Anisotropic surface properties of micro/nanostructured a-C:H:F thin films with self-assembly applications

The singular properties of hydrogenated amorphous carbon (a-C:H) thin filmsdeposited by pulsed DC plasma enhanced chemical vapor deposition (PECVD), such as hardness and wear resistance, make it suitable as protective coating with low surface energy for self-assembly applications. In this paper, we designed fluorine-containing a-C:H (a-C:H:F) nanostructured surfaces and we characterized them for self-assembly applications. Sub-micron patterns were generated on silicon through laser lithography while contact angle measurements, nanotribometer, atomic force microscopy (AFM), and scanning electron microscopy (SEM) were used to characterize the surface. a-C:H:F properties on lithographied surfaces such as hydrophobicity and friction were improved with the proper relative quantity of CH4 and CHF3 during deposition, resulting in ultrahydrophobic samples and low friction coefficients. Furthermore, these properties were enhanced along the direction of the lithographypatterns (in-plane anisotropy). Finally, self-assembly properties were tested with silicananoparticles, which were successfully assembled in linear arrays following the generated patterns. Among the main applications, these surfaces could be suitable as particle filter selector and cell colony substrate.

Blackbody emission under laser excitation of silicon nanopowder produced by plasma-enhanced chemical-vapor deposition

Previous results concerning radiative emission under laser irradiation of silicon nanopowder are reinterpreted in terms of thermal emission. A model is developed that considers the particles in the powder as independent, so under vacuum the only dissipation mechanism is thermal radiation. The supralinear dependence observed between the intensity of the emitted radiation and laser power is predicted by the model, as is the exponential quenching when the gas pressure around the sample increases. The analysis allows us to determine the sample temperature. The local heating of the sample has been assessed independently by the position of the transverse optical Raman mode. Finally, it is suggested that the photoluminescence observed in porous silicon and similar materials could, in some cases, be blackbody radiation

Off-Diagonal Magnetoimpedance Dependence of Magnetostriction and Anisotropy in Co-Based and Fe-Based Amorphous Ribbons

The object of this work is the comparison of domain structure and off-diagonal magnetoimpedance effect in amorphous ribbons with different magnetostriction coefficient. The Co66Fe4Ni1Si15B14 and Fe80B20 samples were obtained by melt-spinning. During the quenching procedure a 0.07 T transverse magnetic field was applied to some of the samples. Domain patterns obtained by the Bitter technique confirm that the differences on the samples are related to the different anisotropy and magnetostriction coefficient, and the quenching procedure. Small changes on the anisotropy distribution and the magnetostriction coefficient can be detected by the off-diagonal impedance spectra as a consequence of the different permeability values of the samples

Gas collisions and pressure quenching of the photoluminescence of silicon nanopowder grown by plasma-enhanced chemical vapor deposition

The quenching of the photoluminescence of Si nanopowder grown by plasma-enhanced chemical vapor deposition due to pressure was measured for various gases ( H2, O2, N2, He, Ne, Ar, and Kr) and at different temperatures. The characteristic pressure, P0, of the general dependence I(P)=I0exp(-P/P0) is gas and temperature dependent. However, when the number of gas collisions is taken as the variable instead of pressure, then the quenching is the same within a gas family (mono- or diatomic) and it is temperature independent. So it is concluded that the effect depends on the number of gas collisions irrespective of the nature of the gas or its temperature

Coprecipitation of trace amounts of silicon with aluminum hydroxide and the determination by flame atomic absorption spectrometry

A simple preconcentration method of silicon based on coprecipitation with aluminum hydroxide prior to its flame atomic absorption (FAAS) determination was established. The recovery values of analyte ion was higher than 95%. The parameters including types of hydroxide ion source for precipitation, acid type for dissolution step, amount of aluminum ion as collector, pH, temperature, standing and centrifuge time, and sample volume were optimized for the quantitative recovery of the analyte. The influences of matrix ions were also examined. The relative standard deviation was found to be 3.2%. The limit of detection was calculated as (0.1 mg L-1). The preconcentration factor is 100 for (200 mL) solution. The proposed method was successfully applied for the determination of silicon in some water and alloy samples.

VIDROS DE OXICARBETO DE SILÍCIO OBTIDOS A PARTIR DE POLISSILOXANOS

AbstractSilicon oxycarbide glasses (SiOC) are a class of amorphous materials with a similar silica glass structure, in which oxygen atoms are partially replaced by tetracoordenated carbon atoms. The presence of carbon atoms covalently bound to the silicon atoms creates a more interconnected structure with better strength, and excellent chemical stability than conventional silica. SiOCs are easily prepared by the pyrolysis of polysiloxanes and can potentially be implemented in several technological applications that require high temperatures. This paper mainly addresses the preparation, structure, and properties of SiOC. Furthermore, potential applications of SiOC are also introduced.

Silicon and rice disease management

The element silicon (Si) is not considered an essential nutrient for plant function. Nevertheless, Si is absorbed from soil in large amounts that are several fold higher than those of other essential macronutrients in certain plant species. Its beneficial effects have been reported in various situations, especially under biotic and abiotic stress conditions. The most significant effect of Si on plants, besides improving their fitness in nature and increasing agricultural productivity, is the restriction of parasitism. There has been a considerable amount of research showing the positive effect of Si in controlling diseases in important crops. Rice (Oryza sativa), in particular, is affected by the presence of Si, with diseases such as blast, brown spot and sheath blight becoming more severe on rice plants grown in Si-depleted soils. The hypothesis underlying the control of some diseases in both mono- and di-cots by Si has been confined to that of a mechanical barrier resulting from its polymerization in planta. However, some studies show that Si-mediated resistance against pathogens is associated with the accumulation of phenolics and phytoalexins as well as with the activation of some PR-genes. These findings strongly suggest that Si plays an active role in the resistance of some plants to diseases rather than forming a physical barrier that impedes penetration by fungal pathogens.

Soluble tissue sugar content and leaf blast severity in response to the application of calcinated serpentinite as a silicon source in irrigated rice

A field experiment conducted with the irrigated rice cultivar BRS Formoso, to assess the efficiency of calcinated serpentinite as a silicon source on grain yield was utilized to study its effect on leaf blast severity and tissue sugar levels. The treatments consisted of five rates of calcinated serpentinite (0, 2, 4, 6, 8 Mg.ha-1) incorporated into the soil prior to planting. The leaf blast severity was reduced at the rate of 2.96% per ton of calcinated serpentinite. The total tissue sugar content decreased significantly as the rates of serpentinite applied increased (R² = 0.83). The relationship between the tissue sugar content and leaf blast severity was linear and positive (R² = 0.81). The decrease in leaf blast severity with increased rates of calcinated serpentinite was also linear (R²= 0.96) and can be ascribed to reduced sugar level.

Porous silicon optical filters in gas sensing applications

In this thesis, the gas sensing properties of porous silicon-based thin-film optical filters are explored. The effects of surface chemistry on the adsorption and desorption of various gases are studied in detail. Special emphasis is placed on investigating thermal carbonization as a stabilization method for optical sensing applications. Moreover, the possibility of utilizing the increased electrical conductivity of thermally carbonized porous silicon for implementing a multiparametric gas sensor, which would enable simultaneous monitoring of electrical and optical parameters, is investigated. In addition, different porous silicon-based optical filter-structures are prepared, and their properties in sensing applications are evaluated and compared. First and foremost, thermal carbonization is established as a viable method to stabilize porous silicon optical filters for chemical sensing applications. Furthermore, a multiparametric sensor, which can be used for increasing selectivity in gas sensing, is also demonstrated. Methods to improve spectral quality in multistopband mesoporous silicon rugate filters are studied, and structural effects to gas sorption kinetics are evaluated. Finally, the stability of thermally carbonized optical filters in basic environments is found to be superior in comparison to other surface chemistries currently available for porous silicon. The results presented in this thesis are of particular interest for developing novel reliable sensing systems based on porous silicon, e.g., label-free optical biosensors.

Understanding the in vitro dissolution rate of glasses with respect to future clinical applications

Glass is a unique material with a long history. Several glass products are used daily in our everyday life, often unnoticed. Glass can be found not only in obvious applications such as tableware, windows, and light bulbs, but also in tennis rackets, windmill turbine blades, optical devices, and medical implants. The glasses used at present as implants are inorganic silica-based melt-derived compositions mainly for hard-tissue repair as bone graft substitute in dentistry and orthopedics. The degree of glass reactivity desired varies according to implantation situation and it is vital that the ion release from any glasses used in medical applications is controlled. Understanding the in vitro dissolution rate of glasses provides a first approximation of their behavior in vivo. Specific studies concerning dissolution properties of bioactive glasses have been relatively scarce and mostly concentrated to static condition studies. The motivation behind this work was to develop a simple and accurate method for quantifying the in vitro dissolution rate of highly different types of glass compositions with interest for future clinical applications. By combining information from various experimental conditions, a better knowledge of glass dissolution and the suitability of different glasses for different medical applications can be obtained. Thus, two traditional and one novel approach were utilized in this thesis to study glass dissolution. The chemical durability of silicate glasses was tested in water and TRIS-buffered solution at static and dynamic conditions. The traditional in vitro testing with a TRISbuffered solution under static conditions works well with bioactive or with readily dissolving glasses, and it is easy to follow the ion dissolution reactions. However, in the buffered solution no marked differences between the more durable glasses were observed. The hydrolytic resistance of the glasses was studied using the standard procedure ISO 719. The relative scale given by the standard failed to provide any relevant information when bioactive glasses were studied. However, the clear differences in the hydrolytic resistance values imply that the method could be used as a rapid test to get an overall idea of the biodegradability of glasses. The standard method combined with the ion concentration and pH measurements gives a better estimate of the hydrolytic resistance because of the high silicon amount released from a glass. A sensitive on-line analysis method utilizing inductively coupled plasma optical emission spectrometer and a flow-through micro-volume pH electrode was developed to study the initial dissolution of biocompatible glasses. This approach was found suitable for compositions within a large range of chemical durability. With this approach, the initial dissolution of all ions could be measured simultaneously and quantitatively, which gave a good overall idea of the initial dissolution rates for the individual ions and the dissolution mechanism. These types of results with glass dissolution were presented for the first time during the course of writing this thesis. Based on the initial dissolution patterns obtained with the novel approach using TRIS, the experimental glasses could be divided into four distinct categories. The initial dissolution patterns of glasses correlated well with the anticipated bioactivity. Moreover, the normalized surface-specific mass loss rates and the different in vivo models and the actual in vivo data correlated well. The results suggest that this type of approach can be used for prescreening the suitability of novel glass compositions for future clinical applications. Furthermore, the results shed light on the possible bioactivity of glasses. An additional goal in this thesis was to gain insight into the phase changes occurring during various heat treatments of glasses with three selected compositions. Engineering-type T-T-T curves for glasses 1-98 and 13-93 were stablished. The information gained is essential in manufacturing amorphous porous implants or for drawing of continuous fibers of the glasses. Although both glasses can be hot worked to amorphous products at carefully controlled conditions, 1-98 showed one magnitude greater nucleation and crystal growth rate than 13-93. Thus, 13-93 is better suited than 1-98 for working processes which require long residence times at high temperatures. It was also shown that amorphous and partially crystalline porous implants can be sintered from bioactive glass S53P4. Surface crystallization of S53P4, forming Na2O∙CaO∙2SiO2, was observed to start at 650°C. The secondary crystals of Na2Ca4(PO4)2SiO4, reported for the first time in this thesis, were detected at higher temperatures, from 850°C to 1000°C. The crystal phases formed affected the dissolution behavior of the implants in simulated body fluid. This study opens up new possibilities for using S53P4 to manufacture various structures, while tailoring their bioactivity by controlling the proportions of the different phases. The results obtained in this thesis give valuable additional information and tools to the state of the art for designing glasses with respect to future clinical applications. With the knowledge gained we can identify different dissolution patters and use this information to improve the tuning of glass compositions. In addition, the novel online analysis approach provides an excellent opportunity to further enhance our knowledge of glass behavior in simulated body conditions.

Investigation on diamond turning of silicon crystal - generation mechanism of surface cut with worn tool

This paper discusses the effect of tool wear on surface finish in single-point diamond turning of single crystal silicon. The morphology and topography of the machined surface clearly show the type of cutting edge wear reproduced onto the cutting grooves. Scanning electron microscopy is used in order to correlate the cutting edge damage and microtopography features observed through atomic force microscopy. The possible wear mechanisms affecting tool performance and surface generation during cutting are also discussed. The zero degree rake angle single point diamond tool presented small nicks on the cutting edge. The negative rake angle tools presented more a type of crater wear on the rake face. No wear was detected on flank face of the diamond tools.

Silicon-containing species in used lube oil re-refining

Nowadays, the re-refining of the used lube oils has gained worldwide a lot of attention due to the necessity for added environmental protection and increasingly stringent environmental legislation. One of the parameters determining the quality of the produced base oils is the composition of feedstock. Estimation of the chemical composition of the used oil collected from several European locations showed that the hydrocarbon structure of the motor oil is changed insignificantly during its operation and the major part of the changes is accounted for with depleted oil additives. In the lube oil re-refining industry silicon, coming mainly from antifoaming agents, is recognized to be a contaminant generating undesired solid deposits in various locations in the re-refining units. In this thesis, a particular attention was paid to the mechanism of solid product formation during the alkali treatment process of silicon-containing used lube oils. The transformations of a model siloxane, tetramethyldisiloxane (TMDS), were studied in a batch reactor at industrially relevant alkali treatment conditions (low temperature, short reaction time) using different alkali agents. The reaction mechanism involving solid alkali metal silanolates was proposed. The experimental data obtained demonstrated that the solids were dominant products at low temperature and short reaction time. The liquid products in the low temperature reactions were represented mainly by linear siloxanes. The prolongation of reaction time resulted in reduction of solids, whereas both temperature and time increase led to dominance of cyclic products in the reaction mixture. Experiments with the varied reaction time demonstrated that the concentration of cyclic trimer being the dominant in the beginning of the reaction diminished with time, whereas the cyclic tetramer tended to increase. Experiments with lower sodium hydroxide concentration showed the same effect. In addition, a decrease of alkali agent concentration in the initial reaction mixture accelerated TMDS transformation reactions resulting in solely liquid cyclic siloxanes yields. Comparison of sodium and potassium hydroxides applied as an alkali agent demonstrated that potassium hydroxide was more efficient, since the activation energy in KOH presence was almost 2-fold lower than that for sodium hydroxide containing reaction mixture. Application of potassium hydroxide for TMDS transformation at 100° C with 3 hours reaction time resulted in 20 % decrease of solid yields compared to NaOH-containing mixture. Moreover, TMDS transformations in the presence of sodium silanolate applied as an alkali agent led to formation of only liquid products without formation of the undesired solids. On the basis of experimental data and the proposed reaction mechanism, a kinetic model was developed, which provided a satisfactory description of the experimental results. Suitability of the selected siloxane as a relevant model of industrial silicon-containing compounds was verified by investigation of the commercially available antifoam agent in base-catalyzed conditions.

Atomic Force Microscopy Investigation of NI Particles Deposited on Porous Silicon

In this thesis properties and influence of modification techniques of porous silicon were studied by Atomic Force Microscope (AFM). This device permits to visualize the surface topography and to study properties of the samples on atomic scale, which was necessary for recent investigation. Samples of porous silicon were obtained by electrochemical etching. Nickel particles were deposited by two methods: electrochemical deposition and extracting from NiCl2 ethanol solution. Sample growth was conducted in Saint-Petersburg State Electrotechnical University, LETI. Kelvin probe force microscopy (KPFM) and Magnetic force microscopy (MFM) were utilized for detailed information about surface properties of the samples. Measurements showed the difference in morphology correlating with initial growth conditions. Submicron size particles were clearly visible on surfaces of the treated samples. Although their nature was not clarified due to limitations of AFM technique. It is expected that surfaces were covered by nanometer scale Ni particles, which can be verified by implication of RAMAN device.

Exchange reactions of organic halides and organo-silicon compounds with boron tribromide and boron triiodide

Reactions of the boron halides with organic halides and organo-silicon compounds have been investigated. The results show exchange of halogens between the BX3 (X = Br# 1) and the organic halidef exchange of the halogen of the C-X bond being proved. The rates of halogen exchange vary. Reaction of the heavier halides with organo-silicon compounds indicated that the silicon-carbon bonds ruptured in the absence of electronegative atom attached to the silicon. The presence of an electronegative atom (halogen or oxygen) attached to the silicon causes the bond between the silicon and the electronegative atom to be preferentially broken. Products of exchange reactions of the boron halides and the organic halides or the organo-silicon compounds were studied by use of 1H NMR and GC/MS. From these results some possible mechanisms for the exchange reactions are postulated, but further work is indicated to prove the real courses of the reactions

Low frequency Raman scattering in amorphous materials: fused quartz, "pyrex" boro-silicate glass and soda-lime silicate glass

Raman scattering in the region 20 to 100 cm -1 for fused quartz, "pyrex" boro-silicate glass, and soft soda-lime silicate glass was investigated. The Raman spectra for the fused quartz and the pyrex glass were obtained at room temperature using the 488 nm exciting line of a Coherent Radiation argon-ion laser at powers up to 550 mW. For the soft soda-lime glass the 514.5 nm exciting line at powers up to 660 mW was used because of a weak fluorescence which masked the Stokes Raman spectrum. In addition it is demonstrated that the low-frequency Raman coupling constant can be described by a model proposed by Martin and Brenig (MB). By fitting the predicted spectra based on the model with a Gaussian, Poisson, and Lorentzian forms of the correlation function, the structural correlation radius (SCR) was determined for each glass. It was found that to achieve the best possible fit· from each of the three correlation functions a value of the SCR between 0.80 and 0.90 nm was required for both quartz and pyrex glass but for the soft soda-lime silicate glass the required value of the SCR. was between 0.50 and 0.60 nm .. Our results support the claim of Malinovsky and Sokolov (1986) that the MB model based on a Poisson correlation function provides a universal fit to the experimental VH (vertical and horizontal polarizations) spectrum for any glass regardless of its chemical composition. The only deficiency of the MB model is its failure to fit the experimental depolarization spectra.