连续碳纤维增强的聚芳醚酮在Ⅰ型循环载荷下的层间破坏

用双悬臂梁(DCB)试件研究了连续碳纤维增强的聚芳醚酮复合材料(CF/PEK-C),在Ⅰ型循环载荷作用下的层间裂纹扩展行为.循环载荷采用载荷控制模式,最小载荷与最大载荷之比为0.5.在疲劳试验中,仍然发现有“阻力曲线”现象存在.层间裂纹扩展速率用指数定律与相应的应变能释放速率联系起来,并对结果进行了讨论.     

连续碳纤维增强的聚芳醚酮在Ⅰ型循环载荷下的层间破坏

 用双悬臂梁(DCB)试件研究了连续碳纤维增强的聚芳醚酮复合材料(CF/PEK-C),在Ⅰ型循环载荷作用下的层间裂纹扩展行为.循环载荷采用载荷控制模式,最小载荷与最大载荷之比为0.5.在疲劳试验中,仍然发现有“阻力曲线”现象存在.层间裂纹扩展速率用指数定律与相应的应变能释放速率联系起来,并对结果进行了讨论.     

白细胞介素-1α与其Ⅰ型可溶性受体的相互作用及动力学特征

研究了基于亲和型生物传感器的白细胞介素-1α(IL-1α)与I型可溶性白细胞介素-1受体(sIL-1RⅠ)相互作用的实时监测,并应用FASTfit软件对数据进行拟合分析。采用共价交联法在样品池表面固定sIL-1RⅠ,其密度为2.13 ng/mm2,用于检测不同浓度IL-1α与sIL-1RⅠ的结合所引起响应信号变化。对浓度为2400 nmol/L IL-1α的响应信号为122.66弧度秒,并且响应信号同IL-1α浓度呈线性关系,相关系数为0.972。FASTfit拟合数据结果表明IL-1α与sIL-1RⅠ相互作用符合一级动力学方程,其误差值不超过0.5弧度秒,其解离平衡常数(KD)和结合平衡常数(KA)分别为4.15×10-6mol/L和2.41×105mol/L。验证了亲和型生物传感器研究IL-1α和sIL-1RⅡ相互作用及动力学分析的可行性,有助于阐明IL-1α和sIL-1RⅠ的重要生物学功能,并为快速筛选其拮抗剂研究提供了理论和实验数据。     

PEK-C/PPS共混体系的相容性和结晶行为

结晶-非晶高聚物共混体系的相容性和结晶行为的研究已有许多报道。本工作研究了含酞侧基聚芳醚酮(PEK-C)与聚苯硫醚(PPS)共混物的相容性和结晶行为。 PEK-C为徐州工程塑料厂产品,未作封端处理,η?p/c=0.70;PPS为日本东丽产品。两者用双螺杆挤出机在320～350℃制成共混物。仪器为Perkin-Elmer DSC-7型差示扫描量热仪,升温速率10℃/min;DDV-Ⅱ-EA型全自动动态粘弹谱仪和理学D/max-ⅡBX-射线衍射仪。     

聚苯醚的结构效应:1,4-二苯氧基苯和1,4-双(4-甲氧基苯氧基)苯的晶体结构

用单晶X射线衍射分析方法测得1,4-二苯氧基苯(Ⅰ)和1,4-双(4-甲氧基苯氧基)苯(Ⅱ)的晶体结构。它们的晶胞参数分别为:(Ⅰ)α=5.876(2),b=7.832(2),c=1.5455(6)nm, β=95.33(3)°;空间群为P2_1/c,Z=2。(Ⅱ)α=6.017(1),b=7.577(1),c=3.6404(5)nm;空间群为Pcab,Z=4.(Ⅰ),(Ⅱ)的分子构象、键长和键角数据表明氧桥两边的苯环的共轭极化效应不能贯通,而苯氧基只是分子中的一个独立片断。从而也阐明了此类聚苯醚体系的电子吸收光谱的同系直线斜率小的原因。     

新型聚芳醚酮与热致性液晶高聚物共混物流变性能和力学性能的研究

本文研究了新型聚芳醚酮与热致性液晶高聚物(PEK-C/LCP)共混物的流变性能及力学性能。结果表明:由于LCP的加入,PEK-C的熔体粘度降低;随着剪切速率的增加,共混物熔体流动活化能从223.5KJ/mol降为102.2KJ/mol。共混物的玻璃化转变温度从纯PEK-C的218℃降为199℃;除模量增加外,其它力学性能均有所下降。同时利用SEM观察了共混物冲击断面形貌,未发现有LCP微纤维生成。     

聚苯醚的结构效应:1,4-二苯氧基苯和1,4-双(4-甲氧基苯氧基)苯的晶体结构

用单晶X射线衍射分析方法测得1,4-二苯氧基苯(Ⅰ)和1,4-双(4-甲氧基苯氧基)苯(Ⅱ)的晶体结构。它们的晶胞参数分别为:(Ⅰ)α=5.876(2),b=7.832(2),c=15.455(6),β=95.33(3)°;空间群为P2_1/c,Z=2。(Ⅱ)α=6.017(1),b=7.577(1),c=36.404(5);空间群为Pcab,Z=4.(Ⅰ),(Ⅱ)的分子构象、键长和键角数据表明氧桥两边的苯环的共轭极化效应不能贯通,而苯氧基只是分子中的一个独立片断。从而也阐明了此类聚苯醚体系的电子吸收光谱的同系直线斜率小的原因。     

一种含酞侧基聚醚醚酮的稀溶液性质的研究（Ⅰ）

本文用光散身的粘度法研究了一种含酞侧基的聚醚醚酮(PEK-C)在氯仿(CKCl_3)和二甲基酰胺(DMF)中的稀溶液性质,建立了PEK-C在两种溶剂中的Mark-Houwink方程:并得到了高分子一溶剂相互作用参数χ_1和PEK-C的特征常数K_θ值: K_θ=6.25×10~(-2)ml/g,X_1=0.48,CHCl_3 K_θ=4.42×10~(-2)ml/g,X_1=0.49,DMF以及流体力学扩张因子α_η~3与分子量间的函数关系。     

那可汀一类物的立体化学

利用那可汀还原产物制备铜络合物的方法测定l-α-那可汀(Ⅰ)(天然)与l-β-那可汀(Ⅱ)(人工制得)的相对构型分别为赤与苏。结合l-α-那可汀(Ⅰ)经一系列化学变化制得1-甲氧基-13-表蛇果碱(Ⅷ)为负旋光性的事实,推论l-α-那可汀(Ⅰ)与l-β-那可汀(Ⅱ)的绝对构型分别为1R:9S与1R:9R。从已知结构关系推知Narcotoline(Ⅺ)的绝对构型为1R:9S,α-(天然)与β-gnoscopine(人工合成)的相对构型分别为赤与苏。     

含磷聚芳醚酮颗粒层间增韧碳纤维/双马树脂RTM复合材料

选用一种在RTM双马来酰亚胺树脂(BMI)注射温度下不溶解的含磷聚芳醚酮(P-PAEK)热塑性树脂作为增韧剂,制备层间颗粒增韧碳纤维增强双马来酰亚胺树脂基复合材料.研究了不同热塑树脂含量对树脂浇铸体冲击性能的影响,利用扫描电镜表征了复相体系的微观形貌并分析其增韧机制,并通过层间断裂韧性测试表征了RTM双马树脂基复合材料增韧前后的层间韧性性能.结果表明,当附载热塑颗粒面密度为2 g/m2时,复合材料的I型层间断裂韧性(GIC)为0.54 k J/m2,II型层间断裂韧性(G_(IIC))为1.36 k J/m~2,较未增韧复合材料分别提升约56%和42%.增韧后的复合材料在保持原有力学性能的同时,其冲击后压缩强度(CAI)提升约29%,层间剪切强度达到111.7 MPa.     

Automated monitoring of the crack propagation in mode I testing of thermoplastic composites by means of digital image correlation

One of the main challenges of the mode I double cantilever beam (DCB) test is the simultaneous determination of the applied load and displacement with the developing delamination length. The present work addresses this issue by side-view tracking the crack propagation by means of digital image correlation (DIC). Two different reduction methods were developed to determine the crack length from the DIC data. On the one hand, the crack tip position was defined by the high strain concentration in the immediate vicinity of the crack tip, and on the other hand, by crack tip opening displacement (CTOD). The data obtained enabled the calculation of the energy release rate of carbon fibre reinforced thermoplastic specimens with either run-arrest or stable crack extension. For reasons of comparability, top surface analysis (TSA), as recently reported, was also carried out. Following this approach, the crack propagation was tracked applying DIC to the top specimen surface. The methods developed showed a good correlation with both the standardised procedure and TSA. It was shown that DIC can be used as an alternative to the conventional optical measuring tools to follow the crack propagation in the mode I DCB test.     

甲醛在α-Al2O3颗粒物表面的非均相反应研究

使用漫反射傅里叶变换红外光谱(DRIFTS)原位反应器研究了273~333 K下甲醛与α-Al2O3颗粒物表面的非均相反应. 结果表明, 甲醛在α-Al2O3颗粒物表面生成产物主要为甲酸盐、二氧亚甲基以及少量多聚甲醛和吸附态甲醛, 甲酸盐是由中间产物二氧亚甲基进一步氧化生成的. 在293 K下, 甲醛在α-Al2O3颗粒物表面的反应级数为0.81±0.05, 以样品池几何面积计算的初始摄取系数γ0GEO为(2.3±0.5)×10-5, 以颗粒物BET面积计算的初始摄取系数γ0BET为(9.4±1.7)×10-9, 表观活化能为33.5 kJ/mol.     

硝基胍H迁移异构化反应动力学的从头计算研究

Theoretical studies on the α- and β-forms nitroguanidine were carried out using ab initio theoretical methods, at the MP2/6-31G(d,p) level. The predicted geometrical parameters were in good agreement with the available theoretical values, which calculated by other author. The three C-N bond lengths in α-form nitroguanidine were different, the longest bond length was 1.430 A, the shortest was 1.283 A. But they were almost similar in β-form, the longest was 1.375 A, the shortest was 1.322 A. Therefore there were conjugative effects in β-form but not in α-form. The calculated results also show that the β-form is stable with respect to the α-form from energetically, lower 28.16 kJ/mol corrected with zero point vibrational energy. The transition-state for the unimolecular isomerization was conformed by the IRC calculation. The calculated energy barrier for the direct intramolecular hydrogen atom transfer isomerization process was 132.95 kJ/mol. The isomerization reaction, exothermal reaction, is a typical intramolecular hydrogen atom synfacial transfer reaction. Rate constants of the isomerization reaction were evaluated within the temperature range of 200-1773 K by the classical transition state theory. The rate constant was 1.99×10-11 s-1 and the equilibrium constant was 1.00×105 at 298 K. With the temperature increasing, the equilibrium value decayed and the reaction process was more difficult.     

Studies on Adsorption Behavior and Mechanism of Copper（ Ⅱ ） onto Amino Methylene Phosphonic Acid Resin

IntroductionThe adsorption ability of the functional poly-mer used to enrich metal ions is strong and the op-eration of the functional polymer is convenient.The polymer having adsorbed metal ions can be re-covered by means of an acid or an alkaline solutionand the recovered polymeric material can bereused.The adsorption ability of the polymer withvarious functional groups is different for differentmetals.Because nucleophilic atoms such as oxy-gen,nitrogen,sulphur and phosphorous atoms cancoord…     

2-吡咯类酰腙的合成、晶体结构及与小牛胸腺DNA的相互作用

以2-吡咯甲酰肼与2,4-二羟基苯甲醛和2-羟基-3-甲氧基苯甲醛经缩合反应合成2,4-二羟基苯甲醛-2-吡咯甲酰腙C₁₂H₁₁N₃O₃(Ⅰ)和2-羟基-3-甲氧基苯甲醛-2-吡咯甲酰腙C₁₃H₁₅N₃O₄(Ⅱ),并利用红外光谱、元素分析、¹H NMR、X射线单晶衍射和热重分析进行表征,结果表明晶体Ⅰ属单斜晶系,空间群为P2₁/c,Z=4,晶胞参数为a=1.2586(4) nm,b=0.8050(3) nm,c=1.1914(4) nm;晶体Ⅱ为正交晶系,空间群为P2₁2₁2₁,Z=4,晶胞参数为a=0.4756(2) nm,b=1.2491(6) nm,c=2.2145(11) nm。 热重结果显示,化合物Ⅰ和Ⅱ最大热分解峰分别出现在267.59和284.79 ℃,表观活化能分别为176.6和122.9 kJ/mol,表明化合物Ⅰ和Ⅱ具有较高的热稳定性。 利用粘度实验和微量热实验研究了化合物Ⅰ和Ⅱ与CT-DNA的相互作用,均显示两种化合物均与CT-DNA发生了插入作用,且相互作用过程放热,焓变值分别为ΔH(Ⅰ)=4.67 kJ/mol和ΔH(Ⅱ)=4.40 kJ/mol。     

Kinetic analysis of one-step solid-state reaction for Li4Ti5O12/C

The kinetics of one-step solid-state reaction of Li(4)Ti(5)O(12)/C in a dynamic nitrogen atmosphere was first studied by means of thermogravimetric-differential thermal analysis technique at five different heating rates. According to the double equal-double steps method, the Li(4)Ti(5)O(12)/C solid-state reaction mechanism could be properly described as the Jander equation, which was a three-dimensional diffusion with spherical symmetry, and the reaction mechanism functions were listed as follows: f(α) = (3)/(2)(1 - α)(2/3)[1 - (1 - α)(1/3)](-1), G(α) = [1 - (1 - α)(1/3)](2). In FWO method, average activation energy, frequency factor, and reaction order were 284.40 kJ mol(-1), 2.51 × 10(18) min(-1), and 1.01, respectively. However, the corresponding values in FRL method were 271.70 kJ mol(-1), 1.00 × 10(17) min(-1), and 0.96, respectively. Moreover, the values of enthalpy of activation, Gibbs free energy of activation, and entropy of activation at the peak temperature were 272.06 kJ mol(-1), 240.16 kJ mol(-1), and 44.24 J mol(-1) K(-1), respectively.     

新型多氨-多酰氨配体和氨基酸的三元铜(Ⅱ)配合物(英)

合成3个多氨-多酰氨配体1，12-二((α-羟甲基)苯基)-2，5，8，11-四氮杂十二烷-1，12-二酮(L₁)，1，13-二((α-羟甲基)苯基)-2，5，9，12-四氮杂十三烷-1，13-二酮(L₂)，1，15-二((α-羟甲基)苯基)2，5，8，11，14-五氮杂十五烷-1，15-二酮（L₃）。利用pH滴定分别在5.0 ℃，15.0 ℃，25.0 ℃，35.0 ℃测定了铜(Ⅱ)与这3种配体在     

苏丹红Ⅱ与肌红蛋白相互作用的分子模拟与实验

用荧光光谱法研究了苏丹红Ⅱ与肌红蛋白(Mb)之间的相互作用, 实验结果表明,二者结合位点数近似为1, 结合常数K=3.84×107L/mol, 有很强的相互作用. 用分子柔性对接技术模拟确定了它们之间的作用位点、作用力类型及相互作用能. 理论计算的结果表明,苏丹红Ⅱ和Mb相互作用的势能为-9419.9 kJ/mol, 静电能为-7468.8 kJ/mol, 范德华能为-1951.0 kJ/mol. 苏丹红Ⅱ与Mb中His64残基形成氢键, 苏丹红Ⅱ也能与疏水氨基酸残基, 如能产生内源荧光的Phe33、Phe43、Phe106 和 Phe138等发生作用, 这与苏丹红Ⅱ能使Mb荧光猝灭的实验结果是一致的.     

Interlaminar fracture toughness of unidirectional DCB specimens: A novel theoretical approach

A novel theoretical approach is presented to calculate the mode I interlaminar fracture toughness (G_Ic) of double cantilever beam (DCB) specimens with low ratio of initial crack length-to-thickness (a₀/2h). This method is based on a sixth-order beam theory, namely Reddy-Bickford beam (RB), on Winkler elastic foundation (WEF) to account for both transverse shear deformation of the beam and local effects at the delamination front (root rotation). RB with only two generalized displacements w and ?; and three boundary conditions at ends and loading points of a shear deformable beam gives more accurate results than the fourth-order Timoshenko beam theory. The accuracy of the proposed method in prediction of initiation G_Ic values is evaluated together with other available models considering the experimental fracture toughness for moderately thick unidirectional E-glass/epoxy DCB specimens with small initial delamination lengths.     

二氟亚烷基卡宾与甲醛环加成反应机理的理论研究

用二阶微扰理论研究单重态二氟亚烷基卡宾与甲醛发生的环加成反应机理,采用MP2/6-31G^*方法计算了势能面上各驻点的构型参数、振动频率和能量.结果表明,单重态二氟亚烷基卡宾与甲醛的环加成反应主要有两种反应通道,通道1中,两个反应物经a,b和c三条反应途径生成三元环构型的产物P1,其中途径c是主反应途径,该途径有两步组成:(Ⅰ)二氟亚烷基卡宾与甲醛生成了1个富能中间体(INT1c),是无势垒放热反应,放出能量为219.18kJ/mol;(Ⅱ)中间体(INT1c)异构化为产物二氟亚烷基环氧乙烷,其势垒为134.71kJ/mol.通道2的反应途径由三步组成:(Ⅰ)反应物首先生成了1个富能中间体(INT1b),为无势垒的放热反应,放出的能量142.77kJ/mol;(Ⅱ)中间体(INT1b)异构化成另一中间体(INT2),其势垒为22.31kJ/mol;(Ⅲ)中间体(INT2)异构化成四元环构型产物P2,其势垒为11.98kJ/mol.