二甲基硅二苯基硅共聚物的紫外光谱研究

本文研究了二甲基硅二苯基硅共聚物(P(DMS-CO-DPS))的紫外光谱。文中得到了共聚物主链Si-Si 链最大紫外吸收波长及摩尔吸收系数与其分子量的定量关系;发现共聚物在高浓度(约大于0.03g/1)的条件下,在λ=325nm 处有一位置不变,吸收大小与共聚物分子量、浓度有关的吸收。     

全氢聚硅氮烷的合成与表征

采用二氢二氯硅烷氨解法合成了氮化硅陶瓷先驱体全氢聚硅氮烷,并用红外光谱、凝胶渗透色谱、热重、X射线衍射和元素分析等进行了表征。所合成的先驱体低聚物的分子骨架为[SiH2NH]n,数均分子量为106,重均分子量为178。固化后的先驱体在氮气下1000℃裂解转变为棕色粉末,陶瓷产率78wt%。将陶瓷产物在氮气下1400℃处理后,其主要成分为α-Si3N4,并含有少量富余硅,化学经验式为SiN1.036O0.060C0.028。陶瓷产物在氮气下1600℃处理后的X射线衍射谱图表明,游离硅已基本消失,α-Si3N4衍射峰加强,但是没有观察到从α-Si3N4到β-Si3N4的相转变。     

液态聚硅烷高温高压合成聚碳硅烷工艺研究

以聚二甲基硅烷裂解制备的液态聚硅烷(LPS)为原料,在高压釜内高温高压反应制备了聚碳硅烷(PCS)先驱体,研究了合成条件对反应终压、Si H键含量、产物产率、软化点、分子量分布及可纺性的影响。研究表明,随着反应温度的提高、反应时间的延长,反应终压逐渐增大,产物的分子量与软化点增高,但同时分子量的分散性增大,使可纺性变差。当LPS在高压釜内460℃下反应3～4h,或450℃下反应6～7h时,可以制得软化点约为210～230℃的PCS,其高分子部分含量约5wt%～10wt%,Si H键含量大于0.9,可纺性较好,适合于制备SiC纤维。     

1,4 -二乙炔苯与1,4-丁炔二醇的共聚及表征研究

本文以(Ph_3P)_2 PdCl_2为催化剂,用各种比例的对二乙炔苯(DEB)与1,4-丁炔二醇(BD)合成出共聚物及两种单体的均聚物。共聚物为褐黑色,不溶不熔。单体配比中DEB比例越高,共聚物交联度和比重越大,产率越高,溶胀度越小。单体摩尔比DEB/BD≥1/2时,共聚物最良溶剂为苯,溶度参数(δP)为9.15卡~(0.5)·cm~(-1.5),而DEB/BD=1/5时,共聚物最良溶剂为无水乙醇,8p=12.7卡~(0.5)·cm~(-1.5).对均聚物及共聚物做了红外光谱表征并讨论了聚合反应机理。     

Si(Al)C纤维先驱体聚铝碳硅烷的合成

采用低分子量固态聚碳硅烷和乙酰丙酮铝为原料,利用Si-H与乙酰丙酮铝之间的交联反应合成适于熔融纺丝的聚铝碳硅烷。研究了反应条件对产物数均分子量、软化点和组成结构的影响及交联反应程度与可纺性之间的关系。实验结果表明:随着反应温度的升高和反应时间的延长,反应程度提高,残余乙酰丙酮基减少,Si-O-Al交联支化结构增多,分子量和软化点增大,可纺性随之下降。当乙酰丙酮铝投料比为8%时,在370℃下反应4~6 h,可得到软化点为206~221℃,Al wt%=0.68%,具有良好可纺性的聚铝碳硅烷。     

复合材料专题-Si(Al)C纤维先驱体聚铝碳硅烷的合成*

采用低分子量固态聚碳硅烷(PCS)和乙酰丙酮铝([Al(acac)3])为原料,利用Si-H与[Al(acac)3]之间的交联反应合成适于多孔连续熔融纺丝的聚铝碳硅烷(PACS)。研究了反应条件对产物数均分子量、软化点和组成结构的影响及交联反应程度和可纺性之间的联系。结果表明,随着反应温度的升高和时间的延长,反应程度提高,残余乙酰丙酮基减少,Si-O-Al交联支化结构增多,分子量和软化点增大,可纺性随之下降。当[Al(acac)3]投料比为8wt%时,在370°C下反应4-6h,可得到软化点为206~221°C,Alwt%=0.68%,具有良好可纺性的PACS     

聚碳硅烷的高温高压合成与减压蒸馏

采用高温高压法合成了聚碳硅烷(PCS),通过改变合成条件与减压蒸馏温度的方法对PCS分子量及其分布进行调控。研究表明,改变PCS的反应温度、反应时间,可以基本控制PCS的分子量及其分布范围。随着反应温度的提高,反应时间的延长,PCS的分子量逐渐增大,分子量分布变宽。当合成温度高于450℃,反应时间大于6h时,或温度高于460℃,反应时间大于4h时,PCS中出现高分子量部分。随着反应条件的强化,高分子量部分逐渐增加,甚至出现超高分子量部分。提高减压蒸馏温度,可以有效降低PCS的低分子含量,提高分子量,降低分散系数。减压蒸馏温度每提高50℃,PCS的低分子含量约降低8%,重均分子量约提高1000,分散系数平均降低约0.3。     

新型硅氮烷先驱体的合成和表征

采用MesiHCI2和Me（CH2=CH）SiCl2共氨解制备出流动性好的含Si-H和SiCH=CH2的低分子硅氮烷,结果表明H2PtCl6（脱水）和DCP是合适的硅氯化交联的催化剂和双键交联的引发剂。交联产物在程序控温的管式炉中裂解,得到高的陶瓷产率（＞74％wt）。     

树脂浸渍裂解对气相硅反应渗透C/SiC的影响

粘胶基碳纤维毡经过CVD工艺进行沉积碳增密处理后,采用酚醛树脂浸渍—裂解对C/C素坯的密度进行调节,通过气相硅渗透反应工艺制备了C/SiC复合材料。研究了树脂浸渍—裂解对C/C素坯密度和气孔率的影响规律,分析了树脂裂解碳对C/SiC显微形貌和力学性能的影响。结果表明:随着树脂浸渍—裂解循环次数的增加,素坯密度增加,孔隙率降低;裂解碳含量为27wt%时,C/SiC复合材料的强度和模量达到最大,分别为231MPa和209GPa。通过控制裂解碳含量,可以实现对C/SiC复合材料力学性能和微观结构的裁剪。     

助溶剂对M15甲醇汽油胶质生成的影响

考察了多种类型甲醇汽油助溶剂对M15甲醇汽油胶质生成的影响。结果表明,初始状态下在M15甲醇汽油中加入醇类助溶剂对未淋洗胶质和溶剂洗胶质含量无明显影响,而加入分子量较大的助溶剂吐温和司盘时胶质含量急剧增加。在储存期内,空白M15甲醇汽油和各加剂M15甲醇汽油的未淋洗胶质以及溶剂洗胶质含量均随储存时间的延长而增大;从线性拟合直线的斜率可以看出,醇类助溶剂在储存期内会加速甲醇汽油中胶质的生成;各加剂M15甲醇汽油的胶质生成速率与醇类助溶剂分子量的大小有关,且红外光谱结果与胶质试验结论一致。     

微波辐射下无溶剂合成3种亚胺

在微波辐射无溶剂条件下,苯甲醛、肉桂醛和二苯甲酮分别与苯胺反应合成了3种亚胺类化合物,解决了此类化合物由于不稳定而在柱层析过程中分解的问题,并对产物进行了提纯和1H NMR表征。在辐射功率为400 W、辐射时间为90 s条件下,前2个反应的产率分别为82%和80%,而由于空间位阻的影响,二苯甲酮与苯胺未发生反应。在增大辐射功率、延长辐射时间后,二苯甲酮与苯胺发生反应并取得了56%的产率。     

超声合成三烷基硼的研究

在超声波作用下通过修正的有机金属路线一步合成三烷基硼,使得反应产率提高、反应时间也大大缩短。     

富马酸二甲酯的固体酸催化合成及HPLC检测

以SO42-/TiO2固体超强酸为催化剂催化富马酸与甲醇合成富马酸二甲酯,探讨了催化剂制备条件、原料配比、反应时间、催化剂用量等因素对富马酸二甲酯收率的影响.并采用HPLC,快速方便地检测富马酸二甲酯的收率,并考察由不同比例的甲醇/水、乙腈/水组成的流动相对分离的影响.试验证明,在最优条件下,富马酸二甲酯的产率可达到78.6%.     

Revisiting inspection game and inspector leadership through reaction networks

The inspection game is a two-player noncooperative game that models a situation where an inspector verifies whether the inspectee complies with the rules (on the assumption that the inspectee has the tendency to violate at least one of the rules). The usual approach in the analysis of this game seeks to find an optimal strategic inspection scheme for each of the two players yielding favorable payoffs. Recently, there have been some developments in the study of such games that use a mathematical structure known as reaction network involving a set of molecular species and the existing reactions among these species. In this paper, we use a reaction network to analyze the inspection game giving an alternative way of modeling the social situation. The molecular species play the role of the players' decision moves and their resulting gain or loss, while the reactions are the encounters of the decisions of the players which, as expected, yield payoffs. We reexamine the dynamics of the inspection game through the lens of reaction network theory and consider various situations that call for more detailed analyses such as equal or unequal reaction rates and inspection leadership. Conditions concerning reaction rates, initial population of decision species, benefits, and costs are determined in order to identify strategies that yield better payoffs both for the inspector and inspectee. These results illustrate practical insights rooted from the formulated simple game models.     

高动物油含量餐饮废油制备生物柴油

针对重庆餐饮废油动物油含量高的特点，用氢氧化钠作催化剂制备生物柴油，得到最佳工艺条件为：醇油质量比25％，催化剂用量1．0％，反应温度60℃，反应时间60min，搅拌强度3000r／min。在该工艺条件下，进行数据放大实验，生物柴油的产率可以达到93．6％，说明该工艺条件适合工业生产。生物柴油产品质量达到国家标准；与0号柴油调和使用可以很好地改善其低温流动性能。     

A unified model incorporating yield,burn‐in,and reliability

The correlated improvement in yield and reliability has been observed in the case studies on integrated circuits and electronic assemblies. This paper presents a model that incorporates yield and reliability with the addition of a burn‐in step to explain their correlated improvement. The proposed model includes as special cases several yield and reliability models that have been previously published and thus provides a unifying framework. The model is used to derive a condition for which yield functions can be multiplied to obtain the overall yield. Yield and reliability are compared as a function of operation time, and an analytical condition for burn‐in to be effective is also obtained. Finally, Poisson and negative binomial defects models are further considered to investigate how reliability is based on yield. © 2004 Wiley Periodicals, Inc. Naval Research Logistics, 2004.     

离子液体[SO3H-Bmim][HSO4]催化餐饮废油制备生物柴油

实验合成了一种磺酸基功能化离子液体,并用于催化高酸值餐饮废油制备生物柴油。当醇油物质的量之比为8∶1,离子液体用量为废油质量的0.8%,反应温度为150℃,反应时间为180min,生物柴油的产率可达到90.6%。该离子液体可以在比较温和的条件下将餐饮废油的酸值从13.22mgKOH/g降低到1mgKOH/g以下,然后利用NaOH催化生产生物柴油,会达到更高的产率,更为经济可行。     

侧链含锑聚硅烷的合成与性能研究

侧链含锑聚硅烷的合成可通过聚甲基硅烷的高分子反应在室温条件下实现,聚合物产率为75.2%,数均分子量为1600.其分子结构与组成可由元素分析、FT-IR、1H-NMR、29Si CP/MAS NMR、GPC和UV来确认.PSA可溶于一般常见的有机溶剂,紫外吸收的最大波长为330nm,其热分解特性表明,陶瓷收率为80%,可用作SiC陶瓷先驱体;其本体电导率为10-8～10-7S/cm,将其与碘掺杂,电导率可以达到10-5S/cm以上.     

Effects of nano-sized aluminum on detonation characteristics and metal acceleration for RDX-based aluminized explosive

Nano-sized aluminum(Nano-Al)powders hold promise in enhancing the total energy of explosives and the metal acceleration ability at the same time.However,the near-detonation zone effects of reaction between Nano-Al with detonation products remain unclear.In this study,the overall reaction process of 170 nm Al with RDX explosive and its effect on detonation characteristics,detonation reaction zone,and the metal acceleration ability were comprehensively investigated through a variety of experiments such as the detonation velocity test,detonation pressure test,explosive/window interface velocity test and confined plate push test using high-resolution laser interferometry.Lithium fluoride(LiF),which has an inert behavior during the explosion,was used as a control to compare the contribution of the reaction of aluminum.A thermochemical approach that took into account the reactivity of aluminum and ensuing detonation products was adopted to calculate the additional energy release by afterburn.Combining the numerical simulations based on the calculated afterburn energy and experimental results,the param-eters in the detonation equation of state describing the Nano-Al reaction characteristics were calibrated.This study found that when the 170 nm Al content is from 0％to 15％,every 5％increase of aluminum resulted in about a 1.3％decrease in detonation velocity.Manganin pressure gauge measurement showed no significant enhancement in detonation pressure.The detonation reaction time and reaction zone length of RDX/Al/wax/80/15/5 explosive is 64 ns and 0.47 mm,which is respectively 14％and 8％higher than that of RDX/wax/95/5 explosive(57 ns and 0.39 mm).Explosive/window interface velocity curves show that 170 nm Al mainly reacted with the RDX detonation products after the detonation front.For the recording time of about 10 μs throughout the plate push test duration,the maximum plate velocity and plate acceleration time accelerated by RDX/Al/wax/80/15/5 explosive is 12％and 2.9 μs higher than that of RDX/LiF/wax/80/15/5,respectively,indicating that the aluminum reaction energy significantly increased the metal acceleration time and ability of the explosive.Numerical simulations with JWLM explosive equation of state show that when the detonation products expanded to 2 times the initial volume,over 80％of the aluminum had reacted,implying very high reactivity.These results are significant in attaining a clear understanding of the reaction mechanism of Nano-Al in the development of aluminized explosives.     

苯乙炔与二苯丁二炔的共聚及共聚物的表征

本文以(Ph_3P)_2PdCl_2作催化剂,合成出聚二苯丁二炔和二苯丁二炔与苯乙炔共聚物。均聚物及共聚物产率都在90%以上,均聚物分子量为900,二苯丁二炔与苯乙炔最佳摩尔比为1/2(数均分子量为1205)。结构分析表明,均聚物及共聚物均具有反—反式结构。