Paulo Sergio Carvalho Pereira da Silva

Influence of phase transformations on dynamical elastic modulus and anelasticity of beta Ti-Nb-Fe alloys for biomedical applications

Recent studies in materials for biomedical applications have focused on β-titanium alloys that are highly biocompatible, free of toxic elements and with an elastic modulus close to that of human bone (10-40 GPa). Beta Ti-xNb-3Fe (x=10, 15, 20 and 25 wt%) alloys were obtained by rapid solidification and characterized by anelastic relaxation measurements at temperatures between 140 K and 770 K, using a free-decay elastometer, as well as analysis by Differential Scanning Calorimetry (DSC), X-ray Diffraction (XRD) and Scanning Electron Microscopy (SEM) and Transmission Electron Microscopy (TEM). The observed stabilization of the β-phase with rising Nb content was linked to the strength of the relaxation peak around 570 K. The phase transformations detected in the anelastic relaxation spectra agreed with those observed in the DSC curves. However, the results from anelastic relaxation spectra provide more detailed information about the kinetics of phase transformations. At temperatures between 140 K and 300 K, there was an indication of a reversible transformation in the alloys studied. The elastic modulus measurements showed a hardening of the material, between 400 K and 620 K, related to the ω-phase precipitation. However, the starting temperature of ω-phase precipitation was clearly influenced by the Nb content, showing a shift to high temperature with increasing percentage of Nb. At temperatures above 620 K, a fall was observed in the dynamical elastic modulus, accompanied by a relaxation peak centered at 660 K, which was attributed to the growing α-phase arising from the ω-phase, which acts as a nucleation sites or from the decomposition of the metastable β-phase. XRD patterns confirmed the formation of β, α and ω phases after mechanical relaxation measurements. A predominant β phase with dendritic morphology was observed, which became more stable with 25 wt% Nb. The lowest elastic modulus was of 65 GPa obtained in the Ti-25Nb-3Fe alloy, representing a good low value for a β-Ti alloy with a relatively low addition of β stabilizing elements (Nb and Fe).

Effect of an amorphous titania nanotubes coating on the fatigue and corrosion behaviors of the biomedical Ti-6Al-4V and Ti-6Al-7Nb alloys

An array of self-organized TiO2 nanotubes with an amorphous structure was produced on the biomedical Ti-6Al-4V and Ti-6Al-7Nb alloys, and the resulting fatigue and corrosion behaviors were studied. The electrochemical response of the nanotubular oxide surfaces was investigated in Ringer physiological solution through potentiodynamic polarization and electrochemical impedance spectroscopy measurements. The absence of transpassivation in the chloride-containing solution, in addition to the micron-scale values of the passivation current density, indicated the excellent corrosion behavior of the coating and the satisfactory protection against the creation of potential stress concentrators in the surface. Axial fatigue tests were performed in physiological solution on polished and coated conditions, with characterization of the treated surfaces by scanning electron microscopy before and after the tests. The surface modification was not deleterious to the fatigue response of both alloys mainly due to the nano-scale dimension of the nanotubes layer. An estimation based on fracture mechanics revealed that a circumferential crack in the range of 5μm depth would be necessary to affect the fatigue performance, which is far from the thickness of the studied coating, although no cracks were actually observed in the oxide surfaces after the tests.

Fatigue behavior of Ti-6Al-4V alloy in saline solution with the surface modified at a micro- and nanoscale by chemical treatment.

This work evaluated the influence of the surface modification using acid etching combined with alkaline treatment on the fatigue strength of Ti-6Al-4V ELI alloy. The topography developed by chemical surface treatments (CST) was examined by scanning electron microscopy (SEM) and confocal laser scanning microscopy (CLSM). Increased roughness and effective surface area were investigated and compared with the Ti-6Al-4V samples without modification. Surface composition was analyzed by energy dispersive X-ray spectroscopy (EDS). Axial fatigue resistance of polished and modified surfaces was determined by stepwise load increase tests and staircase test method. Light microscopy and SEM were employed to examine the fracture surface of the tested specimens. According to the results, a similar fatigue behavior was found and a negligible difference in the fatigue crack nucleation was observed for the Ti-6Al-4V with CST in comparison to the samples without treatment.

Influence of Oxygen on the Damping Properties of Nb-Zr Alloys

Nb-1 wt% Zr polycrystalline and single crystalline samples were submitted to annealing, at pressure of 2.5 x 10-8 Torr and subsequently annealed in an oxygen atmosphere for three hours, in a temperature of 1170 K in oxygen at partial pressure of 5 x 10-5 Torr. Internal friction measurements as a function of temperature were performed between 300 K and 650 K, using a torsion pendulum inverted Kê-type operating in a frequency oscillation in the hertz bandwidth. Three internal friction peaks, which were assigned as Nb-O, Zr-O and Nb-N peaks were observed in oxidized single crystal sample and the relaxation parameters of the three peaks were obtained.

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 bodycentered 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.

Effect of impurities on mechanical relaxation in niobium

Measurements of internal friction as a function of temperature were performed in samples of Nb containing different amounts of substitutional (Zr) and interstitial (O, N) solutes. These data were resolved using the method of successive subtraction, into a series of constituent Debye peaks corresponding to different interactions. For each relaxation process we obtained the height (Q-1max) and temperature (Tp) of the peak, the activation energy (E) and the relaxation time (t0). The height, shape and temperature of the peaks depend on the concentration of interstitial and substitutional elements. With the addition of substitutional solute one can observed interactions between the two types of solutes (substitutional and interstitial), showing that the random distribution of the interstitial atoms was affected by presence of substitutional atoms. The peaks observed were associated with matrix-interstitial (Nb-O, Nb-N) and substitutional-interstitial (Zr-O) interaction processes.

Study of the Anelastic Behavior of PZT and PLZT Ferroelectric Ceramics

The anelastic behavior of the ferroelectric ceramics (Pb)(Zr/Ti)O3 (PZT) and (Pb/La)(Zr/Ti)O3 (PLZT), with Zr/Ti = 65/35, La = 5 at.% and 8 at.%, was investigated in the region of the ferroelectric phase transitions. Anelastic spectroscopy experiments were performed in an acoustic elastometer system, operating in a kilohertz bandwidth, at temperatures rising from 300 K to 770 K, at a heating rate of 1 K/min, under pressure of 10-5mbar. Anelastic measurements on PZT showed only one anomaly, associated with the occurrence of a ferroelectric-paraelectric phase transition, while the PLZT data showed two anomalies, which were associated with the following transitions: the ferroelectric-paraelectric phase transition and a ferro-ferroelectric phase transition between distinct rhombohedral ferroelectric phases. The behavior of the relative variation of the elastic moduli with temperature, near the phase transitions, which describes the change in the type of coupling between strain and the order parameter in ferroelectric-paraelectric phase transition, with the increase of lanthanum amount and, linear coupling in the strain and order parameter type to PZT ceramic and linear coupling in the strain but quadratic in order parameter type for PLZT ceramics.

Elastic Behavior of the Ti-13Nb-13Zr Alloy Obtained by Anelastic Spectroscopy

Measurements of anelastic relaxation (internal friction and frequency) as a function of temperature were carried out in samples of Ti-13Nb-13Zr using two experimental apparatus: Flexural Vibration of the first tone of samples in Acoustic Elastometer System (Vibran Technology®) operating in a kilohertz bandwidth, and Torsional Vibration of the samples in Kê-type Torsion Pendulum operating in a hertz bandwidth. Experimental spectra of anelastic relaxation were determined in the temperature range from 300 K to 450 K for a heating rate of 1K/min under pressure of 10-5 Torr, in both apparatus. The results show a relaxation structure strongly dependent on the microstructure of the material. The dynamical elastic modulus (E) of Ti-13Nb-13Zr alloy can be determined by flexural vibrations by frequency (f) measurements (f  E1/2). The anelastic relaxation spectrum of Ti-13Nb-13Zr alloy was a function of temperature obtained by torsional vibrations, not revealing the presence of interstitial solutes in solid solution in the temperature range of measurements.

Determination of the oxygen and nitrogen interstitial diffusion coeficient in niobium by mechanical spectroscopy

Mechanical spectroscopy measurements have been extensively used in the last decades to obtain information about many aspects of the behavior of solutes in metallic materials. Metals of body-centered cubic lattice that contain heavy interstitial elements (oxygen, nitrogen and carbon) in solid solution, present anelastic relaxation peaks when submitted to cyclic tensions, due to process know stress-induced ordering. Internal friction and frequency as a function of temperature were performed between 300 K and 650 K in a polycrystalline sample of Nb, for three distinct conditions, using a torsion pendulum inverted Ke-type operating in a frequency oscillation between 1Hz and 10 Hz range, with a heating rate of 1 K/min and pressure lower than 2 x 10-5 mbar. The experimental spectra obtained for each condition of the sample, were decomposed by the successive subtraction method in elementary Debye peaks. The following metal-interstitial interactions were identified: Nb-O and Nb-N for all conditions of the sample. From the anelastic relaxation parameters obtained (relaxation strength, peak temperature, activation energy and relaxation time) and lattice parameter (obtained from x ray diffraction), the determination of the oxygen and nitrogen interstitial diffusion coefficient in Nb was possible, for each condition of the sample.

Fatigue resistance, electrochemical corrosion and biological response of Ti-15Mo with surface modified by amorphous TiO2 nanotubes layer: PROPERTIES OF Ti-15Mo MODIFIED BY TiO2 NANOTUBES

The objective of this work was a systemic evaluation of the anodizing treatment in a β-type Ti-15Mo alloy to grow a TiO2 nanostructured layer for osseointegration improvement. The technical viability of the surface modification was assessed based on the resistance to mechanical fatigue, electrochemical corrosion, and biological response. By using an organic solution of NH4 F in ethylene glycol, a well-organized array of 90 nm diameter nanotubes was obtained with a potential of 40 V for 6 h, while undefined nanotubes of 25 nm diameter were formed with a potential of 20 V for 1 h. Nevertheless, the production of the 90 nm diameter nanotubes was followed by micrometer pits that significantly reduced the fatigue performance. The undefined nanotubes of 25 nm diameter, besides the greater cell viability and improved osteoblastic cell differentiation in comparison to the as-polished surface, were not deleterious to the fatigue and corrosion properties. This result strengthens the necessity of an overall evaluation of the anodizing treatment, particularly the fatigue resistance, before suggesting it for the design of implants.