熔融聚合法合成生物材料聚(乳酸-谷氨酸)

以外消旋乳酸(D,L-LA)为单体,与L-谷氨酸(L-Glu)直接熔融聚合,合成了生物降解材料聚(乳酸-谷氨酸)共聚物.用特性粘数[η]、FTIR、1H NMR、GPC、DSC、XRD等手段进行系统表征,探讨了催化剂种类和用量、熔融聚合反应时间、反应温度以及不同投料比对聚合物合成的影响.在单体乳酸和谷氨酸投料物质的量比为98:2、150℃、70Pa、催化荆SnCl2的用量0.7%(质量分数)的条件下熔融聚合8h,聚合物重均相对分子质量(Mw)可达6400.随着谷氨酸投料量的增加,共聚物重均相对分子质量逐渐减小,Tg均低于直接熔融合成的聚外消旋乳酸,且共聚物均为无定形态.     

药物缓释材料聚(乳酸-丙氨酸)的直接法合成与表征

直接以外消旋乳酸(LA)、L-丙氨酸(Ala)为原料[n(LA):n(Ala)=9:1],采用熔融聚合法合成药物缓释材料聚(乳酸-丙氨酸)共聚物[P(LA-co-Ala)],并用特性黏数、FTIR、1H NMR、GPC、DSC、XRD等手段进行系统表征.熔融共聚中采用一次投料并分次预聚,可生成重均相对分子质量(Mw)达3200(分散度Mw/Mn＝1.23)的共聚物,相对分子质量可以达到丙交酯开环共聚法的水平.首次报道了P(LA-co-Ala)]药物缓释材料的DSC与XRD表征结果,其与聚外消旋乳酸(PDLLA)相比,共聚物具有较低的Tg、Tm和结晶度.新方法步骤少、操作简便,且成本更加低廉.     

聚乳酸-聚乙二醇的熔融共聚及结构表征

从L-乳酸缩聚得到预聚物,系统地研究了数均分子量200～2000的聚乙二醇(PEG)与乳酸预聚物的直接熔融共聚,采用对甲苯磺酸/氯化亚锡/辛酸亚锡三元催化体系,通过乳酸预聚物与PEG熔融共聚,制备了重均分子量均在两万以上、分子量分布较窄的左旋聚乳酸(PLLA)-PEG共聚物。利用傅里叶变换远红外、氢核磁表征证明了共聚产物主要为PLLA-PEG结构;差示扫描量热分析表明,共聚物相比均聚物PLLA,玻璃化转变温度Tg、熔点Tm、结晶度Xc均降低;旋光分析表明,共聚物中L-乳酸的旋光度降低,聚合过程存在一定的消旋化;应力流变仪分析表明共聚物韧性有所提高。     

高分子量聚L-乳酸的合成和表征

采用丙交酯开环聚合合成聚L-乳酸(PLLA),研究了引发剂用量、聚合时间对聚L-乳酸分子量的影响.采用FTIR、DSC、TG分析方法对聚乳酸的结构和热性能加以表征.研究结果表明通过对聚合时间以及引发剂用量的控制,合成出高分子量聚L-乳酸.FTIR分析结果证实了聚L-乳酸的结构,DSC分析表明合成出的聚L-乳酸玻璃化转变温度为62℃,结晶度达到42.3%;TG分析表明聚L-乳酸热分解温度为299℃.     

酪氨酸改性聚乳酸共聚物的合成及降解研究

以乳酸(D,L-LA)和L-酪氨酸(Tyr)为原料[n(D,L-LA)/n(Tyr)=95/5],氯化亚锡(Sn(cl)2)为催化剂,采用梯度升温法,通过直接熔融缩聚合成聚(乳酸-酪氨酸)共聚物(PLA-co-Tyr).用特性粘度测试、FT-IR、1 H-NMR、GPC、DSC、XRD、TG等对其进行表征,通过SEM、XRD等方法研究了降解前后材料的表面形态、结晶度及失重率的变化.结果表明:系列共聚物中的重均相对分子量Mw最大可达2900,与聚乳酸相比具有较小的Tg和结晶度,分解温度高于180℃,具有良好热稳定性且降解性能优于聚乳酸.     

外消旋乳酸直接熔融聚合-二异氰酸酯TDI熔融扩链的研究

用2,4-甲苯二异氰酸酯（TDI）对以外消旋乳酸（D,L-LA）直接熔融聚合合成的低分子量聚外消旋乳酸（PDLLA）进行扩链,用粘均分子量、红外光谱（IR）、核磁共振氢谱（^1H NMR）、DSC、X-射线衍射等对扩链产物进行了表征。在SnCl2催化下,NCO／OH=1,160℃下反应60min,可得到Mη为扩链前3．42倍的可溶性聚乳酸类生物降解材料。IR、^1H NMR表明熔融聚合-TDI熔融扩链产物引入了NH和苯环,DSC、XRD等表征发现扩链使Tg、Tm和结晶度等相应提高。但是,温度过高、时间过长、NCO／OH过大时,易生成可溶性差的交联副产物,较多副产物的混杂会导致Tg和结晶性的降低。     

端羟基聚(乳酸-己内酯)共聚物的合成及表征

以乳酸(D,L-LA)和ε-己内酯(-εCL)为原料,采用梯度升温法,通过直接熔融缩聚合成了系列端羟基聚(乳酸-己内酯)共聚物(PLCA)。最佳工艺条件为:压力0.098MPa,催化剂Sn(Oct)2用量0.8%(质量分数),n(D,L-LA)∶n(-εCL)=8∶2,聚合温度170℃,反应7h。用特性粘度、FT-IR1、H-NMR、XRD、DSC等对其进行表征,结果表明,系列PLCA中的粘均分子量最大可达20785,Tg均比PLA的小,且随-εCL含量的增加,Tg越小,有效改善了PLA的脆性。结晶度比PLA有所降低,说明-εCL的加入使柔韧性增强。     

聚(乳酸-酪氨酸)的合成及表征

以乳酸(D,L-LA)和L-酪氨酸(Tyr)为原料[n(D,L-LA)/n(Tyr)=95/5],采用梯度升温法,通过直接熔融缩聚合成了系列聚(乳酸-酪氨酸)共聚物(PLA-co-Tyr)。最佳工艺条件为压力0.095MPa,催化剂Sn(Cl)2用量为0.4%(质量分数),聚合温度170℃,反应10h。用特性粘度测试、FT-IR、1 H-NMR、GPC、XRD、DSC等对其进行表征,结果表明,此方法操作简单且成本低廉,系列共聚物与PLA相比,分子链中引入了活性基团,具有较小的Tg,结晶度有所降低,并且通过控制酪氨酸的加入量可以调节聚合物的结晶度。该聚合物分子量能满足用作药物缓释试剂的要求。     

电纺丝聚乳酸纤维支架的制备及其细胞相容性研究

静电纺丝法制备的聚(D,L-乳酸)超细纤维具有孔隙率高、孔径/结构可调、生物相容性良好等特点,已成为组织工程支架材料研究的热点。探讨了纺丝溶液浓度、流量、电压、干燥方式等影响聚(D,L-乳酸)纤维支架形貌的因素,确定了最佳工艺参数为纺丝溶液浓度为0.20g/mL,流速为0.8mL/h,电压为12kV,经真空冷冻干燥,可获得分布比较均匀,直径大多为500～900nm的聚乳酸纤维。体外细胞形貌观察表明聚(D,L-乳酸)纤维支架具有良好的细胞相容性。     

熔融缩聚法直接合成聚L-乳酸的研究

以L-乳酸为原料,熔融缩聚法直接合成聚L-乳酸.考察了预聚工艺、催化剂配比及用量、反应温度、反应时间及真空度等条件对乳酸聚合反应的影响.通过红外光谱(FTIR)和核磁共振波谱(1H-NMR)分析和表征聚乳酸的结构,凝胶渗透色谱(GPC)测试其分子量及分子量分布.研究表明,较为适宜的工艺条件为:以二水合氯化亚锡(SnCl2·2H2O)和对甲基苯磺酸(TSA)为催化剂,且SrCl2·2H2O相对于乳酸预聚体的质量比为0.5%,真空度-0.98MPa,温度180℃,反应时间10h.得到的聚L-乳酸的粘均分子量为6.17×104,分子量分布1.37,且产率较高,色泽较浅.     

热交换器的分类及优缺点分析

热交换器是将不同温度介质之间的热量通过热传导的形式,由高温介质传递给低温介质,使介质达到生产所需温度的工艺设备,也可作为一种节能设备使用.通过对不同热交换器的结构分析,总结不同热交换器的优缺点、适用环境,为生产工艺设计人员及设备制造单位在选择可降低能耗、提高效率的设备上提供参考.     

聚苯胺及其复合物的制备和结构及形貌分析

通过化学氧化法分别制备盐酸,盐酸和十二烷基苯磺酸,碳纳米管(MWNTs-COOH)掺杂的聚苯胺,利用红外光谱,紫外光谱,扫描电子显微镜和透射电子显微镜对所制备聚苯胺的结构和形貌进行分析。分析不同掺杂物对聚苯胺的结构和形貌的影响;同时研究了超声波作用对聚苯胺形貌以及聚苯胺包裹MWNTs-COOH情况的影响。     

Thermodynamic similarity and prediction of the properties and characteristics of substances and processes

Principles of the theory of thermodynamic similarity are considered in application to all aggregate states of a substance, including phase transitions, and to the change in dissipative structures in open systems.Translated from Inzhenerno-Fizicheskii Zhurnal, Vol. 53, No. 5, pp. 709–716, November, 1987.     

Modelling and computation of curing and damage of thermosets

The curing of thermosets is a complex process involving the transition from a fluid into a (visco-) elastic solid. This phase transition comes along with an increase in stiffness and a volume shrinkage of the polymer. The latter may lead to severe residual strains and stresses, which in turn can cause damage in the final, usually quasi-brittle material. In this contribution a constitutive model is developed which takes into account the curing of a thermosetting material together with the process-induced damage as resulting from curing shrinkage. The curing of the material is governed by a phenomenological hypoelastic constitutive equation which includes temporal evolutions for stiffness and volume shrinkage. Thermal and viscous effects are neglected in the present study. An isotropic gradient-enhanced damage model is adapted to describe the damage evolution. The curing-damage model is implemented into a finite element code and numerical examples for thermosetting materials demonstrate that the proposed model is capable to predict cure-induced damage in thermosets.     

碳化硼陶瓷增韧补强和致密化研究现状及其展望

碳化硼陶瓷具有极高的硬度,然而其低韧性、低抗弯强度、难以致密化限制了它的广泛应用.已有一些研究集中于碳化硼陶瓷增韧补强和致密化,对这一方面国内外研究进展进行了归纳与评述,阐明各种增韧补强和致密化方法的优缺点,提出碳化硼陶瓷增韧补强和致密化研究值得发展的一些方向.     

Measurement and analysis of elastic and anelastic properties of alumina and silicon carbide

Measurements of dynamic Young's modulus, E, and damping as a function of temperature, T, were made for alumina and silicon carbide. The Young's modulus data were compared with some from the literature, and analysed in terms of a theoretical framework relating the Debye temperature, θD, with the elastic constants. For both materials this analysis yielded a ratio T₀/θ_D which was near 0.4, where T₀ is an empirical fitting constant for the plot of (E(0)−E)/T versus 1/T (E(0) is the value of E at 0 K). The analysis of the damping data in terms of an Arrhenius type dependence led to effective activation energies near kT, where k is Boltzmann's constant. This revised version was published online in November 2006 with corrections to the Cover Date.     

Surface-charge density and potential of coal-liquid mixtures and control of their stability and fluidity

The preparation conditions of concentrated (>70%) aqueous suspensions of coal were optimized, as were the surface charge density and the surface potential of the coal-water suspensions. The theoretical study showed that (1–3) or (2–3) electrolytes such as Na₂SO₄ or Na₅P₃O₁₀, greatly increase the surface charge density and the surface potential of the coal particles in water. This study has led to the interesting result that thinners and stabilizing agents of concentrated clay suspensions, such as lignosulphonates, tripolyphosphates, polynaphtalene sulphonates, etc., must also be good thinners and stabilizing agents for ground coal-water suspensions. Two parameters were controlled: the stability and the fluidity of the suspensions. A penetrometry technique revealed the importance of the resistance coefficient,C _r that can be used as a criterion for the evaluation of coal-water mixture stability and fluidity. Concentrated coal suspensions (about 75% of solid by weight) were prepared in water by using different additives, for instance sodium tripolyphosphate (NaTPP) and surfactants like lignosulphonates (by coupling of the dispersion and stabilizing effects) with the optimum concentration ratio of these two products equal to 1.9. The stability of the suspensions was then greater than 2 months and the viscosity was 1900 cP.     

SARS传染病数学建模及预测预防控制机理研究

首先，利用疾病传播的一般规律及人口守恒统计法则建立了四类人的SARS传染病数学模型，然后运用数学方法对四类人的SARS传染病数学模型进行分析，得出了其生理意义和预防、控制机理。其次，利用人工神经网络理论建立了SARS的预测模型，以北京市的SARS数据为例进行了预测和分析，预测结果显示该模型简单易行，预测精度高。     

Mechanisms of Corosion and Oxidation of Metals and Alloys

Selected topics in field of the study of the mechanisms of corrosion and of oxidation of metals or alloys are presented. The first part reports a new model for the mechanism of the breakaway oxidation of ferritic stainless steels in water vapour. The second part is devoted to the physico‐chemical aspects of oxidation and presents experimental methods useful in the kinetic modelling applied to two alloys, the zircalloy‐4 and an AlMg5 % in the liquid state. In the third part the physical and numerical modelling of the stress corrosion cracking behaviour in face‐centered cubic (fcc) alloys is detailed, which enables the study of the influence of macroscopic parameters (such as the temperature or hydrogen activity) on the fracture process.     

PSD和PWELCH函数的分析改进及应用

针对MATLAB中两个内建功率谱密度计算函数psd()和pwelch()计算结果迥异的现象,在功率谱密度估计理论的基础上,根据经典的周期图理论和Welch平均周期图方法,通过详细分析源程序,解析计算方法,发现psd()计算的并不是工程单边功率谱密度,而是采样信号双边谱,故与pwelch()结果迥异,另外pwelch()不能对分段信号数据进行预处理。就上述不足提出了相应的改进措施,比较验证表明改进措施行之有效。