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.

Paper for printed electronics and functionality

Mass-produced paper electronics (large area organic printed electronics on paper-based substrates, “throw-away electronics”) has the potential to introduce the use of flexible electronic applications in everyday life. While paper manufacturing and printing have a long history, they were not developed with electronic applications in mind. Modifications to paper substrates and printing processes are required in order to obtain working electronic devices. This should be done while maintaining the high throughput of conventional printing techniques and the low cost and recyclability of paper. An understanding of the interactions between the functional materials, the printing process and the substrate are required for successful manufacturing of advanced devices on paper. Based on the understanding, a recyclable, multilayer-coated paper-based substrate that combines adequate barrier and printability properties for printed electronics and sensor applications was developed in this work. In this multilayer structure, a thin top-coating consisting of mineral pigments is coated on top of a dispersion-coated barrier layer. The top-coating provides well-controlled sorption properties through controlled thickness and porosity, thus enabling optimizing the printability of functional materials. The penetration of ink solvents and functional materials stops at the barrier layer, which not only improves the performance of the functional material but also eliminates potential fiber swelling and de-bonding that can occur when the solvents are allowed to penetrate into the base paper. The multi-layer coated paper under consideration in the current work consists of a pre-coating and a smoothing layer on which the barrier layer is deposited. Coated fine paper may also be used directly as basepaper, ensuring a smooth base for the barrier layer. The top layer is thin and smooth consisting of mineral pigments such as kaolin, precipitated calcium carbonate, silica or blends of these. All the materials in the coating structure have been chosen in order to maintain the recyclability and sustainability of the substrate. The substrate can be coated in steps, sequentially layer by layer, which requires detailed understanding and tuning of the wetting properties and topography of the barrier layer versus the surface tension of the top-coating. A cost competitive method for industrial scale production is the curtain coating technique allowing extremely thin top-coatings to be applied simultaneously with a closed and sealed barrier layer. The understanding of the interactions between functional materials formulated and applied on paper as inks, makes it possible to create a paper-based substrate that can be used to manufacture printed electronics-based devices and sensors on paper. The multitude of functional materials and their complex interactions make it challenging to draw general conclusions in this topic area. Inevitably, the results become partially specific to the device chosen and the materials needed in its manufacturing. Based on the results, it is clear that for inks based on dissolved or small size functional materials, a barrier layer is beneficial and ensures the functionality of the printed material in a device. The required active barrier life time depends on the solvents or analytes used and their volatility. High aspect ratio mineral pigments, which create tortuous pathways and physical barriers within the barrier layer limit the penetration of solvents used in functional inks. The surface pore volume and pore size can be optimized for a given printing process and ink through a choice of pigment type and coating layer thickness. However, when manufacturing multilayer functional devices, such as transistors, which consist of several printed layers, compromises have to be made. E.g., while a thick and porous top-coating is preferable for printing of source and drain electrodes with a silver particle ink, a thinner and less absorbing surface is required to form a functional semiconducting layer. With the multilayer coating structure concept developed in this work, it was possible to make the paper substrate suitable for printed functionality. The possibility of printing functional devices, such as transistors, sensors and pixels in a roll-to-roll process on paper is demonstrated which may enable introducing paper for use in disposable “onetime use” or “throwaway” electronics and sensors, such as lab-on-strip devices for various analyses, consumer packages equipped with product quality sensors or remote tracking devices.

Regioselective modification of galactose-containing polysaccharides in aqueous media

Biorefining is defined as sustainable conversion of biomass into marketable products and energy. Forests cover almost one third of earth’s land area, and account for approximately 40% of the total annual biomass production. In forest biorefining, the wood components are, in addition to the traditional paper and board products, converted into chemicals and biofuels. The major components in wood are cellulose, hemicelluloses, and lignin. The main hemicellulose in softwoods, which are of interest especially for the Nordic forest industry, is O-acetyl galactoglucomannan (GGM). GGM can be isolated in industrial scale from the waste waters of the mechanical pulping process, but is not yet today industrially utilized. In order to attain desired properties of GGM for specific end-uses, chemical and enzymatic modifications can be performed. Regioselective modifications of GGM, and other galactose-containing polysaccharides were done by oxidations, and by combining oxidations with subsequent derivatizations of the formed carbonyl or carboxyl groups. Two different pathways were investigated: activation of the C-6 positions in different sugar units by TEMPO-mediated oxidation, and activation of C-6 position in only galactose-units by oxidation catalyzed by the enzyme galactose oxidase. The activated sites were further selectively derivatized; TEMPO-oxidized GGM by a carbodiimide-mediated reaction forming amides, and GO-oxidized GGM by indium-mediated allylation introducing double or triple bonds to the molecule. In order to better understand the reaction, and to develop a MALDI-TOF-MS method for characterization of regioselectively allylated GGM, α-D-galactopyranoside and raffinose were used as model compounds. All reactions were done in aqueous media. To investigate the applicability of the modified polysaccharides for, e.g., cellulose surface functionalization, their sorption onto pulp fibres was studied. Carboxylation affects the sorption tendency significantly; a higher degree of oxidation leads to lower sorption. By controlling the degree of oxidation of the polysaccharides and the ionic strength of the sorption media, high degrees of sorption of carboxylated polysaccharides onto cellulose could, however, be obtained. Anionic polysaccharides were used as templates during laccase-catalyzed polymerization of aniline, offering a green, chemo-enzymatic route for synthesis of conducting polyaniline (PANI) composite materials. Different polysaccharide templates, such as, native GGM, TEMPO-oxidized GGM, naturally anionic κ-carrageenan, and nanofibrillated cellulose produced by TEMPO-oxidation, were assessed. The conductivity of the synthesized polysaccharide/PANI biocomposites varies depending on the polysaccharide template; κ-CGN, the anionic polysaccharide with the lowest pKa value, produces the polysaccharide/PANI biocomposites with the highest conductivity. The presented derivatization, sorption, and polymerization procedures open new application windows for polysaccharides, such as spruce GGM. The modified polysaccharides and the conducting biocomposites produced provide potential applications in biosensors, electronic devices, and tissue engineering.

Atrazine and picloram adsorption in organic horizon forest samples under laboratory conditions

Adsorption of two herbicides, atrazine and picloram, displaying different sorption characteristics, were evaluated for O (organic) horizon samples collected from SMZs (streamside management zones) in Piedmont (Ultisol) of Georgia, USA. Samples were randomly collected from within 5 SMZs selected for a study of surface flow in field trials. The five SMZs represented five different slope classes, 2, 5, 10, 15 and 20%. Results indicate that 0 horizons have the potential for sorbing atrazine from surface water moving through forested SMZs. Atrazine adsorption was nearly linear over a 24-hour period. Equilibrium adsorption, determined through 24-hour laboratory tests, resulted in a Freundlich coefficient of 67.5 for atrazine. For picloram, negative adsorption was observed in laboratory experiments. This seemed to be due to interference with ELISA analyses; however, this was not confirmed. The adsorption coefficient (Kd) obtained for atrazine in 0 horizons was greater than it would have been expected for mineral soil (from 1 to 4). Picloram was not sorbed in 0 horizons at any significant degree. Although there is a significant potential for the direct adsorption of soluble forms of herbicides in SMZs, the actual value of this adsorption for protecting water is likely to be limited even for relatively strongly sorbed chemicals, such as atrazine, due to relatively slow uptake kinetics.

Streamside management zone (SMZ) efficiency in herbicide retention from simulated surface flow

Plot-scale overland flow experiments were conducted to evaluate the efficiency of streamside management zones (SMZs) in retaining herbicides in runoff generated from silvicultural activities. Herbicide retention was evaluated for five different slopes (2, 5, 10, 15, and 20%), two cover conditions (undisturbed O horizon and raked surface), and two periods under contrasting soil moisture conditions (summer dry and winter wet season) and correlated to O horizon and site conditions. Picloram (highly soluble in water) and atrazine (moderately sorbed into soil particles) at concentrations in the range of 55 and 35 µg L-1 and kaolin clay (approximately 5 g L-1) were mixed with 13.000 liters of water and dispersed over the top of 5 x 10 m forested plots. Surface flow was collected 2, 4, 6, and 10 m below the disperser to evaluate the changes in concentration as it moved through the O horizon and surface soil horizon-mixing zone. Results showed that, on average, a 10 m long forested SMZ removed around 25% of the initial concentration of atrazine and was generally ineffective in reducing the more soluble picloram. Retention of picloram was only 6% of the applied quantity. Percentages of mass reduction by infiltration were 36% for atrazine and 20% for picloram. Stronger relationships existed between O horizon depth and atrazine retention than in any other measured variable, suggesting that better solid-solution contact associated with flow through deeper O horizons is more important than either velocity or soil moisture as a determinant of sorption.

Rainfall effect on dissipation and movement of diuron and simazine in a vineyard soil

From 2003 to 2007, a field study was performed in a vineyard in Chile to investigate diuron and simazine soil behavior and the effect of additional rainfall. Both herbicides were applied once a year at a rate of 2.0 kg ha-1 a.i. Herbicide concentrations in soil were measured at 0, 10, 20, 40, 90 and 340 days after application, under two pluviometric conditions, natural rainfall and natural rainfall plus irrigation with 180 mm of simulated rainfall during the first 90 days after application. Soil partition coefficient (Kd) varied in the soil profile (0 to 90 cm deep) from 6.75 to 2.04 mL g-1 and from 1.4 to 0.66 mL g-1 and the maximum soil adsorption capacity was approximately 18.3 mg g-1 and 8.3 mg g-1 for diuron and simazine, respectively. Diuron and simazine reached up to 90 and 120 cm of soil depth, with an average of 8.3% and 62.4% of herbicide moved below 15 cm in the soil, respectively. Simazine soil half-life (DT50) was 38.1 days and 7.5 days, whereas the half life for diuron varied from 68.0 and 24.6 for natural rainfall and irrigated, respectively. The average of residual simazine remaining in the whole soil profile after 90 DAA was 25.4% and 39.9% for diuron, with no effect of additional rainfall amount. At 340 DAA the amount of simazine in the whole soil profile corresponded to 13.2% of the initial amount applied, being diuron more persistent with 21.5% of the initial herbicide applied. The high movement in soil of both herbicides could be due to a non-equilibrium sorption process explained by preferential flow, low Kd and high desorption.

VINASSE EFFECT ON HERBICIDES CLOMAZONE AND TEBUTHIURON AVAILABILITY IN DIFFERENT KINDS OF SOILS

ABSTRACT The objective of this study was to evaluate the availability of herbicides clomazone and tebuthiuron in the solution in different kinds of soils saturated with water or vinasse. Samples of 30 soils with different characteristics were arranged on trays to the herbicides spraying. Then they were homogenized, placed in plastic cartridges and saturated with deionized water or vinasse, and remaining at rest during 18 hours. Two extractions were made, the first one quantified the presence of the herbicides in the soil solution and in the second one the total extraction of herbicide remaining in the soil was taken to determine the recovery percentage of each herbicide tested. For quantification, a LC-MS/MS system was used, a compound of a high performance liquid chromatograph (HPLC) coupled to a triple quadruple mass spectrometer. Tebuthiuron was more available in the soil with the vinasse addition when compared to water. Vinasse applications resulted in no significant difference in availability of clomazone between treatments. Tebuthiuron showed the highest availability frequencies, and on average of all samples 32.49% were extracted from total herbicide applied, while for clomazone this value was 16.50%.

Leaching of Sulfentrazone in Soils from the Sugarcane Region in the Northeast Region of Brazil

Sulfentrazone leaching potential is dependent on soil properties such as strength and type of clay, organic matter content and pH, and may result in ineffectiveness of the product and contamination of groundwater. The objective of this study was to evaluate sulfentrazone leaching in five soils of the sugarcane region in the Northeast Region of Brazil, with different physical and chemical properties, by means of bioassay and high-performance liquid chromatography (HPLC) resolution. The experiment was conducted in a split plot in a completely randomized design. The plots had PVC columns with a 10 cm diameter and being 50 cm deep, filled with five different soil classes (quartzarenic neosol, haplic cambisol, yellowish-red latosol, yellowish-red acrisol, and haplic gleysol), and subplots for 10 depths in columns, 5 cm intervals. On top of the columns, sulfentrazone application was conducted and 12 hours later there was a simulated rainfall of 60 mm. After 72 hours, the columns were horizontally placed and longitudinally open, divided into sections of 5.0 cm. In the center of each section of the columns, soil samples were collected for chromatographic analyses and sorghum sowing was carried out as an indicator plant. The bioassay method was more sensitive to detect the presence of sulfentrazone in an assessment for chromatography soil, having provided greater herbicide mobility in quartzarenic neosol and yellowish-red latosol, whose presence was detected by the indicator plant to a depth of 45 and 35 cm, respectively. In the other soils, sulfentrazone was detected up to 20 cm deep. The intense mobility of sulfentrazone in quartzarenic neosol may result in herbicide efficiency loss in the soil because the symptoms of intoxication and the amount of herbicide detected via silica were highest between 15 cm and 35 cm depth regarding the soil surface layer (0-10 cm), indicating that sulfentrazone should be avoided in soils with such characteristics.

SEPARATION OF SATURED AND UNSATURATED FATTY ACIDS FROM PALM FATTY ACIDS DISTILLATES IN CONTINUOUS MULTISTAGE COUNTERCURRENT COLUMNS WITH SUPERCRITICAL CARBON DIOXIDE AS SOLVENT: A PROCESS DESIGN METHODOLOGY

In this work the separation of multicomponent mixtures in counter-current columns with supercritical carbon dioxide has been investigated using a process design methodology. First the separation task must be defined, then phase equilibria experiments are carried out, and the data obtained are correlated with thermodynamic models or empirical functions. Mutual solubilities, Ki-values, and separation factors aij are determined. Based on this data possible operating conditions for further extraction experiments can be determined. Separation analysis using graphical methods are performed to optimize the process parameters. Hydrodynamic experiments are carried out to determine the flow capacity diagram. Extraction experiments in laboratory scale are planned and carried out in order to determine HETP values, to validate the simulation results, and to provide new materials for additional phase equilibria experiments, needed to determine the dependence of separation factors on concetration. Numerical simulation of the separation process and auxiliary systems is carried out to optimize the number of stages, solvent-to-feed ratio, product purity, yield, and energy consumption. Scale-up and cost analysis close the process design. The separation of palmitic acid and (oleic+linoleic) acids from PFAD-Palm Fatty Acids Distillates was used as a case study.

THE GENERALIZED MAXIMUM LIKELIHOOD METHOD APPLIED TO HIGH PRESSURE PHASE EQUILIBRIUM

The generalized maximum likelihood method was used to determine binary interaction parameters between carbon dioxide and components of orange essential oil. Vapor-liquid equilibrium was modeled with Peng-Robinson and Soave-Redlich-Kwong equations, using a methodology proposed in 1979 by Asselineau, Bogdanic and Vidal. Experimental vapor-liquid equilibrium data on binary mixtures formed with carbon dioxide and compounds usually found in orange essential oil were used to test the model. These systems were chosen to demonstrate that the maximum likelihood method produces binary interaction parameters for cubic equations of state capable of satisfactorily describing phase equilibrium, even for a binary such as ethanol/CO2. Results corroborate that the Peng-Robinson, as well as the Soave-Redlich-Kwong, equation can be used to describe phase equilibrium for the following systems: components of essential oil of orange/CO2.

HIGH PRESSURE PHASE EQUILIBRIUM: PREDICTION OF ESSENTIAL OIL SOLUBILITY

This work describes a method to predict the solubility of essential oils in supercritical carbon dioxide. The method is based on the formulation proposed in 1979 by Asselineau, Bogdanic and Vidal. The Peng-Robinson and Soave-Redlich-Kwong cubic equations of state were used with the van der Waals mixing rules with two interaction parameters. Method validation was accomplished calculating orange essential oil solubility in pressurized carbon dioxide. The solubility of orange essential oil in carbon dioxide calculated at 308.15 K for pressures of 50 to 70 bar varied from 1.7± 0.1 to 3.6± 0.1 mg/g. For same the range of conditions, experimental solubility varied from 1.7± 0.1 to 3.6± 0.1 mg/g. Predicted values were not very sensitive to initial oil composition.

Enthalpy-entropy compensation based on isotherms of mango

Moisture equilibrium data of mango pulp were determined using the static gravimetric method. Adsorption and desorption isotherms were obtained in the range of 30-70 ºC, to water activities (a w) from 0.02 to 0.97. The application of the GAB model to the experimental results, using direct nonlinear regression analysis, provided agreement between experimental and calculated values. The net isosteric heat of sorption was estimated from equilibrium sorption data, using the Clausius-Clapeyron equation. Isosteric heats of sorption were found to increase with increasing temperature and could be well adjusted by an exponential relationship. The enthalpy-entropy compensation theory was applied to sorption isotherms and plots of deltaH versus deltaS provided the isokinetic temperatures, indicating an enthalpy controlled sorption process.

Moisture adsorption characteristics of ginger slices

The moisture adsorption characteristics of dried ginger slices was studied to determine the effect of storage conditions on moisture adsorption for the purpose of shelf life prediction, selection of appropriate packaging materials, evaluate the goodness-of-fit of sorption models, and determine the thermodynamics of moisture adsorption for application in drying. There was a highly significant effect (p < 0.05) of water activity (a w), temperature, and pre-treatment on the equilibrium moisture content (EMC) of the dried ginger slices. At constant a w, the EMC decreased as temperature increased. The EMC of all samples increased as the a w increased at constant temperature. The sorbed moisture of the unpeeled ginger slices was higher than the peeled while those of unblanched samples were higher than the blanched. Henderson equation allows more accurate predictions about the isotherms with the lowest %RMS, and therefore, it describes best the adsorption data followed by GAB, Oswin, and Halsey models in that order. The monolayer moisture generally decreased with temperature for all samples. The isosteric heat decreased with moisture content approaching the asymptotic value or the latent heat of vaporization of pure water (∆Hst = 0) while the entropy of sorption was observed to increase with moisture content.

Effect of drying method on the adsorption isotherms and isosteric heat of passion fruit pulp powder

The sorption behavior of dry products is generally affected by the drying method. The sorption isotherms are useful to determine and compare thermodynamic properties of passion fruit pulp powder processed by different drying methods. The objective of this study is to analyze the effects of different drying methods on the sorption properties of passion fruit pulp powder. Passion fruit pulp powder was dehydrated using different dryers: vacuum, spray dryer, vibro-fluidized, and freeze dryer. The moisture equilibrium data of Passion Fruit Pulp (PFP) powders with 55% of maltodextrin (MD) were determined at 20, 30, 40 and 50 ºC. The behavior of the curves was type III, according to Brunauer's classification, and the GAB model was fitted to the experimental equilibrium data. The equilibrium moisture contents of the samples were little affected by temperature variation. The spray dryer provides a dry product with higher adsorption capacity than that of the other methods. The vibro-fluidized bed drying showed higher adsorption capacity than that of vacuum and freeze drying. The vacuum and freeze drying presented the same adsorption capacity. The isosteric heats of sorption were found to decrease with increasing moisture content. Considering the effect of drying methods, the highest isosteric heat of sorption was observed for powders produced by spray drying, whereas powders obtained by vacuum and freeze drying showed the lowest isosteric heats of sorption.

Study of adsorption isotherms of green coconut pulp

Brazil is considered one of the largest producers and consumers of tropical fruits. Green coconut (Cocos nucifera L.) stands out not only for its production and consumption, but also for the high amount of waste produced by coconut water industry and in natura consumption. Therefore, there is a need for utilization of this by-product. This study aims to study the adsorption isotherms of green coconut pulp and determine its isosteric heat of sorption. The adsorption isotherms at temperatures of 30, 40, 50, 60, and 70 °C were analyzed, and they exhibit type III behavior, typical of sugar rich foods. The experimental results of equilibrium moisture content were correlated by models present in the literature. The Guggenheim, Anderson and De Boer (GAB) model proved particularly good overall agreement with the experimental data. The heat of sorption determined from the adsorption isotherms increased with the decrease in moisture content. The heat of sorption is considered as indicative of intermolecular attractive forces between the sorption sites and water vapor, which is an important factor to predict the shelf life of dried products.