工艺参数对自蔓燃制备氮化硅粉体的影响

采用自蔓燃高温合成方法(self-propagating high-temperature synthesis,简称SHS)合成氮化硅粉体,分析了自蔓燃高温合成氮化硅过程中氮气、温度、稀释剂与孔隙率等方面的影响。采用XRD研究相的组成,用SEM观察粉末的显微结构。研究结果表明:只要控制反应中的工艺参数,就可以采用自蔓燃得到不同相含量的Si3N4粉体;考虑到燃烧温度(Tcom),在氮化硅粉体的合成过程中,涉及到3个反应机制:低温机制,中温机制,高温机制;氮气压力下硅粉的自蔓燃合成反应,必须要引入Si3N4稀释剂,来控制反应温度和反应速度,获得不同相含量的粉体;NH4Cl在反应中分解,为反应提供了NH3,并与硅粉反应;压坯气孔率控制在30%~70%,否则反应不能进行。SHS法可以制备纯度很高的氮化硅粉体。此法较传统方法合成的氮化硅设备简单,成本低廉,纯度高,填充性好,烧结活性好。     

冷等静压成型压力对反应烧结氮化硅陶瓷性能的影响

将硅粉冷等静压成型,通过反应烧结得到氮化硅陶瓷,研究了成型压力对反应烧结氮化硅(RBSN)陶瓷性能的影响。结果表明,当成型压力从100MPa增加到300MPa,反应烧结氮化增重率逐渐下降,从60.25%降到47.31%;而残余硅含量随着增加,从10%增加到29%;RBSN开气孔率随着成型压力的增大而减小,开气孔率从20.50%降到13.81%。成型压力小于等于200MPa时,RBSN的密度和强度随成型压力的增大而增大;成型压力大于200MPa时,RBSN的密度随成型压力的增大而减小,强度随成型压力的增大变化不大,变化约为5%;在200MPa时,RBSN的密度达到最大值2.52 g/cm3。冷等静压成型RBSN由晶须状α-Si3N4,柱状β-Si3N4和残余硅组成。     

燃烧合成法制备高韧性氮化硅材料

用硅粉及氮气为原料以燃烧合成法制备β－氮化硅粉。如将其细碎，灾些粉末的密度可以烧结至理论密度的９９％以上，而且具有极高断裂韧度。本文证实如选择合适的烧结环境，也可将β－相就地强化形成氮化硅。文中还探讨了烧结温度、压力、保温时间及冷却速度的影响。     

硅粉直接氮化反应合成氮化硅研究

研究了硅粉直接氮化反应合成氮化硅粉末的工艺因素(包括硅粉粒度、氮化温度、成型压力、稀释剂含量等),借助XRD,SEM等测试手段测定和观察了氮化产物的物相组成和断口形貌.研究结果表明:硅粉在流动氮气氛下,高于1200℃氮化产物中氮含量明显增加;在氮化反应同时还伴随着硅粉的熔结过程,它阻碍硅粉的进一步氮化,其影响程度与氮化温度、氮化速度,素坯成型压力及硅粉粒度等工艺因素有关.在硅粉素坯中引入氮化硅作为稀释剂,提高了硅粉的氮化率,使产物中残留硅量降低;同样在实际生产中可以通过控制适当热处理制度(如分段保温、慢速升温),达到硅粉的完全氮化.在生产中批量合成了含氮量为32.5%,残留硅量为0.05%,主要为α相,含少量β相的针状、柱状的氮化硅.     

硅粉氮化反应合成氮化硅

研究了硅粉直接氮化反应合成氮化硅粉末的工艺因素（包括硅粉粒度、氮化温度、成型压力、稀释剂含量等），借助XRD、SEM等测试手段测定和观察了氮化产物的物相组成和断口形貌。研究结果表明：硅粉在流动氮气氛下，高于1200℃氮化产物中氮含量明显增加；在氮化反应同时还伴随着硅粉的熔结过程，它阻碍硅粉的进一步氮化，其影响程度与氮化温度、氮化速度，素坯成型压力及硅粉粒度等工艺因素有关。在硅粉素坯中引入氮化，其影响程度与氮化温度、氮化速度，素坯成型压力及硅粉粒度等工艺因素有关。在硅粉素坯中引入氮化硅作为稀释剂，提高了硅粉的氮化率，使产物中残留硅量降低；同样在实际生产中可以通过控制适当热处理制度（如分段保温、慢速升温），达到硅粉的完全氮化。在生产中批量合成了含氮量为32．5％，残留硅量为0．05％，主要为α相，含少量β相的针状、柱状的氮化硅。     

低氮气压下燃烧合成氮化硅粉

对硅粉在低压氮气中的高温自蔓延合成（ＳＨＳ）Ｓｉ２Ｎ４粉末过程进行了探讨,实验证明了０．６ＭＰａ－０．７ＭＰａ的低氮气压下燃烧合成Ｓｉ３Ｎ４的可行性,超始原料中加入适量的Ｓｉ３Ｎ４粉作稀释剂,可促进Ｓｉ粉向Ｓｉ３Ｎ４的氮化墨迹。产物为１μｍ－２μｍ纯度较高的Ｓｉ３Ｎ４粉,燃烧温度随氮气压力与孔率而变化,而随配料组成的变化不明显。     

低氮气压下燃烧合成氮化硅粉

对硅粉在低压氮气中的高温自蔓延合成（ＳＨＳ）Ｓｉ３Ｎ４粉末过程进行了探讨,实验证明了０．６ＭＰａ－０．７ＭＰａ的低氮气压下燃烧合成Ｓｉ３Ｎ４的可行性,超始原料中加人适量的Ｓｉ３Ｎ４粉作稀释剂,可促进Ｓｉ粉向Ｓｉ３Ｎ４的氨化转变。产物为１μｍ～２μｍ纯度较高的Ｓｉ３Ｎ４粉,燃烧温度随氮气压力与孔隙率而变化,而随配料组成的变化不明显。     

初始硅粉粒度对自蔓延高温合成氮化硅的影响

研究了平均粒度分别为２,７．８和１５．４μｍ的３种初始硅粉在氮气中的燃烧氮化规律。初始硅粉粒度越细,则在氮气中的燃烧温度高越高,燃烧滤蔓延速度越快,激活能也越低;较细的硅粉表面的硅蒸发通量大,ｐｓｉ高,易于形成延长方向与硅粉表面垂直的针状或柱状、纤维状晶体;而较粗的硅粉则易于形成氮化硅包覆层,且可以通过“包覆爆裂”机制继续进行二次氮化。较细的硅粉在氮气中的燃烧温度曲线上只出现一次燃烧峰,而较粗的硅     

以固态氮化剂燃烧合成AlN-SiC固溶体的研究

通过热爆方式点燃铝粉、氮化硅粉、碳黑的混合粉末压坯,在较低氮气压力下成功地合成了ＡｌＮ－ＳｉＣ固溶体陶瓷．研究了气体环境、氮气压力对燃烧特征的影响．结合热力学分析,解释了ＡｌＮ－ＳｉＣ固溶体的形成机理及反应次序．通过扫描电镜,观察了反应物的形貌特征     

ZnFe2O4粉体的燃烧合成

采用燃烧合成法制备了ZnFe2O4。研究了ZnFe2O4粉体燃烧合成温度、燃烧波速度与放热系数k、氧气压力p和填装密度等参数之间的相互关系，讨论了ZnFe2O4形成机制，并通过SEM，EDS，XRD和Mossbaur谱(MS)等分析测试手段对产物的形貌、物相、结构及性能进行了分析。结果表明：用大颗粒Fe粉(≤45μm)原料制备ZnFe2O4的合成反应属于固-液反应，主要由溶解-析出机制控制；产物中含有部分亚稳相Fel-xO；在l550-l600K之间ZnFe2O4晶格结构完整，转换率较高。     

Combustion of silicon powders containing organic additives in nitrogen gas under pressure: 2. Composition of combustion products

Combustion of silicon powders containing organic dopants in nitrogen gas under pressure was found to yield a mixture of α-Si₃N₄, β-Si₃N₄, SiC, and Si₂N₂O. Relative amount of these compounds in combustion product was found to depend on the pressure of nitrogen gas, type and concentration of dopants, combustion geometry, and cooling rate. The formation of α-Si₃N₄ was found to occur in the presence of oxygen-containing dopants. The type of dopant was also found to affect the morphology of product particles.      

Some New Perspectives on Oxidation of Silicon Carbide and Silicon Nitride

This study provides new perspectives on why the oxidation rates of silicon carbide and silicon nitride are lower than those of silicon and on the conditions under which gas bubbles can form on them. The effects on oxidation of various rate-limiting steps are evaluated by considering the partial pressure gradients of various species, such as O₂, CO, and N₂. Also calculated are the parabolic rate constants for the situations when the rates are controlled by oxygen and/or carbon monoxide (or nitrogen) diffusion. These considerations indicate that the oxidation of silicon carbide and silicon nitride should be mixed controlled, influenced both by an interface reaction and diffusion.     

有机聚硅氧烷在医药中的应用进展

总结了硅橡胶、硅油、硅树脂在医药中的应用,并介绍了硅烷化技术在药物合成、蛋白质分析检测等生物工程方面的应用和一些新型抗肿瘤、抗癌的含硅药物及多孔硅膜的药物缓释体系的发展。     

Nitridation behavior of silicon powder compacts of various thicknesses with Y2O3 and MgO as sintering additives

The effects of the nitriding temperature (1300 and 1350°C), holding time (0‐4 hours), and thickness of Si powder compacts on the nitridation behavior of silicon were investigated by examining the nitridation rates, analyzing phase compositions, and observing the microstructures of nitrided compacts. Si powder compacts doped with Y₂O₃ and MgO as sintering additives were prepared with thicknesses of 3, 6, and 9 mm. The phases of nitrided compacts were transformed from Si to α‐Si₃N₄ and β‐Si₃N₄ with an increase in the nitriding temperature and holding time. The degree of nitridation increased with the nitriding temperature and holding time. The β/(α+β) ratio increased with the nitriding temperature and holding time, and with a decrease in the thickness of the Si powder compacts. However, all compacts exhibited the same tendency for a higher β/(α+β) ratio at the compact surface than in the bulk of the compact. The variation in the β/(α+β) ratio for each compact decreased with an increase in the nitriding temperature and holding time.     

Oxidation of Silicon and Silicon Carbide in Ozone-Containing Atmospheres at 973 K

The oxidation behavior of a silicon wafer, chemically vapor-deposited SiC, and single-crystal SiC was investigated in an oxygen—2%–7% ozone gas mixture at 973 K. The thickness of the oxide film that formed during oxidation was measured by ellipsometry. The oxidation rates in the ozone-containing atmosphere were much higher than those in a pure oxygen atmosphere. The parabolic oxidation kinetics were observed for both silicon and SiC. The parabolic rate constants varied linearly with the ozone-gas partial pressure. Inward diffusion of atomic oxygen formed by the dissociation of ozone gas through the SiO₂ film apparently was the rate-controlling process.     

Volatility Diagrams for Silica, Silicon Nitride, and Silicon Carbide and Their Application to High-Temperature Decomposition and Oxidation

Volatility diagrams—isothermal plots showing the partial pressures of two gaseous species in equilibrium with the several condensed phases possible in a system—are discussed for the Si-O and Si-N systems, and extended to the Si-N-O and Si-C-O systems, in which the important ceramic constituents SiO₂, Si₃N₄, Si₂N₂O, and SiC appear as stable phases. Their use in understanding the passiveactive oxidation transitions for Si, Si₃N₄, and SiC are demonstrated.     

Mössbauer Study of the Influence of Fe-Si-N Liquid in the Synthesis of β-Si3N4 from Silica

Mössbauer spectra of the products obtained by carbothermal reduction and distribution of silica in the presence of iron in the temperatures range 1200^o to 1540^o were studied. The preponderance of β- Si₃N₄ over the α form at a higher reaction temperature were assumed to be related to the formation of an Fe-Si-N liquid. The liquid did not alter its composition with the variation of reduction-temprature, Iron had no effect on the reaction mechanism below 1300^oC.     

硅整流改为可控硅整流技术总结

介绍了硅整流改为可控制硅整流的技术改造过程及应注意的问题，改造后的整流技术具有操作简单，提高经济效益的特点。     

Cathodoluminescence from Implanted and Anodized Polycrystalline Silicon Films

Luminescence emission of LPCVD polycrystalline silicon films has been studied by cathodoluminescence (CL) in the scanning electron microscope. As-deposited films show visible luminescence with dominant blue band. The relative intensity of blue emission is enhanced by implantation and by slight anodization treatments. Our investigations are consistent with previous PL results and indicate that the origin of blue emission is related to quantum confinement effects. On the other hand, the effect of annealing in these samples is a reduction of the CL signal that could be related to the increase of the nanocrystals size.     

Improved Resistance to Damage of Silicon Carbide-Whisker-Reinforced Silicon Nitride-Matrix Composites by Whisker-Oriented Alignment

The effects of whisker-oriented alignment on resistance to damage of SiC( w )/Si₃N₄ composites have been investigated by the Vickers indentation method and R -curve behavior. It is shown that increasing the degree of whisker-oriented alignment decreases the lengths of Vickers impressions and indentation cracks. The results exhibit rising R -curve behaviors for the SiC( w )/Si₃N₄ composites with different degree of whisker-oriented alignment. Moreover, the initial crack length c _i, the threshold of crack growth resistance K _i, and the upper bound of crack growth resistance K _∞ change regularly with increasing degree of whisker-oriented alignment. All results suggest that the whisker-oriented alignment improves the resistance to damage of the composites, resulting in a more reliable and usable composite.