0 AND 02 ADSORPTION ON Ag/Cu[100]

In this work the adsorption mechanisms of atomic and molecular oxygen on Cu(100) surface are studied using ab initio simulation methods. Through the atomistic scale under-standing of the elementary oxidation processes we can further understand the large-scale oxidation. Copper is a material widely used in industry which makes it an interesting subject, and also understanding the oxidation of copper helps us understand the oxidation mechanism of other metals. First we have a look on some theory on surface alloys in general and behaviour of Ag on Cu(100) surface. After that the physical background there is behind the methods of density functional calculations are discussed, and some methods, namely potential energy surfaces and molecular dynamics, are introduced. Then there is a brief look on the numerical details used in the calculations, and after that, the results of the simulations are exhibited.

Quasi real-time Raman studies on the growth of Cu-In-S thin films

In this work annealing and growth of CuInS2 thin films is investigated with quasireal-time in situ Raman spectroscopy. During the annealing a shift of the Raman A1 mode towards lower wave numbers with increasing temperature is observed. A linear temperature dependence of the phonon branch of ¿2 cm¿1/100 K is evaluated. The investigation of the growth process (sulfurization of metallic precursors) with high surface sensitivity reveals the occurrence of phases which are not detected with bulk sensitive methods. This allows a detailed insight in the formation of the CuInS2 phases. Independent from stoichiometry and doping of the starting precursors the CuAu ordering of CuInS2 initially forms as the dominating ordering. The transformation of the CuAu ordering into the chalcopyrite one is, in contrast, strongly dependent on the precursor composition and requires high temperatures.

Oxygen adsorption on Cu(510)

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

Oxygen adsorption on Cu(211) and structurally and chemically modified Cu(100)

Kuparipinnan hapettuminen on viimevuosina ollut suosittu tutkimuskohde materiaalitieteissä kuparin laajan teollisuuskäytön vuoksi. Teollisuussovellusten, kuten suojaavien pintaoksidien kehittäminen vaatii kuitenkin syvällistä tuntemusta hapettumisprosessista ja toisaalta myös normaaliolosuhteissa materiaalissa esiintyvien hilavirheiden vaikutuksesta siihen. Tässä työssä keskitytäänkin tutkimaan juuri niitä mekanismeja, joilla erilaiset pintavirheet ja porrastettu pintarakenne vaikuttavathapen adsorptioprosessiin kuparipinnalla. Tutkimus on tehty käyttämällä laskennallisia menetelmiä sekä VASP- ja SIESTA-ohjelmistoja. Työssätutkittiin kemiallisia ja rakenteellisia virheitä Cu(100)-pinnalla, joka on reaktiivisin matalanMillerin indeksin pinta ja porrastetun pinnan tutkimuksessa käytettiin Cu(211)-pintaa, joka puolestaan on yksinkertainen, stabiili ja aiemmissa tutkimuksissa usein käytetty pintarakenne. Työssä tutkitut hilavirheet, adatomit, vähentävät molekyylin dissosiaatiota kuparipinnalla, kun taas vakanssit toimivat dissosiaation keskuksina. Kemiallisena epäpuhtautena käytetty hopeakerros ei estä kuparin hapettumista, sillä happi aiheuttaa mielenkiintoisen segregaatioilmiön, jossa hopeatyöntyy syvemmälle pinnassa jättäen kuparipinnan suojaamattomaksi. Porrastetulla pinnalla (100)-hollow on todennäköisin paikka molekyylin dissosiaatiolle, kun taas portaan bridge-paikka on suotuisin molekulaariselle adsorptiolle. Lisäksi kuparin steppipinnan todettiin olevan reaktiivisempi kuin tasaiset kuparipinnat.

Self-Organising Maps and Correlation Analysis as a Tool to Explore Patterns in Excitation-Emission Matrix Data Sets and to Discriminate Dissolved Organic Matter Fluorescence Components

Dissolved organic matter (DOM) is a complex mixture of organic compounds, ubiquitous in marine and freshwater systems. Fluorescence spectroscopy, by means of Excitation-Emission Matrices (EEM), has become an indispensable tool to study DOM sources, transport and fate in aquatic ecosystems. However the statistical treatment of large and heterogeneous EEM data sets still represents an important challenge for biogeochemists. Recently, Self-Organising Maps (SOM) has been proposed as a tool to explore patterns in large EEM data sets. SOM is a pattern recognition method which clusterizes and reduces the dimensionality of input EEMs without relying on any assumption about the data structure. In this paper, we show how SOM, coupled with a correlation analysis of the component planes, can be used both to explore patterns among samples, as well as to identify individual fluorescence components. We analysed a large and heterogeneous EEM data set, including samples from a river catchment collected under a range of hydrological conditions, along a 60-km downstream gradient, and under the influence of different degrees of anthropogenic impact. According to our results, chemical industry effluents appeared to have unique and distinctive spectral characteristics. On the other hand, river samples collected under flash flood conditions showed homogeneous EEM shapes. The correlation analysis of the component planes suggested the presence of four fluorescence components, consistent with DOM components previously described in the literature. A remarkable strength of this methodology was that outlier samples appeared naturally integrated in the analysis. We conclude that SOM coupled with a correlation analysis procedure is a promising tool for studying large and heterogeneous EEM data sets.

Disponibilitat per a les plantes de Mn, Cu, Zn i Cd en els sòls de diferents sistemes agrícoles a Catalunya

Es va avaluar el contingut del sòl en Mn, Cu, Zn, Ni i Cd fent una extracció amb DTPA, segons el mètode de Lindsay i Norvell (1969). Les mostres analitzades procedien de parcel·les agrícoles d'arreu de Catalunya, conservades al Banc de Mostres de Sòls del Mapa de Sòls de Catalunya del DARP. Els resultats es van agrupar per sistemes agrícoles en funció de l'origen de les mostres, ja que dins de cada un es pot assumir una reducció important en l'interval de variació de diferents factors. Es va realitzar una comparació estadística entre els valors mitjans dels diferents sistemes agrícoles, entre els valors mitjans de les dues profunditats de sòl considerades, i una interpretació agronòmica. Els resultats van indicar que els sòls procedents d'horticultura intensiva del Maresme són els que tenen continguts disponibles més elevats dels metalls considerats. D'altra banda, es fa palès que els valors estan condicionats tant pel material originari del sòl com per l'acció antròpica. Per al Cu i el Zn en les mostres de sòls del Maresme els continguts trobats estan molt per sobre dels mínims considerats com a agronòmicament satisfactoris.

Technical Note: Dissolved organic matter fluorescence a finite mixture approach to deconvolve excitation-emission matrices

The analysis of the shape of excitation-emission matrices (EEMs) is a relevant tool for exploring the origin, transport and fate of dissolved organic matter (DOM) in aquatic ecosystems. Within this context, the decomposition of EEMs is acquiring a notable relevance. A simple mathematical algorithm that automatically deconvolves individual EEMs is described, creating new possibilities for the comparison of DOM fluorescence properties and EEMs that are very different from each other. A mixture model approach is adopted to decompose complex surfaces into sub-peaks. The laplacian operator and the Nelder-Mead optimisation algorithm are implemented to individuate and automatically locate potential peaks in the EEM landscape. The EEMs of a simple artificial mixture of fluorophores and DOM samples collected in a Mediterranean river are used to describe the model application and to illustrate a strategy that optimises the search for the optimal output.

Mineralización estratiforme de Pb-Zn-Cu en el Paleozoico de Bassegoda (Pirineo Oriental)

Al Sur del pico de Bassegoda existe una mineralización estratiforme de galena, esfalerita y pirita con calcopirita y arsenopirita, en forma de diseminaciones y lentejones masivos, situadas dentro de un tramo de 10 metros de micaesquistos y dolomias negras. Estos niveles mineralizados se hallan en el contacto entre micaesquistos y dolomias masivas que contienen piroclastos cidos. Tanto el tipo de depósito como la litologia encajante, permiten correlacionar esta mineralización con un conjunto de concentraciones metalicas estratiformes y estratoligadas del Cambro-Ordovicico del NE de Cataluña.

Microclima e produção da uva de mesa 'Niagara Rosada' conduzida em espaldeira a céu aberto e em manjedoura na forma de "Y" sob cobertura de telado plástico

Foi desenvolvido um experimento em vinhedos de 'Niagara Rosada', conduzidos em espaldeira e em manjedoura na forma de Y com cobertura de telado plástico, visando a comparar as alterações microclimáticas induzidas pelo sistema de condução e uso de telado plástico, e o efeito na produtividade das videiras. Entre os parâmetros microclimáticos avaliados, apenas a radiação solar foi atenuada pelo telado plástico em cerca de 20%, acima do dossel, tendo sido transmitido para a altura do cacho, cerca de 41% da radiação solar no sistema em Y sob telado plástico e 21% no espaldeira. As temperaturas máximas e mínimas foram semelhantes em ambos os sistemas. A produção por planta e a massa dos cachos foram mais elevadas no sistema em Y sob telado plástico, em comparação ao espaldeira.

Geology of the Cerro-Quema Au-Cu deposit (Azuero Peninsula, Panama)

The Cerro Quema district, located on the Azuero Peninsula, Panama, is part of a large regional hydrothermal system controlled by regional faults striking broadly E-W, developed within the Río Quema Formation. This formation is composed of volcanic, sedimentary and volcano-sedimentary rocks indicating a submarine depositional environment, corresponding to the fore-arc basin of a Cretaceous-Paleogene volcanic arc. The structures observed in the area and their tectono-stratigraphic relationship with the surrounding formations suggest a compressive and/or transpressive tectonic regime, at least during Late Cretaceous-Oligocene times. The igneous rocks of the Río Quema Formation plot within the calc-alkaline field with trace and rare earth element (REE) patterns of volcanic arc affinity. This volcanic arc developed on the Caribbean large igneous province during subduction of the Farallon Plate. Mineralization consists of disseminations of pyrite and enargite as well as a stockwork of pyrite and barite with minor sphalerite, galena and chalcopyrite, hosted by a subaqueous dacitic lava dome of the Río Quema Formation. Gold is present as submicroscopic grains and associated with pyrite as invisible gold. A hydrothermal alteration pattern with a core of advanced argillic alteration (vuggy silica with alunite, dickite, pyrite and enargite) and an outer zone of argillic alteration (kaolinite, smectite and illite) has been observed. Supergene oxidation overprinted the hydrothermal alteration resulting in a thick cap of residual silica and iron oxides. The ore minerals, the alteration pattern and the tectono-volcanic environment of Cerro Quema are consistent with a high sulfidation epithermal system developed in the Azuero peninsula during pre-Oligocene times.

Duração do período de molhamento foliar em pomares de macieira em céu aberto e sob tela antigranizo, em Vacaria-RS

A duração do período de molhamento foliar (DPM) é um importante parâmetro para a determinação do risco de doenças da macieira, especialmente a sarna, principal doença da cultura. O clima regional e as características de implantação e manejo de pomares são fatores determinantes da ocorrência do molhamento foliar. Em função do microclima do dossel, é necessário conhecer a posição com maior DPM, para dar suporte a modelos de previsão de doenças. Poucos trabalhos avaliaram a DPM em pomares de macieira, sendo que inexistem estudos nas condições de cultivo do Sul do Brasil, em particular na região produtora de Vacaria, Rio Grande do Sul. Este trabalho objetivou caracterizar a variação espacial da DPM em dosséis de macieiras em céu aberto e sob tela antigranizo, na região de Vacaria. O experimento foi desenvolvido em pomares de macieiras 'Royal Gala', conduzidos em líder central com apoio (espaçamento de 1m x 3m), sendo um coberto por tela antigranizo e o outro em céu aberto. A DPM foi monitorada nos estratos superior, médio e inferior dos dosséis de macieira. A duração do molhamento foliar foi superior no estrato inferior do dossel, tanto em céu aberto quanto sob tela antigranizo. Houve tendência de mais alta DPM no pomar coberto para todos os estratos do dossel, com diferença significativa entre ambientes nos estratos superior e médio. Os valores de DPM foram mais similares entre os estratos no dossel coberto por tela antigranizo do que no dossel a céu aberto.

Seleção de modelos de regressão para estimar a área foliar de macieiras 'Royal gala' e 'Fuji suprema' sob tela antigranizo e em céu aberto

O objetivo deste trabalho foi ajustar e testar modelos matemáticos simples, precisos e acurados para estimar a área foliar de macieiras 'Royal Gala' e 'Fuji Suprema' cultivadas sob tela antigranizo e em céu aberto. O experimento foi conduzido em pomar comercial no município de Vacaria-RS, nos ciclos vegetativos de 2008/2009 e 2009/2010. Equações de regressão linear e quadrática foram ajustadas para estimativa da área foliar em função das dimensões das folhas. A seleção dos melhores modelos baseou-se no quadrado médio do erro, no coeficiente de determinação, no erro-padrão da estimativa e na significância dos coeficientes das equações. A área foliar estimada pelos melhores modelos foi comparada com dados obtidos de medição por planímetro e estimados por fotografias digitais. A prova dos modelos baseou-se na significância do coeficiente angular, na linha 1:1 e na raiz quadrada do quadrado médio do erro. Modelos linear e quadrático que consideram o comprimento e a largura das folhas estimam com acurácia e precisão a área foliar de macieiras 'Royal Gala' e 'Fuji Suprema', tanto sob tela antigranizo quanto em céu aberto. A área foliar de macieira estimada por modelos de regressão que utilizam comprimento e largura de folhas é similar à obtida por planímetro ou fotografia digital.

Self-Organising Maps and Correlation Analysis as a Tool to Explore Patterns in Excitation-Emission Matrix Data Sets and to Discriminate Dissolved Organic Matter Fluorescence Components

Dissolved organic matter (DOM) is a complex mixture of organic compounds, ubiquitous in marine and freshwater systems. Fluorescence spectroscopy, by means of Excitation-Emission Matrices (EEM), has become an indispensable tool to study DOM sources, transport and fate in aquatic ecosystems. However the statistical treatment of large and heterogeneous EEM data sets still represents an important challenge for biogeochemists. Recently, Self-Organising Maps (SOM) has been proposed as a tool to explore patterns in large EEM data sets. SOM is a pattern recognition method which clusterizes and reduces the dimensionality of input EEMs without relying on any assumption about the data structure. In this paper, we show how SOM, coupled with a correlation analysis of the component planes, can be used both to explore patterns among samples, as well as to identify individual fluorescence components. We analysed a large and heterogeneous EEM data set, including samples from a river catchment collected under a range of hydrological conditions, along a 60-km downstream gradient, and under the influence of different degrees of anthropogenic impact. According to our results, chemical industry effluents appeared to have unique and distinctive spectral characteristics. On the other hand, river samples collected under flash flood conditions showed homogeneous EEM shapes. The correlation analysis of the component planes suggested the presence of four fluorescence components, consistent with DOM components previously described in the literature. A remarkable strength of this methodology was that outlier samples appeared naturally integrated in the analysis. We conclude that SOM coupled with a correlation analysis procedure is a promising tool for studying large and heterogeneous EEM data sets.

Oxygen adsorption on clean and oxygen precovered Cu(100)

Kuparipinnan hapettumisen alkuvaiheet ovat vielä nykyisin tutkijoille epäselviä. Kuitenkin, jotta hapettumisprosessia voitaisiin säädellä, on sangen tärkeää ymmärtää mistä varsinainen hapettuminen lähtee liikkeelle ja mitkä ovat hapettumisen seuraavat vaiheet. Tähän kysymykseen haetaan vastauksia tässä työssä käyttäen puhtaasti teoreettisia menetelmiä pinnan käsittelyssä. Aikaisempien teoreettisten ja kokeellisten tutkimusten välillä on pieni ristiriita liittyen hapen tarttumistodennäköisyyteen. Teoreettisten tutkimusten mukaan happi ei puhtaalle pinnalle tullessaan näe potentiaalivallia, mutta kokeelliset tutkimukset osoittavat sellaisen kuitenkin olevan. Tuohon ristiriitaan pureudutaan käyttäen aikaisemmista laskuista poikkeavaa kvanttimekaaniseen molekyylidynamiikkaan perustuvaa lähestymistapaa. Työssä havaitaan, että aikaisemmin yleisesti käytetty menetelmä hukkaa huomattavan määrän tietoa ja siten tutkijat eivät voi ainoastaan tyytyä tarkastelemaan kyseisellä menetelmällä saatuja tuloksia. Kuparipinnalle havaittiin, että korkeilla molekyylin kineettisen energian arvolla aikaisemmin suoritetut laskut hajottavista trajektoreista pitävät paikkansa, mutta matalilla kineettisen energian arvoilla molekyyli kohtaa erittäin voimakkaan ``steering'' vaikutuksen ja trajektorit joiden piti olla hajottavia johtavatkin molekulaariseen adsorptioon. Kun hapen konsentraatio pinnalla on suurempi kuin 0.5 ML, pinta rekonstruoituu. Myös rekonstruktion jälkeistä pintaa on tutkittu samanlaisilla menetelmillä kuin puhdasta pintaa. Rekonstruoituneelle pinnalle ei löydetty hajottavia trajektoreita ja havaittiin, että hapelle annetun kineettisen energian matalilla arvoilla myös tässä tapauksessa on erittäin voimakas ``steering'' vaikutus.

Hardness of FRHC-Cu determined by statistical analysis

A statistical indentation method has been employed to study the hardness value of fire-refined high conductivity copper, using nanoindentation technique. The Joslin and Oliver approach was used with the aim to separate the hardness (H) influence of copper matrix, from that of inclusions and grain boundaries. This approach relies on a large array of imprints (around 400 indentations), performed at 150 nm of indentation depth. A statistical study using a cumulative distribution function fit and Gaussian simulated distributions, exhibits that H for each phase can be extracted when the indentation depth is much lower than the size of the secondary phases. It is found that the thermal treatment produces a hardness increase, due to the partly re-dissolution of the inclusions (mainly Pb and Sn) in the matrix.