Effect of Deposition Time on Microstructures and Growth Behavior of ZrC Coatings Prepared by Low Pressure Chemical Vapor Deposition with the Br_2-Zr-C_3H_6-H_2-Ar System

ZrC coatings were deposited on graphite substrates by low pressure chemical vapor deposition(LPCVD) with the Br_2-Zr-C_3H_6-H_2-Ar system. The effects of deposition time on the microstructures and growth behavior of ZrC coatings were investigated. ZrC coating grew in an island-layer mode. The formation of coating was dominated by the nucleation of ZrC in the initial 20 minutes, and the rapid nucleation generated a fine-grained structure of ZrC coating. When the deposition time was over 30 min, the growth of coating was dominated by that of crystals, giving a column-arranged structure. Energy dispersive X-ray spectroscopy showed that the molar ratio of carbon to zirconium was near 1:1 in ZrC coating, and X-ray photoelectron spectroscopy showed that ZrC was the main phase in coatings, accompanied by about 2.5mol% ZrO_2 minor phase.     

Effect of salt spray corrosion on tribological properties of HVOF sprayed NiCr-Cr<Subscript>3</Subscript>C<Subscript>2</Subscript> coating with intermediate layer

The objective of the present work was to determine the influence of the neutral salt spray corrosion on the wear resistance of HVOF sprayed NiCr-Cr₃C₂ coating with intermediate layer. Ni-Zn-Al₂O₃ coatings as interlayers were prepared by low pressure cold spray (LPCS) between NiCr-Cr₃C₂ cermet coatings to form a sandwich structure to enhance the corrosion resistance properties. The tribological properties were examined using the UMT-3 fricition and wear tester by line-contact reciprocating sliding under dry and salt spray one week corrosion. The morphology, element distribution, and phase compositions of the coating and worn sufaces were analyzed by using scanning electron microscopy, energy dispersive spectrometry, and X-ray diffraction respectively. The corrosion behavior of the coating was studied by the open-circuit potential, the electrochemical impedance spectroscopy, potentiodynamic polarization, and salt spray corrosion methods. It is found that the sandwich structured coating has better corrosion resistance than the single layer coating. The results show that under dry wear conditions, the wear mechanism is abrasive and adhesive wear, whereas under salt spray corrosion conditions it becomes corrosion wear. The friction coefficient of the sandwich structured coating after salt spray corrosion is slightly lower than the dry friction coefficient, but the weight of the wear loss is lower than that under dry condition.     

Thermal shock resistances of FeMnCr/Cr<Subscript>3</Subscript>C<Subscript>2</Subscript> coatings deposited by arc spraying

Arc spraying with the cored wires was applied to deposit FeMnCr/Cr₃C₂ coatings on low carbon steel substrates, namely FM1, FM2 and FM3. Thermal shock resistances of the coatings were investigated to assess the influence of Cr₃C₂ content on thermal shock resistance. Characteristics of the coatings under thermal cycling test were studied by optical microscopy, field emission scanning electron microscope (FE-SEM) and energy dispersion spectrum (EDS), X-ray diffraction (XRD). The experimental results show that hardness of the coatings increases, bonding strength decreases slightly with increase of the Cr₃C₂ content of the coatings. As a result, FM2 coating possesses the best thermal shock resistance, attributing to its better thermal expansion matches and wettability than those of FM3 coating, less oxide rate than that of FM1 coating restraining from cracks formation and propagation in coatings.     

Microstructure and corrosive property of Ni-P/nano-CeO<Subscript>2</Subscript> coating electrolessly prepared in acidic condition

Electroless Ni-P/nano-CeO₂ composite coating was prepared in acidic condition, and its microstructure and corrosive property were compared with its CeO₂-free counterpart. Scanning electronic microscopy (SEM), transmission electronic microscopy (TEM) and differential scanning calorimeter (DSC) were used to examine surface morphology and microstructure of the coating. Aqueous corrosion was done in 3%NaCl+5%H₂SO₄ solution and high temperature oxidation was done at 750 °C in air. The results showed that Ni-P coating had partial amorphous structure mixed with nano-crystals, while the Ni-P/CeO₂ coating had perfect amorphous structure. At high temperature, Ni3P precipitation and Ni crystallization took place in both coatings at different temperatures. Aqueous corrosion property and high temperature oxidation property of the composite coating were remarkably improved due to the coating’s microstructure change and the rare earth doping effect. During the co-deposition process, some Ce ⁿ⁺(n=3, 4) ions may be adsorbed to metal/solution interface and hinder nickel deposition. Ni-P/CeO₂ coating’s perfect amorphous structure results from the hindered crystal- typed deposition of nickel and the promoted deposition of phosphorous.     

Moisture-proof and enhanced effect of inorganic coating on porous Si<Subscript>3</Subscript>N<Subscript>4</Subscript> ceramic

Inorganic coating was fabricated on the surface of the porous Si₃N₄ ceramic by polymer derived (PD) and spraying technology, via using vinyl-polysilazane (PSN-1) as a preceramic polymer and Si₃N₄ and lithium aluminosilicate (LAS) powders as fillers. The phase and microstructure of the coatings were analyzed by X-ray diffraction (XRD) analysis and scanning electron microscopy (SEM), respectively. The effect of the coatings on mechanical property and humidity resistance of the porous Si₃N₄ ceramic was investigated. The experimental results showed that we successfully fabricated the uniform and dense coating which preferably combined with the substrate upon the addition of fillers. The bending strength of the porous Si₃N₄ ceramic sprayed the coating increased by more than 18%, and the surface hardness increased by 1.7 times. The apparent porosity of the materials reduced by an average of 97.7%, and water absorption was below 0.5%. Therefore, the prepared coating with preferable density had an obviously moisture-proof and enhanced effect on the porous Si₃N₄ ceramic.     

Microstructure and performance analysis of organic coating under high temperature and high CO<Subscript>2</Subscript> partial pressure

To evaluate the property of the organic coatings in oil and gas plants, the aging process was studied in high temperature and high CO₂ partial pressure environment. Correlations were developed between the macroscopic properties and microstructure of the organic coatings. The surface appearance, mechanical properties, and permeability of the organic coatings were measured. Furthermore, the crystal structure of the organic coatings was investigated through synchrotron radiation grazing incidence X-ray diffraction (GIXRD) on the BL14B1 beam line in Shanghai Synchrotron Radiation Facility. Combined with the Fourier transform infrared spectroscopy, the molecular structure of the organic coatings was investigated. The experimental results indicate that the thickness variation and weight loss of the organic coatings increase with the immersion time, and the penetration resistance of the coating obviously decreases as the temperature rises. Moreover, the degradation of the organic coatings with immersion time in high temperature and high CO₂ partial pressure environment is caused by the amorphization of the organic coatings as the groups and bonds of the organic coatings were not damaged.     

Investigation on phase evolution of the ZnO-B<Subscript>2</Subscript>O<Subscript>3</Subscript>-SiO<Subscript>2</Subscript> glass ceramics

ZnO-B₂O₃-SiO₂-Al₂O₃-Na₂O glass doped with nucleating agent TiO₂ was prepared with melting-quenching method and the effect of nucleating agent on the crystallization behavior and phase evolution of this glass was investigated by differential thermal analysis (DTA), X-ray diffraction (XRD), and scanning electron microscopy (SEM). The experimental results show that the glass transition temperature and the first crystallization temperature decrease from 630 °C and 765 °C to 595 °C and 740 °C, respectively, with introduction of TiO₂ into glass. There is no diffraction peaks in the XRD pattern but it is no longer transparent for the base glass without nucleating agent after heat treatment, which suggests the serious phase separation occurred, and the observation by SEM indicates that the phase separation is developed by nucleation and growth mechanism. However, there are two different crystals ZnAl₂O₄ and NaAlSiO₄ present in the glass containing TiO₂ after heat treating at 575 °C for 2 h and 740 °C for 6 h, respectively. What is interesting is that NaAlSiO₄ disappears as the crystallization time at 740 °C increases from 6 h to 12 h, and more ZnAl₂O₄ crystal is formed, namely, the further formation of ZnAl₂O₄ is at cost of NaAlSiO₄ with increasing crystallization time. And observation of the morphology of glass ceramics shows great difference with increasing crystallization time. Moreover, the ability of ZnO-B₂O₃-SiO₂-Al₂O₃-Na₂O glass ceramics against attacking of 1M HCl solution is increased by the crystals precipitated in heat treatment process.     

Phase Evolution and Oxidation Resistance of YSZ/(Ni,Al) Composite Coatings in CH<Subscript>4</Subscript> Atmosphere

YSZ/(Ni, Al) composite coatings with different Ni:Al mole ratios were deposited on superalloy Inconel 600 by electrophoretic deposition (EPD) technique, followed by sintering in CH₄ atmosphere at 1 100 °C for 2 h and isothermally oxidation at 1000 °C for 50 h. After sintering at 1100 °C for 2 h in CH₄ atmosphere, besides ZrC and t-ZrO₂ phases, the phase constitutes of Ni:Al mole ratios with 1:3, 1:2, and 1:1 were (Zr, Al)C, AlNi₃ and Ni phases, respectively. A remarkable difference in the oxidation behaviors of YSZ/(Ni, Al) composite coatings with different Ni:Al mole ratios was observed. For YSZ(Ni:Al=1:3) coated sample, oxidation at 1000 °C causes decomposition of the (Zr,Al)C solid solution to metallic Al, and then most of the Al is oxidized to Al₂O₃. For the YSZ(Ni:Al=1:2) coated sample, oxidation at 1000 °C mainly causes decomposition of the AlNi₃ phase. For YSZ(Ni:Al=1:1) coated sample, after oxidation at 1000 °C, most of the Ni is oxidized to NiO phase, and tolerated 50 h of oxidation and finally cracked and spalled from the specimen. YSZ(Ni:Al=1:3) and YSZ(Ni:Al=1:2) coated samples show superior oxidation resistance than that of YSZ coating. The different oxidation resistance mechanisms of YSZ/(Ni, Al) composite coatings sintered in CH₄ atmosphere were discussed.     

Preparation and characterization of nanocomposite MgFe<Subscript>2</Subscript>O<Subscript>4</Subscript>/SiO<Subscript>2</Subscript>

Nanocomposites MgFe₂O₄/SiO₂ were successfully synthesized by the sol-gel method in the presence of N, N-dimethylformamide (DMF). The formation of pure MgFe₂O₄ was confirmed by powder X-ray diffraction (XRD) and electron diffraction. The structural evolution of MgFe₂O₄ nanocrystals was followed by powder X-ray diffraction and IR absorption spectroscopy. The formation of spinel structure of MgFe₂O₄ started at 800 °C, and completed at 900 °C. The transmission electron microscopy (TEM) measurements suggest that the particle sizes increase with the increasing annealing temperature, and the mean particle sizes of the spherical samples annealed at 800 °C, 900 °C and 1 050 °C are ca. 3 nm, 8 nm and 11 nm, respectively. Magnetization measurements at room temperature and 78 K indicate superparamagnetic nature of these MgFe₂O₄ nanocrystals. Funded by the National Natural Science Foundation of China(No. 30771676), the Natural Science Foundation of Jiangsu Province (No. BK20081842), and the Foundation of Nanjing Bureau of Personal for the Returned Overseas Chinese Excellent Scholars     

Preparation of Nanometer-structured TiO2 Thin Films by-Sol-Gel Method

The transparent anatse TiO2 nanometer thin films were prepared by the sol-gel method on soda-line glass,X-ray diffraction,thermal analysis and UV-visible spectrophotometer were used to analyze the formation of the phases,Only increasing the heat-treatment time,the average graing size has no obvious change,The mechanism of grain growth in TiO2 thin film is probably as follows:the grain of coating will become grain core later;TiO2 sol constantly deposited on the surface of TiO2 grain and formed membrance with increasing of coating cylce time ;TiO2 grain in the film grow steadily.     

Influence of thickness on the properties of solution-derived LiMn<Subscript>2</Subscript>O<Subscript>4</Subscript> thin films

LiMn₂O₄ thin films of different thickness were derived from solution deposition and heat treated by rapid thermal annealing. The phase identification and surface morphology were studied by X-ray diffraction and scanning electron microscopy. The electrochemical properties of the films were examined by galvanostatic charge-discharge experiments and electrochemical impedance spectroscopy. LiMn₂O₄ thin films of different thickness derived from solution deposition and rapid thermal annealing are homogeneous and crack free with the grain size between 20 nm and 50 nm. The specific capacity of these films is between 42 and 47 μAh·cm²·μm⁻¹. The capacity decreases with the increase of discharge current density. The capacity loss per cycle increases from 0.012% to 0.16% after being cycled 50 times as the film thickness increases from 0.18 μm to 1.04 μm. The lithium diffusion coefficients of these films are in the same order of 10⁻¹¹ cm²·s⁻¹.     

Crystallization and Electrical Properties of （Ba0.4Pb0.3）Sr0.3TiO3 Thin Film by Pulsed Laser Deposition

（Ba0.4Pb0.3）Sr0.3TiO3 thin films were fabricated via pulsed laser deposition （PLD） technique on Pt/TiO2/SiO2/Si substrate. The crystallization of the films was characterized by XRD and FSEM, and the experimental results suggested deposition parameters, especially the deposition temperature was the key factor in forming the perovskite structure. The dielectric properties of the film deposited with optimized parameters were studied by an Agilent 4294A impedance analyzer at 1 MHz. The dielectric constant was 772, and the loss tangent was 0.006. In addition, the well-shaped hysteresis loop also showed that the film had a well performance in ferroelectric. The saturated polarization P, remnant polarization Pr and coercive field E were about 4.6 μC/cm2, 2.5 μC/cm2 and 23 kV/cm （the coercive voltage is 0.7 V）, respectively. It is suggested the film should be a promising candidate for microwave applications and nonvolatile ferroelectric random access memories （NvFeRAMs）.     

Synthesis,characterization and thermal stability of CeO<Subscript>2</Subscript> stabilized ZrO<Subscript>2</Subscript> ultra fine nanoparticles via a sol-gel route

CeO₂ stabilized ZrO₂ ultra fine nanoparticles were successfully synthesized via a simple and effective sol-gel synthetic approach by using zirconylchloride octahydrate, cerium nitrate hexahydrate, and citric acid as starting materials. A series of techniques, including X-ray diffraction (XRD), thermogravimetry (TG), differential scanning calorimetry (DSC), Fourier transform infrared spectroscopy (FTIR), transmission electron microscopy (TEM), and N₂-sorption analysis, were used to characterize the structure and morphology of the as-prepared samples. XRD studies indicate that the as-synthesized sample is of well crystallized tetragonal phase of CeO₂ stabilized ZrO₂ with high purity. TEM images show that the as-synthesized sample is composed of a large number of fine dispersive nanoparticles with an average size about 10 nm. The as-synthesized tetragonal CeO₂ stabilized ZrO₂ sample was heated at different temperatures in order to evaluate its thermal stability. The exprimental results reveal that the as-synthesized tetragonal CeO₂ stabilized ZrO₂ sample exhibits excellent stability without the occurrence of phase transformation.     

Solvothermal synthesis and photocatalytic performance of Bi<Subscript>2</Subscript>S<Subscript>3</Subscript> hierarchical nanostructure

The synthesis of Bi₂S₃ hierarchical nanostructure was reported by a solvothermal reaction using ethylene disulfhydrate as the sulfur source and chelating reagent. The as-synthesized samples were characterized by X-ray diffraction (XRD), Raman, X-ray photoelectron spectroscopy (XPS), scanning electron microscopy (SEM) and photoluminescence (PL). The XRD, Raman, and XPS data confirmed that the as-synthesized sample belongs to orthorhombic phase Bi₂S₃. The SEM observations displayed that Bi₂S₃ hierarchical nanostructure assembled from nanorods. A 410 nm ultraviolet photoluminescence (PL) emission of as-synthesized Bi₂S₃ was observed when the sample was excited with wavelength of 320-330 nm. The Bi₂S₃ hierarchical nanostructure also shows a significant enhancement of photocatalytic capability toward degrading methyl orange (MO) under UV light, the photodegradation of MO reaches 95% within 180 min.     

Synthesis and Characteristic of a New Niobate： BasNaCr0.5Nb9.5O30

A new niobate crystal was synthesized for the first time in BaO-NaO-Cr2O3-Nb2O3 system by the solid state reacition and the flux method. The new compound was studied by X-ray diffraction, electron probe, X-ray microanalysis, chemical analysis and SEM. The result of X-ray powder diffraction shows that Ba5NaCr0.5 Nb9.5O30 belongs to the tetragonal tungsten bronze structure, with space group P4 bin(100) and lattice parameters a=b=12. 4450 (2) A, c=3.9931 (2) A and Z=1. The X-ray powder diffraction lines of the compound were well indexed.     

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.     

Crystallization and luminescence properties of Sm<Superscript>3+</Superscript>-doped SrO-Al<Subscript>2</Subscript>O<Subscript>3</Subscript>-SiO<Subscript>2</Subscript> glass-ceramics

The Sm³⁺-doped SrO-Al₂O₃-SiO₂ (SAS) glass-ceramics with excellent luminescence properties were prepared by batch melting and heat treatment. The crystallization behavior and luminescent properties of the glass-ceramics were investigated by DTA, XRD, SEM and luminescence spectroscopy. The results indicate that the crystal phase precipitated in this system is monocelsian (SrAl₂Si₂O₈) and with the increase of nucleation/crystallization temperature, the crystallite increases from 66 % to 79 %. The Sm³⁺-doped SAS glass-ceramics emit green, orange and red lights centered at 565, 605, 650 and 715 nm under the excitation of 475 nm blue light which can be assigned to the ⁴G_5/2→⁶ H _j/2 (j=5, 7, 9, 11) transitions of Sm³⁺, respectively. Besides, by increasing the crystallization temperature or the concentration of Sm³⁺, the emission lights of the samples located at 565, 605 and 650 nm are intensified significantly. The present results demonstrate that the Sm³⁺-doped SAS glass-ceramics are promising luminescence materials for white LED devices by fine controlling and combining of these three green, orange and red lights in appropriate proportion.     

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.     

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）.     

Magnetically Recoverable PEI/Titanate@Fe<Subscript>3</Subscript>O<Subscript>4</Subscript> Photocatalysts: Fabrication and Photocatalytic Properties

The magnetically separable ternary polyetherimide/titanate@Fe₃O₄ (PTF) photocatalysts of special heterostructure between magnetite (Fe₃O₄) microspheres and titanates nanosheets modified by polyetherimide (PEI) were successfully fabricated via a simple facile hydrothermal deposition method. The as-prepared photocatalysts were characterized by Fourier transform infrared spectroscopy, X-ray diffraction, Transmission electron microscopy and UV-vis diffuse reflectance spectroscopy etc. The results showed that the as-fabricated material had a structure of Fe₃O₄ microspheres coated with titanates nanosheets modified by PEI. The special interfacial contact between 3D microsphere and 2D nanosheets in the nanoarchitectures was formed via electrostatic attraction. Furthermore, the resulted photocatalysts were tested by degradation reaction of methylene blue under visible light irradiation and demonstrated an enhanced performance than the pure Fe₃O₄ microspheres, and the photocatalytic activity enhanced with the molar ratio of Fe₃O₄ microspheres and modified titanate gradually, which was attributed to the expansion of the surface area and the different electrostatic contact between the Fe₃O₄ microspheres and titanate nanosheets. Moreover, the obtained results revealed the high yield magnetic separation and efficient reusability of PTF-5 (96.7%) over 3 times reuse.