Optimising element choice for nanoparticle radiosensitisers

There is considerable interest in the use of heavy atom nanoparticles as theranostic contrast agents due to their high radiation cross-section compared to soft tissue. However, published studies have primarily focused on applications of gold nanoparticles. This study applies Monte Carlo radiation transport modelling using Geant4 to evaluate the macro- and micro-scale radiation dose enhancement following X-ray irradiation with both imaging and therapeutic energies on nanoparticles consisting of stable elements heavier than silicon. An approach based on the Local Effect Model was also used to assess potential biological impacts. While macroscopic dose enhancement is well predicted by simple absorption cross-sections, nanoscale dose deposition has a much more complex dependency on atomic number, with local maxima around germanium (Z = 32) and gadolinium (Z = 64), driven by variations in secondary Auger electron spectra, which translate into significant variations in biological effectiveness. These differences may provide a valuable tool for predicting and elucidating fundamental mechanisms of these agents as they move towards clinical application.

Scanning tunneling microscopy and molecular dynamics study of the Li2TiO3(001) surface

We have investigated the (001) surface structure of lithium titanate (Li2TiO3) using auger electron spectroscopy (AES), low-energy electron diffraction (LEED), and scanning tunneling microscopy (STM). Li2TiO3 is a potential fusion reactor blanket material. After annealing at 1200 K, LEED demonstrated that the Li2TiO3(001) surface was well ordered and not reconstructed. STM imaging showed that terraces are separated in height by about 0.3 nm suggesting a single termination layer. Moreover, hexagonal patterns with a periodicity of ∼0.4 nm are observed. On the basis of molecular dynamics (MD) simulations, these are interpreted as a dynamic arrangement of Li atoms.

Wear of coated and uncoated PCBN cutting tool used in turning and milling

This licentiate thesis has the main focus on evaluation of the wear of coated and uncoated polycrystalline cubic boron nitride cutting tool used in cutting operations against hardened steel. And to exam the surface finish and integrity of the work material used. Harder work material, higher cutting speed and cost reductions result in the development of harder and more wear resistance cutting tools. Although PCBN cutting tools have been used in over 30 years, little work have been done on PVD coated PCBN cutting tools. Therefore hard turning and hard milling experiments with PVD coated and uncoated cutting tools have been performed and evaluated. The coatings used in the present study are TiSiN and TiAlN. The wear scar and surface integrity have been examined with help of several different characterization techniques, for example scanning electron microscopy and Auger electron spectroscopy.   The results showed that the PCBN cutting tools used displayed crater wear, flank wear and edge micro chipping. While the influence of the coating on the crater and flank wear was very small and the coating showed a high tendency to spalling. Scratch testing of coated PCBN showed that, the TiAlN coating resulted in major adhesive fractures. This displays the importance of understanding the effect of different types of lapping/grinding processes in the pre-treatment of hard and super hard substrate materials and the amount and type of damage that they can create. For the cutting tools used in turning, patches of a adhered layer, mainly consisting of FexOy were shown at both the crater and flank. And for the cutting tools used in milling a tribofilm consisting of SixOy covered the crater. A combination of tribochemical reactions, adhesive wear and mild abrasive wear is believed to control the flank and crater wear of the PCBN cutting tools. On a microscopic scale the difference phases of the PCBN cutting tool used in turning showed different wear characteristics. The machined surface of the work material showed a smooth surface with a Ra-value in the range of 100-200 nm for the turned surface and 100-150 nm for the milled surface. With increasing crater and flank wear in combination with edge chipping the machined surface becomes rougher and showed a higher Ra-value. For the cutting tools used in milling the tendency to micro edge chipping was significant higher when milling the tools steels showing a higher hard phase content and a lower heat conductivity resulting in higher mechanical and thermal stresses at the cutting edge.

Surface Corrosion of Ti-16Si-4B Powder Alloy Implanted With Nitrogen by Plasma-Based Technique

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Electrochemical and structural characterization of heat-treated Cr3C2-NiCr coatings

The influence of heat-treatments on the electrochemical behavior of thermal spray Cr3C2-NiCr coatings prepared by high velocity oxygen fuel (HVOF) was studied in NaCl solution, at 25 degrees C, using open-circuit potential (E-OC) and electrochemical impedance spectroscopy (EIS) measurements. Coating characterization were performed before and after the heat-treatments and electrochemical tests by scanning electron microscopy, X-ray diffraction, and Auger electron spectroscopy. In addition to the changes in the original powder composition occurring during HVOF process, heat-treatment performed at 450 degrees C caused no significant changes in electrochemical response compared with untreated sample, and at 760 degrees C the main difference was the formation of a thin and defective layer of Cr2O3 at the coating surface, which increased the total impedance at the first day of immersion. Higher influence on the electrochemical was noted for samples treated at 880 degrees C, which also showed higher E-OC and total impedance, and lower corrosion current. This behavior was interpreted considering the formation of a chromium oxide layer on the coating surface, dissolution and decomposition of smaller carbide particles and their surface enrichment with Cr due to C diffusion and dissolution into the matrix, and possible Ni, Cr, and Fe diffusion to coating/substrate interface. (c) 2006 the Electrochemical Society.

Plasma immersion ion implantation of nitrogen into H13 steel under moderate temperatures

Ion implantation of nitrogen into samples of tempered and quenched H13 steel was carried out by plasma immersion technique. A glow discharge plasma of nitrogen species was the ion source and the negative high voltage pulser provided 10-12 kV, 60 mu s duration and 1.0-2.0 kHz frequency, flat voltage pulses. The temperatures of the samples remained between 300 and 450 degrees C, sustained solely by the ion bombardment. In some of the discharges, we used a N-2 + H-2 gas mixture with 1:1 ratio. PIII treatments as long as 3, 6, 9 and up to 12 h were carried out to achieve as thickest treated layer as possible, and we were able to reach over 20 mu m treated layers, as a result of ion implantation and thermal (and possibly radiation enhanced) diffusion. The nitrogen depth profiles were obtained by GDOS (Glow Discharge Optical Spectroscopy) and the exact composition profiles by AES (Auger Electron Spectroscopy). The hardness of the treated surface was increased by more than 250%, reaching 18.8 GPa. No white layer was seen in this case. A hardness profile was obtained which corroborated a deep hardened layer, confirming the high efficacy of the moderate temperature PIII treatment of steels. (c) 2005 Elsevier B.V. All rights reserved.

Modification of surface properties of Ti-16Si-4B powder alloy by plasma immersion ion implantation

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

In vivo evaluation of porous titanium implants with biomimetic coating

The osseointegration of porous titanium implants was evaluated in the present work. Implants were fabricated from ASTM grade 2 titanium by a powder metallurgy method. Part of these implants were submitted to chemical and thermal treatment in order to deposit a biomimetic coating, aiming to evaluate its influence on the osseointegration of the implants. The implants were characterized by Scanning Electron Microscopy (SEM), Electron Dispersive X-Ray Spectroscopy (EDS) and Raman Spectroscopy. Three coated and three control (uncoated) implants were surgically inserted into thirty albino rabbits' left and right tibiae, respectively. Tibiae samples were submitted to histological and histomorphometric analyses, utilizing SEM, optical microscopy and mechanical tests. EDS results indicated calcium (Ca) and phosphorous (P) at the surface and Raman spectra exhibited an intense peak, characteristic of hydroxyapatite (HA). Bone neoformation was detected at the bone-implant interface and inside the pores, including the central ones. The mean bone neoformation percentage in the coated implants was statistically higher at 15 days, compared to 30 and 45 days. The mechanical tests showed that coated implants presented higher resistance to displacement, especially after 30 and 45 days.

A complex structure in the (beta+gamma(0)) region of the Cu-Al alloys

The identification, characterization and stability range of the phases present in a series of Cu-Al alloys, with Al content from 11.0 to 15.0 wt.%, were studied by Differential Thermal Analysis (DTA), Optical Microscopy (OM), Scanning Electron Microscopy (SEM), Transmission Electron Microscopy (TEM), Selected Area Electron Diffraction (SAED), Auger Electron Spectroscopy (AES), Energy Dispersive X-Ray Spectroscopy (EDX) and X-Ray Diffraction (XRD). In some alloys and in a temperature range from 790 degrees C to 850 degrees C the presence of black spots exhibiting regular shapes and an homogeneous distribution was noticed through metallographic microscopy. Data from TEM and AES indicate that these spots are made of two monocrystalline phases having different Al contents and a crystallographic orientation relationship. (C) 1998 Elsevier B.V. S.A. All rights reserved.

Growth and Characterization of Silicon Carbide Thin Films Using a Nontraditional Hollow Cathode Sputtering Technique

Silicon carbide (SiC) is considered a suitable candidate for high-power, high-frequency devices due to its wide bandgap, high breakdown field, and high electron mobility. It also has the unique ability to synthesize graphene on its surface by subliming Si during an annealing stage. The deposition of SiC is most often carried out using chemical vapor deposition (CVD) techniques, but little research has been explored with respect to the sputtering of SiC. Investigations of the thin film depositions of SiC from pulse sputtering a hollow cathode SiC target are presented. Although there are many different polytypes of SiC, techniques are discussed that were used to identify the film polytype on both 4H-SiC substrates and Si substrates. Results are presented about the ability to incorporate Ge into the growing SiC films for the purpose of creating a possible heterojunction device with pure SiC. Efforts to synthesize graphene on these films are introduced and reasons for the inability to create it are discussed. Analysis mainly includes crystallographic and morphological studies about the deposited films and their quality using x-ray diffraction (XRD), reflection high energy electron diffraction (RHEED), transmission electron microscopy (TEM), scanning electron microscopy (SEM), atomic force microscopy (AFM), Auger electron spectroscopy (AES) and Raman spectroscopy. Optical and electrical properties are also discussed via ellipsometric modeling and resistivity measurements. The general interpretation of these analytical experiments indicates that the films are not single crystal. However, the majority of the films, which proved to be the 3C-SiC polytype, were grown in a highly ordered and highly textured manner on both (111) and (110) Si substrates.

The application of X-ray photoelectron spectroscopy to clay science

Photo-electron spectroscopy as an analytical tool has only received limited interest in the field of mineral science. Photo-electron spectroscopy, together with Auger electron spectroscopy, gives information about the positions of the energy levels in atoms or molecules. Application of this technique on solid materials will result in information of the band structure of these materials. The principle of photo electron spectroscopy is rather simple: photons with certain energy (wavelength) are allowed to collide with an atom, molecule or a solid material. These photons can then interact with electrons present in the atoms and one of these electrons can be excited from its orbital resulting in a situation similar to a free electron plus a positively charged atom or molecule.

Pole tip recession in linear tape systems

The tribology of linear tape storage system including Linear Tape Open (LTO) and Travan5 was investigated by combining X-ray Photoelectron Spectroscopy (XPS), Auger Electron Spectroscopy (AES), Optical Microscopy and Atomic Force Microscopy (AFM) technologies. The purpose of this study was to understand the tribology mechanism of linear tape systems then projected recording densities may be achieved in future systems. Water vapour pressure or Normalized Water Content (NWC) rather than the Relative Humidity (RH) values (as are used almost universally in this field) determined the extent of PTR and stain (if produced) in linear heads. Approximately linear dependencies were found for saturated PTR increasing with normalized water content increasing over the range studied using the same tape. Fe Stain (if produced) preferentially formed on the head surfaces at the lower water contents. The stain formation mechanism had been identified. Adhesive bond formation is a chemical process that is governed by temperature. Thus the higher the contact pressure, the higher the contact temperature in the interface of head and tape, was produced higher the probability of adhesive bond formation and the greater the amount of transferred material (stain). Water molecules at the interface saturate the surface bonds and makes adhesive junctions less likely. Tape polymeric binder formulation also has a significant role in stain formation, with the latest generation binders producing less transfer of material. This is almost certainly due to higher cohesive bonds within the body of the magnetic layer. TiC in the two-phase ceramic tape-bearing surface (AlTiC) was found to oxidise to form TiO2.The oxidation rate of TiC increased with water content increasing. The oxide was less dense than the underlying carbide; hence the interface between TiO2 oxide and TiC was stressed. Removals of the oxide phase results in the formation of three-body abrasive particles that were swept across the tape head, and gave rise to three-body abrasive wear, particularly in the pole regions. Hence, PTR and subsequent which signal loss and error growth. The lower contact pressure of the LTO system comparing with the Travan5 system ensures that fewer and smaller three-body abrasive particles were swept across the poles and insulator regions. Hence, lower contact pressure, as well as reducing stain in the same time significantly reduces PTR in the LTO system.

The boundary lubricated friction and wear of low alloy steel

Pin on disc wear machines were used to study the boundary lubricated friction and wear of AISI 52100 steel sliding partners. Boundary conditions were obtained by using speed and load combinations which resulted in friction coefficients in excess of 0.1. Lubrication was achieved using zero, 15 and 1000 ppm concentrations of an organic dimeric acid additive in a hydrocarbon base stock. Experiments were performed for sliding speeds of 0.2, 0.35 and 0.5 m/s for a range of loads up to 220 N. Wear rate, frictional force and pin temperature were continually monitored throughout tests and where possible complementary methods of measurement were used to improve accuracy. A number of analytical techniques were used to examine wear surfaces, debris and lubricants, namely: Scanning Electron Microscopy (SEM), Auger Electron Spectroscopy (AES), Powder X-ray Diffraction (XRD), X-ray Photoelectron Spectroscopy (XPS), optical microscopy, Back scattered Electron Detection (BSED) and several metallographic techniques. Friction forces and wear rates were found to vary linearly with load for any given combination of speed and additive concentration. The additive itself was found to act as a surface oxidation inhibitor and as a lubricity enhancer, particularly in the case of the higher (1000 ppm) concentration. Wear was found to be due to a mild oxidational mechanism at low additive concentrations and a more severe metallic mechanism at higher concentrations with evidence of metallic delamination in the latter case. Scuffing loads were found to increase with increasing additive concentration and decrease with increasing speed as would be predicted by classical models of additive behaviour as an organo-metallic soap film. Heat flow considerations tended to suggest that surface temperature was not the overriding controlling factor in oxidational wear and a model is proposed which suggests oxygen concentration in the lubricant is the controlling factor in oxide growth and wear.

Sulphide ore minerals:surface chemical properties

The surfaces of iron-containing sulphide minerals were oxidised by a range of inorganic oxidants, and the resultant surface alteration products studied using various spectroscopic techniques. The characterisation of surface oxidation is relevant to the alteration of ores in nature and their behaviour during flotation and leaching, of importance to the metallurgical industry. The sulphides investigated included pyrite (FeS2), hexagonal pyrrhotine (Fe9S10), monoclinic pyrrhotine (Fe7Se), violarite (FeNi2S4), pentlandite ((FeiNi)9Se), chalcopyrite (CuFeS2) and arsenopyrite (FeAsS). The surfaces were oxidised by various methods including acid (sulphuric), alkali (ammonium hydroxide), hydrogen peroxide, steam, electrochemical and air/oxygen (in a low-temperature (150ºC) furnace), The surfaces were examined using surface sensitive chemical spectroscopic methods including x-ray photoelectron spectroscopy (ms), Auger electron spectroscopy (LES) and conversion electron Mössbauer spectroscopy (CEKS). Physical characterisation of the surfaces was undertaken using scanning electron microscopy (SM), spectral reflectance measurements and optical microscopy. Bulk characterisation of the sulphide minerals was undertaken using x-ray diffraction and electron microprobe techniques. Observed phases suggested to form in most of the sulphide surfaces include Fe204, Fe1-x0, Fe202, Fe00H, Fe(OH)3, with iron II & III oxy-sulphates. The iron sulphides show variable extents of oxidation, indicating pyrite to be the most stable. Violarite shows stability to oxidation, suggested to result from both its stable spinel crystal structure, and from the rapid formation of sulphur at the surface protecting the sub-surface from further oxidation. The phenomenon of sub-surface enrichment (in metals), forming secondary sulphides, is exhibited by pentlandite and chalcopyrite, forming violarite and copper sulphides respectively. The consequences of this enrichment with regard to processing and leaching are discussed. Arsenopyrite, often a hindrance in ore processing, exhibits the formation of arsenic compounds at the surface, the dissolution of which is discussed in view of the possible environmental hazard caused by the local pollution of water systems. The results obtained allow a characterisation of the sulphides in terms of their relative stability to oxidation, and an order of stability of the sulphide surfaces is proposed. Models were constructed to explain the chemical compositions of the surfaces, and the inter-relationships between the phases determined at the surface and in the sub-surface. These were compared to the thermo-chemically predicted phases shown in Eh/pH and partial pressure diagrams! The results are discussed, both in terms of the mineralogy and geochemistry of natural ores, and the implications for extraction and processing of these ore minerals.

Electrodeposition on magnesium alloy diecasting

Magnesium alloy diecasting AZ91CC, AZ61CC', AZ91HC and AZ71HC were electroplated using different pretreatment sequences which incorporated conventional zincate immersion processes. Satisfactory peel adhesion in excess of 7. 7 KNm -1 was achieved on AZ61CC using a sequence which was designated Canning. The comparatively low adhesion achieved on the AZ91HC was due to its poor surface quality as cast. Growth of deposits was monitored using a strip-and-analysis technique and the morphology of the various deposits were studied using scanning electron microscopy. Different pretreatment sequences resulted in different surface responses for the alloys but all alloys behaved in a similar manner in a particular sequence with regard to potential time-curves and the rate of zinc deposition. The role of fluoride in both the second stage solution and zinc immersion stages of the Canning pretreatment sequence was studied using techniques listed above and Auger electron spectroscopy. Complete coverage of the magnesium alloy surface with immersion zinc was achieved when fluoride was absent from the zincating solution. However, a zero adhesion value was indicated in both thermal cycling and peel tests. The presence of fluoride in the immersion zinc solution suppressed the rate of zinc deposition and affected the time taken to reach equilibrium during potential-time determinations. A mechanism is suggested to explain the significance of fluoride additions to the processing solutions. pH and composition of the zincating solution had a significant effect on the time taken to produce the step observed in the potential/time curves and hence equilibrium potential. Immersion zinc deposition occurred rapidly at first but then changed to a lower uniform rate at a point corresponding approximately to the step in the potential/time curve. Although the minimun levels of adhesion, using the Canning sequence, varied from 7.72 KNm-1 for alloy AZ61CC to 1.54 KNm-1 for alloy AZ91HC, all the alloys revealed ductile failure characteristics in the surface layer of the substrate after peel testing. Plated magnesium alloys exhibited good corrosion resistance when appropriately pretreated and overplated with adequate nickel chromium coatings. The immersion zinc layer was not preferentially attacked when pits penetrated to the coating/substrate interface. Hemispherical pits formed and attack on the substrate was severe. Of the pretreatment sequences investigated, the Canning one was the most premising with respect to peel adhesion and corrosion behaviour.