Oxygen diffusion in superconducting oxides

Since the discovery of high-temperature superconductivity of cuprate oxides, it has been clear that it is strongly affected by the oxygen content, which is also a crucial factor to determine other physical properties of high T-c superconductors. Non-stoichiometric (interstitial) oxygen strongly influences the physical properties of various superconducting oxides, in particular by creating conducting holes. It is now ascertained that the amount of holes injected depends not only on the content of interstitial oxygen, but also on its ordering. Rearrangement of the oxygen ordering may occur even below room temperature due to the unusual high mobility of these atoms. This way, mechanical spectroscopy is one of the most adequate techniques for the study of the mobility (diffusion) of oxygen atoms. This technique allows the determination of the jump frequency of an atomic species precisely, regardless of the model or the different possible types of jumps. In order to evaluate the mobility and the effect of oxygen content on these oxides, ceramic samples we prepared and submitted to several oxygen removal cycles alternately with mechanical relaxation measurements. As for SBCO, it was assumed that the peak was due to O(1)-O(5) jumps of oxygen atoms at the chain terminals or in chain fragments in the orthorhombic phase. In the case of BSCCO, the results showed complex anelastic relaxation structures, which were attributed to interstitial oxygen atom jumps between two adjacent CuO planes.

Nitrogen diffusion in the Nb-1.0wt%Zr measured by mechanical spectroscopy

The scientific and technological development in the area of new materials contributed to several applications of niobium and its alloys in nuclear power plants as well as in aerospace, aeronautics, automobile and naval industries. This paper presents the interstitial diffusion coefficients of nitrogen in solid solution in the Nb-1.0wt%Zr alloy using internal friction measurements obtained by mechanical spectroscopy, which uses a torsion pendulum operating at an oscillation frequency between 1.0 Hz and 10.0 Hz. The temperature range varies from 300K to 700K, at a heating rate of 1 K/min and vacuum better than 2 x 10(-6) Torr. The results showed an increase of the interstitial diffusion coefficient of nitrogen that was correlated with configurational considerations for the octahedral interstitials.

Oxygen Diffusion in an Nb-Ta Alloy Measured by Mechanical Spectroscopy

When metals that present bcc crystalline structure receive the addition of interstitial atoms as oxygen, nitrogen, hydrogen and carbon, they undergo significant changes in their physical properties because they are able to dissolve great amounts of those interstitial elements, and thus form solid solutions. Niobium and most of its alloys possess a bcc crystalline structure and, because Brazil is the largest world exporter of this metal, it is fundamental to understand the interaction mechanisms between interstitial elements and niobium or its alloys. In this study, mechanical spectroscopy (internal friction) measurements were performed on Nb-8.9wt%Ta alloys containing oxygen in solid solution. The experimental results presented complex internal friction spectra. With the addition of substitutional solute, interactions between the two types of solutes (substitutional and interstitial) were observed, considering that the random distribution of the interstitial atoms was affected by the presence of substitutional atoms. Interstitial diffusion coefficients, pre-exponential factors and activation energies were calculated for oxygen in this alloy.

Oxygen Diffusion in Ti-20Mo Alloys, used as Biomaterial, Measured by Mechanical Spectroscopy

Titanium alloys are favorable implant materials for orthopedic applications, due to their desirable properties such as good corrosion resistance, low elasticity modulus, and excellent biocornpatibility. The research on titanium alloys is concentrated in the beta type, as the Ti-20Mo alloys and the addition of interstitial elements in these metals cause changes in their mechanical properties. The mechanical spectroscopy measurements have been frequently used in order to verify the behavior of these interstitials atoms in metallic alloys. This paper presents the study of oxygen diffusion in Ti-20Mo alloys using mechanical spectroscopy measurements. A thermally activated relaxation structure was observed in the sample after oxygen doping. It was associated with the interstitial diffusion of oxygen atoms in a solid solution in the alloy. The diffusion coefficient for the oxygen diffusion in the alloy was obtained by the frequency dependence of the peak temperature and by using a simple mathematical treatment of the relaxation structure and the Arrhenius law.

Nitrogen diffusion in the Nb-2.0wt%Ti measured by mechanical spectroscopy

Metals that present bcc crystalline structure, when receiving addition of interstitial atoms as oxygen, nitrogen, hydrogen and carbon, undergo significant changes in their physical properties, being able to dissolve great amounts of those interstitial elements, thus forming solid solutions. Niobium and most of its alloys possess bcc crystalline structure and, as Brazil is the largest world exporter of this metal, it is fundamental to understand the interaction mechanisms between interstitial elements and niobium or its alloys. In this paper, mechanical spectroscopy (internal friction) measurements were performed in Nb-2.0wt%Ti alloys containing nitrogen in solid solution. The experimental results presented complex internal friction spectra and with the addition of substitutional solute, it was observed interactions between the two types of solutes (substitutional and interstitial), considering that the random distribution of the interstitial atoms was affected by the presence of substitutional atoms. Interstitial diffusion coefficients, pre-exponential factors and activation energies were calculated for nitrogen in the Nb-2.0wt%Ti alloys.

Measurement of oxygen atom diffusion in Nb and Ta by anelastic spectroscopy

Impurity interstitial atoms present in metals with BCC structure can diffuse in the metallic matrix by jumps to energetically equivalent crystallographic sites. Anelastic spectroscopy (internal friction) is based on the measurement of mechanical loss or internal friction as a function of temperature. Due to its selective and nondestructive nature, anelastic spectroscopy is well suited for the study of diffusion of interstitial elements in metals. Internal friction measurements were made using the torsion pendulum technique with oscillation frequency of a few Hz, temperature interval from 300 to 700 K, heating rate of about 1 K/min, and vacuum better than 10-5 mbar. The polycrystalline Nb and Ta samples used were supplied by Aldrich Inc. The results obtained showed thermally activated relaxation structures due to stress-induced ordering of oxygen atoms around the Nb (or Ta) atoms of the metallic matrix. The results were interpreted by three methods and led to activation enthalpy values for the diffusion of oxygen in Nb and Ta of 1.15 eV and 1.10 eV, respectively.

Oxygen diffusion in Ti-10Mo alloys measured by mechanical spectroscopy

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

Blocking Radial Diffusion in a Double-Waved Hamiltonian Model

A non-twist Hamiltonian system perturbed by two waves with particular wave numbers can present Robust Tori, barriers created by the vanishing of the perturbing Hamiltonian at some defined positions. When Robust Tori exist, any trajectory in phase space passing close to them is blocked by emergent invariant curves that prevent the chaotic transport. We analyze the breaking up of the RT as well the transport dependence on the wave numbers and on the wave amplitudes. Moreover, we report the chaotic web formation in the phase space and how this pattern influences the transport.

Vehicle influence on calcium hydroxide pastes diffusion in human and bovine teeth

The purpose of this study was to compare the pH and calcium ion liberation after use of calcium hydroxide pastes with different paste vehicles in human or bovine teeth. Ninety-two single-rooted human and bovine roots were used. The roots were instrumented and an external cavity preparation was performed. The roots were divided in to human and bovine groups. Each group was subdivided into four subgroups (SB) according to the vehicle:SB1, detergent; SB2, saline; SB3, polyethylenoglycol + camphorated paramonochlorophenol (Calen PMCC) and SB4, polyethylenoglycol + furacyn paramonochlorophenol (FPMC). Specimens were immersed into saline solution at 37 degrees C and after 7 and 14 days pH and calcium ion measurements were made. The results were analyzed by ANOVA and Tukey tests (P < 0.05). There was no statistical difference between bovine and human teeth in the pH analysis (P < 0.05), but bovine teeth provided larger calcium ion liberation than human teeth. Calen PMCC was statistically more effective for pH increase and calcium ion liberation in all analyses, followed by FPMC and saline. Detergent showed the lowest pH alterations and calcium ion liberation. The period of 14 days showed more calcium ionic liberation than the 7-day period.

Anelastic relaxation due to interstitial solutes diffusion in Nb and Nb-1 wt% Zr

Metals and alloys containing solute atoms dissolved interstitially often show anelastic behavior due to a process know as stress-induced ordering. The application of mechanical spectroscopy measurements to diffusion studies in body-centered cubic metals has been extensively used in the last decades. However the kind of preferential occupation of interstitial solutes in body-centered cubic metals is still controversial. The anelastic properties of the Nb and Nb-1 wt% Zr polycrystalline alloys were determined by internal friction and oscillation frequency measurements using a torsion pendulum inverted performed between 300K and 650K, operating in a frequency oscillation in the hertz bandwidth. The interstitial diffusion coefficients of oxygen and nitrogen in Nb and Nb-1 wt% Zr samples were determined at two distinct conditions: (a) for low concentration of oxygen and (b) for high concentration of oxygen.

Electrical Properties at Grain Boundaries Influenced by Cr3+ Diffusion in SnO2.ZnO.Nb2O5-Films Varistor Prepared by Electrophoresis Deposition

SnO2-based varistors are strong candidates to replace the ZnO-based varistors due to ordering fewer additives to improve its electrical behavior as well as by showing similar nonlinear characteristics of ZnO varistors. In this work, SnO2-nanoparticles based-varistors with addition of 1.0 %mol of ZnO and 0.05 %mol of Nb2O5 were synthesized by chemical route. SnO2.ZnO.Nb2O5-films with 5 μm of thickness were obtained by electrophoretic deposition (EPD) of the nanoparticles on Si/Pt substrate from alcoholic suspension of SnO2-based powder. The sintering step was carried out in a microwave oven at 1000 °C for 40 minutes. Then, Cr3+ ions were deposited on the films surface by EPD after the sintering step. Each sample was submitted to different thermal treatments to improve the varistor behavior by diffusion of ions in the samples. The films showed a nonlinear coefficient (α) greater than 9, breakdown voltage (VR) around 60 V, low leakage current (IF ≈ 10-6 A), height potential barrier above 0.5 eV and grain boundary resistivity upward of 107 Ω.cm.

Nitrogen diffusion in niobium under low pressure

The interaction among heavy interstitial atoms present in metals with bcc structure is studied using anelastic spectroscopy. This technique makes it possible to obtain information on interstitial concentration, precipitation, solubility limit, and diffusion. The diffusion coefficients of nitrogen in niobium were obtained using the relaxation parameters obtained from anelastic spectroscopy measurements for different oscillation frequencies of the system. The results showed the interstitial diffusion of nitrogen present in solid solution in niobium when submitted to different charges of nitrogen at a temperature of 1373 K and a partial pressure in the order of 10-4 Torr. The exponential variation of the pressure experimentally in function of the time was thus obtained.

Thermophysical Properties of Brazilian Orange Juice as Affected by Temperature and Water Content

The specific heat, thermal conductivity, thermal diffusivity and density of Brazilian orange juice were determined between 0.34 and 0.73 (w/w) water content and with temperatures from 0.5 to 62°C. The experimental data were fitted as functions of temperature and water content and all properties showed a linear dependency with these variables. In the tested range, the water content exhibited a greater influence on the analyzed properties than temperature. © 1998 Elsevier Science Limited. All rights reserved.

Growth of calcium phosphate coating on Ti-7.5Mo alloy after anodic oxidation

Titanium and its alloys are widely used as biomaterials due to their mechanical, chemical and biological properties. To enhance the biocompatibility of titanium alloys, various surface treatments have been proposed. In particular, the formation of titanium oxide nanotubes layers has been extensively examined. Among the various materials for implants, calcium phosphates and hydroxyapatite are widely used clinically. In this work, titanium nanotubes were fabricated on the surface of Ti-7.5Mo alloy by anodization. The samples were anodized for 20 V in an electrolyte containing glycerol in combination with ammonium fluoride (NH4F, 0.25%), and the anodization time was 24 h. After being anodized, specimens were heat treated at 450 °C and 600°C for 1 h to crystallize the amorphous TiO2 nanotubes and then treated with NaOH solution to make them bioactive, to induce growth of calcium phosphate in a simulated body fluid. Surface morphology and coating chemistry were obtained respectively using, field-emission scanning electron microscopy (FEG-SEM), AFM and X-ray diffraction (XRD). It was shown that the presence of titanium nanotubes induces the growth of a sodium titanate nanolayer. During the subsequent invitro immersion in a simulated body fluid, the sodium titanate nanolayer induced the nucleation and growth of nano-dimensioned calcium phosphate. It was possible to observe the formation of TiO2 nanotubes on the surface of Ti-7.5Mo. Calcium phosphate coating was greater in the samples with larger nanotube diameter. These findings represent a simple surface treatment for Ti-7.5Mo alloy that has high potential for biomedical applications. © (2013) Trans Tech Publications, Switzerland.

Diffusion of Interstitial Elements in Ti Alloys used as Biomaterials

Titanium alloys are excellent implant materials for orthopedic applications due to their desirable properties, such as good corrosion resistance, low elasticity modulus, and excellent biocompatibility. The presence of interstitial elements (such as oxygen and nitrogen) causes strong changes in the material's mechanical properties, mainly in its elastic properties. Study of the interaction among interstitial elements present in metals began with Snoek's postulate, that a stress-induced ordering of interstitials gives rise to a peak in the mechanical relaxation (internal friction) spectra. In the mechanical relaxation spectra, each species of interstitial solute atom gives rise to a distinct Snoek's peak, whose temperature and position depend on the measurement frequency. This effect is very interesting because its peculiar parameters are directly related to the diffusion coefficient (D) for the interstitial solute. This paper presents a study of diffusion of heavy interstitial elements in Ti-35Nb-7Zr-5Ta alloys using mechanical spectroscopy. Pre-exponential factors and activation energies are calculated for oxygen and nitrogen in theses alloys.