Influence of temperature on hydrogen electrosorption into palladium-noble metal alloys. Part 2—Palladium–platinum alloys

Hydrogen electrosorption into Pd-rich (>75 at.% Pd in the bulk) Pd–Pt alloys obtained by electrodeposition was studied in acidic solutions (0.5 M H₂SO₄) using cyclic voltammetry and chronoamperometry. The influence of temperature (in the range between 283 and 328 K) on the amount of absorbed hydrogen, the potential of the α–β phase transition, the extent of absorption–desorption hysteresis and the potential of absorbed hydrogen oxidation was examined. It has been found that for the temperature range studied the potentials of the α → β and β → α phase transitions are shifted negatively with both increasing temperature and decreasing Pd content in the alloy bulk. Thermodynamic parameters (Gibbs free energy, enthalpy and entropy) of the β-phase formation and decomposition were determined. With decreasing Pd bulk content the process of the β-phase formation becomes less exothermic and the thermodynamic stability of the β-phase decreases. The maximum hydrogen absorption capacity of Pd–Pt alloys decreases with increasing temperature and decreasing Pd bulk content. The potential of absorbed hydrogen oxidation is shifted negatively with increasing temperature and decreasing Pd bulk content.     

Electrosorption of hydrogen into palladium-rhodium alloys

Hydrogen electrosorption into Pd-Rh alloys has been studied in acidic solutions (0.5 M H₂SO₄) using cyclic voltammetry and chronoamperometry. Pd-Rh electrodes were prepared as thin alloy electrodeposits on Au wires. The influence of electrode potential on the amount of electrosorbed hydrogen was investigated. One can distinguish potential regions of α- and β-phase existence as well as the region of α-β phase transition. For alloys containing less than 20 at.% Rh in the bulk the hydrogen-to-metal ratio, H/(Pd + Rh), is greater than for pure Pd. The maximum value of the H/(Pd + Pt) ratio is 0.80 for an alloy containing in the bulk 94 at.% Pd and 6 at.% Rh. Due to a smaller lattice parameter of the Pd-Rh alloy with respect to pure Pd the α-β phase transition occurs at lower potentials than in Pd. The hysteresis is observed in chronoamperometric absorption and desorption experiments; the effect of hysteresis decreases with the increase in Rh content. Additionally, preliminary results are presented concerning the electrochemical quartz crystal microbalance measurements of hydrogen absorption/desorption into/from Pd-Rh alloys in comparison with Pd.     

Hydrogen electrosorption into Pd-Pt-Au ternary alloys

Thin layers of Pd-Pt-Au alloys were prepared by metal codeposition at constant potential from chloride solutions. The process of hydrogen electrosorption into Pd-Pt-Au alloys was investigated in acidic solution (0.5 M H₂SO₄) using cyclic voltammetry and chronoamperometry, also coupled with the electrochemical quartz crystal microbalance. It was found that Pd alloying with both Pt and Au decreases the maximum hydrogen solubility, but improves the kinetics of absorbed hydrogen oxidation, which is mirrored in a negative shift of the potential of hydrogen desorption peak and shorter hydrogen desorption time. In Pd-Pt-Au alloys the effect of absorption/desorption hysteresis and the stresses connected with hydrogen absorption are reduced in comparison with pure Pd. After prior hydrogen absorption in Pd-Pt-Au alloys, surface oxides are formed and reduced at potentials even by 200 mV lower than before hydrogen treatment.     

Effect of Al content on the corrosion behavior of Mg-Al alloys in aqueous solutions of different pH

The effect of systematic increase of Al content on the electrochemical behavior of the Mg-Al alloys in aqueous solutions of different pH was investigated. Different electrochemical methods such as open-circuit potential measurements, polarization techniques and electrochemical impedance spectroscopy, EIS, were used to investigate the electrochemical behavior of the alloys in aqueous solutions. The results have shown that Mg-5Al is easily corroded due to the microgalvanic effect between α-phase and β-phase, its corrosion rate is even higher than that of Mg itself. The increase of Al content increases the corrosion resistance of the alloy due to the formation of the β-phase (Mg₁₇Al₁₂) together with the Mg α-phase. The ranking of the corrosion rate of these alloys was Mg-5Al > Mg > Mg-10Al ≅ Mg-15Al. The corrosion rates of the alloys in acidic solutions are pronouncedly high compared to those measured in neutral or basic solutions. The impedance measurements are in consistence with the polarization techniques and the impedance data were fitted to theoretical data obtained according to an equivalent circuit model describing the electrode/electrolyte interface.     

Properties of Ni1−xFex (0.1 < x < 0.9) and Invar (x = 0.64) alloys obtained by electrodeposition

Electrodeposition of Ni_1−xFe_x (x = 0.1-0.9) films was carried out from a chloride plating solution containing saccharin as an organic additive at a constant current density (5 mA/cm²) and a controlled pH of 2.5. X-ray diffraction studies revealed the existence of an fcc, or γ phase, in the range of 10-58 wt.% Fe, a mixed fcc/bcc phase in the range of 59-60 wt.% Fe, and a bcc, or α phase in the range of 64-90 wt.% Fe. The saturation magnetization, B_s, of electrodeposited Ni_1−xFe_x alloys at the room temperature was found to increase with the increase of Fe-content and follows the Slater-Pauling curve, but deviates from as-cast bulk NiFe alloys. The coefficient of thermal expansion, CTE, of electrodeposited alloys at room temperature also deviates from as-cast bulk NiFe alloys. Annealing of α-Ni₃₆Fe₆₄ alloy results in a martensitic α → γ phase transformation, which takes place between 300 and 400 °C. It was demonstrated that thermal treatment above 400 °C was necessary to obtain magnetic and mechanical properties similar to those to conventional Invar alloy. Annealing of α-Ni₃₆Fe₆₄ alloy at 700 °C brings about a decrease of B_s from 1.75 to 0.45 T. By controlling the annealing conditions of α → γ martensitic transformation, it is possible to adjust the CTE of Ni₃₆Fe₆₄ alloy over the broad limits from 2.7 to 8.7 × 10⁻⁶/°C.     

Influence of microstructure and composition on the corrosion behaviour of Mg/Al alloys in chloride media

The influence of the microstructure and aluminium content of commercial AZ31, AZ80 and AZ91D magnesium alloys was evaluated in terms of their corrosion behaviour in an aerated 3.5 wt.% NaCl solution at 25 °C. The corrosion process was monitored by electrochemical impedance spectroscopy (EIS). The surface was characterized by scanning electron microscopy (SEM), scanning Kelvin probe force microscopy (SKPFM) and low-angle X-ray diffraction (XRD). The extent of corrosion damage was strongly dependent on the aluminium content and alloy microstructure. Two key factors were observed for the lowest corrosion rates, which occurred for the AZ80 and AZ91D two-phase alloys: the aluminium enrichment on the corroded surface for the AZ80 alloy, and the β-phase (Mg₁₇Al₁₂), which acted as a barrier for the corrosion progress for the AZ80 and AZ91D alloys. Surface potential maps suggested that, between the β-phase and the α-matrix, the galvanic coupling was not significant.     

Electrochemical formation of Mg-Li alloys at solid magnesium electrode from LiCl-KCl melts

This work presents a study on electrochemical formation of Mg-Li alloys on solid magnesium electrode in a molten LiCl-KCl (50:50, wt.%) system at 753 K. Cyclic voltammetry and open circuit chronopotentiometry were employed to investigate the electrode reaction. For an Mg electrode, the electroreduction of Li(I) takes place at more positive potential values than at the inert W electrode indicating the formation of Mg-Li alloys. X-ray diffraction and scanning electron microscopy (SEM) analysis of the deposits indicated that α, α + β and β phases Mg-Li alloys with the thickness of 182, 365 and 2140 μm were obtained by potentiostatic electrolysis at −2.26, −2.30 and −2.39 V (vs. Ag/AgCl), respectively. The results showed that formation of α, α + β and β phases Mg-Li alloys could be controlled by applied potential. Lithium contents of Mg-Li alloys can be decreased via electrolysis at low temperature followed by thermal treatment at higher temperature. Mg-Li alloys with excellent mechanical properties can be produced by this novel method.     

Structure and electric properties of poly(vinylidene fluoride-tetrafluoroethylene) copolymer studied with density functional theory

The internal rotation, geometry, energy, vibrational spectra, dipole moments and molecular mean polarizabilities of poly(vinylidene fluoride-tetrafluoroethylene) (P(VDF-TeFE)) of α- and β-chain models were studied with density functional theory at B3PW91/6-31G(d) level and compared with those of poly(vinylidene fluoride) homopolymer and P(VDF-TrFE) copolymer. The electric properties, chain conformation and stability of the copolymer influenced by the chain length and TeFE content were examined. Based on the internal rotation curves of P(VDF-TeFE) dimer models (H[CH₂CF₂-CF₂CF₂]H and H[CF₂CH₂-CF₂CF₂]H), the conformational angles, relative stabilities of α- and β-conformation, and the transition energy barriers of β → α and α → β were discussed. The results show that the β-conformation is more stable than the α-conformation thermodynamically and the β → α transition in P(VDF-TeFE) is more difficult than that in PVDF. Thus the copolymer should be in favor of preventing the piezoelectric phase from depolarization. The ideal β-chains are curved with a radius of about 30 Å, which is very close to those in both PVDF and P(VDF-TrFE). Similar to P(VDF-TrFE), the α-chain P(VDF-TeFE) containing 0.50 mole fraction of TeFE is also a helical structure. However, the α-chain with 0.33-0.20 mole fraction of TeFE are almost linear in structure, which might be responsible for enhancing crystallinity of the copolymer. The contribution of average dipole moment per monomer unit in the β-chain is affected by the chain curvature and TeFE content, and there is a weakly parabolic dependence on the VDF content. The chain length and TeFE content will not significantly affect the mean polarizability per monomer unit. The calculations show that there are some characteristic vibrational modes that may be used in the identification of the α- and β-phase P(VDF-TeFE) with different TeFE contents.     

Synthesis and electrochemical study of nanoporous Pd-Ag alloys for hydrogen sorption

We report on the synthesis of novel nanoporous Pd-Ag electrocatalysts using a facile hydrothermal method where the portion of Ag was varied from 0 to 40%. Scanning electron microscopy (SEM) was used to examine the morphologies of the prepared nanoporous materials. Energy dispersive X-ray spectroscopy (EDS), X-ray photoelectron spectroscopy (XPS) and inductively coupled plasma (ICP) were used to directly and indirectly characterize the composition of the formed Pd-Ag nanostructures. X-ray diffraction (XRD) analysis confirmed that the formed Pd-Ag nanomaterials were alloys with a face-centered cubic structure. Electrochemical methods were used to study the capacity and kinetics of hydrogen sorption into the nanoporous Pd and Pd-Ag alloys. The nanoporous Pd-Ag alloy with 20% silver possesses the highest capacity for the α phase hydrogen sorption, which is over 4 times higher than the pure nanoporous Pd. The combination of the enhanced α phase hydrogen sorption capacity and diminishing of the α- and β-phase transition makes the nanoporous Pd-Ag alloys promising for hydrogen selective membranes and hydrogen dissociation catalysts.     

Structure, phase transition and electric properties of poly(vinylidene fluoride-trifluoroethylene) copolymer studied with density functional theory

The geometry, energy, internal rotation, vibrational spectra, dipole moments and molecular polarizabilities of poly(vinylidene fluoride-trifluoroethylene) (P(VDF-TrFE)) of α- and β-chain models were studied with density functional theory at B3PW91/6-31G(d) level and compared with those of the poly(vinylidene fluoride) (PVDF) homopolymer. The chain length and the trifluoroethylene (TrFE) concentration were examined to discuss the copolymer chain stabilities, chain conformations and electric properties. The asymmetrical internal-rotation potential energy curve shows that the angles for the g and g′ conformations in the α-chain (tg and tg′) models are 53° and −70°, respectively, and the β-chain (ttt) conformation is a slightly distorted all-trans plane with dihedral angle at 177°. The energy differences, E_β − E_α(g) and E_β − E_α(g′), between the β- and the α-conformation are 2.1 and 7.8 kJ/mol, respectively. These values are smaller than that in PVDF (8.4 kJ/mol), suggesting that the β-conformation in the copolymer will be more stable than in PVDF. The energy barriers for β → α(g) and β → α(g′) transitions are 16.2 and 5.8 kJ/mol, respectively. The former is almost twice of the energy barrier in PVDF by 8.2 kJ/mol and the latter is slightly smaller (by 2.4 kJ/mol) than that in PVDF. The respective energy barriers for α(g) → β and α(g′) → β transitions are 18.3 and 13.6 kJ/mol compared with the value 16.3 kJ/mol in PVDF. The asymmetrical energy barriers may be one of the reasons for the copolymers with 0.5-0.6 (mole fraction) VDF exhibiting complicated phase transition behavior. The conformation of α-chain P(VDF-TrFE) exhibits from a helical (containing higher TrFE) to a nearly beeline (containing lower TrFE). This behavior is different from that in the PVDF and the nearly beeline conformation might be responsible for the increasing crystallizability. The helical might also be associated with the complicated phase transition behavior and the larger lattice strain in the P(VDF-TrFE)s with higher TrFE concentration. The energy difference per monomer unit between the β- and α-chain decreases with increasing TrFE content. The ideal β-chain is curved with a radius of about 30 Å, which is similar to that in PVDF. The chain curvature and the TrFE content will affect the dipole moment contribution per monomer. The chain length and TrFE content will not significantly affect the mean polarizability. The calculations indicated that there are some additional characteristic vibrational modes that may be used in identification of the α- or β-phase P(VDF-TrFE)s with different TrFE contents.     

Electrochemical behavior of palladium-gold alloys

The behavior of Pd-Au alloys, prepared by electrochemical codeposition, has been studied in acidic solutions (1 M H₂SO₄) using mainly the cyclic voltammetry technique. Morphology of the alloy surface and bulk compositions were examined by SEM/EDAX method. Various types of voltametric behavior during potential cycling in the oxygen region are presented. The influence of hydrogen absorption on electrochemical properties of surface oxides is demonstrated. The problem of the nature of oxygen electrochemisorbed on Pd-Au alloys is discussed.     

Separation of hydrogen adsorption and absorption on Pd thin films

Hydrogen sorption at Pd films of 20-80 nm deposited on a polycrystalline gold electrode was studied in sulfuric and perchloric acid. Assuming that the hydrogen adsorption does not vary with the Pd films thickness, hydrogen adsorption/absorption charges in Pd were separated in the two contributions in the hydrogen-poor α-Pd-H phase. The results are compared to those obtained at Pd monolayers on Au(1 1 1). The adsorption on polycrystalline Pd begins at potentials more negative than on 0.8 ML Pd on Au(1 1 1) and is not much affected by the nature of anion (sulfate or perchlorate), contrary to the thin layers on Au(1 1 1). The absorption charge in α-PdH phase in the potential range of 0.08-0.15 V was found to be similar to that at a 25 μm Pd foil in this potential range while at more positive potentials it is larger. In the presence of crystal violet which adsorbs at the electrode surface it was found that some residual H adsorption exists. There is more hydrogen absorbed in Pd in the presence of crystal violet in the hydrogen-poor α phase but in the hydrogen-rich β phase the amount of hydrogen is the same.     

The effect of solvent quality on the chain morphology in solutions of poly(9,9′-dioctylfluorene)

The thermodynamics of the alpha (α) phase to beta (β) phase transition was investigated in solution of poly(9,9′-dioctylfluorene) in a variety of solvents with UV-vis absorption spectroscopy, differential scanning calorimetry, fluorescence spectroscopy, atomic force microscopy, and near-field scanning optical microscopy. The results show that the solvent quality has a strong affect on the α- to β-conformational change. The trend in enthalpies and transition temperatures indicates that the transition results from an increase in intramolecular interactions upon chain collapse at lower temperatures. This transition leads to subsequent gelation and/or aggregation that stabilizes the β-phase at higher temperatures and leads to a large hysteresis in the transition temperature. The enthalpy for the transition from an aggregated β-phase to a fully solvated α-phase is found to be 21.04 kJ mol⁻¹ of monomer for toluene solutions. Differences between the measured heat and those previously reported are discussed.     

Electrolytic loading of hydrogen in Zr65(Pd80Rh20)35 and Zr65Pd35 alloys prepared by mechanical grinding and in their oxidised derivatives

Zr₆₅(Pd₈₀Rh₂₀)₃₅ and Zr₆₅Pd₃₅ alloys were prepared by mechanical grinding of stoichiometric amounts of either ZrH₂ and Pd₈₀Rh₂₀ or ZrH₂ and Pd. Following a suggestion in the literature, these alloys were converted by thermal oxidation in air into the corresponding ZrO₂(Pd₈₀Rh₂₀) and ZrO₂Pd compounds, which are probably composed of Pd₈₀Rh₂₀ and Pd nanostructures embedded in ZrO₂.The aim of our work thereafter was to investigate hydrogen storage in these nanostructures. Both the alloys and their oxidation derivatives were thus loaded with hydrogen by cathodic reduction at 25 °C in 6 M KOH, and loaded hydrogen was then determined by anodic extraction. On comparing the hydriding extent of the alloys with that of the corresponding oxidation derivatives, the metal clusters which formed after thermal oxidation are probably much larger in PdRh than in Pd. The former exhibits the high decomposition pressure typical of massive Pd₈₀Rh₂₀ hydride, and the maximum [H]/[Pd_0.8Rh_0.2] atom ratio is ≈0.82. Conversely, the amount of hydrogen extracted from reduced ZrO₂Pd samples prepared in optimal conditions fits [H]/[Pd] atom ratios between 1 and 2. The shape of the electrochemical hydrogen desorption isotherms indicates that the hydrogen in excess of the β-Pd hydride phase is probably stored in a new, very stable form.     

Study on the preparation of Mg-Li-Zn alloys by electrochemical codeposition from LiCl-KCl-MgCl2-ZnCl2 melts

Electrochemical codeposition of Mg, Li, and Zn on a molybdenum electrode in LiCl-KCl-MgCl₂-ZnCl₂ melts at 943 K to form Mg-Li-Zn alloys was investigated. Cyclic voltammograms (CVs) showed that the potential of Li metal deposition, after the addition of MgCl₂ and ZnCl₂, is more positive than the one of Li metal deposition before the addition. Chronopotentiometry measurements indicated that the codeposition of Mg, Li, and Zn occurs at current densities lower than −0.78 A cm⁻² in LiCl-KCl-MgCl₂ (8 wt.%) melts containing 1 wt.% ZnCl₂. Chronoamperograms demonstrated that the onset potential for the codeposition of Mg, Li, and Zn is −2.000 V, and the codeposition of Mg, Li, and Zn is formed when the applied potentials are more negative than −2.000 V. X-ray diffraction (XRD) indicated that Mg-Li-Zn alloys with different phases were prepared via galvanostatic electrolysis. The microstructure of typical α + β phase of Mg-Li-Zn alloy was characterized by optical microscope (OM) and scanning electron microscopy (SEM). The analysis of energy dispersive spectrometry (EDS) showed that the elements of Mg and Zn distribute homogeneously in the Mg-Li-Zn alloy. The results of inductively coupled plasma analysis showed that the chemical compositions of Mg-Li-Zn alloys are consistent with the phase structures of the XRD patterns, and that the lithium and zincum contents of Mg-Li-Zn alloys depend on the concentrations of MgCl₂ and ZnCl₂.     

Electrochemical growth and dissolution of Ni on bimetallic Pd/Au(1 1 1) substrates

In this work we study the electrochemical growth and dissolution of a Ni on Pd-Au(1 1 1) bimetallic surfaces using in situ scanning tunnelling microscopy. We also compare Ni deposition on monometallic electrodes, i.e. Au(1 1 1) and Pd(1ML)/Au(1 1 1), using electrochemical characterizations. Results evidence that the first Ni monolayer grows preferentially on Au(1 1 1) in a wide potential range, and that a full Ni monolayer covering the entire Pd-Au surface can be selectively dissolved from Pd islands. No such selectivity is observed upon growth of subsequent Ni atomic planes. We demonstrate that the Ni-substrate interactions play a key role in the above mentioned selectivity. The binding energy of Ni to Pd is found to be 80 meV smaller than of Ni to Au. The sign and the amplitude of this difference are discussed in light of the d band filling of the Pd-Au(1 1 1) bimetallic surface and the presence of adsorbed H on Pd before deposition.     

Effects of whisker-like β-Si3N4 seeds on phase transformation and mechanical properties of α/β Si3N4 composites using MgSiN2 as additives

α/β Si₃N₄ composites with β-Si₃N₄ content ranging from 26% to 100% were hot-pressed with or without β-Si₃N₄ seeds, using MgSiN₂ as additives, and their mechanical properties were investigated. When the α-Si₃N₄ content was over 58%, the microhardness of α/β Si₃N₄ composites was in the range of 23–24 GPa, and then the indentation hardness decreases with decreasing the content of α-Si₃N₄, whether with β-Si₃N₄ seeds or not. The toughness increased with increasing elongated β-Si₃N₄ grains, which improved fracture resistance by crack bridging, pull out or the crack deflection mechanism, and reached the maximum value of 7.0 MPa m^1/2 with 1 wt% β-seeds. In comparison with α/β Si₃N₄ composite with a similar phase composition, the fracture strength was improved by adding β-Si₃N₄ seeds because of the relatively smaller grain sizes and higher toughness. The α/β Si₃N₄ composite with 5 wt% β-seeds showed a high strength of 1253 MPa, a high hardness of 20.9 GPa and a toughness of 6.9 MPa m^1/2.     

Novel attempts for the synthesis of calcium sulfate hydrates in calcium chloride solutions under atmospheric conditions

The medical grade calcium sulfate is widely used in clinical applications for treating bone defects. A high-purity and predictable calcium sulfate (CS) synthesis process is desirable in the medical industry. The objective of this study was to develop a one-pot method for the direct preparation of calcium sulfate hemihydrates (CSHs; such as the α- and β-forms) in a CaCl₂ solution. CS was synthesized by mixing K₂SO₄ and Ca(NO₃)₂·4H₂O under various CaCl_2(aq) concentrations and reaction temperatures under atmospheric pressure. The calcium sulfate dihydrate (CSD) was found to be an intermediate phase that converts to CSH during the synthesis process, and α-CSH was gradually transformed from β-CSH over time. Moreover, the kinetic of CSD conversion to CSH was strongly accelerated by increasing the CaCl₂ concentration. As the reaction temperature was fixed in 90 °C, the form of the CS reactant with an increase in the CaCl₂ concentration was in the following sequence: CSD → CSD + β-CSH → CSD + β-CSH + α-CSH → α-CSH. In this study, the synthesis processing window of the CS reactant was established according the test results, and it is worth noting that all phases of CS hydrate could be synthesized with this system and well predicted by the constructed processing window.     

Polymorphism of syndiotactic polystyrene: γ phase crystallization induced by bulky non-guest solvents

The crystallization of amorphous syndiotactic polystyrene (s-PS) films when induced by bulky solvents, whose molecules are too big to be enclosed as guest of s-PS clathrate phases, generally leads to the formation of γ-phase. This kind of solvent induced crystallization in amorphous films generates a preferential (200) uniplanar orientation of the γ-crystalline phase. Moreover, the presence of highly boiling solvents in the amorphous phase of these γ-form samples can induce a γ→β phase transition, as a consequence of thermal annealing procedures at atmospheric pressure. A comparison with literature data suggests that the formation of the thermodynamically stable β-phase is generally favored with respect to the formation of the kinetically favored α-phase, by any s-PS dilution.     

Effects of the initial α-SiC content on the microstructure, mechanical properties, and permeability of macroporous silicon carbide ceramics

By using α- and/or β-SiC staring powders, the effects of the initial α-phase content on the microstructure, mechanical properties, and permeability of macroporous SiC ceramics were investigated. When β-SiC powder or a mixture of α/β powders containing a small amount (≤10%) of α-SiC powder was used, the microstructure consisted of large platelet grains. In contrast, when using α-SiC powder or α/β powders containing a large amount (>10%) of α powders, the microstructure consisted of small equiaxed grains. The development of large α-SiC platelet grains in the microstructure did not result in any improvement of the flexural strength of the macroporous SiC ceramics because of the accompanying pore growth and grain growth. The growth of the platelet-SiC grains was beneficial in increasing the gas permeability of the macroporous SiC ceramics from 4.12 × 10⁻¹³ m² for macroporous SiC with an equiaxed microstructure to 1.89 × 10⁻¹² m² for macroporous SiC ceramics with large platelet grains.