Microstructure and magnetic properties of Co/Al2O3 nanocomposite powders

Nanocomposite powders of magnetic cobalt nanoparticles dispersed by nonmagnetic Al₂O₃ particles have been prepared by planetary ball milling. Ball milling of the CoO and Al mixture powder after a certain milling duration reduces CoO to (fcc and hcp) Co completely and oxidizes Al to -Al₂O₃ simultaneously. The average grain sizes of the nanocomposite powders are 19 nm for Co and 28 nm for -Al₂O₃ after the completion of the reduction reaction. By direct ball milling of the mixture of Co and Al₂O₃, the allotropic phase transformation of Co was observed and the average grain size of Co is reduced to 5 nm. For both the samples of the mechanochemical series and the direct milling series, the saturation magnetizations of the nanocomposite powders decrease with decreasing average grain size of Co. This may be due to the enhancement of the interface effects and the increase of the superparamagnetic particles with decreasing Co grain size. The coercivities of the Co/Al₂O₃ nanocomposite powders increase up to 380 Oe. The increasing grain boundaries with decreasing Co grain size result in the domain wall pinning which predicts the coercivity enhancement. In addition to the grain size effects, the reduction of the particle size toward the size region of single domain also contributes to the increase of coercivity.     

Direct synthesis of A2(Ti(1 − y)Zry)2O7 (A = Gd, Y) solid solutions by ball milling constituent oxides

Different compositions in two solid solutions, A₂(Ti_(1 − y)Zr_y)₂O₇ (A = Gd³⁺, Y³⁺), with high oxygen ion conductivity, have been successfully prepared at room temperature via mechano-chemical synthesis. Stoichiometric mixtures of the constituent oxides were milled in a planetary ball mill by using zirconia vials and balls. Chemical changes in the powder mixtures as a function of composition and milling time were followed by using X-ray diffraction showing that in all cases and after milling for 19 h, the powders consisted of a single phase. Powders were also examined by scanning electron microscopy (SEM) finding out that they basically consist of sub-micron size agglomerates and aggregates of nanoparticles.     

Zinc oxide nanoparticle decorated multi-walled carbon nanotubes and their optical properties

A simple and efficient approach is developed for the synthesis of single crystal zinc oxide (ZnO) nanoparticles on multi-walled carbon nanotubes (MWNT). Moreover, the effect of heat treatment on ZnO-coated MWNT is investigated. The results reveal that the MWNT are decorated by ZnO particles. The MWNT are continuously coated by ZnO nanoparticles at 450 and 600 °C, and the average size of ZnO nanoparticles is about 11 and 48 nm, respectively. However, the coated layer of ZnO on the surface of MWNT becomes discontinuous when the temperature of heat treatment reaches 750 °C. The average size of ZnO particles at 750 °C is about 89 nm. Furthermore, the UV emission of MWNT is improved significantly through modification with ZnO.     

XRD and TEM characterizations of the mechanically alloyed CuIn0.5Ga0.5Se2 powders

The CuIn_0.5Ga_0.5Se₂ (CIGS) nanocrystalline powders were prepared by mechanical alloying method. Effect of various milling times and higher milling speed on the structure of CIGS nanoparticles was investigated by X-ray diffraction measurements. The Rietveld method was used to refine the XRD data using the MAUD program. Refinement process reveals that the main phase of the CIGS powders milled for different milling times is of chalcopyrite structure. Milling time dependence of the unit-cell parameters and crystallite size has also been reported. The TEM observations demonstrated that the size of agglomerated CIGS powder is about 140 nm. The EDAX analysis of various grains of the milled powder shows that the compositions vary from one grain to another. However, the global composition was found slightly copper rich.     

Mechanochemical synthesis of nanocrystalline ZnWO4 at room temperature

Single nanocrystalline ZnWO₄ powders were successfully synthesized by ball milling at room temperature. A stoichiometric mixture of ZnO and WO₃ in a 1:1 molar ratio was subjected to intense mechanical treatment in air using a planetary ball mill (Fritsch - Premium line - Pulversette No. 7) for a period varying from 5 to 300 min. The influence of the four different milling conditions was investigated on the formation of ZnWO₄. The products obtained were characterized by X-ray diffraction (XRD), transmission electron microscopy (TEM), Brunauer-Emmer-Teller (BET) surface area, infrared (IR) spectroscopy and X-ray photoelectron spectroscopy (XPS). The synthesis of ZnWO₄ powder started after 5 min milling time and finished after 30 min milling time at a higher speed (1000 rpm). The mechanical treatment up to 300 min did not lead to phase and structure change of ZnWO₄. The product obtained contained nanoparticles with a size of about 50 nm. The photocatalytic activity of the ZnWO₄ powders obtained was investigated by degradation of a model aqueous solution of Malachite Green (MG) upon UV-light irradiation.     

Synthesis and characterization of molybdenum aluminide nanoparticles reinforced aluminium matrix composites

Aluminium matrix composites reinforced with molybdenum aluminide nanoparticles were synthesized by ball milling and reactive sintering of the mixture of aluminium and 10 wt% hydrated molybdenum oxide powders. Sintering the as milled powder in air below 750 °C produced MoAl₁₂ intermetallic compound nanoparticles, at 750 °C produced a mixture of MoAl₅ and MoAl₄ nanoparticles and at 800 °C under Argon atmosphere produced predominantly MoAl₄ intermetallic nano-particles in the Al matrix. The powder compacts sintered in air below 750 °C produced MoAl₁₂ whereas at 750 °C or above formed the Al matrix composite reinforced with the MoAl₅ nanoparticles. These nanoparticles become agglomerated to take up some irregular shaped flakes in the metal matrix. The reaction between Al and hydrated Mo oxide powders was found to be a favorable way to produce predominantly a particular Mo–Al intermetallic compound at a particular temperature. The Al₂O₃ particles formed as another reaction product, in all the above reactions, remain distributed in these composites. The composites thus formed were characterized by SEM-EDS, DTA, XRD and TEM analysis.     

Microstructure and morphological study of ball-milled metal matrix nanocomposites

Due to the difficulty of preparation and beneficial properties achievable, copper and iron matrix nanocomposites are materials for which fabrication via the powder metallurgy route is attracting increasing research interest. The presence of ceramic nanoparticles in their matrix can lead to considerable changes in the microstructure and morphology. The effects of the type of metallic matrix and ceramic nanoparticle on the distribution of nano reinforcements and the morphology of ball-milled composite powders were evaluated in this study. For this purpose, 25 wt % of Al₂O₃ and SiC nanoparticles were separately ball-milled in the presence of iron and copper metals. The SEM, FESEM, and XRD results indicated that as-received nanoparticles, which were agglomerated before milling, were partially separated and embedded in the matrix of both the metals after the initial stages of ball milling, while prolonged milling was not found to further affect the distribution of nanoparticles. It was also observed that the Al₂O₃ phase was not thermodynamically stable during ball milling with copper powders. Finally, it was found that the presence of nanoparticles considerably reduce the average size of metallic powder particles.     

超细钼铜复合粉末的制备工艺研究

钼铜合金是两种互不相溶的假合金,与钨铜合金相比,钼铜材料的密度较低,且其容易变形加工,被广泛用于航空航天、电力、电子等行业。研究了制备钼铜合金原料粉末——超细钼铜复合粉的制备工艺。用SEM和TEM的选区电子衍射图观察了不同球磨方式和不同球磨时间钼铜复合粉末的粒度和形貌。结果表明:①普通球磨、行星球磨无法得到结构和成分分布均匀的纳米合金粉,而高能球磨方式可以得到;②经过25h高能球磨可以得到结构和成分分布均匀,尺寸为30nm的合金粉末。     

Preparing nano-crystalline rare earth doped WC/Co powder by high energy ball milling

The nano-crystalline rare earth doped WC/Co powder was prepared by high energy ball milling. The nano-crystalline powders were characterized by means of XRD (X-ray diffraction), SEM (scanning electron microscope) and DTA (differential thermal analysis). The results show that adding trace rare earth elements into carbides is effective to minish the grain size of WC/Co powder. The grain size of rare earth doped powder became two times smaller as compared with the undoped powder within ball milling times of 25–45 h. The XRD peak of Co phase disappeared after 25 h ball milling. A sharp peak of heat release at the temperature of 597 °C was emerged in DTA curve within the range of heating temperature. After consolidated the rare earth doped WC/Co alloy by high energy ball milling exhibits ultra-fine grain sizes and better mechanical properties.     

Mechanical Properties of Al/BN Nanocomposites Fabricated by Planetary Ball Milling and Conventional Hot Extrusion

In this study, Al matrix nanocomposites containing 1, 2 and 4 wt% nano-boron nitride were fabricated by mechanical milling and hot extrusion. The mechanical properties of all extruded samples were evaluated. Also, the morphology and microstructure of the milled composite powders were characterized using two types of electron microscope. The results showed that a high fraction of the boron nitride nanoparticles dissolved and formed a solid solution in Al matrix during the milling process. Through the process of solid solution formation, the work hardening rate of the composite powders increased. This led to a morphological change in the composite powders and resulted in equiaxed shape. The powder particle size also decreased after the milling process. By increasing boron nitride content within a range of 0–4 wt% in the hot extruded samples, tensile stress increased from 212 to 333 MPa. The hardness of the nanocomposite samples including 1, 2 and 4 wt% boron nitride improved approximately 55, 70 and 90% in comparison with pure Al,respectively.     

Properties of copper matrix reinforced with various size and amount of Al2O3 particles

Copper matrix was reinforced with Al₂O₃ particles of different size and amount by internal oxidation and mechanical alloying accomplished using high-energy ball milling in air. The inert gas-atomised prealloyed copper powder containing 1 wt.% Al as well as a mixture of electrolytic copper powder and 3 wt.% commercial Al₂O₃ powder served as starting materials. Milling of Cu-1 wt.% Al prealloyed powder promoted formation of fine dispersed particles (1.9 wt.% Al₂O₃, approximately 100 nm in size) by internal oxidation. During milling of Cu-3 wt.% Al₂O₃ powder mixture the uniform distribution of commercial Al₂O₃ particles has been obtained. Following milling, powders were treated in hydrogen at 400 °C for 1 h in order to eliminate copper oxides formed at the surface during milling. Compaction was executed by hot-pressing. Compacts processed from 5 to 20 h-milled powders were additionally subjected to high-temperature exposure at 800 °C in order to examine their thermal stability and electrical conductivity. Compacts of Cu-1 wt.% Al prealloyed powders with finer Al₂O₃ particles and smaller grain size exhibited higher microhardness than compacts of Cu-3 wt.% Al₂O₃ powder mixture. This indicates that nano-sized Al₂O₃ particles act as a stronger reinforcing parameter of the copper matrix than micro-sized commercial Al₂O₃ particles. Improved thermal stability of Cu-1 wt.% Al compacts compared to Cu-3 wt.% Al₂O₃ compacts implies that nano-sized Al₂O₃ particles act more efficiently as barriers obstructing grain growth than micro-sized particles. Contrary, the lower electrical conductivity of Cu-1 wt.% Al compacts is the result of higher electron scatter caused by nano-sized Al₂O₃ particles.     

机械合金化对Cr-W粉末及烧结材料组织的影响

通过机械球磨法制备原子比为4:1的Cr-W预合金粉末,对球磨后的Cr-W粉末进行XRD、SEM、TEM分析,探讨球磨时间对Cr-W粉末形貌、晶粒大小、组织结构及烧结Cr-W合金固溶度的影响。结果表明：采用机械合金化法,可以制备纳米级的Cr-W预合金粉末;球磨初期,晶粒尺寸、微应变变化较大,48 h后趋于稳定获得小于30 nm的纳米晶粉末;经72 h球磨后,粉末中有固溶体形成;球磨过程伴随着晶格常数的变化;球磨时间越长的粉末,烧结后各相分布越均匀,固溶程度越高     

Influence of ball‐milling on the oxidation behavior of Ag–Zn alloy powders

The gas atomized Ag–15.2 at% Zn alloy powders were treated using ball‐milling. The effect of ball‐milling on surface morphology, microstructure, and oxidation behavior of the alloy powders was investigated. The results showed that ball‐milling treatment enhanced the oxidation rate of Ag–Zn alloy powders due to the increase of dislocation density and the decrease of the diffusion distance of oxygen during internal oxidation. The fully oxidized time of Ag–Zn alloy powders decreases with the ball‐milling time. In addition, the ball‐milling treatment not only changes the oxidation mechanism but also improves microstructure and properties of the Ag–ZnO materials fabricated by internal oxidation.     

钼-钴-硅混合粉末的机械合金化研究

采用X射线衍射、扫描电镜及透射电镜研究了配比为Mo5-xCoxSi3(x=0．5，l，2)的混合粉末的机械球磨行为。结果表明：随球磨时间延长，混合粉末中首先形成Co，Si在Mo中的过饱和固溶体Mo(Co，Si)，高能球磨大大扩展了硅和钴在钼中的固溶度。进一步延长球磨时间，过饱和固溶体转变成为非晶。在球磨过程中，Mo(Co，Si)的晶粒不断细化，球磨至40h，晶粒尺寸约为8nm。球磨初期，内应力急剧增加。随球磨时间延长，混合粉末的颗粒尺寸增大，40h后，逐渐减小，且形状球化，100h后成为尺寸不超过100nm的球形粉末。     

Preparation of WC nanoparticles by twice ball milling

In order to improve the ball milling efficiency of WC powders and thus to fabricate nano-grained WC–Co cemented carbides with high mechanical properties, WC nanoparticles were prepared by twice ball milling in nylon vessels. The best technology to disperse WC powders in alcohol was investigated at first. Based on the dispersion results, 2 wt.% PEG was used with La₂O₃ as additive to improve ball milling efficiency. The particle size, crystal structure, surface morphology and surface properties were tested by a laser particle sizer, XRD, FE-SEM and FT-IR, respectively. During the first ball milling, sample d achieved the best milling performance, including average particle size (168 nm) and grain size (27.2 nm) among samples a (pure WC), b (with PEG), c (with La₂O₃) and d (with PEG and La₂O₃). La₂O₃ could greatly decrease particle size and grain size while PEG could narrow particle size distribution. During the second milling, the particle size and grain size of sample d reached 89 nm and 13.2 nm at 96 h, respectively. The results indicated that twice ball milling can greatly improve particle size and grain size compared with the first ball milling, and further narrow the size distribution. In conclusion, multiple ball milling can reduce the particle size of certain powders with suitable milling technology.     

Synthesis of FeS2 and FeS nanoparticles by high-energy mechanical milling and mechanochemical processing

High-energy mechanical milling of the FeS₂ pyrite led to the formation of sub-micron particles with nano-scaled grains. FeS₂ nanoparticles were obtained, when NaCl was used as the dispersion medium. FeS₂ pyrite and FeS troilite phases could be formed after high-energy mechanical milling. The formation of FeS₂ pyrite required a long milling time. The resultant powders consisted of nano-scaled particles. The use of the solid dispersion medium (NaCl) can promote dispersion of nanoparticles. This work has shown that iron sulfide nanoparticles can be synthesized by mechanochemcial process with a solid dispersion medium.     

Structural Evolution During Mechanical Milling of Bimodal-Sized Al_2O_3 Particles Reinforced Aluminum Matrix Composite

Hybrid aluminum matrix composite powders reinforced with bimodal-sized Al_2O_3 particles were synthesized by mechanical milling. Two different approaches were investigated for the addition of submicron-and nano-sized Al_2O_3 particles to the aluminum powders. It was observed that the simultaneous addition of bimodal-sized Al_2O_3 particles to the aluminum powders resulted in an equiaxed morphology of the composite powders and the average particle size stabilized after 5 h of milling, indicating that the presence of bimodal-sized particles has greater effect on accelerating milling process as compared to nano-sized particles; the grain size of the aluminum matrix in composite powders was reduced to under 40 nm, approximate to the value obtained in the separate addition case, while a lower rate of refining was observed due to hindrance of submicron-sized particles on the interactions between nano-sized particles and the aluminum matrix.     

The effect of sequential and continuous high-energy impact mode on the mechano-chemical synthesis of nanostructured complex hydride Mg2FeH6

The effect of sequential and continuous high-energy impact mode in the magneto-mill Uni-Ball-Mill 5 on the mechano-chemical synthesis of nanostructured ternary complex hydride Mg₂FeH₆ was studied by controlled reactive mechanical alloying (CRMA). In the sequential mode the milling vial was periodically opened under a protective gas and samples of the milled powder were extracted for microstructural examination whereas during continuous CRMA the vial was never opened up to 270 h duration. MgO was detected by XRD in sequentially milled powders while no MgO was detected in the continuously milled powder. The abundance of the nanostructured ternary complex hydride Mg₂FeH₆, produced during sequential milling, and estimated from DSC reached 44 wt.% after 188 h, and afterwards it slightly decreased to 42 wt.% after 210 and 270 h. In contrast, the DSC yield of Mg₂FeH₆ after continuous CRMA for 270 h was 57 wt.%. Much higher yield after continuous milling is attributed to the absence of MgO. This behavior provides strong evidence that MgO is a primary factor suppressing formation of Mg₂FeH₆. The DSC hydrogen desorption onset temperatures are close to 200 °C while the desorption peak temperatures for all powders are below 300 °C and the desorption process is completed within the range 10–20 min. Within the investigated nanograin size range of 5–13 nm, the DSC desorption onset and peak temperatures of β-MgH₂ and Mg₂FeH₆ do not exhibit any trend with nanograin (crystallite) size of hydrides. TPD hydrogen desorption peaks from the powders containing a single ternary complex hydride Mg₂FeH₆, are very narrow, which indicates the presence of small but well-crystallized hydride particles. Their narrowness provides good evidence that the phase composition, bulk hydrogen distribution and hydride particle size distribution are very homogeneous. The overall amount of hydrogen desorbed in TPD from single-hydride Mg₂FeH₆ powders is somewhat higher than that observed in DSC and TGA desorption.

The powder milled sequentially for 270 h and desorbed in a Sieverts-type apparatus at 250 and 290 °C, yielded about a half of the hydrogen content obtained during DSC and TGA tests. No desorption of hydrogen was detected in a Sieverts-type apparatus at 250 and 290 °C after 128 and 70 min, respectively, from the powder continuously milled for 270 h. The latter easily desorbed 3.13 and 2.83 wt.% hydrogen in DSC and TGA tests, respectively.     

Features of passivation, oxidation and combustion of tungsten nanopowders by air

The passivation, oxidation and combustion of tungsten nanopowders (NP) (a_s  100 nm), produced by an electrical explosion of wires (WEE) method, has been studied in air medium. The phase transformation for W nanopowders under air-oxidation was investigated. The oxidation process and an analysis of passivated powders were studied by FESEM, EDS, XPS, XRD, TEM, DTA-TGA and size distribution analysis was also observed by a video camera. After the comprehensive testing of passivated, oxidized and burned powders, a chemical process of oxidation of W nanoparticles was suggested.     

Development of nano-structure Cu-Zr alloys by the mechanical alloying process

Cu-Zr alloys have many applications in electrical and welding industries for their high strength and high electrical and thermal conductivities. These alloys are among age-hardenable alloys with capability of having nano-structure with high solute contents obtainable by the mechanical alloying process. In the present work, Cu-Zr alloys have been developed by the mechanical alloying process. Pure copper powders with different amounts of 1, 3 and 6 wt% of commercial pure zirconium powders were mixed. The powder mixtures were milled in a planetary ball mill for different milling times of 4, 12, 48 and 96 h. Ball mill velocity was 250 rpm and ball to powder weight ratio was 10:1. Ethanol was used as process control agent (PCA). The milling atmosphere was protected by argon gas to prevent the oxidation of powders. The milled powders were analysed by XRD technique and were also investigated by SEM observations. Lattice parameters, crystal sizes and internal strains were calculated using XRD data and Williamson-Hall equation. Results showed that the lattice parameter of copper increased with increasing milling time. The microstructure of milled powder particles became finer at longer milling time towards nano-scale structure. SEM observations showed that powder particles took plate-like shapes. Their average size increased initially and reached a maximum value then it decreased at longer milling times. Different zirconium contents had interesting effects on the behavior of powder mixtures during milling.