电子束辐照对聚碳硅烷结构与热解性能的影响

在惰性气氛下,用电子束对聚碳硅烷(PCS)进行辐照改性。利用傅里叶变换红外光谱分析、凝胶含量测定以及热重-气相色谱-质谱连用技术对不同剂量改性的PCS进行了分析表征,研究了辐照剂量对PCS结构与热解性能的影响。结果表明,电子束辐照作用使PCS样品中大量Si—H键和C—H键发生断裂,形成了以Si—C—Si为骨架的三维网状凝胶产物,当辐照剂量高于3MGy时,PCS的凝胶化程度随辐照剂量的增加而明显变大。热重分析表明,电子束辐照有利于提高PCS的热稳定性,其初始失重温度和陶瓷化产率都会随辐照剂量的增加而升高,其中,经20 MGy辐照后的PCS样品的陶瓷化产率可达87%。此外,对于400℃预处理的PCS样品,在相同吸收剂量下,样品的凝胶质量分数、初始失重温度和最终陶瓷化产率都较未处理的高。     

紫外辐照高温硫化硅橡胶的红外光谱分析和老化机理

高温硫化(HTV)硅橡胶复合绝缘子广泛应用于特高压输电线路,其抗紫外老化性能越来越受到人们的关注。采用自行设计的可调式紫外老化试验箱对两个厂家的高温硫化硅橡胶样品进行了紫外辐照(0,500和1 000 h)加速老化实验,辐照光波长范围为320～750 nm。对辐照前后试样进行傅里叶变换衰减全反射红外光谱(ATR-FTIR)测试,分析谱峰的变化与试样(表面)官能团的关系,辅以扫描电子显微镜(SEM)和憎水性、体积电阻率的测试来研究HTV硅橡胶的老化机理。结果表明:高温硫化硅橡胶FTIR全谱图中1 260 cm~(-1)处Si—CH_3反射峰和800 cm~(-1)附近Si—(CH_3)_2反射峰强度随辐照时间的增加而逐渐减弱, 1 000～1 100 cm~(-1)处的Si—O—Si反射峰强度随辐照时间的增加先减弱后增强;扫描电镜观察到辐照后的样品表面出现大颗粒和坑洞、粗糙度变大,其主要元素O, Si和Al重量百分比略增加;喷水分级法在表面形成的水珠随着样品辐照时间的延长由均匀分布变得不均匀且出现合并,憎水性有明确下降;体积电阻率略微降低。分析认为:辐照后紫外线切断了HTV硅橡胶部分Si—C, C—C和C—H键,对称排列的非极性甲基基团—CH_3从硅氧主链上脱落,减弱了对主链强极性的屏蔽作用,使Si—O—Si峰强度减弱,且少量侧链被氧化,形成C—O和—OH(COOH);而主链之间因裸露出来的自由基—Si·发生进一步的交联反应,使得Si—O键相对含量增加,使Si—O—Si峰强度再增强。二方面结果均导致高温硫化硅橡胶表面极性增强,憎水性下降。水本身具有微弱的电离,憎水性下降的高温硫化硅橡胶易吸收空气中的水使其表面载流子浓度增加体积电阻率略有下降。通过红外光谱分析,紫外线是通过切断高温硫化硅橡胶表面的部分Si—C, C—C, C—H键,使其生成新的自由基并发生交联和氧化而使其老化的。红外光谱的应用对于高温硫化硅橡胶复合绝缘子老化研究及其在特高压输电线路上的挂网应用均具有重要意义。     

多孔硅量子点中的电子局域态

经过激光辐照和高温退火加工能够生成多孔硅样品,在650—780 nm处检测到很强的光致荧光（PL）峰,并且有明显的钉扎和增强效应.实验表明,这种PL发光的强度与样品受辐照和退火的时间短密切相关.通过第一性原理模拟计算发现,样品表面用SiO 双键和Si—O—Si桥键钝化,能隙中会出现电子局域态.激光辐照和高温退火的时间长短决定了样品表面SiO双键和Si—O—Si桥键的密度,而该密度正是影响多孔硅量子点中电子局域态生成的关键. 关键词： 多孔硅量子点 硅氧钝化键 电子局域态     

4H-SiC纳米薄膜的微结构及其光电性质研究

采用新设计的电极结构的等离子体增强化学气相沉积(PECVD)技术,在高功率密度、高氢稀释比、低温、偏压及低反应气压的条件下,在衬底表面形成双等离子流,增加了衬底表面SiC的成核概率,增强成核作用,形成纳米晶.采用高H2等离子体刻蚀弱的、扭曲的、非晶Si—C及Si—Si和Si—H等键时,由于H等离子体对纳米SiC晶粒与非晶态键的差异刻蚀作用,产生自组织生长,发生晶化.Raman光谱和透射电子衍射(TEM)的测试结果表明,纳米晶SiC是4HSiC多型结构.电子显微照片表明平均粒径为16nm,形状为微柱体.实验结果指出,SiC纳米晶的形成必须经过偏压预处理成核,并且其晶化存在一个功率密度阈值;当低于这一功率密度阈值时,晶化消失;当超过这一阈值时,纳米晶含量随功率密度的提高而增加.随着晶化作用的加强,电导率增加. 关键词： 4H-SiC PECVD 纳米结构 多型薄膜 纳米电子学     

Kr离子注入SiC的拉曼光谱研究

应用拉曼光谱研究了5 MeV Kr离子（注量分别为5×1013,2×1014,1×1015 ions/cm2）室温注入6H SiC单晶及其高温退火处理后结构的变化。 研究表明, 注入样品的拉曼光谱中不仅出现了Si—C振动的散射峰, 还产生了同核Si—Si键和C—C键散射峰。 Si—C散射峰强度随退火温度升高而增强, 当退火温度高达1000 ℃时, 已接近未辐照SiC的散射峰强度。晶体Si—Si键散射峰强度随退火温度变化不大, 而非晶Si—Si键散射峰强度随退火温度的增加逐渐消失。相对拉曼强度（Relative Raman Intensity, 简称RRI）随注量的增加逐渐减小并趋于饱和, 且不同退火温度样品的饱和注量不相同; RRI随退火温度的增加逐渐升高, 这在低注量样品中表现得尤为明显。 低、中、高3种注量样品的RRI随退火温度的增加从重合逐渐分离, 并且退火温度越高, 分离越大。 Raman spectroscopy was used to study the structure changes of 6H SiC single crystal implanted with 5 MeV Kr (Krypton) at room temperature and subsequently annealed at high temperature. The Raman spectrum of the implanted SiC displays not only Si—C bonds vibration peaks, but also homonuclear Si—Si and C—C bond vibration peaks. Si—C bond vibration peaks gradually strengthen with increasing temperature. When annealing at 1000 ℃, the peak intensity of Raman spectrum is close to that of virgin specimen. It is found that crystal Si—Si bond vibration peaks do not change when annealing, but amorphous Si—Si bond vibration peaks disappear with increasing annealing temperature. The Relative Raman Intensity (RRI) values decrease with increasing fluence and tend to saturate, but the saturation fluences is different for various anneal temperature. The RRI values increases with raising annealing temperature, which is more obvious in low implanted specimens. At the same time, the RRI values separate gradually with increasing temperature and this phenomenon is strengthened by annealing temperature.     

大鼠体内青石棉纤维表面变化的红外光谱研究

肌体蛋白质在与青石棉的相互作用过程中,组织结构对称性降低,结构疏松;青石棉的硅已与蛋白质中的烷基、胺基交联成键,存在明显的Si—O—C(N),Si—R新的吸收谱带;青石棉残留的粉尘仅为以硅为主的物质。石棉小体(斑)内的纤维表面基团和组织内的某些蛋白反应形成新的表面介体。染尘肌体组织在加热过程中,蛋白质类结构对称性降低并逐渐氧化,末端基团如—CH_3,—CH_2振动减弱。C—C长链骨架的分解,并可分成200,400和600℃三个相变温区。Si—O,Si—O-Si吸收加强,新生成的表面介体的稳定性(Si—O—C,Si—C,Si—CH_3)基团介于二者之间。在500℃以上,肌体组织、表面介体和体内残留纤维已全部破坏。体内青石棉被生物作用溶解和生化反应结合后,其热稳定温度大为降低。     

γ射线辐照对a-SiC:H薄膜结构与特性的影响

 采用射频（13.56 MHz）反应溅射方法制备a-SiC:H 薄膜，并将其在空气中进行高能γ射线(平均为1.25 MeV)辐照，5个样品的吸收剂量分别为0，2×10⁴，4×10⁴，6×10⁴，8×10⁴ Gy。采用拉曼及红外光谱对薄膜的结构进行表征,得到了其结构与特性的变化规律。研究与分析表明：随样品吸收剂量的增加，陷入空穴中的电子会被激发，a-SiC:H薄膜中的SiC成份增加，电阻率变小，数量级为105Ω·cm；薄膜存在结晶化的趋势,其主要原因在于由Si－O－Si键断裂而产生的Si取代膜中C－C键中的C而形成晶态SiC，在此过程中出现了Si－O－Si键及a-SiC:H的减少，晶态SiC的增加。经γ射线辐照后薄膜的氢含量降低，折射率从5.19增大到5.53，辐照后薄膜的透过率均低于原膜的透过率。在500~2 300 cm^-1(对应波长为20.00~5.29 μm)波段内，a-SiC:H薄膜存在一定的增透作用。     

射频溅射法制备3C-SiC和4H-SiC薄膜

利用射频溅射法在Si衬底上制备了SiC薄膜，并利用x射线衍射（XRD）和红外（IR）吸收谱对薄膜的结构、成分及化学键合状态进行了分析.XRD结果表明，低温制备的SiC薄膜为非晶相，而在高温下（＞800℃），薄膜呈现4HSiC和3CSiC结晶相.IR谱显示，溅射制备薄膜的吸收特性主要为Si—C键的吸收.此外，还利用原子力显微镜对薄膜的表面形貌进行了研究，并研究了样品的场发射特性. 关键词： 射频溅射 SiC薄膜 结构 表面形貌 场发射     

化学气相沉积-氧化烧结法制备惯性约束聚变靶用空心玻璃微球

为实现惯性约束聚变靶用空心玻璃微球直径、壁厚的可控,采用等离子体辉光放电聚合技术,以四甲基硅烷为掺杂气源,对化学气相沉积-氧化烧结法制备空心玻璃微球(HGM)这一制备方法进行了探索。实验结果表明:制备直径为400~600μm、壁厚为5~15μm的HGM,原子分数为5%是一个较合适的掺硅量,成功将微球直径和壁厚的收缩量控制在38%左右;玻璃化后样品中C含量明显降低,主要以C—Si键合形式存在,而Si含量相对增加,主要以Si—O键合形式存在;预充1.23×106 Pa氘气的微球,96h后球内剩余气压依然高达72.95%。     

低能质子辐照ZnO/silicone白漆产生微观损伤的红外光谱研究

 通过空间综合辐照模拟设备对能量小于200 keV质子辐照下ZnO/silicone白漆光学性能变化及损伤机理进行研究。结果表明,ZnO/silicone白漆的光学性能退化主要发生在可见光区,太阳吸收比随质子辐照能量、注量的增加而增大。借助傅里叶变换红外光谱分析技术研究了质子辐照ZnO/silicone白漆时有机硅树脂的光学性能退化机理。质子辐照使ZnO/silicone白漆中游离氧含量增加,氧化硅原子上的有机取代基使Si—C链断裂,并生成活性羟基,而这种活性羟基能促使有机硅树脂内Si—O—Si键的裂解。同时Si—O—Si链内氧原子未成键的孤对电子与邻近硅原子的3d空轨道配位,降低了π*轨道的能量,提高了对光吸收的几率,增强了n→π*电子跃迁,使吸收带红移,从而导致ZnO/silicone白漆光学性能退化。     

聚-α-甲基苯乙烯热降解产物研究

 降解芯轴技术是制备激光惯性约束聚变靶丸的重要技术之一。采用热分析技术研究了聚-α-甲基苯乙烯（PAMS）热降解温度,采用裂解色谱-质谱联用技术分析了PAMS的热降解产物。研究表明：PAMS降解温度范围为260～320 ℃,在此温度下PAMS降解产物主要是α-甲基苯乙烯单体,另外还有微量四氢呋喃溶剂残留及α-甲基苯乙烯二聚体。因主链上季碳原子的存在,PAMS的热降解过程以端基裂解的解聚反应为主,单体产率超过99%。     

Biomorphous SiC ceramics prepared from cork oak as precursor

Porous ceramic materials of SiC were synthesized from carbon matrices obtained via pyrolysis of natural cork as precursor. We propose a method for the fabrication of complex-shaped porous ceramic hardware consisting of separate parts prepared from natural cork. It is demonstrated that the thickness of the carbon-matrix walls can be increased through their impregnation with Bakelite phenolic glue solution followed by pyrolysis. This decreases the material’s porosity and can be used as a way to modify its mechanical and thermal characteristics. Both the carbon matrices (resulted from the pyrolysis step) and the resultant SiC ceramics are shown to be pseudomorphous to the structure of initial cork. Depending on the synthesis temperature, 3C-SiC, 6H-SiC, or a mixture of these polytypes, could be obtained. By varying the mass ratio of initial carbon and silicon components, stoichiometric SiC or SiC:С:Si, SiC:С, and SiC:Si ceramics could be produced. The structure, as well as chemical and phase composition of the prepared materials were studied by means of Raman spectroscopy and scanning electron microscopy.     

Polymer‐filler derived ceramics with low shrinkage using PCS/SiC/Al mixture

Active Al and inert SiC powders were dispersed in the polycarbosilane to manufacture SiC ceramic composites by a new process of active‐filler‐controlled pyrolysis of polymer. 40 wt% of active Al fillers, 40 wt% of inert SiC fillers and 20 wt% of PCS, were homogenized. The samples were obtained by pyrolysis at 1100 °C for different soaking time. The results showed that due to the incorporation of active Al fillers, formation of crystallite phases such as Al₄C₃, Al₄Si₃ and AlN occured due to the of reaction of Al particles with the polymer decomposition products and the reactive nitrogen atmosphere. The microstructural and mechanical characterization results of the composites are presented in the paper. (© 2007 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Microwave absorption properties of composite powders with low density

The composites of barium ferrite coated on hollow ceramic microspheres were prepared using sol-gel technique. The crystal structure, morphology and microwave absorption properties of composite powders with different weight ratio of microspheres were studied with XRD, EDS, FESEM and vector network analyzer. The results show that the microwave absorption properties of composite powders are greatly improved. The maximum microwave loss of composite powders reaches 31 dB with an amount of 50 wt.% microspheres, and its density is only about 1.80 g/cm³. The effect of hollow ceramic microspheres on the microwave absorption property is also discussed.     

Potato starch-based activated carbon spheres as electrode material for electrochemical capacitor

Potato starch-based activated carbon spheres (PACS) were prepared from potato starch by stabilization, carbonization followed by activation with KOH. The obtained PACS are hollow and retain the original morphology of potato starch with decrease in size, as shown by scanning electron microscopy. Modification of textural properties of the PACS was achieved by varying the carbonization temperature and the ratio of KOH/PCS. The results of N₂ adsorption isotherms indicate that the samples prepared are mainly microporous. The electrochemical behaviors of the hollow PACS were studied by galvanostatic charge-discharge, cyclic voltammetry, and impedance spectroscopy. The results indicate that high specific capacitance of 335 F/g is obtained at current density 50 mA/g for PACS with specific surface area 2342 m²/g. Only a slight decrease in capacitance, to 314 F/g, was observed when the current density increases to 1000 mA/g, indicating a stable electrochemical property.     

Comparative study of high temperature anti-oxidation property of sputtering deposited stoichiometric and Si-rich SiC films

Stoichiometric and silicon-rich (Si-rich) SiC films were deposited by microwave electron cyclotron resonance (MW-ECR) plasma enhanced RF magnetron sputtering method. As-deposited films were oxidized at 800 ℃, 900 ℃, and 1000 ℃ in air for 60 min. The chemical composition and structure of the films were analyzed by x-ray photoelectron spectroscopy (XPS), Raman spectroscopy and Fourier transform infrared spectroscopy (FT-IR). The surface morphology of the films before and after the high temperature oxidation was measured by atomic force microscopy. The mechanical property of the films was measured by a nano-indenter. The anti-oxidation temperature of the Si-rich SiC film is 100 ℃ higher than that of the stoichiometric SiC film. The oxidation layer thickness of the Si-rich SiC film is thinner than that of the stoichiometric SiC film in depth direction. The large amount of extra silicon in the Si-rich SiC film plays an important role in the improvement of its high temperature anti-oxidation property.     

Thermal and electrical properties of a white-eucalyptus carbon preform for SiC/Si ecoceramics

The thermal conductivity κ and electrical resistivity ρ of a white-eucalyptus cellular carbon preform used to fabricate silicon-carbide-based (SiC/Si) biomorphic ceramics have been measured in the 5-to 300-K temperature interval. The carbon preform was obtained by pyrolysis (carbonization) of white-eucalyptus wood at 1000°C in an argon ambient. The κ(T) and ρ(T) relations were measured on samples cut along the tree growth direction. The experimental data obtained were processed.     

Ar离子辐照导致微球玻璃机械性能的变化

为研究离子辐照导致空心玻璃微球机械性能的变化,利用Ar离子辐照与空心玻璃微球组分相同的微球玻璃薄片,结合不同温度下的等时退火处理,采用纳米压痕测试方法研究了辐照前后玻璃机械性能的变化。测试结果表明:辐照后玻璃的硬度和模量均呈下降趋势,恢复阻力明显升高;退火后的未辐照样品硬度和模量呈上升趋势,恢复阻力在误差范围内没有发生变化; 退火后的模量呈下降趋势,恢复阻力呈下降趋势;在退火温度约为300 ℃时,辐照样品退火后的恢复阻力与未辐照样品基本相同。     

Effects of carbonization and substrate temperature on the growth of 3C-SiC on Si(1 1 1) by SSMBE

The growth of 3C-SiC on Si(1 1 1) substrate was performed at different carbonization temperatures and substrate temperatures by solid-source molecular beam epitaxy (SSMBE). The properties of SiC film were analyzed with in situ reflection high energy electron diffraction (RHEED), X-ray diffraction (XRD), atomic force microscopy (AFM) and X-ray photoelectron spectroscopy (XPS). The best carbonization temperature of 810 °C was found to be optimal for the surface carbonization. The quality of SiC film grown on Si at substrate temperature of 1000 °C is best. The worse crystalline quality for the sample grown at higher temperature was attributed to the large mismatch of thermal expansion coefficient between SiC and Si which caused more dislocation when sample was cooled down to room temperature from higher substrate temperature. Furthermore, the larger size of single pit and the total area of the pits make the quality of SiC films grown at higher temperature worse. More Si atoms for the sample grown at lower temperature were responsible for the degradation of crystalline quality for the sample grown at lower temperature.