拉伸氯化聚乙烯微观结构的 X 射线研究

本文采用 X 射线衍射法,对拉伸氯化聚乙烯(CPE)的微观结构进行了研究,求得了不同拉伸倍数下,CPE 的取向因子、结晶度和晶粒尺寸。实验结果表明,随着氯含量的增加,CPE 的取向因子、结晶度和晶粒尺寸均减小;随着拉伸倍数的增加,CPE 的取向因子和结晶度增加,晶粒尺寸减小。     

湿纺凝固负拉伸对初生纤维结构与性能的影响

研究了凝固负拉伸对聚丙烯腈(PAN)纺丝液的膨胀效应、初生纤维聚集态结构和性能的影响,初步揭示了膨胀效应和凝固取向的产生机理及其对初生纤维结构与性能的影响;指出溶剂与水之间的传质速率差是控制初生纤维结构进而控制其性能的最关键因素,它决定了原液细流表面凝固层的组成及结构,而凝固速率反映了凝固层的生长速度。研究发现:随着凝固负拉伸的降低,PAN纺丝液的挤出胀大比减小,其传质速率差与凝固速率均下降,初生纤维的凝固取向、结晶度和晶粒尺寸均增加,其截面形状趋于圆形,内部结构变得均匀致密、缺陷减少,从而使断裂强度得以提高。     

双向拉伸法制备聚醚砜中空纤维

采用双向拉伸的方法制备了聚醚砜中空纤维,探讨了工艺条件对聚醚砜中空纤维取向度和水通量的影响。结果表明:随着纺丝速度的提高,纤维的取向度上升,水通量下降;在总拉伸倍数不变的前提下,随着凝固浴拉伸倍数的提高,纤维的取向度和水通量都减小;随着填充液压力的提高,纤维的取向度下降,水通量增加;随着凝固浴中二甲基亚砜含量的提高,纤维的取向度先增大后减小,出现了一个最大值,水通量先减少后增加,出现了一个最小值。     

凝固浴浓度对离子液体法纤维素纤维结构以及性能的影响

探讨了以离子液体1-丁基-3-甲基咪唑氯盐([BMIM]Cl)为溶剂制备的纤维素纤维纺丝工艺条件中凝固浴浓度对纤维结晶结构以及力学性能的影响。实验表明:在相同拉伸比和气隙条件下,凝固浴浓度对再生纤维素纤维的结构以及性能影响较大。随着凝固浴浓度的增加,纤维的结晶度和无定形取向都呈现先增大后减小的趋势,纤维的横向晶粒变小,拉伸强度、初始模量也呈先增大后减小的趋势。     

拉伸方式对聚醚醚酮纤维结构和性能的影响

采用进口聚醚醚酮(PEEK)树脂为原料,熔融纺丝制备了PEEK初生纤维,研究了一次拉伸和二次拉伸对PEEK纤维结构和力学性能的影响。结果表明:在150～270℃内,随着拉伸温度的提高,PEEK初生纤维的最大拉伸倍数增大,纤维的取向因子和力学性能提高;一次拉伸和二次拉伸时纤维的最大拉伸倍数相同,纤维的取向度、结晶度和力学性能基本相当,但二次拉伸纤维干热收缩率较低。二次拉伸时,总拉伸倍数相同,随着一段拉伸倍数的增大,纤维取向因子增大,力学性能提高;随着二段拉伸温度的提高,纤维结晶度增大,干热收缩率减小,取向因子基本相同,力学性能更优。     

热拉伸过程中PE–UHMW/PE–HD共混纤维的晶体结构演变

将超高分子量聚乙烯(PE–UHMW)与高密度聚乙烯(PE–HD)按照质量比为6︰4进行共混熔融纺丝,并对初生丝进行高倍热拉伸制得PE–UHMW/PE–HD共混纤维。利用广角X射线衍射、差示扫描量热、声速取向试验等方法研究了PE–UHMW/PE–HD共混纤维在热拉伸过程中的晶体结构演变过程。研究显示,随着热拉伸过程的进行,纤维的分子链沿纤维的轴向取向度逐渐增加,熔融峰温度逐渐升高,结晶度逐渐增加;沿径向的晶粒尺寸逐渐减小,而沿轴向的晶粒尺寸逐渐增加,即形成了更细长的晶粒;晶体的取向度逐渐增加。当拉伸倍数由1增大至6时,上述现象变化显著,当拉伸倍数由9增至15时,上述现象变化缓慢。与PE–HD共混后的纤维结晶度、晶体取向度和分子链取向度更高,晶粒更加细长。     

拉伸热定型对PET-PA/PA6共混纤维结构与性能的影响

以聚酯-聚酰胺共聚物/聚酰胺6(PET-PA/PA6)共混物为原料,采用熔融纺丝法制备了PET-PA/PA6共混纤维,讨论了拉伸热定型工艺对PET-PA/PA6共混纤维结构与性能的影响。结果表明:随拉伸倍数的增大,PET-PA/PA6共混纤维的断裂强度、取向度、结晶度以及沸水收缩率均明显增大;拉伸温度和热定型温度对PET-PA/PA6共混纤维的断裂强度和取向度的影响相对较小;随拉伸温度的升高,PET-PA/PA6共混纤维的断裂强度、取向度和结晶度呈现先增大后减小的趋势,并在拉伸温度为85℃时出现最大值;随热定型温度的升高,PET-PA/PA6共混纤维的结晶度增大、沸水收缩率减小;较佳的工艺条件为拉伸倍数1.6,拉伸温度85℃,热定型温度150℃。     

芳砜纶水洗丝在不同热拉伸温度下的结构性能变化

设计了多级多倍连续热拉伸工艺对芳砜纶水洗丝进行热拉伸,研究了从350～390℃的热拉伸温度对纤维结构和性能的影响.通过力学性能、动态热力学分析和热失重分析研究了不同热拉伸温度下纤维的性能变化,结合光学显微镜、同步辐射广角X-射线衍射仪研究了不同温度热拉伸下纤维形态结构和超分子结构的变化.研究发现:纤维热拉伸前后热分解温度(Td)变化不明显,玻璃化转变温度(Tg)有所提高,纤维的断裂强度和模量显著提高;但断裂强度和伸长率对温度的依赖性出现了先增大后减小的变化趋势,过高的拉伸温度导致纤维脆性增加,断裂强度和伸长率减小;随着热拉伸温度的升高,纤维的晶态结构趋于完善,结晶度、取向度和晶粒尺寸随之增大,但密度变化并不显著.     

超拉伸UHMWPE纤维的结晶结构及其形成机理

采用冻胶纺丝-超拉伸技术纺制了超高相对分子质量聚乙烯(UHMWPE)纤维。利用小角X光散射(SAXS)、广角X射线衍射(WAXD)及拉曼光谱等测试手段,研究了拉伸过程中UHMWPE纤维的结晶结构变化。结果表明:随拉伸的进行,纤维非晶区中分子链逐渐参与了结晶,纤维SAXS强度减弱,纤维结构变得紧密规整;纤维结晶长周期及结晶度随拉伸倍数的增加而增大,并趋于平衡,拉伸30倍后,纤维结晶长周期约为50 nm,结晶度约为67.5％;纤维横向晶粒平均尺寸随拉伸倍数的增加而变小,拉伸30倍后,趋于平衡,而纤维晶粒c轴方向的轴向晶粒尺寸随拉伸倍数的增加而变大。     

喷头拉伸对三角形PAN纤维湿法凝固成形的影响

采用三角形喷丝孔,在二甲基亚砜(DMSO)水溶液凝固成形过程中,研究了不同喷头拉伸比对聚丙烯腈(PAN)初生纤维的截面形状和表面形貌、声速、结晶度以及力学性能的影响。结果表明:当喷头拉伸比增大到0.9倍时,初生纤维的截面的"角部钝化"现象消失,截面变形为和喷丝孔相似的形状;与此同时,初生纤维的力学性能也发生了显著的变化;而且,随着喷头拉伸比的增加,初生纤维的声速取向、结晶度及晶粒尺寸都逐渐增加。     

超拉伸过程中UHMWPE纤维结构与性能的研究

利用密度梯度仪、声速取向仪、Instron材料强力仪、WAXD、DSC等手段 ,对超高相对分子质量聚乙烯 (UHMWPE)纤维在超拉伸过程中的结构和性能进行了测试研究。结果表明 ,不同拉伸倍数的UHMWPE纤维的结晶度、取向度、力学性能和熔融温度随着拉伸倍数的增大而增加 ;DSC图谱上的 Tm4 峰和WAXD分析证实了在超拉伸过程中UHMWPE纤维发生了正交晶相向六方晶相的转变 ,超拉伸后期结晶结构的变化对纤维的力学性能影响很大。     

Investigation on the thermal behaviors and mechanical properties of ultrahigh molecular weight polyethylene (UHMW-PE) fibers

Fibers of ultrahigh molecular weight polyethylene (UHMW-PE) were prepared with the gel fiber drawing method, and the solvent and extraction solvent used were a general kerosene and gasoline, respectively. The thermal behaviors and mechanical properties of the fiber were studied using thermal analysis, a wide-angle X-ray diffractiometer, density, the sound orientation factor, as well as mechanical property measurement. The results showed that the morphology of macromolecular chains was changed from the folded state to an extendedcain structure with increasing of the drawing ratio. In addition, the crystal form of the fiber also changed. These changes were more evident while the drawing ratio exceeded 20. The tensile strength, similar to the modulus of the fibers, increases with an increasing draw ratio in the range that we researched, whereas the sonic velocity orientation factor and the degree of crystallinity increase slowly when the draw ratio is over 30. © 1996 John Wiley & Sons, Inc.     

沸水再拉伸速率对聚丙烯腈纤维结构与性能的影响

以1-丁基-3-甲基咪唑氯盐([BMIM]Cl)为溶剂溶解聚丙烯腈(PAN)制成PAN纺丝原液,采用干喷湿法纺丝,经过凝固、预拉伸、沸水拉伸制得PAN纤维,对所得PAN纤维进行沸水再拉伸处理,研究了沸水再拉伸速率对PAN纤维结构和性能的影响。结果表明:PAN纤维中残留质量分数为4.38%的离子液体,为沸水再拉伸起到了增塑作用;随着沸水再拉伸速率的增大,PAN纤维的力学性能提高,断裂强度由2.69cN/dtex提高到4.33 cN/dtex,而断裂伸长率由26%减小到20%,纤维的玻璃化转变温度、晶区取向度、双折射率、结晶度、晶粒尺寸均增大。     

X-ray studies of regenerated cellulose fibers wet spun from cotton linter pulp in NaOH/thiourea aqueous solutions

Regenerated cellulose fibers were fabricated by dissolution of cotton linter pulp in NaOH (9.5 wt%) and thiourea (4.5 wt%) aqueous solution followed by wet-spinning and multi-roller drawing. The multi-roller drawing process involved three stages: coagulation (I), coagulation (II) and post-treatment (III). The crystalline structure and morphology of regenerated cellulose fiber was investigated by synchrotron wide-angle X-ray diffraction (WAXD) and small-angle X-ray scattering (SAXS) techniques. Results indicated that only the cellulose II crystal structure was found in regenerated cellulose fibers, proving that the cellulose crystals were completely transformed from cellulose I to II structure during spinning from NaOH/thiourea aqueous solution. The crystallinity, orientation and crystal size at each stage were determined from the WAXD analysis. Drawing of cellulose fibers in the coagulation (II) bath (H₂SO₄/H₂O) was found to generate higher orientation and crystallinity than drawing in the post-treatment (III). Although the post-treatment process also increased crystal orientation, it led to a decrease in crystallinity with notable reduction in the anisotropic fraction. Compared with commercial rayon fibers fabricated by the viscose process, the regenerated cellulose fibers exhibited higher crystallinity but lower crystal orientation. SAXS results revealed a clear scattering maximum along the meridian direction in all regenerated cellulose fibers, indicating the formation of lamellar structure during spinning.     

凝固条件对PAN初生纤维微孔结构形态的影响

采用一维多取向小角X射线散射研究了聚丙烯腈细流在凝固过程中,凝固浴温度、浓度以及喷丝头拉伸比对初生纤维中微孔结构形态的影响。结果表明,凝固温度由30％提高到60℃时,微孔沿纤维轴取向增强,微孔尺寸减小,但微孔数量增加;凝固浴质量分数由67．5％升高到76．0％,微孔数量减少,但微孔尺寸变大,微孔沿纤维轴取向减弱;喷丝头拉伸比为-36．7％-10％时,微孔尺寸和取向角都增大。在凝固浴温度为52-55℃,凝固浴质量分数为70％,选择负拉伸能得到性能优异的初生纤维。     

凝固条件对PAN初生纤维微结构的影响

通过湿法纺丝工艺制备聚丙烯腈(PAN)初生纤维,借助于X射线衍射仪、声速仪、扫描电子显微镜、小角X光散射仪等,研究了凝固浴温度、凝固浴浓度、喷丝头拉伸等凝固条件对初生纤维晶态结构、取向结构、形态结构的影响。结果表明:PAN纤维的凝聚态结构和形态结构在初生纤维形成时已基本形成;PAN初生纤维的结晶度达40%以上,其结晶度和结晶尺寸受凝固浴温度和浓度的影响;PAN初生纤维和原丝的晶区取向和全取向随着喷丝头拉伸的增大而增大;PAN初生纤维具有沿纤维轴向高度取向的沟槽,通过改变成形条件,可以获得沟槽浅且规整性完美的纤维表面;提高凝固浴浓度,可以形成结构均质、致密的PAN初生纤维,避免皮芯结构及芯部出现较多孔洞。     

Micro‐structure and characteristics of highly oriented polyoxymethylene obtained by press and biaxial drawing

The physical structure of oriented polyoxymethylene (POM) drawn in two steps by press drawing and subsequent simultaneous biaxial drawing was studied. The degree of crystallinity, the orientation, and the tensile modulus depending on draw ratio were analyzed. By the press drawing method, the draw ratio reached 6.0, the tensile modulus was 4.5 GPa, and the degree of crystallinity decreased from 70% to 65%. By the two‐step drawing of press drawing followed by subsequent simultaneous biaxial drawing, the tensile modulus reached 11 GPa when the draw ratio was 14 times, and the degree of crystallinity increased from 71% to 76–80%, but it did not depend on the draw ratio, and showed effectively a constant value (average 77%). The physical structural properties, such as the degree of crystallinity, the orientation of the crystal, and the lamella structure, were analyzed by SEM, X‐ray diffraction, and other methods. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 99: 835–844, 2006     

Effect of zone drawing on the structure and properties of melt‐spun poly(trimethylene terephthalate) fiber

Melt‐spun poly(trimethylene terephthalate) (PTT) fibers were zone‐drawn and the structures and properties of the fibers were investigated in consideration of the spinning and zone‐drawing conditions. The draw ratio increased up to 4 with increasing drawing temperature to 180°C, at a maximum drawing stress of 220 MPa. Higher take‐up velocity gave lower drawability of the fiber. The PTT fiber taken up at 4000 rpm was hardly drawn, in spite of using maximum drawing stress, because a high degree of orientation had been achieved in the spinning procedure. However, an additional enhancement of birefringence was observed, indicating a further orientation of PTT molecules by zone drawing. The exotherm peak at 60°C disappeared and was shifted to a lower temperature with an increase in the take‐up velocity, which means that the orientation and crystallinity of the fiber increased. The d‐spacing of (002) plane increased with increasing take‐up velocity and draw ratio, whereas those of (010) and (001) planes decreased. In all cases, the crystal size increased with take‐up velocity and draw ratio. The cold‐drawn PTT fiber revealed a kink band structure, which disappeared as the drawing temperature was raised. The physical properties of zone‐drawn PTT fibers were improved as the draw ratio and take‐up velocity increased. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 81: 3471–3480, 2001     

High modulus polypropylene fibers. II. Influence of fiber preparation upon structure and morphology

The influence of drawing on the limiting draw ratio upon formation of the morphological structure of fibers spun from binary polypropylene (PP) blends was studied. Fibers were spun from a fiber‐grade CR‐polymer and from the blends of a fiber‐grade CR‐polymer with a molding‐grade polymer in the composition range of 10–50 wt % added. As‐spun fibers were immediately moderately and additionally highly drawn at the temperature of 145°C. The structure and morphology of these fibers were investigated by small‐angle X‐ray scattering, wide‐angle X‐ray scattering, differential scanning calorimetry, scanning electron microscopy, density, birefringence, and sound velocity measurements. It was shown that continuously moderately drawn fibers are suitable precursors for the production of high tenacity PP fibers of very high modulus, because of so called oriented “smectic” structure present in these fibers. With drawing at elevated temperature, the initial metastable structure of low crystallinity was disrupted and a c‐axis orientation of monoclinic crystalline modification was developed. Hot drawing increased the size of crystallites and crystallinity degree, the orientation of crystalline domains, and average orientation of the macromolecular chains and resulted in extensive fibrillation and void formation. It was found that the blend composition has some influence on the structure of discontinuously highly drawn fibers. With increasing the content of the molding‐grade polymer in the blend, the size of crystalline and amorphous domains, density and crystallinity, as well as amorphous orientation decreased. Relationship has been established between the mechanical properties, crystallinity, and orientation of PP fibers. It was confirmed that by blending the fiber‐grade CR‐polymer by a small percentage of the molding‐grade polymer, maximization of elastic modulus is achieved, mainly because of higher orientation of amorphous domains. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 1067–1082, 2006