Novel mixed method for the electrochemical deposition of thick layers of Bi2+xTe3−x with controlled stoichiometry

A new method for the electrochemical deposition of Bi_2+xTe_3−x is presented, which combines voltage-controlled deposition pulses with current-controlled resting pulses. This method is based on results of a comprehensive electrochemical investigation including cyclic voltammetry, chronoamperometry and chronopotentiometry, which has been performed on the system Bi and Te on Pt in 2 M HNO₃. The influence of electrolyte composition, deposition potential and deposition pulse duration on morphology and stoichiometry of the deposited material as well as the variation of the composition over the thickness of the layer has been investigated by means of SEM and EDX. The crystal structure was examined with XRD. Layers deposited with the new method show a constant and reproducible stoichiometry over their entire thickness. Layers of up to 800 μm thickness deposited with deposition rates of up to 50 μm/h have been achieved. The composition and hence the thermoelectric behavior may be adjusted via electrolyte composition or the deposition potential. Fabrication of n-type and, for the first time, p-type Bi_2+xTe_3−x is demonstrated and verified by measurements of the Seebeck coefficients. The suitability of the proposed method for low-cost fabrication of micro-thermoelectric devices is shown. The advantages of this method may also apply for electrochemical deposition of other binary or ternary compounds.     

Synthesis of Bi2Te3 nanopowders by vacuum arc plasma evaporation

Starting from elemental bismuth and tellurium, bismuth telluride (Bi₂Te₃) nanopowders were successfully prepared by vacuum arc plasma evaporation (VAPE) technique for the first time. The phase composition in the obtained nanopowders is closely related with the Bi:Te atomic ratio in starting precursor. The microstructure and morphology of the samples were characterized via X-ray diffraction (XRD), transmission electron microscopy (TEM) and selected area electron diffraction (SAED). Compositional analysis was also carried out by energy dispersive analysis of X-rays (EDAX). The as-synthesized Bi₂Te₃ nanopowders have a rhombohedral crystal structure with lattice parameters a = 4.381 Å and c = 30.310 Å. The average particle size is about 35 nm obtained from TEM and confirmed from XRD results.     

Orientation-controlled synthesis and characterization of Bi2Te3 nanofilms, and nanowires via electrochemical co-deposition

An electrochemical deposition technique based on co-deposition was used to deposit preferentially oriented Bi₂Te₃ nanostructures (nanofilm, and nanowire). The shared underpotential deposition (UPD) potentials for both Bi and Te co-deposition were determined by cyclic voltammetric measurements. The scanning probe microscopy (scanning tunneling microscopy (STM) and atomic force microscopy (AFM)) and the X-ray diffraction (XRD) data indicated that the electrodeposition of Bi₂Te₃ results in nanofilm-structured deposits with a preferential orientation at (0 1 5) and nanowired-structured deposits with a preferential orientation at (1 1 0) in acidic and basic (in the presence of ethylenediaminetetraacetic acid (EDTA)) medium, respectively. The results show that the nucleation and growth mechanism follows 3D mode in acidic solutions and 2D mode in basic solution containing EDTA additive. The optical characterization performed by reflection absorption Fourier transform infrared (RA-FTIR) spectroscopy showed that the band gap energy of Bi₂Te₃ nanostructures depends on the thickness, size, and shape of the nanostructures and the band gap increases as the deposition time decreases. Moreover, the quantum confinement is strengthened in the wire-like deposits relative to the film-like deposits. Energy dispersive X-ray spectroscopy (EDS) analysis demonstrated that Bi₂Te₃ nanostructures were always in 2:3 stoichiometry, and they were made up of only pure Bi and Te.     

The underpotential deposition of Bi2Te3−ySey thin films by an electrochemical co-deposition method

Bi₂Te_3−ySe_y thin films were grown on Au(1 1 1) substrates using an electrochemical co-deposition method at 25 °C. The appropriate co-deposition potentials based on the underpotential deposition (upd) potentials of Bi, Te and Se have been determined by the cyclic voltammetric studies. The films were grown from an electrolyte of 2.5 mM Bi(NO₃)₃, 2 mM TeO₂, and 0.3 mM SeO₂ in 0.1 M HNO₃ at a potential of −0.02 V vs. Ag|AgCl (3 M NaCl). X-ray diffraction (XRD), scanning electron microscopy (SEM), and energy dispersive spectroscopy (EDS) were employed to characterize the thin films. XRD and EDS results revealed that the films are single phase with approximate composition of Bi₂Te_2.7Se_0.3. SEM studies showed that the films are homogeneous and have micronsized granular crystallites.     

Nano-scale surface of ZrO2 ceramics achieved efficiently by peanut-shaped and heart-shaped SiO2 abrasives through chemical mechanical polishing

Zirconia ceramics are regarded as the best development target for 5G mobile phone rear covers. However, it is necessary and urgent to improve the surface quality and processing efficiency of zirconia ceramics. Non-spherical silica abrasives were prepared by the KH550 induction method and were used in chemical mechanical polishing (CMP) of zirconia ceramics for the first time. While achieving low surface roughness of 1.9 nm, it has an efficient polishing rate of 0.31 μm/h which is superior to conventional abrasives. Silica particles are peanut-shaped and heart-shaped in the scanning electron microscopy image, and its distinctive morphology provides the possibility of its excellent polishing performance. X-ray photoelectron spectroscopy analysis shows that during the CMP process, silica abrasives and zirconia ceramic undergo a solid phase chemical reaction to form ZrSiO₄. At the same time, the contact wear model established in combination with the coefficient of friction indicates that the two-dimensional surface contact mode of non-spherical silica abrasives on the surface of zirconia ceramics greatly improves its mechanical effect.     

Study on the preparation of Mg-Li-Zn alloys by electrochemical codeposition from LiCl-KCl-MgCl2-ZnCl2 melts

Electrochemical codeposition of Mg, Li, and Zn on a molybdenum electrode in LiCl-KCl-MgCl₂-ZnCl₂ melts at 943 K to form Mg-Li-Zn alloys was investigated. Cyclic voltammograms (CVs) showed that the potential of Li metal deposition, after the addition of MgCl₂ and ZnCl₂, is more positive than the one of Li metal deposition before the addition. Chronopotentiometry measurements indicated that the codeposition of Mg, Li, and Zn occurs at current densities lower than −0.78 A cm⁻² in LiCl-KCl-MgCl₂ (8 wt.%) melts containing 1 wt.% ZnCl₂. Chronoamperograms demonstrated that the onset potential for the codeposition of Mg, Li, and Zn is −2.000 V, and the codeposition of Mg, Li, and Zn is formed when the applied potentials are more negative than −2.000 V. X-ray diffraction (XRD) indicated that Mg-Li-Zn alloys with different phases were prepared via galvanostatic electrolysis. The microstructure of typical α + β phase of Mg-Li-Zn alloy was characterized by optical microscope (OM) and scanning electron microscopy (SEM). The analysis of energy dispersive spectrometry (EDS) showed that the elements of Mg and Zn distribute homogeneously in the Mg-Li-Zn alloy. The results of inductively coupled plasma analysis showed that the chemical compositions of Mg-Li-Zn alloys are consistent with the phase structures of the XRD patterns, and that the lithium and zincum contents of Mg-Li-Zn alloys depend on the concentrations of MgCl₂ and ZnCl₂.     

Synthesis of high surface area Al2O3-CeO2 composite nanopowder via inverse co-precipitation method

In the present work, Al₂O₃-CeO₂ composite nanopowder was synthesized by inverse co-precipitation method using metal chlorides, aluminum powder and NH₄OH as precipitant agent. The thermal decomposition of the precipitate and subsequent formation of Al₂O₃-CeO₂ were investigated by X-ray diffractometery, scanning electron microscopy, thermogravimetric and differential thermal analysis, Brunauer-Emmett-Teller surface area measurement and Fourier transform infrared spectroscopy. The results showed that the presence of ceria suppressed the formation of α-Al₂O₃. The BET-specific surface area was 173 m²/g for powders calcined at 800 °C. The particle size examined by using scanning electron microscopy was in the range 30-70 nm. The activation energy of Al₂O₃-15 wt.% CeO₂ nanocrystallite growth during calcination was measured to be 32.4 kJ/mol whereas that of Al₂O₃ was about 23.8 kJ/mol.     

Synthesis and Thermoelectric Properties of Bi2Se3 Nanostructures

Bismuth selenide (Bi₂Se₃) nanostructures were synthesized via solvothermal method. The crystallinity of the as-synthesized sample has been analyzed by X-ray diffraction, which shows the formation of rhombohedral Bi₂Se₃. Electron microscopy examination indicates that the Bi₂Se₃ nanoparticles have hexagonal flake-like shape. The effect of the synthesis temperature on the morphology of the Bi₂Se₃ nanostructures has also been investigated. It is found that the particle size increases with the synthesis temperature. Thermoelectric properties of the Bi₂Se₃ nanostructures were also measured, and the maximum value of dimensionless figure of merit (ZT) of 0.096 was obtained at 523 K.     

Effect of double doping on crystal structure and electrical conductivity of CaO and WO3-doped Bi2O3

The atomic arrangement of WO₃-doped Bi₂O₃ was found similar to that of the fluorite structure. However, the electrical conductivity of WO₃-doped Bi₂O₃ is significantly lower than that of commonly used Y₂O₃-doped Bi₂O₃. The structure and electrical conductivity of samples formulated as (Ca_xW_0.15Bi_0.85−x)₂O_3.45−x (x = 0, 0.1, 0.2 and 0.3) were investigated. The as-sintered (W_0.15Bi_0.85)₂O_3.45 and (Ca_0.1W_0.15Bi_0.75)₂O_3.35 exhibit similar single tetragonal structure that is isostructural with 7Bi₂O₃·2WO₃. Therefore, (W_0.15Bi_0.85)₂O_3.45 and (Ca_0.1W_0.15Bi_0.75)₂O_3.35 formed a superstructure consisting of 10 enlarged cubic fluorite subcells. However, the as-sintered samples consist of a tetragonal structure and tetragonal CaWO₄ for x = 0.2 and 0.3 because the oxygen vacancy concentration increases. The conductivities of (Ca_xW_0.15Bi_0.85−x)₂O_3.45−x (x = 0, 0.1, 0.2 and 0.3) did not exhibit linear dependence with x value. The best conductivity is 2.35 × 10⁻² S cm⁻¹ at 700 °C for x = 0.1 that is higher than that of Ca-free (W_0.15Bi_0.85)₂O_3.45. The higher conductivity of (Ca_0.1W_0.15Bi_0.75)₂O_3.35 than (W_0.15Bi_0.85)₂O_3.45 may result from the higher anion vacancy concentration and more symmetrical structure.     

Evaluation of the role played by bismuth molybdates in Bi2Sn2O7–MoO3 catalysts used for partial oxidation of isobutene to methacrolein

The catalytic behaviour of multiphasic catalysts based on -bismuth pyrostannate, Bi₂Sn₂O₇, was investigated in the selective oxidation of isobutene into methacrolein. When -Bi₂Sn₂O₇ is mixed with MoO₃, strong cooperation effects on the yield and selectivity in methacrolein occur. However, XRD analyses performed on samples after test revealed the formation of a low quantity of -bismuth molybdate, -Bi₂Mo₃O₁₂, when the reaction temperature exceeded 673 K. Additional experiments were therefore carried out on the “Bi–Sn–Mo–O” catalysts in order to shed light on the role of Bi₂Mo₃O₁₂ in the synergetic effects observed in the Bi₂Sn₂O₇–MoO₃ system. The experimental results are discussed in terms of several hypotheses. First, the intrinsic activity of Bi₂Mo₃ O₁₂ is probably the simplest explanation for the synergetic effects, although experiments have shown that this phase present in a low quantity is only poorly active. Second, catalytic tests made on Bi₂Sn₂O₇–Bi₂Mo₃O₁₂ mechanical mixtures have evidenced a cooperation between these two ternary oxides, particularly when Bi₂Sn₂O₇ was the major component of the mixture. Consequently, it is likely that a synergy between Bi₂Sn₂O₇ and the in situ generated Bi₂Mo₃O₁₂ might play a role in the synergy observed in the Bi₂Sn₂O₇–MoO₃ association. Third, as bismuth pyrostannate was previously shown to behave as an oxygen donor phase with respect to WO₃, a remote control mechanism could therefore occur between Bi₂Sn₂O₇ and MoO₃, independently from the formation of -Bi₂Mo₃O₁₂.     

Self-assembly preparation of popcorn-like colloidal silica and its application on chemical mechanical polishing of zirconia ceramic

Traditional mobile phone backplane materials are difficult to meet the requirements of the 5G era, and zirconia ceramic is one of the most promising backplane materials. However, its precision machining is difficult due to the hard and brittle nature. In this work, a novel popcorn-like colloidal silica was prepared by the self-assembly growth of nanoparticles for chemical mechanical polishing of the yttria-stabilized tetragonal zirconia ceramic sheets. The surface of the popcorn-like colloidal silica particles has a noticeably uneven shape, and the particle size distribution is uniform. The chemical mechanical polishing results show that the material removal rate of the prepared popcorn-like colloidal silica is increased by about 50% compared with the spherical colloidal silica, and the surface morphology is also obtained improvement. In the process of chemical mechanical polishing, the particles form multi-point contact with the ceramic sheet, resulting in an increase in the coefficient of friction, which is beneficial to the tribochemical reaction. In addition, multi-point contact can distribute the load, make the indentation shallower, and help reduce mechanical scratches. In general, the expected results are expected to provide experimental basis for the optimization of the structure of chemical mechanical polishing abrasive particles.     

Composition-dependent characterization and optimal control of electrodeposited Bi2Te3 films for thermoelectric application

A method to control composition of Bi₂Te₃ films by mass transfer manipulation has been developed. The film composition can be varied by a diffusion-controlled method, which is related to the change of Bi³⁺/HTeO₂⁺ ratios in a controlled diffusion layer. A homogeneous and dense film with precise chemical composition could thus be obtained under constant electrode polarization. Meanwhile, the solo dependence of film properties on composition change of both Te-rich and Bi-rich films were investigated. Firstly, the studies of XRD and FE-SEM showed that different Te contents in deposit would lead to different dimensions of unit cell and grain sizes. The Seebeck coefficient increased apparently when the Te content was over 60 at.% Te. Te-rich films had higher carrier concentration but slower mobility than Bi-rich films. Inverse relations were observed between carrier concentration and carrier mobility and between Seebeck coefficient and conductivity. Therefore, an optimal power factor of 7 × 10⁻⁴ W/m K² was realized near the stoichiometric Bi₂Te₃.     

Fabrication and electrical properties of Bi2-xSbxTe3 ternary nanopillars array films

Highly oriented Bi_2-xSb_xTe₃ (x?=?0, 0.7, 1.1, 1.5, 2) ternary nanocrystalline films were fabricated using vacuum thermal evaporation method. Microstructures and morphologies indicate that Bi_2-xSb_xTe₃ films have pure rhombohedral phase with well-ordered nanopillars array. Bi, Sb and Te atoms uniformly distributed throughtout films with no precipitation. Electrical conductivity of Bi_2-xSb_xTe₃ films transforms from n-type to p-type when x?>?1.1. Metal-insulator transition was observed due to the incorporation of Sb in Bi₂Te₃. Bi_2-xSb_xTe₃ film with x?=?1.5 exhibits optimized electrical properties with maximum electrical conductivity σ of 2.95?×?10⁵ S?m^?1 at T?=?300?K, which is approximately ten times higher than that of the undoped Bi₂Te₃ film, and three times higher than previous report for Bi_0.5Sb_1.5Te₃ films and bulk materials. The maximum power factor PF of Bi_0.5Sb_1.5Te₃ nanopillars array film is about 3.83?μW?cm^?1 K^?2 at T?=?475?K. Highly oriented (Bi,Sb)₂Te₃ nanocrystalline films with tuned electronic transport properties have potentials in thermoelectric devices.     

Preparation of Au2S3 and nanocrystalline gold by sonochemical method

We report a new synthesis of Au₂S₃ by a sonochemical reaction between Au(CH₃COO)₃ and S in decalin at room temperature in nitrogen atmosphere. When gold acetate is sonicated under similar conditions without the presence of sulfur, nanocrystalline gold is formed. The products were characterized by X-ray powder diffraction, transmission electron microscope and thermal analysis (TG and DSC). The synthesis procedure is substantially simpler than the previously reported methods.     

Correlation between microstructure,chemical components and tribological properties of plasma-sprayed Cr2O3-based coatings

The wear resistance of chromium oxide (Cr₂O₃) coatings could be improved by doping modification and changing the structural scale, etc. In this study, micrometric Cr₂O₃ coatings were doped with different additives, CeO₂ and Nb₂O₅. Moreover, Cr₂O₃ coatings were deposited from nanostructured feedstock by the combination process of plasma spraying and dry-ice blasting. The correlation between the microstructure, chemical components and tribological properties of plasma-sprayed Cr₂O₃-based coatings was discussed based on the investigation of their porosity, hardness and friction behaviors. The results showed that the composite coatings doped with additives exhibited a higher microhardness, corresponding to a lower porosity than pure Cr₂O₃ coating under the identical plasma-spray condition. CeO₂ constituent was found to improve the wear resistance of Cr₂O₃ coating while Nb₂O₅ incorporation corresponds to a steep rise in the friction coefficient. The mismatch of coefficient of thermal expansion (CTE) between Cr₂O₃ and Nb₂O₅ lamellae facilitated the origin of fatigue cracks and the formation of microfracture pits. Although the combination process promotes a porosity reduction, the nanostructured Cr₂O₃ (n-Cr₂O₃) coatings present a lower microhardness than micrometric coatings, due to their loosen microstructure from insufficient plasma power compared to microscaled coatings. The wear mechanisms of both the micro- and nanometric Cr₂O₃ coatings are fatigue cracks and material transfer.     

不同制备方法对纳米SiO2/NR复合材料力学性能的影响

本文研究了不同制备方法对纳米SiO2/NR复合材料力学性能的影响,结果表明:乳液共凝法制备的纳米SiO2/NR复合材料的力学性能优于机械共混法制备的纳米SiO2/NR复合材料力学性能.而先用硅酸钠和乙酸乙酯等制备纳米SiO2乳液,再与天然胶乳共凝的方法比用市售纳米SiO2与天然胶乳共凝的方法,纳米SiO2/NR复合材料...     

Electrodeposition and characterization of Bi2Se3 thin films by electrochemical atomic layer epitaxy (ECALE)

Bismuth selenide thin films were grown on Pt substrate via the route of electrochemical atomic layer epitaxy (ECALE) in this work for the first time. The electrochemical behaviors of Bi and Se on bare Pt, Se on Bi-covered Pt, and Bi on Se-covered Pt were studied by cyclic voltammetry and coulometry. A steady deposition of Bi₂Se₃ could be attained after negatively stepped adjusting of underpotential deposition (UPD) potentials of Bi and Se on Pt in the first 40 deposition cycles. X-ray diffraction (XRD) analysis indicated that the films were single phase Bi₂Se₃ compound with orthorhombic structure, and the 2:3 stoichiometric ratio of Bi to Se was verified by EDX quantitative analysis. The optical band gap of the as-deposited Bi₂Se₃ film was determined as 0.35 eV by Fourier transform infrared spectroscopy (FTIR), which is consistent with that of bulk Bi₂Se₃ compound.     

Study on the interaction between SiO2 and ZrO2 in the chemical mechanical polishing of zirconia ceramic with colloidal silica

Colloidal silica is usually used for the chemical mechanical polishing of zirconia ceramic wafer in industry, but the process is often optimized only through experience without a precise understanding of the polishing mechanism. There are still many theoretical and technical issues, especially the material removal mechanism and the effect of polishing on the phase transformation, have not been studied in depth. In this study, the effect of the abrasive concentration, polishing pressure and slurry pH on the material removal rate was analyzed. It is found that the removal rate tends to be stable when the concentration exceeds 30 wt%; the influence of pressure on the polishing rate conforms to the Preston formula. When the pH of the slurry is 6, the removal rate is the highest, but polishing under acidic conditions will leave corrosion pits due to the dissolution of the stabilizer. Through X-ray photoelectron spectroscopy analysis of the residue on the wafer surface, it was found that Si-O-Zr bonds were formed, but it was uncertain whether the residue was zirconium silicate. Through X-ray diffraction analysis, it is found that polishing will not affect the crystal structure of zirconia. The Zr-O-Si bond formed by tribochemical action on the ceramic surface prevents the deep migration of surface hydroxyl groups. At the same time, kinetic factors will cause internal hydroxyl groups to transfer to the surface for recovery oxygen vacancies, thereby stabilizing the tetragonal phase.     

Low temperature preparation of nanocrystalline SrTiO3 and BaTiO3 from alkaline earth nitrates and TiO2 nanocrystals

Using low-melting-point Sr(NO₃)₂ (melting point: 570 °C) and high-reactive-activity TiO₂ nanocrystals (Degussa P25 TiO₂) as the raw materials, phase-pure SrTiO₃ nanocrystals were prepared at 600 °C. X-ray diffraction and X-ray photoelectron spectroscopy revealed that the as-prepared products were cubic phase SrTiO₃ with a surface composition of Sr_0.97TiO_2.92. Transmission electron microscopy image showed that the as-prepared SrTiO₃ comprised nanocrystals with the size of about 24-44 nm. UV-vis absorption spectrum of the as-prepared SrTiO₃ nanocrystals displayed a wide absorption peak centered at around 365 nm (3.4 eV), together with a tail at the lower energy side. This kind of low temperature and cost-effective method can also be extended to prepare BaTiO₃ nanocrystals, simply by substituting Ba(NO₃)₂ for Sr(NO₃)₂.     

Effect of Co substitution for Ni on the structural and electrochemical properties of La2Mg(Ni1−xCox)9 (x = 0.1-0.5) hydrogen storage electrode alloys

The effect of partial substitution of Co for Ni on the structure and electrochemical properties of the thus formed La₂Mg(Ni_1−xCo_x)₉ (x = 0.1-0.5) quaternary alloys was investigated. All alloys are consisted of a main phase with hexagonal PuNi₃-type structure and a few impurity phases (mainly La₂Ni₇ and LaNi). The increase of Co content in the alloys leads to an increase in both the cell volume and the hydride stability, and leads to a noticeable decrease in cell volume expansion rate (ΔV/V) on hydriding. The discharge capacity of the alloys at 50 mA/g increases slightly with the increase of Co content and passes though a maximum of 404.5 mAh/g at x = 0.2. As the Co content increases, the high-rate dischargeability of the alloy electrodes at 800 mA/g (HRD₈₀₀) decreases sharply from 72.8 (x = 0) to 24.5% (x = 0.5), yet the decrease of HRD₈₀₀ of the alloy electrodes with lower Co substitution (with x ≤ 0.2) is much milder. The slower decrease of HRD₈₀₀ (from 72.8 to 64.2%) of the alloys with x from 0 to 0.2 is mainly attributed to the decrease of eletrocatalytic activity for charge-transfer reaction, the more rapid decrease of the alloys with x > 0.2 is mainly attributed to the lowering of the hydrogen diffusion rate in the bulk of alloy. The cycling capacity retention rate (S₁₀₀) of the alloys increase greatly with increasing of Co content, increasing from 60.2% for the alloy with x = 0 to a much higher value of 87.9% for the alloy with x = 0.5. The improvement in cycling stability is attributed to the lower cell volume expansion on hydriding.