Hydriding combustion synthesis of Mg–CaNi5 composites

The composites of Mg–x wt.% CaNi₅ (x = 20, 30 and 50) were prepared by hydriding combustion synthesis (HCS) and the phase evolution during HCS as well as the hydriding properties of the products were investigated. It was found that Mg reacted with CaNi₅ forming Mg₂Ni and Ca during the heating period of HCS. Afterwards, the resultant Mg₂Ni and Ca as well as the remnant Mg reacted with hydrogen during the cooling period. The lower platform in the P–C isotherms corresponds to the hydriding of Mg, and the higher one corresponds to Mg₂Ni. With the increase of the content of CaNi₅ from 20 to 50 wt.%, the hydrogen content of the HCS products increases at first and then decreases. The Mg–30 wt.% CaNi₅ composite has the maximum hydrogen capacity of 4.74 wt.%, and it can absorb 3.51 wt.% of hydrogen in the first hydriding process without activation.     

Thermodynamic and kinetic studies of Mg–Fe–H after mechanical milling followed by sintering

The transition metal complex hydride Mg₂FeH₆ has been successfully synthesized utilizing mechanical milling of a 2Mg–Fe mixture followed by heating at 673 K under 6 MPa of hydrogen pressure, without pressing step. The obtained yield of Mg₂FeH₆ was about 50%. Hydrogen storage properties of the Mg–Fe–H system, i.e. capacities, absorption/desorption kinetics and thermodynamic parameters, were examined. The pressure-composition isotherm (PCI) measurements of the samples at 548–673 K showed that the alloys possessed good cyclic stability and reversibility. Enthalpies and entropies of decomposition of the Mg–Fe–H system were evaluated by van’t Hoff plots. The absorption/desorption rates at 573 K were very fast in comparison with the reported data. The non-isothermal desorption of hydrogen was found greatly dependent on the thermal history of the sample.     

Hydrogen absorption properties of Li–Mg–N–H system

Isothermal hydrogen absorption properties of the ball milled mixture of 3Mg(NH₂)₂ and 8LiH after dehydrogenation at 200 °C under high vacuum were investigated at two different temperatures of 150 and 200 °C. The pressure–composition isotherm (PCT) curve at 200 °C revealed a two-plateaus-like behavior, while the PCT curve at 150 °C showed a single-plateau-like behavior. The hydrogenated phases were composed of LiH and Mg(NH₂)₂ under 9 MPa at 200 °C, while those were observed as mixed phases of LiH and LiNH₂ at 150 °C without any trace of Mg(NH₂)₂ in XRD measurements. These results indicate that there are two-step hydrogenation processes corresponding to high and low pressures at 200 °C, but the kinetics at 150 °C is too slow to proceed with the second hydrogenating step at high pressure region.     

Comparing the anodic reactions of Ni and Ni–P amorphous alloy in alkaline solution

The anodic reactions of amorphous Ni–P alloys prepared by electroless plating were compared with pure Ni in 6 M KOH. The structure and surface components of Ni–P alloys before and after cyclic voltammetry (CV) scan were verified by using X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS). The CVs of Ni and Ni–P show many differences. Their CV properties are compared in different potential regions. The variation of the total anodic charge density suggests that the corrosion resistance of Ni is superior to that of amorphous Ni–P alloy in 6 M KOH under potential polarization.     

Influence of tin on the electrochemical and gas phase hydrogen sorption in Mg2−xSnxNi (x = 0, 0.1, 0.3)

Mg_2−xSn_xNi (x = 0, 0.1, 0.3) alloys were synthesized by reactive ball milling under protective Ar atmosphere and liquid n-heptane. The microstructure and the morphology of the powders were determined by X-ray diffraction and scanning electron microscopy. The as-milled alloys consist of Mg₂Ni nanocrystals with an average grain size in the range 3–7 nm, depending on the alloy composition. Sn containing phases were not detected even in the Sn-rich alloy. Obviously, Sn is dissolved in the Mg₂Ni intermetallic compound. Gas phase sorption of hydrogen was not observed in the alloys containing Sn (Mg_2−xSn_xNi; x = 0.1, 0.3). It was suggested that Sn impedes the process of hydrogen molecules decomposition. The as-milled alloys absorbed reversibly hydrogen electrochemically. Mg₂Ni alloy showed the highest discharge capacity of 300 mAh/g. The capacity of Mg_1.9Sn_0.1Ni and Mg_1.7Sn_0.3Ni was about 260 mAh/g. It was found that Sn improved the cycle life of the electrode.     

Diffusible and residual hydrogen in amorphous Ni(Cu)–Zr–H alloys

The partition of hydrogen into diffusible and residual parts was realized by pulse NMR spectroscopy, by gas chromatography and by prompt gamma activation analysis (PGAA). The total hydrogen content was determined by the two non-NMR methods and the diffusible (mobile) component by CPMG NMR pulse sequence. Results on amorphous Ni(Cu)–Zr–H systems of different compositions are shown. Partially crystallized samples were also studied as an extension. A method proposed by us directly gives the fractional population of hydrogen atoms in the free (mobile) state on the spin–spin relaxation time scale. On the other hand the least values of the residual hydrogen content correlate surprisingly well with the numbers of filled four Zr-type H-sites calculated by Batalla et al. [NATO ASI Ser. 136 (1985) 203] for 0.21-nm exclusion distance.     

Thermal stability and primary phase of Al–Ni(Cu)–La amorphous alloys

Thermal stability and primary phase of Al_85+xNi_9−xLa₆ (x = 0–6) and Al₈₅Ni_9−xCu_xLa₆ (x = 0–9) amorphous alloys were investigated by X-ray diffraction and differential scanning calorimeter. It is revealed that replacing Ni in the Al₈₅Ni₉La₆ alloy by Cu decreases the thermal stability and makes the primary phase change from intermetallic compounds to single fcc-Al as the Cu content reaches and exceeds 4 at.%. When the Ni and La contents are fixed, replacing Al by Cu increases the thermal stability but also promotes the precipitation of single fcc-Al as the primary phase.     

Mg(2-x)AlxNi的燃烧合成及其电极性能

采用燃烧合成法合成了三元镁基储氢合金Mg2-xAlxNi(x=0.1~0.5),XRD衍射研究表明合成产物中出现了具有Ti2Ni型立方结构的新相,SEM结果显示合金表面存在大量缺陷.Al元素部分替代Mg对Mg2Ni电化学性能影响的研究表明:Mg2-xAlxNi合金的电化学容量和循环寿命明显优于无Al的Mg2Ni,这归因于新相Mg3AlNi2的结构特点及形成的Al2O3保护层.此外,对合成产物的进一步的机械研磨有助于改进合金的活化行为及电极容量,但无助于循环能力的提高.     

The effects of graphite on the reversible hydrogen storage of nanostructured lithium amide and lithium hydride (LiNH2 + 1.2LiH) system

The addition of 5 wt.% of graphite was incorporated into the (LiNH₂ + 1.2LiH) hydride system in order to study its effect on the prevention of LiH from hydrolysis/oxidation which leads to the escape of NH₃. The composite hydride system was processed by ball milling for 25 h. Thermal behavior in DSC up to 500 °C and isothermal desorption in a Sieverts-type apparatus were carried out. XRD was used to obtain information about phase changes. It is found that after ball milling graphite becomes amorphous. DSC analysis shows that for the mixture ((LiNH₂ + 1.2LiH) + 5 wt.% graphite) graphite can prevent or at least substantially reduce the oxidation/hydrolysis of LiH since no melting peak of retained LiNH₂ is observed. Both the DSC and Sieverts-type tests show that the addition of graphite increases the apparent activation energy of desorption from the ∼57-58 to ∼85-90 kJ/mol range. On the other hand, the graphite additive increases measurably the desorbed/absorbed capacity of hydrogen at 275, 300 and 325 °C. The ((LiNH₂ + 1.2LiH) + 5 wt.% graphite) system is fully reversible desorbing/absorbing ∼5 wt.% H₂ at 325 °C in the following reaction: (LiNH₂ + LiH ↔ Li₂NH + H₂). Step-wise pressure-composition-temperature (PCT) tests show that the enthalpy and entropy change of this reversible reaction is −62.4 and −61.0 kJ/mol H₂ and 117.8 and 115.8 J/mol K for undoped and 5 wt.% G doped (LiNH₂ + 1.2LiH) system, respectively. It shows that within an experimental error there is no measurable effect of graphite additive on the thermodynamic properties. The Van’t Hoff analysis of the obtained thermodynamic data shows that the equilibrium temperature at atmospheric pressure of hydrogen (1 bar H₂) is 256.8 and 253.9 °C for the undoped and 5 wt.% G doped (LiNH₂ + 1.2 LiH) system ball milled for 25 h, respectively. Such high equilibrium temperatures render it rather obvious that both of these hydride systems cannot be employed for hydrogen desorption/absorption below 100 °C as required by the DOE targets for the automotive hydrogen storage materials.     

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.     

Synthesis of HCP, FCC and BCC structure alloys in the Mg–Ti binary system by means of ball milling

Mg_xTi_100−x (35 ≤ x ≤ 80) alloys with hexagonal close packed (HCP), face centered cubic (FCC) and body centered cubic (BCC) structures were successfully synthesized by means of ball milling. Mg_xTi_100−x alloys with a BCC structure at x = 35 and 50 and with a HCP structure at x = 80 were synthesized by milling of Mg and Ti powder using stainless steel milling balls and pots. At x = 65, the BCC and HCP phases were synthesized. Mg_xTi_100−x alloys with a FCC structure were synthesized at x = 35 and 50 by milling using zirconia milling balls and pots. The FCC and HCP phases were synthesized at x = 65 and 80 using zirconia milling balls and pots. The crystal structure of Mg_xTi_100−x alloys synthesized by the ball milling method depended on the materials of milling balls and pots. That indicates that milling products are determined by the dynamic energy given by the milling setup. The lattice parameters of Mg_xTi_100−x in the HCP, FCC and BCC phases increased with increase of the Mg content, x.     

Analysis of hydrogen distribution on Mg–Ni alloy surface by scanning electron-stimulated desorption ion microscope (SESDIM)

Hydrogen distribution and behavior on a Mg–Ni alloy surface are studied by using a time-of-flight electron-stimulated desorption (TOF-ESD) microscopy and a scanning electron microscope with energy dispersive X-ray spectroscopy (SEM-EDX). The desorbed hydrogen ions are energy-discriminated and distinguished into two characters in the adsorbed states, which belong to Mg₂Ni grains and the other to oxygen-contaminated Mg phase at the grain boundaries. Adsorbed hydrogen is found to be stable up to 150 °C, but becomes thermally unstable around at 200 °C.     

Low-temperature brazing of titanium by the application of a Zr–Ti–Ni–Cu–Bebulk metallic glass (BMG) alloy as a filler

Titanium (Ti) was successfully brazed at low temperatures below 800 °C by employing a Zr_41.2Ti_13.8Ni_10.0Cu_12.5Be_22.5 (at.%) bulk metallic glass (BMG) alloy as a filler. Through the use of this alloy filler, the detrimental segregation of Zr–Cu–Ni filler elements was completely eliminated by heating to well below 800 °C, so the resultant joint was quite homogeneous with a coarse acicular structure. The disappearance of the Zr–Cu–Ni segregated region was rate-controlled by the diffusion of the filler elements in the Ti base metal. Remarkably, the mechanical property and corrosion resistance of the homogeneous joint brazed at 800 °C for 10 min were mostly comparable to those of bulk Ti.     

An investigation on hydrogen storage kinetics of nanocrystalline and amorphous Mg2Ni1−xCox (x = 0-0.4) alloy prepared by melt spinning

In order to improve the hydrogen storage kinetics of the Mg₂Ni-type alloys, Ni in the alloy was partially substituted by element Co, and melt-spinning technology was used for the preparation of the Mg₂Ni_1−xCo_x (x = 0, 0.1, 0.2, 0.3, 0.4) hydrogen storage alloys. The structures of the as-cast and spun alloys are characterized by XRD, SEM and TEM. The hydrogen absorption and desorption kinetics of the alloys were measured by an automatically controlled Sieverts apparatus. The electrochemical hydrogen storage kinetics of the as-spun alloys is tested by an automatic galvanostatic system. The hydrogen diffusion coefficients in the alloys are calculated by virtue of potential-step method. The electrochemical impedance spectrums (EIS) and the Tafel polarization curves are plotted by an electrochemical workstation. The results show that the substitution of Co for Ni notably enhances the glass forming ability of the Mg₂Ni-type alloy. Furthermore, the substitution of Co for Ni, instead of changing major phase Mg₂Ni, leads to forming secondary phases MgCo₂ and Mg. Both the melt spinning treatment and Co substitution significantly improve the hydrogen absorption and desorption kinetics. The high rate discharge ability, the hydrogen diffusion coefficient and the limiting current density of the alloys significantly increase with raising both the spinning rate and the amount of Co substitution.     

Fabrication and characterization of micro‐arc oxidation (MAO) coatings on Mg‐Li alloy in alkaline polyphosphate electrolytes without and with the addition of K2TiF6

Micro‐arc oxidation (MAO) has been accomplished on Mg‐Li alloy in alkaline polyphosphate electrolytes without and with the addition of 10 g/L K₂TiF₆. The surface/cross‐section microstructures of the fabricated coatings were analyzed by scanning electron microscope (SEM); the compositions of the fabricated MAO coatings were analyzed by X‐ray diffraction (XRD) and energy dispersive X‐ray analysis (EDAX); the corrosion behaviors of bare and MAO coated Mg‐Li alloys were evaluated using potentiodynamic polarization (PDP) and electrochemical impedance spectroscopy (EIS) in 3.5 wt% NaCl solution. Novel hybrid MAO coatings which showed hybrid composition of MgF₂/Ti₂O₅/Ti₆O₁₁/MgO, as well as hybrid structure of a dense inner layer, a dense outer layer and an intermediate layer with some sealed/semi‐sealed pores, had been fabricated on Mg‐Li alloy in alkaline polyphosphate electrolytes with the addition of K₂TiF₆. Meanwhile, the corrosion resistance of the fabricated MAO coatings was improved obviously as the result of the addition of K₂TiF₆ in the electrolytes. Moreover, the multiple roles of ${\rm TiF}_{{\rm 6}}^{{\rm 2}{-} } $ on the MAO process accounted for the fabrication of the corrosion‐resistant hybrid MAO coatings.     

Laboratory scale tests on corrosion behavior of boiler materials in simulated combustion atmospheres (EU Project – OPTICORR)

Laboratory scale tests were made in the Plant Simulation Test Laboratory (PSTL) at JRC IE Petten and at VTT Industrial Systems in Finland. The multi‐sample exposure tests were carried out under isothermal conditions at temperatures of 500 and 600 °C in N₂‐8% O₂‐15% H₂O, N₂‐8% O₂‐15% H₂O‐2000 vppm HCl and N₂‐8% O₂‐15% H₂O‐200 vppm SO₂ atmospheres. The experiments were focused mainly on common ferritic and austenitic steels such as X10, X20, 2.25Cr1Mo, AC66, Sanicro28, Esshette 1250 etc. A Scanning Electron Microscope (SEM), with Energy Dispersive Spectrometer (EDS), and X‐ray diffraction (XRD) techniques were used to determine the chemical and phase composition of the corrosion products. The obtained results show that the presence of SO₂ generally suppresses the oxidation rate of ferritic materials. Suppression of the oxidation rate in an SO₂ containing atmosphere could be due to the presence of sulphides at metal/scale interfaces , which probably influences the ion transport through the oxide scale. When the oxidation reaction is surface controlled, absorbed sulphates interfere with the reaction of the oxygen on the surface. The presence of HCl in moist air at temperatures of 500 °C and 600 °C accelerates the oxidation rate of the studied materials, especially for the ferritic steels. The SEM/EDS studies suggest that in HCl containing atmospheres the corrosion mechanism is „active oxidation”︁.     

Crystal structure analysis and thermoelectric properties of p-type pseudo-binary (Al2Te3)x–(Bi0.5Sb1.5Te3)1−x (x = 0 0.2) alloys prepared by spark plasma sintering

Sm³⁺-doped TiO₂ nanocrystalline has been successfully prepared by low temperature combustion synthesis (LCS). Results showed that the samarium doping was found to be able to significantly inhibit the anatase–rutile phase transformation. Photocatalytic degradation experiments indicated that doping samarium ions in TiO₂ could enhance photocatalytic activity in photocatalytic degradation of methylene blue. The increase in photocatalytic activity is probably due to prevention of electron–hole recombination and the existence of a synergistic effect between anatase and rutile. The highest enhancement in photoreactivity was obtained at 0.5 mol% samarium ions doping, which may be in favor of the most efficient separation of the charge carriers. It has been found that the photocatalytic activity is drastically increased under the presence of a small amount of anatase phase (only 5.9% anatase) compared to pure rutile, and the sample calcined at 600 °C with 51.61% rutile shows the highest photocatalytic activity, which suggests the existence of a synergistic effect between anatase and rutile powders in the Sm³⁺-doped TiO₂, which is similar to that of undoped TiO₂.     

Facile autocombustion synthesis of La0.6Sr0.4Co0.2Fe0.8O3−δ (LSCF) perovskite via a modified complexing sol–gel process with NH4NO3 as combustion aid

Ammonia nitrate was applied as an oxidizer and combustion trigger to modify the normal combined EDTA-citrate complexing method into a process with autocombustion and low ignition temperature properties. Therefore, the synthesis procedure was greatly simplified. The effect of NH₄NO₃/metal ions to organic mole ratios and the heating temperature on the autocombustion behavior and the properties of the powders derived were investigated in detail. The critical amount of NH₄NO₃ for the autocombustion to occur was identified at the NO₃⁻ to citric acid to EDTA mole ratio of around 10:2:1. After the experimental optimization, well-crystallized nanostructured La_0.6Sr_0.4Co_0.2Fe_0.8O_3−δ (LSCF) powder with a specific surface area as high as 21 m²/g was obtained; it is comparable with that obtained from a normal complexing process. By adjusting the combustion parameters, the properties of the powders then derived can be tailored for different applications, such as nanograined dense membrane for oxygen separation membrane, and porous cathode for fuel cells and sensors.     

Evaluation of Ni–Ni3Al(5 wt.%)–Al(3 wt.%) as an anode electrode for molten carbonate fuel cell. Part II: wetting ability and performance in unit cell operation

In part I of this paper, the sintering and creep resistances of the five kinds of anode electrodes were compared and those of Ni–Ni₃Al(5)–Al(3) were even better than any other electrodes. In part II of this paper, the wetting abilities of the same five kinds of anode electrodes to the electrolyte and their performance in unit cell operation were investigated. Their contact angles, which indicate the wetting ability, were within the range between 77 and 84°. The contact angles of Al- and/or Ni₃Al-added electrodes such as Ni–Al(5), Ni–Ni₃Al(7) and Ni–Ni₃Al(5)–Al(3) were relatively lower than those of Cr-added electrodes. Although there was no evidence that the effect of Al and/or Ni₃Al addition to pure Ni could enhance the number of pores or improve their structure for more wetting ability, it could be clearly known that the component of Al and/or Ni₃Al in anode electrode could make the electrode be wetted by the electrolyte very well.

In unit cell operation, the electric resistance of Ni–Al(5) and Ni–Ni₃Al(5)–Al(3) were relatively lower than those of any other electrodes. After 120 h operation of the unit cell, the cell performance and the endurance of Ni–Ni₃Al(5)–Al(3) were even better than those of any other electrodes. And also its thickness shrinkage and porosity changes after unit cell operation were the least in five kinds of electrodes. The performance of Ni–Ni₃Al(5)–Al(3) as anode seems to be caused by the synergy effect between the strengthening characteristics of Ni₃Al and electric conductivity of Al.     

Self-propagating high-temperature synthesis with post-heat treatment of La1−xSrxFeO3 (x = 0–1) perovskite as catalyst for soot combustion

La_1−xSr_xFeO₃ (x = 0–1) perovskite, Sr-substituted LaFeO₃, was prepared by Self-propagating high-temperature synthesis (SHS) and its catalytic activity for soot combustion was experimentally examined in comparison with that of a conventional Pt/Al₂O₃ catalyst. The products were also characterized by XRD, FE-SEM, and BET specific surface area. The XRD analysis revealed that all the products had a perovskite phase as the major compound, together with intermediate phases with higher x values (x = 0.7–1). The BET specific surface area of the products increased with x. Moreover, the catalytic activity for soot combustion also increased with x, wherein the BET specific surface area appeared an appropriate index for explaining the observed activity. The sample with x = 0.8 exhibited the highest activity for soot combustion among all the SHS products. The soot combustion temperature of this product was as much as 100 °C lower than that of non-catalytic soot combustion. In other words, it had the same activity as that at only 20 °C higher, in comparison to conventional Pt/Al₂O₃ catalyst. More significantly, average apparent activation energy of sample with x = 0.8 calculated by Friedman method using TG/DTA was approximately 15 kJ/mol lower than that of Pt/Al₂O₃ catalyst. This result suggested that La_1−xSr_xFeO₃ has the possibility to be an alternative catalyst to Pt/Al₂O₃ catalyst.