Formation of ultra-fine amorphous powders in Fe-M-B (M = transition metal) systems by chemical reduction method and their thermal and magnetic properties

Amorphous ultra-fine powders in (Fe or Co)-B and Fe-M-B (M = Cr, Mn, Co, or Ni) systems were produced by reduction of metal ions in an aqueous solution by use of KBH₄. The powders have a spherical shape with diameters ranging from 5 to 20 nm. The boron concentration is in the range of 24.1 to 44.1 at. pct and the composition of metal elements can be controlled by changing the concentration of metal ions. Crystallization temperatures and heats of crystallization for the Fe-Ni-B powders agree with those obtained for the amorphous alloys of the same composition produced by melt spinning. Furthermore, the compositional dependences of the crystallization temperature, coercivity, and magnetization measured in the field of 2 kOe are very similar to those obtained in the chemically synthesized (Fe-Co)₆₃B₃₇ amorphous powders and melt-spun (Fe-Co)₇₈Si₁₀B₁₂ or (Fe-Co)₇₅Si₁₅B₁₀ amorphous ribbons. It is concluded that there is no significant difference in the amorphous structure obtained in chemically synthesized powders and the melt-spun ribbons, in spite of an essential difference in the formation mechanism of these amorphous alloys. JUNJI SAIDA, on leave from Hanshin Research and Development Laboratories, Nisshin Steel Com-pany Ltd., Sakai 592, Japan     

Amorphous Zr-Based Foams with Aligned,Elongated Pores

Interpenetrating phase composites are created by warm equal channel angular extrusion (ECAE) of blended powders of amorphous Zr_58.5Nb_2.8Cu_15.6Ni_12.8Al_10.3 (Vit106a) and a crystalline ductile metal (Cu, Ni, or W). Subsequent dissolution of the continuous metallic phase results in amorphous Vit106a foams with ~40 pct aligned, elongated pores. The extent of Vit106a powder densification in the composites improves with the strength of the crystalline metallic powder, from low for Cu to high for W, with a concomitant improvement in foam compressive strength, ductility, and energy absorption.     

Structural evolution in mechanically alloyed Al-Fe powders

The structural evolution in mechanically alloyed binary aluminum-iron powder mixtures containing 1, 4, 7.3, 10.7, and 25 at. pct Fe was investigated using X-ray diffraction (XRD) and electron microscopic techniques. The constitution (number and identity of phases present), microstructure (crystal size, particle size), and transformation behavior of the powders on annealing were studied. The solid solubility of Fe in Al has been extended up to at least 4.5 at. pct, which is close to that observed using rapid solidification (RS) (4.4 at. pct), compared with the equilibrium value of 0.025 at. pct Fe at room temperature. Nanometer-sized grains were observed in as-milled crystalline powders in all compositions. Increasing the ball-to-powder weight ratio (BPR) resulted in a faster rate of decrease of crystal size. A fully amorphous phase was obtained in the Al-25 at. pct Fe composition, and a mixed amorphous phase plus solid solution of Fe in Al was developed in the Al-10.7 at. pct Fe alloy, agreeing well with the predictions made using the semiempirical Miedema model. Heat treatment of the mechanically alloyed powders containing the supersaturated solid solution or the amorphous phase resulted in the formation of the Al₃Fe intermetallic in all but the Al-25 at. pct Fe powders. In the Al-25 at. pct Fe powder, formation of nanocrystalline Al₅Fe₂ was observed directly by milling. Electron microscope studies of the shock-consolidated mechanically alloyed Al-10.7 and 25 at. pct Fe powders indicated that nanometer-sized grains were retained after compaction.     

Amorphous Phase Formation Analysis of Rapidly Solidified CoCr Droplets

This paper investigates amorphous phase formation and rapid solidification characteristics of a CoCr alloy. High cooling rate and high undercooling-induced rapid solidification of the alloy was achieved by impulse atomization in helium atmosphere. Two atomization experiments were carried out to generate powders of a wide size range from liquid CoCr at two different temperatures. Amorphous fraction and kinetic crystallization properties of impulse atomized powders were systematically quantified by means of differential scanning calorimetry. In addition, different but complementary characterization tools were used to analyze the powders microstructures. The fraction of amorphous phase within the investigated powders is found to be promoted by high cooling rate or smaller powder size. The critical cooling rate for amorphous phase formation, which is influenced by the oxygen content in the melt, is found to be ~3 × 10⁴ K s^?1 and corresponds to a 160-µm-diameter powder atomized in helium. Hardness of the powders is found to follow a trend that is described by the Hall–Petch relation when a relatively high fraction of crystalline structures is present and decreases with the fraction of amorphous phase.     

合金Co-Zr-B纳米粉末的相组成及磁性能研究

将硼氢化钠(NaBH4)的水溶液加入到氯化钴(CoCl2·6H2O)和硫酸锆(Zr(SO4)2·4H2O)的混合水溶液中,利用BH-4把混合溶液中的CO2 和Zr4 同时还原出来,首次成功制备出非晶态Co-Zr-B三元纳米合金粉末.用电感耦合等离子体发射光谱(ICP)、X射线衍射(XRD)、选区电子衍射(SAED)、透射电子显微镜(TEM)、差示扫描量热法(DSC)以及振动样品磁强计(VSM)分析了样品的成分、结构和磁性能.发现所制备的不同成分的粉末颗粒呈球形,粒径在20～60nm之间.纳米粉末由非晶相基体和少量晶体相杂质组成,而非晶相基体又由Zr基非晶颗粒和含有Zr的Co基非晶颗粒构成.还原产物中的Co原子和Zr原子的分数之比与金属盐混合溶液中的Co2 与Zr4 离子的分数之比几乎相等.提高NaBH4溶液的加入速度,可增加产物中B元素的含量.样品的晶化温度在765.1～771.3K之间,样品的热稳定性随Zr含量的增加而增加,样品的磁性能也与样品中Co、Zr原子的含量之比有关.当原子数x(Co)/x(Zr)比值从1.94增加到5.14时,饱和磁化强度从4.76emu/g增加到8.87emu/g,矫顽力在1271.66A/m(15.98Oe)到2133.49A/m(26.81Oe)之间不规则变化.     

Structure and Properties of Dysprosium Titanate Powder Produced by the Mechanochemical Method

The structure and main physicochemical properties of dysprosium titanate powders prepared by mechanochemical synthesis from the low-temperature modification of titanium oxide and modification of dysprosium oxide are investigated applying X-ray phase analysis (XPA), scanning electron microscopy, Raman spectroscopy (Raman spectra), transmission electron microscopy, and chemical analysis. It is established based on XPA that the initial oxides completely transform into X-ray amorphous dysprosium titanate (Dy₂TiO₅) during the mechanochemical treatment of a mixture for 30–60 min. A microelectron diffraction pattern of Dy₂TiO₅ powders prepared by mechanosynthesis has a ring structure characteristic of the X-ray amorphous phase with a certain amount of inclusions of a crystalline phase. The dysprosium titanate powder fabricated by induction melting possesses the regular cubic crystalline lattice with a parameter of 3.4 Å.     

Finely dispersed Si3N4−SiC powders and materials based on them

The objectives of the present research were to investigate the preparation of homogeneous ultrafine composite Si₃N₄−SiC powders by a plasmochemical process and the properties of ceramics produced from them. The chemical and phase compositions of the powders depended on the particle size of the initial powder, silicon input rate, and ratio of ammonium and hydrocarbon flow rates. The particle size and specific surface area of the compounds depended on the concentration of particles in the gas jet, and the cooling rate of the products. Composite powders containing from a few up to 90 mass % SiC, with specific surface areas of 24–80 m²/g and free silicon and carbon content less than 0.5 mass % were obtained. The main phases present were α-Si₃N₄, β-Si₃N₄, β-SiC, and X-ray amorphous Si₃N₄. Dense materials were prepared both by hot pressing at 1800°C under a load of 30 MPa and gas-pressure sintering at 1600–1900°C under a pressure of 0.5 MPa nitrogen. The plasmochemical composites had smaller pore sizes, were finer grained, and densified more rapidly than materials sintered from commercial powders. Institute of Inorganic Chemistry, Latvian Academy of Sciences, Salaspils. Translated from Poroshkovaya Metallurgiya, Nos. 1–2(405), pp. 7–12, January–February, 1999.     

以甲基纤维素作分散剂制备高分散超细银粉

以AgNO3为原料,抗坏血酸为还原剂,甲基纤维素为分散剂,采用化学液相还原法制备超细银粉,研究温度、分散剂用量、pH值等对银粉分散性、粒度和形貌的影响。结果表明,反应温度对银粉形貌有很大的影响,当温度为25和30℃时,银粉为不规则的类球形;当温度为40、50和60℃时,银粉均为树枝状。分散剂用量越大,银粉的分散性越好。pH值对银粉粒度有很大的影响,随pH值增加,银粉粒度逐渐减小,当pH值从2增加至10时,所得银粉粒度分别为2.26和0.053μm。最佳工艺为:温度为25℃,pH值为2,分散剂与抗坏血酸质量比为0.02,所得银粉分散性良好,平均粒度为2.21μm。     

缺碳预还原MoO3+氢气深脱氧工艺制备超细钼粉

以炭黑为还原剂还原MoO₃制备存在少量MoO₂的预还原Mo粉,然后对预还原Mo粉进行氢气深还原,成功制备出平均粒径为99～190 nm的超细钼粉,研究了碳热还原温度对Mo粉平均粒度和残碳量的影响。结果表明,在同一还原温度下,当C/MoO₃摩尔比从2.0增加到2.1时,产物的粒径变化很小。碳热还原温度对产物粒径和纯度有显著影响。当C/MoO₃摩尔比为2.1时,还原温度从950 ℃增加到1150 ℃,氢还原后钼粉的平均粒径从100 nm增加到190 nm,且残碳量（质量分数）由0.030%降低到0.009%。     

Effect of scandia on tungsten oxide powder reduction process

Scandia doped tungsten powders were prepared by spray drying combined with two-step hydrogen reduction. The particle size of doped tungsten powder, powder morphology and doped tungsten matrix were characterized by scanning electron microscope, X-ray diffraction and laser diffraction particle size analyzer, respectively. The reduction behavior of Sc₂O₃ doped tungsten oxide and the effect of Sc₂O₃ on the property of tungsten powder were studied by the temperature programmed reduction. The experimental results showed that the precursor powders prepared by spray drying had spherical shape. The addition of Sc₂O₃ could decrease the reduction temperature of tungsten oxide. The scandia doped tungsten powder had sub-micrometer size in the range of 0.1 to1 μm and scandium distributed evenly in the powder. By using this kind powder, sub-microstructure cathode matrices with semispherical grains and homogenous distribution of scandium were obtained.     

Synthesis, structure, and phase composition of Al-Al4C3 nanostructured materials

The morphology and phase composition of nanocrystalline powders of aluminum and carbon in the form of cluster diamonds are investigated. It is found that the hot compaction of the C-Al powder mixture is accompanied by the formation of an Al₄C₃ phase that has a highly disperse structure. The average crystallite size in hot-compacted materials is 40 nm for the metal matrix and 30 nm for aluminum. It is shown that as the carbon fraction in the initial powder mixture rises, the volume of the threshold space in hot-compacted materials increases.     

Compaction and characterization of mechanically alloyed nanocrystalline titanium aluminides

Blended elemental (BE) Ti-24 at. pct Al-11 at. pct Nb (Ti-24-11) and Ti-55 at. pct Al (Ti-55) powders and prealloyed (PA) Ti-24-11 powders were mechanically alloyed in a SPEX mill or an attritor. After SPEX milling for 10 hours, the BE Ti-24-11 powder contained the B2/bcc phase, while the BE Ti-55 powder showed the presence of an amorphous phase. The PA Ti-24-11 powder containing the B2 phase showed a decrease of crystal size on milling. These powders were consolidated by hot isostatic pressing (“hipping”), Ceracon process, and dynamic methods. On compaction, the B2/bcc phase in the Ti-24-11 sample transformed to a mixture of the B2 and orthorhombic (“O”) phases, while the amorphous phase in the Ti-55 powder crystallized to a mixture of the γ-TiAl and α ₂-Ti₃Al phases. The finest grain size in compacted material was obtained in the dynamically consolidated powder, and the grain size in the hot isostatic pressed (“hipped”) powder became larger with the increasing hipping temperature.     

Erbium photoluminescence response related to nanoscale heterogeneities in sol-gel silicates

Sol-gel glassy films of the SiO2-TiO2-PO2.5-ErO2.5 system containing nanocrystallites of ErPO4, were obtained through suitable heat treatments. Variations in the shape and intensity of the Er3+ photoluminescent signal around 1500 nm were linked to the nature of the host environment of the active ions; the specific features of the photoluminescent emission spectrum of the erbium 4I13/2 metastable level were interpreted in terms of structural changes in the glassy films. The photoluminescent spectrum was found to be sensitive to the order (crystalline) or disorder (amorphous) of the Er3+ ions neighbour within the glassy matrix. An amorphous environment led to a broadening of Er3+ PL emission band while a crystalline one was responsible for a drastic photoluminescent bandwidth narrowing. The presence of nanoscale heterogeneities caused a drastic photoluminescence intensity decrease. Changes in the shape of the decay curve of fluorescence lifetime were found also structurally dependent on volumetric defects, occurrence of phase separation and Er3+-Er3+ clustering effects as well.     

Influence of atomising gas on particle characteristics of Al,Al–1 wt-%Li,Mg, and Sn powders

Abstract

The influence of physical and flow properties of atomising gas on the particle characteristics of gas atomised Al, Al–1 wt-%Li, Mg, and Sn powders was investigated in a pilot plant gas atomiser with IN4/ON18/3·5–4·0 type ‘confined design’ nozzle. In the tests, Al powders were produced under high and low pressures of argon, under air, (N₂ + O₂ ) mixture, nitrogen, and helium; Al–1 wt-%Li binary alloy powders were produced under argon and helium; Mg powders were produced under high and low pressures of argon and helium; and finally Sn powders were produced under argon, nitrogen, and helium. The morphology, size, size distribution, and surface features of the powders used in the present study were examined under SEM together with dry and wet sieving, used for sizing the powders. It was observed that high gas velocities and/or low atomising gas densities not only affect powder particle size, but also shape and surface texture. The oxygen content of the atomising gases also has an influence on the powder particle shape. In this context, powders produced under helium are finer in size owing to efficient secondary breakup; more spherically shaped in their fine size fraction in non-oxidising or difficult to oxidise atomising liquids (such as Sn and Al), because the time to breakup is shorter than that for solidification; and more irregularly shaped in their coarse size fraction in oxidising atomising liquids (such as Mg and Al–Li) owing to oxygen (the time to breakup is longer than that for solidification) compared with other atomising gases such as argon, air, (N₂ +O₂ ) mixtures, and pure nitrogen.     

Recrystallization of silicon nitride powders during hot pressing

Conclusions The hot pressing of comminuted silicon nitride powders enables a uniform fine-grained structure of one and the same mean grain size to be obtained irrespective of the type of starting Si₃N₄, powder. At milling times of more than 100 h no significant decrease in particle size is observed. The recrystallization of milled silicon nitride powders during hot pressing takes place chiefly in the fine fractions appearing during milling. The degree of recrystallization attained is higher with ultrafine active silicon nitride powders (PCS) than with comminuted powders.Translated from Poroshkovaya Metallurgiya, No. 10(238), pp. 43–47, October, 1982.     

Influence of a metal-oxide modifying mixture in ultrafine powder form on the physicochemical characteristics of IChKh28N2 cast iron

Wear-resistant IChKh28N2 cast iron is investigated by X-ray spectral phase analysis and scanning electron microscopy, with and without the introduction of a modifying mixture (d-metal oxides in the form of ultrafine powder and nanopowder) and cryolite (Na₃AlF₆) reducing agent. The elementary and phase composition is determined; the microstructure of the metal matrix and eutectic is studied. The introduction of a modifying mixture and cryolite reducing agent changes the morphological structure, shifts the ratio of the basic phases, reduces the corrosion rate, and increases the corrosion resistance.     

Microstructural Evolution,Powder Characteristics,Compaction Behavior and Sinterability of Al 6061–B<Subscript>4</Subscript>C Composites as a Function of Reinforcement Content and Milling Times

Al 6061_100–x–x wt % B₄C (x = 0, 5, 10, 20, 30 and 40) composites, prepared by mechanical alloying and compacted at room temperature, have been used for the present investigation. The effects of B₄C content and milling time on the powder morphology, powder particle size, and other powder characteristics such as the apparent density, tap density, flow rate, cohesiveness, and hausner ratio are systematically investigated. The steady state of milling process is determined by observing the correlation between apparent densities and milling time explained by the morphological evolution of the powder particles during the milling process. The Hausner ratio (HR), estimated to evaluate friction between the particles, decreases with an increase in milling duration and B₄C content due to the changes in morphology and hardness of the powders. The compressibility behavior of post-compacts as a function of compaction pressure and the B₄C content was analyzed by using several linear and non-linear powder compaction equations. The linear Panelli and Ambrozio Filho, and non-linear Van Der Zwan and Siskens equations give the highest regression coefficients. The results are explained in terms of the plastic deformation capacity and plastic deformation coefficient of the powders, which are influenced by the hardness and the morphology of the powder. After compaction, the supersolidus liquid phase sintering was performed at various temperatures (585, 610 and 630°C) under high purity nitrogen atmosphere. The results revealed that the sinterability was degraded by increasing the reinforcement content, particularly above 10 wt % B₄C. Neutron radiography measurements conducted on the rolled composite sheet have revealed the uniform distribution of B₄C particles in the composite.     

Effect of Process Parameters on the Characteristics of Nanocrystalline Alumina Particles Synthesized by Solution Combustion Process

Nanocrystalline ceramic oxide particles with high purity can be synthesized efficiently by the solution combustion synthesis route, which is based on redox reactions between metal salts and reducing agents such as urea and glycine. In the present study, nanocrystalline alumina powders were synthesized using aluminium nitrate nonahydrate as the metal salt and urea as the fuel. The powders were characterized primarily for the phases present and crystallite size (from X-ray diffractometry) and morphology (by scanning electron microscopy). When stoichiometric amounts of the starting chemicals were taken, X-ray diffraction (XRD) analysis of the synthesized powder revealed it to be phase-pure α-Al₂O₃, with a crystallite size of 42 nm. Electron microscopy of the synthesized powder revealed a flaky morphology. Further, the pH value of the solution containing the stoichiometric amounts of the aluminium salt and the fuel was systematically varied by dissolving in liquid ammonia. It was observed (from XRD analysis) that an increase in the pH progressively stabilized the metastable γ-Al₂O₃ phase. An increase in the fuel (urea) content had no effect on the phase stability, but decreased the crystallite size of α-Al₂O₃. A crystallite size of 29 nm could be achieved with an excess fuel ratio of 1.5 over the stoichiometric value.     

Shape memory effect in a rapidly quenched Ti<Subscript>50</Subscript>Ni<Subscript>25</Subscript>Cu<Subscript>25</Subscript> alloy

The structural and thermomechanical properties of rapidly quenched layered amorphous–crystalline Ti₅₀Ni₂₅Cu₂₅ composite materials with various ratios of amorphous and crystalline phases are studied. These layered composite materials are shown to exhibit the two-way shape memory effect accompanied by bending deformation without additional thermomechanical treatment. The ratio of amorphous and crystalline phases is found to affect the reversible change in the shape of the composite material.