Non-Isothermal Analysis of the Crystallization Kinetics of Amorphous Mg72Zn27Pt1 and Mg72Zn27Ag1 Alloys.

In this study, thin ribbons of amorphous Mg72Zn27Pt1 and Mg72Zn27Ag1 alloys with potential use in biomedicine were analyzed in terms of the crystallization mechanism. Non-isothermal annealing in differential scanning calorimetry (DSC) with five heating rates and X-ray diffraction (XRD) during heating were performed. Characteristic temperatures were determined, and the relative crystalline volume fraction was estimated. The activation energies were calculated using the Kissinger method and the Avrami exponent using the Jeziorny-Avrami model. The addition of platinum and silver shifts the onset of crystallization towards higher temperatures, but Pt has a greater impact. In each case, Eg > Ex > Ep (activation energy of the glass transition, the onset of crystallization, and the peak, respectively), which indicates a greater energy barrier during glass transition than crystallization. The highest activation energy was observed for Mg72Zn27Pt1 due to the difference in the size of the atoms of all alloy components. The crystallization in Mg72Zn27Ag1 occurs faster than in Mg72Zn27Pt1, and the alloy with Pt has higher (temporary) thermal stability. The Avrami exponent (n) values oscillate in the range of 1.7-2.6, which can be interpreted as one- and two-dimensional crystal growth with a constant/decreasing nucleation rate during the process. Moreover, the lower the heating rate, the higher the nucleation rate. The values of n for Mg72Zn27Pt1 indicate a greater number of nuclei and grains than for Mg72Zn27Ag1. The XRD tests indicate the presence of α-Mg and Mg12Zn13 for both Mg72Zn27Pt1 and Mg72Zn27Ag1, but the contribution of the Mg12Zn13 phase is greater for Mg72Zn27Ag1.

Structural characterization of newly-developed Al79Ni5Fe5Y11 and Al79Ni11Fe5Y5 alloys with amorphous matrixes.

The low glass-forming ability of aluminium-based metallic glasses significantly limits their development and preparation. This paper updates the current state of knowledge by presenting the results of structural studies of two newly-developed Al79Ni5Fe5Y11 and Al79Ni11Fe5Y5 alloys with a reduced aluminium content (< 80 at.%). The alloys were produced by conventional casting (ingots) and melt-spinning (ribbons). Structural characterization was carried out for bulk ingots first, and then for the melt-spun ribbons. The ingots possessed a multiphase crystalline structure, as confirmed by X-ray diffraction and scanning electron microscopy observations. The amorphous structure of the melt-spun ribbons was determined by X-ray diffraction and transmission electron microscopy. SEM observations and EDX element maps of the cross-section of melt-spun ribbons indicated a homogeneous elemental composition. Neutron diffraction revealed the presence of nanocrystals in the amorphous matrix of the melt-spun ribbons. DSC data of the melt-spun ribbons showed exothermic events corresponding to the first crystallization at temperatures of 408 °C and 387 °C for Al79Ni5Fe5Y11 and Al79Ni11Fe5Y5, respectively.

Evaluation of the biocompability and corrosion activity of resorbable CaMgZnYbBAu alloys.

Calcium-based alloys can be promising candidates for use as biodegradable implants because of attractive properties as mechanical, corrosive, and biocompatible. In the work, the biocompatibility authors discussed the results of the Ca32Mg12Zn38Yb18-xBx (x = 0, 1, 2, 3 at.%) and Ca32Mg12Zn38Yb18-2xBxAux (x = 1, 2 at.%) alloys. The tests were performed using a MTT assay. The corrosion behavior of such Ca-based alloys in PWE fluid at 37 °C was studied and compared with the results in Ringer's solution from previous works. Electrochemical tests were presented by open circuit potential and potentiodynamic curves. Different concentrations of boron and gold in the alloys caused changes in the corrosion results. The best corrosion resistance in PWE solution was observed for the Ca-based alloy with 2 at.% Au due to the lowest value of the corrosion current density (jcorr), equal to 10.6 µA·cm-2. A slightly higher value of jcorr was obtained for the Ca32Mg12Zn38Yb15B3 alloy with the lowest roughness values. The results of the cytotoxicity tests also showed that the alloy with 3 at.% boron was characterized by the highest cell viability. The investigation results discussed in the work allow us to suggest that the presented calcium alloys with 3 at.% of B, and 2 at.% of Au addition may be promising materials for the use in implantology.

Study of crystallization mechanism of Al-based amorphous alloys by in-situ high temperature X-ray diffraction method.

The role of transition metals (TMs) addition on the formation and crystallization of amorphous Al85TMs10Y5 alloys was described using in-situ high-temperature X-ray diffraction. The structural results were compared with differential scanning calorimetry and dynamical mechanical analysis to obtain detailed information about the nucleation and growth of crystalline phases. The performed analysis confirmed that Fe and Cu addition drastically changes the crystallization temperature and the phase composition of the fully crystallized alloys. While for Al85Ni10Y5 alloy, the second crystallization step is related to the formation of Al19Ni5Y3 phase, for Al85(Ni, Fe)10Y5 and Al85(Ni, Fe, Cu)10Y5 alloys crystallization of Al15Fe9Y2 phase was observed. Interestingly, the performed analysis showed that forming a homogenous amorphous phase is not necessary to obtain the best corrosion resistance. It was noted that the precipitation of the YCr2Al20 phase in the Cu-rich amorphous matrix should be a much more interesting approach.

The Influence of Rapid Solidification on Corrosion Behavior of Mg60Zn20Yb15.7Ca2.6Sr1.7 Alloy for Medical Applications.

Biodegradable magnesium alloys with Zn, Yb, Ca and Sr additions are potential materials with increased corrosion resistance in physiological fluids that ensure a controlled resorption process in the human body. This article presents the influence of the use of a high cooling rate on the corrosion behavior of Mg60Zn20Yb15.7Ca2.6Sr1.7 alloy proposed for medical applications. The microstructure of the alloy in a form of high-pressure die-casted plates was presented using scanning electron microscopy in the backscattered electrons (BSEs) mode with energy-dispersive X-ray spectrometer (EDX) qualitative analysis of chemical composition. The crystallization mechanism and thermal properties were described on the basis of differential scanning calorimetry (DSC) results. The corrosion behavior of Mg60Zn20Yb15.7Ca2.6Sr1.7 alloy was analyzed by electrochemical studies with open circuit potential (EOCP) measurements and polarization tests. Moreover, light microscopy and X-ray photoelectron spectroscopy were used to characterize the corrosion products formed on the surface of studied samples. On the basis of the results, the influence of the cooling rate on the improvement in the corrosion resistance was proved. The presented studies are novel and important from the point of view of the impact of the technology of biodegradable materials on corrosion products that come into direct contact with the tissue environment.

Influence of Magnetite Nanoparticles Shape and Spontaneous Surface Oxidation on the Electron Transport Mechanism.

The spontaneous oxidation of a magnetite surface and shape design are major aspects of synthesizing various nanostructures with unique magnetic and electrical properties, catalytic activity, and biocompatibility. In this article, the roles of different organic modifiers on the shape and formation of an oxidized layer composed of maghemite were discussed and described in the context of magnetic and electrical properties. It was confirmed that Fe3O4 nanoparticles synthesized in the presence of triphenylphosphine could be characterized by cuboidal shape, a relatively low average particle size (9.6 ± 2.0 nm), and high saturation magnetization equal to 55.2 emu/g. Furthermore, it has been confirmed that low-frequency conductivity and dielectric properties are related to surface disordering and oxidation. The electric energy storage possibility increased for nanoparticles with a disordered and oxidized surface, whereas the dielectric losses in these particles were strongly related to their size. The cuboidal magnetite nanoparticles synthesized in the presence of triphenylphosphine had an ultrahigh electrical conductivity (1.02 × 10-4 S/cm at 10 Hz) in comparison to the spherical ones. At higher temperatures, the maghemite content altered the behavior of electrons. The electrical conductivity can be described by correlated barrier hopping or overlapping large polaron tunneling. Interestingly, the activation energies of electrons transport by the surface were similar for all the analyzed nanoparticles in low- and high-temperature ranges.

Surface Modification of Biomedical MgCa4.5 and MgCa4.5Gd0.5 Alloys by Micro-Arc Oxidation.

The aim of this work was to characterize the structure and corrosion properties of the MgCa4.5(Gd0.5) alloys surface treated by the micro-arc oxidation (MAO) process. The MgCa4.5 and MgCa4.5Gd0.5 alloy samples were processed by MAO in an electrolyte composed of NaOH (10 g/dm3), NaF (10 g/dm3), NaH2PO4 (5 g/dm3), Na2SiO2·5H2O (10 g/dm3) and water. Two different voltages (120 V and 140 V) were used in the MAO process. The alloys protected by an oxide layer formed in the MAO were then the subject of corrosion resistance tests in an environment simulating the human body (Ringer's solution). After the experiments, the resulting samples were investigated using SEM, XPS and EDS techniques. The addition of Gd affected the fragmentation of the coating structure, thereby increasing the specific surface; higher voltages during the MAO process increased the number and size of surface pores. Corrosion tests showed that the MgCa4.5Gd0.5 alloys were characterized by low polarization resistances and high corrosion current densities. The studies indicated the disadvantageous influence of gadolinium on the corrosion resistance of MgCa4.5 alloys. The immersion tests confirmed lower corrosion resistance of MgCa4.5Gd0.5 alloys compared to the referenced MgCa4.5 ones. The MgCa4.5 alloy with the MAO coating established at voltage 140 V demonstrated the best anticorrosion properties.

Glass-Forming Ability and Corrosion Resistance of Al88Y8-xFe4+x (x = 0, 1, 2 at.%) Alloys.

The effect of iron and yttrium additions on glass forming ability and corrosion resistance of Al88Y8-xFe4+x (x = 0, 1, 2 at.%) alloys in the form of ingots and melt-spun ribbons was investigated. The crystalline multiphase structure of ingots and amorphous-crystalline structure of ribbons were examined by a number of analytical techniques including X-ray diffraction, Mössbauer spectroscopy, and transmission electron microscopy. It was confirmed that the higher Fe additions contributed to formation of amorphous structures. The impact of chemical composition and structure of alloys on their corrosion resistance was characterized by electrochemical tests in 3.5% NaCl solution at 25 °C. The identification of the mechanism of chemical reactions taking place during polarization test along with the morphology and internal structure of the surface oxide films generated was performed. It was revealed that the best corrosion resistance was achieved for the Al88Y7Fe5 alloy in the form of ribbon, which exhibited the lowest corrosion current density (jcorr = 0.09 µA/cm2) and the highest polarization resistance (Rp = 96.7 kΩ∙cm2).

Structural Characterization of Al65Cu20Fe15 Melt-Spun Alloy by X-ray, Neutron Diffraction, High-Resolution Electron Microscopy and Mössbauer Spectroscopy.

The aim of the work was to characterize the structure of Al65Cu20Fe15 alloy obtained with the use of conventional casting and rapid solidification-melt-spinning technology. Based on the literature data, the possibility of an icosahedral quasicrystalline phase forming in the Al-Cu-Fe was verified. Structure analysis was performed based on the results of X-ray diffraction, neutron diffraction, 57Fe Mössbauer and transmission electron microscopy. Studies using differential scanning calorimetry were carried out to describe the crystallization mechanism. Additionally, electrochemical tests were performed in order to characterize the influence of the structure and cooling rate on the corrosion resistance. On the basis of the structural studies, the formation of a metastable icosahedral phase and partial amorphous state of ribbon structure were demonstrated. The possibility of the formation of icosahedral quasicrystalline phase I-AlCuFe together with the crystalline phases was indicated by X-ray diffraction (XRD), neutron diffraction (ND) patterns, Mössbauer spectroscopy, high-resolution transmission electron microscopy (HRTEM) observations and differential scanning calorimetry (DSC) curves. The beneficial effect of the application of rapid solidification on the corrosive properties was also confirmed.

Effect of the Thickness of TiO2 Films on the Structure and Corrosion Behavior of Mg-based Alloys.

This article discusses the influence of the thickness of TiO2 films deposited onto MgCa2Zn1 and MgCa2Zn1Gd3 alloys on their structure, corrosion behavior, and cytotoxicity. TiO2 layers (about 200 and 400 nm thick) were applied using magnetron sputtering, which provides strong substrate adhesion. Such titanium dioxide films have many attractive properties, such as high corrosion resistance and biocompatibility. These oxide coatings stimulate osteoblast adhesion and proliferation compared to alloys without the protective films. Microscopic observations show that the TiO2 surface morphology is homogeneous, the grains have a spherical shape (with dimensions from 18 to 160 nm). Based on XRD analysis, it can be stated that all the studied TiO2 layers have an anatase structure. The results of electrochemical and immersion studies, performed in Ringer's solution at 37 °C, show that the corrosion resistance of the studied TiO2 does not always increase proportionally with the thickness of the films. This is a result of grain refinement and differences in the density of the titanium dioxide films applied using the physical vapor deposition (PVD) technique. The results of 24 h immersion tests indicate that the lowest volume of evolved H2 (5.92 mL/cm2) was with the 400 nm thick film deposited onto the MgCa2Zn1Gd3 alloy. This result is in agreement with the good biocompatibility of this TiO2 film, confirmed by cytotoxicity tests.

Study of the Morphology and Properties of Biocompatible Ca-P Coatings on Mg Alloy.

Magnesium alloys are considered as potential biomaterials for use in orthopedic implantology. The main barrier to the use of Mg alloys in medicine is their overly fast and irregular degradation in body fluids. The use of protective calcium phosphate coatings to increase the corrosion resistance of Mg alloy (AM50 alloy: 4 wt.% Al, 0.3 wt.% Mn, 0.2 wt.% Zn, rest Mg) was examined in this study. The scientific goal of the study was the assessment of the influence of calcium phosphate layer morphology on the corrosion process in Ringer's solution. Modification of the coating morphology was obtained by changing the chemical composition of the phosphatizing bath using NaOH (NaAM50 sample) or ZnSO4 (ZnAM50 sample). In practice, a more dense and uniform coating could be obtained by the immersion of AM50 alloy in a solution containing ZnSO4 (ZnAM50 sample). In this study, an adhesion test performed on the ZnAM50 sample indicated that the critical load was 1.35 N. XRD phase analysis confirmed that the obtained coatings included dicalcium phosphate dihydrate (CaHPO4*2H2O). The coatings prepared on the NaAM50 and ZnAM50 samples are effective barriers against the progress of corrosion deeper into the substrate. After 120 h immersion in Ringer's solution, the volume of the evolved hydrogen was 5.6 mL/cm2 for the NaAM50 and 3.4 mL/cm2 for the ZnAM50 sample.

Mechanical and Corrosion Properties of Mg-Based Alloys with Gd Addition.

Magnesium alloys with rare earth metals are very attractive materials for medical application because of satisfactory mechanical properties. Nevertheless, low corrosion resistance is an obstacle in the use of Mg alloys as resorbable orthopedic implants. The paper presents results of mechanical and corrosion properties of MgCa5-xZn1Gdx (x = 1, 2, and 3 wt. %) alloys. Based on the microscopic observations it was stated that the studied alloys show a dendritic microstructure with interdendritic solute rich regions. The phase analysis reveals an occurrence of α-Mg and Mg2Ca, Ca2Mg6Zn3 phases that are thermodynamic predictions, and stated Mg26Zn59Gd7 phases in MgCa5-xZn1Gdx (x = 1, 2, and 3 wt. %) alloys. The Mg26Zn59Gd7 phases are visible as lamellar precipitations along interdendritic regions. It was confirmed that an increase of Gd content from 1 to 3 wt. % improves ultimate tensile (Rm; from 74 to 89 MPa) and compressive strength (Rc; from 184 to 221 MPa). Moreover, the studied alloys are active in Ringer's solution. They are characterized by an increase of corrosion potential (Ecorr) of about 150 mV in comparison with values of open circuit potential (EOCP). The best electrochemical parameters (e.g., corrosion current density, icorr, polarization resistance, Rp, and Ecorr) were obtained for the MgCa3Zn1Gd2 alloy.

Atomic structure of Mg-based metallic glass investigated with neutron diffraction, reverse Monte Carlo modeling and electron microscopy.

The structure of a multicomponent metallic glass, Mg65Cu20Y10Ni5, was investigated by the combined methods of neutron diffraction (ND), reverse Monte Carlo modeling (RMC) and high-resolution transmission electron microscopy (HRTEM). The RMC method, based on the results of ND measurements, was used to develop a realistic structure model of a quaternary alloy in a glassy state. The calculated model consists of a random packing structure of atoms in which some ordered regions can be indicated. The amorphous structure was also described by peak values of partial pair correlation functions and coordination numbers, which illustrated some types of cluster packing. The N = 9 clusters correspond to the tri-capped trigonal prisms, which are one of Bernal's canonical clusters, and atomic clusters with N = 6 and N = 12 are suitable for octahedral and icosahedral atomic configurations. The nanocrystalline character of the alloy after annealing was also studied by HRTEM. The selected HRTEM images of the nanocrystalline regions were also processed by inverse Fourier transform analysis. The high-angle annular dark-field (HAADF) technique was used to determine phase separation in the studied glass after heat treatment. The HAADF mode allows for the observation of randomly distributed, dark contrast regions of about 4-6 nm. The interplanar spacing identified for the orthorhombic Mg2Cu crystalline phase is similar to the value of the first coordination shell radius from the short-range order.