电泳沉积法制备钛酸纳米管膜层

采用水热合成法制备钛酸钠纳米管,然后依次与HNO3,正四丁基氢氧化铵水溶液(TBAOH)离子交换后,经过高速离心,将所得沉淀物分散于无水乙醇溶液中,并应用电泳沉积的方法成功地在不锈钢或导电玻璃表面构筑了钛酸纳米管薄膜.采用TEM、XRD、SEM及EDS等对纳米管薄膜的表面形貌、结构和组成等进行表征.结果表明,电泳沉积法制备钛酸纳米管薄膜致密均匀、厚度可控并与基体结合力良好;经高温烧结后,形貌基本保持不变,可望成为一种新的功能材料.文中还对纳米管薄膜的形成机理进行了讨论.     

间歇碾磨在钛酸纳米管水热合成中的作用

针对静态水热法合成的钛酸纳米管纯度较低的缺点,在钛酸纳米管的水热合成过程中引入间歇碾磨步骤,显著提高了钛酸纳米管的纯度.通过X射线衍射(XRD)、透射电子显微镜(TEM)/高分辨透射电子显微镜(HRTEM)、比表面积测定等手段对钛酸纳米管的结构和性质进行了表征.结果表明,与静态水热法相比,在钛酸纳米管的水热合成过程中引入间歇碾磨步骤后不仅使所合成的钛酸纳米管的纯度明显提高,而且使纳米管的比表面积和热稳定性明显增加.     

钛酸纳米管的制备及 TEM表征

采用水热合成法以金红石型纳米TiO2粉为原料制备钛酸纳米管，考察了搅拌、酸洗及焙烧温度对纳米管的形成和结构的影响，并通过TEM观察了产物的形貌、结构．结果显示：持续搅拌能促进原料粉末的定向生长，有利于形成钛酸纳米片；酸洗是纳米管的形成阶段；300℃是纳米管转变为长棒状晶柱的临界温度．实验表明以优化的水热合成法制得的纳米管形貌均一，长度超过1μm，钛酸纳米管长径比为125：1．     

超薄钛酸铅纳米管铁电性和力电耦合特性的第一性原理研究

利用基于密度泛函理论的第一性原理的方法研究了超薄钛酸铅(PbTiO₃)纳米管的铁电性及力电耦合特性。研究发现对于钛酸铅铁电纳米管结构, 即使在其特征尺寸小于铁电薄膜的铁电临界尺寸时, 依然存在自发极化。钛酸铅铁电纳米管结构不存在铁电临界尺寸。对纳米管力电耦合效应的研究发现, 轴向应变作用会引起包括极化沿轴向方向的铁电相、顺电相和极化沿周向方向的铁电相在内的丰富的相转变。这种相的转变是由于轴向应力所导致的Pb-O共价键的变化所引起的。另一方面, 研究了钛酸铅纳米管结构的机械强度, 明确了在轴向拉伸和压缩作用下纳米管的临界载荷。     

多孔氧化铝模板结合sol-gel旋转涂敷法制备PZT纳米管

利用溶胶-凝胶旋转涂敷法在通孔的多孔阳极氧化铝(PAA)模板中制备了锆钛酸铅(PZT)纳米管,研究了溶胶浓度对样品形貌的影响。利用SEM和TEM观察了纳米管阵列和单根纳米管的形貌,采用XRD和EDS图谱分析了纳米管的相结构和化学元素组成。结果表明合成的PZT纳米管结晶良好,具有钙钛矿结构(属于四方晶系);纳米管具有较高的韧性但表面较粗糙,直径和管壁厚度分别约为75和7nm,直径与原始PAA模板的孔径相吻合。在一定范围内调节PZT溶胶的浓度(0.1～0.4mol/L),均能在PAA模板的孔洞中形成PZT多晶纳米管,且组成PZT纳米管的晶粒随着溶胶浓度的增加而变大。     

微波水热法合成钛酸钠盐纳米管

采用微波水热法合成了钛酸钠盐纳米管,考察了原料、反应时间、NaOH浓度等主要影响因素.在微波功率195W、NaOH浓度8—12mol/L、反应时间>70min条件下,得到了形貌均一的钛酸钠盐纳米管,并用TEM、XRD、BET、EDAX和N₂吸附/脱附等对产物进行了表征.研究表明,微波法制得的纳米管合成时间短、热稳定性高,其管壁塌陷温度高于500℃,比普通水热法合成的高100℃左右;所得样品在300℃以上煅烧,可转化为单晶钛酸纳盐纳米管.     

科学家用聚焦激光束改变TiO_2纳米管状结构的折射率

正二氧化钛纳米管(titanium dioxide,TiO2)广泛使用于空气净化、自洁表面制作、光伏装置、感知器以及生医领域。摩尔多瓦、澳洲与英国研究人员最近开发出一种新方法,利用聚焦激光束改变这些纳米管状结构的折射率,此结果能进一步扩展这些材料的应用潜能。此新技术使用聚焦激光束直接照射在TiO2纳米管薄膜表面上,光束所造成的热能可控制薄膜的局部结晶结构,因     

钛酸钾一维纳米结构的构筑及表征

以锐钛矿TiO2为起始原料,通过水热法制备了钛酸钾纳米管/棒,研究了在不同时间内合成不同长度和宽度的钛酸钾纳米管/棒的机理和形态的控制条件。用X射线衍射(XRD)和扫描电子显微镜(SEM)对其结构和形貌进行了表征。实验结果表明水热处理时间对产物形貌的控制有重要影响。处理温度在200℃下,不同的反应阶段得到钛酸钾不规则块状体、纳米管、纳米棒等结构。发现水热处理时间能对钛酸钾特定结构进行有效的控制,确定了水热处理时间和钛酸钾形貌结构的关系,从而可以通过选择反应的合理处理时间和温度,得到特定的钛酸钾纳米结构。此外还对比研究了后处理中加入酸处理时对产物的形貌和晶体结构的影响,发现酸处理过程中H+可取代K+,使得原来的单斜晶体K2Ti6O13转变为H2Ti3O7,从而让纳米棒表面更规整光滑。最后采用紫外-可见吸收光谱对比研究了各个阶段产物的光吸收性能。     

斜切基片上c-取向YBa2Cu3O7-δ薄膜的生长特性及开裂行为

用脉冲激光沉积方法在斜切SrTiO3(001)基片上制备了YBa2Cu3O7-δ薄膜,并用原子力显微镜、X射线衍射仪及透射电镜研究了薄膜表面形貌、取向特征、结晶性和显微结构.结果表明,薄膜表面呈"台阶-台面"结构,并伴有与台阶边缘垂直的裂纹产生,说明薄膜以"台阶流动"方式生长;而且薄膜具有c-轴取向,但其结晶性不好.在薄膜中没有观察到a-b孪晶的存在.薄膜的开裂和结晶性较差均是由于斜切基片台阶表面晶格四方畸变抑制了薄膜正交转变时a-b孪晶的产生,而使晶格错配应变不能释放造成的.     

用纳米级铁粒子作催化剂以色列研究人员发明制备纳米管新方法

沿着蓝宝石表面下不平整的原子级台阶来制备碳纳米管，这是以色列魏兹曼研究院的研究人员新近发明的一种制备纳米管新方法。     

Ultrathin ZnO nanostructures synthesized by thermal oxidation of hexagonal Zn micro/nanostructures

Ultrathin (<5 nm) ZnO nanobelts, as well as porous nanotubes/nanosheets were successfully synthesized via a very simple process: thermal oxidation of hexagonal Zn micro/nanostructures in a tube furnace in 50 sccm N2 flow. The ZnO nanobelt clusters were largely grown from the (0001) end surface of the Zn nanoprisms at 300 degrees C. The porous nanotubes and nanosheets were formed on the downstream substrate by 370-400 degrees C thermal oxidation of Zn films in low pressure. These structures are related to the anisotropic oxidation of Zn and differences of melting point between Zn and ZnO. We propose that the ultrathin nanobelts were formed in a vapor-liquid-solid process while the ultrathin nanotubes and nanosheets were formed via a vapor-solid-resublimation process. The structure of the nanostructures was characterized by transmission electron microscopy. The ultrathin mesoporous nanotubes and nanosheets have been found to possess rich surface defects. These structures may have potential applications in gas sensors, catalysts and hydrogen storage due to their large specific surface area.     

Nanotubular oxide surface and layer formed on the Ti-35Ta-xZr alloys for biomaterials

Titanium and its alloys are widely used as a dental implant material in clinical dentistry and as an orthopedic implant materials due to their good mechanical properties, corrosion resistance, and biocompatibility. In this study, nanotubular oxide surface and layer formed on the Ti-35Ta-xZr alloys for biomaterials have been investigated by using electrochemical methods. Ti-35Ta-xZr alloys were prepared by arc melting and heat treated for 24 hr at 1000 degrees C in argon atmosphere, and then water quenching. Ti oxide nanotubes were formed on the Ti-35Ta-xZr alloys by anodizing in H3PO4 containing 0.8 wt% NaF solution at 25 degrees C. Anodization was carried out using a scanning potentiostat. Microstructures of the alloys and nanotube surface were examined by FE-SEM, EDX, and XRD. Crystallization treatment of nanotube surface was carried out for 3 hr at 450 degrees C. Microstructures of the Ti-35Ta-xZr alloys were changed from beta phase to alpha' phase, and changed from an equiaxed to a needle-like structure with increasing Zr content. Nanotubular oxide surface and layers consisting of highly ordered nanotubes with a wide range of diameters (approximately 150-200 nm) and lengths (approximately 4-10 microm) can be formed on alloys in the Ti-35Ta-xZr alloys with Zr content. As the Zr content increased from 3% to 15%, length of step between the bamboo knob-like had increasing values of approximately 50 nm, 80 nm, and 140 nm, respectively. The nanotubes formed on the Ti-35Ta-xZr alloy surface were amorphous structure before heat treatment, but oxide surface had mainly an anatase structure by heat treatment.     

Study of step instability on Si surfaces

Step instabilities on Si(1 1 1) vicinal surface and Si(1 1 1) vicinal surface induced by Au adsorption were observed by reflection electron microscopy. On the Si(0 0 1) vicinal surface faceting of (0 0 1) surface due to surface reconstruction takes place and surface steps are bunching. The kinetics of mass transport of Si depends on the substrate temperature and steps are impermeable for Si adatoms at lower temperature and they are permeable at higher temperature. On the Si(1 1 1) vicinal surface the permeability of steps depends on the heating current direction. The steps are permeable for step-up current heating and are impermeable for step-down current heating. Above a critical coverage of Au (≈0.3 ML) steps are bunching irrespective of heating current direction and periodic array of extremely straight step bands is formed for the step-down current heating.     

Frequency and Size Dependences of Superfluidity in?Low-Dimensional 4He Fluids

We have studied superfluidity of ⁴He fluids in two- and one-dimensional states. In the 2D state of the ⁴He films on flat substrate, superfluidity was observed in the normal fluid state above the 2D Kosterlitz-Thouless temperature at high measurement frequencies. The superfluidity in 2D also depends on the system size, e.g. pore diameter of porous glasses and grain size of powder. The 1D state was realized for ⁴He fluid nanotubes formed in 1D nanopores 1.8?C4.7 nm in diameter and about 300 nm in length. Superfluidity in the 1D state was observed by the torsional oscillator experiment. The results are qualitatively well reproduced by the Monte Carlo calculation for a classical XY spin system modeled on the present ⁴He nanotubes. Although the 1D state is in the normal fluid state at any finite low temperatures due to the 1D phonon fluctuation, the superfluid frequency shift ??f of the oscillator can be observed. Above a temperature, ??f decreases due to another kind of 1D thermal fluctuation of which excitations destroy the phase coherence in the nanotubes. The excitations depend on the tube length as well as the tube diameter.     

窄直径分布竹节状纳米碳管膜的制备和表征

采用短时间一次阳极氧化法制备了纳米级孔氧化铝(AAO)模板,有效地缩短了模板的制备时间,获得的AAO模板孔洞排列有序程度虽有所下降,但分布依然均匀.该模板有效地增加了表面积,为金属沉积提供了均匀的纳米孔洞.采用电沉积法在AAO模板上沉积了颗粒尺寸一致且分布均匀的钴催化剂层后,用CVD法在该模板上生长纳米碳管.经SEM和TEM观察,所制得的纳米碳管密度高直径分布均匀,具有单一的竹节状结构,而且直径远小于孔径.试用了生长动力学来解释这种竹节状纳米碳管的形成原因.     

Effect of bath type on the formation of TiO2 nanotubes in fluoride containing aqueous solution

TiO2 nanotubes were formed on Ti electrochemically by the application of anodic current in 1 M H3PO4 + 0.3 M HF solution in a glass and Teflon bath. The TiO2 nanotubes could be partly grown in the glass bath while a uniform growth of TiO2 nanotubes was observed over the whole surface in the Teflon bath. The TiO2 nanotubes fabricated in the glass bath broke off readily during ultrasonic cleaning in distilled water while the TiO2 nanotubes formed in the Teflon bath was not damaged by the ultrasonic cleaning up to 5 minutes. The ultrasonic cleaning could remove the surface residuals which are obtained inevitably if TiO2 nanotubes are fabricated in aqueous solutions.     

Electrochemical characteristics of nanotubes formed on Ti-Nb alloys

Titanium and Ti alloys have been used extensively as bone-implant materials due to their high strength-to-weight ratio, good biocompatibility and excellent corrosion resistance. In this work, we have investigated the effects of the β-stabilizing element Nb on the morphology of nanotubes formed on Ti-xNb alloys using 1.0 M H₃PO₄ electrolyte containing 0.8 wt.% NaF and various electrochemical methods. Oxide layers consisting of highly ordered nanotubes with a wide range of diameters (approximately 55-220 nm) and lengths (approximately 730 nm-2 μm) can be formed on alloys in the Ti-xNb system as a function of Nb content. The nanotubes formed on the Ti-Nb alloy surface were transformed from the anatase to rutile structure of titanium oxide. The titanium oxide nanotube surface was observed to have lower corrosion resistance in 0.9% NaCl solution compared to titanium oxides surfaces on Ti-xNb alloys without the nanotube morphology.     

Controlling the synthetic pathways of TiO2-derived nanostructured materials

A comprehensive study of the hydrothermal synthesis of TiO2-derived nanostructured materials, including layered protonic trititanate (H2Ti3O7), metal-ion exchangeable titanate (Na(x)H(2-x)Ti3O7), TiO2(B) and anatase nanotubes and TiO2-anatase nanowires, was conducted. Nanoscaled tubular structures were found to be already present in the samples derived from prolonged hydrothermal process of bulk anatase TiO2 and could be converted to various types of nanotubes, nanowires or nanorodes by post-synthesis treatments. 0.1 M HCI acid wash and air annealing were the two key parameters to select the types of nanotubes/nanowires as the final products. XRD, Raman, TG, and XPS core level and valence band studies were carried out to elucidate our proposed synthetic pathways.     

Adsorption and desorption of CO on Ni decorated stepped Rh(553)

Vicinal surfaces are important in surface science, as they show interesting electronic structures and reactivities due to the steps. In this paper the adsorption and desorption of carbon monoxide on the stepped Rh(553) surface decorated with Ni is reported. With 0.1 to 0.3 monolayer Ni on Rh(553) one and two atoms broad Ni wires along the Rh steps are formed. The adsorption and desorption of carbon monoxide on these surfaces is investigated using thermal desorption spectroscopy (TDS) and reflection absorption infra red spectroscopy (RAIRS). TDS shows a marked change from just one broad TDS peak on pure Rh(553) to 4 distinct peaks with increasing Ni decoration. RAIRS shows that already at 0.1 monolayer Ni the CO adsorption states on bridge sites on the Rh step atoms are completely quenched. In addition it is shown that with Ni films up to 3 monolayer the on top adsorption sites for CO on Ni are preferred over the bridge and hollow adsorption sites in contrast to what is known from the Ni(111) surface.     

Adsorption and desorption of CO on Ni decorated stepped Rh(553)

Vicinal surfaces are important in surface science, as they show interesting electronic structures and reactivities due to the steps. In this paper the adsorption and desorption of carbon monoxide on the stepped Rh(553) surface decorated with Ni is reported. With 0.1 to 0.3 monolayer Ni on Rh(553) one and two atoms broad Ni wires along the Rh steps are formed. The adsorption and desorption of carbon monoxide on these surfaces is investigated using thermal desorption spectroscopy (TDS) and reflection absorption infra red spectroscopy (RAIRS). TDS shows a marked change from just one broad TDS peak on pure Rh(553) to 4 distinct peaks with increasing Ni decoration. RAIRS shows that already at 0.1 monolayer Ni the CO adsorption states on bridge sites on the Rh step atoms are completely quenched. In addition it is shown that with Ni films up to 3 monolayer the on top adsorption sites for CO on Ni are preferred over the bridge and hollow adsorption sites in contrast to what is known from the Ni(111) surface.