二步法制备聚丙烯腈基碳纤维原丝技术研究
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摘要
本文主要针对二步法工艺制备聚丙烯腈(PAN)基碳纤维原丝过程中纺丝原液溶解和纤维纺丝这两个方面开展基础性研究,深入研究了原丝成形过程中PAN溶液和纤维结构、性能的变化规律,力求掌握与工艺之间的相关性来指导实际的生产过程,达到提升PAN原丝及碳纤维性能的最终目的。文中的大部分实验是在实验室自制的纤维纺丝线上展开的,并利用流变仪,紫外可见光分光光度计,X射线衍射仪,表面积和孔径分析仪,立体显微镜,偏光透光显微镜,场发射扫描电镜,纤维强伸度仪,纤维细度仪等测试分析技术,对PAN溶液和纺丝各阶段纤维的结构、性能变化进行了系统研究,探讨了各工艺参数对它们的影响,并建立了PAN纤维的牵伸变形结构模型。
在PAN纺丝原液制备方面,讨论了搅拌速度、温度和溶剂种类对溶解过程中PAN溶液的流变性变化规律的影响。在PAN溶液的溶解过程中,剪切黏度会呈现特定的变化规律：溶液的黏度先随粉料的分散而下降,继而随大分子的溶解有小幅提高,最后随分子链在溶液中的运动取向又有小幅的下滑。加大搅拌速度,提高温度和采用混合溶剂都能促进溶解,其中,加快搅拌主要起提高溶解速度的作用,提高温度能提升溶液的可溶解性,而采用混合溶剂则能综合两种溶剂成分的各自优势,使PAN溶液的溶解具有更好的分散性及溶解性。相同浓度下,以采用二甲基乙酰胺(DMAC)/二甲基亚砜(DMSO)混合溶剂溶解得到的PAN溶液具有最低的黏度。利用紫外可见光分光光度计分析了PAN溶液溶解过程中的吸光性能变化,发现PAN溶液在紫外光区300nm波长附近存在强吸收峰,随着溶解的进行,吸收峰逐渐增强,且溶解温度越高,最终溶液的吸收峰越强。最后对PAN溶液凝固成形薄膜的结构进行了比较分析发现,溶液的溶解性越好,结构越均匀,分子链取向性越好,薄膜表面的网状凸起越明显。
在纤维纺丝方面,主要对PAN纤维的凝固成形及其牵伸变形这两部分做了重点研究。PAN纺丝原液的凝固是一个相分离过程,相分离方式决定了溶液的凝固特性。初生纤维凝固时的相分离方式主要受双扩散速度的影响,本文利用求解Fick第二定律得到的传质系数来表征双扩散速度,根据凝固过程中的扩散速度大小将扩散过程分为扩散初期、中期和末期三个阶段。分析了温度、浓差和纺丝液浓度对各扩散阶段扩散速度的影响,研究发现扩散初期传质系数K1随温度及浓差的升高而增大,与浓差的大小和T’/2基本上成正比关系；凝固扩散中期传质系数K2仍与T1/2呈正比关系,且温度越低,K2与T1/2的正比性越好,但随浓差的增加呈先增大后减小的变化规律；扩散末期的扩散速度随浓差增大而稍减,随温度升高而稍增。扩散速度随聚合物浓度的增加基本上呈线性下降。随后分析了凝固条件对PAN初生纤维结晶、力学性能的影响,降低凝固温度能抑制结晶,提高成形纤维的可牵伸性能,其中凝固浴温度的影响效果要明显大于纺丝液温度；提高纺丝速度能促进初生纤维成形时的塑性变形,增加牵伸比,能细化原纤聚集态结构,降低纤维的结晶度,有利于纤维的细旦化。
在研究初生纤维在不同溶剂含量、不同拉伸速度的牵伸性能时发现,纤维的屈服强度随溶剂量的下降而线性提高,断裂强度也逐渐增加,断裂伸长率大幅提高后略有下降,干燥10h后的纤维牵伸曲线有最低的屈服平台和较高的伸长率,具最佳的常温牵伸性能；加快拉伸能促进高溶剂含量初生纤维的牵伸变形,对充分干燥后纤维的牵伸变形则起抑制作用；在对不同凝固浴牵伸PAN初生纤维在不同温度下的牵伸性能的研究中发现,初生纤维直径越小,越倾向于在低温处达到最大牵伸,加大凝固浴牵伸能促进纤维细旦化,而加大高温牵伸则更容易达到强化纤维的目的。
然后对纤维纺丝过程中的第二凝固浴预牵伸、高温空气牵伸、致密化牵伸和蒸汽牵伸中的牵伸变形行为进行了研究。研究发现,凝固浴牵伸为500%的初生纤维以50mm/min的牵伸速度在浓度为80%和温度为70℃的第二凝固浴中能达到近23.5倍的总牵伸率；凝固浴预牵伸后纤维在250～400℃的温度范围内,纤维的可牵伸率随温度的提高先上升后下降,在350℃处达到最大牵伸率,且随牵伸倍数的增大,纤维强度大幅增加,断裂伸长率快速下降；在PAN纤维的致密过程中施加1.05倍的牵伸能使纤维保持较好的塑性同时增强致密化效果,使纤维强度和密度都得到充分提高；通过蒸汽牵伸能大幅度降低纤维纤度,提高强度,且加大蒸汽压力能促进蒸汽牵伸时纤维的牵伸变形。最后根据PAN纤维牵伸变形时的结构、性能变化构建并验证了PAN纤维牵伸变形的分子结构模型。
在对纺丝过程中各阶段PAN纤维的结构、性能变化的研究中发现,随着纺丝的进行,纤维强度不断增加,断裂伸长率逐渐减小,纤维的双折射率和偏光透光性与力学强度间存在较好的对应关系；纤维在20≈17°附近的衍射峰逐渐增强,其结晶度则与致密性间存在较好的对应关系,结晶度越高,纤维的密度越大,孔隙率越低,致密性越好。在干喷湿纺原丝P1、准干喷湿纺原丝P2和湿纺原丝P3三种纤维的对比研究中发现,三种纤维的结晶度、密度、强度大小比较为：P1>P2>P3；三种纤维的晶粒尺寸、纤度大小比较为：P1This article mainly aims at the dissolution and fiber spinning in the preparation process of polyacrylonitrile (PAN) fibers. The intensive study on evolution of structure and properties during the preparing process and its correlation with techniques has significance in improving performance of PAN precursors and carbon fibers. Most of the experiments were carried out in homemade fiber spinning line. Rheometer, ultraviolet-visible spectrophotometer, X-ray diffractometer, surface area and pore size analyzer, stereo microscope, polarizing microscope, field emission scanning electron microscopy, fiber strength and elongation tester, fiber fineness tester were used to characterize the performance change of PAN solutions and fibers. Influence of drawing technology was studied for establishing molecular deformation structure model.
In the aspect of preparation of PAN spinning solution, the influence of agitating speed, temperature and solvent on the change of rheology for PAN solution was discussed. In normal dissolving process, shear viscosity change will present certain rule:the viscosity firstly declines with the dispersion of powder, then increases slightly with the dissolution of macromolecular, and lastly declines again with the orientation of molecular chain in the solution. Speeding up agitating, increasing temperature and using composite solvent could promote the dissolution. Among them, speeding up agitating had a role of increasing dissolution rate, and increasing temperature could improve solubility, whereas using composite solvent could integrate advantages of both components, making the solution has better dispersibility and solubility. Under same concentration, the solution with composite solvent (DMAC/DMSO) had a lowest viscosity. Change of light absorption properties of the solution during dissolution process was analyzed by ultraviolet-visible spectrophotometer. It was found that the solution had a strong absorption peak near300nm wavelength in ultraviolet region. With the dissolution, the peak gradually strengthened, and the higher was the solution temperature, the stronger the peak was. Finally, the structure of coagulated PAN membranes was compared, and it was found that the solution with better solubility had more uniform structure, and the orientation of molecular chains was presented as raised net structure in the membrane surface.
A detailed study on coagulation and drawing deformation of PAN fibers was made during spinning process. The coagulation of PAN solution is a phase separation process which is affected by double diffusion, determining the structure of PAN nascent fibers. In this paper, mass transfer coefficient obtained from the second Fick's law was utilized to represent double diffusion rate. According to the diffusion rate in the solidification process, the diffusion process was divided into initial stage, middle stage and later stage. The influence of temperature, concentration difference and solution concentration on the diffusion velocity was analyzed, and it was found that the mass transfer coefficient of the initial stage (K1) increased with temperature and concentration difference, and was basically in proportion to concentration difference and T1/2. The mass transfer coefficient of the middle stage (K2) was still proportion to T1/2, and the lower was the temperature the better the proportional relationship was, as it increased first then decreased with the increase of the concentration difference. The diffusion rate of the last stage decreased slightly with the concentration difference and increased slightly with temperature. The diffusion rate basically declined linearly with the increase of polymer concentration, expect the medium and later mass transfer coefficient slightly deviation linear relationship. The influence of coagulation conditions on the crystallization and mechanical performance of PAN nascent fibers was discussed, and it was found that reducing temperature could inhibit crystallization and improve drawing performance, when the change of coagulation bath temperature made a more obvious effect than spinning solution temperature. Speeding up drawing could promote the plastic drawing deformation of PAN nascent fiber, and increasing draw ratio could refine aggregated fibrillar and reduce crystallinity, helpful for making fine-denier precursors.
The influence of solvent content, tensile speed on the drawing performance of PAN nascent fibers was discussed. It was found that yield strength increased linearly, breaking strength increased gradually, and elongation at break increased quickly first and then decreased slightly with solvent content decreasing. The fibers dried for10hours had the lowest yield platform and high elongation, providing the best drawing performance at room temperature. Speeding up drawing can promote deformation of nascent fibers with high solvent content, but not for fibers dried sufficiently. Drawing performance of PAN nascent fibers with the different first coagulation bath draw ratio under different temperature was discussed. It was found that the nascent fibers with small diameter tended to achieve maximum draw ratio in lower temperature, and increasing the first coagulation bath draw ratio could promote thinning fibers, when increasing the high temperature draw ratio was helpful for improving the strength of fibers.
The drawing deformation behavior of the second coagulation bath pre-drawing, high temperature air drawing, collapsing drawing and steam drawing during spinning process was discussed. It was found that the nascent fibers with the first coagulation bath draw ratio of5×could be drawn nearly23.5times in the80%and70℃second coagulation bath under a tensile speed of50mm/min. Afterwards the draw ratio of pre-drawn fibers increased first and then decreased in250～400℃during high temperature air drawing, achieving maximum draw ratio at350℃, and fiber strength increased greatly and elongation at break fell sharply with the increase of drawing ratio. Imposing1.05times drawing could make fibers keep good plasticity at the same time enhance densification effect in the collapsing process, improving strength and density sufficiently. Steam drawing could greatly reduce fiber denier and improve strength at the same time. And increasing steam pressure could promote deformation during steam drawing. According to the evolution of the fibers' structure and performance during drawing deformation, a molecular structure model was constructed for explaining the drawing deformation mechanism.
Evolution of the fibers' structure and performance during various stage of spinning process was discussed. It was found that, along with the spinning, the strength increased while elongation at break decreased gradually. The birefringence and polarizing light transmittance had a good corresponding relation with mechanical strength of the fibers. The diffraction peak at nearly2θ≈17°strengthened gradually, when the degree of crystallinity had a good corresponding relation with the density of the fibers. In the comparison of dry-jet wet spinning precursors P1, quasi dry-jet wet spinning precursors P2and wet spinning precursors P3, it was found that in aspects of crystallinity, density, strength:P1> P2> P3, in aspects of grain size, denier:P1
在PAN纺丝原液制备方面,讨论了搅拌速度、温度和溶剂种类对溶解过程中PAN溶液的流变性变化规律的影响。在PAN溶液的溶解过程中,剪切黏度会呈现特定的变化规律：溶液的黏度先随粉料的分散而下降,继而随大分子的溶解有小幅提高,最后随分子链在溶液中的运动取向又有小幅的下滑。加大搅拌速度,提高温度和采用混合溶剂都能促进溶解,其中,加快搅拌主要起提高溶解速度的作用,提高温度能提升溶液的可溶解性,而采用混合溶剂则能综合两种溶剂成分的各自优势,使PAN溶液的溶解具有更好的分散性及溶解性。相同浓度下,以采用二甲基乙酰胺(DMAC)/二甲基亚砜(DMSO)混合溶剂溶解得到的PAN溶液具有最低的黏度。利用紫外可见光分光光度计分析了PAN溶液溶解过程中的吸光性能变化,发现PAN溶液在紫外光区300nm波长附近存在强吸收峰,随着溶解的进行,吸收峰逐渐增强,且溶解温度越高,最终溶液的吸收峰越强。最后对PAN溶液凝固成形薄膜的结构进行了比较分析发现,溶液的溶解性越好,结构越均匀,分子链取向性越好,薄膜表面的网状凸起越明显。
在纤维纺丝方面,主要对PAN纤维的凝固成形及其牵伸变形这两部分做了重点研究。PAN纺丝原液的凝固是一个相分离过程,相分离方式决定了溶液的凝固特性。初生纤维凝固时的相分离方式主要受双扩散速度的影响,本文利用求解Fick第二定律得到的传质系数来表征双扩散速度,根据凝固过程中的扩散速度大小将扩散过程分为扩散初期、中期和末期三个阶段。分析了温度、浓差和纺丝液浓度对各扩散阶段扩散速度的影响,研究发现扩散初期传质系数K1随温度及浓差的升高而增大,与浓差的大小和T’/2基本上成正比关系；凝固扩散中期传质系数K2仍与T1/2呈正比关系,且温度越低,K2与T1/2的正比性越好,但随浓差的增加呈先增大后减小的变化规律；扩散末期的扩散速度随浓差增大而稍减,随温度升高而稍增。扩散速度随聚合物浓度的增加基本上呈线性下降。随后分析了凝固条件对PAN初生纤维结晶、力学性能的影响,降低凝固温度能抑制结晶,提高成形纤维的可牵伸性能,其中凝固浴温度的影响效果要明显大于纺丝液温度；提高纺丝速度能促进初生纤维成形时的塑性变形,增加牵伸比,能细化原纤聚集态结构,降低纤维的结晶度,有利于纤维的细旦化。
在研究初生纤维在不同溶剂含量、不同拉伸速度的牵伸性能时发现,纤维的屈服强度随溶剂量的下降而线性提高,断裂强度也逐渐增加,断裂伸长率大幅提高后略有下降,干燥10h后的纤维牵伸曲线有最低的屈服平台和较高的伸长率,具最佳的常温牵伸性能；加快拉伸能促进高溶剂含量初生纤维的牵伸变形,对充分干燥后纤维的牵伸变形则起抑制作用；在对不同凝固浴牵伸PAN初生纤维在不同温度下的牵伸性能的研究中发现,初生纤维直径越小,越倾向于在低温处达到最大牵伸,加大凝固浴牵伸能促进纤维细旦化,而加大高温牵伸则更容易达到强化纤维的目的。
然后对纤维纺丝过程中的第二凝固浴预牵伸、高温空气牵伸、致密化牵伸和蒸汽牵伸中的牵伸变形行为进行了研究。研究发现,凝固浴牵伸为500%的初生纤维以50mm/min的牵伸速度在浓度为80%和温度为70℃的第二凝固浴中能达到近23.5倍的总牵伸率；凝固浴预牵伸后纤维在250～400℃的温度范围内,纤维的可牵伸率随温度的提高先上升后下降,在350℃处达到最大牵伸率,且随牵伸倍数的增大,纤维强度大幅增加,断裂伸长率快速下降；在PAN纤维的致密过程中施加1.05倍的牵伸能使纤维保持较好的塑性同时增强致密化效果,使纤维强度和密度都得到充分提高；通过蒸汽牵伸能大幅度降低纤维纤度,提高强度,且加大蒸汽压力能促进蒸汽牵伸时纤维的牵伸变形。最后根据PAN纤维牵伸变形时的结构、性能变化构建并验证了PAN纤维牵伸变形的分子结构模型。
在对纺丝过程中各阶段PAN纤维的结构、性能变化的研究中发现,随着纺丝的进行,纤维强度不断增加,断裂伸长率逐渐减小,纤维的双折射率和偏光透光性与力学强度间存在较好的对应关系；纤维在20≈17°附近的衍射峰逐渐增强,其结晶度则与致密性间存在较好的对应关系,结晶度越高,纤维的密度越大,孔隙率越低,致密性越好。在干喷湿纺原丝P1、准干喷湿纺原丝P2和湿纺原丝P3三种纤维的对比研究中发现,三种纤维的结晶度、密度、强度大小比较为：P1>P2>P3；三种纤维的晶粒尺寸、纤度大小比较为：P1
In the aspect of preparation of PAN spinning solution, the influence of agitating speed, temperature and solvent on the change of rheology for PAN solution was discussed. In normal dissolving process, shear viscosity change will present certain rule:the viscosity firstly declines with the dispersion of powder, then increases slightly with the dissolution of macromolecular, and lastly declines again with the orientation of molecular chain in the solution. Speeding up agitating, increasing temperature and using composite solvent could promote the dissolution. Among them, speeding up agitating had a role of increasing dissolution rate, and increasing temperature could improve solubility, whereas using composite solvent could integrate advantages of both components, making the solution has better dispersibility and solubility. Under same concentration, the solution with composite solvent (DMAC/DMSO) had a lowest viscosity. Change of light absorption properties of the solution during dissolution process was analyzed by ultraviolet-visible spectrophotometer. It was found that the solution had a strong absorption peak near300nm wavelength in ultraviolet region. With the dissolution, the peak gradually strengthened, and the higher was the solution temperature, the stronger the peak was. Finally, the structure of coagulated PAN membranes was compared, and it was found that the solution with better solubility had more uniform structure, and the orientation of molecular chains was presented as raised net structure in the membrane surface.
A detailed study on coagulation and drawing deformation of PAN fibers was made during spinning process. The coagulation of PAN solution is a phase separation process which is affected by double diffusion, determining the structure of PAN nascent fibers. In this paper, mass transfer coefficient obtained from the second Fick's law was utilized to represent double diffusion rate. According to the diffusion rate in the solidification process, the diffusion process was divided into initial stage, middle stage and later stage. The influence of temperature, concentration difference and solution concentration on the diffusion velocity was analyzed, and it was found that the mass transfer coefficient of the initial stage (K1) increased with temperature and concentration difference, and was basically in proportion to concentration difference and T1/2. The mass transfer coefficient of the middle stage (K2) was still proportion to T1/2, and the lower was the temperature the better the proportional relationship was, as it increased first then decreased with the increase of the concentration difference. The diffusion rate of the last stage decreased slightly with the concentration difference and increased slightly with temperature. The diffusion rate basically declined linearly with the increase of polymer concentration, expect the medium and later mass transfer coefficient slightly deviation linear relationship. The influence of coagulation conditions on the crystallization and mechanical performance of PAN nascent fibers was discussed, and it was found that reducing temperature could inhibit crystallization and improve drawing performance, when the change of coagulation bath temperature made a more obvious effect than spinning solution temperature. Speeding up drawing could promote the plastic drawing deformation of PAN nascent fiber, and increasing draw ratio could refine aggregated fibrillar and reduce crystallinity, helpful for making fine-denier precursors.
The influence of solvent content, tensile speed on the drawing performance of PAN nascent fibers was discussed. It was found that yield strength increased linearly, breaking strength increased gradually, and elongation at break increased quickly first and then decreased slightly with solvent content decreasing. The fibers dried for10hours had the lowest yield platform and high elongation, providing the best drawing performance at room temperature. Speeding up drawing can promote deformation of nascent fibers with high solvent content, but not for fibers dried sufficiently. Drawing performance of PAN nascent fibers with the different first coagulation bath draw ratio under different temperature was discussed. It was found that the nascent fibers with small diameter tended to achieve maximum draw ratio in lower temperature, and increasing the first coagulation bath draw ratio could promote thinning fibers, when increasing the high temperature draw ratio was helpful for improving the strength of fibers.
The drawing deformation behavior of the second coagulation bath pre-drawing, high temperature air drawing, collapsing drawing and steam drawing during spinning process was discussed. It was found that the nascent fibers with the first coagulation bath draw ratio of5×could be drawn nearly23.5times in the80%and70℃second coagulation bath under a tensile speed of50mm/min. Afterwards the draw ratio of pre-drawn fibers increased first and then decreased in250～400℃during high temperature air drawing, achieving maximum draw ratio at350℃, and fiber strength increased greatly and elongation at break fell sharply with the increase of drawing ratio. Imposing1.05times drawing could make fibers keep good plasticity at the same time enhance densification effect in the collapsing process, improving strength and density sufficiently. Steam drawing could greatly reduce fiber denier and improve strength at the same time. And increasing steam pressure could promote deformation during steam drawing. According to the evolution of the fibers' structure and performance during drawing deformation, a molecular structure model was constructed for explaining the drawing deformation mechanism.
Evolution of the fibers' structure and performance during various stage of spinning process was discussed. It was found that, along with the spinning, the strength increased while elongation at break decreased gradually. The birefringence and polarizing light transmittance had a good corresponding relation with mechanical strength of the fibers. The diffraction peak at nearly2θ≈17°strengthened gradually, when the degree of crystallinity had a good corresponding relation with the density of the fibers. In the comparison of dry-jet wet spinning precursors P1, quasi dry-jet wet spinning precursors P2and wet spinning precursors P3, it was found that in aspects of crystallinity, density, strength:P1> P2> P3, in aspects of grain size, denier:P1
引文
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