Electrochemical stability and corrosion resistance of Ti-Mo alloys for biomedical applications

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Stability of vacancy clusters in FeCr alloys: A study of the Cr concentration dependence

Fe–Cr based alloys are the leading structural material candidates in the design of next generation reactors due to their high resistance to swelling and corrosion. Despite these good properties there are others, such as embrittlement, which require a higher level of understanding in order to improve aspects such as safety or lifetime of the reactors. The addition of Cr improves the behavior of the steels under irradiation, but not in a monotonic way. Therefore, understanding the changes in the Fe–Cr based alloys microstructure induced by irradiation and the role played by the alloying element (Cr) is needed in order to predict the response of these materials under the extreme conditions they are going to support. In this work we perform a study of the effect of Cr concentration in a bcc Fe–Cr matrix on formation and binding energies of vacancy clusters up to 5 units. The dependence of the calculated formation and binding energy is investigated with two empirical interatomic potentials specially developed to study radiation damage in Fe–Cr alloys. Results are very similar for both potentials showing an increase of the defect stability with the cluster size and no real dependence on Cr concentration for the binding energy.

The structural stability of welds in columbium alloys. Technical documentary report no. ML-TDR-64-210.

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First-principles investigation of the alloy scattering potential in dilute Si1-xCx

A first-principles method is applied to find the intra and intervalley n-type carrier scattering rates for substitutional carbon in silicon. The method builds on a previously developed first-principles approach with the introduction of an interpolation technique to determine the intravalley scattering rates. Intravalley scattering is found to be the dominant alloy scattering process in Si1-xCx, followed by g-type intervalley scattering. Mobility calculations show that alloy scattering due to substitutional C alone cannot account for the experimentally observed degradation of the mobility. We show that the incorporation of additional charged impurity scattering due to electrically active interstitial C complexes models this residual resistivity well.

First-principles calculation of carrier-phonon scattering in n-type Si1−xGex alloys

First-principles electronic structure methods are used to find the rates of inelastic intravalley and intervalley n-type carrier scattering in Si1-xGex alloys. Scattering parameters for all relevant Delta and L intra- and intervalley scattering are calculated. The short-wavelength acoustic and the optical phonon modes in the alloy are computed using the random mass approximation, with interatomic forces calculated in the virtual crystal approximation using density functional perturbation theory. Optical phonon and intervalley scattering matrix elements are calculated from these modes of the disordered alloy. It is found that alloy disorder has only a small effect on the overall inelastic intervalley scattering rate at room temperature. Intravalley acoustic scattering rates are calculated within the deformation potential approximation. The acoustic deformation potentials are found directly and the range of validity of the deformation potential approximation verified in long-wavelength frozen phonon calculations. Details of the calculation of elastic alloy scattering rates presented in an earlier paper are also given. Elastic alloy disorder scattering is found to dominate over inelastic scattering, except for almost pure silicon (x approximate to 0) or almost pure germanium (x approximate to 1), where acoustic phonon scattering is predominant. The n-type carrier mobility, calculated from the total (elastic plus inelastic) scattering rate, using the Boltzmann transport equation in the relaxation time approximation, is in excellent agreement with experiments on bulk, unstrained alloys..

Determination of the thermodynamic stability of TiB2

The standard free energy of formation of titanium boride (TiB2) Was measured by the Electro Motive Force (EMF) method (by using yttria doped thoria (YDT) as the solid electrolyte). Two galvanic cells viz. Cell (I): Pt, TiB2 (s), TiO2 (s), B (s) vertical bar YDT vertical bar NiO (s), Ni (s), Pt and cell (II): Pt, TiB2 (s), TiO2 (s), B (s) vertical bar YDT vertical bar FeO (s). Fe (s), Pt were constructed in order to determine the Delta(f)G degrees, of TiB2. Enthalpy increments on TiB2 were measured by using inverse drop calorimetry over the temperature range 583-1769 K. The heat capacity, entropy and the free energy function have been derived from these experimental data in the temperature range 298-1800 K. The mean value of the standard enthalpy of formation of TiB2 (Delta H-f(298)degrees (TiB2)) was obtained by combining these Delta(f)G degrees, values and the free energy functions of TiB2 derived from the drop calorimetry data. The mean values of Delta H-f(298)degrees (TiB2) derived from the Delta(f)G degrees, data obtained from cell I and II were -322 +/- 1.2 kJ mol(-1) and -323.3 +/- 2.1 kJ mol(-1), respectively. These values were found to be in very good agreement with the assessed data. (C) 2009 Elsevier B.V. All rights reserved.

Role of zirconium addition on stability of UAl3 phase in Al-U system

The microstructural changes of Al-22 wt%U and Al-46 wt%U alloys containing 3 wt% Zr were investigated after heat treatment at 620 degrees C for 1 to 45 days, Though it is reported that addition of similar to 3 wt% Zr stabilizes the (U,Zr)Al-3 phase at room temperature, the present investigation shows that the (U,Zr)Al-3 phase is not stable but slowly transforms to the U0.9Al4 phase, The high temperature creep curves generated for these ternary alloys showed a wavy pattern which also suggests that the (U,Zr)Al-3 phase is not stable.

Phase formation and stability of alloy phases in free nanoparticles: some insights

This paper explores phase formation and phase stability in free nanoparticles of binary alloys. A procedure for estimating the size and composition dependent free energies incorporating the contributions from the interfaces has been presented. Both single phase solid solution and two phase morphology containing interphase interfaces have been considered. A free energy scenario has been evaluated for two binary alloy systems Ag-Ni and Ag-Cu to predict the microstructure of the alloy nanoparticles at different size ranges as a function of composition. Both Ag-Cu and Ag-Ni systems exhibit wide bulk immiscibility. Ag-Ni nanoparticles were synthesized using the wet chemical synthesis technique whereas Ag-Cu nanoparticles were synthesized using laser ablation of a Ag-Cu target immersed in distilled water. Microstructural and compositional characterization of Ag-Ni and Ag-Cu nanoparticles on a single nanoparticle level was conducted using transmission electron microscopy. Nanoparticle microstructures observed from the microscopic investigation have been correlated with thermodynamic calculation results. It is shown that the observed two phase microstructure consisting of Ag-Ni solid solution in partial decomposed state coexisting with pure Ag phases in the case of Ag-Ni nanoparticles can be only be rationalized by invoking the tendency for phase separation of an initial solid solution with increase in nanoparticle size. Smaller sized Ag-Ni nanoparticles prefer a single phase solid solution microstructure. Due to an increase in particle size during the synthesis process the initial solid solution decomposes into an ultrafine scale phase separated microstructure. We have shown that it is necessary to invoke critical point phenomenon and wetting transition in systems showing a critical point that leads to phase separated Ag-Ni nanoparticles providing a catalytic substrate for the nucleation of equilibrium Ag over it. In the case of the Ag-Cu system, we report the experimental observation of a core shell structure at small sizes. This can be rationalized in terms of a metastable solid solution. It is argued that the nucleation barrier can prevent the formation of biphasic morphology with an internal interface. In such a situation, demixing of the solid solution can bring the system to a lower energy configuration. This has lead to the observed core-shell morphology in the Ag-Cu system during room temperature synthesis.

Low-temperature growth properties of Si1-xGex by disilane and solid-Ge molecular beam epitaxy

Low temperature (similar to 500 degrees C) growth properties of Si1-xGex by disilane and solid-Ge molecular beam epitaxy have been studied with an emphasis on surface morphology and growth kinetics. It is found that low-temperature growth(<500 degrees C) is in layer-by-layer mode and atomically-smooth surfaces have been obtained in as-grown samples with large Ge composition (>0.5). Ge composition dependence on substrate temperature, Ge cell temperature and disilane flow rate have been investigated. It is found that in low-temperature growth (less than or equal to 500 degrees C) and under large disilane flux, Ge composition increases with the increase of Ge flux and further increase of Ge flux leads to the saturation of Ge composition. Similar compositional dependence has been found at different growth temperatures. The saturated composition increases with the decrease of substrate temperature. The results can be explained if H desorption is assumed to occur from both Si and Ge monohydrides without diffusional exchange and the presence of Ge enhances H desorption on a Si site. (C) 1998 Elsevier Science B.V. All rights reserved.

CHARGE COMPENSATION AND VALENCY STABILITY OF EU(II)-DOPED KMGF3 CRYSTAL

The spectrochemistry of Eu2+-doped perovskite KMgF3 was examined and discussed. Eu2+ can replace some of the K+ in the KMgF3 crystal, and simultaneously the corresponding cation hole can be compensated with the F- or O2- in the matrix. The emission intensity of Eu2+ due to the f --> f transition increased when Na+, Rb+ or F- was doped in KMgF3:Eu2+. Two mechanisms of charge compensation were proposed. No obvious valence change of Eu2+ occurred in KMgF3:Eu2+ after calcinating at high temperature, e.g. 900-degrees-C. It was found that the valence stability of Eu2+ improved after incorporation into the matrix.

Remarkable stability of ionic gold supported on sulfated lanthanum oxide

Isolated cationic gold deposited on sulfated lanthanum oxide has been shown to exhibit remarkable stability opening a promising way of stabilising ionic gold for catalytic reactions.

Structural stability of the synthetic thermoelectric ternary and nickel-substituted tetrahedrite phases

The purity and structural stability of the high thermoelectric performance Cu12Sb4S13 and Cu10.4Ni1.6Sb4S13 tetrahedrite phases, synthesized by solid–liquid–vapor reaction and Spark Plasma Sintering, were studied at high temperature by Rietveld refinement using high resolution X-ray powder diffraction data, DSC/TG measurements and high resolution transmission electron microscopy. In a complementary study, the crystal structure of Cu10.5Ni1.5Sb4S13 as a function of temperature was investigated by powder neutron diffraction. The temperature dependence of the structural stability of ternary Cu12Sb4S13 is markedly different to that of the nickel-substituted phases, providing clear evidence for the significant and beneficial role of nickel substitution on both sample purity and stability of the tetrahedrite phase. Moreover, kinetic effects on the phase stability/decomposition have been identified and discussed in order to determine the maximum operating temperature for thermoelectric applications. The thermoelectric properties of these compounds have been determined for high density samples (>98%) prepared by Spark Plasma Sintering and therefore can be used as reference values for tetrahedrite samples. The maximum ZT of 0.8 was found for Cu10.4Ni1.6Sb4S13 at 700 K.

Thermal stability of the Al70Ni10Ti10Zr5Ta5 amorphous alloy powder fabricated by mechanical alloying

An Al₇₀Ni₁₀Ti₁₀Zr₅Ta₅ amorphous alloy powder was fabricated by mechanical alloying. The phase structure and characteristic temperatures of the alloy were determined by X-ray diffraction, transmission electron microscopy and differential scanning calorimetry. The glass transition behavior and crystallization kinetics were analyzed using Lasocka and Kissinger functions. The results show that the alloy has a higher crystallization temperature, a higher effective activation energy of crystallization and a wider supercooled liquid region than the previously reported values, suggesting a high thermal stability and promising applications.

Thermal stability of the martensitic transformation of Cu-Al-Ni-Mn-Ti

The development of new shape memory alloys with high martensitic transformation temperature increases the potential for applications. The development and use of these new alloys depends on the stability of the structure during cycling at high temperatures. If it is possible to guarantee that on alloys keeps the structure during cycling, then the alloy can be used because of the shape memory properties. The aim of this work is to obtain a kinetic model of the forward and backward martensitic transformation of two Cu-Al-Ni-Mn-Ti alloys. Differential scanning calorimetry has been performed in order to establish the kinetic stability of the martensite and the beta transformation. (c) 2006 Elsevier B.V. All rights reserved.

Electrochemical behavior of Ti-Mo alloys applied as biomaterial

Electrochemical investigation on the as-cast Ti-Mo alloys (4-20 Mo wt.%) applied as biomaterials in Na2SO4 and Ringer physiological solutions is reported. Analyses of the open-circuit potential indicated that all alloys present spontaneous passivation. SEM and cyclic voltammograms obtained in the Ringer solution showed that the samples studied do not present pitting corrosion at potentials up to 8 V (SCE), indicating high corrosion resistance. Open-circuit potential profiles of the anodic oxides growth in both solutions show that the presence of chloride ions during the anodization does not influence the oxides' chemical stability, and also clearly indicate that adding Mo to pure Ti improves the stability of the anodic oxides. All these results suggest Ti-Mo alloys promissory to be applied as biomaterials. (c) 2008 Elsevier Ltd. All rights reserved.