Physical characterization of a new composition of oxidized zirconium-2.5 wt% niobium produced using a two step process for biomedical applications

Zirconium and particularly Zr-2.5 wt%Nb (Zr2.5Nb) alloy are useful for engineering bearing applications because they can be oxidized in air to form a hard surface ceramic. Oxidized zirconium (OxZr) due to its abrasion resistant ceramic surface and biocompatible substrate alloy has been used as a bearing surface in total joint arthroplasty for several years. OxZr is characterized by hard zirconium oxide (oxide) formed on Zr2.5Nb using one step thermal oxidation carried out in air. Because the oxide is only at the surface, the bulk material behaves like a metal, with high toughness. The oxide, furthermore, exhibits high adhesion to the substrate because of an oxygen-rich diffusion hardened zone (DHZ) interposing between the oxide and the substrate.In this study, we demonstrate a two step process that forms a thicker DHZ and thus increased depth of hardening than that can be obtained using a one step oxidation process. The first step is thermal oxidation in air and the second step is a heat treatment in vacuum. The second step drives oxygen from the oxide formed in the first step deeper into the substrate to form a thicker DHZ. During the process only a portion of the oxide is dissolved. This new composition (DHOxZr) has approximately 4-6 μm oxide similar to that of OxZr. The nano-hardness of the oxide is similar but the DHZ is approximately 10 times thicker. The stoichiometry of the oxide is similar and a secondary phase rich in oxygen is present through the entire thickness. Due to the increased depth of hardening, the critical load required for the onset of oxide cracking is approximately 1.6 times more than that of the oxide of OxZr. This new composition has a potential to be used as a bearing surface in applications where greater depth of hardening is required.     

Density and current response functions in strongly disordered electron systems: diffusion,electrical conductivity and Einstein relation

We study noninteracting quantum charged particles (electron gas) subject to a strong random potential and perturbed by a weak classical electromagnetic field. We examine consequences of gauge invariance and charge conservation in the space of Bloch waves. We use two specific forms of the Ward identity between the one- and two-particle averaged Green functions to establish exact relations between the density and current response functions. In particular, we find precise conditions under which we can extract the current-current from the density-density correlation functions and vice versa. We use these results to prove a formula relating the density response and the electrical conductivity in strongly disordered systems. We introduce quantum diffusion as a response function that reduces to the diffusion constant in the static limit. We then derive Ficks law, a quantum version of the Einstein relation and prove the existence of the diffusion pole in the quasistatic limit of the zero-temperature electron-hole correlation function. We show that the electrical conductivity controls the long-range spatial fluctuations of the electron-hole correlation function only in the static limit.Received: 10 June 2003, Published online: 22 September 2003PACS: 72.10.Bg General formulation of transport theory - 72.15.Eb Electrical and thermal conduction in crystalline metals and alloys - 72.15.Qm Scattering mechanisms and Kondo effect     

Rapid solidification processing in molten salts chemistry: X-ray analysis of deeply undercooled cryolite-alumina melts

Rapid solidification processing (cooling rate from the interval 10⁵–10⁶ K s⁻¹) was used to prepare deeply undercooled cryolite-alumina melts. Such prepared samples were analyzed by the XRD method. Besides cryolite, XRD patterns belonging to ι-Al₂O₃ were recorded. The influence of annealing on the XRD patterns of deeply undercooled melts was also investigated.     

Nanotubes Made from Deeply Undercooled Cryolite/Alumina Melts

The rapid‐solidification processing (by a cooling rate of 10⁵–10⁶ K/s) was used for the preparation of deeply undercooled cryolite/alumina (Na₃AlF₆/Al₂O₃) melts. We found a mass of nanotubes on the surface of these undercooled melts. The nanotubes were preferentially located on the defect places of the surface with the following approximate dimensions: base≈100×100 nm, length≈1000 nm. The solidified samples with the nanotubes on the surface were analyzed by scanning electron microscopy (SEM), energy‐dispersive X‐ray spectroscopy (EDX), X‐ray diffraction (XRD), and infrared spectroscopy (IR).     

Nature of bonding in group 13 dimetallenes: a delicate balance between singlet diradical character and closed shell interactions

The nature of metal-metal bonding in group 13 dimetallenes REER (E = Al, Ga, In, Tl; R = H, Me, (t)Bu, Ph) was investigated by use of quantum chemical methods that include HF, second order M?ller-Plesset perturbation theory (MP2), coupled cluster (CCSD(T)), complete active space with (CASPT2) and without (CAS) second order perturbation theory, and two density functionals, namely, B3LYP and M06-2X. The results show that the metal-metal interaction in group 13 dimetallenes stems almost exclusively from static and dynamic electron correlation effects: both dialuminenes and digallenes have an important singlet diradical component in their wave function, whereas the bonding in the heavier diindenes and, in particular, dithallenes is dominated by closed shell metallophilic interactions. The reported calculations represent a systematic attempt to determine the metal and ligand dependent bonding changes in these systems.     

Novel Mn(III) heterochelates: synthesis,thermal, spectroscopic,and coordination aspects

This article describes the synthesis, structural features, and thermal studies of novel Mn(III) heterochelates of the type [Mn(SB _n )(L)(H₂O)]·xH₂O [H₂SB _n  = Nicotinic acid [1-(3-methyl-5-oxo-1-phenyl-4,5 dihydro-1H-pyrazol-4yl)-acylidene]-hydrazide where acyl = acetyl (H₂SB₁); benzoyl (H₂SB₂); propionyl (H₂SB₃); buteryl (H₂SB₄); phenyl acetyl (H₂SB₅); and HL = 5-Chloro-7-iodo-8-hydroxyquinoline (clioquinol)]. The heterochelates have been characterized on the basis of elemental analyses, magnetic susceptibility measurements, cyclic voltammetric studies, (FTIR and electronic) spectra, and thermal studies. The FAB mass spectrum of [Mn(SB₁)(L)H₂O]·3H₂O has been carried out. The cyclic voltammetric studies reveal that quasi-reversible reduction process of Mn(III)/Mn(II) coupled system suggesting that the ligands readily destabilize higher oxidation states of metal ion. Kinetic parameters such as order of reaction (n) and the energy of activation (Ea) were calculated using Freeman–Carroll method. The pre-exponential factor (A), the activation entropy (S*), the activation enthalpy (H*), and the free energy of activation (G*) were calculated using Horowitz–Metzger equations.     

Elastic properties of GaxIn1−xP semiconductor

A theoretical procedure is presented for the study of elastic properties of the ternary alloy Ga_xIn_1−xP. The calculations are based on the pseudopotential formalism in which local potential coupled with the virtual crystal approximation (VCA) is applied to evaluate elastic constants c₁₁, c₁₂ and c₄₄, bulk modulus, shear modulus, Young's modulus and Poisson's ratio for the entire range of the alloy composition x of the ternary alloy Ga_xIn_1−xP. The effect of compositional disorder is included. Our results for parent compounds are compared to experimental and other theoretical calculations and showed generally good agreement. The inclusion of compositional disorder increases values of all elastic constants. During the present study it is found that elastic constant c₁₁ is largely influenced by compositional disorder.     

Arbitrage without borrowing or short selling?

We show that a trader, who starts with no initial wealth and is not allowed to borrow money or short sell assets, is theoretically able to attain positive wealth by continuous trading, provided that she has perfect foresight of future asset prices, given by a continuous semimartingale. Such an arbitrage strategy can be constructed as a process of finite variation that satisfies a seemingly innocuous self-financing condition, formulated using a pathwise Riemann–Stieltjes integral. Our result exemplifies the potential intricacies of formulating economically meaningful self-financing conditions in continuous time, when one leaves the conventional arbitrage-free framework.