阴极电压脉冲占空比对钛合金微弧氧化膜特性的影响

利用自制多功能微弧氧化电源,在保持双极性电压脉冲幅度不变的条件下,研究了阴极电压脉冲占空比（d_c）对钛合金微弧氧化膜特性的影响.结果表明：阴、阳极的峰值电流随处理时间的变化分为几个不同阶段,各阶段的开始和结束时间与d_c密切相关.氧化膜主要由金红石和锐钛矿相TiO₂组成,金红石相TiO₂的相对含量在d_c=50%附近随d_c的 关键词： 微弧氧化 钛合金 占空比     

电学参数对胶体中工业纯钛微弧氧化膜特性的影响

利用自制多功能微弧氧化(MAO)电源对处在胶体中的工业纯钛表面进行了MAO处理,比较系统地研究了电压脉冲的峰值(U)和占空比(d)对膜层的生长特性、微观结构、相结构和处理后试样耐腐蚀性能的影响.结果表明,随着U的增加或d的加大,膜厚几乎呈线性增加,膜表面微孔尺寸和粗糙度逐渐增大,微孔密度逐渐减小.膜层主要由致密层组成,除U=450V,d=10%时制备试样的膜层中含有少量锐钛矿相TiO2外,其他试样的膜层全由金红石相TiO2组成;在30%硫酸溶液中的耐腐蚀测试表明,MAO处理后试样的耐腐蚀性能与U和d密切相关,随着U的增加或d的加大,试样的耐腐蚀能力逐渐增强.     

工业纯钛微弧氧化膜的结构及拉曼光谱分析

采用微弧氧化技术,用处理电压为300, 350, 400, 450, 500 V在工业纯钛表面制备了5块氧化膜试样,利用扫描电镜和拉曼光谱研究了处理电压对氧化膜结构的影响。结果表明：氧化膜表面布满了微孔,其尺寸随处理电压的升高而增加,而微孔密度则呈相反的变化趋势。氧化膜主要由锐钛矿和金红石相组成,其相含量与处理电压的大小密切相关。当处理电压较低时,氧化膜主要由锐钛矿相组成; 随着处理电压的升高,氧化膜中金红石相的相对含量增加; 当处理电压在400～450 V时,金红石相含量增加迅速,并成为主晶相。     

多孔TiO2/Al/SiO2纳米复合结构的紫外光吸收特性研究

在SiO₂玻璃衬底上用脉冲激光沉积(PLD)技术,分别沉积Ti和Ti/Al膜,经电化学阳极氧化成功制备了多孔TiO₂/SiO₂和TiO₂/Al/SiO₂纳米复合结构. 其中TiO₂薄膜上的微孔阵列高度有序,分布均匀. 实验研究了Al过渡层对多孔TiO₂薄膜光吸收特性的影响. 结果表明：无Al过渡层的多孔TiO₂薄膜其紫外吸收峰在27 关键词： 2薄膜')" href="#">多孔TiO₂薄膜 阳极氧化 紫外光吸收     

电流密度对铝合金微弧氧化膜物理化学特性的影响

利用微弧氧化(MAO)技术，在LYl2铝合金上沉积了显微硬度达42.14GPa的超硬陶瓷膜.采用x射线衍射仪和显微硬度计研究了阳极电流密度j_a和阴极、阳极电流密度比j_c/j_a对MAO膜相构成和力学特性的影响.此外，利用扫描电子显微镜和恒电位仪分别对膜的微结构和抗点腐蚀特性进行了分析.结果表明，高j_a制备的膜主要含α-Al₂O₃相，低j_a制备的膜主要含γ-Al₂O₃相.显微硬度测试表明，这类膜有较高的硬度，但以j_a=15A/dm²和j_c/j_a=0.7制备的陶瓷膜硬度最高.抗点腐蚀测试表明，j_c/j_a对陶瓷膜的微结构有很强的影响. 关键词： 微弧氧化 显微硬度 电流密度 抗点腐蚀     

Microstructured hydroxyl environments and Raman spectroscopy in selected basic transition-metal halides

Raman vibrational spectra of the selected basic (hydroxyl OH and deuteroxyl OD) transition-metal halides, geometrically frustrated material series α-, β-, γ-Cu₂(OH)₃Cl, α-Cu₂(OH)₃Br, β-Ni₂(OH)₃Cl, β-Co₂(OH)₃Cl, β-Co₂(OH)₃Br, γ-Cu₂(OD)₃Cl, and β-Co₂(OD)₃Cl are measured at room temperature and analysed to investigate the relationship between the microstructured OH environments and their respective Raman spectra. Among these selected samples, the last two are used to determine the OH stretching vibration region (3600 cm^-1—3300 cm^-1) and OH bending vibration region (1000 cm^-1—600 cm^-1) of OH systems in the spectra. Through the comparative analysis of the distances d(metal—O), d(O—halogen), and d(OH), the strong metal—O interaction and trimeric hydrogen bond (C_3v, C_s or C₁ symmetry) are found in every material, but both determine simultaneously an ultimate d(OH), and therefore an OH stretching vibration frequency. According to the approximately linear relationship between the OH stretching vibration frequency and d(OH), some unavailable d(OH) are guessed and some doubtful d(OH) are suggested to be corrected. In addition, it is demonstrated in brief that the OH bending vibration frequency is also of importance to check the more detailed crystal microstructure relating to the OH group.     

萤石结构TiO2的电子结构和光学性质

利用第一性原理计算了立方相萤石TiO₂的晶胞参数,能带结构和电子态密度.结果显示萤石TiO₂属于间接带隙半导体材料,其间接禁带宽度(Γ→X)E_g为2.07eV,比常见的金红石和锐钛矿TiO₂的禁带宽度窄.为了更清楚地了解萤石的光学性质,利用Kramers-Kronig色散关系,分别对萤石和金红石TiO₂的复介电常数、吸收率等参数进行了计算,并将二者结果做了 关键词： 2')" href="#">萤石结构TiO₂ 密度泛函理论 能带结构 光学性质     

锐钛矿相和金红石相TiO2:Nb的光电性能研究

采用基于密度泛函理论的第一性原理计算了锐钛矿相和金红石相TiO₂:Nb的晶体结构、电子结构和光学性质. 结果表明, 在相等的摩尔掺杂浓度下(6.25%), 锐钛矿相TiO₂:Nb的导带底电子有效质量小于金红石相TiO₂:Nb, 且前者室温载流子浓度是后者的两倍左右, 即具有更大的施主杂质电离率, 从而解释了锐钛矿相TiO₂:Nb比金红石相TiO₂:Nb具有更优异电学性能的实验现象. 光学计算也表明锐钛矿相在可见光区有更大的透过率, 从而在理论上解释了锐钛矿相TiO₂:Nb比金红石相TiO₂:Nb更适于做透明导电材料的原因. 计算结果与实验数据能较好符合. 关键词： 2:Nb')" href="#">TiO₂:Nb 第一性原理 电子结构 光学性能     

多孔CeO2膜的制备及其光谱性能

以铈箔为原料,采用阳极氧化法和热处理法制备多孔的CeO₂膜。将阳极氧化铈膜分别在400,500和800 ℃下进行热处理,分别研究阳极氧化铈膜的晶体结构、组成和表面形貌,分别研究多孔的CeO₂膜红外光谱特征吸收和热膨胀性能。阳极氧化铈膜是Ce(OH)₃,CeF₃,Ce₂O₃,CeO₂和Ce的混合膜,并吸附水和乙二醇,其中Ce(OH)₃,CeF₃,Ce₂O₃分别为六方晶型结构,CeO₂和Ce分别为立方晶型结构。阳极氧化铈膜中的Ce(OH)₃,Ce₂O₃和Ce分别在400和500 ℃进行热处理时可能分别转变为CeO₂,分别在400和500 ℃热处理后的膜为CeF₃和CeO₂的混合膜。阳极氧化铈膜中的Ce(OH)₃,CeF₃,Ce₂O₃和Ce在800 ℃进行热处理时可能分别转变为CeO₂,在800 ℃热处理后的膜为CeO₂膜。该CeO₂膜是多孔的膜,且孔为直孔,在1 600～4 000 cm-1范围内具有强吸收。该CeO₂膜在170～900 ℃范围内热膨胀系数变化不大,该膜的热稳定性较好。     

C掺杂金红石相TiO2的电子结构和光学性质的第一性原理研究

运用第一性原理的局域密度近似+U(0 ≤U≤9 eV)方法研究了本征金红石相TiO₂在不同U值(对Ti-3d电子)下的禁带宽度、晶体结构以及不同比例C元素掺杂的金红石相TiO₂的电子结构和光学性质, 研究表明, TiO₂的禁带宽度和晶格常数随着U值的增加而增大. 综合考虑取U=3 eV并对其计算结果进行修正. 对于掺杂体系, 发现C 元素的掺杂在金红石相TiO₂中引入杂质能级, 杂质能级主要由O-2p轨道和C-2p轨道耦合形成, 杂质能级的引入可以增加TiO₂对可见光的响应, 从而使TiO₂的吸收范围增大. C原子掺杂最佳比例为8.3%, 此时光学吸收边的红移程度最明显, 可增大光吸收效率, 从而提高了TiO₂光催化效率.     

Growth characteristics of micro-plasma oxidation ceramic coatings on Ti alloy by inductively coupled plasma-atomic emission spectrometer technique

The aim of this work was to study the growth characteristics of micro-plasma oxidation ceramic coatings on Ti-6Al-4V alloy. Compound ceramic coatings were prepared on Ti-6Al-4V alloy by pulsed micro-plasma oxidation (MPO) in NaAlO₂ solution. The phase composition and surface morphology of the coating were investigated by X-ray diffractometry and scanning electron microscopy. The solution of Ti from the substrate and the content of Al in the electrolyte were studied by inductively coupled plasma-atomic emission spectrometer (ICP-AES) technique. Ti from the substrate dissolved and came into the coating and the electrolyte during MPO process. The content of Ti in the electrolyte under the pulsed bi-polar mode was more than that of the pulsed single-polar mode. The phase composition and structure of the coating was attributable to the space steric hindrance of Al congregated on the electrode surface due to the effect of the electric field and the electrolyte characters. For the pulsed single-polar mode, the coating was mainly composed of a large amount of α-Al₂O₃ and a small amount of γ-Al₂O₃. And the coating was mainly structured by Al from the electrolyte. However, the coating was composed of a large amount of Al₂TiO₅ and a little α-Al₂O₃ and rutile TiO₂ for the pulsed bi-polar mode. And the coating was structured both by Ti from the substrate and Al from the electrolyte.     

溶胶-凝胶法制备纳米多孔SiO2薄膜

以正硅酸乙酯(TEOS)为原料，采用旋转涂敷的方法，结合溶胶-凝胶技术在硅衬底上制备超低介电常数多孔SiO₂薄膜.采用两种不同的改性方法对薄膜表面进行改性，傅里 叶变换红外光谱分析发现改性后薄膜中含有大量的—CH₃键，从而减少了孔洞塌陷.用扫 描电子显微镜观察薄膜的表面形貌，发现薄膜内孔洞尺寸在70—80 nm之间.调节溶胶pH值，发现pH值越小凝胶时间越长.对改性样品热处理的结果表明，在300 ℃时介电常数最低达2.05. 关键词： 2')" href="#">多孔SiO₂ 低介电常数 溶胶-凝胶     

Hydroxyapatite Nano Sol Prepared via A Mechanochemical Route

Well-dispersed sol with crystalline hydroxyapatite (HAp) was obtained directly by milling a mixture comprising Ca(OH)₂, an aqueous solution of H₃PO₄ and a dispersant, an ammonium salt of polyacrylic acid. The average crystallite size of HAp was below 20 nm. Ca/P molar ratio of the product was 1.51 ± 0.04, i.e. Ca deficient from stoichiometric HAp. Minimum apparent viscosity was attained at a dispersant concentration 0.92wt% of sol. An as-milled sol was diluted by a factor 10–2.61 solid wt% to give a Newtonian fluid of 2 mPa s. From the diluted sol, we obtained a few m thick dense film of HAp by dip coating on the slide glass precoated by chitosan.     

Enhancement of photoluminescence emission intensity of zirconia thin films via aluminum doping for the application of solid state lighting in light emitting diode

Al doped ZrO₂ thin films were deposited on quartz substrates by sol–gel dip coating technique. X-ray diffraction pattern showed the deterioration of the crystallinity of the films with increase in Al doping concentration due to the formation of stress in the film. Scanning electron microscope images showed crack free surface. An average transmittance of >80% (in UV–vis region) was observed for all samples. Optical band gap was found to vary as a function of doping concentration. Photoluminescence spectra of the films exhibited an increase in the emission intensity with increase in Al doping concentration which is due to the increase in oxygen vacancies in the Al doped films. The “Blueshift” and “Redshift” of the PL spectra with increase in Al concentration originates from the change of stress in the films. The enhancement of PL intensity in the Al doped ZrO₂ thin films make it suitable for generation of solid state lighting in light emitting diode.     

Effect of sol concentration on the properties of ZnO thin films prepared by sol-gel technique

ZnO thin films are deposited on the glass substrates by sol-gel drain coating technique by varying the concentration of the sol. X-ray diffraction (XRD) and scanning electron microscopy (SEM) analysis were used to investigate the effect of sol concentration on the crystallinity and surface morphology of the films. The results show that with increase in sol concentration, the value of full width at half maximum (FWHM) of (0 0 2) peak decreases while the strain first increases and then decreases. The sol with higher concentration results in the increase in the grain size. The studies on the optical properties show that the band gap value increases from 3.27 to 3.3 eV when the sol concentration changes from 0.03 to 0.1 M. The photoconductivity studies reveal that the film for 0.05 M sol shows the maximum photoresponse for ultraviolet (UV) wavelength (<400 nm) which is co-related with the deep-level defects. The growth and decay of the photocurrent is found to be slowest for the same film.     

ICP-OES分析低钙粉煤灰在NaOH溶液中离子浸出规律

低钙粉煤灰潜在的火山灰活性释放缓慢限制了其大规模利用,通过碱激发提高粉煤灰中Si4+,Al3+和Ca2+等离子浸出率对于加快低钙粉煤灰活性释放具有积极作用。采用电感耦合等离子体发射光谱、傅里叶变换红外光谱、X射线衍射和扫描电子显微镜分别测试和分析了5种浓度NaOH溶液对低钙粉煤灰激发过程中Si4+,Al3+和Ca2+的浸出规律、化学基团变化、水化产物生成及微观形貌演化。结果表明：碱激发作用显著提高了低钙粉煤灰中Si4+,Al3+和Ca2+浸出率,三种离子浸出率大小为：Si4+＞Al3+＞Ca2+,其中Si4+和Al3+浸出率随NaOH浓度增加而增加,随浸出时间延长呈对数规律升高;Ca2+由于在NaOH溶液中生成Ca(OH)₂沉淀,其浸出率大小表现为在水中高,在NaOH溶液中低。红外光谱清晰地表征出低钙粉煤灰受碱激发作用后化学基团在指纹区(波数1 300 cm-1以下)的变化,且随碱激发时间的延长和碱浓度的增加变化愈加明显。水化产物和微观形貌的结果显示出粉煤灰颗粒表面受到碱侵蚀发生解聚,在OH-催化下,硅铝单体分子重新排列形成硅酸盐和铝酸盐低聚络合物,通过亲核取代反应形成铝硅酸盐的低聚态溶胶,并进一步与碱金属阳离子通过配位键或静电键的作用缩聚形成水化凝胶类产物。采用ICP-OES测试粉煤灰中离子浸出率可作为评价粉煤灰火山灰活性的一种快速和准确的方法。     

Microstructure and corrosion behavior of coated AZ91 alloy by microarc oxidation for biomedical application

Magnesium and its alloy currently are considered as the potential biodegradable implant materials, while the accelerated corrosion rate in intro environment leads to implant failure by losing the mechanical integrity before complete restoration. Dense oxide coatings formed in alkaline silicate electrolyte with and without titania sol addition were fabricated on magnesium alloy using microarc oxidation process. The microstructure, composition and degradation behavior in simulated body fluid (SBF) of the coated specimens were evaluated. It reveals that a small amount of TiO₂ is introduced into the as-deposited coating mainly composed of MgO and Mg₂SiO₄ by the addition of titania sol into based alkaline silicate electrolytic bath. With increasing concentration of titania sol from 0 to 10 vol.%, the coating thickness decreases from 22 to 18 μm. Electrochemical tests show that the E_corr of Mg substrate positively shifted about 300500 mV and i_corr lowers more than 100 times after microarc oxidation. However, the TiO₂ modified coatings formed in electrolyte containing 5 and 10 vol.% titania sol indicate an increasing worse corrosion resistance compared with that of the unmodified coating, which is possibly attributed to the increasing amorphous components caused by TiO₂ involvement. The long term immersing test in SBF is consistent with the electrochemical test, with the coated Mg alloy obviously slowing down the biodegradation rate, meanwhile accompanied by the increasing damage trends in the coatings modified by 5 and 10 vol.% titania sol.     

镁合金阳极氧化膜腐蚀特性的红外显微成像分析

采用显微红外成像技术对镁合金阳极氧化膜表面的腐蚀特性进行了研究。镁合金在7.3 Wt% Na₂SO₄溶液中浸泡后,表面氧化层中的部分MgO逐渐转化为Mg(OH)₂,进而发生溶解和脱落,使得镁合金失去保护作用。当浸泡时间达到2 h时,显微红外成像结果表明阳极氧化膜中Mg(OH)₂的红外吸收信号最强,Mg(OH)₂的含量最多。而4 h后Mg(OH)₂的红外吸收信号开始减弱,Mg(OH)₂开始减少,镁合金不断被腐蚀。氧化膜中另一成分Al₂O₃随浸泡时间的显微红外成像信息与Mg(OH)₂的变化规律相同。采用电化学阻抗谱技术对阳极氧化膜的阻抗进行测试,其阻抗随时间的变化特点基本符合氧化膜腐蚀规律。本研究对于镁合金阳极氧化膜的表征具有很好的指导作用和推广应用价值。     

Influence of FeSO4 concentration on thermal emissivity of coatings formed on titanium alloy by micro-arc oxidation

Ceramic coatings with high emission were fabricated on Ti6Al4V alloy by microarc oxidation (MAO) with additive FeSO₄ into the electrolyte. The microstructure, chemical composition and chemical state of the coatings were determined by SEM, XRD, EDS and XPS, respectively. The bonding strength between the coating and substrate was studied by tensile strength test, together with the thermal shock resistance of the coating. The results showed that Fe content in the coating layer significantly affect its thermal emissivity. The relative content of Fe in the coatings surface increased at first and then decreased with increasing the concentration of FeSO₄ in electrolytes, so does the emissivity of the coatings. The bonding strength became weaker with increasing the concentration of FeSO₄. In addition, the coating remains stable over 40 cycles of thermal shocking. The coating formed at 3 g/L FeSO₄ demonstrates the highest an average spectral emissivity value around of 0.87, and bonding strength higher than 33 MPa.