Solid state interactions in the La-Au-Mg system: phase equilibria, novel compounds and chemical bonding.

Gold intermetallic chemistry is very rich, covering different classes of compounds ranging from the Hume-Rothery to Zintl phases to polar intermetallics to quasicrystals. Au's relativistic effects are frequently mentioned as responsible for the peculiar structural and physical properties of its compounds, nonetheless the aspects of chemical bonding are far to be clearly understood. In this work, the La-Au-Mg system was targeted for the discovery of new gold intermetallics and their structural and chemical bonding characterization. Studies on solid state interactions resulted in the construction of a partial La-Au-Mg isothermal section at 400 °C. The high reactivity between the constituents is reflected by the formation of five intermetallic compounds in the concentration range of less than 50 at% of Au. A complete crystallographic study was conducted for four of them, namely La1.82Au3+xMg14.36-x (0 ≤ x ≤ 0.90, hP42-3.64-CeMg10.3), La3Au4-xMg12+x (0 ≤ x ≤ 0.75, hP38-Gd3Ru4Al12), LaAuMg2 (oS16-MgCuAl2) and LaAu1+xMg1-x (0 ≤ x ≤ 0.15, hP9-ZrNiAl). A unifying description based on the different stacking sequences of equal slabs along the c-axis is proposed for these intermetallics. Chemical bonding in LaAuMg2 was studied by following the position space approach and including relativistic effects. Among the peculiarities of this LaMg2Au auride, there are two-atomic La-Au bonds showing a classical polar covalent character and that form distorted hexagonal planar layers and multi-atomic bonds involving Mg species. One of these is interpreted as a Mg-Mg bond supported by the neighbouring La and Au atoms, explaining the Mg reduced oxidation state (close to +1) in this compound.

The Ti-Mn system revisited: experimental investigation and thermodynamic modelling.

As the Ti-Mn phase diagram is part of numerous ternary and higher order systems of technological importance, the present paper defines phase relations which have been experimentally established throughout this work from 800 °C to the melting range based on Differential Thermal Analyses (DTA), X-ray powder diffraction, metallography and Electron Probe Micro Analysis (EPMA) techniques on ∼50 alloys, which were prepared by arc melting or high frequency melting under high purity argon starting from freshly cleaned metal ingots. Novel compounds were identified and reaction isotherms were redefined accordingly. In the Ti-rich region a novel compound TiMn was detected, sandwiched between the known phases: TiMn1-x (∼45 at% Mn) and TiMn1+x (∼55 at% Mn). In the Mn-rich region the hitherto unknown crystal structure of TiMn∼3 was solved from X-ray single crystal diffraction data and found to be of a unique structure type Ti6(Ti1-xMnx)6Mn25 (x = 0.462; space group Pbam (#55); a = 0.79081(3) nm, b = 2.58557(9) nm, c = 0.47931(2) nm), which consists of two consecutive layers of the hexagonal MgZn2-type Laves phase (TiMn2) and a combined layer of alternate structure blocks of MgZn2 type and Zr4Al3 type. Whereas TiMn can be considered as a line compound (solubility range <∼1 at%), the homogeneity regions of the Ti-Mn compounds are significant (determined by EPMA): TiMn1-x (44.0 to 46.6 at% Mn), TiMn1+x (54.6 to 56.3 at% Mn), Ti1+xMn2-x (MgZn2-type, 59 to 69 at% Mn at 1000 °C: -0.08 < x < 0.23), TiMn∼3 (unique type; 74 to 76.5 at% Mn) and TiMn∼4 (R-phase: Ti8(TixMn1-x)6Mn39, 80 to 84 at% Ti). Supported by ab initio calculations of the ground state energy for the Laves phase, the new experimental results enabled thermodynamic modelling of the entire Ti-Mn phase diagram providing a complete and novel set of thermodynamic data thus providing a sound basis for future thermodynamic predictions of higher order Ti-Mn-X-Y systems.

Microstructure and in vitro degradation performance of Mg-Zn-Mn alloys for biomedical application.

Manganese and zinc were selected as alloying elements to develop a Mg-based ternary alloy for biomedical applications, taking into account the good biocompatibility of these metals. The microstructures of Mg-Zn-Mn alloys containing 0.5 or 1.0 mass% of manganese and 1.0 or 1.5 mass% of zinc were investigated by scanning electron microscopy coupled with energy dispersive X-ray spectroscopy. Their corrosion properties were assessed by means of potentiodynamic polarization and electrochemical impedance spectroscopy measurements performed in Ringer's physiological solution that simulates bodily fluids. All tested samples are two-phase alloys formed by a Mg-based matrix, consisting of a Mg-Zn-Mn solid solution, and a Mg-Zn binary phase. The electrochemical results show an improvement of the corrosion behavior of the investigated alloys with increasing Zn and Mn content. This is attributed to the formation of a partially protective Mg(OH)(2) surface film whose protective capabilities are increased by the alloying elements. The reduced influence of the Mg-Zn intermetallic compound on the corrosion rate of Mg-Zn-Mn alloys in the presence of a partially protective surface layer can be ascribed to an increasing resistance between the Mg-Zn-Mn solid solution and the second phase, thereby decreasing the effective driving force for microgalvanic corrosion. Owing to its highest corrosion protective ability, the Mg-1.5Zn-1Mn alloy is a promising candidate for the development of degradable implants, such as screws, plates, and rods.

In vitro corrosion behaviour of Ti-Nb-Sn shape memory alloys in Ringer's physiological solution.

The nearly equiatomic Ni-Ti alloy (Nitinol) has been widely employed in the medical and dental fields owing to its shape memory or superelastic properties. The main concern about the use of this alloy derives form the fact that it contains a large amount of nickel (55% by mass), which is suspected responsible for allergic, toxic and carcinogenic reactions. In this work, the in vitro corrosion behavior of two Ti-Nb-Sn shape memory alloys, Ti-16Nb-5Sn and Ti-18Nb-4Sn (mass%) has been investigated and compared with that of Nitinol. The in vitro corrosion resistance was assessed in naturally aerated Ringer's physiological solution at 37°C by corrosion potential and electrochemical impedance spectroscopy (EIS) measurements as a function of exposure time, and potentiodynamic polarization curves. Corrosion potential values indicated that both Ni-Ti and Ti-Nb-Sn alloys undergo spontaneous passivation due to spontaneously formed oxide film passivating the metallic surface, in the aggressive environment. It also indicated that the tendency for the formation of a spontaneous oxide is greater for the Ti-18Nb-5Sn alloy. Significantly low anodic current density values were obtained from the polarization curves, indicating a typical passive behaviour for all investigated alloys, but Nitinol exhibited breakdown of passivity at potentials above approximately 450 mV(SCE), suggesting lower corrosion protection characteristics of its oxide film compared to the Ti-Nb-Sn alloys. EIS studies showed high impedance values for all samples, increasing with exposure time, indicating an improvement in corrosion resistance of the spontaneous oxide film. The obtained EIS spectra were analyzed using an equivalent electrical circuit representing a duplex structure oxide film, composed by an outer and porous layer (low resistance), and an inner barrier layer (high resistance) mainly responsible for the alloys corrosion resistance. The resistance of passive film present on the metals' surface increases with exposure time displaying the highest values to Ti-18Nb-4Sn alloy. All these electrochemical results suggest that Ti-Nb-Sn alloys are promising materials for biomedical applications.

Study of the in vitro corrosion behavior and biocompatibility of Zr-2.5Nb and Zr-1.5Nb-1Ta (at%) crystalline alloys.

The in vitro corrosion behavior and biocompatibility of two Zr alloys, Zr-2.5Nb, employed for the manufacture of CANDU reactor pressure tubes, and Zr-1.5Nb-1Ta (at%), for use as implant materials have been assessed and compared with those of Grade 2 Ti, which is known to be a highly compatible metallic biomaterial. The in vitro corrosion resistance was investigated by open circuit potential and electrochemical impedance spectroscopy (EIS) measurements, as a function of exposure time to an artificial physiological environment (Ringer's solution). Open circuit potential values indicated that both the Zr alloys and Grade 2 Ti undergo spontaneous passivation due to spontaneously formed oxide film passivating the metallic surface, in the aggressive environment. It also indicated that the tendency for the formation of a spontaneous oxide is greater for the Zr-1.5Nb-1Ta alloy and that this oxide has better corrosion protection characteristics than the ones formed on Grade 2 Ti or on the Zr-2.5Nb alloy. EIS study showed high impedance values for all samples, increasing with exposure time, indicating an improvement in corrosion resistance of the spontaneous oxide film. The fit obtained suggests a single passive film presents on the metals surface, improving their resistance with exposure time, presenting the highest values to the Zr-1.5Nb-1Ta alloy. For the biocompatibility analysis human osteosarcoma cell line (Saos-2) and human primary bone marrow stromal cells (BMSC) were used. Biocompatibility tests showed that Saos-2 cells grow rapidly, independently of the surface, due to reduced dependency from matrix deposition and microenvironment recognition. BMSC instead display a reduced proliferation, possibly caused by a reduced crosstalk with the metal surface microenvironment. However, once the substrate has been colonized, BMSC seem to respond properly to osteoinduction stimuli, thus supporting a substantial equivalence in the biocompatibility among the Zr alloys and Grade 2 titanium. In summary, high in vitro corrosion resistance together with satisfactory biocompatibility make the Zr-2.5Nb and Zr-1.5Nb-1Ta crystalline alloys promising biomaterials for surgical implants.

Phase relations and crystal structure of τ6-Ti2(Ti(0.16)Ni(0.43)Al(0.41))3.

Ti(2)(Ti(0.16)Ni(0.43)Al(0.41))(3) is a novel compound (labeled as τ(6)) in the Ti-rich region of the Ti-Ni-Al system in a limited temperature range 870 < T < 980 °C. The structure of τ(6)-Ti(2)(Ti,Ni,Al)(3) was solved from a combined analysis of X-ray single crystal and neutron powder diffracton data (space group C2/m, a = 1.85383(7) nm, b = 0.49970(2) nm, c = 0.81511(3) nm, and ß = 99.597(3)°). τ(6)-Ti(2)(Ti,Ni,Al)(3) as a variant of the V(2)(Co(0.57)Si(0.43))(3)-type is a combination of slabs of the MgZn(2)-Laves type and slabs of the Zr(4)Al(3)-type forming a tetrahedrally close-packed Frank-Kasper structure with pentagon-triangle main layers. Titanium atoms occupy the vanadium sites, but Ti/Ni/Al atoms randomly share the (Co/Si) sites of V(2)(Co(0.57)Si(0.43))(3). Although τ(6) shows a random replacement on 6 of the 11 atom sites, it has no significant homogeneity range (~1 at. %). The composition of τ(6) changes slightly with temperature. DSC/DTA runs (1 K/min) were not sufficient to define proper reaction temperatures due to slow reaction kinetics. Therefore, phase equilibria related to τ(6) were derived from X-ray powder diffraction in combination with EPMA on alloys, which were annealed at carefully set temperatures and quenched. τ(6) forms from a peritectoid reaction η-(Ti,Al)(2)Ni + τ(3) + α(2) ↔ τ(6) at 980 °C and decomposes in a eutectoid reaction τ(6) ↔ η + τ(4) + α(2) at 870 °C. Both reactions involve the η-(Ti,Al)(2)Ni phase, for which the atom distribution was derived from X-ray single crystal intensity data, revealing Ti/Al randomly sharing the 48f- and 16c-positions in space group Fd3̅m (Ti(2)Ni-type, a = 1.12543(3) nm). There was no residual electron density at the octahedral centers of the crystal structure ruling out impurity stabilization. Phase equilibria involving the τ(6) phase have been established for various temperatures (T = 865, 900, 925, 950, 975 °C, and subsolidus). The reaction isotherms concerning the τ(6) phase have been established and are summarized in a Schultz-Scheil diagram.

Bio-corrosion characterization of Mg-Zn-X (X = Ca, Mn, Si) alloys for biomedical applications.

The successful applications of magnesium-based alloys as biodegradable orthopedic implants are mainly inhibited due to their high degradation rates in physiological environment. This study examines the bio-corrosion behaviour of Mg-2Zn-0.2X (X = Ca, Mn, Si) alloys in Ringer's physiological solution that simulates bodily fluids, and compares it with that of AZ91 magnesium alloy. Potentiodynamic polarization and electrochemical impedance spectroscopy results showed a better corrosion behaviour of AZ91 alloy with respect to Mg-2Zn-0.2Ca and Mg-2Zn-0.2Si alloys. On the contrary, enhanced corrosion resistance was observed for Mg-2Zn-0.2Mn alloy compared to the AZ91 one: Mg-2Zn-0.2Mn alloy exhibited a four-fold increase in the polarization resistance than AZ91 alloy after 168 h exposure to the Ringer's physiological solution. The improved corrosion behaviour of the Mg-2Zn-0.2Mn alloy with respect to the AZ91 one can be ascribed to enhanced protective properties of the Mg(OH)(2) surface layer. The present study suggests the Mg-2Zn-0.2Mn alloy as a promising candidate for its applications in degradable orthopedic implants, and is worthwhile to further investigate the in vivo corrosion behaviour as well as assessed the mechanical properties of this alloy.

Clathrates Ba(8){Zn,Cd}(x)Si(46-x), x∼7: synthesis, crystal structure and thermoelectric properties.

Novel ternary type-I clathrate compounds Ba(8){Zn,Cd}(x)Si(46-x), x∼7 have been synthesized from the elements by melting and reacting in quartz ampoules. Structural investigations for both compounds, i.e. x-ray single-crystal data at 300, 200 and 100 K for Ba(8)Zn(7)Si(39) and Rietveld data for Ba(8)Cd(7)Si(39), confirm cubic primitive symmetry consistent with the space group type [Formula: see text] (a(Ba(8)Zn(7)Si(39)) = 1.043 72(1) nm; a(Ba(8)Cd(7)Si(39)) = 1.058 66(3) nm). Whereas for Ba(8)Zn(7)Si(39) site 16i is completely occupied by Si atoms, a random atom distribution with different Zn/Si ratio exists for the two sites, 6d (0.77Zn+0.23Si) and 24k (0.91Si+0.09Zn). No vacancies are encountered and all atom sites are fully occupied. This atom distribution is independent of temperature. Rietveld refinements for Ba(8)Cd(7)Si(39) show that the 6d site is fully occupied by Cd atoms, leaving only the 24k site for a random occupation (0.96Si+0.04Cd) consistent with the chemical formula Ba(8)Cd(7)Si(39). The temperature-dependent x-ray spectra for Ba(8)Zn(7)Si(39) define an Einstein mode, Θ(E,U33) = 80 K. Studies of transport properties show electrons as the majority charge carriers in the system. Although the Cd- and Zn-based samples are isoelectronic, a significantly different electronic transport points towards substantial differences in the electronic density of states in both cases.

Phase analysis of superconducting polycrystalline MgB(2).

Superconducting MgB(2) ceramics were prepared and yield superconducting transition temperatures of about 39 K. For covering the various length scales on which inhomogeneities appear in MgB(2), electron-probe micro-analysis (EPMA) and analytical transmission electron microscopy (TEM) were applied for a phase analysis. Particularly useful were the preliminary electron spectroscopic imaging (ESI) results in the TEM. It could be shown by EPMA that the microstructure consists of a Mg-B-O matrix and boron-rich secondary phases of composition close to MgB(12). It was unclear in which form oxygen was present in the superconducting matrix. By combining the acquisition of B-K and O-K edge jump ratio images and energy-dispersive X-ray spectroscopy in the TEM, we could prove that the matrix consists of superconducting MgB(2) and MgO. Most of the MgO precipitates and grains appear with diameters between 20 and 300 nm. The size distribution of MgO was inhomogeneous and oxygen-rich areas of dimensions >1 microm were also observed. Edge jump ratio images obtained by ESI were analysed for determining the signal values and effects of multiple inelastic scattering.

[Action of aminoglycosides on platelet aggregation in vitro]. / L'azione degli aminoglicosidi sulla aggregazione piastrinica in vitro.

The authors tested the influence of gentamicin, spectinomycin dihydrostreptomycin on the ADP and epinephrine in vitro induced platelet aggregation. Our aim was to demonstrate if platelet aggregation in vitro had some influences by antibiotics. A reduction in platelet aggregability, strictly dependent from the used antibiotic dose was observed. We have studied platelet function thanks to Born's method, adding to PRP gradual therapeutics doses of antibiotics. The results showed a reduction of platelet function which was dose-depended, and, particularly, gentamicin seemed to be the most effective among aminoglycosides. An interference between these drugs and the ADP and epinephrine binding to specific platelet receptor sites is proposed.

[Evaluation of pressure and mechanical effects on the aggregation of human platelets induced by adenosine diphosphate in a system simulating a dialysis circuit]. / Valutazione delle azioni pressorie e meccaniche sull'aggregazione delle piastrine umane indotta con adenosina difosfato (ADP) in un sistema simulante il circuito di dialisi.

Blood samples in sodium citrate 3.8% (ratio 1:10) of 15 healthy people were subjected to the pressure of 0, 50, 150 mm Hg respectively in a circuit operated by a peristaltic pump as during dialysis. The platelet aggregation induced by adenosine diphosphate (ADP) was determined in all cases. We found a significant reduction of the maximum percent aggregation of the samples exposed to the pressure of 150 mm Hg. We then suppose that a positive correlation exists between high pressure in the dialytic circuit and platelet damage.

[Isoenzyme fractions of serum and platelet lactate dehydrogenase in normal subjects]. / Studio delle frazioni isoenzimatiche del lattato deidrogenasi sierico ed endopiastrinico in soggetti normali.

We determined the isoenzymatic fractions of platelets and seric LDH in off healthy people (50 males and 50 females). We broken the platelets by triton X 100 (octylphenoxypolyethoxyethanol) in order to obtain the release of platelet LDH. The seric and platelet LDH isoenzymes were then separated by electrophoresis (Gelman sistem). We confirm the prevalence of LDH2 and LDH3 fractions in human platelets.