Palladium-bismuth intermetallic and surface-poisoned catalysts for the semi-hydrogenation of 2-methyl-3-butyn-2-ol

The effects of poisoning of Pd catalysts with Bi and annealing in a polyol (ethylene glycol) were studied on the semi-hydrogenation of 2-methyl-3-butyn-2-ol (MBY). An increase in the Pd:Bi ratio from 7 to 1 in the Bi-poisoned catalysts decreased the hydrogenation activity due to blocking of active sites, but increased maximum alkene yield from 91.5% for the Pd catalyst to 94–96% for all Bi-poisoned Pd catalysts, by decreasing the adsorption energy of alkene molecules and suppressing the formation of β-hydride phase. Annealing of the catalysts induced the formation of intermetallic phases and decreased its activity due to sintering of the catalytic particles and low activity of intermetallic compounds. Langmuir–Hinshelwood kinetic modelling of the experimental data showed that poisoning of Pd with Bi changed the relative adsorption constants of organic species suggesting ligand effects at high Bi content

Lanthanides extraction processes in molten fluoride media. Application to nuclear spent fuel reprocessing

This paper describes four techniques of extraction of lanthanides elements (Ln) from molten salts in the general frame of reprocessing nuclear wastes; One of them is chemical: the precipitation of Ln ions in insoluble compounds (oxides or oxifluorides); the others use electrochemical methodology in molten fluorides for extraction and measurement of the progress of the processes: first electrodeposition of pure Ln metals on an inert cathode material was proved to be incomplete and cause problems for recovering the metal; electrodeposition of Ln in the form of alloys seems to be far more promising because on one hand the low activity of Ln shifts the electrodeposition potential in a more anodic range avoiding any overlapping with the solvent reduction and furthermore exhibit rapid process kinetics; two ways were examined: (i) obtention of alloys by reaction of the electroreducing Ln and the cathode in Ni or preferably in Cu, because in this case we obtain easily liquid compounds, that enhances sensibly the process kinetics; (ii) codeposition of Ln ions with aluminium ions on an inert cathode giving a well defined composition of the alloy. Each way was proved to give extraction efficiency close to unity in a moderate time

Hydrogen solubility in zirconium intermetallic second phase particles

The enthalpies of solution of H in Zr binary intermetallic compounds formed with Cu, Cr, Fe, Mo, Ni, Nb, Sn and V were calculated by means of density functional theory simulations and compared to that of H in {\alpha}-Zr. It is predicted that all Zr-rich phases (formed with Cu, Fe, Ni and Sn), and those phases formed with Nb and V, offer lower energy, more stable sites for H than {\alpha}-Zr. Conversely, Mo and Cr containing phases do not provide preferential solution sites for H. In all cases the most stable site for H are those that offer the highest coordination fraction of Zr atoms. Often these are four Zr tetrahedra but not always. Implications with respect to H-trapping properties of commonly observed ternary phases such as Zr(Cr,Fe)2, Zr2(Fe,Ni) and Zr(Nb,Fe)2 are also discussed.Comment: manuscript accepted for publication in Journal of Nuclear Materials (2013

Investigations of Zr(IV) in LiF-CaF2: stability with oxide ions and electroreduction pathway on inert and reactive electrodes

In this work, a detailed electrochemical study of the molten LiF-CaF2-ZrF4 system is provided in the 810-920°C temperature range, allowing the determination of the reduction potential, the diffusion coefficient and the reduction mechanism of dissolved Zr(IV) on an inert Ta electrode. Addition of CaO in the molten salt is shown to cause Zr(IV) precipitation into a mixture of solid compounds, most likely ZrO2 and ZrO1.3F1.4. Underpotential deposition of Zr on Cu and Ni electrodes is also evidenced

Reaction cured glass and glass coatings

The invention relates to reaction cured glass and glass coatings prepared by reacting a compound selected from the group consisting of silicon tetraboride, silicon hexaboride, other boron silicides, boron and mixtures with a reactive glass frit composed of a porous high silica borosilicate glass and boron oxide. The glassy composites of the present invention are useful as coatings on low density fibrous porous silica insulations used as heat shields and for articles such as reaction vessels that are subjected to high temperatures with rapid heating and cooling and that require resistance to temperature and repeated thermal shock at temperatures up to about 1482C (2700PF)

Microstructural and XRD analysis and study of the properties of the system Ti-TiAl-B4C processed under different operational conditions

High specific modulus materials are considered excellent for the aerospace industry. The system Ti-TiAl-B4C is presented herein as an alternative material. Secondary phases formed in situ during fabrication vary depending on the processing conditions and composition of the starting materials. The final behaviors of these materials are therefore difficult to predict. This research focuses on the study of the system Ti-TiAl-B4C, whereby relations between microstructure and properties can be predicted in terms of the processing parameters of the titanium matrix composites (TMCs). The powder metallurgy technique employed to fabricate the TMCs was that of inductive hot pressing (iHP) since it offers versatility and flexibility. The short processing time employed (5 min) was set in order to test the temperature as a major factor of influence in the secondary reactions. The pressure was also varied. In order to perform this research, not only were X-Ray Diffraction (XRD) analyses performed, but also microstructural characterization through Scanning Electron Microscopy (SEM). Significant results showed that there was an inflection temperature from which the trend to form secondary compounds depended on the starting material used. Hence, the addition of TiAl as an elementary blend or as prealloyed powder played a significant role in the final behavior of the TMCs fabricated, where the prealloyed TiAl provides a better precursor of the formation of the reinforcement phases from 1100 °C regardless of the pressur

Effect of iron on the microstructure and mechanical property of Al-Mg-Si-Mn and Al-Mg-Si diecast alloys

This article is made available through the Brunel Open Access Publishing Fund. Copyright @ 2012 Elsevier B.V.This article has been made available through the Brunel Open Access Publishing Fund.Al–Mg–Si based alloys can provide super ductility to satisfy the demands of thin wall castings in the application of automotive structure. In this work, the effect of iron on the microstructure and mechanical properties of the Al–Mg–Si diecast alloys with different Mn concentrations is investigated. The CALPHAD (acronym of Calculation of Phase Diagrams) modelling with the thermodynamic properties of the multi-component Al–Mg–Si–Mn–Fe and Al–Mg–Si–Fe systems is carried out to understand the role of alloying on the formation of different primary Fe-rich intermetallic compounds. The results showed that the Fe-rich intermetallic phases precipitate in two solidification stages in the high pressure die casting process: one is in the shot sleeve and the other is in the die cavity, resulting in the different morphologies and sizes. In the Al–Mg–Si–Mn alloys, the Fe-rich intermetallic phase formed in the shot sleeve exhibited coarse compact morphology and those formed in the die cavity were fine compact particles. Although with different morphologies, the compact intermetallics were identified as the same α-AlFeMnSi phase with typical composition of Al24(Fe,Mn)6Si2. With increased Fe content, β-AlFe was found in the microstructure with a long needle-shaped morphology, which was identified as Al13(Fe,Mn)4Si0.25. In the Al–Mg–Si alloy, the identified Fe-rich intermetallics included the compact α-AlFeSi phase with typical composition of Al8Fe2Si and the needle-shaped β-AlFe phase with typical composition of Al13Fe4. Generally, the existence of iron in the alloy slightly increases the yield strength, but significantly reduces the elongation. The ultimate tensile strength maintains at similar levels when Fe contents is less than 0.5 wt%, but decreases significantly with the further increased Fe concentration in the alloys. CALPHAD modelling shows that the addition of Mn enlarges the Fe tolerance for the formation of α-AlFeMnSi intermetallics and suppresses the formation of β-AlFe phase in the Al–Mg–Si alloys, and thus improves their mechanical properties.EPSRC and JL

Investigation on some factors affecting crack formation in high resistance aluminum alloys

Aluminum alloys having good mechanical properties are Al-Zn-Mg alloys (7xxx) and Al-Cu-Li alloys (Weldalite®). These alloys may be subjected to stress corrosion cracking. In order to overcome this problem the Al 7050 alloy has been developed and it is widely used for aerospace applications. Despite that, some components made of this alloy cracked during the manufacturing process including machining and chemical anodization. In a previous work cracked Al 7050 components have been analyzed in order to identify possible causes of crack formation. In this work the susceptibility of this alloy to intergranular corrosion has been analysed and compared with that of other high resistance aluminum alloys