Effect of the substitutional elements on the microstructure of the Ti-15Mo-Zr and Ti-15Zr-Mo systems alloys

Titanium alloys have excellent biocompatibility, and combined with their low elastic modulus, become more efficient when applied in orthopedic prostheses. Samples of Ti-15Mo-Zr and Ti-15Zr-Mo system alloys were prepared using an arc-melting furnace with argon atmosphere. The chemical quantitative analysis was performed using an optical emission spectrometer with inductively coupled plasma and thermal conductivity difference. The X-ray diffractograms, allied with optical microscopy, revealed the structure and microstructure of the samples. The mechanical analysis was evaluated by Vickers microhardness measurements. The structure and microstructure of alloys were sensitive to molybdenum and zirconium concentration, presenting α′, α″ and β phases. Molybdenum proved to have greater β-stabilizer action than zirconium. Microhardness was changed with addition of molybdenum and zirconium, having Ti-15Zr-10Mo (436 ± 2 HV) and Ti-15Mo-10Zr (378 ± 4 HV) the highest values in each system.

Study of the oxygen vacancy influence on magnetic properties of Fe- and Co-doped SnO2 diluted alloys

Transition-metal (TM)-doped diluted magnetic oxides (DMOs) have attracted attention from both experimental and theoretical points of view due to their potential use in spintronics towards new nanostructured devices and new technologies. In the present work, we study the magnetic properties of Sn0.96TM0.04O2 and Sn0.96TM0.04O1.98(V (O))(0.02), where TM = Fe and Co, focusing in particular in the role played by the presence of O vacancies nearby the TM. The calculated total energy as a function of the total magnetic moment per cell shows a magnetic metastability, corresponding to a ground state, respectively, with 2 and 1 mu(B)/cell, for Fe and Co. Two metastable states, with 0 and 4 mu(B)/cell were found for Fe, and a single value, 3 mu(B)/cell, for Co. The spin-crossover energies (E (S)) were calculated. The values are E (S) (0/2) = 107 meV and E (S) (4/2) = 25 meV for Fe. For Co, E (S) (3/1) = 36 meV. By creating O vacancies close to the TM site, we show that the metastablity and E (S) change. For iron, a new state appears, and the state with zero magnetic moment disappears. The ground state is 4 mu(B)/cell instead of 2 mu(B)/cell, and the energy E (S) (2/4) is 30 meV. For cobalt, the ground state is then found with 3 mu(B)/cell and the metastable state with 1 mu(B)/cell. The spin-crossover energy E (S) (1/3) is 21 meV. Our results suggest that these materials may be used in devices for spintronic applications that require different magnetization states.

A simple criterion to predict the glass forming ability of metallic alloys

A new and simple criterion with which to quantitatively predict the glass forming ability (GFA) of metallic alloys is proposed. It was found that the critical cooling rate for glass formation (R-C) correlates well with a proper combination of two factors, the minimum topological instability (lambda(min)) and the Delta h parameter, which depends on the average work function difference (Delta phi) and the average electron density difference (Delta n(ws)(1/3)) among the constituent elements of the alloy. A correlation coefficient (R-2) of 0.76 was found between R-c and the new criterion for 68 alloys in 30 different metallic systems. The new criterion and the Uhlmann's approach were used to estimate the critical amorphous thickness (Z(C)) of alloys in the Cu-Zr system. The new criterion underestimated R-C in the Cu-Zr system, producing predicted Z(C) values larger than those observed experimentally. However, when considering a scale factor, a remarkable similarity was observed between the predicted and the experimental behavior of the GFA in the binary Cu-Zr. When using the same scale factor and performing the calculation for the ternary Zr-Cu-Al, good agreement was found between the predicted and the actual best GFA region, as well as between the expected and the observed critical amorphous thickness. (C) 2012 American Institute of Physics. [doi:10.1063/1.3676196]

Gold-platinum alloys and Vegard's law on the nanoscale

The structure of gold-platinum nanoparticles is heavily debated as theoretical calculations predict core-shell particles, whereas x-ray diffraction experiments frequently detect randomly mixed alloys. By calculating the structure of gold-platinum nanoparticles with diameters of up to approximate to 3.5 nm and simulating their x-ray diffraction patterns, we show that these seemingly opposing findings need not be in contradiction: Shells of gold are hardly visible in usual x-ray scattering, and the interpretation of Vegard's law is ambiguous on the nanoscale. DOI: 10.1103/PhysRevB.86.241403

Preparation and characterization of Zircaloy 4-Tantalum alloys for application in corrosive media

Two Zircaloy 4-Ta alloys (14 and 55 wt.% Ta) were produced by arc-melting. The alloys were hot-rolled at 900 degrees C and heat-treated under argon atmosphere for 100 h at 700 degrees C. The alloys were analyzed by scanning electron microscopy and X-ray diffractometry. The microstructure of both rolled and heat-treated alloys is constituted of (beta Zr,Ta)-II Ta-rich precipitates dispersed in a (alpha Zr) matrix. Corrosion tests performed in boiling concentrated H2SO4 solutions showed that the Zircaloy 4-Ta alloys are more corrosion resistant than Zircaloy 4 and that the corrosion resistance increases with increasing Ta content. (c) 2012 Elsevier Ltd. All rights reserved.

Magnetic Tuning of All-Organic Binary Alloys between Two Stable Radicals

Mixtures of 2-(4,5,6,7-tetrafluorobenzimidazol-2-yl)-4,4,5,5-tetramethyl-4,5-dihydro-1H-imidazole-3-oxide-1-oxyl (F4BImNN) and 2-(benzi-midazol-2-yl)-4,4,5,5-tetramethyl-4,5-dihydro-1H-imidazole-3-oxide-1-oxyl (BImNN.) crystallize as solid solutions (alloys) across a wide range of binary compositions. (F4BImNN)(x)(BImNN)((1-x)) with x < 0.8 gives orthorhombic unit cells, while x >= 0.9 gives monoclinic unit cells. In all crystalline samples, the dominant intermolecular packing is controlled by one-dimensional (1D) hydrogen-bonded chains that lead to quasi-1D ferromagnetic behavior. Magnetic analysis over 0.4-300 K indicates ordering with strong 1D ferromagnetic exchange along the chains (J/k = 12-22 K). Interchain exchange is estimated to be 33- to 150-fold weaker, based on antiferromagnetic ordered phase formation below Neel temperatures in the 0.4-1.2 K range for the various compositions. The ordering temperatures of the orthorhombic samples increase linearly as (1 - x) increases from 0.25 to 1.00. The variation is attributed to increased interchain distance corresponding to decreased interchain exchange, when more F4BImNN is added into the orthorhombic lattice. The monoclinic samples are not part of the same trend, due to the different interchain arrangement associated with the phase change.

Does the casting mode influence microstructure, fracture and properties of different metal ceramic alloys?

The aim of the present study was to evaluate the tensile strength, elongation, microhardness, microstructure and fracture pattern of various metal ceramic alloys cast under different casting conditions. Two Ni-Cr alloys, Co-Cr and Pd-Ag were used. The casting conditions were as follows: electromagnetic induction under argon atmosphere, vacuum, using blowtorch without atmosphere control. For each condition, 16 specimens, each measuring 25 mm long and 2.5 mm in diameter, were obtained. Ultimate tensile strength (UTS) and elongation (EL) tests were performed using a Kratos machine. Vickers Microhardness (VM), fracture mode and microstructure were analyzed by SEM. UTS, EL and VM data were statistically analyzed using ANOVA. For UTS, alloy composition had a direct influence on casting condition of alloys (Wiron 99 and Remanium CD), with higher values shown when cast with Flame/Air (p < 0.05). The factors "alloy" and "casting condition" influenced the EL and VM results, generally presenting opposite results, i.e., alloy with high elongation value had lower hardness (Wiron 99), and casting condition with the lowest EL values had the highest VM values (blowtorch). Both factors had significant influence on the properties evaluated, and prosthetic laboratories should select the appropriate casting method for each alloy composition to obtain the desired property.

Conduction mechanisms in p-type Pb1-xEuxTe alloys in the insulator regime

Electrical resistivity measurements were performed on p-type Pb1-xEuxTe films with Eu content x = 4%, 5%, 6%, 8%, and 9%. The well-known metal-insulator transition that occurs around 5% at room temperature due to the introduction of Eu is observed, and we used the differential activation energy method to study the conduction mechanisms present in these samples. In the insulator regime (x>6%), we found that band conduction is the dominating conduction mechanism for high temperatures with carriers excitation between the valence band and the 4f levels originated from the Eu atoms. We also verified that mix conduction dominates the low temperatures region. Samples with x = 4% and 5% present a temperature dependent metal insulator transition and we found that this dependence can be related to the relation between the thermal energy k(B)T and the activation energy Delta epsilon(a). The physical description obtained through the activation energy analysis gives a new insight about the conduction mechanisms in insulating p-type Pb1-xEuxTe films and also shed some light over the influence of the 4f levels on the transport process in the insulator region. (C) 2012 American Institute of Physics. [http://dx.doi.org/10.1063/1.4729813]

New constraints on the genesis and long-term stability of Os-rich alloys in the Earth's mantle

A variety of seemingly unrelated processes, such as core-mantle interaction, desulfurization, and direct precipitation from a silicate melt have been proposed to explain the formation of Ru-Os-Ir alloys (here referred to as osmiridiums) found in terrestrial mantle rocks. However, no consensus has yet been reached on how these important micrometer-sized phases form. In this paper we report the results of an experimental study on the solubilities of Ru, Os and Ir in sulfide melts (or mattes) as a function of alloy composition at 1300 degrees C. Considering the low solubilities of Ru, Os, and Ir in silicate melts, coupled with their high matte/silicate-melt partition coefficients, our results indicate that these elements concentrate initially at the ppm level in a matte phase in the mantle source region. During partial melting, the extraction of sulfur into silicate melt leads to a decrease in fS(2) that triggers the exsolution of osmiridiums from the refractory matte in the residue. The newly formed osmiridiums may persist in the terrestrial mantle for periods exceeding billions of years. (C) 2012 Elsevier Ltd. All rights reserved.

Effects of chemical composition on the corrosion of dental alloys

The aim of this study was to determine the effect of the oral environment on the corrosion of dental alloys with different compositions, using electrochemical methods. The corrosion rates were obtained from the current-potential curves and electrochemical impedance spectroscopy (EIS). The effect of artificial saliva on the corrosion of dental alloys was dependent on alloy composition. Dissolution of the ions occurred in all tested dental alloys and the results were strongly dependent on the general alloy composition. Regarding the alloys containing nickel, the Ni-Cr and Ni-Cr-Ti alloys released 0.62 mg/L of Ni on average, while the Co-Cr dental alloy released ions between 0.01 and 0.03 mg/L of Co and Cr, respectively.The open-circuit potential stabilized at a higher level with lower deviation (standard deviation: Ni-Cr-6Ti = 32 mV/SCE and Co-Cr = 54 mV/SCE). The potenciodynamic curves of the dental alloys showed that the Ni-based dental alloy with >70 wt% of Ni had a similar curve and the Co-Cr dental alloy showed a low current density and hence a high resistance to corrosion compared with the Ni-based dental alloys. Some changes in microstructure were observed and this fact influenced the corrosion behavior for the alloys. The lower corrosion resistance also led to greater release of nickel ions to the medium. The quantity of Co ions released from the Co-Cr-Mo alloy was relatively small in the solutions. In addition, the quantity of Cr ions released into the artificial saliva from the Co-Cr alloy was lower than Cr release from the Ni-based dental alloys.

Influence of alloy microstructure on the microshear bond strength of basic alloys to a resin luting cement

The aim of this study was to evaluate the influence of microstructure and composition of basic alloys on their microshear bond strength (µSBS) to resin luting cement. The alloys used were: Supreme Cast-V (SC), Tilite Star (TS), Wiron 99 (W9), VeraBond II (VBII), VeraBond (VB), Remanium (RM) and IPS d.SIGN 30 (IPS). Five wax patterns (13mm in diameter and 4mm height) were invested, and cast in a centrifugal casting machine for each basic alloy. The specimens were embedded in resin, polished with a SiC paper and sandblasted. After cleaning the metal surfaces, six tygon tubes (0.5 mm height and 0.75 mm in diameter) were placed on each alloy surface, the resin cement (Panavia F) was inserted, and the excess was removed before light-curing. After storage (24 h/37°C), the specimens were subjected to µSBS testing (0.5 mm/min). The data were subjected to a one-way repeated measures analysis of variance and Turkey's test (α=0.05). After polishing, their microstructures were revealed with specific conditioners. The highest µSBS (mean/standard deviation in MPa) were observed in the alloys with dendritic structure, eutectic formation or precipitation: VB (30.6/1.7), TS (29.8/0.9), SC (30.6/1.7), with the exception of IPS (31.1/0.9) which showed high µSBS but no eutectic formation. The W9 (28.1/1.5), VBII (25.9/2.0) and RM (25.9/0.9) showed the lowest µSBS and no eutectic formation. It seems that alloys with eutectic formation provide the highest µSBS values when bonded to a light-cured resin luting cement.

Microstructural characterization of as-cast hf-b alloys

An accurate knowledge of several metal-boron phase diagrams is important to evaluation of higher order systems such as metal-silicon-boron ternaries. The refinement and reassessment of phase diagram data is a continuous work, thus the reevaluation of metal-boron systems provides the possibility to confirm previous data from an investigation using higher purity materials and better analytical techniques. This work presents results of rigorous microstructural characterization of as-cast hafnium-boron alloys which are significant to assess the liquid composition associated to most of the invariant reactions of this system. Alloys were prepared by arc melting high purity hafnium (minimum 99.8%) and boron (minimum 99.5%) slices under argon atmosphere in water-cooled copper crucible with non consumable tungsten electrode and titanium getter. The phases were identified by scanning electron microscopy, using back-scattered electron image mode and X-ray diffraction. In general, a good agreement was found between our data and those from the currently accepted Hafnium-Boron phase diagram. The phases identified are αHfSS and B-RhomSS, the intermediate compounds HfB and HfB2 and the liquide L. The reactions are the eutectic L ⇔ αHfSS + HfB and L ⇔ HfB2 + B-Rhom, the peritectic L + HfB2 ⇔ HfB and the congruent formation of HfB2.

Influence of the substitutional solute on the mechanical properties of Ti-Nb binary alloys for biomedical use

Titanium alloys are widely used in the manufacture of biomedical implants because they possess an excellent combination of physical properties and outstanding biocompatibility. Today, the most widely used alloy is Ti-6Al-4V, but some studies have reported adverse effects with the long-term presence of Al and V in the body, without mentioning that the elasticity modulus value of this alloy is far superior to the bone. Thus, there is a need to develop new Ti-based alloys without Al and V that have a lower modulus, greater biocompatibility, and similar mechanical strength. In this paper, we investigated the effect of Nb as a substitutional solute on the mechanical properties of Ti-Nb alloys, prepared in an arc-melting furnace and characterized by density, X-ray diffraction, optical microscopy, hardness and elasticity modulus measurements. The X-ray and microscopy measurements show a predominance of the α phase. The microhardness values showed a tendency to increase with the concentration of niobium in the alloy. Regarding the elasticity modulus, it was observed a nonlinear behavior with respect to the concentration of niobium. This behavior is associated with the presence of the α phase.

On Ti-18Si-6B and Ti-7.5Si-22.5B powder alloys prepared by high-energy ball milling and sintering

Recently, a new ternary phase was discovered in the Ti-Si-B system, located near the Ti6Si2B composition. The present study concerns the preparation of titanium alloys that contain such phase mixed with α-titanium and other intermetallic phases. High-purity powders were initially processed in a planetary ball-mill under argon atmosphere with Ti-18Si-6B and Ti-7.5Si-22.5B at. (%) initial compositions. Variation of parameters such as rotary speed, time, and ball diameters were adopted. The as-milled powders were pressureless sintered and hot pressed. Both the as-milled and sintered materials were characterized by X-ray diffraction, scanning electron microscopy and energy-dispersive spectrometry. Sintered samples have presented equilibrium structures formed mainly by the α-Ti+Ti6Si2B+Ti5Si3+TiB phases. Silicon and boron peaks disappear throughout the milling processes, as observed in the powder diffraction data. Furthermore, an iron contamination of up to 10 at. (%) is measured by X-ray spectroscopy analysis on some regions of the sintered samples. Density, hardness and tribological results for these two compositions are also presented here.

Active fibre-reinforced composites with embedded shape memory alloys

This dissertation concerns active fibre-reinforced composites with embedded shape memory alloy wires. The structural application of active materials allows to develop adaptive structures which actively respond to changes in the environment, such as morphing structures, self-healing structures and power harvesting devices. In particular, shape memory alloy actuators integrated within a composite actively control the structural shape or stiffness, thus influencing the composite static and dynamic properties. Envisaged applications include, among others, the prevention of thermal buckling of the outer skin of air vehicles, shape changes in panels for improved aerodynamic characteristics and the deployment of large space structures. The study and design of active composites is a complex and multidisciplinary topic, requiring in-depth understanding of both the coupled behaviour of active materials and the interaction between the different composite constituents. Both fibre-reinforced composites and shape memory alloys are extremely active research topics, whose modelling and experimental characterisation still present a number of open problems. Thus, while this dissertation focuses on active composites, some of the research results presented here can be usefully applied to traditional fibre-reinforced composites or other shape memory alloy applications. The dissertation is composed of four chapters. In the first chapter, active fibre-reinforced composites are introduced by giving an overview of the most common choices available for the reinforcement, matrix and production process, together with a brief introduction and classification of active materials. The second chapter presents a number of original contributions regarding the modelling of fibre-reinforced composites. Different two-dimensional laminate theories are derived from a parent three-dimensional theory, introducing a procedure for the a posteriori reconstruction of transverse stresses along the laminate thickness. Accurate through the thickness stresses are crucial for the composite modelling as they are responsible for some common failure mechanisms. A new finite element based on the First-order Shear Deformation Theory and a hybrid stress approach is proposed for the numerical solution of the two-dimensional laminate problem. The element is simple and computationally efficient. The transverse stresses through the laminate thickness are reconstructed starting from a general finite element solution. A two stages procedure is devised, based on Recovery by Compatibility in Patches and three-dimensional equilibrium. Finally, the determination of the elastic parameters of laminated structures via numerical-experimental Bayesian techniques is investigated. Two different estimators are analysed and compared, leading to the definition of an alternative procedure to improve convergence of the estimation process. The third chapter focuses on shape memory alloys, describing their properties and applications. A number of constitutive models proposed in the literature, both one-dimensional and three-dimensional, are critically discussed and compared, underlining their potential and limitations, which are mainly related to the definition of the phase diagram and the choice of internal variables. Some new experimental results on shape memory alloy material characterisation are also presented. These experimental observations display some features of the shape memory alloy behaviour which are generally not included in the current models, thus some ideas are proposed for the development of a new constitutive model. The fourth chapter, finally, focuses on active composite plates with embedded shape memory alloy wires. A number of di®erent approaches can be used to predict the behaviour of such structures, each model presenting different advantages and drawbacks related to complexity and versatility. A simple model able to describe both shape and stiffness control configurations within the same context is proposed and implemented. The model is then validated considering the shape control configuration, which is the most sensitive to model parameters. The experimental work is divided in two parts. In the first part, an active composite is built by gluing prestrained shape memory alloy wires on a carbon fibre laminate strip. This structure is relatively simple to build, however it is useful in order to experimentally demonstrate the feasibility of the concept proposed in the first part of the chapter. In the second part, the making of a fibre-reinforced composite with embedded shape memory alloy wires is investigated, considering different possible choices of materials and manufacturing processes. Although a number of technological issues still need to be faced, the experimental results allow to demonstrate the mechanism of shape control via embedded shape memory alloy wires, while showing a good agreement with the proposed model predictions.