Magnetic interactions between transition metal impurities and clusters mediated by low-dimensional metallic hosts: A first principles theoretical investigation

The magnetic properties and interactions between transition metal (TM) impurities and clusters in low-dimensional metallic hosts are studied using a first principles theoretical method. In the first part of this work, the effect of magnetic order in 3d-5d systems is addressed from the perspective of its influence on the enhancement of the magnetic anisotropy energy (MAE). In the second part, the possibility of using external electric fields (EFs) to control the magnetic properties and interactions between nanoparticles deposited at noble metal surfaces is investigated. The influence of 3d composition and magnetic order on the spin polarization of the substrate and its consequences on the MAE are analyzed for the case of 3d impurities in one- and two-dimensional polarizable hosts. It is shown that the MAE and easy- axis of monoatomic free standing 3d-Pt wires is mainly determined by the atomic spin-orbit (SO) coupling contributions. The competition between ferromagnetic (FM) and antiferromagnetic (AF) order in FePtn wires is studied in detail for n=1-4 as a function of the relative position between Fe atoms. Our results show an oscillatory behavior of the magnetic polarization of Pt atoms as a function of their distance from the magnetic impurities, which can be correlated to a long-ranged magnetic coupling of the Fe atoms. Exceptionally large variations of the induced spin and orbital moments at the Pt atoms are found as a function of concentration and magnetic order. Along with a violation of the third Hund’s rule at the Fe sites, these variations result in a non trivial behavior of the MAE. In the case of TM impurities and dimers at the Cu(111), the effects of surface charging and applied EFs on the magnetic properties and substrate-mediated magnetic interactions have been investigated. The modifications of the surface electronic structure, impurity local moments and magnetic exchange coupling as a result of the EF-induced metallic screening and charge rearrangements are analysed. In a first study, the properties of surface substitutional Co and Fe impurities are investigated as a function of the external charge per surface atom q. At large inter-impurity distances the effective magnetic exchange coupling ∆E between impurities shows RKKY-like oscillations as a function of the distance which are not significantly affected by the considered values of q. For distances r < 10 Å, important modifications in the magnitude of ∆E, involving changes from FM to AF coupling, are found depending non-monotonously on the value and polarity of q. The interaction energies are analysed from a local perspective. In a second study, the interplay between external EF effects, internal magnetic order and substrate-mediated magnetic coupling has been investigated for Mn dimers on Cu(111). Our calculations show that EF (∼ 1eV/Å) can induce a switching from AF to FM ground-state magnetic order within single Mn dimers. The relative coupling between a pair of dimers also shows RKKY-like oscillations as a function of the inter-dimer distance. Their effective magnetic exchange interaction is found to depend significantly on the magnetic order within the Mn dimers and on their relative orientation on the surface. The dependence of the substrate-mediated interaction on the magnetic state of the dimers is qualitatively explained in terms of the differences in the scattering of surface electrons. At short inter-dimer distances, the ground-state configuration is determined by an interplay between exchange interactions and EF effects. These results demonstrate that external surface charging and applied EFs offer remarkable possibilities of manipulating the sign and strength of the magnetic coupling of surface supported nanoparticles.

The effect of light exposure on the degradation of latent fingerprints on brass surfaces: the use of silver electroless deposition as a visualization technique

We have studied the degradation of sebaceous fingerprints on brass surfaces using silver electroless deposition (SED) as a visualization technique. We have stored fingerprints on brass squares either (i) in a locked dark cupboard or (ii) in glass-filtered natural daylight for periods of 3 h, 24 h, 1 week, 3 weeks, and 6 weeks. We find that fingerprints on brass surfaces degrade much more rapidly when kept in the light than they do under dark conditions with a much higher proportion of high-quality prints found after 3 or 6 weeks of aging when stored in the dark. This process is more marked than for similar fingerprints on black PVC surfaces. Identifiable prints can be achieved on brass surfaces using both SED and cyanoacrylate fuming (CFM). SED is quick and straightforward to perform. CFM is more time-consuming but is versatile and can be applied to a wider range of metal surfaces than SED, for example brass surfaces which have been coated by a lacquer.

Probing the functionalization of gold surfaces and protein adsorption by PM-IRRAS

The control of morphology and coating of metal surfaces is essential for a number of organic electronic devices including photovoltaic cells and sensors. In this study, we monitor the functionalization of gold surfaces with 11-mercaptoundecanoic acid (MUA, HS(CH(2))(10)CO(2)H) and cysteamine, aiming at passivating the surfaces for application in surface plasmon resonance (SPR) biosensors. Using polarization-modulated infrared reflection-absorption spectroscopy (PM-IRRAS), cyclic voltammetry, atomic force microscopy and quartz crystal microbalance, we observed a time-dependent organization process of the adsorbed MUA monolayer with alkyl chains perpendicular to the gold surface. Such optimized condition for surface passivation was obtained with a systematic search for experimental parameters leading to the lowest electrochemical signal of the functionalized gold electrode. The ability to build supramolecular architectures was also confirmed by detecting with PM-IRRAS the adsorption of streptavidin on the MUA-functionalized gold. As the approaches used for surface functionalization and its verification with PM-IRRAS are generic, one may now envisage monitoring the fabrication of tailored electrodes for a variety of applications.

Modelling water adsorption on Au(210) surfaces: II. Monte Carlo simulations

Canonical Monte Carlo simulations for the Au(210)/H(2)O interface, using a force field recently proposed by us, are reported. The results exhibit the main features normally observed in simulations of water molecules in contact with different noble metal surfaces. The calculations also assess the influence of the surface topography on the structural aspects of the adsorbed water and on the distribution of the water molecules in the direction normal to the metal surface plane. The adsorption process is preferential at sites in the first layer of the metal. The analysis of the density profiles and dipole moment distributions points to two predominant orientations. Most of the molecules are adsorbed with the molecular plane parallel to surface, while others adsorb with one of the O-H bonds parallel to the surface and the other bond pointing towards the bulk liquid phase. There is also evidence of hydrogen bond formation between the first and second solvent layers at the interface. (c) 2007 Elsevier B.V. All rights reserved.

Effect of metal conditioners on the adhesive bonding of resin cements to cast titanium

Objective: To assess the effect of metal conditioners on the bond strength between resin cements and cast titanium. Method and Materials: Commercially pure titanium (99.56%) was cast using an arc casting machine. Surfaces were finished with 400-grit silicon carbide paper followed by air abrasion with 50-mu m aluminum oxide. A piece of double-coated tape with a 4-mm circular hole was then positioned on the metal surface to control the area of the bond. The prepared surfaces were then divided into 4 groups (n=10): G1, unprimed Panavia F; G2, Alloy Primer-Panavia F; G3, unprimed Bistite DC; G4, Metaltite-Bistite DC. Forty minutes after insertion of the resin cements, the specimens were detached from the mold and stored in water at 37 C for 24 hours. Shear bond strength was performed in a testing machine (MTS 810) at a crosshead speed of 0.5 mm/min. Data were analyzed using ANOVA and Tukey's test with a .05 significance level. The fractured surfaces were observed through an optical microscope at 10x magnification. Results: the G1 group demonstrated significantly higher shear bond strength (17.95 MPa) than the other groups. G3 (13.79 MPa) and G4 (12.98 MPa) showed similar mean values to each other and were statistically superior to G2 (9.31 MPa). Debonded surfaces generally presented adhesive failure between metal surfaces and resin cements. Conclusion: While the Metaltite conditioner did not influence the bond strength of the Bistite DC cement, the Alloy Primer conditioner significantly decreased the mean bond strength of the Panavia F cement.

Modulation of human osteoblasts by metal surface chemistry

The use of metal implants in dental and orthopedic surgery is continuously expanding and highly successful. While today longevity and load-bearing capacity of the implants fulfill the expectations of the patients, acceleration of osseointegration would be of particular benefit to shorten the period of convalescence. To further clarify the options to accelerate the kinetics of osseointegration, within this study, the osteogenic properties of structurally identical surfaces with different metal coatings were investigated. To assess the development and function of primary human osteoblasts on metal surfaces, cell viability, differentiation, and gene expression were determined. Titanium surfaces were used as positive, and surfaces coated with gold were used as negative controls. Little differences in the cellular parameters tested for were found when the cells were grown on titanium discs sputter coated with titanium, zirconium, niobium, tantalum, gold, and chromium. Cell number, activity of cell layer-associated alkaline phosphatase (ALP), and levels of transcripts encoding COL1A1 and BGLAP did not vary significantly in dependence of the surface chemistry. Treatment of the cell cultures with 1,25(OH)2 D3 /Dex, however, significantly increased ALP activity and BGLAP messenger RNA levels. The data demonstrate that the metal layer coated onto the titanium discs exerted little modulatory effects on cell behavior. It is suggested that the microenvironment regulated by the peri-implant tissues is more effective in regulating the tissue response than is the material of the implant itself.

Antimicrobial efficacy of copper surfaces against spores and vegetative cells of Clostridium difficile: the germination theory

OBJECTIVES: Persistent contamination of surfaces by spores of Clostridium difficile is a major factor influencing the spread of C. difficile-associated diarrhoea (CDAD) in the clinical setting. In recent years, the antimicrobial efficacy of metal surfaces has been investigated against microorganisms including methicillin-resistant Staphylococcus aureus. This study compared the survival of C. difficile on stainless steel, a metal contact surface widely used in hospitals, and copper surfaces. METHODS: Antimicrobial efficacy was assessed using a carrier test method against dormant spores, germinating spores and vegetative cells of C. difficile (NCTC 11204 and ribotype 027) over a 3 h period in the presence and absence of organic matter. RESULTS: Copper metal eliminated all vegetative cells of C. difficile within 30 min, compared with stainless steel which demonstrated no antimicrobial activity (P < 0.05). Copper significantly reduced the viability of spores of C. difficile exposed to the germinant (sodium taurocholate) in aerobic conditions within 60 min (P < 0.05) while achieving a >or=2.5 log reduction (99.8% reduction) at 3 h. Organic material did not reduce the antimicrobial efficacy of the copper surface (P > 0.05).

Tratamento de superfícies metálicas por nanotecnologia

Trabalho Final de Mestrado para obtenção do grau de Mestre em Engenharia Química e Biológica

Deeper insights into SRB-driven biocorrosion mechanisms

Dissertação para obtenção do Grau de Doutor em Química Sustentável

Surface phenomena and hydrodynamic effects on the deposition of Pseudomonas fluorescens

Biofilm adhesion to metals (copper, aluminium and brass) was studied at two different velocities and pH values of 7 and 9. Both bacteria and metals showed negative surface charges at those values of pH, which tends to slow down adhesion. Film densities increased with the fluid velocity and were also affected by the pH and by the growth rate of the bacteria. Long duration tests based on heat transfer measurements were run at five different fluid velocities and at pH = 7, showing in general an asymptotic behaviour and a control of deposition by adhesion and growth phenomena.

Comment on the plasmon model for image-potential-induced surface states

Calculations of the binding energy of bound positron states in metal surfaces, with explicit inclusion of plasmon dispersion and single-particle effects, are presented. The binding energy is greatly reduced with respect to the undispersed case.

From nonwetting to prewetting: The asymptotic behavior of 4He drops on alkali substrates

We investigate the spreading of 4He droplets on alkali-metal surfaces at zero temperature, within the frame of finite range density-functional theory. The equilibrium configurations of several 4HeN clusters and their asymptotic trend with increasing particle number N, which can be traced to the wetting behavior of the quantum fluid, are examined for nanoscopic droplets. We discuss the size effects inferring that the asymptotic properties of large droplets correspond to those of the prewetting film.

Oxygen adsorption on Cu(510)

Tässä työssä on tutkittu kuparin (510)-askelpinnan reaktiivisuutta käyttäen apuna kvanttimekaanisia ab initio laskentamenetelmiä. Tutkimus on toteutettu laskemalla happiatomin adsorptioenergia ja tilatiheys erilaisissa potentiaalisissa adsorptiopaikoissa pinnalla. Myös happimolekyylin adsorptiota ja hajoamista ontarkasteltu laskemalla pintaa lähestyvälle molekyylille potentiaalienergiapintoja. Energiapintojen tuloksia on myös täydennetty kvanttimekaanisilla molekyylidynamiikkalaskuilla. Metallisia askelpintoja pidetään yleisesti sileitä pintoja reaktiivisempina happea kohtaan, johtuen askeleen reunan pienentävästä vaikutuksesta molekyylin hajoamisen tiellä olevaan energiavaliin. On kuitenkin olemassa myös tuloksia, jotka osoittavat hapen tarttumisprosessin olevan hallitseva juuri terassialueella, askeleen reunan sijasta. Tässä työssä on todettu hapen adsorboituvan Cu(510)-pinnalla tehokkaimmin juuri terassilla olevaan hollow-paikkaan. Myös adsorptioenergiat ovat tällä pinnalla pienempiä kuin sileällä (100)-pinnalla. Potentiaalienergiapintojen perusteella Cu(510)-pinnan todetaan myös olevan vähemmän reaktiivinen kuin askelpintojen yleisesti odotetaan olevan, vaikka askeleen reunan todetaankin pienentävän happiatominhajoamisen esteenä olevaa energiavallia.

Fiber Laser Cutting of Mild Steel

Fiber laser for materials processing have undergone a rapid development in the pastseveral years. As fiber laser provides a combination of high beam quality and awavelength that is easily absorbed by metal surfaces, the named future laser isexpected to challenge the CO2 and Nd:YAG lasers in the area of metal cutting. This thesis studied the performance of fiber laser cutting mild steel. In the literature review part, it introduced the laser cutting principle and the principle of fiber laser including the newest development of fiber laser cuttingtechnology. Because the fiber laser cutting mild steel is a very young technology, a preliminary test was made in order to investigate effect of the cutting parameters on cut quality. Then the formal fiber laser cutting experiment was madeby using 3 mm thickness S355 steel with oxygen as assistant gas. The experimentwas focused on the cut quality with maximum cutting speed and minimum oxygen gas pressure. And the cut quality is mainly decided by the kerf width, perpendicularity tolerance, surface roughness and striation patterns. After analysis the cutting result, several conclusions were made. Although the best result got in the experiment is not perfect as predicted, the whole result of the test can be accepted. Compared with CO2 laser, a higher cutting speed was achieved by fiber laser with very low oxygen gas pressure. A further improvement about the cutting quality might be possible by proper selection of process parameters. And in order to investigate the cutting performance more clearly, a future study about cutting different thickness mild steel and different shape was recommended.

Surface Studies of Thiolate Adsorbates on Some Metals

The results and discussions in this thesis are based on my studies about selfassembled thiol layers on gold, platinum, silver and copper surfaces. These kinds of layers are two-dimensional, one molecule thick and covalently organized at the surface. They are an easy way to modify surface properties. Self-assembly is today an intensive research field because of the promise it holds for producing new technology at nanoscale, the scale of atoms and molecules. These kinds of films have applications for example, in the fields of physics, biology, engineering, chemistry and computer science. Compared to the extensive literature concerning self-assembled monolayers (SAMs) on gold, little is known about the structure and properties of thiolbased SAMs on other metals. In this thesis I have focused on thiol layers on gold, platinum, silver and copper substrates. These studies can be regarded as a basic study of SAMs. Nevertheless, an understanding of the physical and chemical nature of SAMs allows the correlation between atomic structure and macroscopic properties. The results can be used as a starting point for many practical applications. X-ray photoelectron spectroscopy (XPS) and synchrotron radiation excited high resolution photoelectron spectroscopy (HR-XPS) together with time-offlight secondary ion mass spectrometry (ToF-SIMS) were applied to investigate thin organic films formed by the spontaneous adsorption of molecules on metal surfaces. Photoelectron spectroscopy was the main method used in these studies. In photoelectron spectroscopy, the sample is irradiated with photons and emitted photoelectrons are energy-analyzed. The obtained spectra give information about the atomic composition of the surface and about the chemical state of the detected elements. It is widely used in the study of thin layers and is a very powerful tool for this purpose. Some XPS results were complemented with ToF-SIMS measurements. It provides information on the chemical composition and molecular structure of the samples. Thiol (1-Dodecanethiol, CH3(CH2)11SH) solution was used to create SAMs on metal substrates. Uniform layers were formed on most of the studied metal surfaces. On platinum, surface aligned molecules were also detected in investigations by XPS and ToF-SIMS. The influence of radiation on the layer structure was studied, leading to the conclusion that parts of the hydrocarbon chains break off due to radiation and the rest of the layer is deformed. The results obtained showed differences depending on the substrate material. The influence of oxygen on layer formation was also studied. Thiol molecules were found to replace some of the oxygen from the metal surfaces.