Pd掺杂量对有机无机杂化SiO2膜H2/CO2分离性能和水热稳定性能的影响

以1,2-二(三乙氧基硅基)乙烷(BTESE)为前驱体、PdCl₂为钯源, 制备Pd掺杂有机无机杂化SiO₂(POS)溶胶, 涂膜后在水蒸气氛围中煅烧, 制备得到POS膜。采用X射线衍射(XRD)、傅里叶变换红外光谱(FT-IR)、N₂吸附-脱附和透射电子显微镜(TEM)对POS粉体的微观结构进行表征。考察了钯/硅摩尔比(n(Pd/Si)=0.1、0.5和1)对POS膜的气体分离性能与水热稳定性能的影响。结果表明: 随着Pd掺杂量的增加, POS膜的H₂渗透率逐渐增大, H₂/CO₂的理想选择性逐渐下降。经100 kPa水蒸气处理180 h后, 采用n (Pd/Si)=1制备的POS膜的H₂渗透率达到1.62× 10^-7 mol·m^-2·s^-1·Pa^-1, H₂/CO₂理想分离因子达到13.6, 表明该膜具有较好的H₂渗透性能、H₂/CO₂分离性能和水热稳定性能。     

疏水耐环境型SiO2/TiO2/SiO2-TiO2太阳能宽光谱增透膜的制备及性能研究

利用TFCcal设计软件构建膜系结构, 采用溶胶-凝胶工艺和提拉法在超白玻璃上制备出厚度精确可控的宽光谱、高增透型SiO₂/TiO₂/SiO₂-TiO₂减反膜, 同时结合甲基三乙氧基硅烷(MTES)改性碱催化的SiO₂溶胶, 通过提拉法一次制备出高透过率疏水型薄膜。研究表明, 高增透型三层宽光谱减反膜的理论膜层厚度依次为: 80.9 nm(内层SiO₂-TiO₂)、125.0 nm(中间层TiO₂)、95.5 nm(外层SiO₂), 其在400~700 nm可见光范围内平均透过率实际可高达97.03%以上。多层膜经过退火处理后, 膜面的水接触角高达131.5°, 同时陈化两个月以后的多层膜透过率仅下降0.143%, 表明制备的SiO₂/TiO₂/ SiO₂-TiO₂多层减反膜具有优良的疏水和耐环境性能。     

TiO2/WO3微纳米纤维复合材料的制备及光催化性能

通过溶胶-凝胶和静电纺丝技术相结合的方法, 成功制备不同复合浓度聚乙烯吡咯烷酮(PVP)/钛酸四正丁酯(Ti(OC₄H₉)₄)/钨酸铵(N₅H₃₇W₆O₂₄·H₂O)前驱体。通过控温煅烧获得不同煅烧温度、不同复合浓度的TiO₂/WO₃微纳米纤维复合材料。采用X射线衍射(XRD)、傅里叶变换红外光谱(FT-IR)、场发射扫描电子显微镜(FE-SEM)和紫外-可见漫反射光谱(UV-Vis )技术对样品进行表征。以亚甲基蓝(MB)的光降解为模型反应, 研究TiO₂/WO₃微纳米纤维复合材料在紫外光照射下的光催化活性。结果表明, 煅烧温度500℃时, n(Ti):n(W) = 12:1形成WO₃掺杂的TiO₂微纳米纤维及n(Ti):n(W) = 4:1形成的TiO₂/WO₃复合微纳米纤维的光催化活性均高于纯TiO₂。     

自清洁SiO2/TiO2减反膜的制备与性能研究

采用溶胶-凝胶技术制备了SiO₂溶胶和TiO₂溶胶，利用浸渍提拉法在光伏玻璃上制备了SiO₂/TiO₂减反膜。用光谱透射比测量仪和椭偏仪测定了薄膜的透光率和折射率，通过场发射扫描电子显微镜观察了薄膜的形貌结构，最后考察了薄膜的自洁性能和耐候性能。结果表明：随着溶胶中TiO₂浓度的升高，SiO₂/TiO₂减反膜的厚度不断增加，而透光率逐渐减小，折射率逐渐增大。在波长为600nm时，TiO₂浓度最低的减反膜(ST-300)的透光率为94.4%,折射率为1.33。ST-300减反膜的表面平整，结构致密。光催化2h后，ST-300减反膜可将10mg/L的甲基蓝溶液降解11.2%,经过耐候处理后，其透光率衰减值仅0.08%～0.15%。     

基于共价键作用的四氧化三铁-还原氧化石墨烯复合材料的合成及其储锂性能

采用溶剂热法制备单分散的Fe₃O₄微球, 对其表面进行包覆SiO₂和氨基化处理, 再与氧化石墨烯复合, 化学还原后得到Fe₃O₄-W-RGO复合材料。SEM和TEM照片显示, SiO₂均匀包覆在Fe₃O₄微球(直径~440 nm)表面形成Fe₃O₄@SiO₂核壳微球, 紧密束缚于RGO纳米片表面。XRD测试结果表明Fe₃O₄微球结晶度好、纯度高。电化学性能测试结果表明: 在0.01~3.00 V电压范围和0.1C倍率下, Fe₃O₄-W-RGO复合材料的首次放电容量为1246 mAh/g, 100次循环后保持830 mAh/g; 在2C倍率下放电容量达到484 mAh/g, 具有较好的倍率性能和循环性能。     

基于AZO的光谱选择性反射膜制备及其在聚光器中的应用研究

铝掺杂氧化锌(AZO)薄膜在红外波段具有高反射率的特性。设计了SiO₂/AZO/Al₂O₃/Glass/SiO₂光谱选择性反射膜。通过软件仿真和实验研究，探究了SiO₂、AZO、Al₂O₃薄膜的光学常数以及物理厚度对SiO₂/AZO/Al₂O₃/Glass/SiO₂薄膜光谱特性的影响，确定了光谱选择性反射薄膜的制备工艺参数。根据工艺制得了对可见光平均透射率接近90%、红外(2.5～20μm)平均反射率大于85%的光谱选择性反射膜，薄膜的辐射率为0.08～0.12。以表面镀有光谱选择性反射膜的玻璃作为线性菲涅尔式聚光系统中的二次聚光器窗口，设计了新型二次聚光器。光谱选择性反射玻璃有效阻挡了集热管的热辐射，使聚光器辐射热损失降低约66%。     

电解液组分对TiCP/Ti6Al4V复合材料微弧氧化膜耐蚀性及耐磨性影响

采用微弧氧化技术在 TiC_P/Ti6Al4V 复合材料表面制备陶瓷膜。在NaAlO₂和NaH₂PO₂两种溶液体系中通过添加不同添加剂 NaOH、C₁₀H₁₂CaNa₂N₂O₈·4H₂O和Na₂SiO₃, 研究电解液组分对陶瓷膜组织、耐蚀性和耐磨性的影响。结果表明: 在NaH₂PO₂电解液体系中生成的膜层由金红石型和锐钛矿型TiO₂相组成, 而在NaAlO₂体系中除了生成TiO₂外, 还生成了Al₂TiO₅和γ-Al₂O₃。添加NaOH可以加快微弧氧化反应速率, 添加NaAlO₂和Na₂SiO₃有利于提高膜层的硬度, NaH₂PO₂溶液体系中形成的膜层厚度是NaAlO₂溶液体系的2~3倍。 在NaAlO₂和NaH₂PO₂电解液体系中生成的膜层, 其耐腐蚀性能排序均为: Na₂SiO₃>C₁₀H₁₂CaNa₂N₂O₈·4H₂O>NaOH。在NaAlO₂电解液体系中生成的膜层的耐磨性能排序为: Na₂SiO₃>NaOH>C₁₀H₁₂CaNa₂N₂O₈·4H₂O, 而在NaH₂PO₂电解液体系中生成的膜层的耐磨性能排序为: Na₂SiO₃>C₁₀H₁₂CaNa₂N₂O₈·4H₂O>NaOH。TiC_P/Ti6Al4V复合材料经过微弧氧化处理后, 耐磨性和耐蚀性均优于基体, 在NaH₂PO₂+Na₂SiO₃电解液中生成的微弧氧化膜的耐蚀性最好, 耐磨性也较好, 其腐蚀电流密度较钛基复合材料基体降低约2个数量级, 因此综合性能最好。     

溶胶-凝胶SiO2减反膜的制备与光学性能研究

碱催化溶胶-凝胶多孔SiO₂减反膜具有优异的光学性能及抗激光损伤性能,是高功率激光装置中的重要组成部分,但其与光学元件之间的结合强度低,使得膜层易发生接触破坏。本研究以“神光II”高功率激光装置溶胶-凝胶多孔SiO₂减反膜为基础,通过提拉法在其表层涂覆致密的SiO₂薄层后得到机械强度提升的双层SiO₂减反膜(SiO₂-MTES),并与常用的单层氨固化SiO₂减反膜(SiO₂-HMDS)进行相关应用性能的综合比较。结果表明,涂覆SiO₂-MTES的熔石英在约800 nm处的峰值透过率大于99.6%,运用1-on-1激光损伤阈值测试方法测得该双层SiO₂减反膜的零几率激光损伤阈值为51.9 J/cm²(1064 nm, 9.1 ns),与涂覆SiO₂-HMDS的性能相当。同时, SiO₂-MTES膜层与水的接触角达到117.3°,...     

超导Nb膜表面减反膜技术研究

针对单光子探测芯片中超导Nb膜减反的问题,研究了磁控溅射Nb膜折射率光谱特性随Nb膜厚度变化的规律,同时研究了化学气相沉积法制备的SiO₂和SiN_x介质膜的折射率光谱特性。为降低超导Nb膜对633 nm光的反射比,在Nb膜表面设计和制备了SiO₂和SiN_x减反膜。测试结果表明:SiO₂和SiN_x使反射比明显减小,计算结果验证了这一趋势。     

Fe3O4-氮掺杂生物炭材料催化芬顿反应吸附有机污水中磷酸根离子的研究

以竹粉废料为原料,利用尿素热解制得氮掺杂生物炭(NBC),再通过原位沉积法在生物炭表面生长纳米Fe₃O₄,得到Fe₃O₄-氮掺杂生物炭复合材料(NBC-Fe₃O₄)。以KH₂PO₄溶液模拟含磷废水测试了NBC-Fe₃O₄复合材料的吸附性能,结果表明复合材料在pH值7时达到最佳吸附效果,吸附效率接近100%,最大吸附量为20.3 mg/g;复合材料对磷的吸附符合朗格缪尔模型和二级动力学方程。另外,复合材料中含有大量的Fe(Ⅱ)和Fe(Ⅲ),可以通过外加H₂O₂溶液形成芬顿氧化体系,实现同步催化降解腐殖酸和吸附磷酸根污染物。     

锐钛矿型TiO2纳米棒薄膜的溶胶-凝胶法制备研究

以钛酸丁酯Ti（OC₄H₉）₄、冰醋酸、去离子水和聚乙二醇（PEG）1000为原料,采用溶胶-凝胶法和旋转涂膜工艺,在玻璃衬底上制备出锐钛矿型TiO₂纳米棒。利用X射线衍射仪（XRD）、SEM和紫外可见光谱（UV/Vis）对TiO₂纳米棒薄膜进行了表征。结果表明,实验制备的TiO₂纳米棒为锐钛矿晶型,在TiO₂反应体系中,胶体粒子在加热过程中偶联在一起,1h后形成了TiO₂纳米棒,其直径为30～50nm,长度为100～200nm。同时,在42mL钛的胶体溶液中添加0.30g PEG（1000）后,纳米TiO₂薄膜的可见光透射峰值降低,TiO₂薄膜表面孔径为20～50nm。     

Influence of substrate properties on the growth of titanium films: Part II

In situ internal stress measurements were used to investigate the influence of the chemical properties of the substrate on the growth of a titanium film deposited under UHV conditions. The substrate films used were titanium films evaporated at different water partial pressures. When the titanium film is evaporated at substrate temperatures of 130 °C and higher the shape of the stress vs thickness curve is interpreted to indicate island growth. Comparing the internal stress curve of titanium on Al₂O₃ and Ti/H₂O substrates it is seen that the initial tensile stress is significantly larger on the Ti/H₂O substrate film. This larger tensile stress is interpreted to originate from a redistribution of oxygen at the substrate interface during the early growth stage of the clean titanium film. A compressive stress contribution at higher thickness of the titanium film is interpreted to be due to hydrogen interdiffusion from the substrate into the titanium film. Annealing of the Ti/H₂O substrate films at 350 °C for 20 min reduces the concentration of the surface oxygen species and the amount of hydrogen incorporated in the films.

Dosing of previously annealed Ti/H₂O substrate films with water affects both the oxygen concentration on the surface of these substrate films and the amount of hydrogen incorporated in the films. Oxygen dosing of these films only increases the concentration of the oxygen species on the substrate surface; thus only the initial tensile stress built up in the titanium film is affected. Dosing the films with hydrogen, on the other hand, only increases the amount of hydrogen incorporated in the substrate film, which by way of interdiffusion into the growing titanium film gives rise to a larger compressive stress at higher film thickness     

过氧化氢处理胶粉对橡胶-沥青黏弹性的影响

为了研究废胎胶粉经过氧化氢（H₂O₂）溶液处理后其孔结构和表观形貌的变化及对所制备橡胶-沥青高温性能的影响,采用三种不同比例的H₂O₂溶液对废胎胶粉进行表面改性处理,并制备橡胶-沥青。通过胶粉气体吸附试验、扫描电镜试验、沥青旋转黏度试验和动态剪切流变试验分析了不同比例的H₂O₂溶液对胶粉的孔隙结构、微观形貌和所制备橡胶-沥青的黏度、黏弹性等宏观力学性能的影响规律。结果表明:胶粉经H₂O₂溶液处理后,平均孔径明显变小,孔体积和孔面积的变化呈现一定的规律;随H₂O₂溶液比例的增加,胶粉颗粒间接触面增加,表面絮状物和孔隙增多,加强了胶粉与沥青的界面结合度。这使得胶粉中的橡胶烃在沥青中的溶解度增加,炭黑颗粒释放增多,胶粉颗粒的强度、弹性和耐磨性等力学性能下降,导致橡胶-沥青的弹性、黏度和高温抗车辙能力降低。      

Preparation of ultrafine particles of silicon base intermetallic compound by arc plasma method

The purpose of this paper was to prepare ultrafine particles of Si-based intermetallic compounds, TiSi₂, MoSi₂ and VSi₂, by an arc plasma method with hydrogen addition. The properties of the prepared particles were affected by the vapor pressure ratio (Ti/Si, V/Si: 10⁻¹; Mo/Si: 10⁻³) of the constituent metals. The vaporization and condensation rates of the constituent metals should be controlled to prepare intermetallic compound particles in the case of large different vapor pressures. The vaporization rate can be controlled by H₂ concentration in the arc; for example, an increase in H₂ concentration leads to an increase in Ti fraction in the prepared particles in a Si---Ti system. The preparation of ultrafine particles of TiSi₂ was most successful from the 60-wt.% Ti raw material with the 50%-H₂ arc. MoSi₂ particles were prepared from the 85-wt.% Mo raw material with the 50%-H₂ arc. A single phase of VSi₂ particles was prepared successfully from the 60-wt.% V raw material with the 50%-H₂ arc. Another purpose was to investigate the mechanism of vaporization enhancement of particular metals from a metal mixture by hydrogen in arc plasmas. The vaporization enhancement was mainly attributed to the formation of intermediate products such as hydride and/or activity modification by hydrogen in molten metals.     

Cubic Boron Nitride Formation by PECVD in the B-N-Cl-H System: Ionic and Chemical Aspects

BN thin films have been synthesized by r.f. Plasma Enhanced Chemical Vapor Deposition (PECVD) from BCl₃ / N₂ /H₂ / Ar mixtures. c-BN formation has been studied through correlations between gas phase characterization (by Optical Emission Spectroscopy, Mass Spectrometry and electrical measurements) and thin film analysis (by Fourier Transformed Infra Red Spectrometry for structure determination).

In particular, the occurrence of physical and possible chemical mechanisms is studied with the help of post-treatments of as-deposited BN coatings in pure Ar, Ar/H₂ and Ar/Cl_b plasma mixtures. It is shown that, in addition to the well known ion-induced formation of the cubic phase, chemical etching also occurs, due to the presence of hydrogen and chlorine species, which leads to a relative increase in the cubic content of the thin film.     

Copper metallization of hydroxyl-modified amorphous Si:C:H films

X-ray photoelectron spectroscopy (XPS) was used to examine the initial stages of copper deposited by Physical vapor deposition (PVD), or sputter deposition, interacting with amorphous silicon:carbon:hydrogen (a-Si:C:H) films and hydroxyl modified amorphous silicon:carbon:hydrogen (a-Si:C:H/OH) films under Ultra-high vacuum (UHV) conditions. Amorphous-Si:C:H films were formed by condensing vinyltrimethylsilane (VTMS) on a titanium substrate (temperature ≤90 K) followed by electron beam bombardment (500 eV), and annealing to 300 K in UHV. Amorphous Si:C:H/OH films were formed by condensing H₂O on the condensed VTMS multilayer (≤90 K) followed by electron beam bombardment (500 eV) and annealing to 300 K in UHV. The stoichiometry of the unmodified and modified a-Si:C:H films was determined by XPS to be C_4.5:Si and C_4.3:O_0.44:Si, respectively. XPS measurements of PVD Cu on the modified film at 300 K indicate initial conformal growth with Cu(I) and Cu(0) formation at the Cu/Si:C:H/OH film interface. At higher Cu coverages, only Cu(0) was observed. In contrast, 3-dimensional island formation (Volmer–Weber growth) of Cu(0) was observed on the unmodified film. Annealing both the modified and unmodified films up to 800 K in UHV produced no significant change in the Cu(3p)/Cu(2p_3/2) intensity ratio, indicating negligible Cu diffusion through the film into the titanium substrate below 800 K.     

Comparative photocatalytic study of two selected pesticide derivatives, indole-3-acetic acid and indole-3-butyric acid in aqueous suspensions of titanium dioxide

Heterogeneous photocatalysed degradation of two selected pesticide derivatives such as indole-3-acetic acid (IAA) and indole-3-butyric acid (IBA) has been investigated in aqueous suspensions of titanium dioxide by monitoring the change in substrate concentration employing UV spectroscopic analysis technique and depletion in total organic carbon (TOC) content as a function of irradiation time. The degradation kinetics was studied under different conditions such as pH, types of TiO_2, substrate and catalyst concentration, and in the presence of electron acceptor such as hydrogen peroxide (H₂O₂) besides molecular oxygen. The degradation rates were found to be strongly influenced by all the above parameters. The photocatalyst Degussa P25 showed comparatively highest photocatalytics. The pesticide derivative, indole-3-acetic acid was found to degrade slightly faster than indole-3-butyric acid.     

生物活性玻璃-二氧化锰复合支架的制备与表征

骨修复支架在植入缺损处后出现的炎症与氧化应激有关, 其中过氧化氢(H₂O₂)浓度过高是引起氧化应激的主要原因之一。二氧化锰(MnO₂)能够通过催化分解H₂O₂来消除植入物周围环境过量的H₂O₂, 同时催化H₂O₂分解产生的氧气(O₂)能够缓解骨缺损处因血供不足而导致的缺氧环境, 从而有利于骨组织再生与骨缺损修复。本研究采用简单的氧化还原法在3D打印制备的生物活性玻璃(BG)支架表面原位沉积MnO₂颗粒, 得到BG-MnO₂复合支架(BGM), 赋予BG支架清除H₂O₂的同时提供O₂的能力。研究结果表明, BGM支架表面沉积MnO₂含量随反应溶液中高锰酸钾浓度升高而增加, 其抗压强度随MnO₂含量增加而增强, 但这些支架的孔隙率和降解速度基本保持不变。更为重要的是, BGM支架能够在H₂O₂环境中持续催化分解H₂O₂产生O₂, 当不同Mn含量的BGM (BGM5和BMG9)支架在浓度为2 mmol/L的H₂O₂溶液中催化分解H₂O₂产生的O₂能使溶液中饱和氧浓度分别达到8.4和11 mg/L。细胞实验结果表明, BGM支架对骨髓间充质干细胞的增殖和碱性磷酸酶活性有一定促进作用。因此, BGM支架在骨组织修复领域具有较大的应用潜力。     

Effects of inductively coupled plasma conditions on the etch properties of GaN and ohmic contact formations

In this study, n-GaN was etched using inductively coupled Cl₂/H₂ plasmas and the effects of plasma conditions on the etch properties, surface composition and ohmic contact formation were investigated as a function of gas composition using OES (optical emission spectroscopy), SEM (scanning electron microscope), XPS (X-ray photoelectron spectroscopy), AES (Auger electron spectroscopy) and TLM (transmission line method). The addition of hydrogen to Cl₂ plasma decreased GaN etch rate and changed the surface composition from Ga-rich to N-rich. Etched profiles were near vertical with a smooth sidewall, however, the pure Cl₂ case showed the most anisotropic etch profile. Specific contact resistivity was increased with increasing hydrogen percent in Cl₂/H₂, however, most of contact resistivities of the contacts fabricated on the GaN etched with Cl₂/H₂ (≤75% H₂) were less than those fabricated on the non-etched GaN.     

铝酸盐体系下反应时间对ZrH1.8表面阻氢膜层制备的影响

采用微弧氧化技术在NaAlO₂电解液体系下制备ZrH_1.8表面阻氢膜层, 采用场发射扫描电子显微镜(FE-SEM), X射线衍射(XRD), 真空脱氢实验对膜层进行表征, 考察不同反应时间对ZrH_1.8表面阻氢膜层的厚度、形貌、相结构以及阻氢性能的影响规律。研究结果表明：当反应时间在7.5~15 min变化时, 膜层厚度由78.4 μm增大至152.8 μm。膜层由单斜相M-ZrO₂、四方相T-ZrO₂以及立方相C-ZrO₂组成, 反应时间对膜层的相组成并无明显影响。阻氢膜层由致密层和疏松层构成, 膜层外侧为疏松层, 靠近基体一侧为致密层。当反应时间为10 min时, 获得的膜层表面平整, 致密性较好, 厚度适中, 膜层的氢渗透降低因子PRF值为20。