Les fontes à graphite sphéroïdal sont aujourd’hui très largement utilisées en raison de leurs bonnes propriétés mécaniques. La forme sphéroïdale du graphite est obtenue le plus souvent par l’ajout de magnésium ou de cérium lors de l’élaboration des fontes. Le graphite sphéroïdal peut être obtenu par graphitisation à l'état solide des fontes totalement ou partiellement solidifiées dans le système métastable. L’objectif de ce travail est d’étudier l’effet du traitement de graphitisation à l’état solide sur la croissance du graphite nodulaire d’une fonte à paroi mince qui présente une structure truitée à l'état brut de coulée. Cette fonte a été étudiée par microscopie optique, microscopies électronique à balayage et en transmission, spectroscopie Raman et spectroscopie de perte d'énergie des électrons. Des traitements thermiques assurant une graphitisation totale et partielle pour décomposer la cémentite formée à la solidification en graphite et en austénite ont été réalisés. Les nodules deviennent plus nombreux et leur taille augmente en fonction du temps de graphitisation. La microstructure après traitement thermique est composée de nodules de graphite et de ferrite. La spectroscopie Raman a été utilisée pour caractériser les nodules de graphite d’échantillons ayant été entièrement graphitisés à différentes températures dans le domaine austénitique. L’analyse par spectroscopie Raman ne montre aucune différence significative entre les spectres Raman enregistrés sur le graphite formé lors de la solidification et à l’état solide. Les caractérisations microstructurales par microscopie électronique en transmission montrent que le graphite à l’état brut de coulée présente une structure caractérisée par une zone interne où le graphite est désorienté. Une déformation mécanique due à la contraction lors de la solidification métastable induit la formation de cette zone. Cette zone disparaît par recristallisation après traitement de graphitisation totale pour former à la fin des secteurs coniques rayonnant à partir du germe et se développant vers la périphérie. Les résultats de ces travaux ont permis une meilleure compréhension de la structure de graphite nodulaire à l’état solide et montre aussi que le mécanisme de croissance du graphite nodulaire est le même lors de la solidification et de la transformation à l'état solide. / Spheroidal graphite iron castings are today widely used because of their good mechanical properties. The spheroidal shape of graphite is most often obtained by the addition of magnesium or cerium during the casting process. Spheroidal graphite can be formed at the solid-state by graphitization of cast irons which solidified partly or totally in the metastable system. The purpose of this work is to study the effect of solid-state graphitization treatment on the growth of nodular graphite of a thin wall casting which has a mottled structure at the as-cast state. This cast iron was studied using optical microscopy, scanning and transmission electron microscopy, Raman spectroscopy and electron energy loss spectroscopy. Heat treatments ensuring a total and partial graphitization to decompose the cementite formed at the solidification in graphite and austenite were realized. The nodules become more numerous and their size increases according to the time of graphitization. The microstructure after heat treatment is composed of graphite nodules and ferrite. Raman spectroscopy has been used to characterize graphite nodules in as-cast state and in samples having been fully graphitized at various temperatures in the austenite field. The results show no significant difference between Raman spectra recorded on these various samples, suggesting graphite grows with the same mechanism during either solidification or hightemperature (so-called first stage) graphitization. Transmission electron microscopy characterizations show that nodules in the as-cast material presents a multi-fold structure characterized by an inner zone where graphite is misoriented and an outer zone where it is well crystallized. In heat-treated samples, graphite nodules consist of well crystallized sectors radiating from the nucleus. These observations suggest that the misoriented zone appears because of mechanical deformation when the liquid contracts during its solidification. During heat-treatment, this zone disappears by recrystallization. The results of the present work lead to a better understanding of the nodular graphite structure in the solid state and also show that nodular graphite growth mechanism is the same during solidification and solid-state transformation.

京都大学 / 0048 / 新制・課程博士 / 博士(工学) / 甲第22067号 / 工博第4648号 / 新制||工||1725(附属図書館) / 京都大学大学院工学研究科材料工学専攻 / (主査)教授 安田 秀幸, 教授 辻 伸泰, 教授 宇田 哲也 / 学位規則第4条第1項該当 / Doctor of Philosophy (Engineering) / Kyoto University / DGAM

A good understanding of the solidification process of a cast material is essential to understand how the combination of alloy composition and the casting process variables combines into the solid cast component and its performance. The wrong combination may result in poor performance or casting defects. Spheroidal graphite has been well researched in ductile irons (SGI) where it is predominant. Spheroidal graphite is also present in smaller amounts in compacted graphite irons (CGI), but its nature and role in this material is less understood. Recent associations of spheroidal graphite in CGI with shrinkage porosity problems highlights the need for better understanding in this area. The importance of the dendritic austenite structure to the properties and solidification behaviour of cast irons has been highlighted in recent research. However, progress is to a degree limited by lack of practical means to characterize the structure. In the present work, the transition of a cast iron from SGI to CGI though remelting was studied. As the fraction of SG dropped, the tips of the compacted graphite tended to lose contact with the melt at a later stage. After this occurred, solidification appeared to be dominated by spheroidal graphite. Compacted and spheroidal graphite was found to solidify mostly segregated, and the increased recallescence induced by a higher fraction of compacted graphite displayed small influence on the size distribution of spheroidal graphite apart from the total number and fraction. The partitioning of Si, Mn and Cu in SGI and CGI was found to agree well with each other, as well as with theoretical predictions under the assumptions of zero diffusion of the elements in the solid. This shows that the proportions of spheroidal and compacted graphite has small or no influence on the evolution of these elements in the melt during solidification. A method for characterization of the dendritic austenite in quenched cast irons was introduced and evaluated. The method includes a technique for producing a visual contrast between the ledeburite matrix and the dendritic austenite, and a scheme for producing binary images from the resulting micrographs which are suitable for automatic image analysis. Measurements of the volume fraction and surface area per unit volume of the dendritic austenite structure using the introduced method was found to agree reasonably with traditional point counting and line intercept techniques. The difficulty in finding the exact boundary was proposed to be the major source of systematic disagreement. / En god förståelse för stelningsprocessen av ett gjutet material är väsentligt för att förstå hur kombinationen av legeringens kemiska sammansättning och gjutprocessens variabler resulterar i den stelnade komponenten och dess prestanda. Fel kombination kan resultera i sänkt prestanda eller gjutdefekter. Sfärisk grafit är väl studerad i segjärn (SGI) där grafitmorfologin är dominant. Mindre mängder sfärisk grafit är dock närvarande även i kompaktgrafit, där dess karaktär och roll är mindre känd. Samband mellan sfärisk grafit i kompaktgrafitjärn och krympporositet understryker behovet av bättre förståelse inom detta område. Dessutom har betydelsen av den tidiga dendritiska austenitstrukturen för senare delen av stelningen uppmärksammats. Utveckling inom detta område är dessvärre till en grad begränsad av bristen på kunskap om praktiska metoder för att karaktärisera dess struktur. I detta arbete studerades övergången från segjärn till kompaktgrafit genom omsmältning. Vid sänkt fraktion sfärisk grafit visade sig kompaktgrafiten tappa kontakten med smältan vid senare stadie av stelningen. Efter detta inträffade, dominerades stelningen till synes av tillväxt av sfärisk grafit. Kompaktgrafit och sfärisk grafit bildades i huvudsak segregerade. Ökad rekallesens till följd av ökad fraktion kompaktgrafit visade sig ha låg inverkan på storleksfördelningen av eutektisk sfärisk grafit bortsett från dess totala antal och fraktion. Omfördelningen av Si, Mn och Cu mellan stelnad matris och smälta i segjärn och kompaktgrafitjärn fanns stämma bra överens med varandra, samt med teoretiska värden med antagande om försumbar diffusion i stelnad matris. Detta visar att proportionerna av sfärisk och kompaktgrafit har liten eller ingen inverkan på halten av dessa ämnen i smältan under stelningen. En metod för karaktärisering av den dendritiska austenitstrukturen i släckt gjutjärn introducerades och utvärderades. Metoden inkluderar en teknik för att åstadkomma kontrast mellan ledeburitmatrisen och den dendritiska austeniten, och en teknik för att producera binära bilder från resulterande mikroskopbilder som är lämpliga för automatisk bildanalys. Mätningar av volymfraktion och yta per volymenhet av dendritstrukturen genom tillämpning av den introducerade metoden visade rimlig överensstämmelse med traditionella punktfraktion‐ och linjetekniker. Svårigheten att hitta den exakta gränslinjen mellan dendritisk struktur och ledeburit föreslogs vara den huvudsakliga källan till systematisk oöverensstämmelse.

The amount and morphology of the graphite phase largely controls the resulting properties of cast iron. For instance, in flake graphite cast irons the mechanical properties are low while the thermal conductivity is high. This is in contrast with spheroidal graphite cast irons where the mechanical properties are high and the thermal conductivity is low. These differences are due to the different graphite morphologies and must be accounted for in the design work and material selection of cast iron components. In this work the influence of the graphite phase on the elastic and plastic deformation behaviour of cast irons has been studied. The material grades studied originate from castings for marine diesel engine piston rings with different chemical analyses. Two groups of pearlitic cast iron materials were studied; one with differences in graphite morphology and one with grey irons that differed in graphite content. For these different material grades the mechanical properties were correlated to microstructural parameters. In addition to standard uniaxial tensile tests, acoustic emission measurements were used for the study of deformation. When studying the modulus of elasticity of the cast iron it was found that the modulus of elasticity of the inherent graphite phase depends on the roundness of the graphite particles and is due to the strong anisotropy of the graphite phase. A linear correlation between nodularity and the modulus of elasticity of the graphite phase was derived. This correlation made it possible to account for the anisotropy of the graphite phase in the model used. By applying the linear function when modelling the effective modulus of elasticity, a high accuracy between experimental and theoretical values was achieved. Another factor affecting the elastic response when subjecting a cast iron component to tensile load was found to be the plastic deformation that actually occurs at very low strains for all of the studied cast iron grades. It was observed that the plastic deformation in the low strain elastic region, quantified by using acoustic emission measurements, increased linearly with decreasing modulus of elasticity. These measurements showed that the amount of plastic deformation in the elastic region was largely controlled by the graphite morphology. It was concluded that as the roundness of the graphite particles increases, the plastic deformation activity in the elastic region decreases. The plastic deformation activity continued linearly into the pronounced plastic region of the tensile tests. A decrease in roundness or increase in graphite fraction resulted in an increase of the amount of plastic deformation and the strain hardening exponent. A dependence between strength coefficient and graphite fraction was observed. Models for the flow curves for pearlitic cast irons were developed and shown to accurately reproduce the observed experimental curves. The surveys performed and conclusions from this thesis will be helpful in the design of new cast iron materials.

The thesis is concerned with relationships between progressive technological processes of spheroidal graphite cast iron’s production and their structural properties. The aim of the work is to explain causal relationship between parameters of the proposed manufacturing technology of the iron type given (involving selected variants of modification and inoculation of melt and the parameters of melt crystallization, solidification and cooling down in a mould), their structure and even chemical heterogeneity of elements in this structure. For close specification of presented relationships three-dimensional model of spheroidal graphite growth was used, which was developed at the Brno University of Technology, Faculty of Mechanical Engineering. Its usability in praxis has been verified on the basisis of the application of this model on experimentally acquired data. The U GRAFIT 20 model of the authors Stránský and Million counting segregation in the frame of eutectic cell has not still been used for prediction of segregation in real condition in greater extent. On the basis of the above mentioned model microsegregation within “on average” of the cell has been discovered during experimental melts. Microsegregation has been described by segregation and heterogeneity indexes. Calculated values of segregation and heterogeneity indexes have been compared with experimentally verified values. On the basis of comparison of calculated and measured values the possibility of further usage of the mentioned model in praxis has been explored.

Les pompes sèches primaires dédiées aux procédés de fabrication en microélectronique sont soumises à des environnements très corrosifs de plus en plus oxydants et halogénés (Cl2, F2 et O2). Or pour des raisons mécaniques et économiques, les parties fonctionnelles des pompes sont usinées dans la fonte à graphite sphéroïdale EN-GJS-500-7. La fonte est alors protégée par un dépôt de nickel-phosphore (NiP) chimique. Cette thèse, reprend des études classiques sur la cinétique et le mécanisme de nickelage d'une part, et sur l'optimisation des propriétés mécaniques et la résistance à la corrosion des couches de NiP d'autre part. Cependant, le caractère innovant de ce travail repose sur la réalisation de couches NiP sur un substrat en fonte à graphite sphéroïdale.L'étude de la cinétique de nickelage et la caractérisation morphologique des revêtements en fonction du temps de dépôt a montré l'influence de la nature chimique du substrat. Les sphères de graphite affleurantes à la surface du substrat n'étant pas catalyseur du nickel chimique, provoque des défauts dans le revêtement, dommageables pour la conformité du dépôt. Il a été montré qu'une polarisation cathodique de la surface du substrat pouvait, dans les premiers instants du dépôt, amorcer le nickelage à l'aplomb des sphères de graphite.Une relation entre la microstructure des dépôts en fonction des traitements thermiques subis et des propriétés mécaniques des couches de NiP a été mise une évidence. Les dépôts NiP amorphes présentent une faible dureté et un comportement ductile tandis que les dépôts cristallisés possèdent une dureté élevée et un comportement fragile. Ces dépôts ont une bonne tenue à la corrosion en milieux halogéné lorsqu'ils sont intacts. Actuellement, au niveau industriel, les dépôts les plus fragiles sont choisis, bien qu'ils présentent une résistance à la corrosion plus faible : en effet, la durée de vie des pompes est alors supérieure car les effets de grippage sont atténués.Mots-clés : nickel chimique, résistance à la corrosion, fonte à graphite sphéroïdale, caractérisation physico-chimique, couches minces, durabilité mécanique / Primary dry pumps dedicated to manufacturing processes in microelectronics are subjected to highly corrosive environments that are increasingly oxidizing and halogenous (Cl2, F2 and O2). However, for mechanical and economic reasons, the functional parts of the pumps are machined in EN-GJS-500-7 spheroidal graphite cast iron. The cast iron is consequently protected by a nickel-phosphorus chemical deposit. This thesis is based on classical studies on the kinetics and the nickel-plating mechanism on the one hand, and on the optimization of the mechanical properties and corrosion resistance of the NiP layers on the other hand. The innovative nature of this work is based on the production of NiP layers on a spheroidal graphite cast iron substrate.The study of the kinetics of nickel-plating as well as the morphological characterization of coatings as a function of the deposit time showed the influence of the chemical nature of the substrate. The flush graphite spheres on the surface of the substrate being not a catalyst for the chemical nickel, they can cause defects in the coating and a loss of compliance. It has been shown that a cathodic polarization of the surface of the substrate, in the first moments of the deposit, could initiate the nickel-plating right on the graphite spheres.A relationship exists between the microstructure of the deposits as a function of the thermal treatments undergone and the mechanical properties of the NiP layers. The amorphous NiP deposits have a low hardness and a ductile behavior while crystallized deposits have a high hardness and a brittle behavior. These deposits have a good resistance to corrosion in halogenated environments when they are intact. Actually, at the industrial level, the most brittle deposits are chosen, although they have a lower corrosion résistance: indeed, the service life of the pumps is higher because the seizing effect are minimized.Keywords: electroless nickel, resistance to corrosion, spheroidal graphite cast iron, physicochemical characterization, thin layers, mechanical durability

Bei der Herstellung von dickwandigem GJS treten zahlreiche ungeklärte Effekte durch die sehr langsamen Abkühlungs- und Erstarrungsgeschwindigkeiten auf. Bisherige Untersuchungsmethoden ermöglichen keine definierte Temperaturführung analog zum realen Bauteil und benötigen trotzdem große Schmelzemengen und einen hohen Trennaufwand für die Probenherstellung. Das Ziel der Arbeit bestand in der Entwicklung einer Versuchsmethode zur experimentellen Simulation extrem langer Abkühl- und Erstarrungszeiten von GJS. Die Verwendung einer geeigneten Abdeckung der Schmelze zur Minimierung des Mg-Abbrandes und eines druckfesten Kaltwandofens inkl. dynamischer Temperatursteuerung ermöglichte reproduzierbare Versuche zur Einstellung verschiedener Gefügezustände durch Variation der Abkühlregime und des Impfzustandes. Es gelang, Chunkygrafit und Grafitflotation gezielt herzustellen und dadurch die Entstehungsmechanismen wissenschaftlich zu untersuchen. Ein Chunkygrafit-Index-Diagramm konnte erarbeitet werden.

This work is focused on segregation processes in the matrix of spheroidal graphite cast iron with different silicon and nickel content during heat treatment. The aim of this work is to trace the redistribution of the elements of interest during homogenization annealing with different dwell time by comparison of the effective distribution coefficients. Comparison of some specific properties and description of structure development of spheroidal graphite cast iron matrix from initial state to the state after ferritization and homogenization annealing is included in this work.

This doctoral thesis deals with the comparison of different methods of alloying elements’ concentration measurement based on energy dispersive spectroscopy and also with the suitability of particular methods of quantitative assessment of heterogeneity of the spheroidal graphite cast iron matrix. The segregation curves construction, distribution coefficient and heterogeneity index formulation is also discussed. The notion “normalized distribution coefficient” is introduced newly. The goal of the thesis, which is to be achieved by means of evaluation of large experimental data sets, is the evaluation of applicability of homogenization annealing of spheroidal graphite cast iron with the aim to eliminate segregation of silicon, and mainly nickel, as pearlite- and carbide-forming agent at the border of an eutectic cell. The result is an optimized homogenization annealing schedule maximizing the suppression of silicon and nickel segregation while taking into account the minimization of financial expenses and risk of grain coarsening.