Low temperature metal oxide film deposition and reaction kinetics in supercritical carbon dioxide

An effective method is developed for low temperature metal oxide deposition through thermal decomposition of metal diketonates in supercritical carbon dioxide (scCO₂) solvent. The rates of Al(acac)₃ (Aluminum acetyl acetonate) and Ga(acac)₃ (Gallium acetyl acetonate) thermal decomposition in scCO₂ to form conformal Al₂O₃ and Ga₂O₃ thin films on planar surfaces were investigated. The thermal decomposition reaction of Al(acac)₃ and Ga(acac)₃ was found to be initialized at  150 °C and 160 °C respectively in scCO₂ solvent, compared to  250 °C and 360 °C in analogous vacuum-based processes. By measuring the temperature dependence of the growth rates of metal oxide thin films, the apparent activation energy for the thermal decomposition of Al(acac)₃ in scCO₂ is found to be 68 ± 6 kJ/mol, in comparison with 80–100 kJ/mol observed for the corresponding vacuum-based thermal decomposition reaction. The enhanced thermal decomposition rate in scCO₂ is ascribed to the high density solvent which effectively reduces the energy of the polar transition states in the reaction pathway. Preliminary results of thin film deposition of other metal oxides including ZrO_x, FeO_x, Co₂O₃, Cr₂O₃, HfO_x from thermal decomposition of metal diketonates or fluorinated diketonates in scCO₂ are also presented.     

Ionic Conductivity and Mechanical Properties of Post-HIPed Cubic Zirconia/Alumina Composites

8 mol.% yttria-doped cubic zirconia (8Y-CSZ)/AI₂O₃ composites containing 0-30 vol.% Al₂O₃ particles were fabricated by sintering, followed by hot isostatic pressing (post-HIPing). All composites were densified to at least 99·5% of the theoretical density by post-HIPing. The bending strength of composites sintered at 1500°C in air was independent of A1₂O₃ content, but a significant improvement in the bending strength was achieved by the post-HIPing technique. The bending strength and the fracture toughness of the HIPed composites increased with increasing A1₂O₃ content. Ionic conductivity of the composites was evaluated and the total, lattice, and grain boundary conductivities slightly decreased with increasing A1₂O₃ content. The HIPed composites containing up to 20 vol.% A1₂0₃ appear to be suitable candidate materials as electrolyte for solid oxygen fuel cell.     

Grain growth mechanisms in a spray-formed Ni3Al/Al2O3 composite in the presence of a liquid phase

Grain growth in the two-phase (liquid + solid) region of Ni₃Al reinforced with 0.8 vol.% Al₂O₃ participates synthesized by a spray atomization and co-injection technique was investigated. The grain growth of the as-sprayed and hot isostatically pressed (HIPed) materials in the two-phase region was found to be consistent with cube law kinetics, i.e., grain growth exponent was approximately 3. The activation energy for grain growth for the as-sprayed material was determined to be 308 ± 19 kJ mol⁻¹ while that of the HIPed material was calculated to be 327 ± 23 kJ mol⁻¹. The activation energy for grain growth was not a function of the amount of liquid phase or the composition of the liquid. Furthermore, the activation energy for grain growth was higher than that for diffusion through the liquid phase, suggesting that the mechanism for grain growth of the as-sprayed and HIPed Ni₃Al composite in the two-phase region was controlled by an interface reaction. The role of the second-phase Al₂O₃ particles on grain growth for the as-sprayed and HIPed Ni₃Al materials was not significant.     

Infrared Transmission Curves of Pb0.1 Ca0.9La2S4 Pellets Densified by Pressureless Sintering

Highly sinterable submicron Pb_0.l Ca_0.9La₂S₄(PCLS) powders were prepared by sulfidizing calcium and lanthanum alkoxides al 500°C under CS, atmosphere for 8 hours and then in pure H₂S atmosphere at 600-800°C for 8 hours. After sintering the pellets were used as infrared transmitting window material of 8-14 μm wavelength. The CdS was added from 3 to 7 wt.% lo improve the sinterability by forming liquid phase during sintering. For sulfidization of lanthanum alkoxide, sulfide powder with LaS₂ phase was formed at 500°C, and a pure Th3P4 phase formed follow by 700°C heat treatment. A powder with β-La₂S₃phase formed at 800°C, and a pure Th₃ P₄phase formed follow by 900°C heat treatment. The powder with β-La₂S₃ phase was sintered to full density at 1350°C by adding 3 wt.% CdS. The PCLS powder with Th3P4 phase sintered to full density at 1400°C by also adding 3 wt.% CdS. The pellet exhibited 45% transmittanceat 13 μm when sintered from the powder with p-La₂S₃phase. The transmittance at 2.5 μm for the pellet sintered from the PCLS powder with Th₃P₄ type structure was 3 times higher than that from the p-La₂S₃ powder.     

Deposition of HfO2 thin films on ZnS substrates

HfO₂ thin films with columnar microstructure were deposited directly on ZnS substrates by electron beam evaporation process. SiO₂ thin films, deposited by reactive magnetron sputtering, were used as buffer layers, HfO₂ thin films of granular microstructure were obtained on SiO₂ interlayer by this process. X-ray diffraction patterns demonstrate that the as-deposited HfO₂ films are in an amorphous-like state with small amount of crystalline phase while the HfO₂ films annealed at 450 °C in O₂ for 30 min and in Ar for 150 min underwent a phase transformation from amorphous-like to monoclinic phase. Antireflection effect in certain infrared wave band, such as 3–6 μm, 4–12 μm, 4–8 μm and 3–10 μm, can be observed, which was dependent on the thickness of thin films. The cross-sectional images of HfO₂ films, obtained by field emission scanning electron microscopy, revealed that there was no distinct morphological change upon annealing.     

Activation energy and grain growth in nanocrystalline Y-TZP ceramics

Grain growth of nanocrystalline yttria-stabilized tetragonal zirconia polycrystals (Y-TZP) was studied between 1250 and 1650 °C and compared to the Y-TZP data from the literature. All the results exhibited two distinctly different behaviour, where slow and fast grain growth regimes with activation energies 280 and 546 kJ mol⁻¹ prevail below and above 1400 °C, respectively. Analysis of the data with respect to the grain growth mechanisms and the diffusion kinetics was in agreement with limited Y³⁺ lattice diffusion within the cubic zirconia nano-grains below 1400 °C. This results in slow grain growth kinetics. Redistribution of Y³⁺ above 1400 °C together with the equilibrium phase assemblage lead to enhanced grain boundary diffusion of Y³⁺ and results in enhanced grain growth of the sub-micrometer tetragonal grains.     

Kinetics of Carbon Multi-wall Nanotube Synthesis by Catalytic Pyrolysis of Methane

By method of isothermal gravimetry at 600-700°C, CH₄ concentration 32-100% in Ar and 91-100% in H₂ under atmospheric pressure the kinetics of CH₄ pyrolysis under Ni/La₂O₃ catalysts is studied. Estimated apparent activation energy of reaction is 73 kJ/mol for fresh catalyst and 71 kJ/mol for aged one. The reaction order on CH₄ changes from 1.05 at 600°C to 1.3 at 700°C. The influence of H₂ concentration on the reaction rate is more complicated. On the basis of kinetics measurements continuously working laboratory-scale reactor with gas and catalyst counter-flow is constructed and tested.     

Microstructure and properties of MoSi2–MoB and MoSi2–Mo5Si3 molybdenum silicides

MoSi₂-based intermetallics containing different volume fractions of MoB or Mo₅Si₃ were fabricated by hot-pressing MoSi₂, MoB, and Mo₅Si₃ powders in vacuum. Both classes of alloys contained approximately 5 vol.% of dispersed silica phase. Additions of MoB or Mo₅Si₃ caused the average grain size to decrease. The decrease in the grain size was typically accompanied by an increase in flexure strength, a decrease in the room temperature fracture toughness, and a decrease in the hot strength (compressive creep strength) measured around 1200 °C, except when the Mo₅Si₃ effectively became the major phase. Oxidation measurements on the two classes of alloys were carried out in air. Both classes of alloys were protected from oxidation by an in-situ adherent scale that formed on exposure to high temperature. The scale, although not analyzed in detail, is commonly recognized in MoSi₂ containing materials as consisting mostly of SiO₂. The MoB containing materials showed an increase in the scale thickness and the cyclic oxidation rate at 1400 °C when compared with pure MoSi₂. However, in contrast with the pure MoSi₂ material, oxidation at 1400 °C began with a weight loss followed by a weight gain and the formation of the protective silica layer. The Mo₅Si₃ containing materials experienced substantial initial weight losses followed by regions of small weight changes. Overall, the MoB and Mo₅Si₃ additions to MoSi₂ tended to be detrimental for the mechanical and oxidative properties.     

Low-temperature growth and orientational control in RuO2 thin films by metal-organic chemical vapor deposition

For growth temperatures in the range of 275°C to 425°C, highly conductive RuO₂ thin films with either (110)- or (101)-textured orientations have been grown by metal-organic chemical vapor deposition (MOCVD) on both SiO₂/Si(001) and Pt/Ti/SiO₂/Si(001) substrates. Both the growth temperature and growth rate were used to control the type and degree of orientational texture of the RuO₂ films. In the upper part of this growth temperature range ( 350°C) and at a low growth rate (< 3.0 nm/min.), the RuO₂ films favored a (110)-textured orientation. In contrast, at the lower part of this growth temperature range ( 300°C) and at a high growth rate (> 3.0 nm/min.), the RuO₂ films favored a (101)-textured orientation. In contrast, higher growth temperatures (> 425°C) always produced randomly-oriented polycrystalline films. For either of these low-temperature growth processes, the films produced were crack-free, well-adhered to the substrates, and had smooth, specular surfaces. Atomic force microscopy showed that the films had a dense microstructure with an average grain size of 50–80 nm and a rms. surface roughness of 3–10 nm. Four-probe electrical transport measurements showed that the films were highly conductive with resistivities of 34–40 μΩ-cm (at 25°C).     

Effect of negatively charged species on the growth behavior of silicon films in hot wire chemical vapor deposition

The deposition behavior of silicon in hot wire chemical vapor deposition was investigated, focusing on the generation of negatively charged species in the gas phase using a gas mixture of 20% SiH₄ and 80% H₂ at a 450 °C substrate temperature under a working pressure of 66.7 Pa. A negative current of 6–21 µA/cm² was measured on the substrate at all processing conditions, and its absolute value increased with increasing wire temperature in the range of 1400 °C–1900 °C. The surface roughness of the films deposited on the silicon wafers increased with increasing wire temperature in the range of 1510 °C–1800 °C. The film growth rate on the positively biased substrates (+ 100 V, + 200 V) was higher than that on the neutral (0 V) and negatively biased substrates (− 100 V, − 200 V, − 300 V). These results indicate that the negatively charged species are generated in the gas phase and contribute to deposition. The surface roughness evolved during deposition was attributed to the electrostatic interaction between these negatively charged species and the negatively charged growing surface.     

CHEMICAL VAPOR DEPOSITION OF TiB2 FOR TiN-TiB2 LAMINAR COMPOSITES

TiB₂ is a material with very interesting properties with respect to erosion and corrosion resistance. Deposition on metallic substrates using TiCI₄, BBr₃ or BCI₃ and H₂ at temperatures around 900° C results in coronation of the substrate, which is most severe when using BBr₃. Therefore, a TiN diffusion barrier is applied. Here we discuss the deposition of TiB₂ using BCI₃ on molybdenum and TiN and compare the results with those of the thermodynamically more favorable reaction with BBr₃. Smooth TiB₂ layers are formed when using BCI₃, with faceting occurring above 900° C. The morphology seems to be independent of the BCI₃/TiCl₄ ratio in the gas phase for values between 0·5 and 4. With an excess of boron in the gas phase - BCI₃/TiCl₄ = 8, depletion occurs already at 800° C. An apparent activation energy of 210 KJ/mol has been determined for a stoichiometric gas phase with BCl₃/TiCI₄ = 2. When the supply of boron is limiting - BCl₃/TiCl₄ = 0·5, the activation energy is 120 KJ/mol.     

Microwave dielectric characteristics of Ba(Mg1/3Ta2/3)O3 ceramics sintered at low-temperatures

The microwave dielectric properties and microstructures of Ba(Mg_1/3Ta_2/3)O₃ (BMT) ceramics sintered at low temperatures with 2–3 wt.% NaF additives were investigated. BMT ceramics sintered at 1340 °C for 3–12 h showed dielectric constants (_r) of 25.5–25.7, Qf values of 41 500–50 400 GHz and temperature coefficients of the resonator frequency (τ_f) of 10.9–21.4 ppm °C⁻¹. The variation of sintering time almost had no effect on the dielectric constant. The Qf value increased and the τ_f decreased with increasing sintering time. The ordering degree of Mg²⁺ and Ta⁵⁺ at B-sites increased with increasing sintering time.     

复配偶联剂对SiO_2/聚四氟乙烯复合材料性能的影响

制备了不同组分配比的氨丙基三乙氧基硅烷(KH550)-苯基三甲氧基硅烷(Z6124)复配偶联剂(KH550-Z6124)改性SiO2/聚四氟乙烯(PTFE)复合材料,系统地研究了KH550-Z6124组分配比对复合材料介电性能、吸水率和导热性能的影响。采用Lichtenecker模型计算了SiO2/PTFE复合材料的介电常数和介电损耗理论值,并与实验值进行对比。结果表明:当KH550、Z6124的含量(以SiO2的质量为基准)分别为0.3wt%和1.7wt%时,KH550-Z6124改性SiO2/PTFE复合材料的介电损耗由Z6124改性SiO2/PTFE复合材料的1.7×10-3降低至1.0×10-3,吸水率由0.082 6wt%降低至0.020 3wt%,导热率提高66%;SEM形貌分析发现KH550-Z6124改性SiO2颗粒在PTFE基体中均匀分散,界面连接更紧密;KH550-Z6124改性SiO2/PTFE复合材料的介电常数和介电损耗实验值更接近其理论值。     

Al2O3纤维对SiO2基陶瓷型芯的烧缩阻滞

向SiO₂基体粉料中添加Al₂O₃纤维,采用热压注法制备Al₂O₃/SiO₂陶瓷型芯。分析Al₂O₃纤维含量对陶瓷型芯性能的影响。研究结果表明：Al₂O₃纤维含量对Al₂O₃/SiO₂陶瓷型芯的线收缩率、体积密度和抗弯强度均有较大的影响。当Al₂O₃纤维含量大于1wt%时,Al₂O₃/SiO₂陶瓷型芯的线收缩率大幅度降低,稳定在0.335%左右,体积密度随之降低,稳定在1.790 g · cm^-3左右;当Al₂O₃纤维含量为1wt%时,陶瓷型芯抗弯强度达最大值20.48 MPa。分析了Al₂O₃纤维对Al₂O₃/SiO₂陶瓷型芯烧结收缩的阻滞作用机制。     

Influence of Mn doping on microstructure and DC-accelerated aging behaviors of ZnO–V2O5-based varistors

The microstructure, electrical properties, dielectric characteristics, and DC-accelerated aging behavior of the ZnO–V₂O₅–MnO₂ system sintered were investigated for MnO₂ content of 0.0–2.0 mol% by sintering at 900 °C. For all samples, the microstructure of the ZnO–V₂O₅–MnO₂ system consisted of mainly ZnO grain and secondary phase Zn₃(VO₄)₂. The incorporation of MnO₂ to the ZnO–V₂O₅ system was found to restrict the abnormal grain growth of ZnO. The nonlinear properties and stability against DC-accelerated aging stress improved with the increase of MnO₂ content. The ZnO–V₂O₅–MnO₂ system added with MnO₂ content of 2.0 mol% exhibited not only a high nonlinearity, in which the nonlinear coefficient is 27.2 and the leakage current density is 0.17 mA/cm², but also a good stability, in which %ΔE_1 mA = −0.6%, %Δ = −26.1%, and %Δtan δ = +22% for DC-accelerated aging stress of 0.85E_1 mA/85 °C/24 h.     

Porous SnO2 sputtered films with high H2 sensitivity at low operation temperature

Undoped and Pd-doped SnO₂ films were deposited at various substrate temperatures and discharge gas pressures using reactive magnetron sputtering. Structural factors of the films, such as crystallite size, grain size, and film density, were systematically investigated. The main objectives of this study are to clarify the operation temperature dependence of the H₂ sensitivity of these films as well as to clarify the dominant structural factor in the determination of the sensitivity. The operation temperature at which the sensitivity defined by (R_a−R_g)/R_g, where R_a and R_g are the resistances before and after exposure to H₂, showed a maximum decreased with decreasing film density. The highest sensitivity of 4470 was obtained for a Pd-doped film with the lowest density of 3.1 g/cm³ at 100 °C. It was found that the sensitivity correlated with film density rather than with crystallite size and grain size. The high sensitivity of a Pd-doped porous film at a low temperature was discussed in relation to the Schottky-barrier-limited transport as well as the chemical and electronic effects of Pd.     

Microwave dielectric properties and microstructures of MgTa2O6 ceramics with CuO addition

The effect of CuO addition on the microstructures and the microwave dielectric properties of MgTa₂O₆ ceramics has been investigated. It is found that low level-doping of CuO (up to 1 wt.%) can significantly improve the density of the specimens and their microwave dielectric properties. Tremendous sintering temperature reduction can be achieved due to the liquid phase effect of CuO addition observed by scanning electronic microscopy (SEM). The sintered samples exhibit excellent microwave dielectric properties, which depend upon the liquid phase and the sintering temperature. With 0.5 wt.% CuO addition, MgTa₂O₆ ceramic can be sintered at 1400 °C and possesses a dielectric constant (_r) of 28, a Q × f value of 58000 GHz and a temperature coefficient of resonant frequency (τ_f) of 18 ppm/°C.     

Thermolysis and Photolysis of C60 Diozonides

Ozonation of C₆₀ in o-xylene produced three C₆₀(O₃)₂ diozonides that were separated from one another and from two C₆₀(O₃)₃ triozonides by High Performance Liquid Chromatography (HPLC). Upon thermolysis at 10, 15, and 16.6°C, each of the diozonides dissociated sequentially, first to a C₆₀O(O₃) oxyozonide, then to a C₆₀O₂ diepoxide. The three diepoxides were stable in solution for at least 3 weeks. The mean lifetimes of the three diozonides were 52 ± 5, 62 ± 6, and 17.3 ± 1.8 min, respectively (all at 15°C). The mean lifetimes of the three oxyozonides were 69.7 ± 0.7 and 58 ± 6 min at 16.6°C, respectively and about 240 min at 10°C. Photolysis of the diozonides yielded two dioxidoannulenes with UV-Vis adsorption maxima at 333 and 332 nm, and what appeared to be an epoxide-oxidoannulene with UV-Vis adsorption maximum at 327 nm. These annulenes were observed to form dimers. We have synthesized and characterized six C₆₀O₂ dioxides, at least three and possibly four of which were hitherto unknown. We report the discovery of oxyozonides that form during the dissociation of diozonides.     

SiO_2包覆改性纳米TiO_2粒子对聚丙烯拉伸流变性能和结晶行为的影响

为了探究光催化功能性聚丙烯(PP)纤维的可纺性及加工性能,首先以SiO2包覆改性纳米TiO2粒子(SiO2@TiO2)为添加剂,对PP进行共混改性。然后,用毛细管流变仪测试了SiO2@TiO2/PP共混熔体的拉伸流变性能,用XRD和DSC研究了SiO2@TiO2对PP性能的影响。结果表明:SiO2@TiO2/PP共混熔体属于拉伸变稀型流体。熔体的拉伸应力和拉伸黏度均随温度的升高而下降;拉伸黏度随添加剂用量的增加而增大,拉伸流动活化能随拉伸应变速率的提高而降低。SiO2@TiO2的加入不会明显改变PP的结晶结构,但会使结晶性能增强,当SiO2@TiO2的含量为4wt%时,共混熔体的结晶度比纯PP的高8.6%。SiO2@TiO2能使PP形成更为紧密的晶体结构,这对材料的性能具有重要影响。     

Multiwalled Carbon Nanotubes Catalytically Grown from Amorphous Silica Films Deposited by Combustion CVD

Homogeneous mixtures containing iron oxide and amorphous SiO₂ were obtained through the co-deposition of these oxides via combustion chemical vapor deposition technique (CCVD). This technique allows the deposition of thin films with low-cost precursors and equipments. After deposition, the deposited samples were submitted to a heat treatment in an atmosphere composed of natural gas and H₂ at 1000°C, in order to promote the growth of carbon nanotubes. Multiwalled carbon nanotubes, with diameters smaller than 15 nm, were obtained.