超高相对分子质量PA6冻胶的流变行为研究

以氯化钙为络合剂,将聚酰胺6(PA6)粉末与氯化钙溶解在甲酸/氯仿混合溶剂中制得冻胶样品,研究了PA6/氯化钙/甲酸冻胶体系的流变性能,以及温度、PA6的相对黏度、CaCl2与PA6的摩尔比和PA6的质量分数对冻胶的ηa-γ觶流变曲线、非牛顿指数和结构黏度指数的影响。结果表明:冻胶溶液属于宾汉流体,具有明显的非牛顿性;体系的表观黏度随着温度的升高而降低,随PA6的质量分数的升高、络合剂CaCl2与PA6的摩尔比的增大或PA6的相对黏度增大而增大;溶液的结构黏度指数随温度的升高而减少,随溶液PA6的相对黏度的升高或PA6的质量分数的升高而增大。     

高相对粘度聚酰胺6冻胶的研究

采用阴离子淤浆聚合方法制备了聚酰胺6(PA6)冻胶,用扫描电镜、差示扫描量热和广角X射线衍射等手段对冻胶结构和性能进行了分析。探讨了PA6的相对粘度(η_r)、浓度和络合剂用量及不同溶剂对PA6冻胶的溶胶-冻胶转变点(T_f)的影响。结果发现:随冻胶中PA6的浓度、三氯化镓与PA6摩尔比的增加,T_f都会随之升高,呈较好的线性关系;η_r的增加使T_f升高,η_r小于12.5时,η_r和T_f呈线性关系,当η_r大于12.5时,则会发生偏离;冻胶表面有均匀的层状结构,有利于纺丝和高倍拉伸,络合剂三氯化镓能有效地将PA6分子间的氢键屏蔽,对冻胶的形成有很大作用。     

超高相对分子质量PA6冻胶体系的结构与性能

以三氯化镓(GaCl_3)、氯化锂(LiCl)、苯甲醇、氯化钙(CaCl_2)作为络合剂或溶剂,分别配制PA6/GaCl_3/硝基甲烷(CH_3NO_2)、PA6/LiCl/甲酸、PA6/苯甲醇和PA6/CaCl_2/甲酸等体系,制得冻胶试样,采用差示扫描量热法、红外光谱分析、X射线衍射和扫描电子显微镜等方法对冻胶试样的结构与性能进行了分析对比。结果表明:各个PA6冻胶体系的形成机理不同,各体系冻胶结构和性能差异较大。GaCl_3,LiCl,CaCl_2主要是通过破坏PA6的内部氢键,对其进行络合成冻胶,但三者的络合能力又有所区别。苯甲醇主要是通过溶剂效应而形成冻胶。     

凝固浴温度对超高相对分子质量聚酰胺6冻胶纺纤维结构和性能的影响

以氯化钙为络合剂,采用冻胶纺丝技术制备超高相对分子质量(UHMW)聚酰胺(PA)6纤维,重点研究凝固浴温度对UHMW PA6冻胶纺纤维结构和性能的影响,以期获得高强高模PA6纤维。试验结果表明:在较低凝固浴温度(4~8℃)下得到的纤维表面较为光滑;凝固浴温度越低,分子间排列越规整,取向度越好,成品丝条的双折射率越高,越易形成α晶型,结晶度越高,所得纤维的强度和模量也较大。综合考虑力学性能测试结果和室温的影响,凝固浴温度选为8℃。     

凝固浴温度对超高相对分子质量聚酰胺6冻胶纺纤维结构和性能的影响

以氯化钙为络合剂,采用冻胶纺丝技术制备超高相对分子质量（UHMW）聚酰胺（PA）6纤维,重点研究凝固浴温度对UHMW PA6冻胶纺纤维结构和性能的影响,以期获得高强高模PA6纤维。试验结果表明：在较低凝固浴温度（4～8 ℃）下得到的纤维表面较为光滑;凝固浴温度越低,分子间排列越规整,取向度越好,成品丝条的双折射率越高,越易形成α晶型,结晶度越高,所得纤维的强度和模量也较大。综合考虑力学性能测试结果和室温的影响,凝固浴温度选为8 ℃。     

氯化钙对尼龙6/硫酸钙晶须增强材料结构与力学性能的影响研究

本文用熔融共混法成功制备氯化钙/(尼龙6/硫酸钙晶须)复合力学增强材料,采用DSC、FTIR、XRD研究氯化钙对尼龙6/硫酸钙晶须复合材料结构性能的影响。结果表明:与硫酸钙晶须对尼龙6起异相成核作用的机理不同,引入少量的氯化钙对尼龙6的结晶性能、分子链间作用力产生很大影响;且当CaCl2含量3%时,PA6拉伸强度能提高至33%左右,缺口冲击强度有小幅度降低。     

络合剂对溶胶-凝胶法制备LiNi_(0.80)Co_(0.15)Al_(0.05)O_2正极材料电化学性能影响

以马来酸、甘氨酸或柠檬酸作为络合剂,采用溶胶-凝胶法制备锂离子电池Li Ni0.80Co0.15Al0.05O_2正极材料,对比了络合剂种类对样品电化学性能的影响。结果表明:采用不同络合剂制备的样品都具有层状结构,以柠檬酸为络合剂制备的样品存在较多的八面体单晶体。电化学分析显示,以马来酸为络合剂制备的样品具有最佳的充放电和循环性能:0.2C下首次放电容量为176 m A·h/g,30次循环后容量保持率为97.3%;1C下首次放电容量为162 m A·h/g,30次循环后容量保持率为92.3%。根据循环伏安曲线得到的锂离子的扩散系数表明,采用马来酸为络合剂制备的样品具有最大的扩散系数。     

两种体系合成的TS-1分子筛表征及其丙烯直接环氧化反应性能比较

采用SEM、XRD、微结构分析、IR等对以络合剂提高钛源稳定性体系和以传统体系合成的两种TS-1分子筛样品进行对比测试,并在高的双氧水浓度下考察了丙烯直接环氧化反应效果。结果表明,两种体系合成的TS-1分子筛样品的骨架结构、晶形、比表面积、孔径分布等基本一致,对丙烯直接环氧化的催化性能基本相当,但传统法合成的晶粒大小不一,而以络合剂提高钛源稳定性体系合成的晶粒为均一的均匀薄片状结构。这为较价廉体系合成TS-1分子筛的进一步研究、放大与工业应用提供了可能。     

局部络合PA6纤维和膜的拉伸性能及形态

以氯化钙(CaCl2)为络合剂,分别在纯甲酸溶剂和氯仿/甲酸混合溶剂中对超高相对分子质量聚己内酰胺(UHMWPA6)进行了低摩尔比的局部络合,对UHMWPA6络合液进行了制膜和干法纺丝,研究了纤维及膜的拉伸性能和形态。结果表明:在氯仿/甲酸混合溶剂中,氯仿的加入可明显提高局部络合UHMWPA6纤维及膜的拉伸性能,络合比为0.5时,UHMWPA6膜的最大拉伸倍数达10。SEM观察表明,纤维和膜中所含的络合剂在干燥过程中会重结晶析出,且随络合比的增加,纤维拉伸性能提高,结晶析出量增大。     

络合剂对镁-镍储氢合金电沉积的影响

通过循环伏安法、交流阻抗法研究了一种有机络合剂对有机镀液中镁-镍合金在铜上共沉积的影响。并通过以合金镀层为电极的充放电性能测试,确定了镀液中络合剂的最佳浓度。结果表明,络合剂对电沉积是有利的,适量络合剂的加入能显著提高以镁-镍合金镀层为电极的最高放电比容量。     

金属离子配位作用下PA6的受限结晶

采用熔融共混法,制备了聚酰胺6/氯化钙(PA6/CaCl2)复合材料。通过差示扫描量热法(DSC)、X射线衍射法(XRD)研究了PA6基体在受限条件下的非等温结晶及晶型转变行为。结果表明:金属离子Ca2+与酰胺基团的络合配位作用使PA6/CaCl2复合材料中PA6的结晶行为和结晶度受到了限制。随着CaCl2含量的增加,PA6的结晶度、结晶峰温度、熔融峰温度逐渐降低,结晶速率减小,结晶半峰宽增大,当CaCl2的含量大于8%时,PA6变为无定形态;此外,CaCl2的引入有利于PA6中α晶的生成。     

PA6/CaCl2复合材料络合配位的红外研究

采用傅里叶变换红外光谱分析(FTIR)研究了尼龙6/氯化钙复合材料中胺基、酰胺Ⅰ带和酰胺Ⅱ带伸缩振动峰随氯化钙用量的变化情况。通过配位化合物中氧、氮原子参与配位的优先次序,以及酰胺基团的红外形成机理,提出两种络合机理假设,证实了钙离子通过与尼龙6分子链上的氮原子发生络合作用,插入尼龙6分子链,破坏尼龙6的氢键,降低其结晶度。     

Preparation of porous nylon 6 fiber via electrospinning

Porous nylon‐6 fibers were obtained by electrospinning of ultra‐high molecular polyamide 6 (UHMW‐PA6). First, UHMW‐PA6/calcium formate composite nanofibers were prepared as precursors by electrospinning UHMW‐PA6 solutions containing different contents of calcium formate particles. Scanning electron microscopy (SEM) and transmission electron microscopy (TEM) were used to examine the surface morphology and inner structure of composite nanofibers. It was found that calcium formate particles were distributed both inside and on the surface of nanofibers. Fourier transform infrared (FTIR), differential scanning calorimetry, and thermal gravimetric analysis (TGA) were used to study the structure and properties of these nanofibers. Then, porous UHMW‐PA6 nanofibers were obtained by soaking the electrospun web in water for 24 h, to remove calcium formate particles. The removal of calcium formate particles was confirmed using FTIR and TGA tests. SEM and TEM observations revealed the formation of porous structure in these nanofibers. In addition, CaCl₂ was used instead of calcium formate to prepare the UHMW‐PA6 nanoporous fiber. POLYM. ENG. SCI., 55:1133–1141, 2015. © 2014 Society of Plastics Engineers     

Study on dry spinning and structure of low mole ratio complex of calcium chloride‐polyamide 6

Polyamide 6 (PA 6) filaments with initial modulus around 48 GPa were produced by dry spinning from low mole ratio (MR) complex of calcium chloride and high molecular weight PA 6 (CaCl₂‐PA 6) in formic acid. From the results of XRD, DSC, FTIR, and SEM, the complexation of CaCl₂‐PA 6 in the MR range of 0.15–0.3 was efficient. The spinnability of the complex solution was excellent, which allowed a maximum draw ratio of 14.4 for as‐spun fibers. After decomplexing and annealing, the birefringence of drawn fiber could reach around 0.08. Porous structure was found in fibers spun from formic acid‐chloroform cosolvent but not observed by using pure formic acid. When MR of CaCl₂/PA 6 exceeded 0.3, some irregular particles formed on the fiber surface due to the recrystallization of CaCl₂. However, fibers with smooth surface could be obtained when the MR decreased to 0.15. During the process of decomplexing in ethyl alcohol, an axial shrinkage of drawn fibers in a relaxed state was observed. It turned out that this shrinkage could be avoided by decompexing the fibers under tension. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

A new method to prepare low melting point polyamide‐6 and study crystallization behavior of polyamide‐6/calcium chloride complex by rheological method

A new method to prepare low melting point polyamide‐6 (LPA6) by complex reaction of calcium chloride (CaCl₂) and polyamide‐6 (PA6) in a co‐rotating twin screw extruder was reported. We employed a new rheological method to study the crystallization behavior of PA6/CaCl₂ complex and the mechanism of confined crystallization of PA6. Compared with differential scanning calorimetry (DSC), this method was more capable of detecting crystalline information. What's more, it was also an effective method for studying mechanism of confined crystallization. From the results of X‐ray diffraction, DSC, infrared spectroscopy, rheology, and mechanical properties, the complex reaction of CaCl₂ with the carbonyl oxygen atom in the amide group disrupted the intermolecular hydrogen bonding and confined the mobility of PA6 molecules. This could significantly reduce the crystallinity and melting temperature of PA6, and improve tensile strength and notched Izod impact strength. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41513.     

High performance polyamide 6 composites prepared by reactive extrusion

To improve the properties of polyamide 6 (PA6) composites, a series of modified PA6 composites was prepared by reaction extrusion. An amorphous PA6 was first obtained by the complexing reaction of Li⁺ in lithium chloride with amino groups, and then epoxy resins, nano‐SiO₂ as well as POE‐g‐MAH were in turn added into the PA6/LiCl system. The effect of different additives on the crystallization behavior and mechanical properties of PA6 composites was well‐studied by X‐ray diffraction (XRD), differential scanning calorimetry (DSC), dynamic mechanical analysis (DMA), scanning electron microscopy (SEM), and mechanical properties tests. The results demonstrated that PA6 was amorphous at 6 phr lithium chloride and a network structure was formed in PA6 matrix in the presence of epoxy resins, thus the mechanical properties of composites greatly were enhanced. However too many nano‐SiO₂ particles might impair the tensile strength of PA6 composites. Additionally, a PA6 composite with excellent properties was obtained in the presence of POE‐g‐MAH due to the crystal form change in PA6 matrix and the strong interaction between PA6 and POE‐g‐MAH. POLYM. COMPOS., 35:985–992, 2014. © 2013 Society of Plastics Engineers     

Calcium phytate: Effect of ph and molar ratio on in vitro solubility

Calcium and phytate phosphorus were highly soluble below pH 4 at all molar ratios of calcium (Ca) to phytic acid (PA) studied (0.512.67). As pH is increased above 4, there is a drop in solubility, the magnitude of which depends on the Ca:PA molar ratio. Above pH 6, the greatest calcium precipitation occurred at molar ratios between 4 and 6.5; both lower and higher Ca:PA molar ratios showed higher calcium solubility. In contrast, phytate phosphorus solubility decreased in proportion to the Ca:PA molar ratio, showing essentially complete precipitation above the Ca:PA ratio of 5. The pentacalcium phytate salt probably predominates when calcium is not limiting. Under calcium-limiting conditions, the complexes resolubilize as the pH is increased above 7.     

接枝率对PVC/PA6-g-SMA共混物结构与性能的影响

采用熔融共混方法制备了聚氯乙烯（PVC）与不同接枝率苯乙烯-马来酸酐共聚物(SMA）接枝改性聚酰胺6（PA6-g-SMA）的共混物,研究了PA6-g-SMA接枝率对PVC/PA6-g-SMA共混物力学性能及凝聚态结构的影响。结果表明,接枝率越高,PA6-g-SMA与PVC的相容性越好,在PVC基体中能以更小的相畴均匀分散,对PVC的增韧增强作用越明显;当PA6-g-SMA的接枝率为5.12 %,添加量为15 ％（质量分数,下同）时,共混物的冲击强度为64.7 kJ/m2,拉伸强度为55 MPa。