SiC陶瓷纤维先驱体——聚铝碳硅烷的合成与表征

在高温常压下,以聚二甲基硅烷(Polydimethylsilane,PDMS)和乙酰丙酮铝(Al(AcAc)3)为原料,合成了碳化硅(SiC)陶瓷纤维先驱体———聚铝碳硅烷(Polyaluminocarbosilane,PACS)。采用红外光谱法和凝胶渗透色谱法对制备的PACS进行了结构和分子量表征;通过正交实验设计,研究了反应温度、裂解温度、反应时间和原料配比4种因素对PACS的Si-H键含量、支化度和数均分子量Mn的影响,并用极差分析法进行了主次因素分析,结果表明反应温度是上述三指标的主要影响因素。综合分析各指标对PACS后续纺丝性能和高温碳化过程的影响,确定制备PACS较优的实验条件为:反应温度390℃、裂解温度490℃、反应时间10h及原料Al(AcAc)3与PDMS配比4%(质量分数)。     

SiC(Al)陶瓷纤维先驱体聚铝碳硅烷的合成与表征

利用聚二甲基硅烷(PDMS)热解聚合的液相产物聚硅碳硅烷(PSCS)与乙酰丙酮铝(Al(AcAc)3)反应制备了SiC(Al)陶瓷纤维的先驱体聚铝碳譬烷(PACS)，选用PSCS为原料消除了Al(AcAc)3在合成反应过程中出现的升华现象。合成的PACS化学式为：SiC2.0，H2.6Al0.018。数均分子量Mn=2265。研究反应过程发现PSCS发生裂解重排反应，Si-H键在反应中显示出巨大的活性，反应时伴随有乙酰丙酮气相副产物产生。反应机理研究表明，PACS分子量的增加是PSCS形成的Si-H键与Al(AcAc)3的配位基发生交联反应形成Si～Al键的结果。     

先驱体转化法制备耐高温Si-Al-C-O纤维

以聚硅碳硅烷(PSCS)与乙酰丙酮铝为原料,在常压高温条件下反应制备出聚铝碳硅烷(PACS),经过熔融纺丝、空气预氧化、烧成等工艺,制备出性能优异的耐高温Si-Al-C-O(KD-A)纤维.研究了PACS纤维组成,预氧化过程中的质量增加、Si-H反应程度、凝胶含量,探讨了氧对KD-A纤维性能的影响;通过元素分析、AES和SEM等一系列分析,研究了KD-A纤维的结构组成以及耐高温性能.研究表明,PACS纤维空气预氧化过程中,主要是Si-H键与氧发生反应生成Si-O-Si交联结构;KD-A纤维的组成SiC1.51O0.31Al0.013耐高温性能明显优于普通SiC纤维,在空气中1000℃下加热100h后,强度保留率达到60%左右.     

聚二甲基硅烷高温高压合成聚碳硅烷工艺研究

以聚二甲基硅烷(PDMS)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、分子量及其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PDMS在高压釜内460℃下反应4～6h,或450℃下反应6～7h时,可以制得软化点约为200～220℃的PCS,其高分子部分含量约 5%～10 %(质量分数),Si-H键含量大于0.9,可纺性较好,适合于制备SiC纤维.     

添加填料合成SiC（Al）纤维的先驱体聚铝碳硅烷

以聚硅碳硅烷和乙酰丙酮铝为原料,在反应装置的裂解柱中加入填料,在常压下合成了聚铝碳硅烷.结果表明:添加填料使合成聚铝碳硅烷的时间缩短46%,聚铝碳硅烷的从1008增大到2436,分子量的分布变窄,—Si—Si—键的含量低;在N_2气氛中,在400℃以下失重减少,在1200℃陶瓷的产率从65%提高到69%;加入填料可促进—Si—Si—链转化为—Si—C—Si—链,制备出的聚铝碳硅烷纤维在预氧化过程中氧的增重少,预氧化烧成后得到的Si—Al—C—O连续纤维强度为2.1 GPa,在Ar中1800℃烧结可得到致密的SiC(Al)纤维.纤维的结晶行为与不加填料时的类似.     

异型截面聚碳硅烷纤维的制备

以聚碳桂烷为原料,运用三叶型纺丝组件,通过熔融纺丝,制备出了异型截面聚碳硅烷纤维。研究了纺丝温度、压力、牵伸速度对纤维异形度和当量直径的影响,确立了异型截面聚碳硅烷纤维的溶融纺丝工艺。     

以四烯丙基(二甲基)硅烷为核的超支化聚硅碳烷的合成与表征

以四烯丙基(二甲基)硅烷(B4)为核、甲基氢二烯丙基硅烷(AB2)为单体,通过硅氢加成反应,采用无核一步法、核一步法、核多步法合成了超支化聚有机硅碳烷。用FT-IR1、H-NMR、MALLS-GPC对该聚合物的结构进行了表征。研究了核多步法对超支化聚合物分子量及其分布的控制,结果表明,用核多步法合成超支化聚有机硅碳烷可有效地控制产物的分子量及其分布。     

高分子量聚碳硅烷的合成及其表征

以常压合成的低分子量聚碳硅烷(PCS)为原料,分别在470℃高压及常压下反应一定时间,制备了高分子量PCS先驱体。研究了反应时间对：PCS分子量及其分布、软化点、Si—H键含量及可纺性的影响。研究表明,随着反应时间的延长,PCS低分子量部分逐渐减少,高分子量部分逐渐增加,分子量分布逐渐变宽,从而PCS分子量逐渐增大,软化点逐渐升高,Si—H键含量逐渐降低,可纺性逐渐变差。在相同的反应时间下,高压比常压对PCS分子量的增长更有利。在470℃高压或常压下反应时间2～3h时,可获得分子量高、可纺性良好的PCS先驱体。     

高压合成聚碳硅烷的分子量分布与可纺性

采用高压合成方法合成了聚碳硅烷（PCS）,研究了高低分子含量、分散系数对PCS软化点、分子量分布及可纺性的影响。结果表明,可以用软化点加分子量分布来判断PCS的熔融可纺性．当PCS的软化点低于200℃,分散系数小于1．8,高、中分子含量比例小于0．1时,可纺性很好;随着分子量的增大,软化点的升高,高分子含量增加,分子量分布宽化,可纺性开始变差,当软化点大于260℃,分散系数大于2．2,高、中分子含量比例大于0,3时,可纺性很差,甚至失去可纺性。要得到软化点高、分散系数低、可纺性好的PCS,必须控制PCS的高、中分子含量比例约为0．1～0．3,低、中分子含量比例约0．8左右,分散系数约为1．8～2．2。     

耐高温的SiC(Al)纤维

聚硅碳硅烷 (PSCS)与乙酰丙酮铝(Al(AcAc)₃)在一定条件反应制备了耐高温SiC(Al)纤维先驱体聚铝碳硅烷( PACS)。PACS通过熔融纺丝、预氧化处理、低温烧成、高温烧结等一系列工艺过程制备了耐高温SiC (Al)纤维 。SiC (Al) 纤维的化学组成为Si₁C_1.15O_0.026Al_0.013,主要结构是平均晶粒为95 nm的β-SiC,O和游离C含量均大大低于Nicalon纤维 ( O>10wt%,游离C>10wt%),同时含有微量的Al和少量的 α -SiC。纤维表层O含量和Si含量略高于纤维内部,表面光滑平坦,没有明显表面缺陷。 SiC (Al) 纤维的平均直径为13 μm,平均强度为2.3 GPa,1400℃氩气中处理1 h,强度保留率95%以上;1800℃氩气中处理1 h,强度保留率为71%。纤维的高温稳定性高于Nicalon纤维,低于Tyranno SA纤维。      

La0.5Y0.5Ni4.8Mn0.1Al0.1和La0.5Y0.5Ni4.8Al0.2合金的储氢性能研究

针对两种新型稀土型储氢合金La0.5Y0.5Ni4.8Mn0.1Al0.1和La0.5Y0.5Ni4.8Al0.2的储氢特性进行研究分析。实验表明,相同温度下,La0.5Y0.5Ni4.8Mn0.1Al0.1和La0.5Y0.5Ni4.8Al0.2合金的PCT曲线基本重合,且都具有优良的吸氢动力学性能;相比之下,后者的滞后系数要小于前者,吸氢量较大,吸氢速率也较快,故其储氢性能较优。300次吸放氢循环实验结果表明,La0.5Y0.5Ni4.8Al0.2合金的吸氢动力学性能虽然略有下降,但抗粉化性能较好。     

Dy0.6Tb0.3Pr0.1(Fe0.95Mn0.05)x取向晶体的结构与磁致伸缩

采用Ｃｚｏｃｈｒａｌｓｋｉ方法生长了Ｄｙ０．６Ｔｂ０．３Ｐｒ０．１（Ｆｅ０．９５Ｍｎ０．０５）ｘ（１．８５≤ｘ≤１．９５）取向合金。所有合金主相为立方Ｌａｖｅｓ相结构,择优取向不完整择优取向的方向与Ｘ的大小有关。研究了沿着这些样品的生长方向的磁致伸缩性能以及磁致伸缩性能与压力之间的关系。     

Thermal Stability of Amorphous Hydride Mg_(50)Ni_(50)H_(54) and Mg_(30)Ni_(70)H_(45)

The thermal stability of amorphous ternary hydrides Mg_(50)Ni_(50)H_(54) and Mg_(30)Ni_(70)H_(45) and their corre-sponding amorphous binary alloys Mg_(50)Ni_(50) and Mg_(30)Ni_(70) were studied with X-ray diffraction(XRD) and differential scanning calorimetry(DSC). Samples of the amorphous alloys were preparedby mechanical alloying and the amorphous hydrides were obtained by charging the alloys with gas-eous hydrogen at 3.0 MPa and 423 K. It was found that the amorphous hydrides released most oftheir hydrogen before the crystallization of the essentially hydrogen depleted amorphous alloy. Thecrystallization temperature of amorphous Mg_(50)Ni_(50)H_(54) elevated and that of amorphousMg_(30)Ni_(70)H_(45) did not change in relation to the original binary amorphous alloy. This is very excep-tional for amorphous hydrides. The reason for the effects of hydrogen absorption/desorption on thecrystallization of amorphous alloys was discussed.     

Plasma surface treatments of poly(l-lactic acid) (PLLA) and poly(hydroxybutyrate-co-hydroxyvalerate) (PHBV)

The surfaces of poly(l-lactic acid) (PLLA) and poly(hydroxybutyrate-co-hydroxyvalerate) (PHBV) were modified by oxygen and nitrogen plasma treatments. The physical and chemical surface characteristics were evaluated by contact angle tests, scanning electron microscopy (SEM), atomic force microscopy (AFM), and X-ray photoelectron spectroscopy (XPS). The plasma treatments caused an increase in both contact angle and roughening, altered the surface morphology, inserted polar groups, and, consequently, enhanced the hydrophilicity for both PLLA and PHBV polymers.     

Nanomechanical characterization of one-step combustion-synthesized Al(4)B(2)O(9) and Al(18)B(4)O(33) nanowires

Two kinds of aluminum borate nanowires, Al(4)B(2)O(9) and Al(18)B(4)O(33), were successfully synthesized by a one-step combustion method through control of the Al:B atomic ratio and synthesis temperature. Both nanowires are single crystalline but have distinguishing growth habits. Nanoindentation tests were performed directly on individual nanowires to reveal their mechanical properties. A 70% reduction in elastic modulus was found in Al(18)B(4)O(33) nanowires compared with their bulk counterpart. Al(18)B(4)O(33) nanowires exhibited higher hardness and elastic modulus than Al(4)B(2)O(9) nanowires.     

非晶态半导体 As_(24)Se_(76)、As_(40)Se_(60)和 As_(50)Se_(50)的光量子效率研究

光量子效率是非晶态光电导材料的一个重要参数。本文利用静电放电的方法,探讨和研究了 As—Se 系统非晶态半导体材料的光量子效率与电场和组份的关系,得出的结果与 Onsager 理论描述的相一致。由分析而得到了等剂量组份、富 As 和富 Se 系统光量子效率的变化趋势。     

Natural Passivity of Amorphous Fe_(40)Ni_(40)P_(14)B_6 and Fe_(54.6)Ni_(38)Si_(4.1)B_(2.3)V_1 Alloys

The natural passive films forrned on Fe_(40)Ni_(40)P_(14)B_6 and Fe_(54.6)Ni_(38)Si_(4.1)B_(2.3)V_1 amorphous alloys long-term exposed in air have been studied by X-ray photoelectron spectroscopy (XPS) and Auger electron (including Ar+ ion depth profiling) spectroscopy (AES). The following aspects have been investigated: (1) chemical states of the elements in the films. binding energies and the chemical shifts measured by XPSf (2) structure and composition of the films fand (3) thickness of the passive films determined by AES depth profiling and XPS analysis.     

Work Functions of Pd_(83.5)Si_(16.5)and Cu_(70)Ti_(30)Glassy Alloys

The work functions before and aftercrystallization of two glassy alloys,Pd_(83.5)Si_(16.5) andCu_(70)Ti_(30) have been measured by means of the con-tact potential difference method in the secondaryelectron field at room temperature under 10~(-5) Pavacuum.The results show that the work functionsof both glassy alloys are higher than those of thecorresponding crystalline alloys.     

An SANS Study of Decomposition Kinetics in Amorphous Cu_(12.5)Ni_(10)Zr_(41)Ti_(14)Be_(22.5)

Phase decomposition in amorphous Cu12.5Ni10Zr411Ti14Be22.5 alloy as annealed in the super-cooled liquid range was studied by applying small angle neutron scattering (SANS). As annealed between 600 K and 700 K, the alloy was observed to decompose into two new amorphous phases,with the second phase precipitates embedded in the matrix of the first. Long time annealing of the alloy results in crystallization in addition to evolution of the decomposed microstructure.The kinetic diagram of the decomposition and crystallization for this alloy is given. The second phase precipitates have several nanometers in size and occupy a quite low volume fraction. The decomposition of the supercooled liquid in overall temperature range exhibits the features of spinodal reaction.