机械合金化制备Cu-Cr-C复合粉体

以Cu、Cr、C粉末为原料,采用机械合金化方法制备CuCr-C复合粉体,其中Cr、C的添加量按照Cr_3C_2质量分数为5%来计算;利用X射线衍射(XRD)和扫描电镜(SEM)研究机械合金化过程中粉末的物相和微观形貌,并结合能谱仪(EDS)面扫描得到粉末的元素微观分布。结果表明:随着机械合金化的进行,C、Cr和Cu形成Cu-Cr-C过饱和固溶体,随着球磨时间的延长,粉末粒径细化,颗粒形态由片状向球状发展;球磨30 h后,生成Cr_3C_2增强相,粉末细化趋势变缓并逐渐产生团聚,故原位生成Cr_3C_2的最佳球磨时间为30 h。     

Formation mechanism of titanium silicide by mechanical alloying

The syntheses of five titanium silicides (Ti₃Si, TiSi₂, Ti₅Si₄, Ti₅Si₃, and TiSi) by mechanical alloying (MA) have been investigated. Rapid, self-propagating high temperature synthesis (SHS) reactions were involved in producing the last three materials during room temperature high-energy ball-milling of elemental powders. Such reactions appeared to occur through ignition by mechanical impact in the fine powder mixture formed after a critical milling period. From in-situ thermal analyses, each critical milling period for the formation of Ti₅Si₄, Ti₅Si₃, and TiSi was observed to be 22, 35.5 and 53.5 minutes, respectively. However, the formation of Ti₃Si and TiSi₂ did not occur even after 360 minutes of milling of as-received Ti and Si powder mixture, due to the lack of homogeneity of the powder mixture. Other ball-milling procedures were employed for the syntheses of Ti₃Si and TiSi₂ using different sizes of Si powder and milling medium materials. Ti₃Si was synthesized by milling a Ti and 60 minutes premilled Si powder mixture for 240 minutes. -TiSi₂ and TiSi₂ were produced by high energy partially stabilized zirconia (PSZ) ball-milling for 360 minutes in a steel vial followed by jar-milling of a Ti and 60 min premilled Si powder mixture for 48 hr. The formation of Ti₃Si and TiSi₂ occurs through a slow solid state diffusion reaction, and the product(s) and reactants coexist for a certain period of time. The formation of titanium silicides by MA and the reaction rate appeared to depend on the homogeneity of the powder mixture, milling medium materials, and heat of formation of the product involved.     

Sintering of nanostructured W-Cu alloys prepared by mechanical alloying

Nanostructured (NS) powders with compositions corresponding to W-20wt%Cu and W-30wt%Cu were prepared by mechanical alloying. The microstructure and grain size of as-milled and annealed powders were analyzed by transmission electron microscopy. The compacted specimens were sintered at temperatures in the range 1000 °–1300 °, and then the microstructures of sintered parts were analyzed by scanning electron microscopy. Sintering of mechanically alloyed W-Cu alloys appears to be independent of Cu content, and may be explained in terms of recovery and grain growth in the mechanically alloyed powders as well as impurity activated sintering of W. After sintering, Cu pools are formed outside the mechanically alloyed powders. A relative sintered density of more than 95% is obtained by particle rearrangement during liquid-phase sintering, and the greatest homogeneity of W and Cu phases is achieved by sintering at 1200 °.     

Thermoelectric properties of chromium disilicide prepared by mechanical alloying

CrSi and Cr_1?x Fe _x Si particles embedded in a CrSi₂ matrix have been prepared by hot pressing from CrSi_1.9, CrSi₂, and CrSi_2.1 powders produced by ball milling using either WC or stainless steel milling media. The samples were characterized by powder X-ray diffraction, scanning, and transmission electron microscopy and electron microprobe analysis. The final crystallite size of CrSi₂ obtained from the XRD patterns is about 40 and 80 nm for SS- and WC-milled powders, respectively, whereas the size of the second phase inclusions in the hot pressed samples is about 1–5 μm. The temperature dependence of the electrical resistivity, Seebeck coefficient, thermal conductivity, and figure of merit (ZT) were analyzed in the temperature range from 300 to 800 K. While the ball-milling process results in a lower electrical resistivity and thermal conductivity due to the presence of the inclusions and the refinement of the matrix microstructure, respectively, the Seebeck coefficient is negatively affected by the formation of the inclusions which leads to a modest improvement of ZT.     

Structural,electronic, and mechanical properties of niobium nitride prepared by thermal diffusion in nitrogen

Niobium nitride (NbN_x) was prepared by heating Nb sample in a nitrogen atmosphere (133 Pa) at a temperature of 900 °C. The structural, electronic, nanomechanical and surface properties of the deposited layers have been determined as a function of processing time. The results suggested that the niobium nitride was crystalline in the single phase of hexagonal β-Nb₂N and the nitrogen-to-niobium ratio was found to be in the range of 0.67 ± 0.03 to 0.74 ± 0.03. Longer processing times resulted in layers with higher nitrogen-to-niobium ratios. The mean grain size of these nitrides was about 18 nm. The valence band photoemission and calculated density of state spectra characterized by two peaks were associated with N 2p-Nb 4d hybridization. X-ray photoemission spectra of Nb 3p and 3d core levels revealed a strong interaction with nitrogen along with binding energy shift. As the processing time was increased, the film growth continued with consistent improvement in hardness and modulus.     

Lead free solder alloys Sn-Zn and Sn-Sb prepared by mechanical alloying

The mechanical alloying (MA) processes of tin-9zinc (Sn-9Zn) and tin-5antimony (Sn-5Sb) were analyzed using an X-ray diffractometer, a differential scanning calorimeter (DSC) and a scanning electron microscope (SEM). The results showed that supersaturated solid solution and intermetallic compound were produced during the MA process. The size of powder particles could be controlled under the proper MA conditions and was reduced to 5 to 20 m. As a surfactant, proper addition of rosin allows MA to occur smoothly. However, it may also be a source of contamination of the metallic powder. It is considered that MA may be a technique analogous to casting to prepare solder alloys.     

Grain growth in nanocrystalline NbAl3 prepared by mechanical alloying

Grain growth and its kinetics were studied on an intermetallic compound, NbAl₃ powder prepared by mechanical alloying of elemental Nb and Al powders for 1.8 Ms in an argon atmosphere at ambient temperature. The initial and grown grain sizes were measured from the X-ray line broadening of as-alloyed and annealed powders. Isochronal annealing of mechanically alloyed powders from 573 to 1373 K indicated that substantial grain growth occurs only in a temperature range of 1048 to 1173 K and ceases at 1273 K regardless of anneal time. Accordingly isothermal annealing of 1.8 to 18 ks was carried out at 1048, 1073 and 1098 K to obtain the grain growth kinetic that is described by In (dD/dt) = In(r_o/3) –2.0 In D where D is the measured grain size and r _o a constant. This r _o depends on temperature according to r _o=r_o exp (– Q/kT) where Q is the activation energy for grain growth, k the Boltzmann constant and T the absolute temperature. Arrhenius plots of r _o against the reciprocal of temperature yield a straight line, from whose slope the activation energy for grain growth is deduced to be 162±2 kJ mol^–1. Of significance is the fact that the ultimate grain size at 1273 K is approximately 70 nm, which will not grow by further annealing even at 1373 K.On leave from Ibaraki University, Japan.     

Thermal and mechanical properties of uranium nitride prepared by SPS technique

Nitride fuel is a promising nuclear fuel in fast breeder reactor (FBR) or accelerator-driven subcritical reactor (ADSR) system. In this study, high-density UN pellets were prepared by Spark plasma sintering (SPS) technique. The sample density strongly depended on the sintering temperature and pressure, and the pellets with 90% of theoretical density were easily obtained with low sintering temperature and short sintering time without any milling process. The grain size and pore size were much smaller compared with those for samples prepared by conventional sintering process. Despite of the small grain size, the thermal conductivity remains the high value. The SPS process permits easy densification of nitrides without any deterioration of thermal and mechanical properties, considered to be suitable as a preparation method of nitride fuels.     

The reaction of hydrogen with Mg-Cd alloys prepared by mechanical alloying

In this paper, we present the hydrogen storage properties of Mg-Cd alloys prepared by ball milling. Mechanical alloying of a mixture of Mg and Cd elemental powders containing up to 20 at.%Cd leads to a magnesium solid solution. The lattice spacings of the hcp Mg phase shrink with dissolution of cadmium atoms in Mg. The mechanically alloyed pure Mg-Cd alloys are very difficult to activate for hydrogen absorption. However, if vanadium and graphite additives are added, a Mg(Cd)-V-C nanocomposite forms after ball milling and the activation then becomes very easy. The hydrogen absorption/desorption kinetics are very fast. The plateau pressure and slope of hydrogen absorption/desorption increase, while the hydrogen storage capacity decreases with increasing cadmium content.     

Application of AFM to study functional nanomaterials prepared by mechanical alloying

Two-phase hard magnetic Nd₂Fe₁₄B/α-Fe nanocomposites and nanocrystalline TiFe electrode materials were prepared by mechanical alloying and heat treatment. The microstructure of both types of functional nanomaterials was investigated by atomic force microscopy. In the case of Nd₂Fe₁₄B magnetic phase, the microstructure refinement was realised by careful heat treatment and Zr addition. AFM investigations showed that Zr reduces a grain size of a parent alloy in the range of 20-40%. More than 90% grains have size below 50 nm, and more than 50% grains have size below 20 nm, which results in enhanced remanence. On the other hand, in TiFe alloy, a fine microstructure is known to improve greatly the properties of hydrogen storage alloys, when compared with their conventional polycrystalline counterparts. Additionally, the substitution of Fe by some amount of nickel improves the activation property of TiFe. Two types of AFM imaging modes, height and deflection, are accurate for agglomerate and grain size presentation, respectively.     

Structural and microstructural characterizations of nanocrystalline hydroxyapatite synthesized by mechanical alloying

Single phase nanocrystalline hydroxyapatite (HAp) powder has been synthesized by mechanical alloying the stoichiometric mixture of CaCO₃ and CaHPO₄ powders in open air at room temperature, for the first time, within 2 h of milling. Nanocrystalline hexagonal single crystals are obtained by sintering of 2 h milled sample at 500 °C. Structural and microstructural properties of as-milled and sintered powders are revealed from both the X-ray line profile analysis and transmission electron microscopy. Shape and lattice strain of nanocrystalline HAp particles are found to be anisotropic in nature. Particle size of HAp powder remains almost invariant up to 10 h of milling and there is no significant growth of nanocrystalline HAp particles after sintering at 500 °C for 3 h. Changes in lattice volume and some primary bond lengths of as-milled and sintered are critically measured, which indicate that lattice imperfections introduced into the HAp lattice during ball milling have been reduced partially after sintering the powder at elevated temperatures. We could achieve ~ 96.7% of theoretical density of HAp within 3 h by sintering the pellet of nanocrystalline powder at a lower temperature of 1000 °C. Vickers microhardness (VHN) of the uni-axially pressed (6.86 MPa) pellet of nanocrystalline HAp is 4.5 GPa at 100 gm load which is close to the VHN of bulk HAp sintered at higher temperature. The strain-hardening index (n) of the sintered pellet is found to be > 2, indicating a further increase in microhardness value at higher load.     

Nanostructured electrode materials for Ni-MH x batteries prepared by mechanical alloying

Nanocrystalline TiFe- and Mg₂Ni-type alloys were prepared by mechanical alloying followed by annealing. The structure and electrochemical properties of these materials were studied. The properties of hydrogen host materials can be modified substantially by alloying to obtain the desired storage characteristics. It was found that the respective replacement of Fe in TiFe by Ni and Mn improved not only the discharge capacity but also the cycle life of these electrodes. On the other hand, a partial substitution of Mg by Mn in Mg_2?x M _x Ni alloy leads to an increase in discharge capacity, at room temperature. Furthermore, the effect of the nickel and graphite coating on the structure of the nanocrystalline alloys and the electrodes characteristics were investigated. In Mg₂Ni-type alloy mechanical coating with graphite effectively reduced the degradation rate of the studied electrode materials.     

Morphology and preferred orientation of titanium nitride plates prepared by chemical vapour deposition

Thick titanium nitride (TiN _x ; x = 0.74–1.0) plates (up to 2 mm thick) were prepared by chemical vapour deposition using TiCl₄, NH₃ and H₂ as source gases at a total gas pressure, P _tot, of 4 kPa, deposition temperatures, T _dep, from 1373–1873 K, and NH₃/TiCl₄, m _N/Ti, gas molar ratio from 0.17–1.74. The effects of deposition conditions on morphology, preferred orientation and composition of CVD-TiN _x plates were investigated. Surface morphology changed from faceted to nodular texture with increasing m _N/Ti and T _dep. The faceted and nodular deposits showed columnar and shell-like fracture cross-sections, respectively. The composition (x = N/Ti) increased with increasing m _N/Ti and T _dep below m _N/Ti = 1.0, and was constant above m _N/Ti = 1.0. Three kinds of preferred orientations were observed: (100) orientation at low T _dep, (110) orientation at intermediate T _dep and low m _N/Ti, and (111) orientation at high T _dep and high m _N/Ti. This tendency is discussed thermodynamically, and explained as being due to changes in the degree of supersaturation in the gas phase.     

Linear and non-linear optical properties of capped CdTe nanocrystals prepared by mechanical alloying

CdTe nanocrystals were prepared by mechanical alloying the elemental Cd and Te powders. The formation of CdTe with a single cubic phase after 20 h of ball milling was confirmed by X-ray diffraction (XRD). The surface of as-milled CdTe nanoparticles was then capped with polarization TOP/TOPO or (Na₃PO₄)_n organic ligand, which resulted in colorful dispersion solution with optical absorption peaks located at 573 nm and 525 nm, respectively. The third-order non-linearity, namely, the non-linear refraction and two-photon absorption (TPA) coefficient, of the capped CdTe dispersion samples were evaluated using Z-scan technique. The fitting of Z-scan experimental data with a special equation demonstrated that the capped CdTe nanocrystals possess large third-order susceptibilities at resonant wavelength. The non-linear figure of merit (γ/β) for 20 h as-milled CdTe nanocrystals after capping with TOP/TOPO was determined to be ∼ −2 × 10⁻⁵ m, which is nearly 215 times larger than the value reported for bulk CdTe crystals.     

Grain growth and recrystallization of nanocrystalline Al3Ti prepared by mechanical alloying

The grain sizes and lattice strains during mechanical alloying of Ti-75 at.% Al powder mixtures were studied using X-ray diffraction methods. Nanocrystalline L1₂-Al₃Ti was obtained after a certain time period of ball milling. Minimum grain sizes of 17 nm for Al and 28 nm for Ti have been determined using XRD. During subsequent thermal annealing processing, an obvious recrystallization resulting in significant reduction of grain size was observed. The recrystallization in nanocrystalline Al₃Ti was affected by both the temperature and the degree of order. The incubation period for recrystallization at 400°C was about 6 hours while those at 510 and 700°C were about 2 hours. The completion time of recrystallization in Al₃Ti at 400 and 700°C was about 15 hours and 8 hours at 510°C. It is clear that the recrystallization at 700°C was retarded as a result of the higher degree of order structure which limited the mobility of the boundaries. Phase transformation occurring within the recrystallization temperature range was observed to have little influence on the recrystallization itself. However, transformation products do have significant effects on it which is originated from the degree of order in the products. The recrystallization in this alloy system provides an excellent means to maintain the nanocrystalline microstructure during the necessary consolidation thermal cycle by decreasing the processing temperature and increasing the hold time considerably.     

机械合金化法制备锂离子电池Si基负极材料及其电化学性能研究

Si具有高的储锂容量,但是其循环性能很差。采用机械合金化方法,对纯Si进行处理。同时以石墨、炭黑对纯Si进行掺杂以改善Si的循环特性。对于纯Si,随着球磨时间的延长,材料的非晶化程度增加;经过球磨后材料的平均粒径由原来的29μm变成0.2μm;由大的块状变为小的圆形颗粒。充放电结果表明未经球磨处理的纯Si的首次放电比容量较高,但放电比容量损失较大,循环性能差,而经过球磨的纯Si能增加首次放电比容量,循环性能变化不大;对纯Si采用石墨、炭黑掺杂后材料的首次放电比容量下降,循环性能有所提高;球磨和掺杂没有改变Si储锂的电位。经过阻抗分析发现,球磨后纯Si材料中Li的扩散系数增大。     

On some physical properties of nanostructured Cu-Pb alloy prepared by mechanical alloying

Cu-Pb alloys have no solubility in the whole solid state and their physical properties are very different from each other. In the present study, nanostructured Cu-Pb alloy powders were synthesized by the mechanical alloying process, and their nanostructural characteristics were evaluated in order to elucidate the relationship between structure and properties. By appropriate control of mechanical alloying process variables, the Pb solid solubility in Cu matrix was increased up to 10 wt.%. The monotectic temperature of Cu-Pb alloy was also decreased by decreasing the crystalline size. The relation between the structure and properties of this nanostructured Cu-Pb alloy is discussed on the basis of the experimental results.     

On the crystallization behavior of amorphous Fe-Cr-Mo-B-P-Si-C powder prepared by mechanical alloying

The crystallization behavior and thermal stability of Fe-Cr-Mo-B-P-Si-C amorphous alloy, prepared by mechanical alloying (MA), were investigated by using differential scanning calorimetry (DSC). One exothermic peak was observed on DSC traces, implying that the crystallization process undergoes only one stage. The crystallization kinetic parameters, including activation energy (E_a), Avrami exponent (n) were determined with non-isothermal analysis method based on the DSC data. The results suggest that the crystallization mechanism is governed dominantly by a three-dimensional diffusion-controlled growth. In addition a relatively high value of activation energy of crystallization (386.04 ± 10 kJ/mol) was found, indicating that this amorphous alloy has high thermal stability.