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.     

Phase formation process of bulk MgB2 analyzed by Differential Thermal Analysis during sintering

In order to clarify the reaction process of bulk MgB₂ phase, Differential Thermal Analysis (DTA), as the main measurement, was used to prepare bulk MgB₂ samples and monitor the sintering reaction process. Combined with microstructure observation by SEM and X-ray diffraction analysis, the formation process of MgB₂ phase was summarized. The reaction between Mg and B powders onsets before the melting point of pure Mg. The whole formation process of MgB₂ includes two different stages: (1) solid–solid reaction stage, in which Mg and B powder cannot react completely and the growth of MgB₂ grain is restricted by the pinning effects of pore; (2) solid–liquid reaction stage, in which the fused Mg promotes the reaction process and the regular hexagon bulky MgB₂ grain forms by means of solution-reprecipitation and growth.     

The oxidation of nanocrystalline Ni3Al fabricated by mechanical alloying and spark plasma sintering

Nanocrystalline Ni₃Al was fabricated through mechanical alloying of elemental powders and spark plasma sintering. The nanocrystalline Ni₃Al has a nearly full density after being sintered at 1223 K for 10 min under a pressure of 65 MPa. Isothermal and cyclic oxidations of nanocrystalline Ni₃Al were tested at 1173–1373 K with intervals of 100 K. The results indicate that nanocrystalline Ni₃Al exhibits excellent isothermal and cyclical oxidation resistance. The oxide scales consist primarily of dense and continuous -Al₂O₃. The grain refinement is beneficial for improving the oxidation resistance of Ni₃Al by providing more nucleation centers for the Al₂O₃ formation, promoting the selective formation of Al₂O₃ and improving the adhesion of oxide scales to the matrix.     

Microstructures and Mechanical Properties of Mg–xAl–1Sn–0.3Mn( x = 1, 3, 5) Alloy Sheets

The influence of Al alloying on the microstructures and the mechanical properties of Mg–x Al–1 Sn–0.3 Mn alloy sheets was investigated. The microstructure of Mg– x Al–1 Sn–0.3 Mn consisted of α-Mg and Mg 17 Al 12 precipitates. Alloying with Al increased the amount of Mg_(17)Al_(12) and the average grain size. Uniaxial tensile tests were carried out along the extrusion direction(ED), the transverse direction(TD) and 45° toward the ED. Mg–5 Al–1 Sn–0.3 Mn alloy sheet exhibited the best combination of mechanical properties along the ED: a yield strength of 142 MPa, an ultimate tensile strength of 282 MPa and an elongation of 23%. The good performance of Mg–5 Al–1 Sn–0.3 Mn sheet was mainly attributed to the large quantity of Mg_(17)Al_(12) precipitates and a weak basal texture. Annealing caused static dynamic recrystallization, refined the grain size and enhanced the mechanical properties: yield strength of 186 MPa, ultimate tensile strength of 304 MPa, elongation of 21% along ED. Both strength and ductility were enhanced by Al alloying.     

Structure, hyperfine interactions and magnetization studies of mechanically alloyed Fe50Ge50 and Fe62Ge38

X-ray diffraction, Mössbauer spectroscopy and magnetization measurements were used to study the structure and some magnetic properties of Fe₅₀Ge₅₀ and Fe₆₂Ge₃₈ prepared by mechanical alloying from the elemental powders. In both cases in the early stages of milling the intermediate paramagnetic FeGe₂ phase was formed. The mechanical alloying process of Fe₅₀Ge₅₀ resulted in the formation of the paramagnetic FeGe (B20) phase with an average crystallite size of about 15 nm. In the case of the Fe₆₂Ge₃₈, the ferromagnetic Fe₅Ge₃ (β) phase with a Curie temperature of about 430 K was obtained. The average crystallite size was about 9 nm. The average hyperfine magnetic field of about 16 T allowed it to determine that more than four germanium atoms exist in the nearest environment of the ⁵⁷Fe isotopes in the Fe₅Ge₃ phase.     

Phase evolution of Mg–Al–Zr nanophase alloys prepared by mechanical alloying

Al–Mg and Al–Mg–Zr alloys were processed by mechanical alloying. The phase constitution of the powders was strongly dependent on the composition of the starting mixture. In as-milled powders, an Al(Mg) solid solution was formed with up to 40 at% Al, which after annealing transformed to the equilibrium β-Al₃Mg₂ phase. For high Mg concentrations (60–90 at%) the dominant phase was γ-Al₁₂Mg₁₇ in accordance with the equilibrium phase diagram. The addition of Zr led to the appearance of Zr–Al intermetallics causing Mg to precipitate out of the Al(Mg) solution. The effect of zirconium was also to refine the structure and to retard grain growth.     

Mechanically activated reactive synthesis of refractory molybdenum and tungsten silicides

In this study, processing of elemental powders mixtures was carried out by mechanical alloying (MA) and heat treatment in vacuum at 700–1000 °C for 1 h. The phase transformation of the powders was investigated by X-ray diffractometer (XRD). The results showed that mechanical alloying promoted the formation of a solid solution of elemental powders. The energy stored in the powders was increased as a result of exterior energy and the barrier energy of the formation of the compound could be exceeded easily. Intermetallics of MoSi₂, WSi₂, Mo₅Si₃, Mo₃Si and SiC/MoSi₂ composite powders were synthesized by mechanically activated reactive synthesis (MARS). The mechanically induced self-sustaining reaction was observed in MoSi₂ and MoSi₂ + 10 wt%SiC stoichiometry system. It has concluded that mechanically activated reactive synthesis is an effective method for the preparation of high melting-point refractory compounds.     

Unexpected kinetic effect of MgB2 in reactive hydride composites containing complex borohydrides

Complex borohydrides of light metals are promising hydrogen storage materials due to their high hydrogen capacity. However, they exhibit two main drawbacks: their high thermodynamic stability and their slow kinetics. In the present work, the effect of various reactants on the formation kinetics of complex borohydrides is investigated. It is found that the kinetic barriers for the formation of LiBH₄, NaBH₄ and Ca(BH₄)₂ are drastically reduced when MgB₂ is used instead of B as starting material. Since this kinetic enhancement is observed in all borohydride studied so far, the observed effect is attributed to the higher reactivity of B in MgB₂ to form [BH₄]⁻ complexes. In addition, by using MgB₂ instead of elemental B, the corresponding reaction enthalpies are reduced by about 10 kJ/mol H, while the high gravimetric hydrogen capacities are largely preserved, i.e. LiBH₄ + MgH₂ with 11.4 wt%, Ca(BH₄)₂ + MgH₂ with 8.3 wt%, and NaBH₄ + MgH₂ with 7.8 wt%.     

Zn元素对Mg-25Sn合金组织和力学性能的影响

以Mg粉、Sn粉和Zn粉为初始原料,采用机械合金化和热压烧结的方法制备Mg-25Sn-x Zn合金。研究了Zn添加量对Mg-25Sn合金显微组织和性能的影响。结果表明:Mg-25Sn-x Zn体系的机械合金化过程中,Zn元素不参与合金化反应,但Zn的引入降低了Mg+Mg2Sn混合物的尺寸。除固溶外,烧结态Mg-25Sn-x Zn中Zn完全转变成MgZn2相。且随Zn含量的增加,MgZn2相的尺寸逐步增大,Mg晶界和Mg2Sn颗粒相周围是MgZn2相的择优分布位置。添加6%Zn(质量分数)的Mg-25Sn合金具有最优的力学性能,其显微维氏硬度为1.60GPa、屈服强度为388MPa、抗压强度为497 MPa、断裂应变7.5%。     

Nanocrystalline LaNi4−xMn0.75Al0.25Cox electrode materials prepared by mechanical alloying (0≤x≤1.0)

Polycrystalline hydrogen storage alloys based on lanthanum (La) are commercially used as negative electrode materials for the nickel–metal hydride (Ni–MH_x) batteries. In this paper, mechanical alloying (MA) was used to synthesize nanocrystalline LaNi_4−xMn_0.75Al_0.25Co_x (x=0, 0.25, 0.5, 0.75 and 1.0) hydrogen storage materials. XRD analysis showed that, after 30 h milling, the starting mixture of the elements decomposed into an amorphous phase. Following the annealing in high purity argon at 700 °C for 0.5 h, XRD confirmed the formation of the CaCu₅-type structures with a crystallite sizes of about 25 nm. The nanocrystalline materials were used as negative electrodes for a Ni–MH_x battery. Cobalt substituting nickel in LaNi₄Mn_0.75Al_0.25 greatly improved the discharge capacity and cycle life of the LaNi₅ material. For example, in the nanocrystalline LaNi_3.75Mn_0.75Al_0.25Co_0.25 powder, discharge capacities up to 258 mA h g⁻¹ (at 40 mA g⁻¹ discharge current) were measured. Mechanical alloying is a suitable procedure to obtain LaNi₅-type alloy powders for electrochemical energy storage.     

Microstructure and mechanical properties of mechanically alloyed and spark plasma sintered amorphous–nanocrystalline Al65Cu20Ti15 intermetallic matrix composite reinforced with TiO2 nanoparticles

Multiphase Al₆₅Cu₂₀Ti₁₅ intermetallic alloy matrix composite, dispersed with 10 wt.% of TiO₂ nanoparticles, has been processed by mechanical alloying, followed by spark plasma sintering under pressure in the temperature range of 623–873 K. Differential scanning calorimetry and X-ray diffraction suggest that equilibrium crystalline phases evolve from the amorphous or intermediate crystalline phases. Transmission electron microscopy shows that the composite sintered at 873 K has partially amorphous microstructure, with dispersion of equilibrium, crystalline, intermetallic precipitates of Al₅CuTi₂, Al₃Ti, and Al₂Cu of 25–50 nm size, besides the TiO₂. The composite sintered at 873 K exhibits little porosity, hardness of 5.6 GPa, indentation fracture toughness in the range of 3.1–4.2 MPa√m, and compressive strength of 1.1 GPa. Indentation crack deflection by TiO₂ particle aggregates causes increase in fracture resistance with crack length, and suggests R-curve type behaviour. The study provides guidelines for processing high strength amorphous–nanocrystalline intermetallic composites based on the Al–Cu–Ti ternary system.     

Low temperature synthesis of nanocrystalline lanthanum monoaluminate powders by chemical coprecipitation

Nanocrystalline lanthanum monoaluminate (LaAlO₃) powders were prepared by chemical coprecipitation using 25 vol.% of NH₄OH, 0.05 M La(NO₃)₃·6H₂O and 0.05 M Al(NO₃)₃·9H₂O aqueous solutions as the starting materials. Fourier transform infrared spectroscopy (FT-IR), thermogravimetric and differential thermal analyses (TGA/DTA), X-ray diffraction (XRD), Raman spectrometry, specific surface area (BET) analysis, scanning electron microscopy (SEM), transmission electron microscopy (TEM) and electron diffraction (ED) were utilized to characterize the LaAlO₃ powders prepared by chemical coprecipitation. The crystallization temperature of the LaAlO₃ precursor gels precipitated at pH 9 is estimated as 810 °C by TG/DTA. The XRD pattern of the LaAlO₃ precursor gels precipitated at pH 8–12 and calcined at 700 °C for 6 h shows a broad arciform continuum exist between 24° and 32° and sharp peaks of LaAlO₃ except the precursor gels precipitated at pH 9. For the LaAlO₃ precursor gels precipitated at pH 9 and calcined at 700 °C for 6 h, the formation of the perovskite LaAlO₃ phase occurs and the presence of crystalline impurities is not found. The crystallite size of LaAlO₃ slightly increases from 37.8 to 41.5 nm with calcination temperature increasing from 700 to 900 °C for 6 h. The LaAlO₃ powders prepared by chemical coprecipitation have a considerably large specific surface of 30 m²/g. The relative density greater than 97% is obtained when these nanocrystalline LaAlO₃ powders are sintered at 1550 °C for 2 h.     

Synthesis of nanocrystalline NiAl by mechanical alloying

The nanocrystalline NiAl intermetallic compound was synthesized by mechanical alloying of the elemental powders. The structural changes of powder particles during mechanical alloying were studied by X-ray diffractometery, scanning electron microscopy and microhardness measurements. The mechanical alloying resulted in the gradual formation of nanocrystalline NiAl with a grain size of 20 nm. It was found that NiAl phase develops by continuous diffusive reaction at Ni/Al layers interfaces. The NiAl compound exhibited high microhardness value of about 1035 Hv.     

Nanocrystalline Mg and Mg alloy powders by hydriding-dehydriding processing

The process of mechanically assisted hydriding and subsequent thermal dehydriding was proposed to produce nanocrystalline Mg and Mg alloy powders using pure Mg and Mg-5.5%Zn-0.6%Zr(mass fraction)(ZK60 Mg) alloy as the starting materal.The hydriding was achieved by room-temperature reaction milling in hydrogen.The dehydriding was carried out by vacuum annealing of the as-milled powders.The microstructure and morphology of both the as-milled and subsequently dehydrided powders were characterized by X-ray diffraction analysis(XRD) ,transmission electron microscopy(TEM) ,and scanning electron microscopy(SEM) ,respectively.The results show that,by reaction milling in hydrogen,both Mg and ZK60 Mg alloy can be fully hydrided to form nanocrystalline MgH2 with an average grain size of 10 nm.After subsequent thermal dehydriding at 300℃,the MgH2 can be turned into Mg again,and the newly formed Mg grains are nanocrystallines,with an average grain size of 25 nm.     

Preparation of W–Al–Mo ternary alloys by mechanical alloying

Single phase W_XAl₅₀Mo_50−X (X = 40, 30, 20 and 10) powders have been synthesized directly by mechanical alloying (MA). The structural evolutions during MA and subsequent as-milled powders by annealing at 1400 °C have been analyzed using X-ray diffraction (XRD). Different from the Mo₅₀Al₅₀ alloy, W₄₀Al₅₀Mo₁₀ and W₃₀Al₅₀Mo₂₀ alloys were stable at 1400 °C under vacuum. The results of high-pressure sintering indicated that the microhardnesses of two compositions, namely W₄₀Al₅₀Mo₁₀ and W₃₀Al₅₀Mo₂₀ alloys have higher values compared with W₅₀Al₅₀ alloy.     

Direct synthesis of MgCNi3 by mechanical alloying

MgCNi₃, an intermetallic compound with superconductivity, was synthesized from the Mg (or Mg₂Ni), Ni and graphite powders by mechanical alloying (MA). It is shown that the preliminary condition for the formation of MgCNi₃ is that Mg₂Ni must form in advance of MgCNi₃ in the MA process or be the starting component.     

Microstructure and thermoelectric properties of n-type Bi2Te2.85Se0.15 prepared by mechanical alloying and plasma activated sintering

Starting from elemental bismuth, tellurium and selenium powders, n-type Bi₂Te_2.85Se_0.15 solid solution with fine microstructure was prepared by mechanical alloying (MA) and plasma activated sintering (PAS) in the present work. The effect of PAS process on microstructure and thermoelectric properties of the sintered samples was investigated. The sintering temperature of PAS process (683 K) was 80–100 K lower than that of conventional hot pressing and the whole PAS process was also greatly shortened to about 30 min. A preferentially orientated microstructure with the basal planes (0 0 l) perpendicular to pressing direction was formed in the PASed sample and the maximum figure of merit (Z) at room temperature was 1.80 × 10⁻³ K⁻¹.     

Improving the performance of hydrogen storage electrodes based on mechanically alloyed Mg61Ni30Y9

Amorphous Mg₆₁Ni₃₀Y₉ powder was produced by mechanical alloying using a Retsch planetary ball mill under liquid nitrogen cooling. Additional gentle milling with graphite powder resulted in a thin graphite coating of powder particles. Further milling with a high energy SPEX mill transferred the alloy into a fully nanocrystalline state. The morphological and microstructural changes were followed by means of XRD, SEM, TEM and DSC. Hydrogen storage electrodes based on those alloy powders were fabricated and their cathodic and anodic polarization behaviour and their charge–discharge cycling behaviour in 6 M KOH solution were investigated. It was found that the alloy modification from a non-defective amorphous to a highly defective nanocrystalline state is more effective for improving the hydrogen sorption properties of the alloy than the graphite coating, but is detrimental for the alloy passivation. Accordingly, a SPEX-milled powder electrode exhibits with C_max = 570 mAh/g a higher maximum discharge capacity than a coated Retsch-milled powder electrode with C_max = 435 mAh/g, but degrades faster during repeated cycling. Using graphite powder supporting material for electrode preparation on a nickel foam carrier was found to be much more beneficial than nickel powder for achieving maximum discharge performance.     

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.     

Crystal growth of MgAlB14-type compounds using metal salts and some properties

LEAlB₁₄ (orthorhombic, Imam) (LE = Li, Mg) crystals were grown using metal salts (Li₂CO₃, LiF, LiI, MgO, MgF₂, MgI₂) and crystalline boron from a high-temperature aluminium metal flux. The growth conditions for growing LEAlB₁₄ were established using the starting mixtures of B/LE = 2.0, and Al metal was added to each mixture at a mass ratio of 1:15–20. LEAlB₁₄ crystals from the Al-self flux using metal salts could be obtained from all the different salts. The maximum dimensions of LiAlB₁₄ and MgAlB₁₄ crystals were approximately 18 and 12 mm for the crystals obtained from LiF and MgF₂. The unit-cell parameters of as-grown LEAlB₁₄ are as follows: for LiAlB₁₄, obtained from LiF, a = 0.5846 (2) nm, b = 0.8144 (2) nm, c = 1.0355 (3) nm, V = 0.4930 (2) nm³: for MgAlB₁₄, obtained from MgF₂, a = 0.5845 (2) nm, b = 0.8114 (2) nm, c = 1.0330 (3) nm, V = 0.4899 (3) nm³. Microhardness, oxidation resistance and magnetic susceptibility of these materials are described in detail.