Influence of composition on the structure, electric and magnetic properties of Pd-Mn-P and Pd-Co-P amorphous alloys

The influence of composition on the structure and on the electric and magnetic properties of amorphous Pd-Mn-P and Pd-Co-P prepared by rapid quenching techniques were investigated in terms of (1) the 3d band filling of the first transition metal group, (2) the phosphorus concentration effect which acts as an electron donor and (3) the transition metal concentration.

The structure is essentially characterized by a set of polyhedra subunits essentially inverse to the packing of hard spheres in real space. Examination of computer generated distribution functions using Monte Carlo random statistical distribution of these polyhedra entities demonstrated tile reproducibility of the experimentally calculated atomic distribution function. As a result, several possible "structural parameters" are proposed such as: the number of nearest neighbors, the metal-to-metal distance, the degree of short-range order and the affinity between metal-metal and metal-metalloid. It is shown that the degree of disorder increases from Ni to Mn. Similar behavior is observed with increase in the phosphorus concentration.

The magnetic properties of Pd-Co-P alloys show that they are ferromagnetic with a Curie temperature between 272 and 399°K as the cobalt concentration increases from 15 to 50 at.%. Below 20 at.% Co the short-range exchange interactions which produce the ferromagnetism are unable to establish a long-range magnetic order and a peak in the magnetization shows up at the lowest temperature range . The electric resistivity measurements were performed from liquid helium temperatures up to the vicinity of the melting point (900°K). The thermomagnetic analysis was carried out under an applied field of 6.0 kOe. The electrical resistivity of Pd-Co-P shows the coexistence of a Kondo-like minimum with ferromagnetism. The minimum becomes less important as the transition metal concentration increases and the coefficients of ℓn T and T^2 become smaller and strongly temperature dependent. The negative magnetoresistivity is a strong indication of the existence of localized moment.

The temperature coefficient of resistivity which is positive for Pd- Fe-P, Pd-Ni-P, and Pd-Co-P becomes negative for Pd-Mn-P. It is possible to account for the negative temperature dependence by the localized spin fluctuation model and the high density of states at the Fermi energy which becomes maximum between Mn and Cr. The magnetization curves for Pd-Mn-P are typical of those resulting from the interplay of different exchange forces. The established relationship between susceptibility and resistivity confirms the localized spin fluctuation model. The magnetoresistivity of Pd-Mn-P could be interpreted in tenns of a short-range magnetic ordering that could arise from the Rudennan-Kittel type interactions.

I. Reactively sputtered Ti-Si-N thin films for diffusion barrier applications. II. Oxidation, diffusion and crystallization of an amorphous Zr_(60)Al_(15)Ni_(25) alloy.

Films of Ti-Si-N obtained by reactively sputtering a TiSi_2, a Ti_5Si_3, or a Ti_3Si target are either amorphous or nanocrystalline in structure. The atomic density of some films exceeds 10^23 at./cm^3. The room-temperature resistivity of the films increases with the Si and the N content. A thermal treatment in vacuum at 700 °C for 1 hour decreases the resistivity of the Ti-rich films deposited from the Ti_5Si_3 or the Ti_3Si target, but increases that of the Si-rich films deposited from the TiSi_2 target when the nitrogen content exceeds about 30 at. %.

Ti_(34)Si_(23)N_(43) deposited from the Ti_5Si_3 target is an excellent diffusion barrier between Si and Cu. This film is a mixture of nanocrystalline TiN and amorphous SiN_x. Resistivity measurement from 80 K to 1073 K reveals that this film is electrically semiconductor-like as-deposited, and that it becomes metal-like after an hour annealing at 1000 °C in vacuum. A film of about 100 nm thick, with a resistivity of 660 µΩcm, maintains the stability of Si n+p shallow junction diodes with a 400 nm Cu overlayer up to 850 °C upon 30 min vacuum annealing. When used between Si and Al, the maximum temperature of stability is 550 °C for 30 min. This film can be etched in a CF_4/O_2 plasma.

The amorphous ternary metallic alloy Zr_(60)Al_(15)Ni_(25) was oxidized in dry oxygen in the temperature range 310 °C to 410 °C. Rutherford backscattering and cross-sectional transmission electron microscopy studies suggest that during this treatment an amorphous layer of zirconium-aluminum-oxide is formed at the surface. Nickel is depleted from the oxide and enriched in the amorphous alloy below the oxide/alloy interface. The oxide layer thickness grows parabolically with the annealing duration, with a transport constant of 2.8x10^(-5) m^2/s x exp(-1.7 eV/kT). The oxidation rate is most likely controlled by the Ni diffusion in the amorphous alloy.

At later stages of the oxidation process, precipitates of nanocrystalline ZrO_2 appear in the oxide near the interface. Finally, two intermetallic phases nucleate and grow simultaneously in the alloy, one at the interface and one within the alloy.

A generalized treatment of the order-disorder transformation in alloys and its effects on their magnetic properties

A theory of the order-disorder transformation is developed in complete generality. The general theory is used to calculate long range order parameters, short range order parameters, energy, and phase diagrams for a face centered cubic binary alloy. The theoretical results are compared to the experimental determination of the copper-gold system, Values for the two adjustable parameters are obtained.

An explanation for the behavior of magnetic alloys is developed, Curie temperatures and magnetic moments of the first transition series elements and their alloys in both the ordered and disordered states are predicted. Experimental agreement is excellent in most cases. It is predicted that the state of order can effect the magnetic properties of an alloy to a considerable extent in alloys such as Ni₃Mn. The values of the adjustable parameter used to fix the level of the Curie temperature, and the adjustable parameter that expresses the effect of ordering on the Curie temperature are obtained.

Avaliação da microestrutura, microdureza e resistência à corrosão de juntas soldadas de uma liga de Ni-Cr obtidas através de diferentes processos de soldagem

Este trabalho avaliou o comportamento eletroquímico do metal de base (MB) de uma liga a base de níquel-cromo em relação a juntas soldadas desta liga obtidas pelos processos de brasagem (BRA) e Tungsten Inert Gas (TIG), imersos em saliva artificial com pH 2,5 e 5,5. Foram também realizados ensaios de microdureza e caracterização microestrutural, por meio de microscopia óptica e eletrônica de varredura e análise química semi-quantitativa por EDS, nos grupos MB, TIG, BRA e no cordão de solda a laser (LAS). O MB apresentou uma matriz rica em níquel e cromo, distribuída em um arranjo dendrítico típico, apresentando inclusões metálicas de silício e titânio, além de porosidades. As soldas TIG e LAS revelaram uma microestrutura mais refinada que o MB, mostrando, entretanto, uma mesma composição química e distribuição de seus elementos. A solda BRA apresentou diferenças marcantes em sua microestrutura, composição química e distribuição de seus elementos em relação ao MB. Os dados de microdureza Vickers (HV), potencial de corrosão (Ecorr) e densidade de corrente de corrosão (jcorr) foram analisados com ANOVA e teste de Tukey (p<0,05). Para determinação da influência do pH quanto a resistência à corrosão dos grupos MB, TIG e BRA, empregou-se o teste t de Student (p<0,05). O MB apresentou menor média de microdureza (256,13 9,39 HV), seguido pelos grupos TIG (271,53 8,07 HV), LAS (303,73 13,93 HV) e BRA (551,99 37,73 HV). Em pH 2,5 as médias do Ecorr (mV) para o MB, TIG e BRA foram, respectivamente, -67,9 8,43, -52,78 16,74, e -284,33 19,04; e em pH 5,5, médias de -54,03 21,15, -62,08 20,16 e -278,8 28,96. Os valores médios de jcorr (A.cm-2) para o MB, TIG e BRA em pH 2,5 foram, respectivamente, 2,49 0,95, 5,584 1,64 e 27,45 4,9; e em pH 5,5, médias de 1,929 0,83, 4,267 1,51 e 54,2 11,96. Os grupos MB e TIG apresentaram boa resistência à corrosão, com maior módulo de impedância em relação ao grupo BRA. As diferenças no pH da saliva artificial não alteraram o comportamento corrosivo dos grupos MB e TIG. Entretanto, observou-se uma redução marcante na jcorr e no módulo de impedância nas soldas obtidas pelo processo de brasagem. O grupo BRA apresentou corrosão galvânica ao ser analisado formando par com o MB, mostrando uma jcorr de 5,3 A.cm-2. Entretanto, o mesmo não foi observado quando o MB foi associado à solda TIG, onde a jcorr foi cerca de 150 vezes menor. O grupo BRA, além de apresentar um comportamento eletroquímico muito diferente do MB, revelou diferenças marcantes quanto a composição química, aspecto microestrutural e microdureza. As juntas TIG e LAS mostraram semelhanças químicas e microestruturais em relação ao MB, sendo que na solda TIG esta semelhança foi ainda mais evidente. Além disto, a solda TIG apresentou um comportamento eletroquímico muito semelhante ao MB e, portanto, parecendo ser mais recomendável para soldar ligas odontológicas de níquel-cromo em relação aos demais processos de soldagem aqui avaliados.

NiO removal of Ni/Au Ohmic contact to p-GaN after annealing

The Ni/Au contact was treated with oxalic acid after annealing in O_2 ambient, and its I-V characteristic showed the property of contact has been obviously improved. An Auger electron spectroscopy (AES) depth pro-file of the contact as-annealed showed that the top layer was highly resistive NiO, while an X-ray photo-electron spectroscopy (XPS) of oxalic acid treated samples indicated that the NiO has been removed effectively. A scanning electron microscope (SEM) was used to observe the surface morphology of the contacts, and it was found that the lacunaris surface right after annealing became quite smooth with lots of small Au exposed areas after oxalic acid treatment. When the test probe or the subsequently deposited Ti/Au was directly in contact with these small Au areas, they worked as low resistive current paths and thus decrease the specific contact resistance.

Synthesis and field emission of diamond-like carbon nanorods on TiO2/Ti nanotube arrays

Highly ordered TiO2/Ti nanotube arrays were fabricated by anodic oxidation method in 0.5 wt% HF. Using prepared TiO2/Ti nanotube arrays deposited Ni nanoparticles as substrate, high quality diamond-like carbon nanorods (DLCNRs) were synthesized by a conventional method of chemical vapor deposition at 750 degrees C in nitrogen atmosphere. DLCNRs were analyzed by filed emission scanning electron microscopy and Raman spectrometer. It is very interesting that DLCNRs possess pagoda shape with the length of 3-10 mu m. Raman spectra show two strong peaks about 1332 cm (1) and 1598 cm (1), indicating the formation of diamond-like carbon. The field emission measurements suggest that DLCNRs/TiO2/Ti has excellent field emission properties, a low turn-on field about 3.0 V/mu m, no evident decay at 3.4 mA/cm(2) in 480 min. (C) 2009 Elsevier B. V. All rights reserved.

Structures and electrochemical characteristics of Ti0.26Zr0.07V0.24Mn0.1Ni0.33Mox (x=0-0.1) hydrogen storage alloys

Microstructures and electrochemical properties of Ti0.26Zr0.07V0.21Mn0.1Ni0.33Mox (x=0,0.025,0.05,0.075, 0.10) electrode alloys have been investigated. The results of XRD analysis show that the alloys are mainly composed of V-based solid solution phase with body centered cubic (bcc) structure and C14 Laves phase with hexagonal structure. The addition of Mo element can imp ove the activation characteristics, maximum discharge capacity and cyclic durability for the electrode alloys

Electrochemical Hydrogen Storage in Ti1.6V0.4Ni1-xCox Icosahedral Quasicrystalline Alloys

The discovery of the icosahedral phase (i-phase) in rapidly quenched Ti1.6V0.4Ni1-xCox (x=0.02-01) alloys is described herein. The i-phase occurs in a similar amount relative to the coexisting beta Ti phase. The electron diffraction patterns show the distinct spot anisotropy, indicating that the i-phase is metastable. The electrochemical hydrogen storage performance of these five alloy electrodes are also reported herein. The hydrogen desorption of nonelectrochemical recombination in the cyclic voltammetric (CV) response exhibits the demand for electrocatalytic activity improvement.

MICROSTRUCTURE AND MECHANICAL PROPERTIES OF TI-BASED METALLIC GLASS MATRIX COMPOSITES

Ti40Cu40Ni10Zr10-xScx (x = 0.5 and 1, at%) alloys were prepared by copper mould casting method. Microstructures of the phi 3 mm rod alloys were investigated by XRD and SEM. The results showed that the phi 3 mm rods were glassy matrix with TiCu crystalline phase. Mechanical properties were studied by compressive test. Ti40Cu40Ni10Zr9Sc1 alloy exhibited good compressive strength over 2200 MPa and superior compressive deformation is about 7.9%.

Effect of La-Mg-based alloy addition on structure and electrochemical characteristics of Ti0.10Zr0.15V0.35Cr0.10Ni0.30 hydrogen storage alloy

Effect of La-Mg-based alloy (AB(5)) addition on Structure and electrochemical characteristics of Ti0.10Zr0.15V0.35Cr0.10Ni0.30 hydrogen storage alloy has been investigated systematically. XRD shows that the matrix phase structure is not changed after adding AB(5) alloy, however, the amount of the secondary phase increases with increasing AB(5) alloy content. The electrochemical measurements show that the plateau pressure Ti0.10Zr0.15V0.35Cr0.10Ni0.30 + x% La0.85Mg0.25Ni4.5Co0.35Al0.15 (X = 0, 1, 5, 10, 20) hydrogen storage alloys increase with increasing x, and the width of the pressure plateau first increases when x increases from 0 to 5 and then decreases as x increases further, and the maximum discharge capacity changes in the same trend.

Catalytic oxidation of cyclohexane over Ti-Zr-Co catalysts

Ti-Zr-Co alloys have been fabricated and characterized, and their catalytic performance was discussed for the oxidation of cyclohexane with oxygen under solvent-free condition. The icosahedral quasicrystalline phase (I-phase)-forming ability of Ti-Zr-Co alloys with different compositions was discussed, and it was confirmed that I-phase could be formed as a dominating phase at the Ti-rich composition region from Ti53Zr27Co20 to Ti75Zr5Co20 in as-cast alloys. The composition and microstructure of Ti-Zr-Co alloys present crucial influences on its catalytic activity and selectivity in the oxidation of cyclohexane. The influences of some reaction parameters such as temperature, reaction time, and catalyst amounts were also investigated. Ti70Zr10Co20 alloy containing quasicrystal microstructure showed good catalytic performance with a 6.8% conversion of cyclohexane and 90.4% selectivity of cyclohexanol and cyclohexanone. It behaves as an efficient heterogeneous catalyst for the oxidation of cyclohexane and could be recycled five times without loss in activity and selectivity.

Ti基准晶材料制备和贮氢性能研究进展

Ti基准晶材料具有热力学稳定的正二十面体构造,表现出特殊的传输特性、贮氢特性和力学特性等,相关研究受到广泛关注.近年,作者所在研究组在Ti基准晶的制备和贮氢性能研究方面取得了一些新进展.综合报道了Ti-Zr-Ni-Cu系准晶相及其复合相材料的制备和贮氢性能.

Structure and electrochemical characteristics of TiV1.1Mn0.9Nix (x=0.1-0.7) alloys

The structure and electrochemical properties of TiV1.1Mn0.9Nix (x = 0.1-0.7) solid solution electrode alloys have been investigated. It is found that these alloys mainly consist of a solid solution phase with body centered cubic (bcc) structure and a C14 Laves secondary phase. The solid solution alloys show easy activation behavior, high temperature dischargeability, high discharge capacity and favorable high-rate dischargeability as a negative electrode material in Ni-MH battery. The maximum discharge capacity is 502 mAh g(-1) at 303 K when x = 0.4. Electrochemical impedance spectroscopy (EIS) test shows that the charge-transfer resistance at the surface of the alloy electrodes decreases obviously with increasing Ni content.

Microstructure and some dynamic performances of Ti0.17Zr0.08V0.34RE0.01Cr0.1Ni0.3 (RE = Ce, Dy) hydrogen storage electrode alloys

Microstructure and some dynamic performances of Ti0.17Zr0.08V0.34RE0.01Cr0.1Ni0.3 (RE=Ce, Dy) hydrogen storage electrode alloys have been investigated using XRD, FESEM-EDS, ICP-MS and EIS measurements. The alloy is composed of V-based solid solution phase with a dendritic shape and a continuous C14 Laves phase with a network shape surrounding the dendrite. Pressure-composition isotherm curves indicate that the alloy with Dy addition has a lower equilibrium hydrogen pressure and a wider plateau region. The alloy electrode with Dy addition has higher discharge capacity, while the alloy electrode with Ce addition has better activation and higher cycle stability. The alloy electrode with Ce addition has better electrochemical activity with higher exchange current density (127.5 mA g(-1)), lower charge transfer resistance (1.37 Omega) and lower apparent activation energy (30.5 kJ mol(-1)). The capacity degradation behavior for the alloy electrode is attributed to two main factors: one is the dissolutions of V and Zr element to KOH solution, and another is the larger charge transfer resistance which increases with increasing cycle number.

Crystal structure and electrochemical properties of rare earth non-stoichiometric AB(5)-type alloy as negative electrode material in Ni-MH battery

The La0.85MgxNi4.5Co0.35Al0.15 (0.05less than or equal toxless than or equal to0.35) system compounds have been prepared by are melting method under Ar atmosphere. X-ray diffraction (XRD) analysis reveals that the as-prepared alloys have different lattice parameters and cell volumes. The electrochemical properties of these alloys have been studied through the charge-discharge recycle testing at different temperatures and discharge currents. It is found that the La0.85Mg0.25Ni4.5Co0.35Al0.(15) alloy electrode is capable of performing high-rate discharge. Moreover, it has very excellent electrochemical properties as negative electrode materials in Ni-MH battery at low temperature, even at -40degreesC.