疏水性对溶胶-凝胶SiO2薄膜抗真空污染及抗激光损伤能力的影响

以正硅酸乙酯作为前驱体,利用碱催化方式制备了SiO2溶胶,通过在溶胶中添加含疏水基团(-CH3)的六甲基二硅氮烷(HMDS)对溶胶进行改性,使用添加不同物质的量比HMDS改性后的溶胶用提拉法在K9基片上镀膜,获得了具有疏水性能的SiO2薄膜。采用自制接触角测量仪、紫外-可见-近红外分光光度计研究了薄膜的水接触角和透过率。测试了薄膜的激光损伤阈值,并观察了激光辐照后薄膜的损伤形貌。通过真空污染实验对薄膜的抗污染能力及抗激光损伤能力进行了研究。实验结果表明:经疏水改性的溶胶所镀制的薄膜激光损伤阈值由未改性样品的24.3 J·cm-2增加到37 J·cm-2(1 064 nm,10 ns),且抗真空污染能力大大加强:在真空环境下保存168 h后,未改性样品的峰值透过率下降了2%,而疏水改性后的样品峰值透过率仅下降了0.25%,并保持了较高的激光损伤阈值(30.8 J·cm-2)。     

自生纳米纤维增强SiO2气凝胶的制备及性能研究

采用溶胶-凝胶法和乙醇超临界干燥工艺制备ZrO_X/SiO₂复合气凝胶,再经1200℃高温热处理得到自生纳米纤维增强SiO₂复合气凝胶。利用扫描电子显微镜、透射电子显微镜、X射线衍射、热重和氮气吸附等手段对气凝胶的结构和性能进行了分析,并且测试了样品的压缩强度及真密度。实验结果表明：自生纳米纤维增强SiO₂复合气凝胶具有均匀的多孔网络结构,锆氧纳米纤维是以化学键连接复合的方式无序穿插在气凝胶中,对复合气凝胶的机械强度和隔热性能有明显的改善。经1200℃热处理后的ZrO_X/SiO₂复合气凝胶比表面积为827.22m₂·g^-1,压缩强度为9.68MPa,真密度为0.23g·cm^-3。     

氧离子导体La1.9Ba0.1Mo2O9-α的合成及其电性能研究

通过固相法合成了La_1.9Ba_0.1Mo₂O_9-α氧离子导体,对样品进行了XRD、SEM表征,采用交流阻抗谱、氧浓差电池、氧泵等电化学方法研究了该陶瓷样品在600～1 000 ℃下的离子导电特性。结果表明,该陶瓷样品在氧化性气氛中是纯的氧离子导体,1 000 ℃时的氧离子电导率达到0.09 S·cm^-1,高于母体La₂Mo₂O₉的氧离子电导率。本文还研究了样品的燃料电池性能,在1 000 ℃时氢气/氧气燃料电池的最大输出电流密度为280 mA·cm^-2,最大输出功率密度为112 mW·cm^-2。     

介孔SiO2气凝胶的常压干燥制备研究

以廉价的水玻璃为硅源，用乙醇(EtOH) / 三甲基氯硅烷(TMCS) / 庚烷(Heptane)溶液对湿凝胶进行改性，采用一种新的常压干燥工艺合成了SiO₂气凝胶。通过TMCS与乙醇、湿凝胶孔隙水及Si-OH基团之间的反应，使湿凝胶的溶剂交换和表面改性得以在一步完成。所合成的SiO₂气凝胶为轻质透明的块状固体，密度为0.128～0.136 g·cm^-3，孔隙率93.8%～94.2%。利用FTIR、SEM、TEM和BET吸附对气凝胶的微观结构、形貌和性质进行了研究。结果表明，气凝胶为海绵状结构，粒子直径和孔径分布均匀，比表面积559～618 m²·g^-1，表面带有较多的Si-CH₃基团，呈现出明显的疏水性。     

Li1.2Mn0.54Ni0.13Co0.13O2正极材料的Ga2O3包覆改性及电化学性能

首先采用共沉淀方法制备富锂锰基正极材料 Li_1.2Mn_0.54Ni_0.13Co_0.13O₂原始样品(P-LRMO), 然后通过简单的湿化学法以及低温煅烧方法对其进行不同含量 Ga₂O₃原位包覆。透射电子显微镜(TEM)以及 X射线光电子能谱(XPS)结果表明在 P-LRMO表面成功合成了 Ga₂O₃包覆层。电化学测试结果表明:含有 3 %Ga₂O₃的改性材料 G3-LRMO具有最优的电化学性能, 其在 0.1C倍率(电流密度为 25 mA·g^-1)下首圈充放电比容量可以达到 270.1 mAh·g^-1, 在 5C倍率下容量仍能保持 127.4 mAh·g^-1, 优于未改性材料的 90.7 mAh·g^-1, 表现出优异的倍率性能。G3-LRMO在 1C倍率下循环 200圈后仍有 190.7 mAh·g^-1的容量, 容量保持率由未改性前的 72.9 %提升至 85.6 %, 证明 Ga₂O₃包覆改性能有效提升富锂锰基材料的循环稳定性。并且, G3-LRMO在 1C倍率下循环 100圈后, 电荷转移阻抗(R_ct)为 107.7 Ω, 远低于未改性材料的 251.5 Ω, 表明 Ga₂O₃包覆层能提高材料的电子传输速率。     

新型纳米多孔SiO2气凝胶微球材料的制备

A new type of nanoporous SiO₂ aerogel microsphere materials were synthesized by using SiO₂ sols as raw materials in the W/O emulsion formed by the emulsification of Tween-85 and Span-80. The obtained wet gel microspheres were aged by a successive solvent exchanging of alcohol, tetraethylorthosilicate (TEOS)/ethanol solution and ethanol at 60 ℃, and then were dried at ambient pressure to produce SiO₂ aerogel microspheres. The resultant SiO₂ aerogel microspheres were characterized by SEM, TEM and nitrogen adsorption-desorption. The results show that the prepared SiO₂ aerogel microspheres are nanoporous materials with coherent network nanoporous structure consisting of SiO₂ nanoparticles with an average diameter of about 10 nm. The apparent density of a typical sample is 0.4 g·cm^-3, while the specific surface area is 386 m²·g^-1, and the average pore size is 18 nm with the porosity of 84%. Various SiO₂ aerogel microspheres with the apparent particle sizes of 10～200 μm can be synthesized by controlling the stirring speed at 600～2 000 r·min^-1, the volume ratio of water/oil from 0.10 to 0.30, and the weight ratio of Tween-85/Span-80 less than 0.40.     

脉冲激光沉积NiCo2S4薄膜及其电化学特征

采用脉冲激光沉积法制备了NiCo₂S₄薄膜,利用恒流充放电和循环伏安测试研究了NiCo₂S₄薄膜作为锂离子电池负极材料的电化学性能和充放电机理。采用高分辨电子显微镜和选区电子衍射(TEM&SAED)表征了NiCo₂S₄薄膜首次循环过程中的组成与结构变化。恒流充放电测试结果显示NiCo₂S₄薄膜在3 μA·cm^-2的放电电流下,0~3 V(vs Li⁺/Li)范围内,薄膜的首次放电容量为698 mAh·g^-1,经过200次循环之后的放电容量为365 mAh·g^-1;在循环伏安测试中得到了分步反应的可逆氧化还原峰。TEM和SAED分析结果揭示了NiCo₂S₄薄膜与Li的电化学反应机理：首次放电过程中NiCo₂S₄与Li发生转化反应生成了Li₂S、Ni和Co,充电后生成了CoS和NiS复合薄膜。后续循环为CoS和NiS复合薄膜的可逆分解与形成。研究表明NiCo₂S₄是一种有潜在应用价值的锂离子电池负极材料。     

KBi4F13:一个具有高激光损伤阈值的中红外非线性光学材料

通过KF和Bi₂O₃在HF的水溶液中的水热反应合成了化合物KBi₄F₁₃,首次用X-射线单晶衍射技术鉴定了它的晶体结构。对它进行了XRD、ATR-FTIR、UV-Vis-NIR、TG、SHG测试。测试结果表明该化合物具有能够相位匹配的二阶非线性光学性能,其粉末倍频效应强度约为KDP的一半;粉末激光损伤阈值为120 MW·cm^-2,远远高于同等条件下测试的商品化红外非线性光学材料AgGaS₂的粉末激光损伤阈值(5 MW·cm^-2);粉末的红外吸收边可达20 μm;热分解温度为220℃。以上结果表明该物是有潜在应用价值的具有高激光损伤阈值的中红外非线性光学晶体材料。     

KBi4F13:一个具有高激光损伤阈值的中红外非线性光学材料

通过KF和Bi₂O₃在HF的水溶液中的水热反应合成了化合物KBi₄F₁₃,首次用X-射线单晶衍射技术鉴定了它的晶体结构。对它进行了XRD、ATR-FTIR、UV-Vis-NIR、TG、SHG测试。测试结果表明该化合物具有能够相位匹配的二阶非线性光学性能,其粉末倍频效应强度约为KDP的一半;粉末激光损伤阈值为120MW·cm^-2,远远高于同等条件下测试的商品化红外非线性光学材料AgGaS₂的粉末激光损伤阈值(5MW·cm^-2);粉末的红外吸收边可达20μm;热分解温度为220℃。以上结果表明该物是有潜在应用价值的具有高激光损伤阈值的中红外非线性光学晶体材料。     

脉冲激光沉积NiCo2S4薄膜及其电化学特征研究

采用脉冲激光沉积法制备了NiCo₂S₄薄膜,利用恒流充放电和循环伏安测试研究了NiCo₂S₄薄膜作为锂离子电池负极材料的电化学性能和充放电机理。采用高分辨电子显微镜和选区电子衍射(TEM&SAED)表征了NiCo₂S₄薄膜首次循环过程中的组成与结构变化。恒流充放电测试结果显示NiCo₂S₄薄膜在3 μA·cm^-2的放电电流下,0~3 V(vs Li⁺/Li)范围内,薄膜的首次放电容量为698 mAh·g^-1,经过200次循环之后的放电容量为365 mAh·g^-1;在循环伏安测试中得到了分步反应的可逆氧化还原峰。TEM和SAED分析结果揭示了NiCo₂S₄薄膜与Li的电化学反应机理：首次放电过程中NiCo₂S₄与Li发生转化反应生成了Li₂S、Ni和Co,充电后生成了CoS和NiS复合薄膜。后续循环为CoS和NiS复合薄膜的可逆分解与形成。研究表明NiCo₂S₄是一种有潜在应用价值的锂离子电池负极材料。     

Effect of hydrophobicity on the stability of sol–gel silica coatings in vacuum and their laser damage threshold

Silica antireflective coatings modified by hexamethyldisilazane (HMDS) were deposited on clean substrates (silicon wafer or K9 glass blanks) by sol–gel processing. The effects of HMDS on the contamination resistant capability and laser-induced damage threshold (LIDT) of coatings were investigated. Transmission electron microscopy revealed that a stable sol with uniformly distributed silica particles with an average particle size of about 15 nm was acquired by adding appropriate amount of HMDS into the standard SiO₂ sol. With the modified sol the resultant coatings were hydrophobic and the contact angle for water increased with increasing amount of HMDS in the reaction mixture. Such increase in hydrophobicity was not the result of surface roughness. The antireflective properties were retained after HMDS-treatment and the maximum transmission values were above 99 %. The introduction of HMDS into silica sols had also increased the LIDT of coatings from 24.3 to 37.0 J cm^?2 when the molar ratio of HMDS to tetraethoxysilane was 0.05:1. The increase in LIDT was attributed to the decrease of nodular defect and uniform microstructures of coatings as an effect of the HMDS modification. After some of the hydroxyl groups on the surface of the SiO₂ particle were replaced by methyl groups, from which the SiO₂ particle gained a water-repellent surface, the stability of coatings in vacuum was increased. The maximum transmission values of modified coatings decreased by only 0.25 % after storage under vacuum for 168 h. In contrast, the standard sol–gel silica coatings decreased about 2 % under similar conditions. The LIDT of modified coatings remained as high as 30.8 J cm^?2, more than that of standard coatings stored for the same duration in air.     

The stability of sol–gel silica coatings in vacuum with organic contaminants

Sol–gel SiO₂ antireflective coatings were prepared with different post-treatments, and their performance in a vacuum environment with intentionally induced organic contaminants were studied in detail. The pores of the silica coating can be filled with contaminants, which can increase the refractive index of the film and also absorb or scatter the light and therefore reduce the transmittance. Heat treatment at low temperature can insure against the possible volatilization of the components of the coating, but does not prevent the adsorption of organic contaminants and the degeneration of the transmittance. If an ammonia and hexamethyldisilazane (HMDS) vapor treatment is adopted before heat treatment, the optical stability can be greatly enhanced by reducing the adsorption of contaminants. The increased resistance to contamination is due to changes in the coating’s structure and composition, including a reduction of the specific surface area and surface polarity as a result of ammonia treatment and HMDS treatment, respectively.     

Field effect conductance of conducting polymer nanofibers

We report on the electrical conductance of nanofibers of regioregular poly(3‐hexylthiophene) (RRP3HT) as a function of gate‐induced charge. Nanofibers of RRP3HT were deposited onto SiO₂/Si substrates by casting from dilute p‐xylene solutions. An analysis of the nanofibers by atomic force microscopy revealed fiber lengths of 0.2–5 μm, heights of 3–7 nm, and widths of approximately 15 nm. A field effect transistor geometry was used to probe the conductance of webs of nanofibers and single nanofibers; in these measurements, gold electrodes served as source and drain contacts, and the doped SiO₂/Si substrate served as the gate. Temperature‐dependent transport studies on webs of nanofibers revealed an activation energy of 108 meV at a gate‐induced hole density of 3.8 × 10¹² charges/cm². Pretreating SiO₂ with a hydrophobic hexamethyldisilazane (HMDS) layer reduced the activation energy to 65 meV at the same charge density. The turn‐on gate voltage on treated and untreated substrates increased in magnitude with decreasing temperature. Conductance measurements on single nanofibers on HMDS‐treated SiO₂ yielded hole mobilities as high as 0.06 cm²/Vs with on/off current ratios greater than 10³. © 2003 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 41: 2674–2680, 2003     

Heptacene: Synthesis and Its Hole-Transfer Property in Stable Thin Films

Heptacene ( 1 ) has been produced via a monoketone precursor, 2 , which was prepared from 1,2,4,5-tetrabromobenzene in nine steps in a total yield of 10 %. Compound 2 was converted to 1 quantitatively by heating at 202 °C. Heptacene exhibited high thermal stability in the solid state without any observable change over two months. To investigate the potential value of 1 as a material for p-type organic field-effect transistors (OFETs), top-contact OFET devices were fabricated by vacuum deposition of 1 onto a hexamethyldisilazane (HMDS)/SiO₂/Si substrate. The best hole mobility performance was 2.2 cm² V⁻¹ s⁻¹. This is the first report of stable heptacene being used in an effective device and examined for its charge carrier properties.     

Sol–gel silica antireflective coating with enhanced abrasion-resistance using polypropylene glycol as porogen

Silica antireflective (AR) coatings with high transmittance and enhanced abrasion-resistance were synthesized by sol–gel process using polypropylene glycol (PPG) as porogen. The effects of molecular weight of PPG and weight ratio of PPG to SiO₂ on the refractive index and abrasion-resistance of the coating were systematically studied and compared with those of polyethylene glycol (PEG). Experimental data showed that the refractive index decreased with increasing the weight ratio to SiO₂ and molecular weight of both PEG and PPG, but PPG was much more effective than PEG. In the case of same molecular weight, PPG modified coating has the higher porosity than PEG modified one. When the weight ratio of PPG to SiO₂ is in a low level, the PPG-containing silica AR coatings exhibit the good abrasion-resistance. PPG is liquid at room temperature and the better solubility than PEG. These effective and economic AR coatings with enhanced abrasion-resistance have potential value in the field of solar thermal collectors.     

Modification of nano-hybrid silicon acrylic resin with anticorrosion and hydrophobic properties

Silicone-acrylic resin (SAR) was prepared from acrylic monomers and silicone prepolymer by the free radical solution polymerization, and then mixed TiO₂ and SiO₂ nanoparticles modified by KH570 were added to prepare nanocomposite coating. Thermogravimetric analysis and contact angle measurements showed that the acrylic resin modified by silicone prepolymer exhibited an improved thermostability and a better hydrophobicity compared with the unmodified sample. The adding of nanoparticles further increased the hydrophobicity. The contact angle of modified silicone-acrylic resin with mixed TiO₂ and SiO₂ nanoparticles of 3 wt% is the highest, 108.4°. The UV resistance and weather resistance of the modified silicone-acrylic resin are significantly improved. It was also found through electrochemical impedance spectroscopy that the corrosion resistance was significantly improved by the addition of mixed TiO₂ and SiO₂ nanoparticles. Modified silicone-acrylic resin with mixed TiO₂ and SiO₂ nanoparticles of 3 wt% and 5 wt% coating system maintains an excellent anticorrosion performance (coating resistance R_c of more than 10⁹ Ω cm²) even at 3.5% NaCl electrolyte medium till to 1800 h.     

DC plasma polymerization of hexamethyldisiloxane

Hexamethyldisiloxane (HMDS) was polymerized onto metallic and insulating substrates in a parallel-plate DC reactor. The limits of the DC reactor with respect to pressure and power were determined for deposition of PP-HMDS films. In all conditions ranging from 5 Pa/0.3 W to 100 Pa/50 W, solid films were deposited. No powders or oily films were obtained under any condition in this operating range. The films were polymeric in nature,i.e., they were neither carbon-like nor SiO _x -like films. The structures and crosslink densities of the plasma films dependend strongly on the deposition conditions. The highest deposition rates, up to 2 μm per minute (or0.3 mg/cm² min), were obtained at high power, pressure, and flow rate conditions. An efficiency ɛ is introduced, defined as the fraction of the monomer that is retained in the form of a polymer deposited on the substrate. Efficiencies as high as 25% could be obtained in certain conditions. Pulsing the discharge power increased the conversion efficiency markedly, but the effect depended strongly on the monomer used. In addition to HMDS, plasma polymers were also deposited from pyrrole in pulsed conditions for comparison. A method is described for depositing films on insulators from a DC glow discharge using two wire meshes held at a negative potential.     

Growth mechanism of gold particles on Al2O3 substrates

We investigated the growth of small gold particles on thin alumina substrates obtained by oxidation of aluminum. The particles were vapor deposited in vacuum from a Knudsen cell source with a vapor rate of 1·10¹³ cm^?2·s^?1. In our experiments small Au particles on Al₂O₃ were examined by electron microscopy. From electron micrographs we draw a size histogram of Au particles depending on the mean deposit thickness and the deposition rate. For a mean thickness larger than 1.5 nm the particle size distributions show two peaks. The shapes and the positions of these two peaks allow us to determine the particle growth mechanism and to evidence the importance of the liquid-like coalescence resulting of diffusion and collision of the aggregates.     

自组装铝/氧化铜和铝/氧化铁及其性能评估

本文分别采用模板法制备氧化铜纳米花, 水热法制备氧化铁纳米环, 并自组装制备了铝-氧化铜和铝-氧化铁2种铝热剂。自组装增大了异相材料之间的接触, 分别使得铝-氧化铜的反应放热量和压力由523 J·g^-1、1 858 kPa增加至1 069 J·g^-1、 4 389 kPa;铝-氧化铁的反应放热量和压力由1 448 J·g^-1、749 kPa增加至2 039 J·g^-1、2 280 kPa。两种铝热剂的放热量和压力差别较大, 且铝-氧化铜的静电感度高于大多数含能材料, 铝-氧化铁的撞击感度特别低, 显示出不同的应用特点。