Ab initio pseudopotential study of vacancies and self-interstitials in hcp titanium

By means of an ab initio plane-wave pseudopotential method, monovacancy, divacancy and self-interstitials in hcp titanium are investigated. The calculated monovacancy formation energy is 1.97 eV, which is in excellent agreement with other theoretical calculations, and agrees qualitatively with published experimental results. The relaxation of the atoms around a single vacancy is observed to be small. Two divacancy configurations, the in-plane and the off-plane, have also been shown to be equally stable. With regards to the interstitials, of the eight configurations studied, two (octahedral and basal octahedral) have relatively lower formation energies and are, thus, the most likely stable configurations. We find small energy differences between them, suggesting their possible co-existence. It is also observed that the tetrahedral configuration decays to a split dumbbell configuration, whereas both the basal tetrahedral and the basal pseudocrowdion interstitials decay to the basal octahedral configuration. Using the nudged elastic band method (NEB), we determine a possible minimum energy path (MEP) for the diffusion of self-interstitial titanium atoms from an octahedral site to the nearest octahedral site. The energy barrier for this migration mechanism is shown to be about 0.20 eV.     

Defects in ion-implanted hcp-titanium: A first-principles study of electronic structures

The electronic structures of hexagonal closed-packed (h.c.p) titanium containing a vacancy and krypton impurity atoms at various insertion sites are calculated by first-principles methods in the framework of the density-functional theory (DFT). The density of states (DOS) for titanium containing a vacancy defect shows resonance-like features. Also, the bulk electron density decreases from ∼0.15/ų to ∼0.05/ų at the vacancy centre. Electronic structure calculations have been performed to investigate what underlies the krypton site preference in titanium. The DOS of the nearest-neighbour (NN) titanium atoms to the octahedral krypton appears to be less distorted (relative to pure titanium) when compared to the NN titanium atoms to the tetrahedral krypton. The electronic density deformation maps show that polarization of the titanium atoms is stronger when the krypton atom is located at the tetrahedral site. Since krypton is a closed-shell atom, thus precluding any bonding with the titanium atoms, we may conclude that the polarization of the electrons in the vicinity of the inserted krypton atoms and the distortion of the DOS of the NN titanium atoms to the krypton serve to indicate which defect site is preferred when a krypton atom is inserted into titanium. Based on these considerations, we conclude that the substitutional site is the most favourable one, and the octahedral is the preferred interstitial site, in agreement with recent DFT calculations of the energetics of krypton impurity sites.     

Influence of nitrogen implantation on thermoluminescence of synthetic quartz

Thermoluminescence (TL) of synthetic quartz exposed to beta irradiation following implantation with 60?keV N⁺ ions at fluences ranging between 1?×?10¹⁴ and 5?×?10¹⁵?ions/cm² is reported. The glow curve measured at 5°C/s typically consists of a prominent peak near 110°C, studied in this work, and minor glow peaks at around 130°C and 190°C. The TL intensity of the main peak increased both with implantation and with fluence of implantation. The dependence of the intensity on heating rate and fluence suggests that the implantation introduces new defects that may possibly act as recombination centres. The increase in TL intensity with the heating rate exhibited by implanted samples has been observed in other luminescence materials. This anti-quenching phenomenon has been described as a competition effect between multiple luminescence pathways in luminescence materials. Kinetic analysis of the main glow peak using the initial rise, various heating rate and glow curve deconvolution methods shows that the activation energy of the main peak is about 0.7?eV with no systematic change due to ion fluence.     

Thermal expansion of synthetic fused silica as a function of OH content and fictive temperature

A matrix of synthetic fused silica samples with OH contents from 30 to 1300 ppm and of a fictive temperature from 1000 to 1300 °C has been characterized regarding their thermal expansion with high precision. The thermal expansion increases with fictive temperature and drops with OH content. Although fictive temperature and OH are coupled due to the influence of OH on the relaxation of the network, an independent influence of the OH content on thermal expansion has been observed. This may provide a deeper insight into the impact of impurities incorporated into the fused silica network.     

Optimization of solvent selectivity for the chromatographic separation of fat-soluble vitamins using a mixture-design statistical technique

Summary A systematic approach, using a mixture-design statistical technique, has been developed for selecting the optimum mobile phase for the separation of fat-soluble vitamins in reversed-phase high-performance liquid chromatography. A quaternary mixture of methanol, acetonitrile, tetrahydrofuran and water was used as mobile phase. Retention time and peak width were recorded in ten runs augmented with five replicates and the data were subsequently fitted to special cubic polynomial models. The resulting mathematical equations enabled prediction of resolution over the entire parameter space. Contour plots of minimum effective resolution and maximum retention time as a function of mobile phase composition are presented and discussed. Visual inspection of these plots provides an overview of the quality of the separation and the analysis time required for each possible mobile-phase composition with n the parameter space. It is demonstrated that the methodology followed was an important tool which enabled the taking of informed decisions necessary for selection of the optimum mobile phase for a chromatographic separation. A combination ofR _S minimum andt _R maximum as optimization criteria in a multicriteria decision-making plot using pareto-optimality concept is discussed. This combination enabled visual demonstration of the compromise between separation quality and the economics of analysis time. Our methodology has been compared with the common used technique of ‘overlapping resolution mapping’.     

Influence of argon-implantation on conventional and phototransferred thermoluminescence of synthetic quartz

Conventional and phototransferred thermoluminescence of crystalline synthetic quartz implanted with 70 keV Ar ions at fluences in the range 1?×?10¹⁴–5?×?10¹⁵?ions/cm² is reported. The glow curves, recorded at 5°C/s from beta-irradiated samples of similar mass, show a prominent peak between 100°C and 120°C. The thermoluminescence intensity of all implanted samples was greater than that of the unimplanted one. The increase in sensitivity is attributed to a corresponding increase in the concentration of point defects, as a result of the implantation, which act as electron traps or recombination centres. Kinetic analysis carried out using the peak shape, whole glow-peak and curve-fitting methods produced values of the activation energy, frequency factor and order of kinetics that are generally independent of implantation fluence. This result suggests that implantation did not necessarily affect the nature of the electron traps. With respect to phototransferred thermoluminescence, it was observed that it only appeared in the sample implanted at the highest fluence of 5?×?10¹⁵?ions/cm². This may be so because the concentration of deep traps produced as a result of implantation at low fluence is too low to give rise to phototransferred thermoluminescence. The intensity of the phototransferred thermoluminescence goes through a peak with illumination time. We attribute this behaviour to the relative concentration of holes at recombination centres and phototransferred electrons at shallow traps.