Archaeometallurgical study of artefacts from Castro de Vila Nova de São Pedro (Azambuja, Portugal)

Dissertação para obtenção do Grau de Mestre em Conservação e Restauro

The early metallurgy in Southwestern Iberia: metals from the Chalcolithic Settlement of São Pedro (Redondo)

Archaeological excavations carried out in the archaeological site of São Pedro (Southern Portugal) revealed a Chalcolithic settlement occupied in different moments of the 3rd millennium BC. The material culture recovered includes different types of materials, such as ceramics, lithics and metals. The later comprises about 30 artefacts with different typologies such as tools (e.g. awls, chisels and a saw) and weapons (e.g. daggers and arrowheads) mostly belonging to the 2nd and 3rd quarter of the 3rd millennium BC. In the present work the collection of chalcolithic metallic artefacts recovered in São Pedro was characterized. Analytical studies involved micro energy dispersive X-ray fluorescence spectrometry (micro-EDXRF) to determine elemental composition, together with optical microscopy and Vickers microhardness testing for microstructural characterisation and hardness determination. Main results show copper with variable amounts of arsenic and very low content of other impurities, such as iron. Moreover, nearly half of the collection is composed by arsenical copper alloys (As > 2 wt.%) and an association was found between arsenic content and typology since the weapons group (mostly daggers) present higher values than tools (mostly awls). These results suggest some criteria in the selection of arsenic-rich copper ores or smelting products. Furthermore, after casting an artefact would have been hammered, annealed and sometimes, finished with a hammering operation. Additionally, microstructural variations in this collection reveal somewhat different operational conditions during casting, annealing and forging, as expected in such a primitive metallurgy. Moreover the operational sequence seems to be used to achieve the required shape to the object, rather than to intentionally make the alloy harder. Overall, this study suggests that Chalcolithic metallurgists might have a poor control of the addition of arsenic and/or were unable to use this element to increase the hardness of tools and weapons. Finally, the compositions, manufacturing processes and hardness were compared to those from neighbouring regions and different chronological periods.

Kuparin hitsaus kattavilla laatuvaatimuksilla

Kuparin ja kupariseosten hitsaus eroaa merkittävästi esimerkiksi terästen hitsauksesta. Suuri lämmönjohtavuus, lämpölaajeneminen, pehmeneminen ja kuparin taipumus liuottaa kaasuja sulaan asettavat hitsaukselle haasteita. Kuparia on perinteisesti hitsattu kaasuhitsaamalla ja kaasukaarihitsausprosesseilla, mutta uudemmat menetelmät kuten laserhitsaus, elektronisuihkuhitsaus ja FSW-hitsaus tarjoavat uudenlaisia käyttökohteita korkealla laadulla. ISO 3834-2 asettaa noudatettavat vaatimukset hitsaustoiminnalle laatuvaatimusten ollessa kattavia. Ydinvoimalaitoksella hitsauksessa tulee lisäksi noudattaa Säteilyturvakeskuksen YVL-ohjeita, joissa on määritetty lisävaatimuksia liitosten materiaalivalinnoille, pätevöittämiselle ja tarkastamiselle. Tässä työssä tutkittiin kuparimetallien hitsauksen mahdollisuutta Loviisan ydinvoimalaitoksella juottamisen sijasta siten, että kattavat laatuvaatimukset täyttyisivät. Hitsauskokeissa ja laboratoriotutkimuksissa testattiin hitsausta erilaisilla hitsausaineilla ja hitsausprosesseilla. Koetulosten pohjalta toteutettiin hitsausmenetelmä deoksidoidun kupariputken ja tinapronssilaipan TIG-hitsaukselle.

Les grelots mésoaméricains : sons et couleurs du pouvoir?

Ce mémoire prend la forme d’une réflexion critique sur le modèle proposé par Hosler afin d’expliquer les taux quantifiés d’étain et d’arsénique dans des objets de statut métalliques Mésoaméricains provenant principalement de l’Occident mésoaméricain et couvrant les deux phases de développement de la métallurgie mésoaméricaine. Ces objets font partie de la collection du Museo Regional de Guadalajara. Plus particulièrement, ce mémoire s’intéresse aux grelots mésoaméricains puisqu’ils représentent un élément important de la métallurgie préhispanique en Mésoamérique. Cette réflexion critique soulève plusieurs considérations techniques, méthodologiques, étymologiques, iconographiques, ethnohistoriques et logiques du modèle de Hosler relativement à la couleur des alliages constituant les grelots mésoaméricains. Les paramètres sur lesquels Hosler base son modèle sont questionnables à plusieurs niveaux. Ainsi, le fait que les niveaux d’arsenic ou d’étain observés dans les alliages cupriques de biens utilitaires sont généralement inférieurs à ceux quantifiés dans les alliages cupriques usités pour la fabrication de biens de statut de la Période 2 pourrait s’expliquer par le fait qu’il s’agit de deux méthodes de fabrication distinctes ayant des contraintes techniques différentes ou que ces artéfacts ont des paramètres et des fonctions distinctes. Les limites de l’association soleil-or, lune-argent y sont également exposées et un chapitre est consacré à la sonorité.

Fliesslochformen und Gewindefurchen in dünne Bleche und Rohre aus Kupfer und Kupferlegierungen

This thesis in Thermal Flow Drilling and Flowtap in thin metal sheet and pipes of copper and copper alloys had as objectives to know the comportment of copper and copper alloys sheet metal during the Thermal Flow Drill processes with normal tools, to know the best Speed and Feed machine data for the best bushing quality, to known the best Speed for Form Tapping processes and to know the best bush long in pure copper pipes for water solar interchange equipment. Thermal Flow Drilling (TFD) and Form Tapping (FT) is one of the research lines of the Institute of Production and Logistics (IPL) at University of Kassel. At December 1995, a work meeting of IPL, Santa Catarina University, Brazil, Buenos Aires University, Argentine, Tarapacá University (UTA), Chile members and the CEO of Flowdrill B.V. was held in Brazil. The group decided that the Manufacturing Laboratory (ML) of UTA would work with pure copper and brass alloys sheet metal and pure copper pipes in order to develop a water interchange solar heater. The Flowdrill BV Company sent tools to Tarapacá University in 1996. In 1999 IPL and the ML carried out an ALECHILE research project promoted by the DAAD and CONICyT in copper sheet metal and copper pipes and sheet metal a-brass alloys. The normal tools are lobed, conical tungsten carbide tool. When rotated at high speed and pressed with high axial force into sheet metal or thin walled tube generated heat softens the metal and allows the drill to feed forward produce a hole and simultaneously form a bushing from the displacement material. In the market exist many features but in this thesis is used short and longs normal tools of TFD. For reach the objectives it was takes as references four qualities of the frayed end bushing, where the best one is the quality class I. It was used pure copper and a-brass alloys sheet metals, with different thickness. It was used different TFD drills diameter for four thread type, from M-5 to M10. Similar to the Aluminium sheet metals studies it was used the predrilling processes with HSS drills around 30% of the TFD diameter (1,5 – 3,0 mm D). In the next step is used only 2,0 mm thick metal sheet, and 9,2 mm TFD diameter for M-10 thread. For the case of pure commercial copper pipes is used for ¾” inch diameter and 12, 8 mm (3/8”) TFD drill for holes for 3/8” pipes and different normal HSS drills for predrilling processes. The chemical sheet metal characteristics were takes as reference for the material behaviour. The Chilean pure copper have 99,35% of Cu and 0,163% of Zinc and the Chilean a-brass alloys have 75,6% of Cu and 24,0% of Zinc. It is used two German a-brass alloys; Nº1 have 61,6% of Cu, 36,03 % of Zinc and 2,2% of Pb and the German a-brass alloys Nº2 have 63,1% of Cu, 36,7% of Zinc and 0% of Pb. The equipments used were a HAAS CNC milling machine centre, a Kistler dynamometer, PC Pentium II, Acquisition card, TESTPOINT and XAct software, 3D measurement machine, micro hardness, universal test machine, and metallographic microscope. During the test is obtained the feed force and momentum curves that shows the material behaviour with TFD processes. In general it is take three phases. It was possible obtain the best machining data for the different sheet of copper and a-brass alloys thick of Chilean materials and bush quality class I. In the case of a-brass alloys, the chemical components and the TFD processes temperature have big influence. The temperature reach to 400º Celsius during the TFD processes and the a-brass alloys have some percents of Zinc the bush quality is class I. But when the a-brass alloys have some percents of Lead who have 200º C melting point is not possible to obtain a bush, because the Lead gasify and the metallographic net broke. During the TFD processes the recrystallization structures occur around the Copper and a-brass alloy bush, who gives more hardness in these zones. When the threads were produce with Form Tapping processes with Flowtap tools, this hardness amount gives a high limit load of the thread when hey are tested in a special support that was developed for it. For eliminated the predrilling processes with normal HSS drills it was developed a compound tool. With this new tool it was possible obtain the best machining data for quality class I bush. For the copper pipes it is made bush without predrilling and the quality class IV was obtained. When it is was used predrilling processes, quality classes I bush were obtained. Then with different HSS drill diameter were obtained different long bush, where were soldering with four types soldering materials between pipes with 3/8” in a big one as ¾”. Those soldering unions were tested by traction test and all the 3/8” pipes broken, and the soldering zone doesn’t have any problem. Finally were developed different solar water interchange heaters and tested. As conclusions, the present Thesis shows that the Thermal Flow Drilling in thinner metal sheets of cooper and cooper alloys needs a predrilling process for frayed end quality class I bushings, similar to thinner sheets of aluminium bushes. The compound tool developed could obtain quality class I bushings and excludes predrilling processes. The bush recrystalization, product of the friction between the tool and the material, the hardness grows and it is advantageous for the Form Tapping. The methodology developed for commercial copper pipes permits to built water solar interchange heaters.

Estudio de los procesos de corrosion de una aleacion metalica de cobre usada en odontologia

Corrosion phenomena in a dental copper-based alloy are experimentally studied using electrochemical techniques. Two heating sources, torch and induction, were used in the casting experiments. In the corrosion essays, the optimum casting cycle and the polarization curves were obtained. It was found that the heating sources have little influence on the corrosion processes of the metallic alloys studied.

Influence of silver additions on the structure and phase transformation of the Cu-13 wt % Al alloy

The influence of silver additions on the structure and phase transformation of the Cu-13 wt % Al alloy was studied by differential thermal analysis, X-ray diffraction, scanning electron microscopy and energy dispersive analysis of X-rays. The results indicate that the presence of silver modifies the phase-stability field, the transition temperature and the structure of the alloy. These effects are more pronounced for silver concentrations up to 8 wt %.

Influence of silver additions on the aging characteristics of the Cu-10.4at.%Al alloy

The influence of additions of 1.3, 2.5, 3.8, 5.1, and 6.3 at.% Ag on the aging behavior of the Cu-10.4at.%Al alloy was studied using microhardness measurements, scanning electron microscopy (SEM) and energy dispersive X-ray (EDX) analysis. The results indicated that with silver additions it is possible to obtain a response to age hardening, and that for large aging times there is a decrease in the alloy hardness, with a process that leads to Ag and Al segregation. © 1998 Elsevier Science S.A.

Phase transformations in the Cu-Al alloy with Ag addition

The effect of Ag addition on the phase transformations that occur in the Cu-10% Al alloy was studied using differential thermal analysis, scanning electron and optical microscopies and energy dispersive X-ray analysis. The results indicated that Ag addition is responsible for the separation of the reverse martensitic transformation in two stages, and for the refinement of the α-phase grains. The relative amount of the β1 martensitic phase, retained on slow cooling (above 2 K min-1 of cooling rate), and the relative fraction of phase α2 are increased. The solubility limit of Ag in the matrix is close to 6 mass% and at this concentration the maximum stability of the β-phase is reached. © 2005 Akadémiai Kiadó, Budapest.

Kinetics of martensitic phase decomposition in the Cu-10wt.%Al alloy with Ag additions

The study of the kinetics of martensitic phase decomposition in the Cu-10wt.%Al alloy with Ag additions showed that the presence of Ag retarded the eutectoid decomposition reaction and enhanced martensite stabilization. This stabilization effect was attributed to Ag atoms redistribution as structure defects, increase in the numbers of Cu-Al pairs due to Ag-Al interaction and the Al atoms redistribution around one Cu atom at the sub-lattice of the martensitic crystal. © 2008 Trans Tech Publications.

Corrosion and tribocorrosion behaviour of Al-Si-Cu-Mg alloy and its composites reinforced with B4C particles in 0.05M NaCl solution

The corrosion behaviour of metal matrix composites (MMCs) is strictly linked with the presence of heterogeneities such as reinforcement phase, microcrevices, porosity, secondary phase precipitates, and interaction products. Most of the literature related to corrosion behaviour of aluminium matrix composites (AMCs) is focused on SiC reinforced AMCs. On the other hand, there is very limited information available in the literature related to the tribocorrosion behaviour of AMCs. Therefore, the present work aims to investigate corrosion and tribocorrosion behaviour of Al-Si-Cu-Mg alloy matrix composites reinforced with B4C particulates. Corrosion behaviour of 15 and 19% (vol) B4C reinforced Al-Si-Cu-Mg matrix composites and the base alloy was investigated in 0.05M NaCl solution by performing immersion tests and potentiodynamic polarisation tests. Tribocorrosion behaviour of Al-Si-Cu-Mg alloy and its composites were also investigated in 0.05M NaCl solution. The tests were carried out against alumina ball using a reciprocating ball-on-plate tribometer. Electrochemical measurements were performed before, during, and after the sliding tests together with the recording of the tangential force. Results suggest that particle addition did not affect significantly the tendency of corrosion of Al-Si-Cu-Mg alloy without mechanical interactions. During the tribocorrosion tests, the counter material was found to slide mainly on the B4C particles, which protected the matrix alloy from severe wear damage. Furthermore, the wear debris were accumulated on the worn surfaces and entrapped between the reinforcing particles. Therefore, the tendency of corrosion and the corrosion rate decreased in Al-Si-Cu-Mg matrix B4C reinforced composites during the sliding in 0.05M NaCl solution. © 2013 Elsevier B.V.

Estudo da geometria da aresta de corte de ferramentas aplicadas ao torneamento de superligas à base de níquel com alta velocidade de corte

Pesquisadores e indústrias de todo o mundo estão firmemente comprometidos com o propósito de fazer o processo de usinagem ser precisamente veloz e produtivo. A forte concorrência mundial gerou a procura por processos de usinagem econômicos, com grande capacidade de produção de cavacos e que produzam peças com elevada qualidade. Dentre as novas tecnologias que começaram a ser empregadas, e deve tornar-se o caminho certo a ser trilhado na busca da competitividade em curto espaço de tempo, está a tecnologia de usinagem com altas velocidades (HSM de High Speed Machining). A tecnologia HSM surge como componente essencial na otimização dos esforços para manutenção e aumento da competitividade global das empresas. Durante os últimos anos a usinagem com alta velocidade tem ganhado grande importância, sendo dada uma maior atenção ao desenvolvimento e à disponibilização no mercado de máquinas-ferramentas com rotações muito elevadas (20.000 - 100.000 rpm). O processo de usinagem com alta velocidade está sendo usado não apenas para ligas de alumínio e cobre, mas também para materiais de difícil usinabilidade, como os aços temperados e superligas à base de níquel. Porém, quando se trata de materiais de difícil corte, têm-se observado poucas publicações, principalmente no processo de torneamento. Mas, antes que a tecnologia HSM possa ser empregada de uma forma econômica, todos os componentes envolvidos no processo de usinagem, incluindo a máquina, o eixo-árvore, a ferramenta e o pessoal, precisam estar afinados com as peculiaridades deste novo processo. No que diz respeito às máquinas-ferramenta, isto significa que elas têm que satisfazer requisitos particulares de segurança. As ferramentas, devido à otimização de suas geometrias, substratos e revestimentos, contribuem para o sucesso deste processo. O presente trabalho objetiva estudar o comportamento de diversas geometrias ) de insertos de cerâmica (Al2O3 + SiCw e Al2O3 + TIC) e PCBN com duas concentrações de CBN na forma padrão, assim como modificações na geometria das arestas de corte empregadas em torneamento com alta velocidade em superligas à base de níquel (Inconel 718 e Waspaloy). Os materiais foram tratados termicamente para dureza de 44 e 40 HRC respectivamente, e usinados sob condição de corte a seco e com utilização da técnica de mínima quantidade de lubrificante (minimal quantity lubricant - MQL) visando atender requisitos ambientais. As superligas à base de níquel são conhecidas como materiais de difícil usinabilidade devido à alta dureza, alta resistência mecânica em alta temperatura, afinidade para reagir com materiais da ferramenta e baixa condutividade térmica. A usinagem de superligas afeta negativamente a integridade da peça. Por essa razão, cuidados especiais devem ser tomados para assegurar a vida da ferramenta e a integridade superficial de componentes usinados por intermédio de controle dos principais parâmetros de usinagem. Experimentos foram realizados sob diversas condições de corte e geometrias de ferramentas para avaliação dos parâmetros: força de corte, temperatura, emissão acústica e integridade superficial (rugosidade superficial, tensão residual, microdureza e microestrutura) e mecanismos de desgaste. Mediante os resultados apresentados, recomenda-se à geometria de melhor desempenho nos parâmetros citados e confirma-se a eficiência da técnica MQL. Dentre as ferramentas e geometrias testadas, a que apresentou melhor desempenho foi a ferramenta cerâmica CC650 seguida da ferramenta cerâmica CC670 ambas com formato redondo e geometria 2 (chanfro em T de 0,15 x 15º com raio de aresta de 0,03 mm).

Observation of crack initiation during hot tearing

While the general mechanisms of hot tearing are understood, i.e. the inability of liquid to feed imposed strain on the mushy material, work continues on improving the understanding of the mechanisms at play. A hot tear test rig that measures the temperature and load imposed on the mushy zone during solidification has been successfully used to study hot tearing. The mould has now been modified to incorporate a window above the hot spot region to allow observation of hot tear formation and growth. Combining information from visual observation with load and temperature data has led to a better understanding of the mechanism of hot tearing. Tests were carried out on an Al-0.5 wt-% Cu alloy. It was found that load development began at about 90% solid and a hot tear formed a short time later, at between 93% and 96% solid. Hot tearing started at a very low load.

Desenvolvimento de eletrocatalisadores de PdM (M= Ni, Cu, Ag) para reação de redução de oxigênio em meio básico na ausência e presença de álcool

Tese (Doutorado em Tecnologia Nuclear)