Rietveld analysis of the effect of annealing atmosphere on phase evolution of nanocrystalline TiO2 powders

The structural evolution of nanocrystalline TiO2 was studied by X-ray diffraction (XRD) and the Rietveld refinement method (RRM). TiO2 powders were prepared by the sol-gel technique. Post annealing of as-synthesized powders in the temperature range from 500 degrees C to 800 degrees C under air and argon atmospheres led to the formation of TiO2 nanoparticles with mean crystallite size in the range of 37-165 nm, based on the Rietveld refinement results. It was found that the phase structure, composition, and crystallite size of the resulting particles were dependent on not only the annealing temperature, but also the annealing atmosphere. Rietveld refinement of the XRD data showed that annealing the powders under argon atmosphere promoted the polymorphic phase transformation from anatase to rutile. Field emission scanning electron microscopy (FESEM) was employed to investigate the morphology and size of the annealed powders.     

Fabrication and characterization of nanocrystalline oxides by crystallization of amorphous precursors

Amorphous zirconia and alumina powders were produced by the electrochemical deposition. Hot-pressing of the zirconia powder at 2.5 GPa and 360°C for 30 min caused simultaneous consolidation of the powder to a dense body and crystallization of a nanocrystalline tetragonal phase. Cold-pressing of the same powder at 2.5 GPa and sintering at 600°C or 800°C for 1 hr resulted in large tetragonal crystallites within the highly porous compacts. Cold-pressing of alumina powder at 2.5 GPa and sintering at 500°C, or 900°C for 2 hrs resulted in partial crystallization of the amorphous phase to a mixture of various polymorphs of alumina. The microstructure was inhomogeneous and composed of both nanometer and submicrometer grains. Microhardness of the hot-pressed partially crystallized nanocrystalline tetragonal zirconia was comparable to that of single crystal monoclinic phase, and decreased after annealing at 450°C for 30 min. Microhardbess of the nanocrystalline alumina was lower by on order of magnitude than that of conventional polycrystalline alumina. The decrease in the microhardness of the sintered specimens was related both to the grain size and the porosity.     

Effects of the annealing temperature on the structure and up-conversion photoluminescence of ZnO film

The up-conversion film is being tried to increase the photoelectric conversion efficiency of the silicon solar cell. To improve the efficiency of the photoluminescence film, the effects of the annealing temperature were investigated on the structure and photoluminescence of the ZnO up-conversion film, which was prepared using the sol-gel method and the spin-coating technique. The results show that the organic compounds and water in the ZnO film were completely eliminated when the annealing temperature reached 500?°C. The crystallinity of film is improved and the average grain size continuously increases as increasing the annealing temperature. The transmittance in the wavelength range of 400–2000?nm continuously increases as the annealing temperature increases from 500?°C to 700?°C, whilst it decreases first and then increases as the annealing temperature increases from 800?°C to 1000?°C. When the film is excited with a laser of 980?nm, there are two intense emission bands in the up-conversion emission spectra, 542-nm green light and 660-nm red light, corresponding to Ho³⁺: ⁵S₂/⁵F₄?→?⁵I₈?and ⁵F₅?→?⁵I₈ transitions, respectively. In addition, the intensity of up-conversion luminescence for the film increases first and then decreases with the increase of the annealing temperature. When the annealing temperature is at 900?°C, the film consists of small round compact particles with a high degree of crystallization, reaching maximum up-conversion intensity of the film.     

Preparation of novel calcia-stabilized TZP ceramics

The preparation of tetragonal zirconia polycrystal (TZP) ceramics stabilized by the addition of calcia is presented. These novel ceramics were obtained by means of a fast-firing treatment applied to compacts of nanocrystalline powders with a composition of ZrO₂ — 4 mol% CaO. Powders were synthesized by a nitrate-citrate gel-combustion process and they exhibited the tetragonal phase at room temperature due to their small crystallite size (12–13 nm). These powders were compacted by uniaxial pressing and fired at 1400–1500 °C for 3–5 min, obtaining fine-grained, dense ceramics, which also retained the metastable tetragonal phase. Longer heat treatments increased the average grain size leading to large amounts of the monoclinic phase. It was also found that the critical grain size for the tetragonal-to-monoclinic transformation is about 150 nm for this composition. This small value explains the necessity of a fast-firing treatment of the samples, allowing densification but avoiding a significant grain growth.     

Study on martensitic transformation of mechanically alloyed nanocrystalline Fe–Ni

Phase transformation of Fe–Ni powders with different nickel content during mechanical alloying was studied, as well as reverse transformation of mechanically alloyed nanocrystalline Fe–Ni upon heating. Results show that nickel content plays an important role in the phase transformation tendency during mechanical alloying. When heated at 300 °C, neither grain size nor phase changes in Fe–30 wt.% Ni milled for 80 h, indicating the nanometer-sized martensite is very stable below 300 °C. When the temperature increases to 350 °C, concurrently with grain growth reverse transformation takes place. The reverse transformation temperature of mechanically alloyed nanocrystalline Fe–Ni is higher than that of bulk alloys.     

Y2O3∶Eu$1纳米晶的尺寸调控与发光性能研究

以尿素为沉淀剂,柠檬酸为表面活性剂,通过水热法得到了非晶态的水合硝酸氧钇前驱体,进一步烧结处理后生成了立方相Y2 O3纳米晶．利用X－射线衍射（ XRD）、扫描电镜（ SEM）、透射电镜（ TEM）、红外光谱（ FTIR）和荧光光谱（ PL）分别对所得样品的相结构、形貌粒度、表面结构以及发光性能进行研究．结果表明：当烧结温度从600℃升高到900℃,Y2 O3∶Eu3＋纳米颗粒的结晶性增强,并实现了粒径调控,由13．0 nm增加至27．9 nm．随着Y2 O3∶Eu3＋纳米颗粒尺寸的增加,比表面积减小会导致发光离子附近的表面晶格缺陷降低,同时纳米晶表面吸附水、硝酸根以及柠檬酸根等杂质离子逐渐被去除,减少了荧光猝灭中心,从而有利于增强荧光发射强度以及延长荧光寿命．     

纳米铌酸钾钠陶瓷的制备及性能

以新型溶胶-凝胶法制备的平均晶粒尺寸为30 nm的铌酸钾钠粉体为原料, 采用放电等离子体烧结工艺, 在烧结温度为900℃, 压力30 MPa, 烧结时间1 min的条件下, 制备得到纯正交相, 相对密度高达99%以上, 平均晶粒尺寸为40 nm的纳米铌酸钾钠陶瓷, 并对该陶瓷的相结构、微观形貌、介电性能和铁电性能进行了研究。结果表明, 与普通微米晶陶瓷不同, 纳米铌酸钾钠陶瓷的室温介电常数仅为341, 并且随温度变化不明显, 表现出明显的介电弛豫现象, 弥散因子γ为1.60, 并具有明显的电滞回线, 矫顽场强度为13.5 kV/cm, 剩余极化为1.5 μC/cm²。尺寸降低所引起的纳米铌酸钾钠陶瓷中晶界相所占的比例增大是其性能变化的主要原因, 并且可以推断, 如果铌酸钾钠陶瓷具有“临界尺寸”, 那么其值应该在40 nm以下。     

Surface Nanocrystalline of Martensite Steel Induced by Sandblasting at High Temperature

The mechanical and tribological properties were conducted to investigate surface nanocrystalline of martensite steel with hardness of 5 GPa by using sandblasting technique at 500 °C. The average grain size of surface is 30 nm. In contrast, the average grain size of the martensite steel surface, which processed by sandblasting at room temperature and post‐annealing at 500 °C, is 112 nm. Fine grains and Fe₃C phase in situ form during sandblasting at 500 °C that is favor for producing nanoscale structure of the martensite steel. The nanostructure surface of the martensite steel has higher hardness and better wear resistance.     

Effect of Hf additions on phase transformation,microstructural stability,and hardness of nanocrystalline 304L stainless steels synthesized by mechanical alloying

304L stainless steels with Hf additions were nanostructured by mechanical alloying (MA) and annealed at temperatures up to 1100 °C. The results showed that face-centered cubic (fcc) phase in 304L transformed to body-centered cubic (bcc) phase during MA. The in-situ studies revealed that bcc-to-fcc phase transformation completed after 105 min annealing at 900 °C for 304L, whereas Hf addition increased the required time and temperature for the complete transformation. The grain size of 304L stainless steel was ~10 nm after MA and remained ~167 and ~293 nm after annealing at 900 and 1100 °C, respectively, with Hf addition in comparison to 960 nm average grain size of base 304L stainless steel after annealing at 900 °C. The hardness of 304L increased from ~200 HV to 408 HV after MA and remained 329 HV after annealing at 1100 °C with Hf addition as opposed to 195 HV hardness of 304L.     

Bi3.45Eu0.55Ti3O12铁电薄膜的光学性能

采用化学溶液沉积法在石英衬底上制备了Bi3.45Eu0.55Ti3O12(BEuT)铁电薄膜,研究了BEuT薄膜的结构和光学性能。XRD测试结果表明,BEuT薄膜皆形成铋层状钙钛矿型结构,其晶粒尺寸随着退火温度的提高而增加。薄膜的光学透过率曲线显示,在大于500nm的波段BEuT的透过率比较高,而其禁带宽度大约为3.61eV。BEuT薄膜的发光强度随着退火温度的提高,先是增强后减弱,在700℃时达到最大。这与薄膜的结晶状况有关。     

Incontinuous grain growth in cobalt nanocrystalline powders prepared by high-energy mechanical milling

Cobalt nanocrystalline powders with the average grain size of about 17 nm were prepared by high-energy mechanical milling. Grain growth in highly pure and particle-containing nanocrystalline Co powders were investigated respectively by a series of annealing experiments at different temperatures. The characteristics of incontinuous grain growth were found in both the pure and the particle-containing nanocrystalline powders. It is proposed by the authors that the sharp increase in nanograin size in the transition between the low and high temperature regions is a result of enhanced grain growth promoted by the stored energy as a supplied driving force, based on which rapid grain growth occurs through a particular dominant mechanism of nanograin rotations in the pure nanocrystalline powders, and that through off-pinning of grain boundaries in the particle-containing nanocrystalline powders.     

Annealing Effect of Magnetostriction in Fe49Co49V2 Alloy

Research Institute of Industrial Science & Technology, P.O.Box 135 Pohang, 790-600, Korea A Fe49Co49V2 alloy was annealed at 500, 750, 800 and 900℃. The magnetostriction was measured by Michelson laser interferometer to receive the feedback signal of OPL variation. With the increase of annealing temperature, the grain size of texture in samples increases due to the recrystallization. Magnetostriction of 2× 10-6 at H＝60 Oe increases up to 38 × 10-6 at annealing temperature of 900C, suggesting that the magnetostrictive characteristics are improved by the microstructural modification.     

Grain growth behavior of nanocrystalline Inconel 718 and Ni powders and coatings

Nanocrystalline Inconel 718 and Ni powders were prepared using two approaches: methanol and cryogenic attritor milling. High velocity oxy-fuel (HVOF) spraying of milled Inconel 718 powders was then utilized to produce coatings with a nanocrystalline grain size. Isothermal heat treatments were carried out to study the thermal stability of the methanol milled and cryomilled powders, as well as the HVOF-derived coatings. All nanocrystalline Inconel 718 powders and coatings studied herein exhibited significant thermal stability against grain growth by maintaining a grain size around 100 nm following annealing at 1273 K for 60 min. In the case of the cryomilled nanocrystalline Ni powders, isothermal grain growth behavior was studied, from which the parameters required for the prediction of the microstructural evolution during a non-isothermal annealing were acquired. The theoretical simulation of grain growth behavior of nanocrystalline Ni during non-isothermal annealing conditions yields results that are in good agreement with the experimental results.     

Fabrication of Mg2Si thermoelectric materials by mechanical alloying and spark-plasma sintering process

A mixture of pure Mg and Si powders with an atomic ratio 2:1 has been subjected to mechanical alloying (MA) at room temperature to prepare the Mg2Si thermoelectric material. Mg2Si intermetallic compound with a grain size of 50 nm can be obtained by MA of Mg66.7Si33.3 powders for 60 hours and subsequently annealed at 620 degrees C. Consolidation of the MA powders was performed in a spark plasma sintering (SPS) machine using graphite dies up to 800-900 degrees C under 50 MPa. The shrinkage of consolidated samples during SPS was significant at about 250 degrees and 620 degrees C. X-ray diffraction data shows that the SPS compact from 60 h MA powders consolidated up to 800 degrees C consists of only nanocrystalline Mg2Si compound with a grain size of 100 nm.     

Phase stabilization and structural studies of nanocrystalline La<Superscript>2</Superscript>O<Superscript>3</Superscript>-ZrO<Superscript>2</Superscript>

La²O³ doped nanocrystalline zirconia (ZrO²) has been prepared by chemical co-precipitation method for various dopant concentrations, varying from 3 to 30 mol%. Structural phases have been characterized by X-ray diffraction technique. All the as-synthesized samples were found to be in monoclinic phase. Annealing of the samples at different temperatures from 400 to 1000∘C stabilized ZrO² either partially or fully the tetragonal/cubic phases. When they were annealed at 1200∘C, the monoclinic phase appeared again with a new cubic pyrochlore structured La²Zr²O⁷ at the expense of stabilized tetragonal phase. Formability of the tetragonal/cubic phase has been influenced by the dopant concentration and the annealing temperature. Sample with 8 mol% La²O³ has been stabilized completely in tetragonal/cubic phase after annealing at 900∘C for 1 h. Smallness of the grain in these nanocrystalline materials may also have assisted in the formation of La²O³-ZrO² solid solution.     

Influence of the Cd/S Molar Ratio on the Optical and Structural Properties of Nanocrystalline CdS Thin Films

Nanocrystalline CdS thin films have been deposited using precursors with different thiourea concentrationonto glass substrates by sol-gel spin coating method.The crystalline nature of the films has been observedto be strongly dependent on thiourea concentration and annealing temperature.The CdS films are found tobe nanocrystalline in nature with hexagonal structure.The grain size is found to be in the range of 7.6 to11.5 nm depending on the thiourea concentration and annealing temperature.The high resolution transmissionelectron microscopy (HRTEM) results of the CdS films prepared using cadmium to thiourea molar ratio of0.3:0.3 indicate the formation of nanocrystalline CdS with grain size of 5 nm.Fourier transform infrared (FTIR)analysis shows the absorption bands corresponding to Cd and S.The optical study carried out to determinethe band gap of the nanostructured CdS thin films shows a strong blue shift.The band gap energy has beenobserved to lie in the range of 3.97 to 3.62 eV following closely the quantum confinement dependence ofenergy on crystallite radius.The dependence of band gap of the CdS films on the annealing temperature andthiourea concentration has also been studied.The photoluminescence (PL) spectra display two main emissionpeaks corresponding to the blue and green emissions of CdS.     

Synthesis,luminescence, and effect of heat treatment on the properties of Y<Subscript>3</Subscript>Al<Subscript>5</Subscript>O<Subscript>12</Subscript>:Ce phosphor

YAG:Ce nanosized spherical precursors were synthesized by coprecipitation using ammonium hydrogen carbonate as precipitant. Composition, phase transition, morphologies, and luminescence properties of the powders during calcination were studied. The precursors directly convert to pure YAG structure at about 900°C. The mean size of precursors is about 100 nm, and the grain size increases with increase of calcination temperature. When calcined above 1400°C, the grain size comes into a micrometer. With increase of calcination temperature, the luminescent intensity increases, and the emission band shows a redshift, while the lifetime increases.     

钆锆烧绿石粉体的高温固相制备工艺

为获得钆锆烧绿石(Gd2Zr2O7)粉体的制备工艺条件,以Gd2O3和ZrO2粉体为原料,在温度为1 300～1 500℃的条件下,采用高温固相法制备钆锆烧绿石粉体;采用X射线衍射法对所制备的样品进行物相与结构分析,用扫描电子显微镜观察样品的微观形貌。结果表明,在常压、保温72 h的条件下,钆锆烧绿石的最佳煅烧温度为1 500℃,此时所制备的晶体结晶程度高,晶粒尺寸在3μm左右。     

Preparation and optical properties of GaN nanocrystalline powders

Abstract

GaN nanocrystalline powders were synthesised by decomposition of gallium nitrate, followed by nitrogenising with ammonia under different temperature. X-ray diffraction (XRD) and the transmission electron microscopy (TEM) indicated that the crystallinity of the powder is improved and the average size of the GaN nanocrystallites increases from 4·8 to 23·9 nm as the temperature increases from 850 to 1050°C. The Raman spectra displayed four broadened peaks corresponding to A₁ (LO), A₁ (TO), E₁ (TO) and E₂ (high) modes of würtzite GaN respectively. Two additional modes at 252 and 421 cm^–1 attributed to boundary phonons activated by the finite size effects and octahedral Ga–N₆ bonds were observed respectively. A strong blue photoluminescence (～353 nm) was detected for room temperature measurement, indicating that the GaN nanocrystalline powders have few defects and high quality.     

溶胶-凝胶法制备Sb掺杂的α-Fe2O3纳米晶过程的结构研究

以FeCl3·6H2O为源物质，用溶胶－凝胶法制备了Sb掺杂的α-Fe2O3纳米晶粉末，并用X射线衍射、穆斯堡尔谱仪、差热分析和透射电镜对系统的相转变和显微结构进行了研究．干凝胶为Fe（OH）3非晶相，经一定温度热处理晶化为α-Fe2O3相．体系中掺杂适量的Sb后，Sb分布在非晶颗粒的表面，不影响非晶相的结构，但显著提高了晶化温度，阻缓了α-Fe2O3晶粒的生长，有利于获得纳米晶；对其机理进行了讨论．