摘要
碳纤维以其卓越的性能而被广泛应用于航空航天、一般工业、体育休闲等众多领域。由于种种原因,我国高性能碳纤维的研究水平一直与国外有较大差距。而原丝质量不过关,一直是制约我国碳纤维高性能化的最重要因素,因此,对高性能碳纤维原丝的研究是实现高性能碳纤维国产化的关键。目前,国际上通过高分子量PAN来制造高强高模超细碳纤维是一个研究热点,但也遇到了一系列困难,包括如何制备高性能的PAN原丝。针对这一问题,本论文从PAN的三元共聚角度出发,采用混合溶剂法沉淀聚合得到了粘均分子量为56万的高分子量PAN,并综合利用SEM、XRD、强力仪、密度仪等分析测试手段,系统研究了聚合物共聚序列结构,沉淀聚合PAN的分子量控制和粒径分布,以及高分子量PAN湿法纺丝凝固成形及原丝的生产工艺,对生产高强高模超细碳纤维提供了详实可靠的实验数据基础和理论基础。本文的主要研究结论如下：
由PAN共聚物的序列均匀性角度出发,利用第四统计力学理论,提出了两单体共聚过程中其竞聚率的乘积即R1··R2可称为共聚物序列结构的均匀性标度。通过理论计算与推导,由前人的实验数据证明了共聚过程中溶解度参数与共聚序列标度的关系,即1n(r1r2)=k/(δ1-δ2)2,并从理论角度分析了控制高分子量PAN分子链序列均匀度的聚合方法。
在PAN共聚合过程中,通过改变混合溶剂配比,可以有效地调节PAN的分子量。并且,当混合溶剂为DMSO与H20时,不良溶剂H20(链转移常数为0)含量越高,PAN分子量和转化率越高,这是由于随着H20含量的增加,溶剂极性增加,PAN分子量呈增大的趋势；当混合溶剂为DMSO和C2H5OH或C4H90H时,随着DMSO含量的减少,溶剂极性减少,PAN分子量呈减小的趋势。
在混合溶剂中对AN、MA及IA三元共聚合,由于良溶剂DMSO的加入,单体在反应介质中的溶解度提高,并沉淀析出的聚合物颗粒的溶胀性也有所提高,聚合物颗粒结构比较疏松。随着DMSO组分的增加,聚合物的颗粒特性发生变化,由结实的不规则珠状变成松软的块状。
应用第四统计力学理论,得到聚合物颗粒粒径分布的均匀度标度r1*r2,r1*r2数值越小,PAN聚合物粒径的分布越均匀；r1*r2数值大,PAN聚合物粒径分布越不均匀。由粒径分布参数的计算可知,当DMSO与溶剂的配比为5：5时,得到的PAN聚合物颗粒粒径分布均匀。通过理论计算与推导,求得PAN聚合物粒径分布均匀度的对数值与混合溶剂的内聚能密度有着良好的线性关系,即1nr1*r2=A+BeCED；在进一步理论研究中发现表面张力与内聚能密度的关系,即1nM/f=A0+KoeCDE,并通过实验数据确定,混合溶剂体系对此关系式的影响可分成两大类区域：Ⅰ区是烷类；Ⅱ区是含羟基的醇类。
高分子量PAN溶液属于切力变稀的非牛顿流体,随着浓度的提高,PAN溶液的粘度降低。高分子量PAN纺丝溶液体系以弹性为主,粘性表现不明显。在固含量为10%时,纺丝液的物理稳定性较好,适合制备优质PAN原丝。
在一定浓度的凝固浴中,水和DMSO的扩散系数都随着凝固浴浓度的提高而增大,都随着凝固浴温度的提高而增大；凝固浴的浓度越高,其凝固扩散活化能越小,扩散进行越快。凝固浴的凝固能力对初生纤维的横截面及表面形貌都有很大的影响,要制得具有良好形貌的初生纤维,凝固浴的凝固能力要适中。凝固能力太大或太小会引起初生纤维表面或横截面的缺陷。
凝固浴浓度,凝固浴温度及凝固浴表观负牵伸倍数对初生纤维圆形横截面形状的影响大小程度为：凝固浴浓度>凝固浴表观负牵伸倍数>凝固浴温度。随着凝固浴浓度从50%升高至85%,PAN初生纤维的圆形横截面异形度先减小后增大,在80%浓度下,PAN初生纤维的圆形横截面异形度达到极小值,即纤维具有最接近圆形的横截面。随着凝固浴表观负牵伸倍数从40%降低至0牵伸倍数,PAN初生纤维的圆形横截面异形度减小,即在凝固浴表观负牵伸为0的条件下,PAN初生纤维具有更接近圆形的横截面。随着凝固浴温度从70℃降低至30℃,PAN初生纤维的圆形横截面异形度先增大,后减小,而后又增大,在凝固浴温度为40℃下,PAN初生纤维具有更近于圆形的横截面形貌。在凝固浴浓度为80%、凝固浴表观负牵伸倍数为O、凝固浴温度为40℃下得到的高分子量PAN湿法纺丝初生纤维,不仅具有圆形横截面,还具有良好的表面形貌及物理机械性能。
高分子量PAN的沸水牵伸倍数在4.5倍下可以极大的提高纤维的力学性能,但过牵易使纤维结构破坏,降低力学性能；对高分子量PAN纤维,在干燥致密化温度为130℃,干燥致密化时间为60s的条件下,有利制备具有良好的物理机械性能的原丝；在蒸汽牵伸倍数为2.5时,高分子量PAN原丝的物理机械性能最优。运用第四统计力学理论,定量分析和说明了牵伸和干燥致密化工艺以及在致密化过程中施加一定张力的重要作用。经过优化后的纺丝工艺,最终制备了强度达到0.96GPa (8.2cN/dtex)的高分子量PAN原丝。
For its excellent performance, carbon fiber is widely used in aerospace, general industrial, leisure and sports fields. However, our national levels of high performance carbon fiber still have a great gap compared with international advanced level for various reasons. The inferior quality of PAN precursor is the most important factor which has been restricting our development of high performance carbon fiber. Currently, using high molecular weight PAN to produce ultra high strength and high modulus carbon fiber in foreign is a research hotspot which also encountered a number of difficulties, including how to prepare high performance PAN precursor from high molecular weight PAN. To solve this problem, the study on high performance carbon fiber precursor is critical to solve this embarrassing situation. Start from the synthesis of copolymerization of AN, MA and IA, this paper polymerized PAN with 560,000 viscosity-average molecular weight by precipitation polymerization in mixture solvent, and studied sequence structure of polymer, control of PAN molecular weight and distribution of PAN particle size in precipitation polymerization, coagulation process of high molecular weight PAN in wet spinning and the spinning technology of PAN precursor through comprehensive utilization of SEM, XRD, strength tester, density gradient tube and other analytical testing methods which provides fine detailed and reliable experimental data and theoretical basis for the production of high strength and high modulus carbon fiber. The main conclusions are as follows:
From uniformity of the sequence structure of PAN, scale R1·R2 which is related to reactivity ratio of two monomers in copolymerization is introduced to be representative of uniformity degree of copolymer sequence structure. Through theoretical calculation and deduction, the relationship between solubility parameters and the scale of copolymer sequence is confirmed, which can be expressed as:In (r1r2)= k'(δ1-δ2)2. In addition, the control of sequence structure of PAN copolymer is also studied from the theoretical point of view.
During the copolymerization process of PAN, the molecular weight of PAN can be effectively adjusted by changing the ratio of mixed solvent. When the mixed solvent is DMSO and H2O, the molecular weight and conversion rate increase with the increase of H2O content, which is due to the increase of polarity of the solvent. When the mixed solvent consists with DMSO and C2H5OH or C4H9OH, the molecular weight of resulting PAN decreases with the increase of the content of C2H5OH or C4H9OH.
During the copolymerization of AN, MA and IA in mixed solvent, the solubility of monomer increases with the addition of DMSO, which makes better swelling of PAN particles and a loose structure of PAN. With the increase of DMSO components, PAN particles changes from irregular beads into a solid block.
The uniformity scale r1*r2of the distribution of PAN particle size is introduced according to the Fourth Statistical Mechanics theory. A smaller r1*r2 value is corresponding to a more uniform distribution of PAN particle size and a larger r1*r2 value is corresponding to a more non-uniform distribution of PAN particle size. According to the calculation, in a mixed solvent with the content of DMSO or other solvent in equal portions, the distribution of resulting PAN particles size is more uniform. Through theoretical calculation and deduction, good linear relationship between logarithmic value of uniformity scale of the distribution of PAN particles size and the cohesive energy density of mixed solvent can be confirmed, which can be expressed as In r1*r2=A+BeCED. In addition, the relationship between surface tension and cohesive energy density is also determined, which is lnf/M=A0+K0eCDE.
High molecular weight PAN solution exhibits a shear-thinning phenomenon which shows that it is a Non-Newtonian Fluids. With the increase of PAN concentration, viscosity of PAN solution decreases. Elasticity of high molecular weight PAN spinning solution is more obvious than its viscosity. In the solid content of 10%, spinning solution shows good physical stability which is suitable for preparing high-quality PAN precursor.
In a certain concentration of coagulation bath, the diffusion coefficient of H2O and DMSO are increased with the increase of coagulation bath concentration, increased with the increase of coagulation bath temperature; the higher coagulation bath concentration is corresponding to a smaller coagulation diffusion activation energy which results in faster diffusion. Coagulation ability of coagulation bath has a significant impact on cross section and surface morphology of nascent fiber. To obtain a nascent fiber with good morphology, coagulation ability should be moderate. Too large or too small is easier to cause defects in cross section and surface morphology of nascent fiber
The order of the influence of coagulation bath concentration, coagulation temperature and coagulation negative draw ratio on the cross section of nascent fiber is:coagulation bath concentration> coagulation negative draw ratio> coagulation temperature. As the concentration of coagulation bath increased from 50% to 85%, De (degree of deviation from circular cross section) of nascent fiber decreases first and then increases, in 80% of concentration, De achieves the minimum value, which means the cross section of nascent fiber is closest to circular. With the apparent negative draw ratio decreases from -40% to 0, De of nascent fiber reduced, which means under 0 negative draw ratio, the cross section shape of nascent fiber is closest to a circular. As the coagulation bath temperature decreased from 70℃to 30℃, De increases first, then decreases, and then increases. At 40℃, PAN fiber has a cross-section morphology most closer to circular. PAN nascent fiber obtained in a coagulation bath concentration of 80%, the apparent negative draw ratio is 0 and the coagulation bath temperature is 40℃, not only has circular cross-section, but also has a good surface morphology and mechanical properties.
To high molecular weight PAN, a draw ratio of 4.5 times can greatly improve the mechanical properties of fiber in drawing process of boiling water. But too large draw ratio will damage the fiber structure which results in reduction of mechanical properties of fiber. The condition that the temperature of dry densification at 130℃and drying time is 60s, is conducive to good mechanical properties of fiber. A draw ratio of 2.5 times in the steam stretch is favor to produce PAN precursor with optimal physical and mechanical properties. And the importance of drawing and drying densification process and exert tension in drying densification are also analyzed quantitatively according to the Fourth Statistical Mechanics theory. After optimization of the spinning process, the strength of final high molecular weight PAN precursor can reach 0.96GPa (8.2cN/dtex).
引文
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