Controllable synthesis of hexagonal close-packed nickel nanoparticles under high nickel concentration and its catalytic properties

The hexagonal close-packed (hcp) Ni nanoparticles have been synthesized successfully in triethylene glycol with high ionic Ni concentration under the presence of protective agent (PVP or PEG). The protective agent (PVP or PEG) played an important role in the formation of hcp Ni. The crystal structure of nickel can be tuned by changing the concentration of Ni ions, reaction temperature, and amount of protectors. The X-ray diffraction and magnetic studies revealed the formation of pure hcp Ni. The VSM study showed that the magnetic properties of hcp Ni is quite different from that of face-centered cubic (fcc) Ni. The hcp Ni nanoparticle had a low saturation magnetization, while the coercivity value of hcp Ni was nearly the same as that of fcc Ni. A stable hcp Ni supported on γ-Al₂O₃ catalyst was also prepared successfully for the first time and its catalytic activity was investigated in the aqueous-phase reforming of glycerol. The achieved conversion of glycerol and selectivity to hydrogen was high up to 52 and 64%, while the selectivity to methane was only 5%, indicating the preventing of methanation on hcp Ni.     

Structure and magnetic properties of hcp and fcc nanocrystalline thin Ni films and nanoparticles produced by radio frequency magnetron sputtering

We report on the growth of thin Ni films by radio frequency magnetron sputtering in Ar-plasma. The growth temperature was about 350 K and the films were deposited on various substrates such as glass, silicon, sapphire and alumina. The thickness of the thinnest films was estimated by the appearance of Kiessig fringes up to about 2theta = 8 degrees in the small-angle X-ray diffraction pattern, as expected for high-quality atomically-flat thin films. With the help of this, a quartz balance system was calibrated and used for measuring the thickness of thicker samples with an accuracy of better than 5%. Structural characterization via X-ray diffraction and high resolution transmission electron microscopy revealed an Ar-gas pressure window, where single phase hcp Ni films may be grown. The magnetic response of the Ni films was checked at room temperature via a newly established and fully automatic polar magneto-optic Kerr effect magnetometer. The hcp films show no magnetic response. Interestingly, the magnetic saturation field of fcc films deposited at low Ar pressure is comparable to the one of bulk Ni, while the one of fcc films deposited at high Ar pressures is decreased, revealing the presence of residual strain in the films. Finally, it is shown that it is possible to form films which contain magnetic Ni fcc nanoparticles in a non-magnetic hcp matrix, i.e., a system interesting for technological applications demanding a single Ni target for its production.     

Magnetic properties of Er-Ta granular thin films

The magnetic and structural properties of granular Er-Ta films have been studied with SQUID magnetometry and transmission electron microscopy (TEM). The films have been fabricated by co-sputtering using DC magnetron sputtering. The particle size of granular films was found to be affected by both the composition and annealing temperature. Electron diffraction patterns showed that the as-sputtered Er-Ta films have an amorphous structure. After annealing at different temperatures, the amorphous phase transforms first into an intermediate fcc structure and finally into an Er hcp phase and Ta phase, in which granular particles are clearly observed by TEM. The intermediate fcc structure shows only one magnetic transition whereas the hcp Er granular solids show a superparamagnetic and a modulated magnetic phase transitions. The modulated phase is not as obvious as in hcp Er films and this may be due to finite size effects.     

High coercive field and magnetization reversal in core-shell cum nanotwin driven Ni/NiO nanospheres

We report here nanotwin-core-shell Ni(core)NiO(shell) spheres of average size 25 nm prepared through polyol method. They exhibit high coercive field at 2 K, sharp peak at approximately 20 K in magnetization curve and magnetization reversal. Interestingly, exchange bias due to antiferromagnetic NiO shell is absent. Among other possibilities, anisotropy variations due to particle size distribution and twinning associated with disorder appear to play an important role. Further, magnetic interactions of twinned bigger spheres, which may also act as superferrimagnetic-like Ni multilayer cores, with superparamagnetic Ni of smaller spheres, might be the additional causes. These nanostructures therefore seem to have potential interest in memory effect.     

Revealing the Role of Electrocatalyst Crystal Structure on Oxygen Evolution Reaction with Nickel as an Example

Establishing a correlation between the crystal structure and electrocatalytic activity is crucial to the rational design of high performance electrocatalysts. In this work, taking the widely investigated nickel (Ni) based nonprecious oxygen evolution reaction (OER) catalyst as an example, for the first time, it is reported that the crystal structure plays a critical role in determining the OER performance. Similar‐sized nickel nanoparticles but in different hexagonal close‐packed phase and face‐centered cubic phase coated with N‐doped carbon shells, noted as hcp‐Ni@NC and fcc‐Ni@NC, are successfully prepared, respectively, in which the N‐coated carbon shell structures were also similar. Surprisingly, a dramatically enhanced OER performance of hcp‐Ni@NC in comparison with fcc‐Ni@NC is observed. The hcp‐Ni@NC only requires 305 mV overpotential to achieve the current density of 10 mA cm^?2, which is 55 mV lower than that of fcc‐Ni@NC, which can be ascribed to the influence of nickel crystal phase on the electron structure of N‐doped carbon shell. This finding will bring new thinking toward the rational design of high performance non‐noble metal electrocatalysts.     

Thermodynamic Calculation of Phase Equilibria in the Ti–Co and Ni–Sn Systems

A thermodynamic model for the titanium-cobalt system has been developed utilizing measured enthalpies of mixing of the liquid and evaluated phase-diagram data. The free energies of the liquid, bcc, fcc, and hcp solid solutions, and TiCo, Ti2Co, TiCo2, and TiCo3 compounds were calculated for a temperature of 400 K. The model and measured heats of crystallization have been used to predict the free energy of the metastable amorphous phase at 400 K, needed for comparison with experimental results on the mechanical alloying of Ti and Co. The predicted glass-forming range for alloys prepared by mechanical alloying is from 10 to 81.5 at. % Co. We adopted a similar approach for modeling the Ni–Sn system to calculate the free energies of Ni3Sn, and Ni3Sn2, and the liquid (amorphous) and fcc solid solutions in the nickel-rich region at 240 K. In this system the inclusion of the magnetic contribution to the free energy of the Ni-rich fcc solid solution is important in interpreting the results of mechanical alloying. We propose a simple transformation of the free-energy curves, which assists in the graphical identification of the glass-forming ranges.     

Magnetic force microscopy on nanocrystalline Co films

Pioneer works in ultrathin magnetic films have shown perpendicular magnetic domains in the demagnetized state. The source of this perpendicular anisotropy is the interface anisotropy developed at the interface. Similar domains could be observed in tetragonally distorted ultrathin films due to the magnetoelastic anisotropy. On the other hand, single-crystalline hexagonal close packed (hcp) Co films when grown epitaxially with the c-axis oriented perpendicular to the film plane may show perpendicular stripe magnetic domains even up to a thickness of about 500 nm. In that case the source of perpendicular anisotropy was the magnetocrystalline anisotropy of bulk Co, which favors the c-axis. In this work, we have grown by radio frequency magnetron sputtering Co films in the thickness range 15-4500 nm. We have used various substrates, such as Corning glass, silicon and Al-foil. The substrate temperature was about 350 K. The films have been found by X-ray diffraction experiments to present various structures and textures depending on the preparation conditions, mainly the Ar-pressure and deposition rate. Stripe- and labyrinth-like domain configurations are observed in films textured along the c-axis, and in films with a mixture of hcp and fcc grains, repectively. Films which show mainly fcc or amorphous structure do not form perpendicular domains. The results are discussed with respect to magnetization loops.     

The low temperature magnetic properties of austenitic Fe---Cr---Ni alloys. 3. The effect of chromium concentration in Fe---Cr-17wt% Ni alloys

The magnetic properties of ternary Fe---Cr---Ni alloys containing 17 wt% Ni and 18–24% Cr have been studied over a range of temperature from 4.2–35 K by both ac and dc techniques in fields from 5 Am⁻¹ − 6 MA m⁻¹. At room temperature, the matrix of all the alloys was the paramagnetic fcc austenite phase (with an unavoidable 0.1 – 0.5 wt% δ ferrite) and on cooling all the alloys showed distinct peaks in ac susceptibility, though equivalent peaks in dc susceptibility were only observed at low fields in the alloy containing 18 wt% Cr. An analysis of the magnetization/field/temperature results showed that all the alloys were superparamagnetic at low temperature, due to the formation of ferromagnetic clusters in the disordered antiferromagnetic matrix, and that the chromium atoms make no measureable contribution to the magnetization of these clusters. Appropriate susceptibility values are tabulated for use as design data.     

Scanning of nickel sulfamate concentration in electrodeposition bath used for production of Ni–Co alloys

The Ni–Co films were produced by using the electrodeposition technique from the electrolytes with different Ni(SO₃·NH₂)₂·4H₂O concentrations (from 0 to 0.45 M). The Ni content of the films changed gradually from 0 to 57 %. The Ni–Co system exhibited anomalous codeposition. For 0 at.% Ni content, the saturation magnetization, M_s of the film was found to be 1298 emu/cm³, which is close to that of bulk Co (1420 emu/cm³). As the Ni content increased, M_s decreased since the M_s value of bulk Ni (480 emu/cm³) is lower than that of bulk Co. The coercivity, H_c, of Co film was found as 37 Oe. When the Ni content increased to 6 at.%, the H_c value dramatically increased to 109 Oe. The hexagonal closed packed (hcp) structure was observed for the films containing 0 and 6 at.% Ni. When the Ni content increased to 25 at.%, a mixed phase of face centered cubic (fcc) and hcp structure (mostly fcc) was detected. For further increase in Ni content (39 and 57 at.%), the peaks which occurred from the reflections of fcc phase were obtained. As a result of structural analysis, the Co content can be determined as 62–64 at.% for changing of crystal structure. The transfiguration from spherical granular to acicular surface morphology occurred around 75 at.% Co content. Magnetoresistance of the films was measured and it was found that the films show anisotropic magnetoresistance.     

相分离Gd_5Ge_4合金的低温磁化行为及温度依赖性研究

系统研究了Gd_5Ge_4合金的晶体结构和低温磁化行为.结果表明,Gd_5Ge_4具有相分离特征,低温下出现反铁磁(AFM)和铁磁(FM)共存现象.由于相分离的存在导致127K时发生奈尔反铁磁转变.在外磁场诱导下,在4.2K以下发生AFM-FM磁转变,并导致台阶式磁化现象发生,但仅发生在第一次外加磁场增加过程中,表现出磁不可逆性.随磁场升高,在10K以下体系存在类台阶式响应和不可逆的磁滞行为,并在5572kA/m下均达到饱和磁化.在温度50～60K温区,磁循环所出现的台阶式磁化转变则是完全可逆的,更高温区域则表现为部分铁磁直至室温下的顺磁特性.     

A New hcp Phase Formed in the Ni-Nb System during Ion-beam-assisted Deposition

The Ni80Nb20 films were prepared by ion beam assisted deposition (IBAD) with various Ar+ ion energies. A phase evolution of fcc→amorphous→Ni+Nb→Ni+hcp was observed with the increasing of ion beam energy from 2 keV to 8 keV. When bombarded by Ar+ ions of 8 keV during deposition, a new crystalline phase with hcp structure was obtained, of which the lattice parameters are a=0.286 nm and c=0.483 nm, different from those of the similar A3B-type hcp phase previously reported. The experimental results were discussed in terms of thermodynamics and restricted kinetic conditions in the far-from-equilibrium process of IBAD. The formation of hep phase may also be related to the valence electron effect.     

The magnetic properties of ultrafine particles of Ni(OH)2

Ultrafine particles of Ni(OH)₂ were prepared by precipitation from aqueous solution. The susceptibility of the ultrafine particles shows a distinctive maximum at temperature which is rather lower than T_N of the large particles. Using the c-axis oriented ultrafine particles prepared by the sedimentation method, the magnetic susceptibility and the magnetization curve perpendicular and parallel to the c-axis of the ultrafine particles were measured. The magnetization curve showed a small hysteresis in low field and a remanent magnetization which increased with decrease of the particle size. Two-step jump was observed in the magnetization curve of the ultrafine particles when the external field was applied along the c-axis. The magnetic properties characteristic of the Ni(OH)₂ ultrafine particles are discussed.     

Carbon-Doped Nickle Via a Fast Decarbonization Route for Enhanced Hydrogen Oxidation Reaction in Alkaline Media

Nickel (Ni) based materials with non-metal heteroatom doping are competitive substitutes for platinum group catalyst toward alkaline hydrogen oxidation reaction (HOR). However, the incorporation of non-metal atom into the lattice of conventional fcc phase Ni can easily trigger a structural phase transformation, forming hcp phase nonmetallic intermetallic compounds. Such tangle phenomenon makes it difficult to uncover the relationship between HOR catalytic activity and doping effect on fcc phase Ni. Herein, taking trace carbon doped Ni (C-Ni) nanoparticles as an example, a new nonmetal doped Ni nanoparticles synthesized by a simple fast decarbonization route using Ni₃C as precursor is presented, which provides an ideal platform to study the structure-activity relationship between alkaline HOR performance and non-metal doping effect toward fcc phase Ni. The obtained C-Ni exhibits an enhanced alkaline HOR catalytic activity compared with pure Ni, approaching to commercial Pt/C. X-ray absorption spectroscopy confirms that the trace carbon doping can modulate the electronic structure of conventional fcc phase nickel. Besides, theoretical calculations suggest that the introducing of C atoms can effectively regulate the d-band center of Ni atoms, resulting in the optimized hydrogen absorption, thereby improving the HOR activity.     

Surface spin-glass freezing in interacting core-shell NiO nanoparticles

Magnetization and AC susceptibility measurements have been performed on ～3?nm NiO nanoparticles in powder form. The results indicate that the structure of the particles can be considered as consisting of an antiferromagnetically ordered core, with an uncompensated magnetic moment, and a magnetically disordered surface shell. The core magnetic moments block progressively with decreasing temperature, according to the distribution of their anisotropy energy barriers, as shown by a broad maximum of the low field zero-field-cooled magnetization (M(ZFC)) and in the in-phase component χ' of the AC susceptibility, centred at ～70?K. On the other hand, surface spins thermally fluctuate and freeze in a disordered spin-glass-like state at much lower temperature, as shown by a peak in M(ZFC) (at 17?K, for H = 50?Oe) and in χ'. The temperature of the high temperature χ' peak changes with frequency according to the Arrhenius law; instead, for the low temperature maximum a power law dependence of the relaxation time was found, τ = τ(0)(T(g)/(T(ν)-T(g)))(α), where α = 8, like in spin glasses, τ(0) = 10(-12)?s and T(g) = 15.9?K. The low temperature surface spin freezing is accompanied by a strong enhancement of magnetic anisotropy, as shown by the rapid increase of coercivity and high field susceptibility. Monte Carlo simulations for core/shell antiferromagnetic particles, with an antiferromagnetic core and a disordered shell, reproduce the qualitative behaviour of the temperature dependence of the coercivity. Interparticle interactions lead to a shift to a high temperature of the distribution of the core moment blocking temperature and to a reduction of magnetization dynamics.     

Microstructure Variation of Cold Deformed MP159 Alloy during Aging

By comparing the relationship of room temperature yield strength with the reduction of cold rolled MP159 alloy before and after aging at 650℃, and by means of TEM examination on the corresponding microstructures, the occurrence of fcc(α)→hcp(ε) martensitic transition in MP159 alloy during cold deformation and the variation of the platelet E phase during aging have been Studied. The results show that the platelet E phase is really formed when the cold deformation reaches a critical value, and both the amount and the width of the platelet B phase would further increase during 650℃ aging. The increases of the amount and the width of the platelet εphase result in an additional increase of yield strength. Therefore, it is concluded that the additional hardening effect of MP159 alloy after aging is not only from the precipitation of Ni3X disperse phase but also from the volume fraction increase of the platelet ε phase. Further occurrence of the martensitic transition during aging may be due to the elimination of residual compression stress within matrix induced by the fcc(α)→hcp(ε) transition during cold deformation     

Large magnetoresistance in carbon-coated Ni/NiO nanoparticles

We report here a large magnetoresistance (MR) observed in carbon-coated Ni/NiO nanostructures synthesized by a chemical method. The crystalline nature and particle size of the graphitic-carbon-coated Ni/NiO nanostructure was investigated by X-ray diffraction study and field emission scanning electron microscope images. The Raman spectroscopy confirms the presence of graphite layer over the Ni/NiO nanostructure. The field-cooled (FC) magnetic hysteresis curves show exchange bias effect suggesting possible Ni/NiO core–shell structure. The temperature-dependent magnetization data show bifurcation in FC–zero-field-cooled curves, indicating the superparamagnetic behaviour and competing ferromagnetic (FM) and antiferromagnetic interactions in the nanocomposite. MR studies show a large negative MR of \(\sim \)20% at 18 K and \(\sim \)4.2% at room temperature, revealing significant enhancement of FM interactions at low temperatures and spin-dependent tunnelling of current through the nanocomposite.     

La_(1-x)Pr_xFe_(11.206)Al_(1.794)(x=0、0.1、0.2、0.3)化合物的磁热效应研究

对La1-xPrx(Fe0.862Al0.138)13(x=0、0.1、0.2、0.3)化合物的磁性能进行了研究。该系列化合物在1223K下退火15天后,室温下表现为NaZn13型结构。升温过程中,该系列化合物经历从铁磁态到反铁磁态的一级磁性转变。随着Pr含量的逐渐增多,磁性转变温度逐渐升高,铁磁态下化合物的磁化强度增大。在2T外磁场下,La0.8Pr0.2Fe11.206Al1.794化合物升温过程中的最大磁熵变为-4.21J/kg·K,降温过程中的最大磁熵变为-4.39J/kg·K。     

Observation of the morphology of thin films of solid helium deposited from the fluid onto sapphire

Thin layers of solid helium were grown on sapphire single-crystal substrates at pressures from about 500 bar to 9 kbar. Grain boundaries can be observed in these layer crystals. The morphology of the grains depends on the crystal modification. In the hcp phase (below about 1.13 kbar) a system of parallel bands is observed, probably due to slip and twinning. In the fcc phase (above 1.13 kbar) a polygonal structure similar to a helium froth is found. Melting of this froth in the fcc phase shows grain boundary melting; fluid helium is wetting the fcc grains. Grain boundaries in the hcp phase are, in contrast, not wetted by fluid helium. Near the triple point at 1.13 kbar and 15.0 K one can deposit both crystalline phases side by side. In such structures, the transition fcc hcp⁴He can be observed during isothermal holding. The transition proceeds by the parallel motion of low-energy grain boundaries.     

Defect mediated magnetic interaction and high Tc ferromagnetism in Co doped ZnO nanoparticles

Structural, optical and magnetic studies have been carried out for the Co-doped ZnO nanoparticles (NPs). ZnO NPs are doped with 3% and 5% Co using ball milling and ferromagnetism (FM) is studied at room temperature and above. A high Curie temperature (Tc) has been observed from the Co doped ZnO NPs. X-ray diffraction and high resolution transmission electron microscopy analysis confirm the absence of metallic Co clusters or any other phase different from würtzite-type ZnO. UV-visible absorption and photoluminescence studies on the doped samples show change in band structure and oxygen vacancy defects, respectively. Micro-Raman studies of doped samples shows defect related additional strong bands at 547 and 574 cm(-1) confirming the presence of oxygen vacancy defects in ZnO lattice. The field dependence of magnetization (M-H curve) measured at room temperature exhibits the clear M-H loop with saturation magnetization and coercive field of the order of 4-6 emu/g and 260 G, respectively. Temperature dependence of magnetization measurement shows sharp ferromagnetic to paramagnetic transition with a high Tc = 791 K for 3% Co doped ZnO NPs. Ferromagnetic ordering is interpreted in terms of overlapping of polarons mediated through oxygen vacancy defects based on the bound magnetic polaron (BMP) model. We show that the observed FM data fits well with the BMP model involving localised carriers and magnetic cations.     

Large-scale and shape-controlled synthesis and characterization of nanorod-like nickel powders under microwave radiation

The nanorod-like nickel powders were fabricated via hydrothermal liquid phase reduction route under microwave irradiation with hydrazine hydrate as a reducing agent as well as polyvinyl alcohol as a dispersant and/or structure directing agent. The morphology and structure of as-prepared products could be easily tuned by adjusting process parameters such as pH value and microwave irradiation time. The resulting materials were characterized by X-ray diffraction (XRD), scanning electron microscope, transmission electron microscopy and selected-area electron diffraction (SAED). The results demonstrated that pure nickel powders with face-centered cubic (fcc) structure were prepared at relatively mild condition and no characteristic peaks of nickel oxide in the XRD pattern were found. The phenomenon of lattice expansion for Ni powders was explained in details according to the XRD theory. As-prepared Ni sample was of obvious shape anisotropy with length diameter ratio of 5. Magnetic measurements shown that the magnetic properties of nanorod-like (fcc) Ni powders were quite different from those of hexagonal closed-packed (hcp) Ni nanoparticles. Furthermore, it had more strong ferromagnetic properties than that of Ni powders both bulk and nanoparticles.