Mikrostrukturierte Sensoren für die pH-Wert-Bestimung auf Basis von dünnen, intrinisch leitfähigen Polyanilinschichten

Der pH-Wert stellt in der Chemie, Physik, Biologie, Pharmazie und Medizin eine wichtige Meßgröße dar, da eine Vielzahl von Reaktionen durch den pH-Wert bestimmt wird. In der Regel werden zur pH-Wert-Messung Glaselektroden eingesetzt. Hierbei konnte der pH-sensitive Bereich zwar bis auf einige Mikrometer reduziert werden, aber die Gesamtab-messungen betragen immer noch 15-20 cm. Mit der Einführung miniaturisierter Reaktionsgefäße ist daher der Bedarf an miniaturisierten Sensoren enorm gestiegen. Um in solchen Gefäßen Reaktionsparameter wie z. B. den pH-Wert zu kontrollieren, müssen die Gesamtabmessungen der Sensoren verringert werden. Dies lässt sich mit Hilfe der Mikrostrukturtechnik von Silizium realisieren. Hiermit lassen sich Strukturen und ganze Systeme bis in den Nanometerbereich herstellen. Basierend auf Silizium und Gold als Elektrodenmaterial wurden im Rahmen dieser Arbeit verschiedene Interdigitalstrukturen hergestellt. Um diese Strukturen zur pH-Wert-Messungen einsetzen zu können, müssen sie mit einer pH-sensitiven Schicht versehen werden. Hierbei wurde Polyanilin, ein intrinsisch leitendes Polymer, aufgrund seine pH-abhängigen elektrischen und optischen Verhaltens eingesetzt. Die Beschichtung dieser Sensoren mit Polyanilin erfolgte vorwiegend elektrochemisch mit Hilfe der Zyklovoltammetrie. Neben der Herstellung reiner Polyanilinfilme wurden auch Kopolymerisationen von Anilin und seinen entsprechenden Aminobenzoesäure- bzw. Aminobenzensulfonsäurederivaten durchgeführt. Ergebnisse dazu werden vorgestellt und diskutiert. Zur Charakterisierung der resultierenden Polyanilin- und Kopolymerfilme auf den Inter-digitalstrukturen wurden mit Hilfe der ATR-FT-IR-Spektroskopie Spektren aufgenommen, die gezeigt und diskutiert werden. Eine elektrochemische Charakterisierung der Polymere erfolgte mittels der Zyklovoltammetrie. Die mit Polyanilin bzw. seinen Kopolymeren beschichteten Sensoren wurden dann für Widerstandsmessungen an den Polymerfilmen in wässrigen Medien eingesetzt. Polyanilin zeigt lediglich eine pH-Sensitivität in einem pH-Bereich von pH 2 bis pH 4. Durch den Einsatz der Kopolymere konnte dieser pH-sensitive Bereich jedoch bis zu einem pH-Wert von 10 ausgeweitet werden. Zur weiteren Miniaturisierung der Sensoren wurde das Konzept der interdigitalen Elektroden-paare auf Cantilever übertragen. Die pH-sensitive Zone konnte dabei auf 500 µm2 bei einer Gesamtlänge des Sensors (Halter mit integriertem Cantilever) von 4 mm reduziert werden. Neben den elektrischen pH-abhängigen Eigenschaften können auch die optischen Eigen-schaften des Polyanilins zur pH-Detektion herangezogen werden. Diese wurden zunächst mit Hilfe der UV-VIS-Spektroskopie untersucht. Die erhaltenen Spektren werden gezeigt und kurz diskutiert. Mit Hilfe eines Raster-Sonden-Mikroskops (a-SNOM, Firma WITec) wurden Reflexionsmessungen an Polyanilinschichten durchgeführt. Zur weiteren Miniaturisierung wurden Siliziumdioxidhohlpyramiden (Basisfläche 400 µm2) mit Spitzenöffnungen in einem Bereich von 50-150 nm mit Polyanilin beschichtet. Auch hier sollten die optischen Eigenschaften des Polyanilins zur pH-Wert-Sensorik ausgenutzt werden. Es werden erste Messungen an diesen Strukturen in Transmission diskutiert.

Root-induced increases in soil pH and nutrient availability to field-grown cereals and legumes on acid sandy soils of Sudano-Sahelian West Africa

A field experiment with millet (Pennisetum glaucum L.), sorghum [Sorghum bicolor (L.) Moench], cowpea (Vigna unguiculata L.) and groundnut (Arachnis hypogeae L.) was conducted on severely P-deficient acid sandy soils of Niger, Mali and Burkina Faso to measure changes in pH and nutrient availability as affected by distance from the root surface and by mineral fertiliser application. Treatments included three rates of phosphorus (P) and four levels of nitrogen (N) application. Bulk, rhizosphere and rhizoplane soils were sampled at 35, 45 and 75 DAS in 1997 and at 55 and 65 DAS in 1998. Regardless of the cropping system and level of mineral fertiliser applied, soil pH consistently increased between 0.7 and two units from the bulk soil to the rhizoplane of millet. Similar pH gradients were observed in cowpea, but pH changes were much smaller in sorghum with a difference of only 0.3 units. Shifts in pH led to large increases in nutrient availability close to the roots. Compared with the bulk soil, available P in the rhizoplane was between 190 and 270% higher for P-Bray and between 360 and 600% higher for P-water. Exchangeable calcium (Ca) and magnesium (Mg) levels were also higher in the millet rhizoplane than in the bulk soil, whereas exchangeable aluminium (Al) levels decreased with increasing pH close to the root surface. The results suggest an important role of root-induced pH increases for crops to cope with acidity-induced nutrient deficiency and Al stress of soils in the Sudano-Sahelian zone of West Africa.

Short-term effects of human urine fertiliser and wood ash on soil pH and electrical conductivity

The fertiliser value of human urine has been examined on several crops, yet little is known about its effects on key soil properties of agronomic significance. This study investigated temporal soil salinization potential of human urine fertiliser (HUF). It further looked at combined effects of human urine and wood ash (WA) on soil pH, urine-NH_3 volatilisation, soil electrical conductivity (EC), and basic cation contents of two Acrisols (Adenta and Toje series) from the coastal savannah zone of Ghana. The experiment was a factorial design conducted in the laboratory for 12 weeks. The results indicated an increase in soil pH by 1.2 units for Adenta series and 1 unit for Toje series after one week of HUF application followed by a decline by about 2 pH units for both soil types after twelve weeks. This was attributed to nitrification of ammonium to nitrate leading to acidification. The EC otherwise increased with HUF application creating slightly saline conditions in Toje series and non-saline conditions in Adenta series. When WA was applied with HUF, both soil pH and EC increased. In contrast, the HUF alone slightly salinized Toje series, but both soils remained non-saline whenWA and HUF were applied together. The application ofWA resulted in two-fold increase in Ca, Mg, K, and Na content compared to HUF alone. Hence, WA is a promising amendment of acid soils and could reduce the effect of soluble salts in human urine fertilizer, which is likely to cause soil salinity.

Incidència del pH de la matèria primera dels nivells de sal afegit i de la temperatura sobre el grau de proteòlisi i la textura del pernil curat

Estudi de l’efecte del pH de la matèria primera, del nivell de sal afegit i de la temperatura sobre el grau de proteòlisi i sobre la textura final del pernil curat per tal de millorar els criteris que s’utilitzen per a la selecció de la matèria primera, avaluar les condiciones de procés òptimes (nivell de sal afegit i de la temperatura de curació) per l’elaboració del pernils destinats al llencat mecànic

Plan de Mejoramiento Para la Empresa AAA PH SAS Asistencia y Administración A Propiedad Horizontal

La oportunidad del mercado se define como la necesidad de abarcar el mercado de la administración de propiedad horizontal y la venta de copropiedades. Mercado que se encuentra en crecimiento en Bogotá. Enfocándonos en los estratos 5 y 6 de las localidades de Usaquén, Suba y Chapinero. En la actualidad son muy pocas las empresas especializadas en la administración de propiedad horizontal. Existen muchas empresas que intentan abarcar este mercado, pero no hay estrategias de fondo que permitan la satisfacción de los clientes, ni que generen valor agregado. Por lo tanto consideramos que es posible incursionar en el mercado con una idea que introduzca valor, que sea flexible, que cuente con estándares de calidad y que involucre la tecnología, de la mano del internet y la intención de hacerle la vida más fácil a los consejeros y copropietarios. El servicio principal de este emprendimiento es la administración de propiedad horizontal y el servicio secundario es la administración inmobiliaria para la venta de copropiedades. Nuestra capacidad de generar valor está dada a través de nuestra oficina virtual, nuestra estrategia de comunicación, nuestros aliados estratégicos y la asistencia personal dedicada. Las cuales creemos son la base fundamental para aprovechar esta oportunidad de negocio, generando empleo y obteniendo muy buenas ganancias y rentabilidades en el mediano y largo plazo. Hoy el mercado de la propiedad horizontal se encuentra en crecimiento. El tamaño del mercado es de (61.200’000.000) sesenta y un mil doscientos millones de pesos anuales, y crece en promedio alrededor del 1 %. Lo anterior según un estudio de proyección - Perspectivas del mercado de vivienda nueva y del sector edificador en 2012- realizado por la Cámara Colombiana de La Construcción (CAMACOL). AAA PH SAS o Asistencia y Administración a Propiedad Horizontal, cuanta en la actualidad con una participación en el mercado del 0,07843 por ciento, pero para el final de esta proyección se contara con una participación del 0.3921 por ciento. El proyecto se encuentra ubicado en la Avenida carrera 15 número 144-43 apartamento 101, Bogotá DC. El radio de acción está enfocado en las localidades de Suba, Chapinero y Usaquén en las copropiedades estrato 5 y 6. En el futuro se espera abarcar un radio mucho más amplio con oficinas en puntos estratégicos de la ciudad e involucrar municipios aledaños a la ciudad de Bogotá (Chía, Cota, Cajicá), y tal vez otras ciudades del país (Cartagena, Medellín) La inversión es de 22 millones de pesos. Los ingresos por ventas en el primer año son de 77 millones de pesos, en el segundo año de 135 millones de pesos y en el tercer año de 211 millones de pesos. La utilidad neta del primer año es de $ 631.866 pesos, en el segundo año de $ 17.827.602 pesos y en el tercer año de $ 28.024.867 pesos. Los gastos en su mayoría se ven reflejados en la mano de obra fija, ya que nuestros empleados tienen muy buenas capacidades y son retribuidos con un salario por encima del promedio del mercado. Esto porque nuestra intención es posicionar nuestra marca por nuestra exclusiva calidad de servicio, experiencia y alto contenido tecnológica para agilizar y facilitar procesos. La rentabilidad bruta es de del 77.63% anual. La rentabilidad sobre las ventas es de 0.82% anual, pero es necesario considerar que los valores de venta están siendo aproximados y según nuestra experiencia estos valores de venta serán mucho mayores, debido a la capacidad y el reconocimiento que ya tiene la empresa. Teniendo en cuenta que en la actualidad tenemos contratos que representan ingresos del doble del promedio presentado en esta proyección. De igual forma hay que considerar que en el mercado inmobiliario las comisiones por ventas pueden aumentar significativamente. La rentabilidad sobre la inversión supera a la del comportamiento del mercado o interés de oportunidad en un poco más de 9 millones de pesos. Esto significa que es un proyecto viable que genera mejores resultados que los del mercado de oportunidad, evidenciando que podríamos generar muy buenos ingresos. La tasa interna de retorno o TIR es igual a 33.22 %. Es un valor considerado alto pero que está de acuerdo a la tendencia del mercado de los servicios, en donde la TIR suele ser mucho más alta. Con este valor se recomienda seguir con el proyecto. Eso significa que por cada peso invertido en el proyecto se recupera cada peso y se generaran beneficios adicionales por 33.22 pesos. El valor del VPN o valor presente neto arrojado es de $9, 152,729 pesos. Esto quiere decir que se generan 9 millones de pesos adicionales al invertir los recursos en este proyecto, que en uno que rente el 14 % anual, por lo tanto se sugiere continuar con el proyecto e invertir los recursos. El indicador de viabilidad financiera, es el periodo de recuperación de la inversión (PRI). La inversión es de 22 millones de pesos, como la suma de las utilidades de los tres años es superior se afirma que la inversión se recupera en el tercer año.

Icosaedro y ph.

Resumen basado en el de la publicación

PH-Exao.

Programa para MS-Dos para realizar procesos de experimentación, simulación y modelización de valoraciones ácido-base. Incluye actividades para el alumnado.

La utilización del concepto de pH en la publicidad y su relación con las ideas que manejan los alumnos : aplicaciones en el aula.

Resumen basado en el de la publicación

Oxidation of silicon: further tests for the interfacial silicon emission model

The classical description of Si oxidation given by Deal and Grove has well-known limitations for thin oxides (below 200 Ã). Among the large number of alternative models published so far, the interfacial emission model has shown the greatest ability to fit the experimental oxidation curves. It relies on the assumption that during oxidation Si interstitials are emitted to the oxide to release strain and that the accumulation of these interstitials near the interface reduces the reaction rate there. The resulting set of differential equations makes it possible to model diverse oxidation experiments. In this paper, we have compared its predictions with two sets of experiments: (1) the pressure dependence for subatmospheric oxygen pressure and (2) the enhancement of the oxidation rate after annealing in inert atmosphere. The result is not satisfactory and raises serious doubts about the model’s correctness

Effects of short-term pH fluctuations on cadmium, nickel, lead, and zinc availability to ryegrass in a sewage sludge-amended field

In this field experiment, sewage sludge was applied at 0, 5, 10, and 50 t ha(-1), and the availability of Cd, Ni, Pb, and Zn was assessed both by ryegrass uptake and by DTPA extractions. The aim was to investigate the role of important soil parameters, particularly pH, on heavy metal availability. It was found that metal uptake and extractability increased significantly in the 50 t ha(-1) treatment. In the 16th week of the experiment there was a significant, although temporary, increase in DTPA-extractable Cd, Ni, and Zn concentrations. Metal concentrations in ryegrass were also significantly elevated in week 20 compared to the subsequent cuttings. These fluctuations in both DTPA and ryegrass uptake occurred only at 50 t ha(-1) and were probably induced by a sudden pH decrease measured in the same treatment in week 16. This suggests that soils which have received high applications of sewage sludge may be prone to fluctuations in metal availability. (c) 2007 Elsevier Ltd. All rights reserved.

Incorporating Legacy Soil pH Databases into Digital Soil Maps

Soil data and reliable soil maps are imperative for environmental management. conservation and policy. Data from historical point surveys, e.g. experiment site data and farmers fields can serve this purpose. However, legacy soil information is not necessarily collected for spatial analysis and mapping such that the data may not have immediately useful geo-references. Methods are required to utilise these historical soil databases so that we can produce quantitative maps of soil propel-ties to assess spatial and temporal trends but also to assess where future sampling is required. This paper discusses two such databases: the Representative Soil Sampling Scheme which has monitored the agricultural soil in England and Wales from 1969 to 2003 (between 400 and 900 bulked soil samples were taken annually from different agricultural fields); and the former State Chemistry Laboratory, Victoria, Australia where between 1973 and 1994 approximately 80,000 soil samples were submitted for analysis by farmers. Previous statistical analyses have been performed using administrative regions (with sharp boundaries) for both databases, which are largely unrelated to natural features. For a more detailed spatial analysis that call be linked to climate and terrain attributes, gradual variation of these soil properties should be described. Geostatistical techniques such as ordinary kriging are suited to this. This paper describes the format of the databases and initial approaches as to how they can be used for digital soil mapping. For this paper we have selected soil pH to illustrate the analyses for both databases.

The Representative Soil Sampling Scheme of England and Wales: the spatial variation of topsoil nutrient status and pH between 1971 and 2001

The Representative Soil Sampling Scheme (RSSS) has monitored the soil of agricultural land in England and Wales since 1969. Here we describe the first spatial analysis of the data from these surveys using geostatistics. Four years of data (1971, 1981, 1991 and 2001) were chosen to examine the nutrient (available K, Mg and P) and pH status of the soil. At each farm, four fields were sampled; however, for the earlier years, coordinates were available for the farm only and not for each field. The averaged data for each farm were used for spatial analysis and the variograms showed spatial structure even with the smaller sample size. These variograms provide a reasonable summary of the larger scale of variation identified from the data of the more intensively sampled National Soil Inventory. Maps of kriged predictions of K generally show larger values in the central and southeastern areas (above 200 mg L-1) and an increase in values in the west over time, whereas Mg is fairly stable over time. The kriged predictions of P show a decline over time, particularly in the east, and those of pH show an increase in the east over time. Disjunctive kriging was used to examine temporal changes in available P using probabilities less than given thresholds of this element. The RSSS was not designed for spatial analysis, but the results show that the data from these surveys are suitable for this purpose. The results of the spatial analysis, together with those of the statistical analyses, provide a comprehensive view of the RSSS database as a basis for monitoring the soil. These data should be taken into account when future national soil monitoring schemes are designed.

The influence of Fe-rich coatings on the dissolution of anorthite at pH 2.6

Surface coatings are very common on mineral grains in soils but most laboratory dissolution experiments are carried out on pristine, uncoated mineral grains. An experiment designed to unambiguously isolate the effect of surface coatings on mineral dissolution from any influence of solution saturation state is reported. Two aliquots of 53 to 63 mum anorthite feldspar powder were used. One was dissolved in pH 2.6 HCl, the other in pH 2.6 FeCl3 solution, both for similar to6000 h in flow-through reactors. An amorphous Fe-rich, Al-, Ca- and Si-free orange precipitate coated the anorthite dissolved in the FeCl3 solution. BET surface area of the anorthite increased from 0.16 to 1.65 m(2) g(-1) in the HCl experiment and to 3.89 m(2) g(-1) in the FeCl3 experiment. The increase in surface area in the HCl experiment was due to the formation of etch pits on the anorthite grain surface whilst the additional increase in the FeCl3 experiment was due to the micro- and meso-porous nature of the orange precipitate. This precipitate did not inhibit or slow the dissolution of the anorthite. Steady state dissolution rates for the anorthite dissolved in the HCl and FeCl3 were similar to2.5 and 3.2 X 10(-10) mol(feldspar) m(-2) s(-1) respectively. These rates are not significantly different after the cumulative uncertainty of 17% in their value due to uncertainty in the inputs parameters used in their calculation is taken into account. Results from this experiment support previous theoretical and inference-based conclusions that porous coatings should not inhibit mineral dissolution. Copyright (C) 2003 Elsevier Ltd.

Does reactive surface area depend on grain size? Results from pH 3, 25 circle C far-from-equilibrium flow-through dissolution experiments on anorthite and biotite

Laboratory determined mineral weathering rates need to be normalised to allow their extrapolation to natural systems. The principle normalisation terms used in the literature are mass, and geometric- and BET specific surface area (SSA). The purpose of this study was to determine how dissolution rates normalised to these terms vary with grain size. Different size fractions of anorthite and biotite ranging from 180-150 to 20-10 mu m were dissolved in pH 3, HCl at 25 degrees C in flow through reactors under far from equilibrium conditions. Steady state dissolution rates after 5376 h (anorthite) and 4992 h (biotite) were calculated from Si concentrations and were normalised to initial- and final- mass and geometric-, geometric edge- (biotite), and BET SSA. For anorthite, rates normalised to initial- and final-BET SSA ranged from 0.33 to 2.77 X 10(-10) mol(feldspar) m(-2) s(-1), rates normalised to initial- and final-geometric SSA ranged from 5.74 to 8.88 X 10(-10) mol(feldspar) m(-2) s(-1) and rates normalised to initial- and final-mass ranged from 0.11 to 1.65 mol(feldspar) g(-1) s(-1). For biotite, rates normalised to initial- and final-BET SSA ranged from 1.02 to 2.03 X 10(-12) mol(biotite) m(-2) s(-1), rates normalised to initial- and final-geometric SSA ranged from 3.26 to 16.21 X 10(-12) mol(biotite) m(-2) s(-1), rates normalised to initial- and final-geometric edge SSA ranged from 59.46 to 111.32 x 10(-12) mol(biotite) m(-2) s(-1) and rates normalised to initial- and final-mass ranged from 0.81 to 6.93 X 10(-12) mol(biotite) g(-1) s(-1). For all normalising terms rates varied significantly (p <= 0.05) with grain size. The normalising terms which gave least variation in dissolution rate between grain sizes for anorthite were initial BET SSA and initial- and final-geometric SSA. This is consistent with: (1) dissolution being dominated by the slower dissolving but area dominant non-etched surfaces of the grains and, (2) the walls of etch pits and other dissolution features being relatively unreactive. These steady state normalised dissolution rates are likely to be constant with time. Normalisation to final BET SSA did not give constant ratios across grain size due to a non-uniform distribution of dissolution features. After dissolution coarser grains had a greater density of dissolution features with BET-measurable but unreactive wall surface area than the finer grains. The normalising term which gave the least variation in dissolution rates between grain sizes for biotite was initial BET SSA. Initial- and final-geometric edge SSA and final BET SSA gave the next least varied rates. The basal surfaces dissolved sufficiently rapidly to influence bulk dissolution rate and prevent geometric edge SSA normalised dissolution rates showing the least variation. Simple modelling indicated that biotite grain edges dissolved 71-132 times faster than basal surfaces. In this experiment, initial BET SSA best integrated the different areas and reactivities of the edge and basal surfaces of biotite. Steady state dissolution rates are likely to vary with time as dissolution alters the ratio of edge to basal surface area. Therefore they would be more properly termed pseudo-steady state rates, only appearing constant because the time period over which they were measured (1512 h) was less than the time period over wich they would change significantly. (c) 2006 Elsevier Inc. All rights reserved.

Effect of pH on the development of acidic sites in clayey and sandy loam Oxisol from the Cerrado Region, Brazil

Titration curves were determined for soil from horizon samples of a clayey and a sandy loam Oxisol by (a) adding NaOH to soil suspensions and (b) incubating moist soils with Ca(OH)(2). The organic fraction was primarily responsible for buffering in both soils. Humic acids were more important than fulvic acids in buffering against NaOH additions. With Ca(OH)(2), greater buffer capacities were found due to carboxyl sites, primarily on fulvic acids, becoming complexed with Ca2+ so that in the clay soil humic and fulvic acids were equally important as buffering components while fulvic acids were more important in the sandy loam soil. The buffer capacity of organic matter against Ca(OH)(2) additions was 1.1 mol(c) kg(-1) pH(-1). In the incubated soils, exchangeable cations were also determined and changes in the amounts of exchangeable and non-exchangeable Ca2+ acidity and effective cation exchange capacity were calculated. Up to half the added Ca2+ became complexed and was nonexchangeable. Aluminum complexed by organic matter appears to be an important buffering component, together with non exchangeable H+. With the increase of pH the dissociated sites from the carboxyl groups could complex Ca2+. (c) 2005 Elsevier B.V. All rights reserved.