PAN/CNTs复合纤维中CNTs对PAN大分子结构诱导效应的研究
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摘要
聚丙烯腈(PAN)纤维是较早实现工业化的合成纤维之一,以PAN原丝为前驱体制备的碳纤维综合性能最好。应用纳米粒子对PAN纤维进行复合,可以制备改性PAN纤维。目前碳纳米管(CNT)在高分子复合材料领域的研究十分活跃,通过添加碳纳米管可以改善纤维材料的力学和导电性能,具有很好的研究和应用价值。本文选用PAN为基体,以改性碳纳米管(CNTs)为填充组分,制备了PAN/cNTs复合纤维,研究了碳纳米管对PAN大分子结构的诱导效应,主要开展了以下几个方面的研究工作:
1)采用硝酸氧化法和聚丙烯腈接枝法对碳纳米管进行纯化、改性,改善碳纳米管在溶液和聚合物基体里的分散性和相容性。Raman,FTIR,XPS,SEM,TEM和TGA测试证明硝酸处理使得碳纳米管上的碳原子氧化,生成羧基,随着处理温度的升高氧化程度加剧,碳管的结构遭到进一步破坏。酸处理产生的羧基通过酰氯化、胺化后可以与共聚单体衣康酸的羧基反应,从而将聚丙烯腈大分子接枝到碳纳米管的表面,接枝率接近144%,同时接枝使得碳纳米管和聚合物分子形成一种网络结构。
2)采用原位聚合法制备了聚丙烯腈/酸处理碳纳米管复合溶液和聚丙烯腈/接枝处理碳纳米管复合溶液,对复合溶液的动态流变行为进行了详细分析。结果表明,PAN/CNTs复合溶液呈现典型的切力变稀现象,少量加入酸处理碳管和接枝碳管都会起到增塑效果,酸处理碳管的增塑效果更明显;随着接枝碳纳米管含量的增加,溶液体系中的网络结构开始影响其流变行为,使得η~*,G'和G''明显升高,同时使得溶液由黏性向弹性转变,这些结果对湿法纺丝成形具有很好的指导意义,证明复合溶液具有一定的可纺性。碳纳米管的引入还使得聚合物的玻璃化转变温度明显提高,但是对其环化放热行为影响并不大。
3)采用湿法纺丝制备了聚丙烯腈/接枝碳纳米管复合纤维,对纺丝工艺各个阶段复合纤维的形态和结构进行了详细研究。XRD结果表明碳纳米管的加入使得初生纤维的结晶度,取向因子和晶面间距略有提高,SEM表明碳纳米管的引入抑制了凝固的双扩散过程,避免了大的孔洞的形成,但是纤维微晶结构的致密化程度下降;XRD结果表明,在预牵伸过程中残留溶剂对碳纳米管的作用有一定的影响,但是复合预牵伸纤维和空白纤维一样,在预牵伸作用下取向,微晶结构变得致密;XRD结果表明,和空白纤维一样复合纤维中的牵伸力也直接作用在大分子链上,在碳纳米管的诱导作用下PAN大分子在结晶中的构型更容易转变,随着牵伸的进行,复合纤维的微晶结构更加致密,但是取向在一个恒定范围内波动,略小于空白纤维,并且取向沿纤维轴向具有不对称性。
4)对PAN/CNTs复合纤维中碳纳米管的取向进行了研究,结果表明,初生纤维中碳纳米管的取向就达到较高值,并且随着牵伸的增大,碳纳米管的取向逐渐增大。
5)对PAN/CNTs复合原丝的结构和性能进行研究,结果表明,碳纳米管的引入使得复合原丝的结晶度,取向度和微晶结构致密化程度下降,结晶取向沿纤维轴向有不对称性;当碳纳米管的添加量为1wt%时,复合原丝的拉伸模量和拉伸强度分别提高了82.2%和11.0%;复合原丝断口表现为微纤剥离状。
Polyacrylonitrile fiber is a common commercial fiber which has been produced for a long time and regard as the ideal precursor for high performance carbon fiber.By introduceing nanoparticles in to PAN fiber can make them functionalized.Nowadays,CNTs as an ideal reinforcement have been introduced into many polymeric matrixes and the resulting nanocomposite showed an improvement of mechanical properties and electronical properties.In this article,PAN was chose as polymeric matrix and CNTs as reinforcement to prepare PAN/CNTs nanocomposite fiber,the main aim of this is to investigate the induced effect of CNTs to PAN macromoleculers.The main content was as followed:
1) In order to improve the dispersion of CNTs and compatibility with polymeric matrix,modification of CNTs was conducted by acid treatment and PAN grafted method.Raman,FTIR,XPS,SEM,TEM and TGA results showed that the acid treatment had introduced carboxyl on the surface of CNTs,with the increase of treated temperature,the intensity of oxidation increase and the raw structure of CNTs were destroied deeply.By changing the carboxyl introduced by acid treatment into acyl and amido,the CNTs can react with comonomer IA,leading to graft of PAN onto CNTs surface,the weight ratio of grafted PAN was nearly 144%and there is a new network structure formed by CNTs and PAN.
2) In situ polymerization was used to prepare PAN/acid treated CNTs composite solution and PAN/PAN grafted CNTs composite solution.The rheological result of the composite solution showed that with low content of CNTs,the CNTs act as a plasticzer and the acid treated CNTs are more effective.With the addition of PAN grafted CNTs,the network structure became dominating,increasing theη~*,G' and G" properties,and the elasticity overcome emplastic.The resulting composite also showed an increase of T_g.
3) Wet spinning was used to prepare PAN/PAN grafted CNTs composite fiber, the effect of coagulation,pre-stretch and stretch to the structure of composite fiber were investigated.XRD result showed that with the incorporation of CNTs,the crystallization,f~a and d-space of nascent composite fiber increased slightly,SEM results showed CNTs inhibit the diffusion of solvent and water during coagulation,avoiding the formation of large hole in composite nascent fiber;Due to the effect of residual solvent,XRD result showed that the effect of CNTs was weakened,but the pre-stretched composite showed the same reaction to pre-stretch as neat fiber;XRD result showed that with the incorporation of CNTs,the stretch force also act on macromoleculer in composite fiber during stretch directly.The structure of PAN moleculer changed easily in composite fiber and the orientation of crystal was constant but inequipotential along with axial direction.
4) The orientation of CNTs in composite fiber was investigated by polarized Raman spectrum,the result showed that CNTs achieved a relatively high orientation during coagulation and with the increase of stretch the orientation of CNTs increase constantly.
5) The structure and property of the composite precursor fiber were investigated.With the incorporation of the CNTs,the crystallization,f~a and d-space of composite precursor fiber decreased and the orientation of crystal in composite fiber exhibit inequipotential along with axial direction;At 1 wt% CNTs loading,the tensile modulus and tensile strength increased 82.2%and 11.0%respectively;and the fibril ends were observed at the fracture of composite fiber.
1)采用硝酸氧化法和聚丙烯腈接枝法对碳纳米管进行纯化、改性,改善碳纳米管在溶液和聚合物基体里的分散性和相容性。Raman,FTIR,XPS,SEM,TEM和TGA测试证明硝酸处理使得碳纳米管上的碳原子氧化,生成羧基,随着处理温度的升高氧化程度加剧,碳管的结构遭到进一步破坏。酸处理产生的羧基通过酰氯化、胺化后可以与共聚单体衣康酸的羧基反应,从而将聚丙烯腈大分子接枝到碳纳米管的表面,接枝率接近144%,同时接枝使得碳纳米管和聚合物分子形成一种网络结构。
2)采用原位聚合法制备了聚丙烯腈/酸处理碳纳米管复合溶液和聚丙烯腈/接枝处理碳纳米管复合溶液,对复合溶液的动态流变行为进行了详细分析。结果表明,PAN/CNTs复合溶液呈现典型的切力变稀现象,少量加入酸处理碳管和接枝碳管都会起到增塑效果,酸处理碳管的增塑效果更明显;随着接枝碳纳米管含量的增加,溶液体系中的网络结构开始影响其流变行为,使得η~*,G'和G''明显升高,同时使得溶液由黏性向弹性转变,这些结果对湿法纺丝成形具有很好的指导意义,证明复合溶液具有一定的可纺性。碳纳米管的引入还使得聚合物的玻璃化转变温度明显提高,但是对其环化放热行为影响并不大。
3)采用湿法纺丝制备了聚丙烯腈/接枝碳纳米管复合纤维,对纺丝工艺各个阶段复合纤维的形态和结构进行了详细研究。XRD结果表明碳纳米管的加入使得初生纤维的结晶度,取向因子和晶面间距略有提高,SEM表明碳纳米管的引入抑制了凝固的双扩散过程,避免了大的孔洞的形成,但是纤维微晶结构的致密化程度下降;XRD结果表明,在预牵伸过程中残留溶剂对碳纳米管的作用有一定的影响,但是复合预牵伸纤维和空白纤维一样,在预牵伸作用下取向,微晶结构变得致密;XRD结果表明,和空白纤维一样复合纤维中的牵伸力也直接作用在大分子链上,在碳纳米管的诱导作用下PAN大分子在结晶中的构型更容易转变,随着牵伸的进行,复合纤维的微晶结构更加致密,但是取向在一个恒定范围内波动,略小于空白纤维,并且取向沿纤维轴向具有不对称性。
4)对PAN/CNTs复合纤维中碳纳米管的取向进行了研究,结果表明,初生纤维中碳纳米管的取向就达到较高值,并且随着牵伸的增大,碳纳米管的取向逐渐增大。
5)对PAN/CNTs复合原丝的结构和性能进行研究,结果表明,碳纳米管的引入使得复合原丝的结晶度,取向度和微晶结构致密化程度下降,结晶取向沿纤维轴向有不对称性;当碳纳米管的添加量为1wt%时,复合原丝的拉伸模量和拉伸强度分别提高了82.2%和11.0%;复合原丝断口表现为微纤剥离状。
Polyacrylonitrile fiber is a common commercial fiber which has been produced for a long time and regard as the ideal precursor for high performance carbon fiber.By introduceing nanoparticles in to PAN fiber can make them functionalized.Nowadays,CNTs as an ideal reinforcement have been introduced into many polymeric matrixes and the resulting nanocomposite showed an improvement of mechanical properties and electronical properties.In this article,PAN was chose as polymeric matrix and CNTs as reinforcement to prepare PAN/CNTs nanocomposite fiber,the main aim of this is to investigate the induced effect of CNTs to PAN macromoleculers.The main content was as followed:
1) In order to improve the dispersion of CNTs and compatibility with polymeric matrix,modification of CNTs was conducted by acid treatment and PAN grafted method.Raman,FTIR,XPS,SEM,TEM and TGA results showed that the acid treatment had introduced carboxyl on the surface of CNTs,with the increase of treated temperature,the intensity of oxidation increase and the raw structure of CNTs were destroied deeply.By changing the carboxyl introduced by acid treatment into acyl and amido,the CNTs can react with comonomer IA,leading to graft of PAN onto CNTs surface,the weight ratio of grafted PAN was nearly 144%and there is a new network structure formed by CNTs and PAN.
2) In situ polymerization was used to prepare PAN/acid treated CNTs composite solution and PAN/PAN grafted CNTs composite solution.The rheological result of the composite solution showed that with low content of CNTs,the CNTs act as a plasticzer and the acid treated CNTs are more effective.With the addition of PAN grafted CNTs,the network structure became dominating,increasing theη~*,G' and G" properties,and the elasticity overcome emplastic.The resulting composite also showed an increase of T_g.
3) Wet spinning was used to prepare PAN/PAN grafted CNTs composite fiber, the effect of coagulation,pre-stretch and stretch to the structure of composite fiber were investigated.XRD result showed that with the incorporation of CNTs,the crystallization,f~a and d-space of nascent composite fiber increased slightly,SEM results showed CNTs inhibit the diffusion of solvent and water during coagulation,avoiding the formation of large hole in composite nascent fiber;Due to the effect of residual solvent,XRD result showed that the effect of CNTs was weakened,but the pre-stretched composite showed the same reaction to pre-stretch as neat fiber;XRD result showed that with the incorporation of CNTs,the stretch force also act on macromoleculer in composite fiber during stretch directly.The structure of PAN moleculer changed easily in composite fiber and the orientation of crystal was constant but inequipotential along with axial direction.
4) The orientation of CNTs in composite fiber was investigated by polarized Raman spectrum,the result showed that CNTs achieved a relatively high orientation during coagulation and with the increase of stretch the orientation of CNTs increase constantly.
5) The structure and property of the composite precursor fiber were investigated.With the incorporation of the CNTs,the crystallization,f~a and d-space of composite precursor fiber decreased and the orientation of crystal in composite fiber exhibit inequipotential along with axial direction;At 1 wt% CNTs loading,the tensile modulus and tensile strength increased 82.2%and 11.0%respectively;and the fibril ends were observed at the fracture of composite fiber.
引文
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[1]张旺玺,王艳芝.活性炭对聚丙烯腈共混溶液流变性的影响[J].广东化纤,1999,3:17-19
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[1]张引枝,樊颜贞,贺福等.添加剂种类对活性碳纤维中孔结构的影响[J].炭素技术,1997,(4):11-13
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[3]Yu T,Lin J,Xu J,etc.Novel Polyacrylonitrile Nanocomposites Containing Na montmorillonite and Nano SiO2 Particle[J].Polymer,2005,46:5695-5697
[4]Screekumar T V,Liu T,etc.Polyacrylonitrile Single-Walled Carbon Nanotube Composite Fibers[J].Advanced Materials,2004,16(1):58-61
[5]Han Gi Chae,Marilyn L Minus,Satish Kumar.Oriented and exfoliated single wall carbon nanotubes in polyacrylonitrile[J].Polymer,2006,47:3494-3504
[6]Liu Tao,Kumar S.Quantitative characterization of SWNT orientation by polarized Raman spectroscopy[J].Chemical Physics Letters,2003,378:257-262
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