The trend towards a more circular economy presents a unique challenge for the pyrometallurgical engineer. Secondary feeds bring complexity to the smelter in the form of non-traditional chemistries and minor elements. Models of furnaces will play an important role in this paradigm. Models should be able to predict operations in dynamic systems that do not always operate at equilibrium.The development of a top submerged lance (TSL) model was the subject of this study because the TSL has proven to be capable of treating secondary materials.The furnace consists of a vertical cylindrical vessel, containing molten slag and bullion at the bottom. A lance enters through the roof and the tip is submerged in the slag, into which gas and fuel are blown. Secondary or primary feeds, fluxes and reductants can be fed to the furnace. The reactions and interplay between the liquid phases, gas and added reductants set the temperatures and partial oxygen pressures in the furnace. The Connected Local Equilibria (CLE) method was followed to model the furnace. This approach offers the benefit that speciation can be modelled simultaneously for many elements from thermochemical databases. The methodology is to divide the furnace into several equilibrium volumes, based on expected material flows. With each time step, equilibrium in each volume is calculated by Gibbs free energy minimization. Material is then exchanged between volumes according to expected flows. To validate the method, small scale crucible experiments were carried out. Molten lead-containing ferric calcium silicate slags (PbO-FCS slag, also containing GeO2, TeO2 and SnO2 in concentrations ˂ 1 wt%) were reduced under controlled CO/CO2 atmospheres to produce lead bullion. The kinetics of the process were measured. Similar experiments were carried out with a copper-containing ferric calcium silicate system. The CLE method was applied to simulate the data, using HSC Sim software. The crucible was divided into four equilibrium volumes: slag-gas contact; slag; slag-hearth contact; hearth. The gas flowrate to the slag-gas contact was determined by following a rate-law in the form of chemical reaction control (e.g. Rg-s = kapp.pCO (mol O.cm-2.s-1)). By using a single fitting factor (kapp), the dynamic behaviour of lead and the minor elements (tin, tellurium, germanium) could be predicted. The same method was successfully used for the CuO-FCS system. The use of this method enhanced understanding of the experiments, by showing the component speciation during reduction. Full-scale TSL models were then developed using HSC Chemistry software and SimuSage software. In both cases the CLE method was applied. The flow patterns in the furnace were gleaned from published computational fluid dynamics (CFD) work. The interface areas were not known, and assumptions thus needed to be made to model an industrial process for lead-oxide FCS slag reduction. It was shown that the model can provide useful insight into real-world problems. Two branches of modelling might develop from this work. In one, CFD work can quantify interface areas in the furnace, so that CLE models similar to the current work are possible. In the second, only bulk fluid movement might be used. In either case, this work validates the approach of using a thermochemical approach to model kinetics.:1 INTRODUCTION 1.1 THE METALLURGICAL CHALLENGE TO ACHIEVE A CIRCULAR ECONOMY 1.2 APPLICATION OF UNIT MODELS IN TECHNO-ECONOMIC, EXERGY AND ENVIRONMENTAL FOOTPRINT ANALYSES 1.3 FOCUS OF THE CURRENT WORK 2 RESEARCH OBJECTIVES 3 LITERATURE REVIEW 3.1 LEAD METALLURGY (INCLUDING WEEE) 3.2 COPPER METALLURGY 3.3 EQUILIBRIUM BEHAVIOUR OF MINOR ELEMENTS IN LEAD AND COPPER METALLURGY 3.4 SLAG REDUCTION KINETICS 3.5 TSL FURNACE 3.6 MODELLING OF BATH-TYPE SMELTERS 3.6.3 CFD Modelling 4 EXPERIMENTAL METHODOLOGY 4.1 MASTER SLAG PREPARATION 4.2 EXPERIMENTAL SETUP 4.3 REDUCTION EXPERIMENT PROCEDURE 4.4 LIST OF EXPERIMENTS 4.5 ANALYTICAL METHOD 4.6 REACTION OF SLAGS WITH CRUCIBLE WALLS 5 EXPERIMENTAL ERROR EVALUATION 5.1 ERROR IN MASTER SLAG COMPOSITION MEASUREMENTS 5.2 REPEAT TESTS 5.3 EXPERIMENTAL ERROR 6 MODELLING OF KINETICS WITH HSC SIM 6.1 HSC CHEMISTRY DYNAMIC MODULE AND CONNECTED LOCAL EQUILIBRIA MODELLING 6.2 RESULTS FOR MODELLING LEAD EXPERIMENTAL RESULTS WITH HSC CHEMISTRY 6.3 RESULTS FOR MODELLING COPPER EXPERIMENTAL RESULTS WITH HSC CHEMISTRY 7 TSL MODEL IN HSC CHEMISTRY 7.1 FLUID FLOW IN TSL FOR CONNECTED LOCAL EQUILIBRIA MODELLING 7.2 TANKS AND OPERATIONS IN HSC SIM MODEL 7.3 EXAMPLE OF HSC SIM CLE MODEL APPLICATION 8 TSL MODEL ON SIMUSAGE PLATFORM 8.1 METHOD FOR SIMUSAGE MODEL 8.2 SPECIES SELECTION IN SIMUSAGE MODEL 8.3 EXAMPLE OF SIMUSAGE CLE MODEL APPLICATION 9 COMPARISON OF HSC SIM AND SIMUSAGE RESULTS 10 CRITICAL ANALYSIS OF MODEL METHODOLOGY 10.1 MEASUREMENT OF BULK VOLUME COMPOSITIONS 10.2 HEAT TRANSFER IN HSC SIM AND SIMUSAGE MODELS 10.3 USING BULK FLUID FLOWS VS INTERFACE APPROACH 11 CONCLUSIONS 11.1 MOTIVATION 11.2 LABORATORY KINETIC MEASUREMENTS AND MODELLING WITH CLE METHOD 11.3 TSL MODELLING WITH HSC SIM AND SIMUSAGE 12 REFERENCES

In the copper smelting processes, the viscosity of the matte and the slag is an important factor for establishing efficiency. Impurities in the concentrates affect the viscosity not only by changing the melt structure but also by promoting precipitation of solid phase which sharply rises it. In this master thesis, a comprehensive methodology was established to study the MgO effects on the properties of a copper smelting slag. Thus, glassy samples were obtained and after confirmation of the composition and the glassy structure with EDS, SEM, and XRD analysis, they were examined through Ramanspectroscopy to study their glassy structure. Moreover, Mössbauer spectroscopy was used to determine the amount of Fe3+ in the samples. Models from the literature were compared to the experimental data. Coherence with the literature was found with the effect of MgO as a network modifier of the oxide melt structure and a promoter of high coordinated structures. Estimations through models were performed to study the iron redox equilibria of the melt and were compared with experimental data, but it was not possible to find the limit of Fe3+ at which precipitation of solid phase initiates. / I kopparsmältningsprocesserna är mattans och slaggens viskositet en viktig faktor för att uppnå effektivitet. Föroreningar i koncentraten påverkar viskositeten inte bara genom att ändra smältstrukturen utan också genom att främja utfällning av fast fas som kraftigt höjer den. I denna magisteruppsats fastställdes en omfattande metod för att studera MgO-effekterna på egenskaperna hos en kopparsmältningsslagg. Således erhölls glasiga prover och efter bekräftelse av kompositionen och den glasiga strukturen med EDS-, SEM- och XRD-analys undersöktes de genom Ramanspektroskopi för att studera deras glasstruktur. Dessutom användes Mössbauerspektroskopi för att bestämma mängden Fe3+ i proverna. Modeller från litteraturen jämfördes med experimentella data. Överensstämmelse med litteraturen hittades med effekten av MgO som ett nätverksmodifierare av oxidsmältstrukturen och en promotor för högkoordinerade strukturer. Uppskattningar genom modeller utfördes för att studera smältans järnredoxjämvikter och dessa jämfördes med experimentella data, men det var inte möjligt att hitta gränsen för Fe3+ vid vilken utfällning av fast fas initierades.

Les objectifs de cette thèse ont été de contribuer à l'évaluation des niveaux de contamination en éléments traces métalliques et métalloïdes (ETMM) des sols du site de l'ancienne fonderie de plomb de l'Escalette (sud-est de Marseille), d'en approcher les processus de transport et transfert dans l'environnement en particulier leurs mobilités dans le sol et leurs transferts aux plantes. La contribution à l'établissement d'une cartographie de la contamination sur un périmètre plus vaste que celui de l'usine (zone des Calanques) a permis de mettre clairement en évidence l'impact de cette dernière. Sur le site industriel, les formes et niveaux de contamination des sols diffèrent d'une zone à l'autre. Les sols formés en surface des crassiers se caractérisent par leurs fortes teneurs en Cu, Zn et Pb, dont les fractions mobilisables sont notables (2 à 30%), l'influence des scories est nette. Les sols prélevés à proximité de la cheminée présentent les plus fortes contaminations en Pb, Sb et As, avec de 10 à 30% de fractions mobilisables. Cette contamination est liée aux émissions anciennes via la cheminée rampante mais aussi à la dégradation de cette dernière. Le potentiel de libération des éléments As et Sb des sols de ces 2 zones conduirait à leurs stockages dans des décharges pour déchets dangereux. Les essais de solubilisation en milieu acide ont mis en évidence des risques pour la santé par ingestion concernant Pb et As. Les zones en proche périphérie de l'usine sont moins impactées mais sont néanmoins considérées comme fortement contaminées. G. alypum et R. officinalis, présentes sur le site, sont tolérantes aux ETMM et peuvent les accumuler. / The overall objective of this thesis was to contribute to the assessment of the level of contamination by trace metals and metalloids (TMM) on the site of Escalette (a former lead smelter in southeastern Marseille). The study of TMM transfer and transport processes on this site, taking into account their mobility in the soil and their transfer to plants, was a specific objective. The mapping of TMM contamination in an extended area around the factory site (on Calanques zone) has clearly highlighted the impact of the former industry. So, on the Escalette site, forms and levels of soil contamination differ from one area to another. Soils formed on the surface of the slag deposits are characterized by high levels of Cu, Zn and Pb, whose mobilizable fractions are significant (2-30%), showing a clear influence of slag. Soils collected near a chimney creeping uphill the slope, present the highest contamination levels in Pb, Sb and As, with from 10 to 30 % of mobilizable fractions. This contamination is linked to emissions through the damaged chimney but also to the degradation of this latter. The potential release of As and Sb from the soils of these two areas requires that these soils must be disposed of in landfills for hazardous wastes and their solubilization in acid medium have highlighted the health risks by ingestion for Pb and As. On areas in near periphery of the smelter, soils are less affected but must be still considered heavily contaminated. G. alypum and R. officinalis were observed on the site. They are tolerant and can accumulate TMM. Concentrations in roots were significantly correlated with the concentrations in soils, except for Cu.

This study deals with the association of trace elements with colloids and particles in surface waters and groundwaters of mining and smelting district of Příbram. Colloids were studied using combination of cascade filtration a tangential flow ultrafiltration method to separate individual colloid fractions. Colloids were separated by filtration membranes with nominal pore size 0,8 μm, 0,45 μm, 0,1 μm, 100 kDa, and 5 kDa. Water samples were analyzed using ICP-OES, ICP-MS and HPLC. The data were used for thermodynamic modeling using PHREEQC-2 programme. The results show that major and trace elements can be divided into several groups, based on their abundance in individual size fractions. Most elements dominate in fraction of truly dissolved matter as dissociated ions (< 5 kDa), maximum concentration in colloid fraction is 5-20 % and almost exclusively in fraction 5 kDa - 100 kDa. Gradual decrease of concentration in all fractions at low ionic strength (1,2 mmol/l) was observed in case of elements such as As, Co, Cr, Si, Sb and U. Gradual decrease of concentration in several samples was observed for Cd, Fe, Pb, Mn and Zn. Dominant binding to colloids and particles in surface waters was observed for Fe and Pb, where these fractions accounted for over 90 %. The main factor influencing colloid...

The aim of this thesis is to reach further understanding of the development of environmental adaptation in Swedish heavy industry by studying the case of the Rönnskär Smelter 1960-2000. More specifically, the aim of the thesis is to investigate the interplay between firm level environmental adaptation and national environmental politics and economic development. To fulfil this aim, the following questions are asked: How have company activities such as production processes, organisation and company strategies been developed and adopted in order to meet environmental demands with maintained competitiveness? How have company activities been framed by environmental policies and the specific environmental regulations, relevant for this case? What other factors, beside environmental regulations, have driven and framed the environmental adaptation process of the firm? The study concludes that a long-range competitive environmental adaptation was reached by a combination of investments in environmental technology with an overall rationalisation and modernisation of the enterprise. The study suggests that the environmental adaptation process of the Rönnskär Smelter became part of an overall process of industrial modernisation during the period, which reflects a wider context than the environmental issue itself. It mirrors technological development on other fields than the environment, and an increasing competition on a global scale that called for lower unit costs of production. This led to a modernisation for pollution reduction strategy that enabled the firm to increase production but still cutting its pollution levels considerably over time. The result is partly consistent with the Porter hypothesis that suggests that strict environmental regulation can strengthen firms’ and nations’ competitiveness. Time series data shows that emissions from the Rönnskär factory have radically declined since the 1960s. For these changes, process technology has proven to be most important. Technological adjustments came about through a step-by-step adaptation. It is clear that internal solutions, developed by the companies’ own engineers were more important at an early stage, when the supply of external solutions was limited. The study also concludes that environmental regulation has strongly influenced the environmental adaptation at the Rönnskär Smelter. Of most importance is the Environmental Protection Act (EPA: Miljöskyddslagen) implemented in 1969. In the economic historian Nathan Rosenberg’s terminology, this study suggests that the EPA model of individual testing promoted long-term innovative and cost-effective technical solutions, because it was consistent with decentralised experimental activity and the specific conditions that characterise the dynamics of technological development. However, not much can be said before comparative studies within the Swedish system have been conducted, or perhaps most fruitful, between various national systems of environmental protection. This study also concludes that the environmental issue became of strategic dignity at the very beginning of the 1970s, mainly as a consequence of the implementation of the EPA. Even though environmental issues did not become important for market strategies until the 1990s, the environmental issue called already in the 1970s for adjustments that required financial and personnel resources that demanded priorities and strategic decisions at the highest level of the organisation. The study also concludes that even though the technological dimension has played the most decisive role for lowering emissions, the significance of organisation has increased over time. While the 1960s, and especially the 1970s, brought about substantial pollution reductions through new technology, organisational aspects became relatively more important when the costs of abatement were rising in the 1980s. Organisational co-ordination, division of local responsibilities and education of personnel became a supplement to technology to obtain further pollution reductions. The technician as the “environmental hero” of the firm was successively replaced by the organisational co-ordinator.

Η επεξεργασία των νικελιούχων λατεριτικών μεταλλευμάτων της χώρας μας για την παραγωγή σιδηρονικέλιου στη Λάρυμνα συνοδεύεται με την εκπομπή 200000t/y λεπτομερούς σκόνης που συλλέγεται στα συστήματα αντιρρύπανσης των περιστροφικών κάμινων (Π/Κ), μέσης περιεκτικότητας 1.2-1.5% σε Ni και 4-5% σε C. Η διατριβή αυτή συνέβαλε στην ανάπτυξη μεθόδου ανακύκλωσης της σκόνης αυτής με απευθείας αναγωγική της τήξη σε ηλεκτρική κάμινο συννεχούς ρεύματος (DC-HEP) με εμφυσησή της μέσω του κεντρικού διάτρητου γραφιτικού ηλκετρόδιου. Την προκαταρκτική θεωρητική διερεύνηση και τις εργαστηριακές προδοκιμές ακολούθησαν βιομηχανικές δοκιμές στην κάμινο 125t DC-HEP στη χαλυβουργία Georgsmarienhutte της Γερμανίας, όπου έλαβε χώρα τήξη 70t σκόνης και 2.5t φιλομερούς μεταλλεύματος.Η ανάκτηση Ni ήταν πολύ υψηλή 93-99%. Παρήχθησαν χάλυβες χαμηλής κραμάτωσης σε σε Ni καθώς και ποικίλοι τύποι σκωρίας προς διερεύνηση της χρήσης τους στην παραγωγή σύνθετων τσιμέντων Portland και σκωριωτσιμέντων. Πραγματοποιήθηκε μεταλλουργική αξιολόγηση των δοκιμών και αναπτύχθηκε μοντέλο προσομοίωσης της αναγωγικής τήξης της σκόνης. / The tratment of the laterite nickel ferrous ores in Hellas for the production of ferronickel at Larymna is associated with the emission of 200000t/y of fine dust collected in the gas cleaning systems of the rotary kilns (R/Ks), with 1.2-1.5% and 4-5% . Average Ni and C contents respectively . This thesis contributed to the development of a method for the recycling of this dust by means of its direct reduction smelting in a DC-HEP furnace (Direct Current-Hollow Electrode Powder) by its injection through the central hollow graphite electrode. The preliminary theoretical study and the laboratory trials were followed by industrial heat campaigns in the 12st DC-HEP furnace at georgsmarienhutte steelwork in Germany, where around 70t of dust and 2.5t of ore fines were smelted. The Ni-recovery was very high 93-99.9%. Low Nickel alloyed steel grades were produced and various slag types for the investigation of their utilization for the production of composite-portland cements and slag cements. The metallurgical evaluation of the trials was performed and model for the dust reduction smelting process was developed.

No description available.

Abstract Industrial ecology provides the scientific and technological understanding upon which the increased environmental, economic and social efficiencies necessary to progress towards sustainability can be based. Industrial ecosystem is the creation of synergies between various industries, agriculture, and communities to profitably convert waste into valuable products or feedstock. Copper and nickel flash smelters developed by Outokumpu form the heart of the Harjavalta industrial ecosystem, which consists of thirteen different firms. The ideas found in Harjavalta industrial ecosystem consideration can be applied to carbon steelmaking and other related industry sectors to add product efficiency, improve energy utilization and start new local business, when different firms can concentrate to their own core know-how areas. When planning to add the amount of recycled material in steel production the waste oxides from steel industry, pyrite roasting residues and slags from the copper and nickel smelters are rich iron sources. When processing dusts, scales and sludge in the separate treatment plant, the main thing is that the primary production of the steel plant is not disturbed. The big problem when using secondary iron raw materials will be the contamination of steel by tramp elements similar to scrap based steel manufacture. Today's industry is facing significant change from the process related environmental thinking towards product based environmental thinking seen in the EU product policy. This will mean need for the research covering raw material acquisition, production, products, in-use phase, recycling and disposal. Steel has very unique properties, which can be improved, if steel manufacturers can concentrate on their core know-how area. The essential difference between the technical and natural systems is the human control. Based on the experiences of Harjavalta industrial ecosystem the occupational safety and accident security risk prevention should be included into the metaphor of industrial ecology. If we consider the human control in global scale the future development will depend on the ethical decisions made by humankind. / Tiivistelmä Teollisessa ekologiassa pyritään aine- ja energiavirtojen tutkimiseen siten, että jäljitellään luontoa lopullisena tavoitteena jätevirtojen eliminointi tai ainakin minimointi, jolloin se on osa kestävälle kehitykselle välttämätöntä ekologista, taloudellista ja sosiaalista toimintaa. Teollinen ekosysteemi on teollisuuslaitosten ja yhteiskunnan sekä mahdollisesti maatalouden synerginen liittymä, jonka avulla integroidaan tuotannon ja kulutuksen lohkot yhteen tavoitteena vähentää sekä raaka-aineiden kulutusta että ympäristöpäästöjä. Harjavallan teollinen ekosysteemi on syntynyt ja kehittynyt Outokummun kehittämän liekkisulatusmenetelmään perustuvien kupari- ja nikkelisulattojen ympärille. Harjavallan Suurteollisuuspuistosta saatuja ajatuksia ja kokemuksia voidaan soveltaa luovasti hiiliteräksen valmistukseen ja muihin vastaaviin teollisuuden haaroihin. Eri yritysten keskittyessä omalle ydinosaamisalueelleen voidaan parantaa raaka-aine- ja energiatehokkuutta sekä perustaa uutta paikallista teollisuutta. Terästeollisuuden hyödyntämättömät jäteoksidit, pyriitin pasuttamisesta saatavat pasutteet sekä nikkelin ja kuparin valmistuksen kuonat ovat potentiaalisia uusioraaka-aineita. Uusioraaka-aineille on kehitettävä hiiliteräksen valmistuksen pääprosessin viereen omat käsittelyratkaisut, sillä muuten rautapohjaisten poisteiden kierrätyksen ekologiset ja taloudelliset säästöt saatettaisiin menettää pääprosessin tuottavuuden laskuna. Ongelmallista on myös teräksen laatua haittaavien harmeaineiden kumuloituminen teräkseen, mitä tapahtuu myös käytettäessä romua uusioraaka-aineena. Kestävää kehitystä tavoiteltaessa täydennetään EU:n perinteistä prosessi- ja tuotantoyksikköperusteista ympäristölainsäädäntöä tuotelähtöisellä ympäristölainsäädännöllä. Säädöksissä huomioidaan laajemmin koko tuotteen elinkaari, jolloin tutkimuksen on katettava raaka-aineen hankinta, tuotanto, tuotteet, käyttö ja käytöstä poistoon liittyvä kierrätys tai sijoittaminen takaisin luontoon. Teräksen ainutkertaisia ominaisuuksia voidaan entisestään parantaa, jos teräksen valmistajat saavat keskittyä omalle ydinosaamisalueelleen. Teknisen järjestelmän sisältä löytyy aina ihminen suorittamassa tietoisen ohjauksen, mitä ei luonnonjärjestelmissä löydy. Harjavallan Suurteollisuuspuistosta saatujen kokemusten perusteella voidaan todeta, että työturvallisuus ja teollisuusonnettomuuksia ehkäisevä turvallisuustyö on otettava teollisen ekologian viitekehykseen. Jos tarkastellaan ihmisen vaikutusta globaalissa viitekehyksessä, voidaan todeta, että ihmisen vaikutus riippuu tulevaisuudessa tehtävistä eettisistä päätöksistä ja päätösten edellyttämistä toimenpiteistä.

The present thesis gives a summary of results obtained through theoretical and experimental studies of systems with relevance to copper smelting and converting. Many chemical elements are involved in the copper production pro­cesses and a detailed experimental study would be very time- consuming and expensive. A complicating fact is also the corrosivity of the liquid phases towards container material. A powerful alternative is equilibrium calculations, in which models for the liquid phases as well as reliable basic thermodynamic data are needed. In the present thesis, a generalized structure based model for liquid silicates was developed and used in assessments of the sys­tems PbO-SiO2, Fe-O-SiO2, CuO0.5-SÌO2 and Cu-Fe-O-SiO2. In the model, the non-ideal silicate melt is treated as an ideal solu­tion but containing a few complexes. The PbO-Si02 melt could be described by introducing the complexes Pb3Si207, Pb4Si4010 and Pb13Si12O37 in addition to the components PbO and Pb2Si04. The species considered in the Fe-O-SiO2 melt were FeO, FeO1.5, Fe2Si04, Fe3Si207, Fe3Si6O15 and in the CUO0.5-SiO2 melt CuO0.5 ana CU4SiO4. Trie calculated phase diagrams, the activities of me­tal oxides and the oxygen partial pressures were all in good agreement with the published data. Two of the papers in this thesis concern the determination of Gibbs free energies for Cu2S(s,l) and Ca2Fe2O5(s) through emf measurements utilizing a solid electrolyte. Activities and termi­nal solubilities in the solid solution [Fet,Ca]0 were also deter­mined. The results obtained from the quantitative equilibrium calcula­tions for conventional copper smelting and converting were used to outline the overall reactions taking place and the outcome of changes in process parameters. Comparison with observed values, however, showed that the copper and magnetite contents in slag were calculated too low. These discrepancies could be completely explained by using a non-equilibrium approach in which the con­verter was assumed to consist of several segments with concentra­tion gradients between the segments. / digitalisering@umu.se

L’objet de la présente étude est le développement, l’application et la diffusion de la technologie associée à divers types d’alliages de cuivre, en particulier l’alliage du plomb-bronze, en Grèce ancienne, dans ses colonies, ainsi qu’en Étrurie. Le plomb-bronze est un mélange de diverses proportions d’étain, de cuivre et de plomb. Le consensus général chez les archéométallurgistes est que le plomb-bronze n’était pas communément utilisé en Grèce avant la période hellénistique; par conséquent, cet alliage a reçu très peu d’attention dans les documents d’archéologie. Cependant, les analyses métallographiques ont prouvé que les objets composés de plomb ajouté au bronze ont connu une distribution étendue. Ces analyses ont aussi permis de différencier la composition des alliages utilisés dans la fabrication de divers types de bronzes, une preuve tangible que les métallurgistes faisaient la distinction entre les propriétés du bronze d’étain et celles du plomb-bronze. La connaissance de leurs différentes caractéristiques de travail permettait aux travailleurs du bronze de choisir, dans bien des cas, l’alliage approprié pour une utilisation particulière. L’influence des pratiques métallurgiques du Proche-Orient a produit des variations tant dans les formes artistiques que dans les compositions des alliages de bronze grecs durant les périodes géométrique tardive et orientalisante. L’utilisation du plomb-bronze dans des types particuliers d’objets coulés montre une tendance à la hausse à partir de la période orientalisante, culminant dans la période hellénistique tardive, lorsque le bronze à teneur élevée en plomb est devenu un alliage commun. La présente étude analyse les données métallographiques de la catégorie des objets coulés en bronze et en plomb-bronze. Elle démontre que, bien que l’utilisation du plomb-bronze n’était pas aussi commune que celle du bronze d’étain, il s’agissait néanmoins d’un mélange important d’anciennes pratiques métallurgiques. Les ères couvertes sont comprises entre les périodes géométrique et hellénistique. / The subject of this study is the development, application and diffusion of the technology of various types of copper alloys, particularly that of leaded bronze, in ancient Greece, its colonies, and in Etruria. Leaded bronze is a mixture of tin, copper and lead in various proportions. The general consensus among archaeometallurgists is that leaded bronze was not commonly used in Greece until the Hellenistic period, and thus this alloy has not received very much attention in archaeological literature. However, metallographic analyses demonstrate that objects composed of leaded bronze had a wide distribution. The analyses also show differentiation in the composition of alloys that were used in the manufacture of various types of bronzes, a tangible indication that metalworkers distinguished between the properties of both tin bronze and leaded bronze. The knowledge of their different working characteristics is what enabled a bronzeworker to choose, in many cases, the appropriate alloy for a specific application. The influence of Near Eastern metallurgical practices produced variations in both the artistic forms as well as alloy compositions of Greek bronzes during the Late Geometric and Orientalizing periods. The use of leaded bronze for particular types of cast objects shows an increasing tendency from the Orientalizing period onwards, culminating in the late Hellenistic period when high-lead bronze became a common alloy. This study analyzes the metallographic data of specific categories of bronze and leaded bronze cast objects, and it will demonstrate that although the use of leaded bronze was not as prevalent as that of tin bronze, it was nevertheless a significant adjunct of ancient metallurgical practices. The periods surveyed range from the Geometric to the Hellenistic periods.