Corrosion Behaviour of Zr-Ag Alloys for Dental Implant Application

The electrochemical corrosion behaviour of three Zr-Ag alloys (Zr-1Ag, Zr-3Ag and Zr-5Ag) was investigated. Open circuit potential, linear potentiodynamic polarization and electrochemical impedance spectroscopy (EIS) techniques were employed in aerated artificial saliva (pH = 4.0) at 37°C. Silver alloying additions are found to be effective in enhancing the corrosion resistance of zirconium in artificial saliva environment. In fact, Zr-Ag alloys exhibit higher open circuit potentials, larger breakdown potentials and higher impedance values as compared to cp Zr. This behaviour can be ascribed to the formation of a thicker and more stable passive film with increasing compactness, able to provide better protection against the corrosion attack

Cu3As: Uncommon Crystallographic Features, Low-Temperature Phase Transitions, Thermodynamic and Physical Properties

The formation and crystal structure of the binary Cu3As phase have been re-investigated. Some physical properties were then measured on both single crystal and polycrystalline bulk. Cu3As melts congruently at 835 °C. At room temperature (RT), this compound has been found to crystallize in the hexagonal Cu3P prototype (hP24, P63cm) with lattice parameters: a = 7.1393(1) Å and c = 7.3113(1) Å, rather than in the anti HoH3-type (hP24, P-3c1) as indicated in literature. A small compositional range of 74.0-75.5 at.% Cu (26.0-24.5 at.% As) was found for samples synthesized at 300 and 400 °C; a corresponding slight understoichiometry is found in one out of the four Cu atomic sites, leading to the final refined composition Cu2.882(1)As. The present results disprove a change in the crystal structure above RT actually reported in the phase diagram (from γ' to γ on heating). Instead, below RT, at T = 243 K (-30 °C), a first-order structural transition to a trigonal low-temperature superstructure, LT-Cu3-xAs (hP72, P-3c1) has been found. The LT polymorph is metrically related to the RT one, having the c lattice parameter three times larger: a = 7.110(2) Å and c = 21.879(4) Å. Both the high- and low-temperature polymorphs are characterized by the presence of a tridimensional (3D) uncommon and rigid Cu sublattice of the lonsdaleite type (Cu atoms tetrahedrally bonded), which remains almost unaffected by the structural change(s), and characteristic layers of triangular 'Cu3As'-units (each hosting one As atom at the center, interconnected each other by sharing the three vertices). The first-order transition is then followed by an additional structural change when lowering the temperature, which induces doubling of also the lattice parameter a. Differential scanning calorimetry nicely detects the first low-temperature structural change occurring at T = 243 K, with an associated enthalpy difference, ΔH(TR), of approximately 2 J/g (0.53 kJ/mol). Low-temperature electrical resistivity shows a typical metallic behavior; clear anomalies are detected in correspondence to the solid-state transformations. The Seebeck coefficient, measured as a function of temperature, highlights a conduction of n-type. The temperature dependence of the magnetic susceptibility displays an overall constant diamagnetic response

Solving Redox Reactions: The Advantages of the Thermodynamic Method

Redox reactions and their balancing are one of the basic chemistry subjects in which students may experience remarkable learning difficulties at the beginning of their university career. This topic represents an evolution of stoichiometry concepts related to the balancing of chemical reactions and can be taught with different approaches as a function of the in-depth analysis of the connected concepts as well as of the students’ backgrounds and educational objectives. In this article, we focus our attention on the thermodynamic approach, highlighting its versatility along with its strengths and weaknesses

Cu3As: Uncommon Crystallographic Features, Low-Temperature Phase Transitions, Thermodynamic and Physical Properties

ABSTRACT: The formation and crystal structure of the binary Cu3As phase have been re-investigated. Some physical properties were then measured on both single crystal and polycrystalline bulk. Cu3As melts congruently at 835 C. At room temperature (RT), this compound has been found to crystallize in the hexagonal Cu3P prototype (hP24, P63cm) with lattice parameters: a = 7.1393(1) Å and c = 7.3113(1) Å, rather than in the anti HoH3-type (hP24, P–3c1) as indicated in literature. A small compositional range of 74.0–75.5 at.% Cu (26.0–24.5 at.% As) was found for samples synthesized at 300 and 400 C; a corresponding slight understoichiometry is found in one out of the four Cu atomic sites, leading to the final refined composition Cu2.882(1)As. The present results disprove a change in the crystal structure above RT actually reported in the phase diagram (from Gamma’ to Gamma, on heating). Instead, below RT, at T = 243 K (-30 C), a first-order structural transition to a trigonal low-temperature superstructure, LT-Cu3-xAs (hP72, P–3c1) has been found. The LT polymorph is metrically related to the RT one, having the c lattice parameter three times larger: a = 7.110(2) Å and c = 21.879(4) Å. Both the high- and low-temperature polymorphs are characterized by the presence of a tridimensional (3D) uncommon and rigid Cu sublattice of the lonsdaleite type (Cu atoms tetrahedrally bonded), which remains almost unaffected by the structural change(s), and characteristic layers of triangular ‘Cu3As’-units (each hosting one As atom at the center, interconnected each other by sharing the three vertices). The first-order transition is then followed by an additional structural change when lowering the temperature, which induces doubling of also the lattice parameter a. Differential scanning calorimetry nicely detects the first low-temperature structural change occurring at T = 243 K, with an associated enthalpy difference, DH(TR), of approximately 2 J/g (0.53 kJ/mol). Low-temperature electrical resistivity shows a typical metallic behavior; clear anomalies are detected in correspondence to the solid-state transformations. The Seebeck coefficient, measured as a function of temperature, highlights a conduction of n-type. The temperature dependence of the magnetic susceptibility displays an overall constant diamagnetic response