Investigation on the effect of recasting palladium-silver alloy by argon arc vacuum pressure casting process.

Background/purpose: Palladium-silver (Pd-Ag) alloys are important as an alternative to gold-based alloys. The purpose of this study was to investigate the effect of an argon-arc vacuum pressure casting process on the recasting of the Pd-Ag alloy. Materials and methods: The recasting Pd-Ag alloys were compared with conventional horizontal centrifugal (HC) casting to an argon (Ar)-arc vacuum pressure (Ar-arc/VP) casting. The first-generation castings were made from a Pd-Ag alloy purchased from a supplier. Next-generation castings were made from 50 wt% Pd-Ag alloy before casting and 50 wt% from previous castings. This sequence was repeated over three generations to form the 2nd, 3rd and 4th recasting ingots. The ingots were then measured for marginal accuracy, interfacial oxidation, hardness and phase identification. Results: The recasting success rate of recastibility reached 100%. Compared with the HC group, the Ar-arc/VP group had better edge precision, smaller oxide layer thickness and lower hardness. The comparison of X-ray diffraction intensity showed that the relative intensities of Pd and Ag in the first, second and third generations recasting of the Ar-arc/VP group were significantly higher than those of the HC group. Phase analysis showed that the trace elements of indium and tin contents in the Pd-Ag recasting ingots of the Ar-arc/VP group were higher than those of the HC group. Conclusion: The results showed that the casting process used for recasting affected the quality of the Pd-Ag alloy. Therefore, Ar-arc/VP casting process could improve the effect of Pd-Ag recasting and maintain the alloy properties in comparison with HC casting.

Ultrathin Dendritic Pd-Ag Nanoplates for Efficient and Durable Electrocatalytic Reduction of CO2 to Formate.

CO2 reduction reactions (CO2 RR) powered by renewable electricity can directly convert CO2 to hydrocarbons and fix the sustainable but intermittent energy (e. g., sunlight, wind, etc.) in stable and portable chemical fuels. Advanced catalysts boosting CO2 RR with high activity, selectivity, and durability at low overpotentials are of great importance but still elusive. Here, we report that the ultrathin Pd-Ag dendritic nanoplates (PdAg DNPs) exhibited boosted activity, selectivity, and stability for producing formate from CO2 at a very low overpotential in aqueous solutions under ambient conditions. As a result, the PdAg DNPs exhibited a Faradaic efficiency (FE) for formate of 91% and a cathodic energy efficiency (EE) of ∼90% at the potential of -0.2 V versus reversible hydrogen electrode (vs. RHE), showing significantly enhanced durability as compared with pure Pd catalysts. Our strategy represents a rational catalyst design by engineering the surface geometrical and electronic structures of metal nanocrystals and may find more applicability in future electrocatalysis.

Palladium-Coated Single Silver Nanowire Electrodes: Size-Dependent Voltammetry, Enhanced Chemical Stability, and High Performance for Methanol Oxidation.

Silver nanowires (AgNWs) have been extensively studied as promising nanomaterials in optics, next-generation flexible electronics, and energy-related fields, but the stability and the properties at single-nanowire level still need to be investigated carefully. We have successfully prepared single palladium@silver nanowire electrodes (Pd@AgNWEs) by using a laser-assisted pulling method, followed by a galvanic replacement reaction (GRR). The results show that the chemical stability of AgNWs can be improved greatly by coating a small amount of Pd, and the Pd@AgNWEs exhibit superior electrocatalytic performance in methanol oxidation. This work can give us a new insight to investigate the performance of devices/catalysts at the single-particle/nanowire level that will benefit research in flexible electronics and energy-related fields.

Pd-Ag Electrical Resistivity in Hydrogen and Deuterium: Temperature Effect.

The electrical resistivity of Pd-Ag (silver 21 wt.%) in hydrogen and deuterium atmosphere at 100 kPa has been investigated via electrochemical impedance spectroscopy. The electrical resistivity of Pd-Ag vs. the temperature presents the characteristic S-shaped curve with a minimum and a maximum of the resistivity in different positions for the tests in hydrogen and deuterium. The results have been related to: (1) the different isotope ratios, H/M and D/M, and (2) their position in the Pd-Ag lattice. The behavior of the electrical resistivity is discussed in details by considering the hydrogen and deuterium uploading into the alloy, its effect on the conduction electrons, and the scattering of the isotopes atoms into the metal lattice. Measurements carried out in hydrogen with slow temperature ramping between 25-250 °C evidenced a hysteresis effect that can be explained by the different energy levels of isotopes in O-sites and T-sites.

Hydrogen Absorption in Pd-Ag Systems: A TPD and Electrical Resistivity Study.

Hydrogen retention in Pd-Ag (silver 21 wt. %) thin foil has been tested by means of temperature-programmed desorption (TPD) in the temperature range 25-200 °C and compared to the resistivity measurements for the purpose of explaining the characteristic S-shaped resistivity curve and its minimum observed in the same temperature range. The TPD results indicated that the highest uptake of hydrogen was between 65 °C and 105 °C, with a maximum at ~85 °C. Furthermore, in all examined cases, the hydrogen desorption peak was between 140 °C and 180 °C. The resistivity measurements in argon, hydrogen, and vacuum allowed us to examine the influence of hydrogen on the resistivity of a Pd-Ag alloy. The results showed evidence of two kinds of hydrides: (1) a weak absorption at low temperature (T < 70 °C) with the hydrogen present mainly in tetrahedral sites, and (2) a strong absorption up to 150 °C with the hydrogen present mainly in octahedral sites. The behaviour of the electrical resistivity and the minimum between 90 °C and 110 °C can be explained by the two kinds of hydrogen uploaded into the metal lattice.

Effect of pretreatments on the metal-ceramic bonding strength of a Pd-Ag alloy.

OBJECTIVES: The purpose of this study was to evaluate the efficacy of surface treatments on the bonding properties between a metal and ceramic. METHODS: Sixty metal specimens were divided equally into four groups of 15 samples each. These groups received different treatments (Gr1: 250µm Al2O3+preoxidation; Gr2: 250µm Al2O3+degassing; Gr3: 120µm Al2O3+preoxidation; Gr4: 120µm Al2O3+degassing). Bond strengths were evaluated using a three-point bending test. The results were analyzed using 2-way ANOVA and Tukey's test. Scanning electron microscopy and energy dispersive spectroscopy were used to observe the microscopic features, elemental compositions and distributions, and diffusion in the specimens. Mechanical profiler was used to measure the roughness of metal surface. RESULTS: The bond strengths of the four groups ranged from 45.00±3.63MPa to 51.61±5.91MPa, with significant differences (P<.05). The specimen that received the pretreatment of 250µm Al2O3 air-particle abrasion+degassing had the highest bond strength. Heating under different oxygen partial pressures caused the final Pd-Ag alloys to have varying degrees of internal oxidation and different quantities of metallic nodules. None of the elements in either the ceramic or the Pd-Ag alloy layer diffused into the other layer. CONCLUSIONS: The metal-ceramic specimen subjected to air-particle abrasion with 250µm Al2O3 and degassed before porcelain firing had significantly higher bond strength than specimens treated differently.

Correlation between metal-ceramic bond strength and coefficient of linear thermal expansion difference

The purpose of this study was to evaluate the metal-ceramic bond strength (MCBS) of 6 metal-ceramic pairs (2 Ni-Cr alloys and 1 Pd-Ag alloy with 2 dental ceramics) and correlate the MCBS values with the differences between the coefficients of linear thermal expansion (CTEs) of the metals and ceramics. Verabond (VB) Ni-Cr-Be alloy, Verabond II (VB2), Ni-Cr alloy, Pors-on 4 (P), Pd-Ag alloy, and IPS (I) and Duceram (D) ceramics were used for the MCBS test and dilatometric test. Forty-eight ceramic rings were built around metallic rods (3.0 mm in diameter and 70.0 mm in length) made from the evaluated alloys. The rods were subsequently embedded in gypsum cast in order to perform a tensile load test, which enabled calculating the CMBS. Five specimens (2.0 mm in diameter and 12.0 mm in length) of each material were made for the dilatometric test. The chromel-alumel thermocouple required for the test was welded into the metal test specimens and inserted into the ceramics. ANOVA and Tukey's test revealed significant differences (p=0.01) for the MCBS test results (MPa), with PI showing higher MCBS (67.72) than the other pairs, which did not present any significant differences. The CTE (10-6 oC-1) differences were: VBI (0.54), VBD (1.33), VB2I (-0.14), VB2D (0.63), PI (1.84) and PD (2.62). Pearson's correlation test (r=0.17) was performed to evaluate of correlation between MCBS and CTE differences. Within the limitations of this study and based on the obtained results, there was no correlation between MCBS and CTE differences for the evaluated metal-ceramic pairs.