橡胶在动态载荷下的能量损耗分析

以交联密度不同的同类轮胎胎面胶A1和A2为研究对象,通过动态拉伸实验得到储能模量及损耗模量随频率变化的曲线.建立了黏弹性广义Maxwell模型来定量分析不同温度的橡胶在不同频率的动态载荷下的能量损耗.采用非线性规划的方法分别在低频(10~25 Hz)及高频(25~60 Hz)下拟合模量-频率曲线,得到黏弹性广义Maxwell模型的参数值.采用有限元软件Abaqus模拟胎面胶动态拉伸过程并计算胎面胶的损耗角正切,得到不同温度下胎面胶的损耗角正切随激振频率的变化规律,通过和实验结果的比较证明文中所述黏弹性广义Maxwell模型及其参数获取方法可准确应用于胎面胶的动态拉伸性能分析.预测了在不同温度及频率下每一循环载荷周期中胎面胶的应力-应变迟滞回线以及单位体积胶料的能量损耗,阐释了不同温度下的胎面胶的能量损耗随频率的变化规律,同时结合2种胎面胶的交联密度测试数据分析了胶料的构效关系.     

热塑性聚氨酯微孔发泡材料的表观密度与其力学性能的关系

用高压CO2流体通过升温发泡法制备了一系列不同表观密度的热塑性聚氨酯(TPU)微孔发泡材料,探究了TPU发泡材料的表观密度与其力学性能的关系.微孔发泡材料的泡孔结构和表皮结构由扫描电子显微镜表征;不同表观密度材料的力学性能利用万能材料试验机和旋转流变仪表征.研究发现:TPU微孔发泡材料的表观密度主要是由材料皮层厚度占比和泡孔层密度决定的,皮层厚度占比越小和泡孔面积占有率越高,泡沫的表观密度越小;微孔发泡材料在线性应变区的压缩模量E与材料表观密度ρ的关系为:E∝ρ1.7,符合泡沫材料压缩模量与表观密度呈指数关系的基本结论;循环压缩实验中,随微孔发泡材料表观密度减小,损耗百分比增大,残余应变减小;流变实验中,微孔发泡材料的模量随表观密度变化没有明显的变化,阻尼因子tanδ随泡沫表观密度变化不呈单一的规律性.同时,阐明了微孔发泡材料的压缩模量E和损耗百分比随表观密度变化的机理.     

基于广义Maxwell模型的轮胎橡胶动态压缩性能分析

为了定量分析轮胎胎面胶动态力学性能及能量损耗,建立了基于广义Maxwell模型的黏弹性本构关系,根据胎面胶在各个温度下恒温动态压缩时的储能模量与损耗模量的频率扫描实验数据并采用非线性回归法求解误差函数的极小值的方法,确定各个温度下的黏弹性广义Maxwell模型参数.利用ABAQUS/Standard有限元软件数值模拟胎面胶动态压缩过程,得到不同温度下胎面胶的损耗角正切随激振频率的变化规律,并与实验结果进行对比分析.结果表明,黏弹性广义Maxwell模型及其参数的获取方法可以准确地用于胎面胶动态力学性能分析.在此基础上,定量预测了在不同温度及频率下每一循环载荷周期中胎面胶的应力-应变迟滞回线以及单位体积胶料的能量损耗,分析显示随频率增大,单位体积胶料的能量损耗逐渐增大,并且随着温度降低,能量损耗增大的幅度加大.     

Mg-Gd-Sc-Mn耐热镁合金的热变形行为

采用GLEEBLE-1500热模拟机对Mg-10．2Gd-0．8Se-1．7Mn合金在温度为573～773K、应变速率为0．001～1s^-1、最大变形程度为60％的条件下,进行高温压缩模拟实验研究。分析了合金流变应力和应变速率及变形温度之间的关系,计算了高温变形时的变形激活能和应力指数,为选择这种合金的热变形加工条件提供实验依据。采用金相显微镜分析了合金在不同温度下压缩变形的组织演变。结果表明：合金的稳态流变应力随应变速率的增大而增大,在恒定应变速率的条件下,合金的真应力随温度的升高而降低;合金的变形激活能随着变形温度的升高而增大,特别是在723K时迅速增大。合金在变形过程中发生了不同程度的动态再结晶,变形温度和变形速率对合金再结晶组织有明显的影响。根据实验分析,合金的热加工宜在673～723K范围内进行。     

机械剪切对天然橡胶分子量及其性能的影响

通过机械剪切力作用改变天然橡胶(SCRWF)的分子量及其分布,采用凝胶渗透色谱法测试发现,SCRWF在处理后的相对分子量和分布的变化明显,比较分析不同胶样塑性初值(P_0)、塑性保持率(PRI)、门尼粘度和应力松弛时间等生胶性能,对硫化胶的热稳定性、力学性能,及加工性能进行分析。结果表明,随着机械剪切力作用增加,天然橡胶分子量减小,其单峰趋势明显,生胶质量受其影响变化较大,对热稳定性有影响,且硫化胶的力学性能下降。RPA分析表明,在应变扫描中,随着应变的增加,机械剪切力作用增加的胶样的损耗因子(tanδ)线性增加而弹性模量(G′)线性减小;频率扫描中,随着频率增加,机械剪切力作用增加的胶样损耗因子(tanδ)线性减小而弹性模量(G′)线性增加。     

范性形变过程中氢释放的二次离子质谱研究

利用LT-1A型离子探针研究了工程上广泛应用的结构材料马氏体时效钢范性形变过程中氢释放行为。结果表明,在弹性形变阶段,氢释放速率随着应力的增加而增大;在范性形变开始不久,在屈服点附近氢释放速率达到最大值,后随应变量的增加而减小。范性变形后钢中氢的表观扩散系数为10~(-13)cm~2/s量级,较未形变的马氏体时效钢中的扩散系数要小3～4个数量级。     

活性氧响应性可降解不饱和聚氨酯的合成及其性能研究

设计合成了一类具有活性氧(ROS)响应性的新型不饱和聚氨酯. 3种不同比例的聚富马酸丙二醇酯(PPF)和聚酮缩硫醇(PTK)与六亚甲基二异氰酸酯(HDI)反应后,通过L-赖氨酸甲酯二盐酸盐(Lys-OMe)扩链,合成了含有双键和酮缩硫醇键的聚氨酯(PFTU),同时合成了只含有双键的聚氨酯(PPFU)和只含有酮缩硫醇键的聚氨酯(PTKU)作为对照.示差扫描量热分析(DSC)和热重分析(TGA)显示5种聚氨酯材料均为非晶态聚合物且在200℃以下具有良好的热稳定性.应力应变曲线显示PPFU是一种硬而韧的材料,而PTK的引入则改善了聚氨酯的弹性并使其保留良好的延伸性能.同时,含有PTK软段的聚氨酯PFTU和PTKU均具有较好的自由基清除能力;随着聚氨酯中PTK比例的增加,材料在过氧化氢/CuCl_2溶液中的降解速率也逐渐增大.体外细胞培养实验表明,本文合成的5种聚氨酯材料均不存在明显的细胞毒性.     

微孔对HDPE缺口冲击强度及断面形貌特征的影响研究

在-196℃～+23℃的温度范围内,系统测试了微孔发泡和未发泡高密聚乙烯(HDPE)的Izod缺口冲击强度,进行了动态粘弹谱(DMA)和冲击断口系统观察分析.根据实验结果,研究了外加冲击力场作用下微发泡高密度聚乙烯变形断裂过程和机理,揭示了微孔的存在导致一定实验温度下的材料变形断裂机制发生了变化,微孔的引入一方面减小了试样(材料)的有效承载面积,另一方面导致HDPE试样芯部基体材料的应力状态改变为平面应力状态,易于在冲击载荷下产生塑性变形或在低温脆断条件下裂纹尖端钝化阻止裂纹扩展,其综合作用的结果导致微孔发泡和未发泡HDPE的Izod缺口冲击强度随实验温度的变化规律存在差异,且实验温度高于-35℃时,微孔发泡HDPE的缺口冲击强度低于未发泡的,实验温度低于-35℃后,微孔发泡HDPE的缺口冲击强度高于未发泡的.     

聚乳酸基可降解形状记忆聚合物的制备、结构与性能

以三枝化低不饱和度聚环氧丙烷/聚乳酸两嵌段共聚物(POLA)为原料, 甲苯二异氰酸酯(TDI)交联制备可降解聚环氧丙烷/聚乳酸基聚氨酯(POLA-PU). 通过对POLA共聚物序列结构的调控, 制备了由高模量低断裂伸长率的脆性到低模量高断裂伸长率的韧性POLA-PU可降解形状记忆材料. 由TMA测得POLA-PU的形变温度为96～153 ℃. POLA-PU试样在140 ℃的形状记忆恢复时间不超过20 s. 在200%拉伸形变条件下, POLA-PU的形变固定率在65%～100%之间, 形变回复率均可达100%. 实验表明, 形状记忆行为取决于链的交联密度, 记忆效应归属于不同温度下柔性链的构象熵变化. 降解实验结果表明, 聚乳酸链段的引入赋予了该形状记忆材料良好的降解性能, 且随着聚乳酸含量的降低而下降.     

HDPE/CB高分子导电复合体系的单轴形变与压阻行为

根据基体形变及其与渗流网络结构之间的关系,研究了高密度聚乙烯(HDPE)/炭黑(CB)复合材料压阻行为的发生机制及其影响稳定性的力学因素.结果表明,单轴压阻行为的产生源于材料受外力变形而导致的渗流网络微结构变化,且这种变化强烈依赖于填料含量.当填料含量较低时(渗流阈值附近),体系电阻率随压力升高而表现为电阻正压力系数行为;当填料含量较高时,体系电阻率随压力升高显现电阻负压力系数效应.完全卸载的零压力下,电阻基线随压缩循环随循环次数增大而发生漂移,这种漂移与轴向残余压缩应变有关,可以通过增加循环次数来加以稳定.交联可以减小残余压缩应变,并抑制高填充复合体系电阻基线的漂移.     

二氧化碳和丙烯直接合成甲基丙烯酸的NiPMo/TiO2催化剂的研究

用溶胶-凝胶法以磷钼酸(MPA)的镍盐溶液水解钛酸四丁酯制备了NiPMo/TiO2催化剂.使用ICP、 XRD、 TG-DTA、 IR、 TPD-MS和微反应技术研究了催化剂的化学组成、热稳定性、化学吸附性质和催化反应性能.杂多钼酸盐与TiO2通过O2-在TiO2表面发生了键合.在623 K下,杂多阴离子仍保持原有的Keggin结构.CO2在Lewis酸位Ni(Ⅱ)和Lewis碱位Ni-O-Mo的桥氧协同作用下生成CO2卧式吸附态Ni(Ⅱ)←O-(CO)←(O--Ni).丙烯有多种吸附态在催化剂上吸附.在563 K、 1 MPa和空速1500 h-1的反应条件下,丙烯的摩尔转化率为3.2%,产物MAA选择性为95%.     

Synthesis of 1-benzyloxypyrazin-2(1H)-one derivatives

Different approaches for the synthesis of 1-benzyloxypyrazin-2(1H)-one derivatives from simple amino acids have been investigated. A library of 33 precursors for the preparation of N-hydroxy pyrazinones was obtained in moderate to good yields.     

α-Amino acid derived enaminones and their application in the synthesis of N-protected methyl 5-substituted-4-hydroxypyrrole-3-carboxylates and other heterocycles

A new and simple synthesis of novel N-protected methyl 5-substituted-4-hydroxypyrrole-3-carboxylates, which exist in equilibrium with their 4-oxo tautomers, has been developed in two steps starting from N-protected α-amino acids. The key intermediates are enaminones, which can also be isolated, characterized, and used for the construction of other functionalized heterocycles, before they spontaneously decompose to pyrrole products. 4-Hydroxypyrroles are prone to partial aerial oxidation but can be efficiently alkylated or reduced to stable polysubstituted pyrrolidine derivatives.     

Specific intramolecular aromatic CH insertion of diazosulfonamides

The chemoselectivity in the intramolecular CH insertion of various diazosulfonamides has been experimentally studied. The results reveal that the aliphatic 1,4-, 1,5-, or 1,6-C(sp³)?H insertions of diazosulfonamides are not accessible, while the aromatic 1,5-C(sp²)?H insertion can be realized specifically by adjusting the diazo-adjacent group. In addition, the general chemoselectivities in the intramolecular CH insertions of diazosulfonyl compounds are summarized. Generally, diazosulfones undergo both aromatic 1,5-C(sp²)?H and aliphatic 1,5- and 1,6-C(sp³)?H insertions, while diazosulfonates undergo aliphatic 1,5- and 1,6-C(sp³)?H insertions. However, diazosulfonamides only undergo aromatic 1,5-C(sp²)?H insertion.     

A general and convenient synthesis of 4-(tosylmethyl)semicarbazones and their use in amidoalkylation of hydrogen,heteroatom, and carbon nucleophiles

A general synthesis of previously unknown semicarbazone-based α-amidoalkylating reagents, 4-(tosylmethyl)semicarbazones, has been developed. The synthesis involved three-component condensation of semicarbazones of aliphatic or aromatic aldehydes with the same or other aldehydes and p-toluenesulfinic acid. The scope and limitations of this reaction were investigated. The compounds obtained were demonstrated to be an efficient α-(4-semicarbazono)alkylating agents. They were reacted with H- (sodium borohydride), O- (sodium methylate), S- (sodium phenylthiolate), N- (pyrrolidine, sodium succinimide), P- (trialkyl phosphites), and C-nucleophiles (sodium diethyl malonate) to give the corresponding products of the tosyl group substitution, 4-substituted semicarbazones, including analogues of nitrofurazone. Among the prepared compounds tested in vitro for antibacterial and antifungal activity, three nitrofuryl-containing semicarbazones exhibited high biological activities with minimum inhibitory concentration (MIC) values of 8–32 μg/mL.     

Synthesis of novel chiral bidentate hydroxyalkyl-N-heterocyclic carbene ligands and their application in palladium-catalyzed Mizoroki–Heck couplings and asymmetric addition of diethylzinc to benzaldehyde

A small library of new chiral bidentate hydroxyalkyl-imidazolium salts 1 is conveniently synthesized on multi-gram scale from inexpensive and commercially available chiral pool amino acids. The corresponding carbenes, generated by deprotonation of imidazolium salts 1, in combination with palladium(II) chloride were tested in the Mizoroki–Heck coupling reaction. The most significant results in terms of yields and reactivities were achieved with low catalyst loading. The catalytic activities of these imidazolium salts were also investigated in the asymmetric addition of diethylzinc to benzaldehyde. The use of MgO nanoparticles as an additive in conjunction with these ligands played a crucial role in increasing the efficiency of these reactions.     

Toward new camptothecins. Part 6: Synthesis of crucial ketones and their use in Friedländer reaction

In the context of the preparation of camptothecin and luotonin A analogs, the synthesis of some key keto-precursors and their use in Friedländer condensation are described. This paper also focuses on the stability of these keto intermediates and emphasizes the major differences between indolizinones and pyrroloquinazolinones series. Noteworthy is also the report of some original structures isolated as by-products of some experiments.     

N-Heterocyclic carbene-palladacyclic complexes: synthesis,characterization and their applications in the C-N coupling and α-arylation of ketones using aryl chlorides

N-Heterocyclic carbene-palladacyclic complexes 3 were successfully achieved in a one-pot procedure under mild conditions. The structure of 3a was unambiguously confirmed by X-ray single crystal diffraction and it was an active catalyst in the Buchwald-Hartwig amination and α-arylation of ketones even at very low catalyst loadings (0.01?mol%).     

Iodine-mediated oxidative Pictet-Spengler reaction using terminal alkyne as the 2-oxoaldehyde surrogate for the synthesis of 1-aroyl-β-carbolines and fused-nitrogen heterocycles

An efficient iodine-mediated oxidative Pictet-Spengler reaction in dimethyl sulphoxide (DMSO) using terminal alkynes as the 2-oxoaldehyde surrogate for the synthesis of aryl (9H-pyrido[3,4-b]indol-1-yl)methanones is described. The scope of the protocol includes the total synthesis of Fascaplysin, Eudistomins Y₁ and Y₂. The methodology is extended for preparing pyrrolo[1,2-a]-quinoxaline and indolo[1,5-a]quinoxaline derivatives. The utility of 1-aroyl-β-carbolines was demonstrated by performing palladium-catalyzed β-carboline directed ortho-C(sp2)-H functionalization of the phenyl ring with thiomethyl (SMe) group using DMSO as source and for accessing 4-aryl-canthin-6-ones.     

CoFe2O4自形成磁性液体场致结构化对磁化的影响

The Langevin paramagnetic theory can’t describe the relation between magnetization of ferrofluids and applied magnetic field. The structuralization of ferrofluids, which is considered the main influence factor of the magnetization, is regarded. The part of magnetization works is deposited when the structure is forming. This action influences the magnetization of ferrofluids directly or indirectly. On the base of the “compressing” model, the Langevin function that usually describes the magnetization of ferrofluid is modified, and a well-fitted curve is obtained. An equation of the relation between the equivalent volume fraction after being “compressed” and the intensity of magnetic field is discovered, which approximately describes the process of magnetization. The relation between the approximate initial susceptibility and the volume fraction can be obtained from modified formula.