纤维的有效方法。
为了探索完善Lyocell纤维聚集态结构的合适方法,本论文还对Lyocell纤维结晶结构的形成过程进行了研究分析,结果发现:尚未干燥过的湿态初生Lyocell纤维中,纤维素的三维有序排列还未完全形成。Lyocell纤维的结晶结构是在其湿态初生纤维的失水干燥过程中形成的,随着纤维含水率的减小,准晶结构逐渐消失,结晶结构逐渐完善。当初生Lyocell纤维完全干燥后,其结晶结构便比较稳定,很难再被改变。因此,有望通过对尚未干燥过的初生Lyocell纤维进行适当的后处理来有效改善最终Lvocell纤维的聚集态结构,从而达到提高纤维力学性能的目的。
为此,本论文进一步利用自制的热处理装置对尚未干燥过的初生Lyocell纤维进行了张力下热处理,探讨了预张力、热处理温度及时间和张力对最终纤维力学性能等性质的影响,并在最佳热处理条件下制得了强度和模量比室温干燥的Lyocell纤维分别提高29.7%和97.4%的纤维,且其干热收缩率和蠕变率也显著减小,相关性能均符合轮胎帘子线用纤维要求,由此表明对尚未干燥过的初生Lyocell纤维进行热处理也是获得轮胎帘子线用Lyocell纤维的一种可行方法。在此基础上,本论文还将氯化铵改性与热处理相结合,对湿态初生氯化铵改性Lyocell纤维在适当条件下进行热处理,最终可得到断裂强度高达到7.21cN/dtex、初始模量达到92.6cN/dtex、蠕变率低于0.5%、干热收缩率小于0.8%的高性能Lyocell纤维。由此可见,采用氯化铵改性和热处理相结合的方法有利于获得高性能的轮胎帘子线用Lvocell纤维。
此外,由于Lyocell纤维具有易原纤化的特性,这种性能会影响纤维的耐疲劳性等性能,为此,为了提高Lyocell纤维的抗原纤化能力,以保证其具有优良的耐疲劳性和耐磨擦性能,本论文还摸索出了最佳的交联剂处理工艺,对尚未干燥过的初生Lyocell纤维进行了适当的交联处理,发现经交联处理后的Lyocell纤维中,基纤以及基纤聚集束尺寸均明显减小且含量增加,由此降低了微原纤从纤维主干上劈裂的可能性,使最终所得Lyocell纤维在保持原有力学性能的基础上,湿摩擦值(该值与抗原纤化能力成正比)达到733s左右,比普通Lyocell纤维提高了约13倍,且纤维的耐疲劳性也明显提高。这些研究结果表明,适当的交联处理可以改善Lyocell纤维应用于轮胎帘子线的综合性能。在此基础上,本论文进一步对尚未干燥过的初生氯化铵改性Lyocell纤维进行了交联处理及热处理,发现最终所得Lyocell纤维的力学性能、耐疲劳性、耐热性及尺寸稳定性等指标均远优于高模低收缩涤纶轮胎帘子线和高强粘胶轮胎帘子线。
由本论文上述研究表明,(1)以高相对分子质量纤维素或其与中等相对分子质量纤维素的混合体系为原料、(2)添加氯化铵改性、(3)对尚未干燥过的初生Lyocell纤维进行张力下热处理等几种方法均为有效提高Lyocell纤维力学性能和获得轮胎帘子线用Lyocell纤维的可行方法,并且,通过氯化铵改性和热处理相结合(或进一步结合交联处理),可以获得综合指标佳、高性能的轮胎帘子线用Lyocell纤维。
Lyocell fiber is a new kind of regenerated cellulose fiber developed in the 1990s.Compared with traditional rayon fibers,it has higher strength and modulus.Lyocell process is a simple and environmentally friendly process. It can use higher relative molecular weight cellulose as raw material to prepare fiber directly,which is impossible for rayon process.Therefore, Lyocell fiber can expectedly be used as tire cord to replace the existing rayon tire cord.
To date,there is no report on Lyocell fiber used as tire cord.In this thesis,the dissolving characteristic of various celluloses and the rheological properties of the spinning dopes were investigated firstly.Then the effects of various factors such as the raw material properties,the spinning condition, the addition of ammonium chloride,heat treatment and cross-link treatment on the structure and properties of the resultant Lyocell fiber were also investigated.Base on the above studies,some feasible ways for preparing Lyocell fiber used as tire cord have been found.
In this thesis,the dissolving process of cellulose pulps were observed by using a polarizing microscopy with CCD and a heating stage and the rheological properties of the cellulose solutions were studied by HAAKE rheometer.The results showed that the higher the relative molecular weight of cellulose,the stronger the dependence of dissolving rate on temperature and the higher the activation energy of the cellulose solution.Also,the homogeneity of the solution became poorer and its critical shear rate was decreased.Therefore,the parameters for dissolution and spinning,such as temperature and so on,should be controlled strictly when the cellulose pulp having a higher relative molecular weight was used to prepare Lyocell fiber.
The results based on the mechanical properties of the resultant fibers also showed that the relative molecular weight of cellulose played a more important role in improving the mechanical properties of fibers thanα-cellulose content.If the relative molecular weights of celluloses were similar,the mechanical properties of Lyocell fibers can be improved with the increasing ofα-ceUulose content in cellulose.The highα-cellulose content in cellulose had positive effect on heat and size stability of Lyocell fiber.Moreover,the properties of spinning dopes from the cellulose mixed by high(or super-high) relative molecular weight cellulose and medium relative molecular weight cellulose were analyzed by GPC.It was found that the mechanical properties of Lyocell fiber could be improved by mixing an appropriate amount of high relative molecular weight cellulose with medium relative molecular weight cellulose.However,if the difference between the relative molecular weights for two celluloses was too big,the resultant dope would be separated during its passing through filter of spinning components and therefore the mechanical properties of prepared Lyocell fiber could not be improved effectively.Therefore,using high relative molecular weight cellulose or its mixture with medium relative molecular weight cellulose as raw material is a feasible way for improving mechanical properties of Lyocell fiber and preparing Lyocell fiber used as tire cord.
In this thesis,the feasibility of preparing high performance Lyocell fiber by adding ammonium chloride in the dope was further investigated. The results showed that the effect of adding ammonium chloride on the rheological properties of cellulose/NMMO·H_2O solution was similar to that of increasing relative molecular weight of cellulose.With the increase of ammonium chloride in the solution,the apparent viscosity,zero-shear viscosity and structural viscosity index for cellulose solution were increased, while the dissolution homogeneity of cellulose was decreased.In order to insure good spinnablity and spinning stability,the adding amount of ammonium chloride couldn't be too high.It was also found that the mechanical properties of resultant Lyocell fiber modified by an appropriate amount of ammonium chloride were improved and the modified Lyocell fiber has a mixture structure of celluloseⅡcrystal and celluloseⅢcrystal. Furthermore,the total crystallinity and orientation could be increased with adding ammonium chloride.This means that the modification by ammonium chloride is also an effective way to prepare Lyocell fiber with excellent mechanical properties.
In order to find an effective method to improve the crystalline and orientation structure of Lyocell fiber,the formation of crystal structure of Lyocell fiber was also studied in this thesis.It was found the tridimensional order of never dried as-spun Lyocell fiber was not fully formed yet.With the decreasing water content of as-spun Lyocell fiber,its paracrystal structure disappeared gradually and meanwhile the crystal structure was improved.Once the Lyocell fiber was dried completely,its crystal structure had been stabilized and was difficult to be destroyed and rearranged. Therefore,it is hopeful to improve crystalline structure and mechanical properties of Lyocell fiber by appropriate post treatment using never dried Lyocell fiber as precursor.
Therefore,in this thesis the never dried as-spun Lyocell fiber was heat-treated under tension by using a home-made heat treatment equipment. And the effect of pretension,temperature and time as well tension of heat treatment on the mechanical properties of resultant Lyocell fiber was also investigated.It was found that after optimal heat treatment,the tensile strength and initial modulus of Lyocell fiber could be increased by 29.7% and 97.4%,respectively,and its dry heat shrinkage and creep ratio were decreased obviously,which could accord with the requirements of tire cord. That means the heat treatment is a feasible way to obtain the Lyocell fiber used as tire cord.Based on the above studies,the never dried Lyocell fiber, which had been modified by ammonium chloride,was heat-treated.The strength and the modulus of resultant Lyocell fiber could reach 7.21 cN/dtex and 92.6cN/dtex,respectively.And the creep ratio and dry heat shrinkage were lower than 0.5%and 0.8%,respectively.Therefore,the modification by ammonium chloride combined with heat treatment was an effective method to prepare high performance Lyocell fiber.
It is generally believed that the Lyocell fiber has high fibrillation tendency,which has negative effect on its fatigue properties.In order to increase the fibrillation resistance of Lyocell fiber to improve its fatigue resistance and wear resistance,the optimal cross-link treatment was also investigated by using the never dried Lyocell fiber as precursor.The results showed that the cross-link treatment could effectively decrease the sizes of elementary fibril and elementary fibril cluster and increase their contents, which led to reduce the possibility of the fibril separating from the fiber and improve fatigue resistance of Lyocell fiber.Therefore,the wet abrasion value of Lyocell fiber after cross-link treatment was 13 times higher than that of common Lyocell fiber.These results indicated that the appropriate cross-link treatment could improve the comprehensive properties of Lyocell fiber,which were necessary for tire cords.Based on the above studies,the never dried Lyocell fiber modified by ammonium chloride was cross-link treated firstly and then heat-treated.It can be found that the mechanical properties,fatigue resistance,heat and size stability of the resultant Lyocell fiber are much better than those of HLMS polyester tire cord and high strength rayon tire cord.
The above investigations showed that the Lyocell fiber used as tire cord could be prepared by(1) using high relative molecular weight cellulose or its mixture with medium relative molecular weight cellulose as raw material, (2) modification by adding ammonium chloride,and(3) the heat treatment under tension using never dried Lyocell fiber as precursor.The high performance Lyocell fiber with excellent comprehensive properties,which can be used as tire cord,could be obtained by combining the modification by ammonium chloride with the heat treatment(or further with cross-link treatment).
迄今为此,国内外尚未见Lyocell纤维应用于轮胎帘子线领域的相关报道。为此,本论文在研究各种纤维素原料溶解特性及其溶液流变性能的基础上,探讨了原料的性质、纺丝条件、氯化铵改性、热处理及交联处理等因素对最终所制得的Lyocell纤维结构和性能的影响,由此探索出了制备轮胎帘子线用Lyocell纤维的几种可行的方法。
本论文首先采用带有CCD和热台的偏光显微镜跟踪观察了纤维素原料在N-甲基吗啉-N-氧化物一水合物(NMMO·H_2O)溶剂中的溶解过程,并利用HAAKE流变仪分析了各种溶液的流变性能。研究发现:纤维素的相对分子质量越高,溶解过程对温度依赖性越强,相应溶液出现切力变稀的临界剪切速率也越小,同时粘流活化能升高,且溶液均匀性下降。因此,采用较高相对分子质量的纤维素原料纺制Lyocell纤维时,应特别注意溶解工艺的合理选择及纺丝温度等纺丝条件的稳定控制。
在上述研究基础上,本论文探讨了纤维素原料性质对所制得的Lyocell纤维性能的影响,结果表明:纤维素原料的相对分子质量(或聚合度)相对于α-纤维素含量而言对纤维力学性能的影响更大一些,原料相对分子质量越高,所得纤维的力学性能越好;当原料的相对分子质量接近时,纤维的力学性能则随原料中α-纤维素含量的增加而改善;并且,较高的α-纤维素含量还有利于纤维耐热性的提高。与此同时,本论文还利用凝胶渗透色谱(GPC)等手段分析了高(或超高)相对分子质量纤维素与中等相对分子质量纤维素的混合原料所形成的纺丝液的纺丝性能,发现通过在中等相对分子质量纤维素原料中混合适量的高相对分子质量纤维素原料可以改善所得Lyocell纤维的力学性能,但若两种原料的相对分子质量相差过大,则易引起纺丝液在流经纺丝组件过滤层时发生分层从而无法有效地提高纤维的力学性能。通过上述研究表明,采用以高相对分子质量纤维素或其与中等相对分子质量纤维素的混合体系为原料是提高Lyocell纤维力学性能和制备轮胎帘子线用Lyocell纤维的一种可行的途径。
除了采用高相对分子质量纤维素为原料的方法外,本论文还探讨了在纺丝液中加入氯化铵添加剂来制备高性能Lyocell纤维的可行性,发现添加氯化铵对纤维素/NMMO·H_2O溶液流变性能的影响规律与提高纤维素相对分子质量十分相似:随着体系中氯化铵添加量的增加,溶液体系表观粘度、零切粘度和结构化程度均呈上升趋势,纤维素分子级溶解均匀性变差。因此,为确保良好的可纺性和纺丝稳定性,在纤维素/NMMO·H_2O纺丝液中氯化铵的添加量不宜过多。对所纺得纤维的分析结果表明:氯化铵的添加有利于纤维素Ⅲ结晶结构的形成,经适量氯化铵改性后的Lyocell纤维具有纤维素Ⅱ和纤维素Ⅲ两种结晶变体的混合结构,并且纤维总的结晶度和取向度均有所增加,力学性能也明显改善。由此可见,氯化铵改性也不失为制备高力学性能Lyocell纤维的有效方法。
为了探索完善Lyocell纤维聚集态结构的合适方法,本论文还对Lyocell纤维结晶结构的形成过程进行了研究分析,结果发现:尚未干燥过的湿态初生Lyocell纤维中,纤维素的三维有序排列还未完全形成。Lyocell纤维的结晶结构是在其湿态初生纤维的失水干燥过程中形成的,随着纤维含水率的减小,准晶结构逐渐消失,结晶结构逐渐完善。当初生Lyocell纤维完全干燥后,其结晶结构便比较稳定,很难再被改变。因此,有望通过对尚未干燥过的初生Lyocell纤维进行适当的后处理来有效改善最终Lvocell纤维的聚集态结构,从而达到提高纤维力学性能的目的。
为此,本论文进一步利用自制的热处理装置对尚未干燥过的初生Lyocell纤维进行了张力下热处理,探讨了预张力、热处理温度及时间和张力对最终纤维力学性能等性质的影响,并在最佳热处理条件下制得了强度和模量比室温干燥的Lyocell纤维分别提高29.7%和97.4%的纤维,且其干热收缩率和蠕变率也显著减小,相关性能均符合轮胎帘子线用纤维要求,由此表明对尚未干燥过的初生Lyocell纤维进行热处理也是获得轮胎帘子线用Lyocell纤维的一种可行方法。在此基础上,本论文还将氯化铵改性与热处理相结合,对湿态初生氯化铵改性Lyocell纤维在适当条件下进行热处理,最终可得到断裂强度高达到7.21cN/dtex、初始模量达到92.6cN/dtex、蠕变率低于0.5%、干热收缩率小于0.8%的高性能Lyocell纤维。由此可见,采用氯化铵改性和热处理相结合的方法有利于获得高性能的轮胎帘子线用Lvocell纤维。
此外,由于Lyocell纤维具有易原纤化的特性,这种性能会影响纤维的耐疲劳性等性能,为此,为了提高Lyocell纤维的抗原纤化能力,以保证其具有优良的耐疲劳性和耐磨擦性能,本论文还摸索出了最佳的交联剂处理工艺,对尚未干燥过的初生Lyocell纤维进行了适当的交联处理,发现经交联处理后的Lyocell纤维中,基纤以及基纤聚集束尺寸均明显减小且含量增加,由此降低了微原纤从纤维主干上劈裂的可能性,使最终所得Lyocell纤维在保持原有力学性能的基础上,湿摩擦值(该值与抗原纤化能力成正比)达到733s左右,比普通Lyocell纤维提高了约13倍,且纤维的耐疲劳性也明显提高。这些研究结果表明,适当的交联处理可以改善Lyocell纤维应用于轮胎帘子线的综合性能。在此基础上,本论文进一步对尚未干燥过的初生氯化铵改性Lyocell纤维进行了交联处理及热处理,发现最终所得Lyocell纤维的力学性能、耐疲劳性、耐热性及尺寸稳定性等指标均远优于高模低收缩涤纶轮胎帘子线和高强粘胶轮胎帘子线。
由本论文上述研究表明,(1)以高相对分子质量纤维素或其与中等相对分子质量纤维素的混合体系为原料、(2)添加氯化铵改性、(3)对尚未干燥过的初生Lyocell纤维进行张力下热处理等几种方法均为有效提高Lyocell纤维力学性能和获得轮胎帘子线用Lyocell纤维的可行方法,并且,通过氯化铵改性和热处理相结合(或进一步结合交联处理),可以获得综合指标佳、高性能的轮胎帘子线用Lyocell纤维。
Lyocell fiber is a new kind of regenerated cellulose fiber developed in the 1990s.Compared with traditional rayon fibers,it has higher strength and modulus.Lyocell process is a simple and environmentally friendly process. It can use higher relative molecular weight cellulose as raw material to prepare fiber directly,which is impossible for rayon process.Therefore, Lyocell fiber can expectedly be used as tire cord to replace the existing rayon tire cord.
To date,there is no report on Lyocell fiber used as tire cord.In this thesis,the dissolving characteristic of various celluloses and the rheological properties of the spinning dopes were investigated firstly.Then the effects of various factors such as the raw material properties,the spinning condition, the addition of ammonium chloride,heat treatment and cross-link treatment on the structure and properties of the resultant Lyocell fiber were also investigated.Base on the above studies,some feasible ways for preparing Lyocell fiber used as tire cord have been found.
In this thesis,the dissolving process of cellulose pulps were observed by using a polarizing microscopy with CCD and a heating stage and the rheological properties of the cellulose solutions were studied by HAAKE rheometer.The results showed that the higher the relative molecular weight of cellulose,the stronger the dependence of dissolving rate on temperature and the higher the activation energy of the cellulose solution.Also,the homogeneity of the solution became poorer and its critical shear rate was decreased.Therefore,the parameters for dissolution and spinning,such as temperature and so on,should be controlled strictly when the cellulose pulp having a higher relative molecular weight was used to prepare Lyocell fiber.
The results based on the mechanical properties of the resultant fibers also showed that the relative molecular weight of cellulose played a more important role in improving the mechanical properties of fibers thanα-cellulose content.If the relative molecular weights of celluloses were similar,the mechanical properties of Lyocell fibers can be improved with the increasing ofα-ceUulose content in cellulose.The highα-cellulose content in cellulose had positive effect on heat and size stability of Lyocell fiber.Moreover,the properties of spinning dopes from the cellulose mixed by high(or super-high) relative molecular weight cellulose and medium relative molecular weight cellulose were analyzed by GPC.It was found that the mechanical properties of Lyocell fiber could be improved by mixing an appropriate amount of high relative molecular weight cellulose with medium relative molecular weight cellulose.However,if the difference between the relative molecular weights for two celluloses was too big,the resultant dope would be separated during its passing through filter of spinning components and therefore the mechanical properties of prepared Lyocell fiber could not be improved effectively.Therefore,using high relative molecular weight cellulose or its mixture with medium relative molecular weight cellulose as raw material is a feasible way for improving mechanical properties of Lyocell fiber and preparing Lyocell fiber used as tire cord.
In this thesis,the feasibility of preparing high performance Lyocell fiber by adding ammonium chloride in the dope was further investigated. The results showed that the effect of adding ammonium chloride on the rheological properties of cellulose/NMMO·H_2O solution was similar to that of increasing relative molecular weight of cellulose.With the increase of ammonium chloride in the solution,the apparent viscosity,zero-shear viscosity and structural viscosity index for cellulose solution were increased, while the dissolution homogeneity of cellulose was decreased.In order to insure good spinnablity and spinning stability,the adding amount of ammonium chloride couldn't be too high.It was also found that the mechanical properties of resultant Lyocell fiber modified by an appropriate amount of ammonium chloride were improved and the modified Lyocell fiber has a mixture structure of celluloseⅡcrystal and celluloseⅢcrystal. Furthermore,the total crystallinity and orientation could be increased with adding ammonium chloride.This means that the modification by ammonium chloride is also an effective way to prepare Lyocell fiber with excellent mechanical properties.
In order to find an effective method to improve the crystalline and orientation structure of Lyocell fiber,the formation of crystal structure of Lyocell fiber was also studied in this thesis.It was found the tridimensional order of never dried as-spun Lyocell fiber was not fully formed yet.With the decreasing water content of as-spun Lyocell fiber,its paracrystal structure disappeared gradually and meanwhile the crystal structure was improved.Once the Lyocell fiber was dried completely,its crystal structure had been stabilized and was difficult to be destroyed and rearranged. Therefore,it is hopeful to improve crystalline structure and mechanical properties of Lyocell fiber by appropriate post treatment using never dried Lyocell fiber as precursor.
Therefore,in this thesis the never dried as-spun Lyocell fiber was heat-treated under tension by using a home-made heat treatment equipment. And the effect of pretension,temperature and time as well tension of heat treatment on the mechanical properties of resultant Lyocell fiber was also investigated.It was found that after optimal heat treatment,the tensile strength and initial modulus of Lyocell fiber could be increased by 29.7% and 97.4%,respectively,and its dry heat shrinkage and creep ratio were decreased obviously,which could accord with the requirements of tire cord. That means the heat treatment is a feasible way to obtain the Lyocell fiber used as tire cord.Based on the above studies,the never dried Lyocell fiber, which had been modified by ammonium chloride,was heat-treated.The strength and the modulus of resultant Lyocell fiber could reach 7.21 cN/dtex and 92.6cN/dtex,respectively.And the creep ratio and dry heat shrinkage were lower than 0.5%and 0.8%,respectively.Therefore,the modification by ammonium chloride combined with heat treatment was an effective method to prepare high performance Lyocell fiber.
It is generally believed that the Lyocell fiber has high fibrillation tendency,which has negative effect on its fatigue properties.In order to increase the fibrillation resistance of Lyocell fiber to improve its fatigue resistance and wear resistance,the optimal cross-link treatment was also investigated by using the never dried Lyocell fiber as precursor.The results showed that the cross-link treatment could effectively decrease the sizes of elementary fibril and elementary fibril cluster and increase their contents, which led to reduce the possibility of the fibril separating from the fiber and improve fatigue resistance of Lyocell fiber.Therefore,the wet abrasion value of Lyocell fiber after cross-link treatment was 13 times higher than that of common Lyocell fiber.These results indicated that the appropriate cross-link treatment could improve the comprehensive properties of Lyocell fiber,which were necessary for tire cords.Based on the above studies,the never dried Lyocell fiber modified by ammonium chloride was cross-link treated firstly and then heat-treated.It can be found that the mechanical properties,fatigue resistance,heat and size stability of the resultant Lyocell fiber are much better than those of HLMS polyester tire cord and high strength rayon tire cord.
The above investigations showed that the Lyocell fiber used as tire cord could be prepared by(1) using high relative molecular weight cellulose or its mixture with medium relative molecular weight cellulose as raw material, (2) modification by adding ammonium chloride,and(3) the heat treatment under tension using never dried Lyocell fiber as precursor.The high performance Lyocell fiber with excellent comprehensive properties,which can be used as tire cord,could be obtained by combining the modification by ammonium chloride with the heat treatment(or further with cross-link treatment).
引文
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