Conformation of Organic Chain in Phase Transition of Hybrid （Cl2H25NH3）2MnCl4

The structural change in phase transition of hybrid （Cl2H25NH3）2MnCl4 was investigated. The temperature and the structures of the phase transition is investigated by thermal gravimetry （TG） and differential scanning calorimetry （DSC）, infrared spectrum （IR） and X-ray diffraction （XRD）. The results suggest that the phase transition is reversible and the structural change arises from the conformation change of the organic chain. The interlayer distance increases when the hybrid transforms from low temperature phase to high temperature phase. This is explained by the diffusion of gauche-bond along the organic chains and they move away from each other when the phase transition occurs. Combining the experimental data with theoretical calculation, we propose that organic chain of the hybrid in high temperature phase is the conformation of gauche-bond alternating with trans bond （noted as GTG＇TGTG＇TGTG＇T）.     

Tensile properties of an aluminum matrix composite reinforced by SnO<Subscript>2</Subscript>-coated Al<Subscript>18</Subscript>B<Subscript>4</Subscript>O<Subscript>33</Subscript> whisker

Al18B4O33 whisker was coated by SnO2 particles using a chemical precipitation method, and an aluminum matrix composite reinforced by the coated whisker was fabricated by squeeze casting technique. It is found that the SnO2 coating can react with aluminum matrix during squeeze casting process, and Sn particles are induced near the interface between Al18B4O33 whisker and matrix. The tensile test at room temperature indicated that the tensile strength of Al18B4O33 whisker reinforced aluminum matrix composite can be enhanced by suitable content of SnO2 coating. The composites with various whisker coating contents exhibit maximum tensile plasticity at about 300 ℃, and the composite with a suitable whisker coating content could enhance its tensile plasticity evidently, which suggest that an Al18B4O33 whisker-Al composite with both high strength at room temperature and high formability at elevated temperature can be designed.     

Grain growth kinetics of SnO<Subscript>2</Subscript> nanocrystals synthesized by precipitation method

Monodispersed spheroidal SnO₂ nanocrystals with the grain size of 8–30 nm were synthesized by the precipitation method using SnCl₄·5H₂O (stannic chloride hydrate) as raw materials. Differential scanning calorimetry/thermogravimetry (DSC/TG), X-ray diffraction (XRD) and transmission electron microscope (TEM) were used to characterize the structure of SnO₂ nanocrystals. The influences of the calcination temperature and time on the lattice constant, the lattice distortion and the grain size of SnO₂ nanocrystals were discussed based on the XRD results. The grain growth kinetics of SnO₂ nanocrystals during calcination process was simulated with a conventional grain growth model which only took into account of diffusion and with a new isothermal model proposed by our group, which took into account of both diffusion and surface reactions. Using conventional model, the grain growth rate constant of SnO₂ crystals is 1.55×10⁴ nm⁵/min with a pre-exponential factor of 5 and an activation energy of 108.62 kJ/mol. Compared with the convention model, the new isothermal model is more realistic in reflecting the grain growth behavior of SnO₂ nanocrystals during the calcination process. This indicates that the grain growth of SnO₂ nanocrystals is controlled by both diffusion and reaction factors, and the effect of surface reactivity on the grain growth of SnO₂ nanocrystals could not be ignored. A combined activation energy estimated with the new isothermal model is 53.46 kJ/mol.     

Preparation and characterization of CeO<Subscript>2</Subscript>-TiO<Subscript>2</Subscript>/SnO<Subscript>2</Subscript>:Sb films deposited on glass substrates by R.F. sputtering

CeO2-TiO2 films and CeO2-TiO/SnO2：Sb （6 mol%） double films were deposited on glass substrates by radio-frequency magnetron sputtering （R.F. Sputtering）, using SnO2：Sb（6 mol%） target, and CeO2- TiO2 targets with different molar ratio of CeO2 to TiO2 （CeO2：TiO2-0：1.0; 0.1：0.9; 0.2：0.8; 0.3：0.7; 0.4：0.6; 0.5：0.5; 0.6：0.4; 0.7：0.3; 0.8：0.2; 0.9：0.1; 1.0：0）. The films are characterized by UV-visible transmission and infrared reflection spectra, scanning electron microscopy （SEM）, Raman spectroscopy, X-ray photoelectron spectroscopy （XPS） and X-ray diffraction （XRD）, respectively. The obtained results show that the amorphous phases composed of CeO2-TiO2 play an important role in absorbing UV, there are Ce^3-, Ce^4- and Ti^4- on the surface of the films; the glass substrates coated with CeO2-TiO2 （Ce/Ti=0.5：0.5; 0.6：0.4）/SnO2：Sb（6 mol%） double films show high absorbing UV（〉99）, high visible light transmission （75%） and good infrared reflection （〉70%）. The sheet resistance of the films is 30-50 Ω/□. The glass substrates coated with the double functional films can be used as window glass of buildings, automobile and so on.     

Sensing characterization of Sn/In/Ti nanocomplex oxides for CO,CH<Subscript>4</Subscript> and NO<Subscript>2</Subscript>

The nanocomplex oxides of Sn-In and Sn-In-Ti were prepared by controlled co-precipitation method as sensing materials of semiconductor gas sensors for detection of CO, CH4 and NO2. Through manipulating the Sn/In cation ratio, metal salt total concentration, precipitation pH value and aging time, the nanocrystalline powders were successfully derived with chemical homogeneity and superior thermal stability, compared with the single component oxides. The particle size and morphology, surface area, and thermal and phase stabilities were characterized using TEM, TG-DTA, BET and XRD. The sensing tests showed that the Sn-In composites exhibit high sensitivity and selectivity for CO and NO2. The introduction of TiO2 enhanced CH4 sensitivity and selectivity, particularly, additives of Pd and Al2O3 as a dopant and surface modification greatly enhanced the sensing properties. The sensitivity depended on the composition of composites, calcination temperature and operating temperature. The optimal values were (25%In2O3- 75%SnO2)-20%TiO2 for ternary composite, 600 and 300℃, respectively. Temperature-programmed desorption (TPD) studies were employed to explain the gas adsorption behavior displayed by the surface of nanocomposites and X-ray photoelectron spectroscopic (XPS) analysis was used to confirm the electronic interactions existing between oxide components. The sensing mechanism of the nanocomposites was attributed to chemical and electronic synergistic effects.     

Electrochemical Sensing of Heavy Metal Ions based on Monodisperse Single-crystal Fe<Subscript>3</Subscript>O<Subscript>4</Subscript> Microspheres

Single-crystal Fe₃O₄ with monodisperse microspheres structure has been used for individual electrochemical detection of heavy metal ions. Morphology and structure of the as-prepared Fe₃O₄ microspheres were characterized by scanning electron microscopy (SEM), transmission electron microscopy (TEM) and X-ray diffraction (XRD). Meanwhile the electrochemical properties of the Fe₃O₄ microspheres modified glass carbon electrodes (GCE) were characterized by cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS), and the enhanced electrochemical response in stripping voltammetry for individual detection of Pb(II), Hg(II), Cu(II), and Cd(II) was evaluated using square wave anodic stripping voltammetry (SWASV). With high specific surface area and excellent catalytic activity toward heavy metal ions, the as-prepared monodisperse and single-crystal Fe₃O₄ microspheres show a preferable sensing sensitivity (22.2 μA/μM) and limit of detection (0.0699 μM) toward Pb(II). Furthermore, the electrochemical sensor of Fe₃O₄ microspheres exhibits excellent stability and it also offers potential practical applicability for the determination of heavy metal ions in real water samples. This study provides a potential simple and low cost iron oxide for the construction of sensitive electrochemical sensors applied to monitor and control the pollution of toxic metal ions.     

Self-Propagating High-Temperature Reduetive Synthesis of TiB2-Al2O3 Composite Powders

TiB2-Al2O3 composite powders were produced by self-propagating high-temperature synthesis（SHS） method with reductive process from B2O3-TiO2-AI system. X-ray diffraction（XRD） and scanning electron microscopy（SEM） analyses show the presence of TiB2 and Al2O3 only in the composite powders produced by SHS. The powders are uniform and free-agglomerate. Transmission electron microscopy （TEM） and high resolution electron microscopy （HREM） observation of microstructure of the composite powders indicate that the interfaces of the TiB2-Al2O3 bond well, without any interfacial reaction products. It is proposed that the good interfacial bonding of the composite powders can be resulted from the TiB2 particles crystallizing and growing on the Al2O3 particles surface with surface defects acting as nucleation centers.     

Synthesis of mesoporous silica-embedded TiO<Subscript>2</Subscript> loaded with Ag nanoparticles for photocatalytic hydrogen evolution from water splitting

Ag loaded mesoporous silica-embedded TiO₂ nanocomposites were successfully synthesized via two different routes, including one-pot solvothermal method and solvothermal-chemical reduction method, both using Titanium (IV) n-butoxide (Ti(OC₄H₉)₄) as a precursor, formic acid as a solvent and reducing agent, silver nitrate as a silver source and tetraethyl silicate (TEOS) as a stabilizer. The transmission electron microscopic (TEM) images showed that silica-embedded anatase TiO₂ sample exhibited approximately rhombic shape and Ag nanoparticles could be embedded into the nanocomposites or deposited on the surface with high dispersion. The N₂ adsorption-desorption isotherms indicated that the silica-embedded anatase TiO₂ had obvious mesoporous structure with a BET specific surface area of 203.5 m²·g^-1. All Ag loaded silica-embedded TiO₂ composites showed a higher photocatalytic H₂-generation activity from water splitting under simulative solar light irradiation than that of TiO₂ products. The maximum H₂ production rate (6.10 mmol·h^-1·g^-1) was obtained over 2% Ag/silica-embedded TiO₂ nanocomposites (2% Ag/MST) prepared by solvothermal-chemical reduction method, which was 20 times that achieved on the silica-embedded TiO₂ sample. The enhanced photocatalytic H₂-evolution activity of Ag loaded mesoporous silica-embedded TiO₂ nanocomposites can be attributed to the multi-function of surface Ag co-catalyst, mesoporous structure, and embedding of silica.     

Fluorescence detection for H<Subscript>2</Subscript>PO<Subscript>4</Subscript><Superscript>-</Superscript> based on carbon dots/Fe<Superscript>3+</Superscript> composite

A novel fluorescent probe for H₂PO₄ ^- was designed and fabricated based on the carbon dots/Fe³⁺ composite. The carbon dots were synthesized by an established one-pot hydrothermal method and characterized by transmission electron microscope, X-ray diffractometer, UV-Vis absorption spectrometer and fluorescence spectrophotometer. The carbon dots/Fe³⁺ composite was obtained by aqueous mixing of carbon dots and FeCl₃, and its fluorescence property was characterized by fluorescence spectrophotometer. The fluorescence of carbon dots was quenched by aqueous Fe³⁺ cations, resulting in the low fluorescence intensity of the carbon dots/Fe³⁺ composite. On the other hand, H₂PO₄ ^- reduced the concentration of Fe³⁺ by chemical reaction and enhanced the fluorescence of the carbon dots/Fe³⁺ composite. The Stern-Volmer equation was introduced to describe the relation between the relative fluorescence intensity of the carbon dots/Fe³⁺ composite and the concentration of H₂PO₄ ^-, and a fine linearity (R ²=0.997) was found in the range of H₂PO₄ ^- concentration of 0.4-12 mM.     

Synthesis and characterization of VO<Subscript>2</Subscript>/mesoporous carbon composites for hybrid capacitors

VO₂/ordered mesoporous carbon (CMK-3) composites were prepared by solid-state reaction process. The microstructures were characterized by X-ray diffraction (XRD), nitrogen adsorption and desorption, field-emission scanning electron microscopy (FE-SEM) and transmission electron microscopy (TEM). The experimental results showed that the vanadium oxide in the composites was vanadium dioxide (VO₂) with monoclinic structure, which was artificially loaded on the outer surface of CMK-3. VO₂/ordered mesoporous carbon composites present a significantly improved capacitive performance (131 F/g) increased by 40.86% compared to that of CMK-3 carbon (93 F/g). Therefore, as-prepared VO₂/mesoporous carbon composites suggest promising applications in hybrid capacitors.     

Hydrothermal preparation and photocatalytic water splitting properties of ZrW<Subscript>2</Subscript>O<Subscript>8</Subscript>

ZrW₂O₈ was prepared by adjusting Zr:W mole ratio and HCl concentration in hydrothermal reaction processes. The obtained sample was crystallized in α-ZrW₂O₈ phase (cubic, P2₁3), with band gap energy of 4.0 eV. The properties of photocatalytic water splitting were examined under UV light irradiation. The average rate of H₂ evolution over 0.3wt% Pt/ZrW₂O₈ in the presence of CH₃OH as electron donor (ED) was 23.4 μmol/h, while the average rate of O₂ evolution over ZrW₂O₈ in the presence of AgNO₃ as electron scavenger (ES) was 9.8 μ mol/h. Moreover, H₂ was evolved over 0.3wt% Pt/ZrW₂O₈ from pure water splitting at a rate of 5.2 μ mol/h. The study indicated that the band structure of ZrW₂O₈ was suitable for reducing H⁺ to H₂ and oxidizing H₂O to O₂. The band structure and photocatalytic water splitting properties of ZrW₂O₈, different from either ZrO₂ (5.0 eV) or WO₃ (2.7 eV), were attributed to the hybridization of W5d and Zr4d in conduction band (CB) as well as the change in crystal structure.     

Influence of Aluminum Ions Implantation on Corrosion Behavior of Zircaloy-2 Alloy in 1M H2SO4

The specimens were implanted with aluminum ions with fluence ranging from 1× 10^16 to 1× 10^17 ions/cm^2 to study the effect of aluminum ion implantation on the aqueous corrosion behavior of zircaloy-2 by metal vapor vacuum arc source （MEVVA） at an extraction voltage of 40 kV. The valence states and depth distributions of elements in the surface layer of the samples were analyzed by X-ray photoelectron spectroscopy （XPS） and Auger electron spectroscopy （AES）, respectively. Transmission electron microscopy （TEM） was used to examine the microstructure of the aluminum-implanted samples. Glancing angle X-ray diffraction （GAXRD） was employed to examine the phase transformation due to the aluminum ion implantation. The potentiodynamic polarization technique was employed to evaluate the aqueous corrosion resistance of implanted zircaloy-2 in a 1 M H2SO4 solution. It is found that a significant improvement was achieved in the aqueous corrosion resistance of zircaloy-2 implanted with aluminum ions. Finally, the mechanism of the corrosion behavior of aluminum- implanted zircaloy-2 was discussed.     

Development of Zr/ZrO<Subscript>2</Subscript> high temperature and high pressure sensors for <Emphasis Type="Italic">in-situ</Emphasis> measuring chemical parameters of deep-sea water

In order to in situ measure chemical parameters of deep-sea water and hydrothermal fluids at midocean ridge(MOR), it is necessary to use high temperature and high pressure chemical sensors.Developing new sensors is essential to measure in-situ pH and other chemical parameters(dissolved H2, dissolved H2S) of deep-sea water and hydrothermal fluids in a wide temperature range(2℃―400℃) at MOR vents.The YSZ(Yttria Stabilized Zirconia, 9%Y2O3) ceramic-based(HgO/Hg) chemical sensors possess excellent electrochemic...     

Fabrication of homogenous dispersion TiB<Subscript>2</Subscript>-Al<Subscript>2</Subscript>O<Subscript>3</Subscript> composites

In order to get a homogenous mixture and compact of TiB2-Al2O3, hybridization as a surface modification method was used to prepare nano-scale Al2O3 coated TiB2 particles. PE-wax particles were first coated onto TiB2 particles by hybridization, and then the nano-scale Al2O3 particles were coated onto the surface of TiB2 coated by PE-wax particles again. SEM, TEM and EDS were used to characterize the microstructure of as-received core/shell particles and its compacts. The experimental results show that a particle-scale homogenous dispersion of TiB2 and Al2O3 can be formed not only in mixed powder but also in dewaxed compacts. The compacts then were sintered by gas-pressing sintering (GPS). Finial products show improved mechanic properties comparing with reference samples fabricated by normal ways.     

Detection of Methanol by a Sensor Based on Rare-earth Doped TiO<Subscript>2</Subscript> Nanoparticles

The rare earth doped TiO₂ was prepared and characterized with Nd, Ho and Y as the doping agents, which have obvious absorption in visible light area. The particle size of the glomeration was about 200–400 nm. TiO₂ sensor performed a significant change in resistance when exposed to methanol vapor. By comparison, the Nd, Ho and Yb doped TiO₂ sensors exhibited a response of 2.22, 4.05 and 3.78, and lowered response and recovery times of 91, 56 and 67 s, respectively. The Ho doped TiO₂ showed the best methanol-sensing properties, which exhibited high selectivity and response to methanol compared with the other tested vapors. In concentration of 0–10 ppm, the sensor exhibited excellent stability for detecting methanol at various concentrations.     

Investigation on extremal and critical characteristics of ignition time for H<Subscript>2</Subscript>/O<Subscript>2</Subscript> combustion system and their applications

The L, H and C curves in P-T phase are proposed to describe the minimal, maximal and critical characteristics of ignition time of H₂/O₂ combustion system, respectively. The features of H₂/O₂(Air) combustion system, including explosion or not as well as the time delay to achieve its explosion status, can be well shown by explosion limits and these proposed curves. These curves can be described by 1.2k ₁=k _s [M_s], (k ₁₁/k ₁₀+1)k ₁=k _s [M_s], and 2k ₁=k _s [M_s], respectively, which provide a physical explanation for these curves and give another way to establish them. Based on the contour of ignition time, the Z-type explosion limits can be explained by thermal explosion theory. Furthermore, the ignition distance of supersonic combustion is predicted according to the ignition time obtained in a Semenov system, which is very reasonable.     

Synthesis of Ti3SiC2/TiB2 Composite by In-situ Hot Pressing （HP） Method

Ti3SiC2/TiB2 composite was successfully obtained by hot pressing Ti/TiC/Si/B4C power mixtures.Volume fraction of TiB2 in Ti3SiC2/TiB2 composite can not exceed 10%.Incorporation of excessive TiB2 will affect the reactions process.TiC and Ti5Si3 were two important intermediate phases during the whole reactions.The microstructure characteristics of the Ti3SiC2/TiB2 composites were analyzed using scanning electron microscopy （SEM） and transmission electron microscopy （TEM）.The experimental results show that the grains of Ti3SiC2/TiB2 composite are structured in a layered form,and the formation of TiB2 particles as reinforcements with elongated or equiaxed shape distributes in Ti3SiC2 matrix.     

Two-step synthesis of TiC<Subscript>0.7</Subscript>N<Subscript>0.3</Subscript>@WC-MoC<Subscript>2</Subscript> core-shell microspheres and fabrication of TiC<Subscript>0.7</Subscript>N<Subscript>0.3</Subscript>@WC-MoC<Subscript>2</Subscript>-based cermets by SPS

The precursor with TiC0.7N0.3@WO3-MO3 microspheres were prepared by a novel method from the WO3-MoO3 sol dipping. Subsequently, TiC0.7N0.3@WC-MoC2 core-shell structural microspheres were successfully obtained by carburizing the precursor at 900 °C in a flowing mixture of CH4 (20 ml·min-1) and H2 (200 ml·min-1) for 2 h. Then TiC0.7N0.3@WC-MoC2-15Co cermets were prepared utilizing the core-shell powders by spark plasma sintering (SPS). Powders of the precursors with TiC0.7N0.3@WO3-MO3 microspheres, TiC0.7N0.3@WC-MoC2 microspheres and TiC0.7N0.3@WC-MoC2-15Co cermets were characterized by scanning electron microscopy (SEM), transmission electron microscopy (TEM) and X-ray diffraction (XRD). The obtained TiC0.7N0.3@WC-MoC2 microspheres have a dense WC-MoC2 coatings shell. The thickness of the shell could be easily controlled by adjusting the number of sol dipping cycles. It was found that the TiC0.7N0.3@WC-MoC2 microspheres were more beneficial to fabricate the "core-rim" structures by SPS.     

Spark plasma sintering of undoped SnO<Subscript>2</Subscript> ceramics

Various parameters in spark plasma sintering(SPS),such as sintering temperature,holding time,heating rate,and pressure,were adopted to investigate their effects on the densification of pure SnO2 power.The obtained experimental data show that the SPS process enhances densification.The high-density undoped SnO2 ceramics (96.6% of theoretical) was obtained at much lower temperature (1000℃),within a much shorter time,compared to the conventional sintering process.The high-density undoped SnO2 ceramics (96.6% of theoretical) were obtained by SPS,under the condition of temperature:1000℃,pressure:40MPa,heating-rate:200℃/min,and holding time:3min     

Synthesis ofNanocrystalline RuO2（60%）-SnO2（40%） Powders by Amorphous Citrate Route

Nanometer RuO2-SnO2 was synthesized by the citrate-gel method using RuCl3, SnCl4 as cation sources, citric acid as complexing agent and anhydrous ethanol as solvent. The structures of the derived powders were characterized by thermogravimetric and differential thermal analysis, X-ray diffraction, transmission electron microscope, and Brunauer-Emmett-Teller surface area measurement. The pure, fine and amorphous powders was obtained at 160℃. The materials calcined at above 400 ℃ were composed of rutile-type oxide phases having particle sizes of fairly narrow distribution and good thermal resistant properties. By adding SnO2 to RuO2, the Ru metallic phase can be effectively controlled under a traditional temperature of preparation for dimensional stable anode.