HTMS改性SiO2减反膜的制备和耐环境稳定性研究

本文将正硅酸乙酯（TEOS）做前驱体, 氨水（NH3?H2O）做催化剂制备碱性SiO2溶胶,通过十六烷基三甲氧基硅烷（HTMS）修饰SiO2颗粒来 “钝化”SiO2颗粒,最终获得HTMS改性SiO2溶胶。然后采用提拉法在BK7玻璃表面制备HTMS改性氧化硅薄膜。利用傅里叶变换红外光谱仪（FTIR）、UV-Vis-NIR分光光度计、Film Wizard膜系设计软件和扫描电子显微镜（SEM）等表征方法对薄膜表面结构、光学性能、耐环境稳定性做了研究。结果表明：经过HTMS改性后的薄膜有高透过率和优异的耐环境稳定性,其透过率在峰值可达～99.8%,在90%RH湿度环境下经过两个月时间后,薄膜的峰值透过率仅仅下降了0.3%,改性后其耐环境稳定性得到较大提高。     

溶胶-凝胶法制备HMDS/SiO_2复合减反膜的疏水性和光学性能的研究（英文）

采用溶胶-凝胶法制备得到同时具有超疏水性能和高透过率的SiO_2减反膜。将适量的六甲基二硅氮烷(HMDS)添加到碱性催化的二氧化硅溶胶中,得到HMDS改性溶胶。使用浸渍-提拉法在基底上镀出的薄膜同时具有超疏水性能和高透过率。薄膜的性能可以由傅里叶变换红外光谱仪、UV-Vis-NIR分光光度计、FilmWizard32膜系设计软件和接触角测试仪进行测量。实验结果表明:当HMDS与TEOS的摩尔比为2:1时,薄膜的水接触角可达151.5°,透过率能达到99.7%;此外,在长波段,薄膜折射率可以达到1.12。     

先驱体配比对薄膜结构与性能的影响

以正硅酸乙酯(TEOS)和甲基丙烯酰氧基丙基三甲氧基硅烷(KH-570)分别为无机和有机溶胶先驱体,采用溶胶-凝胶法制备涂膜液;并采用浸渍提拉涂膜技术在聚碳酸酯(PC)表面制备有机/无机复合耐磨涂层;利用热失重/差热分析法(TG/DTA),傅里叶红外分析(FTIR),紫外可见光分光光度计(UV-VIS),金相显微镜等技术分析了不同先驱体配比T/K(TEOS/KH-570摩尔比)对涂膜液的热性能及薄膜性能及结构的影响机制.结果表明,随着T/K比值的增加,涂膜的无机结构增强,热失重及薄膜柔韧性降低,涂膜表面易开裂涂膜PC片的透过率降低,但仍优于未涂膜PC片.涂膜的结构以带有有机基团的无机交联网络为主,升高热处理温度有利于Si-O-Si键的形成,而热处理时间对其影响不大.     

接枝改性硅丙复合涂层的制备及性能研究

以γ-甲基丙烯酰氧丙基-三甲氧基硅烷(KH-570)和甲基丙烯酸酯类(MMA)为原料,过氧化苯甲酰(BPO)为引发剂,在非水溶剂中聚合先制得丙烯酸酯和KH-570的预聚体,通过预聚体与正硅酸乙酯(TEOS)共同水解制得了稳定的改性二氧化硅溶胶,同时,用一步法由TEOS、KH-570及MMA共聚也制备了丙烯酸酯改性硅溶胶.2种接枝后的二氧化硅溶胶通过浸渍提拉法在金属或者玻璃基片上成膜.运用激光光散射,FTIR、UV分光光度仪、铅笔硬度测试仪和附着力试验等对改性二氧化硅硅溶胶及涂层样品进行了分析和表征.结果表明,丙烯酸酯预聚体水解法具有很高的接枝率,制备的溶胶粒径易于控制,随水解条件的改变,可得到纳米至亚微米粒度的改性二氧化硅溶胶,并且成膜性能好.丙烯酸酯接枝改性后的二氧化硅涂层光学透过率高,对上述基材具有较好附着力,铅笔硬度均达到4H以上,对基材具有较好保护作用.     

溶胶-凝胶法制备硅铝溶胶增强有机/无机复合薄膜

以甲基三甲氧基硅烷(MTMS)的水解缩聚产物作为主要成膜物质、正硅酸乙酯(TEOS)和异丙醇铝的水解缩聚产物硅溶胶和铝溶胶作为无机增强物、甲基丙烯酰氧基丙基三甲氧基硅烷(KH-570)作为表面改性剂,通过共缩聚反应在聚碳酸酯(PC)板表面制备硅铝溶胶增强有机/无机复合薄膜;采用乌氏粘度计、TG/DTA、FTIR、UV-VIS、金相显微镜、铅笔硬度测试方法及划格法对涂膜液及薄膜性能进行表征.研究结果表明,加入KH-570改性铝溶胶后的涂膜液稳定性较好,MTMS水解缩聚产物与硅溶胶、铝溶胶通过共缩聚反应在PC板表面形成带有机基团的无机交联网络结构,基本骨架由Si-O-Si、Si-O-Al、Al-O-Al组成;铝溶胶的引入提高了薄膜的耐热性能及薄膜硬度,但KH-570改性的效果不明显;薄膜对PC片有增透效果,涂膜液陈化2 d后,加入KH-570改性铝溶胶后薄膜的增透效果更理想;加入KH-570改性铝溶胶后薄膜的表面平整性得到改善.     

溶胶内甲基改性法和表面气相处理法制备的SiO_2减反射薄膜疏水性的比较（英文）

基于溶胶-凝胶过程采用2种方法制备具有疏水性能的SiO_2减反射薄膜。在室温下,以六甲基二硅氮烷作为甲基改性剂制备改性SiO_2溶胶,并以此溶胶提拉镀膜。另外,采用对标准TEOS基溶胶-凝胶SiO_2薄膜进行表面气相硅烷化后处理法,获得了疏水性能、激光损伤阈值均高于普通未经后处理薄膜的SiO_2减反射薄膜。比较研究了2种方法获得的减反膜在真空环境下的稳定性,以及抗激光损伤性能。实验发现,表面气相硅烷化后处理更适合制备具有优异光学性能的疏水减反射薄膜。     

氢化锆表面KH570/A171改性硅溶胶膜层结构及性能

以硅酸乙酯(TEOS)、γ-(甲基丙烯酰氧)丙基三甲氧基硅烷(硅烷偶联剂KH570)和乙烯基三甲氧基硅烷(硅烷偶联剂A171)等为主要原料制备硅烷偶联剂KH570/A171改性硅溶胶,进而采用浸渍提拉法在氢化锆表面制备溶胶膜层。红外光谱(FTIR)分析显示,硅烷偶联剂能有效参与溶胶共聚反应。透射电镜(TEM)分析表明,硅烷偶联剂的逐一加入有利于胶粒粒径细化,提高和维持胶粒之间亲和能力。扫描电镜(SEM)分析显示,使用硅烷偶联剂KH570和A171改性的有机硅溶胶,可在氢化锆表面制备干燥后无裂纹溶胶膜层,烧结溶胶膜层存在微裂纹而无明显崩落;溶胶膜层表面元素分布均匀,烧结后存在碳残余。真空热放氢实验表明,在氢化锆表面制备的烧结硅溶胶膜层,起到了阻氢渗透的作用。600℃二氧化碳气氛中,烧结硅溶胶膜层具备阻碍氧渗透能力,对氢化锆基体有抗高温氧化作用。     

TiO_2-SiO_2复合薄膜的常温制备及其性能

采用溶胶-凝胶法合成具有锐钛矿型TiO2晶粒的TiO2-SiO2复合溶胶,通过浸渍提拉工艺常温制备TiO2-SiO2复合薄膜。考察正硅酸乙酯(TEOS)用量对薄膜结构及性能的影响。结果表明:随着TEOS用量的增加,溶胶的稳定性降低,薄膜的透光率及光催化活性先增大后减小。在Si:Ti摩尔比为1:8时,复合溶胶与薄膜的综合性能达到最优;与单一TiO2溶胶相比,TiO2-SiO2复合溶胶的平均粒度从44增大到75nm;与单一TiO2薄膜相比,TiO2-SiO2复合薄膜的表面粗糙度增大,对罗丹明B的分解率从46.1%提高到67.0%,对水接触角由16°下降到3°,透光率显著增强。     

溶胶-凝胶法制备用于太阳能电池的SiO2减反射膜

以正硅酸乙酯为前驱体,氨水、盐酸为催化剂,通过溶胶-凝胶法制备了二氧化硅薄膜.采用提拉法将该二氧化硅薄膜镀在用于太阳能电池组件的低铁玻璃基底上.对薄膜进行了表面处理,薄膜疏水性大大提高,与水的接触角由40°提高到了110°.设计并制备了大面积的样品,400 nm到800 nm的平均透过率增加了5%以上.疏水性和耐刮擦性能达到工业化生产的需要.     

加水量与TEOS/MTES比例对有机-无机复合涂层防腐性能的影响

采用溶胶-凝胶法,以正硅酸乙酯(TEOS)和甲基三乙氧基硅烷(MTES)为前驱体,在钢片上制备有机-无机复合防腐薄膜。通过傅里叶红外光谱(FTIR)、扫描电镜(SEM)等测试手段研究薄膜材料的结构及性质的变化,并通过盐雾腐蚀试验和电化学阻抗谱测试对复合薄膜的防腐蚀性能进行检测,探讨加水量(R)、两种前驱体比例等溶胶凝胶过程工艺条件对防腐涂层结构及防腐性能的影响。结果表明,随加水量的增加,涂层防腐性能下降,随着TEOS/MTES比例由1:1到1:4,涂层防腐性能增强,涂层在R=2,TEOS/MTES=4时防腐性能最佳,较空白钢片阻抗提高2个数量级。     

改进型镁扩散法制备高临界电流密度MgB2超导体性能研究

本文采用一种改进型镁扩散法成功制备出密度达到1.95g/cm₃的MgB₂超导块材。论文研究了不同的热处理条件对MgB₂块材的超导转变温度(T_c)和临界电流密度(J_c)性能的影响。采用最佳热处理条件制备的MgB₂超导体T_c和J_c分别达到了38.1K和0.53MA/cm₂(10K,自场)。为了改进镁扩散法MgB₂超导体中弱的高场磁通钉扎性能,本文还研究了nano-Pr₆O₁₁和C掺杂对MgB₂超导体的临界电流密度和不可逆场(H_irr)的影响。结果表明C掺杂的MgB₂超导体临界电流密度在10K,6T下达到了10₄A/cm₂,该结果比未掺杂MgB₂超导体在同样条件下性能提高了两个量级,甚至比固态反应法制备的nano-C掺杂MgB₂超导体性能更好。利用该方法制备的nano-Pr₆O₁₁掺杂的MgB₂超导体在10K,2T下也比未掺杂样品J_c提高达9.4倍。根据大量的实验结果和理论分析我们提出基于改进型镁扩散法和化学掺杂,包括纳米粒子和C掺杂,很有可能是一种制备高性能MgB₂超导体非常有效的途径。     

废旧锂离子电池中Li, Fe和V的回收及xLiFePO4-yLi3V2(PO4)3的制备

由于LiFePO_4和Li_3V_2(PO_4)_3材料的特征相近,制备方法类似,提供了一种从废旧LiFePO_4和Li_3V_2(PO_4)_3混合电池中回收Li、Fe和V,再制备xLiFePO_4-yLi_3V_2(PO_4)_3的方法。在空气气氛中600℃热处理1h后,去除粘结剂PVDF使活性物质与集流体分离。调节Li、Fe、V和P摩尔比,球磨、锻烧,配制不同比例的xLiFePO_4-yLi_3V_2(PO_4)_3(x:y=5:1,7:1,9:1)复合电极材料。表征了其形貌、结构和电化学性能,结果表明,回收制备的复合材料将同时具备LiFePO_4和Li_3V_2(PO_4)_3两种材料的电化学性能,能显著改善LiFePO_4的倍率性能。     

Improved capacity and rate capability of Ru-doped and carbon-coated Li4Ti5O12 anode material

Pure Li₄Ti₅O₁₂, modified Li₄Ti₅O₁₂/C, Li₄Ru_0.01Ti_4.99O₁₂ and Li₄Ru_0.01Ti_4.99O₁₂/C were successfully prepared by a modified solid-state method and its electrochemical properties were investigated. From the XRD patterns, the added sugar or doped Ru did not affect the spinel structure. The results of electrochemical properties revealed that Li₄Ru_0.01Ti_4.99O₁₂/C showed 120 and 110 mAh/g at 5 and 10 C rate after 100 charge/discharge cycles. Li₄Ru_0.01Ti_4.99O₁₂/C exhibited the best rate capability and the highest capacity at 5 and 10 C charge/discharge rate owing to the increase of electronic conductivity and the reduction of interface resistance between particles of Li₄Ti₅O₁₂.It is expected that the Li₄Ru_0.01Ti_4.99O₁₂/C will be a promising anode material to be used in high-rate lithium ion battery.     

Preparation and characteristic of spherical Li3V2(PO4)3

Spherical Li₃V₂(PO₄)₃ was synthesized by using N₂H₄ as reducer. The products were characterized by X-ray diffraction (XRD) and scanning electron microscopy (SEM). The results show that single-phase, spherical and well-dispersed Li₃V₂(PO₄)₃ has been successfully synthesized in our experimental process. Electrochemical behaviors have been characterized by charge/discharge measurements. The initial discharge capacities of Li₃V₂(PO₄)₃ were 123 mAh g⁻¹ in the voltage range of 3.0–4.3 V and 132 mAh g⁻¹ in the voltage range of 3.0–4.8 V.     

Alloyed W–(Co,Ni,Fe)–C phases for reaction sintering of hardmetals

It has been shown that W–Co–C phases could dissolve a substantial amount of metals such as V, Cr and Ta, which are known to positively influence the microstructure of hardmetals with respect to uniform grain size distribution and fine grain size. This offers a tool to circumvent the conventional doping of hardmetals with individual carbides. In the present study we used double- and triple-alloyed κ-W₉Co₃C₄ (i.e. κ-(W,V,Cr)₉Co₃C₄ and κ-(W,V,Cr,Ta)₉Co₃C₄) and applied a variety of sintering experiments to obtain WC–Co, WC–(Ti,Ta,Nb)C–Co and WC–(Ti,Ta,Nb)(C,N)–Co hardmetals. We also prepared κ-W₉Fe₃C₄, alloyed κ-W₉Ni₃C₄, and κ-W₉(Fe/Ni)₃C₄, and used the latter for sintering.     

Effects of Mo and Al Additions on the Sulfidation Behavior of 310 Stainless Steel

The high-temperature sulfidation behavior of 310stainless steel (310SS) with Mo and Al additions (up to10 at.%) was studied over the temperature range700-900°C in pure-sulfur vapor over the range of 10^-3 to 10^-1 atm. Thecorrosion kinetics followed the parabolic rate law inall cases and the sulfidation rates increased withincreasing temperature and sulfur pressure. Thesulfidation rates decreased with increasing Mo and Al contents and it wasfound that the addition of 10 at.% Mo resulted in themost pronounced reduction among the alloys studied. Thescales formed on 310SS with Mo additions were complex, consisting of an outer layer of ironsulfide (with dissolved Cr), (Fe,Ni)₉S₈, andCr₂S₃/Cr₃S₄(with dissolved Fe), and an inner heterophasic layer ofFe_1-xS,Cr₂S₃/Cr₃S₄,NiCr₂S₄,Fe_1.25Mo₆S_7.7, FeMo₂S₄, andMoS₂. The scales formed on 310SS with Mo andAl additions had a similar mixture as above, except thatAl_0.55Mo₂S₄ was alsoobserved in the inner layer. The formation ofMoS₂ andAl_0.55Mo₂S₄ partly blocked the transport of cations throughthe inner scale, resulting in the reduction of thesulfidation rates compared to 310SS.     

The high-temperature corrosion behavior of Nb-Al alloys in a H2/H2S/H2O gas mixture

The corrosion behavior of pure Nb and three Nb Al alloys containing 12.5, 25, and 75 at.% Al was studied over the temperature range of 800–1000°C in a H₂/H₂S/H₂O gas mixture. Except for the Nb-12.5Al alloy consisting of a two phase structure of -Nb and Nb₃Al, other alloys studied were single phase. The corrosion kinetics followed the parabolic rate law in all cases, regardless of temperature and alloy composition. The parabolic rate constants increased with increasing temperature, but fluctuated with increasing Al content. The Nb-75Al alloy exhibited the best corrosion resistance among all alloys studied, whose corrosion rates are 1.6–2.2 orders of magnitude lower than those of pure-Nb (depending on temperature). An exclusive NbO₂ layer was formed on pure Nb, while heterophasic scales were observed on Nb-Al alloys whose compositions and amounts strongly depended on Al content and temperature. The scales formed on Nb-12.5Al consisted of mostly NbO₂ and minor amounts of Nb₂O₅, NbS2, and -Al₂O₃, while the scales formed on Nb-25Al consisted of mostly Nb₂O₅ and some -Al₂O₃. The scales formed on Nb-75Al consisted of mostly -Al₂O₃ and Nb₃S₄ atT 900°C, and mostly -Al₂O₃ , Nb₃S₄ and some AlNbO₄ at 1000°C. The formation of -Al₂O₃ and Nb₃S₄ resulted in a significant reduction of the corrosion rates.     

Effects of K2O-Li2O doping on surface and catalytic properties of Fe2O3/Cr2O3 system

The effects of K₂O and Li₂O-doping (0.5, 0.75 and 1.5 mol%) of Fe₂O₃/Cr₂O₃ system on its surface and the catalytic properties were investigated. Pure and differently doped solids were calcined in air at 400-600 °C. The formula of the un-doped calcined solid was 0.85Fe₂O₃:0.15Cr₂O₃. The techniques employed were TGA, DTA, XRD, N₂ adsorption at −196 °C and catalytic oxidation of CO oxidation by O₂ at 200-300 °C. The results revealed that DTA curves of pure mixed solids consisted of one endothermic peak and two exothermic peaks. Pure and doped mixed solids calcined at 400 °C are amorphous in nature and turned to α-Fe₂O₃ upon heating at 500 and 600 °C. K₂O and Li₂O doping conducted at 500 or 600 °C modified the degree of crystallinity and crystallite size of all phases present which consisted of a mixture of nanocrystalline α- and γ-Fe₂O₃ together with K₂FeO₄ and LiFe₅O₈ phases. However, the heavily Li₂O-doped sample consisted only of LiFe₅O₈ phase. The specific surface area of the system investigated decreased to an extent proportional to the amount of K₂O and Li₂O added. On the other hand, the catalytic activity was found to increase by increasing the amount of K₂O and Li₂O added. The maximum increase in the catalytic activity, expressed as the reaction rate constant (k) measured at 200 °C, attained 30.8% and 26.5% for K₂O and Li₂O doping, respectively. The doping process did not modify the activation energy of the catalyzed reaction but rather increased the concentration of the active sites without changing their energetic nature.     

固相-水热法制备LiFePO4-Li3V2（PO4）3复合材料及其电化学性能（英文）

分别采用固相-水热法和球磨法制备磷酸亚铁锂-磷酸钒锂复合正极材料(LiFePO4-Li3V2(PO4)3)。电化学性能测试表明,LiFePO4-Li3V2(PO4)3复合正极材料的电化学性能远远高于 LiFePO4和 Li3V2(PO4)3单独作为正极材料的性能,并且以固相-水热法制备的复合材料性能优于以球磨法制得的复合材料。研究发现 LiFePO4-Li3V2(PO4)3复合材料有 4 个氧化还原峰,相当于 LiFePO4 和 Li3V2(PO4)3 氧化还原峰的叠加。采用固相-水热法制备的LiFePO4-Li3V2(PO4)3 复合材料形貌较为规则,且有新相物质产生,这是导致其电化学性能较好的原因。     

Synthesis of lanthanum carbonate nanoparticles via sonochemical method for preparation of lanthanum hydroxide and lanthanum oxide nanoparticles

Lanthanum carbonate nanoparticles were synthesized from the reaction of lanthanum acetate and Na₂CO₃ under sonication via sonochemical method. Lanthanum hydroxide nanoparticles were prepared by facial hydrothermal processing from the resulted product at 110 °C for 24 h. The role of surfactant, calcination temperature and sonication time were investigated on the morphology and particle size of the products. Products were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), X-ray photoelectron spectrum (XPS), and Fourier transform infrared (FT-IR) spectra. La₂O₃ nanoparticles were obtained by calcinations of the nanoparticles of lanthanum carbonate at 600 °C.