Monte Carlo Simulation of Copolymer Heterogeneity in Atom Transfer Radical Copolymerization of Styrene and N-Butyl Acrylate

A high-performance Monte Carlo simulation, which simultaneously takes diffusion-controlled and chain-length-dependent bimolecular termination reactions into account, is developed to simulate atom transfer radical copolymerization of styrene and nbutyl acrylate. As expected, increasing initial feed fraction of styrene raises the fraction of styrene-styrene dyads (fAA) and reduces that of n-butyl acrylate dyads (fBB). The trend of variation in randomness parameter (fAB) during the copolymerization also varies significantly. Also, there is a drift in copolymer heterogeneity and the highest drift occurs in the initial feeds containing lower percentages of styrene, i.e. 20% and 5%.

Absorption of Volatile Organic Compounds into Polydimethylsiloxane: Phase Equilibrium Computation at Infinite Dilution

Group contribution methods such as the UNIFAC are very useful to researchers and engineers involved in synthesis, feasibility studies, design and optimization of separation processes. They can be applied successfully to predict phase equilibrium and excess properties in the development of chemical and separation processes. The main focus of this work was to investigate the possibility of absorbing selected volatile organic compounds (VOCs) into polydimethylsiloxane (PDMS) using three selected UNIFAC group contribution methods. Absorption followed by subsequent stripping is the predominant available abatement technology of VOCs from flue gases prior to their release into the atmosphere. The original, modified and effective UNIFAC models were used in this work. The thirteen selected VOCs that have been considered in this research are: pentane, hexane, heptanes, trimethylamine, toluene, xylene, cyclohexane, butyl acetate, diethyl acetate, chloroform, acetone, ethyl methyl ketone and isobutyl methyl ketone. The computation was done for solute VOC concentration of 8.55x10-8 which is well in the infinite dilution region. The results obtained in this study compare very well with those published in literature obtained through both measurements and predictions. The phase equilibrium obtained in this study show that PDMS is a good absorbent for the removal of VOCs from contaminated air streams through physical absorption.

Synthesis and Characterization of Plasma Polymerized Thin Films Deposited from Benzene and Hexamethyldisiloxane using (PECVD) Method

Polymer-like organic thin films were deposited on both aluminum alloy type 6061 and glass substrates at room temperature by Plasma Enhanced Chemical Vapor Deposition (PECVD) methodusing benzene and hexamethyldisiloxane (HMDSO) as precursor materials. The surface and physical properties of plasma-polymerized organic thin films were investigated at different r.f. powers. The effects of benzene/argon ratio on the properties of plasma polymerized benzene films were also investigated. It is found that using benzene alone results in a non-coherent and non-adherent powdery deposited material. The chemical structure and surface properties of the asgrown plasma polymerized thin films were analyzed on glass substrates with FTIR and contact angle measurements. FTIR spectra of benzene deposited film indicated that the benzene rings are preserved when increasing benzene ratio and/or decreasing r.f. powers. FTIR spectra of HMDSO deposited films indicated an increase of the hydrogen concentration and a decrease of the oxygen concentration with the increase of r.f. power. The contact angle (θ) of the films prepared from benzene was found to increase by about 43% as benzene ratio increases from 10% to 20%. θ was then found to decrease to the original value (51°) when the benzene ratio increases to 100%. The contact angle, θ, for both benzene and HMDSO deposited films were found to increase with r.f. power. This signifies that the plasma polymerized organic films have substantially low surface energy as the r.f power increases. The corrosion resistance of aluminum alloy substrate both bare and covered with plasma polymerized thin films was carried out by potentiodynamic polarization measurements in standard 3.5 wt. % NaCl solution at room temperature. The results indicate that the benzene and HMDSO deposited films are suitable for protection of the aluminum substrate against corrosion. The changes in the processing parameters seem to have a strong influence on the film protective ability. Surface roughness of films deposited on aluminum alloy substrate was investigated using scanning electron microscopy (SEM). The SEM images indicate that the surface roughness of benzene deposited films increase with decreasing the benzene ratio. SEM images of benzene and HMDSO deposited films indicate that the surface roughness decreases with increasing r.f. power. Studying the above parameters indicate that the films produced are suitable for specific practical applications.

Effect of CW Laser Annealing on Silicon Surface for Application of Power Device

As application of re-activation of backside on power device Insulated Gate Bipolar Transistor (IGBT), laser annealing was employed to irradiate amorphous silicon substrate, and resistivities were measured using four point probe measurement. For annealing the amorphous silicon two lasers were used at wavelength of visible green (532 nm) together with Infrared (793 nm). While the green laser efficiently increased temperature at top surface the Infrared laser reached more deep inside and was effective for melting the top surface. A finite element method was employed to evaluate time dependent thermal distribution in silicon substrate.

Patterned Growth of ZnO Nanowire Arrays on Zinc Foil by Thermal Oxidation

A simple approach is demonstrated for growing large scale, nearly vertically aligned ZnO nanowire arrays by thermal oxidation method. To reveal effect of temperature on growth and physical properties of the ZnO nanowires, gold coated zinc substrates were annealed at 300 °C and 400 °C for 4 hours duration in air. Xray diffraction patterns of annealed samples indicated a set of well defined diffraction peaks, indexed to the wurtzite hexagonal phase of ZnO. The scanning electron microscopy studies show formation of ZnO nanowires having length of several microns and average of diameter less than 500 nm. It is found that the areal density of wires is relatively higher, when the annealing is carried out at higher temperature i.e. at 400°C. From the field emission studies, the values of the turn-on and threshold field, required to draw emission current density of 10 μA/cm2 and 100 μA/cm2 are observed to be 1.2 V/μm and 1.7 V/μm for the samples annealed at 300 °C and 2.9 V/μm and 3.7 V/μm for that annealed at 400 °C, respectively. The field emission current stability, investigated over duration of more than 2 hours at the preset value of 1 μA, is found to be fairly good in both cases. The simplicity of the synthesis route coupled with the promising field emission properties offer unprecedented advantage for the use of ZnO field emitters for high current density applications.

Bactericidal Properties of Carbohydrate-Stabilized Platinum Oxide Nanoparticles

Platinum oxide nanoparticles were prepared by a simple hydrothermal route and chemical reduction using carbohydrates (Fructose and sucrose) as the reducing and stabilizing agents. The crystallite size of these nanoparticles was evaluated from X-ray diffraction (XRD), atomic force microscopy (AFM) and transmission electron microscopy (TEM) and was found to be 10 nm as shown in figure 1, which is the demonstration of EM bright field and transmission electron microscopy. The effect of carbohydrates on the morphology of the nanoparticles was studied using TEM (Figure 1). The nanoparticles (100 μg/ml) were administered to the Pseudomonas Stutzeri and Lactobacillus cultures and the incubation was done at 35 oC for 24 hours. The nanocomposites exhibited interesting inhibitory as well as bactericidal activity against P. Stutzeri and and Lactobacillus species. Incorporation of nanoparticles also increased the thermal stability of the carbohydrates.

Carbothermic Reduction of Mechanically Activated Mixtures of Celestite and Carbon

The effect of dry milling on the carbothermic reduction of celestite was investigated. Mixtures of celestite concentrate (98% SrSO4) and activated carbon (99% carbon) was milled for 1 and 24 hours in a planetary ball mill. Un-milled and milled mixtures and their products after carbothermic reduction were studied by a combination of XRD and TGA/DTA experiments. The thermogravimetric analyses and XRD results showed that by milling celestite-carbon mixtures for one hour, the formation temperature of strontium sulfide decreased from about 720°C (in un-milled sample) to about 600°C, after 24 hours milling it decreased to 530°C. It was concluded that milling induces increasingly thorough mixing of the reactants to reduction occurring at lower temperatures

Model Based Monitoring Using Integrated Data Validation, Simulation and Parameter Estimation

Efficient and safe plant operation can only be achieved if the operators are able to monitor all key process parameters. Instrumentation is used to measure many process variables, like temperatures, pressures, flow rates, compositions or other product properties. Therefore Performance monitoring is a suitable tool for operators. In this paper, we integrate rigorous simulation model, data reconciliation and parameter estimation to monitor process equipments and determine key performance indicator (KPI) of them. The applied method here has been implemented in two case studies.

Estimating the Absorption of Volatile Organic Compounds in Four Biodiesels Using the UNIFAC Procedure

This work considered the thermodynamic feasibility of scrubbing volatile organic compounds into biodiesel in view of designing a gas treatment process with this absorbent. A detailed vapour – liquid equilibrium investigation was performed using the original UNIFAC group contribution method. The four biodiesels studied in this work are methyl oleate, methyl palmitate, methyl linolenate and ethyl stearate. The original UNIFAC procedure was used to estimate the infinite dilution activity coefficients of 13 selected volatile organic compounds in the biodiesels. The calculations were done at the VOC mole fraction of 9.213x10-8. Ethyl stearate gave the most favourable phase equilibrium. A close agreement was found between the infinite dilution activity coefficient of toluene found in this work and those reported in literature. Thermodynamic models can efficiently be used to calculate vast amount of phase equilibrium behaviour using limited number of experimental data.

SWNT Sensors for Monitoring the Oxidation of Edible Oils

There are several means to measure the oxidation of edible oils, such as the acid value, the peroxide value, and the anisidine value. However, these means require large quantities of reagents and are time-consuming tasks. Therefore, a more convenient and time-saving way to measure the oxidation of edible oils is required. In this report, an edible oil condition sensor was fabricated by using single-walled nanotubes (SWNT). In order to test the sensor, oxidized edible oils, each one at a different acid value, were prepared. The SWNT sensors were immersed into these oxidized oils and the resistance changes in the sensors were measured. It was found that the conductivity of the sensors decreased as the oxidation level of oil increased. This result suggests that a change of the oil components induced by the oxidation process in edible oils is related to the conductivity change in the SWNT sensor.

The Effects of Sodium Chloride in the Formation of Size and Shape of Gold (Au)Nanoparticles by Microwave-Polyol Method for Mercury Adsorption

Mercury is a natural occurring element and present in various concentrations in the environment. Due to its toxic effects, it is desirable to research mercury sensitive materials to adsorb mercury. This paper describes the preparation of Au nanoparticles for mercury adsorption by using a microwave (MW)-polyol method in the presence of three different Sodium Chloride (NaCl) concentrations (10, 20 and 30 mM). Mixtures of spherical, triangular, octahedral, decahedral particles and 1-D product were obtained using this rapid method. Sizes and shapes was found strongly depend on the concentrations of NaCl. Without NaCl concentration, spherical, triangular plates, octahedral, decahedral nanoparticles and 1D product were produced. At the lower NaCl concentration (10 mM), spherical, octahedral and decahedral nanoparticles were present, while spherical and decahedral nanoparticles were preferentially form by using 20 mM of NaCl concentration. Spherical, triangular plates, octahedral and decahedral nanoparticles were obtained at the highest NaCl concentration (30 mM). The amount of mercury adsorbed using 20 ppm mercury solution is the highest (67.5 %) for NaCl concentration of 30 mM. The high yield of polygonal particles will increase the mercury adsorption. In addition, the adsorption of mercury is also due to the sizes of the particles. The sizes of particles become smaller with increasing NaCl concentrations (size ranges, 5- 16 nm) than those synthesized without addition of NaCl (size ranges 11-32 nm). It is concluded that NaCl concentrations affects the formation of sizes and shapes of Au nanoparticles thus affects the mercury adsorption.

Behavior of Generated Gas in Lost Foam Casting

In the Lost Foam Casting process, melting point temperature of metal, as well as volume and rate of the foam degradation have significant effect on the mold filling pattern. Therefore, gas generation capacity and gas gap length are two important parameters for modeling of mold filling time of the lost foam casting processes. In this paper, the gas gap length at the liquidfoam interface for a low melting point (aluminum) alloy and a high melting point (Carbon-steel) alloy are investigated by the photography technique. Results of the photography technique indicated, that the gas gap length and the mold filling time are increased with increased coating thickness and density of the foam. The Gas gap lengths measured in aluminum and Carbon-steel, depend on the foam density, and were approximately 4-5 and 25-60 mm, respectively. By using a new system, the gas generation capacity for the aluminum and steel was measured. The gas generation capacity measurements indicated that gas generation in the Aluminum and Carbon-steel lost foam casting was about 50 CC/g and 3200 CC/g polystyrene, respectively.

Deposition Rate and Energy Enhancements of TiN Thin-Film in a Magnetized Sheet Plasma Source

Titanium nitride (TiN) has been synthesized using the sheet plasma negative ion source (SPNIS). The parameters used for its effective synthesis has been determined from previous experiments and studies. In this study, further enhancement of the deposition rate of TiN synthesis and advancement of the SPNIS operation is presented. This is primarily achieved by the addition of Sm-Co permanent magnets and a modification of the configuration in the TiN deposition process. The magnetic enhancement is aimed at optimizing the sputtering rate and the sputtering yield of the process. The Sm-Co permanent magnets are placed below the Ti target for better sputtering by argon. The Ti target is biased from –250V to – 350V and is sputtered by Ar plasma produced at discharge current of 2.5–4A and discharge potential of 60–90V. Steel substrates of dimensions 20x20x0.5mm3 were prepared with N2:Ar volumetric ratios of 1:3, 1:5 and 1:10. Ocular inspection of samples exhibit bright gold color associated with TiN. XRD characterization confirmed the effective TiN synthesis as all samples exhibit the (200) and (311) peaks of TiN and the non-stoichiometric Ti2N (220) facet. Cross-sectional SEM results showed increase in the TiN deposition rate of up to 0.35μm/min. This doubles what was previously obtained [1]. Scanning electron micrograph results give a comparative morphological picture of the samples. Vickers hardness results gave the largest hardness value of 21.094GPa.

Polyethylenimine Coated Carbon Nanotube for Detecting Rancidity in Frying Oil

Chemical detection is still a continuous challenge when it comes to designing single-walled carbon nanotube (SWCNT) sensors with high selectivity, especially in complex chemical environments. A perfect example of such an environment would be in thermally oxidized soybean oil. At elevated temperatures, oil oxidizes through a series of chemical reactions which results in the formation of monoacylglycerols, diacylglycerols, oxidized triacylglycerols, dimers, trimers, polymers, free fatty acids, ketones, aldehydes, alcohols, esters, and other minor products. In order to detect the rancidity of oxidized soybean oil, carbon nanotube chemiresistor sensors have been coated with polyethylenimine (PEI) to enhance the sensitivity and selectivity. PEI functionalized SWCNTs are known to have a high selectivity towards strong electron withdrawing molecules. The sensors were very responsive to different oil oxidation levels and furthermore, displayed a rapid recovery in ambient air without the need of heating or UV exposure.

Influence of Taguchi Selected Parameters on Properties of CuO-ZrO2 Nanoparticles Produced via Sol-gel Method

The present paper discusses the selection of process parameters for obtaining optimal nanocrystallites size in the CuOZrO2 catalyst. There are some parameters changing the inorganic structure which have an influence on the role of hydrolysis and condensation reaction. A statistical design test method is implemented in order to optimize the experimental conditions of CuO-ZrO2 nanoparticles preparation. This method is applied for the experiments and L16 orthogonal array standard. The crystallites size is considered as an index. This index will be used for the analysis in the condition where the parameters vary. The effect of pH, H2O/ precursor molar ratio (R), time and temperature of calcination, chelating agent and alcohol volume are particularity investigated among all other parameters. In accordance with the results of Taguchi, it is found that temperature has the greatest impact on the particle size. The pH and H2O/ precursor molar ratio have low influences as compared with temperature. The alcohol volume as well as the time has almost no effect as compared with all other parameters. Temperature also has an influence on the morphology and amorphous structure of zirconia. The optimal conditions are determined by using Taguchi method. The nanocatalyst is studied by DTA-TG, XRD, EDS, SEM and TEM. The results of this research indicate that it is possible to vary the structure, morphology and properties of the sol-gel by controlling the above-mentioned parameters.

Fabrication of Carbon Doped TiO2 Nanotubes via In-situ Anodization of Ti-foil in Acidic Medium

Highly ordered TiO2 nanotube (TNT) arrays were fabricated onto a pre-treated titanium foil by anodic oxidation with a voltage of 20V in phosphoric acid/sodium fluoride electrolyte. A pretreatment of titanium foil involved washing with acetone, isopropanol, ethanol and deionized water. Carbon doped TiO2 nanotubes (C-TNT) was fabricated 'in-situ' with the same method in the presence of polyvinyl alcohol and urea as carbon sources. The affects of polyvinyl alcohol concentration and oxidation time on the composition, morphology and structure of the C-TN were studied by FE-SEM, EDX and XRD techniques. FESEM images of the nanotubes showed uniform arrays of C-TNTs. The density and microstructures of the nanotubes were greatly affected by the content of PVA. The introduction of the polyvinyl alcohol into the electrolyte increases the amount of C content inside TiO2 nanotube arrays uniformly. The influence of carbon content on the photo-current of C-TNT was investigated and the I-V profiles of the nanotubes were established. The preliminary results indicated that the 'in-situ' doping technique produced a superior quality nanotubes compared to post doping techniques.

Photoluminescence Properties of β-FeSi2 on Cu- or Au-coated Si

The photoluminescence (PL) at 1.55 μm from semiconducting β-FeSi2 has attracted a noticeable interest for silicon-based optoelectronic applications. Moreover, its high optical absorption coefficient (higher than 105 cm-1 above 1.0 eV) allows this semiconducting material to be used as photovoltanics devices. A clear PL spectrum for β-FeSi2 was observed by Cu or Au coating on Si(001). High-crystal-quality β-FeSi2 with a low-level nonradiative center was formed on a Cu- or Au- reated Si layer. This method of deposition can be applied to other materials requiring high crystal quality.

Methanol Concentration Sensitive SWCNT/Nafion Composites

An aqueous methanol sensor for use in direct methanol fuel cells (DMFCs) applications is demonstrated; the methanol sensor is built using dispersed single-walled carbon nanotubes (SWCNTs) with Nafion117 solution to detect the methanol concentration in water. The study is aimed at the potential use of the carbon nanotubes array as a methanol sensor for direct methanol fuel cells (DMFCs). The concentration of methanol in the fuel circulation loop of a DMFC system is an important operating parameter, because it determines the electrical performance and efficiency of the fuel cell system. The sensor is also operative even at ambient temperatures and responds quickly to changes in the concentration levels of the methanol. Such a sensor can be easily incorporated into the methanol fuel solution flow loop in the DMFC system.

Field Emission Properties of Multi-wall Carbon Nanotube Field Emitters using Graphite Tip by Electroporetic Deposition

We fabricated multi-walled carbon nanotube (MCNT) emitters by an electroporetic deposition (EPD) method using a MCNT-sodium dodecyl sulfate (SDS) suspension. MCNT films were prepared on graphite tip using EPD. We observe field emission properties of MCNT film after heat treatment. Consequently, The MCNT film on graphite tip exhibit good electron emission current.

Kinetic Modeling of the Fischer-Tropsch Reactions and Modeling Steady State Heterogeneous Reactor

The rate of production of main products of the Fischer-Tropsch reactions over Fe/HZSM5 bifunctional catalyst in a fixed bed reactor is investigated at a broad range of temperature, pressure, space velocity, H2/CO feed molar ratio and CO2, CH4 and water flow rates. Model discrimination and parameter estimation were performed according to the integral method of kinetic analysis. Due to lack of mechanism development for Fisher – Tropsch Synthesis on bifunctional catalysts, 26 different models were tested and the best model is selected. Comprehensive one and two dimensional heterogeneous reactor models are developed to simulate the performance of fixed-bed Fischer – Tropsch reactors. To reduce computational time for optimization purposes, an Artificial Feed Forward Neural Network (AFFNN) has been used to describe intra particle mass and heat transfer diffusion in the catalyst pellet. It is seen that products' reaction rates have direct relation with H2 partial pressure and reverse relation with CO partial pressure. The results show that the hybrid model has good agreement with rigorous mechanistic model, favoring that the hybrid model is about 25-30 times faster.