Sulfate-enhanced catalytic destruction of 1,1,1-trichlorethane over Pt(111)

The catalytic destruction of 1,1,1-trichloroethane (TCA) over model sulfated Pt(111) surfaces has been investigated by fast X-ray photoelectron spectroscopy and mass spectrometry. TCA adsorbs molecularly over SO4 precovered Pt(111) at 100 K, with a saturation coverage of 0.4 monolayer (ML) comparable to that on the bare surface. Surface crowding perturbs both TCA and SO4 species within the mixed adlayer, evidenced by strong, coverage-dependent C 1s and Cl and S 2p core-level shifts. TCA undergoes complete dechlorination above 170 K, accompanied by C−C bond cleavage to form surface CH3, CO, and Cl moieties. These in turn react between 170 and 350 K to evolve gaseous CO2, C2H6, and H2O. Subsequent CH3 dehydrogenation and combustion occurs between 350 and 450 K, again liberating CO2 and water. Combustion is accompanied by SO4 reduction, with the coincident evolution of gas phase SO2 and CO2 suggesting the formation of a CO−SOx surface complex. Reactively formed HCl desorbs in a single state at 400 K. Only trace (<0.06 ML) residual atomic carbon and chlorine remain on the surface by 500 K.

Analysis of femtosecond laser surface patterning on bulk single-crystalline diamond

Preliminary work is reported on 2-D and 3-D microstructures written directly with a Yb:YAG 1026 nm femtosecond (fs) laser on bulk chemical vapour deposition (CVD) single-crystalline diamond. Smooth graphitic lines and other structures were written on the surface of a CVD diamond sample with a thickness of 0.7mm under low laser fluences. This capability opens up the opportunity for making electronic devices and micro-electromechanical structures on diamond substrates. The fabrication process was optimised through testing a range of laser energies at a 100 kHz repetition rate with sub-500fs pulses. These graphitic lines and structures have been characterised using optical microscopy, Raman spectroscopy, X-ray photoelectron spectroscopy and atomic force microscopy. Using these analysis techniques, the formation of sp2 and sp3 bonds is explored and the ratio between sp2 and sp3 bonds after fs laser patterning is quantified. We present the early findings from this study and characterise the relationship between the graphitic line formation and the different fs laser exposure conditions. © 2012 Taylor & Francis.

Physical and biological properties of a novel siloxane adhesive for soft tissue applications

The aim of this study was to investigate the adhesive properties of an in-house amino-propyltrimethoxysilane-methylenebisacrylamide (APTMS-MBA) siloxane system and compare them with a commercially available adhesive, n-butyl cyanoacrylate (nBCA). The ability of the material to perform as a soft tissue adhesive was established by measuring the physical (bond strength, curing time) and biological (cytotoxicity) properties of the adhesives on cartilage. Complementary physical techniques, X-ray photoelectron spectroscopy, Raman and infrared imaging, enabled the mode of action of the adhesive to the cartilage surface to be determined. Adhesion strength to cartilage was measured using a simple butt joint test after storage in phosphate-buffered saline solution at 37°C for periods up to 1 month. The adhesives were also characterised using two in vitro biological techniques. A live/dead stain assay enabled a measure of the viability of chondrocytes attached to the two adhesives to be made. A water-soluble tetrazolium assay was carried out using two different cell types, human dermal fibroblasts and ovine meniscal chondrocytes, in order to measure material cytotoxicity as a function of both supernatant concentration and time. IR imaging of the surface of cartilage treated with APTMS-MBA siloxane adhesive indicated that the adhesive penetrated the tissue surface marginally compared to nBCA which showed a greater depth of penetration. The curing time and adhesion strength values for APTMS-MBA siloxane and nBCA adhesives were measured to be 60 s/0.23 MPa and 38 min/0.62 MPa, respectively. These materials were found to be significantly stronger than either commercially available fibrin (0.02 MPa) or gelatin resorcinol formaldehyde (GRF) adhesives (0.1 MPa) (P <0.01). Cell culture experiments revealed that APTMS-MBA siloxane adhesive induced 2% cell death compared to 95% for the nBCA adhesive, which extended to a depth of approximately 100-150 μm into the cartilage surface. The WST-1 assay demonstrated that APTMS-MBA siloxane was significantly less cytotoxic than nBCA adhesive as an undiluted conditioned supernatant (P <0.001). These results suggest that the APTMS-MBA siloxane may be a useful adhesive for medical applications. © VSP 2005.

Direct observation of extremely low temperature catalytic dehydrochlorination of 1,1,1-trichloroethane over platinum

Fast X-ray photoelectron spectroscopy reveals that the efficient catalytic destruction of 1,1,1-trichloroethane occurs over Pt{111} surfaces at temperatures as low as 150 K. Decomposition occurs via rapid, sequential C-Cl bond scission to form an alkylidyne surface intermediate that in turn dehydrogenates above room temperature. Atomic chlorine liberated during dehydrochlorination undergoes efficient reaction with surface hydrogen, resulting in the evolution of gaseous HCl and small amounts of ethane, presumably via ethylidyne hydrogenation. Irreversible dehydrogenation of residual hydrocarbon fragments results in significant surface coking above 500 K.

Epitaxial growth and magnetic properties of half-metallic Fe3O4 on GaAs(100)

The growth and magnetic properties of epitaxial magnetite Fe3O4 on GaAs(100) have been studied by reflection high-energy electron diffraction, x-ray photoelectron spectroscopy, magneto-optical Kerr effect, and x-ray magnetic circular dichroism. The epitaxial Fe3O4 films were synthesized by in situ post growth annealing of ultrathin epitaxial Fe films at 500K in an oxygen partial pressure of 5×10−5mbar. The XMCD measurements show characteristic contributions from different sites of the ferrimagnetic magnetite unit cell, namely, Fetd3+, Feoh2+, and Feoh3+. The epitaxial relationship was found to be Fe3O4(100)⟨011⟩∕∕GaAs(100)⟨010⟩ with the unit cell of Fe3O4 rotated by 45° to match that of GaAs(100) substrate. The films show a uniaxial magnetic anisotropy in a thickness range of about 2.0–6.0nm with the easy axes along the [011] direction of the GaAs(100) substrate.

Low temperature 1,1,1-trichloroethane dehydrochlorination over Pt catalysts:from model surfaces to the real world

Fast X-ray photoelectron spectroscopy reveals efficient C–Cl activation of 1,1,1-trichloroethane occurs over platinum surfaces at 150 K, and in the presence of hydrogen, sustained ambient temperature dehydrochlorination to HCl and ethane is possible over supported Pt/Al2O3 catalysts.

Ferroelectric and dielectric properties of Nd2−xCexTi2O7 ceramics

The solid solution system Nd2−xCexTi2O7 has been investigated. The solubility limit of Ce in Nd2−xCexTi2O7 was found to be 0·5–0·75 according to X-ray diffraction and X-ray photoelectron spectroscopy results. Ce substitution increases the b and c axes and the volume of the unit cell due to its larger ionic radius. Nd2−xCexTi2O7 (x  = 0·05, 0·25, 0·5, 0·75) textured ceramics were fabricated using spark plasma sintering. The ferroelectric and dielectric properties of the ceramics were studied. Ce substitution decreases the Curie point Tc of Nd2−xCexTi2O7 compounds. The results suggest that the Tc of Ce2Ti2O7 is <1445°C.

Fibronectin/phosphorylcholine coatings on fluorocarboned surfaces: a study upon adsorption and grafting processes

Depuis ces dernières décennies, le domaine des biomatériaux a connu un essor considérable, évoluant de simples prothèses aux dispositifs les plus complexes pouvant détenir une bioactivité spécifique. Outre, le progrès en science des matériaux et une meilleure compréhension des systèmes biologiques a offert la possibilité de créer des matériaux synthétiques pouvant moduler et stimuler une réponse biologique déterminée, tout en améliorant considérablement la performance clinique des biomatériaux. En ce qui concerne les dispositifs cardiovasculaires, divers recouvrements ont été développés et étudiés dans le but de modifier les propriétés de surface et d’améliorer l’efficacité clinique des tuteurs. En effet, lorsqu’un dispositif médical est implanté dans le corps humain, son succès clinique est fortement influencé par les premières interactions que sa surface établit avec les tissus et les fluides biologiques environnants. Le recouvrement à la surface de biomatériaux par diverses molécules ayant des propriétés complémentaires constitue une approche intéressante pour atteindre différentes cibles biologiques et orienter la réponse de l’hôte. De ce fait, l’élucidation de l’interaction entre les différentes molécules composant les recouvrements est pertinente pour prédire la conservation de leurs propriétés biologiques spécifiques. Dans ce travail, des recouvrements pour des applications cardiovasculaires ont été créés, composés de deux molécules ayant des propriétés biologiques complémentaires : la fibronectine (FN) afin de promouvoir l’endothélialisation et la phosphorylcholine (PRC) pour favoriser l’hémocompatibilité. Des techniques d’adsorption et de greffage ont été appliquées pour créer différents recouvrements de ces deux biomolécules sur un polymère fluorocarboné déposé par traitement plasma sur un substrat en acier inoxydable. Dans un premier temps, des films de polytétrafluoroéthylène (PTFE) ont été utilisés en tant que surface modèle afin d’explorer l’interaction de la PRC et de la FN avec les surfaces fluorocarbonées ainsi qu’avec des cellules endothéliales et du sang. La stabilité des recouvrements de FN sur l’acier inoxydable a été étudiée par déformation, mais également par des essais statiques et dynamiques sous-flux. Les recouvrements ont été caractérisés par Spectroscopie Photoéléctronique par Rayons X, immunomarquage, angle de contact, Microscopie Électronique de Balayage, Microscopie de Force Atomique et Spectrométrie de Masse à Ionisation Secondaire à Temps de Vol (imagerie et profilage en profondeur). Des tests d’hémocompatibilité ont été effectués et l’interaction des cellules endothéliales avec les recouvrements a également été évaluée. La FN greffée a présenté des recouvrements plus denses et homogènes alors que la PRC quant à elle, a montré une meilleure homogénéité lorsqu’elle était adsorbée. La caractérisation de la surface des échantillons contenant FN/PRC a été corrélée aux propriétés biologiques et les recouvrements pour lesquels la FN a été greffée suivie de l’adsorption de la PRC ont présenté les meilleurs résultats pour des applications cardiovasculaires : la promotion de l’endothélialisation et des propriétés d’hémocompatibilité. Concernant les tests de stabilité, les recouvrements de FN greffée ont présenté une plus grande stabilité et densité que dans le cas de l’adsorption. En effet, la pertinence de présenter des investigations des essais sous-flux versus des essais statiques ainsi que la comparaison des différentes stratégies pour créer des recouvrements a été mis en évidence. D’autres expériences sont nécessaires pour étudier la stabilité des recouvrements de PRC et de mieux prédire son interaction avec des tissus in vivo.

Air sensitivity of MoS2, MoSe2, MoTe2, HfS2 and HfSe2

A surface sensitivity study was performed on different transition-metal dichalcogenides (TMDs) under ambient conditions in order to understand which material is the most suitable for future device applications. Initially, Atomic Force Microscopy and Scanning Electron Microscopy studies were carried out over a period of 27 days on mechanically exfoliated flakes of 5 different TMDs, namely, MoS2, MoSe2, MoTe2, HfS2, and HfSe2. The most reactive were MoTe2 and HfSe2. HfSe2, in particular, showed surface protrusions after ambient exposure, reaching a height and width of approximately 60 nm after a single day. This study was later supplemented by Transmission Electron Microscopy (TEM) cross-sectional analysis, which showed hemispherical-shaped surface blisters that are amorphous in nature, approximately 180–240 nm tall and 420–540 nm wide, after 5 months of air exposure, as well as surface deformation in regions between these structures, related to surface oxidation. An X-ray photoelectron spectroscopy study of atmosphere exposed HfSe2 was conducted over various time scales, which indicated that the Hf undergoes a preferential reaction with oxygen as compared to the Se. Energy-Dispersive X-Ray Spectroscopy showed that the blisters are Se-rich; thus, it is theorised that HfO2 forms when the HfSe2 reacts in ambient, which in turn causes the Se atoms to be aggregated at the surface in the form of blisters. Overall, it is evident that air contact drastically affects the structural properties of TMD materials. This issue poses one of the biggest challenges for future TMD-based devices and technologies.

Physico-chemical properties of sol-gel synthesized titanosilicates for the uptake of radionuclides from aqueous solutions

Harnessing the power of nuclear reactions has brought huge benefits in terms of nuclear energy, medicine and defence as well as risks including the management of nuclear wastes. One of the main issues for radioactive waste management is liquid radioactive waste (LRW). Different methods have been applied to remediate LRW, thereunder ion exchange and adsorption. Comparative studies have demonstrated that Na2Ti2O3SiO4·2H2O titanosilicate sorption materials are the most promising in terms of Cs+ and Sr2+ retention from LRW. Therefore these TiSi materials became the object of this study. The recently developed in Ukraine sol-gel method of synthesizing these materials was chosen among the other reported approaches since it allows obtaining the TiSi materials in the form of particles with size ≥ 4mm. utilizing inexpensive and bulk stable inorganic precursors and yielded the materials with desirable properties by alteration of the comparatively mild synthesis conditions. The main aim of this study was to investigate the physico-chemical properties of sol-gel synthesized titanosilicates for radionuclide uptake from aqueous solutions. The effect of synthesis conditions on the structural and sorption parameters of TiSi xerogels was planned to determine in order to obtain a highly efficient sorption material. The ability of the obtained TiSis to retain Cs+, Sr2+ and other potentially toxic metal cations from the synthetic and real aqueous solutions was intended to assess. To our expectations, abovementioned studies will illustrate the efficiency and profitability of the chosen synthesis approach, synthesis conditions and the obtained materials. X-ray diffraction, low temperature adsorption/desorption surface area analysis, X-ray photoelectron spectroscopy, infrared spectroscopy and scanning electron microscopy with energy dispersive X-ray spectroscopy was used for xerogels characterization. The sorption capability of the synthesized TiSi gels was studied as a function of pH, adsorbent mass, initial concentration of target ion, contact time, temperature, composition and concentration of the background solution. It was found that the applied sol-gel approach yielded materials with a poorly crystalline sodium titanosilicate structure under relatively mild synthesis conditions. The temperature of HTT has the strongest influence on the structure of the materials and consequently was concluded to be the control factor for the preparation of gels with the desired properties. The obtained materials proved to be effective and selective for both Sr2+ and Cs+ decontamination from synthetic and real aqueous solutions like drinking, ground, sea and mine waters, blood plasma and liquid radioactive wastes.

Diamond Surface Modification to Enhance Interfacial Thermal Conductivity in Al/Diamond Composites

Diamond/metal composites are very attractive materials for electronics because their excellent thermal properties make them suitable for use as heat sink elements in multifunctional electronic packaging systems. To enlarge the potential applications of these composites, current efforts are mainly focused on investigating different ways to improve the contact between metal and diamond. In the present work, a theoretical study has been carried out to determine the differences between the interfacial thermal conductance of aluminum/diamond and aluminum/graphite interfaces. Additionally, diamond particles were surface modified with oxygen to observe how it affects the quality of the diamond surface. The characterization of the surface of diamonds has been performed using different surface analysis techniques, especially x-ray photoelectron spectroscopy and temperature-programmed desorption.

Sn@Pt and Rh@Pt core–shell nanoparticles synthesis for glycerol oxidation

The development and optimization of electrocatalysts for application in fuel cell systems have been the focus of a variety of studies where core–shell structures have been considered as a promising alternative among the materials studied. We synthesized core–shell nanoparticles of Sn x @Pt y and Rh x @Pt y (Sn@Pt, Sn@Pt2, Sn@Pt3, Rh@Pt, Rh@Pt2, and Rh@Pt3) through a reduction methodology using sodium borohydride. These nanoparticles were electrochemically characterized by cyclic voltammetry and further analyzed by cyclic voltammetry studying their catalytic activity toward glycerol electro-oxidation; chronoamperometry and potentiostatic polarization experiments were also carried out. The physical characterization was carried out by X-ray diffraction, energy-dispersive X-ray spectroscopy, X-ray photoelectron spectroscopy, and transmission electron microscopy. The onset potential for glycerol oxidation was shifted in 130 and 120 mV on the Sn@Pt3/C and Rh@Pt3/C catalysts, respectively, compared to commercial Pt/C, while the stationary pseudo-current density, taken at 600 mV, increased 2-fold and 5-fold for these catalysts related to Pt/C, respectively. Thus, the catalysts synthesized by the developed methodology have enhanced catalytic activity toward the electro-oxidation of glycerol, representing an interesting alternative for fuel cell systems.