Effect of physical aging on Johari-Goldstein relaxation in La-based bulk metallic glass.

The influence of physical aging on the ß relaxation in La60Ni15Al25 bulk metallic glass has been investigated by mechanical spectroscopy. The amplitude of the ß relaxation (ΔG″) decreases while its relaxation time (τ(ß)) increases during aging. We find that, as in organic glasses, the changes of ln (τ(ß)) and ln (ΔG(max) ) are linearly correlated with ln (τ(ß)) = b - a ln (G(max)″). This behavior is discussed in term of the asymmetric double-well potential (ADWP) model, with U and Δ the energies characterizing the ADWP. It is suggested that during aging the ratio U/Δ remains approximately constant, with a value close to the coefficient describing the linear correlation between ln (τ(ß)) and ln (G(max)″)(U/Δ ~ a). Moreover, the evolution versus aging time of ΔG(max) can be described by a simple stretched exponential equation giving values of τ(aging) consistent with tan(δ) measurements during aging. The very similar behavior of the ß relaxation during aging in metallic glasses and organic material strongly suggests a common nature for this relaxation.

On the Potential of Bulk Metallic Glasses for Dental Implantology: Case Study on Ti40Zr10Cu36Pd14.

Ti40Zr10Cu36Pd14 Bulk Metallic Glass (BMG) appears very attractive for future biomedical applications thanks to its high glass forming ability, the absence of toxic elements such as Ni, Al or Be and its good mechanical properties. For the first time, a complete and exhaustive characterization of a unique batch of this glassy alloy was performed, together with ISO standard mechanical tests on machined implant-abutment assemblies. The results were compared to the benchmark Ti-6Al-4V ELI (Extra-Low-Interstitial) to assess its potential in dental implantology. The thermal stability, corrosion and sterilization resistance, cytocompatibility and mechanical properties were measured on samples with a simple geometry, but also on implant-abutment assemblies' prototypes. Results show that the glassy alloy exhibits a quite high thermal stability, with a temperature range of 38 °C between the glass transition and crystallization, a compressive strength of 2 GPa, a certain plastic deformation (0.7%), a hardness of 5.5 GPa and a toughness of 56 MPa.√m. Moreover, the alloy shows a relatively lower Young's modulus (96 GPa) than the Ti-6Al-4V alloy (110-115 GPa), which is beneficial to limit bone stress shielding. The BMG shows a satisfactory cytocompatibility, a high resistance to sterilization and a good corrosion resistance (corrosion potential of -0.07 V/SCE and corrosion current density of 6.0 nA/cm²), which may ensure its use as a biomaterial. Tests on dental implants reveal a load to failure 1.5-times higher than that of Ti-6Al-4V and a comparable fatigue limit. Moreover, implants could be machined and sandblasted by methods usually conducted for titanium implants, without significant degradation of their amorphous nature. All these properties place this metallic glass among a promising class of materials for mechanically-challenging applications such as dental implants.

Characteristics of the structural and Johari-Goldstein relaxations in Pd-based metallic glass-forming liquids.

The dynamics of Pd-based metallic glass-forming liquids (Pd(40)Ni(10)Cu(30)P(20), Pd(42.5)Ni(7.5)Cu(30)P(20), Pd(40)Ni(40)P(20), and Pd(30)Ni(50)P(20)) was studied by mechanical spectroscopy and modulated differential scanning calorimetry (MDSC). We found that the change in composition has a significant effect on the α relaxation dynamics; the largest difference corresponds to an increase of the glass transition temperature Tg of ∼ 15 K, for materials in which 30% Ni was substituted by 30% Cu (i.e., from Pd(40)Ni(40)P(20) to Pd(40)Ni(10)Cu(30)P(20)). We also found that all Pd-based metallic glasses have very similar fragilities, 59 < m < 67, and Kohlrausch stretched exponents, 0.59 < ßKWW < 0.60. It is interesting that the values of m and ßKWW correlate well with the general relation proposed by Böhmer et al. for nonmetallic glass formers (Böhmer, R.; et al. J. Chem. Phys. 1993, 99, 4201-4209), which for the observed ßKWW values predicts 58 < m < 61. From a linear deconvolution of the α and ß relaxations, we find that the substitution of the Ni with Cu induced a large change in the time constant of the Johari-Goldstein relaxation, τß. The activation energy, Uß, of the ß relaxation was largely independent of chemical composition. In all cases, 25 < Uß/RT < 28, a range in agreement with results for other glass formers (Kudlik, A.; et al. Europhys. Lett. 1997, 40, 649-654 and Ngai, K. L.; et al. Phys. Rev. E 2004, 69, 031501). From the heat capacity and mechanical loss, estimates were obtained for the number of dynamically correlated units, Nc; we find significantly larger values for these metallic glass-forming liquids than Nc for other glass-forming materials.

Relaxation of bulk metallic glasses studied by mechanical spectroscopy.

The relaxational dynamics in metallic glasses (MGs) is investigated by using mechanical spectroscopy. The spectra show that in MGs there are two relaxations: (i) the α relaxation, linked to the glass transition, as observed in other classes of amorphous materials; and (ii) the ß relaxation, well observed below the glass transition, with an intensity strongly dependent on the MG composition, the nature of which has been linked to the local microstructure of MGs. For the investigated MGs we find that the intensity and relaxation time of the ß relaxation depends, in a reproducible fashion, on the thermal history of the samples. During aging experiments, the intensity decreases (as well as the τß) with a time dependence described well by a stretched exponential, with an exponent ß(aging) independent of the driving frequency. Moreover, we find that the activation energy Uß and the peak temperature Tßp of the ß relaxation follow the approximate relationship: Uß ≈ 31.5RTßp (for driving frequency 1 Hz), indicating that the high temperature limit of the peak frequency is approximately the same for all the MGs investigated. Finally, the frequency separation of the α and ß processes in the mechanical loss spectra for La-and Pd-based metallic glasses is tested against the prediction of the Coupling Model.

Characterization of the drastic increase in molecular mobility of a deformed amorphous polymer.

Original experiments of dynamic mechanical analysis and small angle x-ray scattering on a deformed amorphous polymer below its glass transition temperature are reported. The mechanical treatment reveals high mobility zones induced by shearing and leads to a drastic increase in the molecular mobility of the system. These domains are evidenced by small angle x-ray scattering measurements, and their geometrical characteristics are independent of the applied deformation. An experimental procedure is proposed to determine an apparent activation energy associated with high mobility domains. The energy values obtained for intermediate modes rise from the beta to the alpha relaxation ones.