Nano-tribological characteristics of TiO<Subscript>2</Subscript> films on 3-mercaptopropyl trimethoxysilane sulfonated self-assembled monolayer

Silane coupling reagent (3-mercaptopropyl trimethoxysilane (MPTS)) was used to prepare twodimensional self-assembled monolayer (SAM) on silicon substrate. The terminal -SH group was in situ oxidized to −SO₃H group to endow the film with good chemisorption ability. Then TiO₂ thin films were deposited on the oxidized MPTS-SAM to form composite thin films, making use of the chemisorption ability of the −SO₃H group. Atomic force microscope (AFM) and contact angle measurements were used to characterize TiO₂ films. Adhesive force and friction force of TiO₂ thin films and silicon substrate were measured under various applied normal loads and scanning speed of AFM tip. Results showed that the friction force increased with applied normal loads and scanning speed of AFM tip. In order to study the effect of capillary force, tests were performed in various relative humidities. Results showed that the adhesive force of silicon substrate increases with relative humidities and the adhesive force of TiO₂ thin films only increases slightly with relative humidity. Research showed that surfaces with more hydrophobic property revealed the lower adhesive and friction forces.     

Preparation and tribological studies of self-assembled triple-layer films

A self-assembled triple-layer film was grafted onto a silicon surface with a simple three-step method. Firstly, 3-glycidoxypropyltrimethoxysilane molecules were self-assembled on silicon surfaces, then coupled to 3-aminopropyltriethoxysilane through a surface ring-opening reaction, and finally octadecyltrichlorosilane (OTS) molecules were attached to the resultant alkoxysilane-terminated surface via Si-O-Si bonds. The structure and morphology of this triple-layer film were characterized with various techniques, such as contact angle measurement, ellipsometry, X-ray photoelectron spectroscopy, and atomic force microscopy (AFM). The influence of different surface chemical groups on surface adhesion properties was identified using the AFM force-volume technique. The micro- and macro-tribological properties of the triple-layer film were evaluated by friction force microscopy and a ball-on-plate tribometer. The triple-layer film shows good adhesive resistance and can greatly reduce the micro- and macro-friction force. Moreover, compared to self-assembled monolayer of OTS, this triple-layer film exhibited much better wear-resistance. This improvement was mainly ascribed to the network structure of a lateral cross-linked polysiloxane layer formed within the film which can enhance the stability of the film.     

Preparation and tribological properties of novel carbon nanotube self-assembled composite films

Carbon nanotube (CNT) composite thin films were prepared on a single-crystal silicon substrate by a self-assembling process from a specially formulated solution. Rare earth solution (RES) surface modification and appropriate acid-treatment methods were used to functionalise carbon nanotubes (CNTs). Silane coupling regent (3-mercaptopropyl trimethoxysilane (MPTS)) was prepared first. The terminal thiol groups (–SH) in the film was oxidised to sulphonic acid groups (–SO₃H) in situ to enhance the film with good chemisorption ability. Treated Caron nanotubes were deposited on the oxidised MPTS–SAM by means of chemisorption with the SO₃H group. The surface energy, chemical composition, phase transformation and surface morphology of the films were analysed using contact angle measurements, X-ray photoelectron spectroscopy (XPS), scanning electron microscope (SEM) and atomic force microscopy. As a result, a conclusion could be made that some lanthanum elements react with –SO₃H groups on the surface of the substrate by a chemical bond, which will improve the bonding strength between the films and the CNTs. Since the CNT thin films were well adhered to the silicon substrate, it might find promising application in the surface-modification of single-crystal Si and SiC in microelectromechanical systems (MEMS).     

Study of (3-mercaptopropyl)trimethoxysilane reactivity on zinc: Comparison with organothiol and organosilane thin films

To assess the reactivity of both terminal functions of the (3-mercaptopropyl)trimethoxysilane molecule, three types of zinc substrate (mechanically polished, electrochemically reduced and electrochemically oxidized) were modified concurrently by 1H,1H,2H,2H-perfluorooctyl-triethoxysilane and 1H,1H,2H,2H-perfluorooctanethiol. Surface characterization has been carried out with X-ray photoelectron spectroscopy, polarization modulation infrared reflection-absorption spectroscopy and contact angle measurements. Classical electrochemical techniques were employed to investigate corrosion inhibition of zinc along with thin films grafting. It is found that electrochemical oxidation enhances the grafting of the -Si(OCH₃)₃ groups while electrochemical reduction facilitates the formation of thiolate bonds, leading both to modified surfaces of much better quality compared to modified polished zinc samples.     

纳米TiO2薄膜的制备及其表面形貌AFM观测

采用溶胶-凝胶法在玻璃载波片及ITO导电玻璃片上制备出负载型纳米TiO2薄膜,并用原子力显微镜(AFM)对不同条件下制备的TiO2的表面形貌进行了表征.结果表明,TiO2薄膜能较好地负载在玻片表面,并且TiO2薄膜的表面形貌与前驱物的配比浓度、基片、热处理温度等都有密切的关系.随浓度和镀膜层数的增大,薄膜中TiO2纳米微晶的颗粒尺寸逐渐增大,从细小均匀粒子膜变为较大不规则的板块结构.在ITO薄膜面形成的TiO2薄膜具有较小的颗粒和均匀的分布.     

稀土Ce2O3掺杂TiO2薄膜的结构和光学特性

采用真空热蒸发法在玻璃、单晶硅衬底上制备Ce2O3掺杂TiO2薄膜，研究热处理和Ce2O3掺杂对薄膜性能的影响。结果显示，热处理可明显改善薄膜的结构和光学性能，Ce2O3掺杂可降低薄膜晶型转化温度。TiO2薄膜（玻璃衬底）经600℃热处理由锐钛矿转为金红石结构；当掺Ce2O3含量为5at％时热处理温度为500℃薄膜就已开始发生晶型转变。薄膜表面颗粒较均匀，存在程度不同的孔洞和颗粒聚集现象；掺Ce2O3后薄膜表面致密度明显增强。薄膜（玻璃衬底）的光学带隙从3．74eV降至3．60eV。     

Molecular dynamic simulation and characterization of self-assembled monolayer under sliding friction

The frictional mechanisms of a self-assembled monolayer (SAM) during nano-scale sliding are studied using molecular dynamics (MD) simulation. The MD model consists of a gold slider and gold substrate with n-hexadecanethiol SAM chemisorbed to the substrate. The trajectory, tilt angles, normal forces, frictional forces, friction coefficients and potential energies per molecular chain of the SAM molecules are evaluated during the frictional process for various parameters including as sliding height, sliding direction (i.e. pro- or anti- the SAM tilt angle), sliding velocity and system temperature. The various parameters are discussed with regard to frictional forces, mechanisms and SAM structural transition. Results show that stick-slip occurs and is related to the sliding period and tilt angle of the SAM molecules. Amplitude of the stick-slip cycle increases with decreasing sliding height until reaching a critical sliding height, which is characterized such that sliding below the critical height causes irreversible changes in the SAM molecular organization and cumulative loss of SAM lubricating efficiency. Different SAM recovery mechanisms were found for different sliding directions relative to SAM tilt angle (pro- or anti-tilt). In both cases, minimum friction occurred during the SAM tilt-angle recovery phase. The friction force curves for these two cases also showed a regular phase shift above the critical height. For stick-slip sliding above the critical height, anti-tilt sliding had significantly lower average friction, but this trend inverted below the critical height. Sliding lower than the critical height cause progressive disorder of the SAM structure and the characteristic differences between pro- and anti-tilt sliding were progressively lost.     

TiO_2自组装膜的制备及抗菌性能研究

以TiCl4为主要原料,采用自组装工艺,在玻璃基底表面制备TiO2薄膜。考察了(NH4)2SO4的添加、热处理温度、TiCl4浓度、反应温度、反应时间等工艺参数对TiO2薄膜结构和抗菌性能的影响规律。结果表明:未添加(NH4)2SO4时生成金红石型TiO2,而添加(NH4)2SO4可生成锐钛矿型TiO2,并且有利于TiO2膜均匀沉积。升高热处理温度,提高了TiO2的结晶度和薄膜附着力。但是,晶型和结晶度对薄膜的抗菌性能没有显著影响。随着TiCl4浓度增加,反应温度提高和反应时间延长,TiO2薄膜的抗菌性能得到提高。在最佳工艺条件,热处理温度为600℃、TiCl4浓度为0.2mol/L、反应温度为80℃、反应时间为80min时,抗菌率达100%。     

纳米La2O3／TiO2复合薄膜的制备及光催化性能研究

采用溶胶-凝胶法在陶瓷基体上制备了纳米La2O3／TiO2复合薄膜。利用XRD研究了La2O3不同复合量对纳米TiO2晶型转化的影响，利用SEM研究了Al2O3底膜对La2O3／TiO2复合薄膜形貌的影响，利用亚甲基兰溶液紫外光降解实验研究了La2O3／TiO2复合薄膜的光催化性能．结果表明：复合0．5％（物质的量）La2O3的TiO2干凝胶经850℃煅烧后仍为锐钛矿（64％（质量分数））占主导的混晶结构，平均粒径在10nm左右；当Al2O3底膜和La2O3／TiO2复合薄膜的厚度分别为4层和3层时，经850℃煅烧后，复合薄膜致密且无微裂纹出现，而且具有佳的光催化性能．     

自组装单层膜表面的Bi2Ti2O7薄膜制备与表征

以硝酸铋和钛酸四丁酯为原料,以三氯十八烷基硅烷(OTS)为模板,采用自组装单层膜(self-as-sembled monolayers,SAMs)技术,在玻璃基板上成功制备了Bi2Ti2O7晶态薄膜。借助X射线衍射(XRD)、场发射扫描电子显微镜(FE-SEM)、X射线能谱(EDS)及原子力显微镜(AFM)等测试手段对Bi2Ti2O7薄膜进行了表征。结果表明,以OTS为模板利用自组装技术,经540℃煅烧2h可成功制得立方相Bi2Ti2O7晶态薄膜,且薄膜表面平整光滑,均匀致密。     

壳聚糖/纳米TiO2杂化材料的制备及抗菌性能表征

制备了壳聚糖/纳米TiO2杂化膜,表征了其抗菌性能,分析了影响TiO2纳米粒子在壳聚糖溶液中分散性的影响因素。FT-IR、AFM分析了杂化膜的结构与形态。表明促进TiO2颗粒良好分散有四个主要因素:(1)表面电荷的重新分布;(2)空间保护作用;(3)化学键的相互作用;(4)超声分散。抗菌实验表明壳聚糖/纳米TiO2杂化膜具有很强的抗菌性能,细菌的形态学变化具有两个显著的特点:(1)细胞内物质渗漏,在细胞周围形成了环状结构;(2)细胞表面囊泡的形成。     

纳米结构TiN薄膜的制备及其摩擦学性能

在室温条件下,用磁过滤等离子体装置在单晶硅基底上制备了纳米结构TiN薄膜分析了薄膜的表面形貌、晶体结构,测量了TiN薄膜的硬度,研究了基底偏压对薄膜结构性能的影响.结果表明,用此方法制备的TiN薄膜表面平整光滑,颗粒尺寸为50～80 nm;随着基底偏压的增大薄膜发生(111)面的择优取向随着偏压的提高,薄膜的颗粒度稍有增大,摩擦系数增大,偏压提高,晶面在较密排的(111)面有强烈的择优取向,硬度也有所增大.在其它条件相同的情况下载荷越大,摩擦系数越大.不起用磁过滤等离子体法制备的纳米结构TiN薄膜具有较低的摩擦系数(0.14～0.25).     

F-TiO_2组装微球的溶胶-微波水热合成及生长机理

采用溶胶-微波水热法使TiO2前驱体微球表面形成自组装介孔结构,得到F掺杂的介孔TiO2微球。利用SEM、TEM、XRD、XPS、PL对样品进行表征,并对其生长机理进行简要的分析。结果表明,微球的直径约为400nm,由于NaF的加入,纳米晶粒(12±0.5)nm和介孔(约10nm)的形成使粗糙度明显增强;F的掺杂没有引起新的萤光现象,但F的掺杂能够增加TiO2微球PL光谱的强度。PL谱表明样品在396和464nm范围内有很强的蓝光发射特性,这与样品的微观结构有很大关系。     

AFM characterisation of sol‐gel TiO2 films deposited on stainless steel

One‐layer, two‐layer and three‐layer titania films on AISI 304 stainless steel were deposited by sol‐gel process and dip‐coating method. Two sols were prepared by using titanium isopropoxide as a precursor, propanol as a solvent, nitric acid as a catalyst and acetylacetone for peptization. Both of the prepared sols contained the same amount of mentioned components, the only difference was in the addition of polyethylene glycol (PEG) as templating reagent to one of the sols. After calcination at 550°C, deposited films on the stainless steel substrate were characterized by atomic force microscope (AFM). Influence of layer number as well as addition of polyethylene glycol on morphology of titania films was analysed and discussed. Generally, by increasing the number of layers and by addition of polyethylene glycol, roughness parameters increase by changing surface topography. The surface topography analysis is very important when choosing the adequate industrial application of prepared layers.     

Preparation and characterization of nanocrystalline porous TiO2/WO3 composite thin films

TiO₂ materials possessing not only photocatalytic but also electrochromic properties have attracted many research and development interests. Though WO₃ exhibits excellent electrochromic properties, the much higher cost and water-sensitivity of WO₃ as compared with the TiO₂ may restrict the practical application of WO₃ materials. In the present study, the feasibility of preparing nanocrystalline porous TiO₂/WO₃ composite thin films was investigated.Precursors of sols TiO₂ and/or WO₃ and polystyrene microspheres were used to prepare nanocrystalline pure TiO₂, WO₃, and composite TiO₂/WO₃ thin films by spin coating. The spin-coated thin films were amorphous and, after heat treating at a temperature of 500 °C, nanocrystalline TiO₂, TiO₂/WO₃, and WO₃ thin films with or without pores were prepared successfully. The heat-treated thin films were colorless and coloration-bleaching phenomena can be observed during cyclic voltammetry tests. The heat-treated thin films exhibited good reversible electrochromic behavior while the porous TiO₂/WO₃ composite film exhibited improved electrochromic properties.     

Patterning of ITO films on flexible substrates by using self-assembled monolayer

The patterning of indium tin oxide (ITO) films on flexible polyester (PET) substrates by using a self-assembled monolayer (SAM) of octadecyltrimethoxysilane (OTMS) was investigated. After a SAM is deposited on ITO films, the ITO surface hydrophilicity and electron transfer characteristics are altered. The contact angle and electrochemical cyclic voltammetry analyses indicate the optimal process to form a SAM on ITO films operated in a low-humidity environment at 25 ºC for 24 h. The AFM observation shows that the ITO films covered by a SAM can be protected during etching in an oxalic solution, which means a SAM can well play the role of a photoresist during lithographic process.     

APCVD法制备掺氮二氧化钛薄膜及其性能研究

采用常压化学气相沉积(APCVD)法,以四氯化钛(TiCl4)、氧气(O2)氨气(NH3)作为先驱体,成功制备了掺氮二氧化钛(TiO2)薄膜.通过对其进行扫描电镜(SEM)、X射线衍射(XRD)、紫外可见透过光谱(UV-VIS)研究后发现,氮掺杂后在二氧化钛薄膜中引入Ti4O7相,抑制了锐钛矿相向金红石相的转变,光吸收限发生红移,相应从365.8nm红移到了402.6nm,提高了薄膜在可见光照射下的光催化效率,并改善了薄膜表面的亲水性能.     

塑料基TiO2电致变色薄膜制备及性能研究

采用溶胶-凝胶法分别在镀有ITO透明电极的玻璃和塑料基体上制备了TiO2电致变色薄膜,对比研究了不同基体上溶胶的成膜性及薄膜的电致变色性能.结果表明:在相对湿度低于15%的环境中,采用0.4mol/L的溶胶可以通过多次提拉制得表面光洁的较厚透明TiO2薄膜;随热处理温度的升高,薄膜的电色可逆性变好,循环寿命变大,但离子储存能力下降;塑料基TiO2薄膜与相同条件下制备的玻璃基薄膜具有相似的性能,呈现出较弱的阴极电致变色效应和较强的Li 储存能力,有望用作柔性电致变色器件的对电极.     

Preparation and photocatalytic activity of N-doped TiO2 nanotube array films

The N-doped TiO₂ nanotube array films were fabricated directly by one-step electrochemical anodic oxidation of Ti foils in an HF electrolyte containing ammonium and nitrate ions. The as-prepared samples were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), energy dispersive spectrometer (EDX), and ultraviolet–visible (UV–vis) absorption spectroscopy, respectively. The photocatalytic activities were evaluated by the degradation of methyl orange (MO) under visible light irradiation. The results showed that N dopant was successfully introduced into the TiO₂ nanotube array films. The N-doped TiO₂ nanotube array films showed a red shift and an enhancement of the absorption in the visible light region compared to the undoped sample. The photocatalytic activities of the N-doped TiO₂ samples were much higher than those of the undoped sample. A maximum enhancement of photocatalytic activity was achieved for the N-doped TiO₂ sample prepared in 0.07 M HF electrolyte containing 1.0 M NH₄NO₃, and 81% of MO was degraded in 150 min under visible light irradiation.     

SiCN薄膜的制备及其性能研究

利用射频溅射法在Si衬底上制备了SiCN薄膜，并利用X射线衍射（XRD）、红外吸收谱（FTIR）和X射线光电子谱（XPS）对薄膜的结构、成份及化学键合状态进行了分析。结果表明，室温制备的SiCN薄膜为非晶状态，并形成了Si-C、Si-N和C－N键；而在高温下（衬底温度为800℃），薄膜中含有SiCN的晶体成分。此外，还利用原子力显微镜（AFM）对薄膜的表面形貌进行了研究，并进一步研究了样品的场发射性能。在场强为24V／μm时，最大发射电流可达3.3mA/cm^2。