Abstract This research work focuses on how to improve the toughness of heat affected zones (HAZs) of low heat input welds in the case of high strength thermomechanically processed (TMCP) and recrystallization controlled rolled and accelerated cooled (RCR) plates with yield strengths of 355–500 MPa. Experimental work was aimed at the investigation of the intragranular nucleation of acicular ferrite or bainite in hot-rolled plates and the evaluation of the Charpy V and CTOD toughness of the most critical sub-zones of the weld HAZ using simulated specimens with a cooling time t8/5 = 5 s. The zones studied were the coarse grained HAZ (CGHAZ), the intercritically reheated coarse-grained HAZ (ICCGHAZ) and the intercritical HAZ (ICHAZ), the metallographical analyses consisted of microstructural investigations complemented with hardness measurements. Optical, scanning and transmission electron microscopy techniques were employed together with image and electron backscatter diffraction (EBSD) analysis. The test results showed that the toughness of the various sub-zones of the HAZ is improved by promoting intragranularly nucleated ferritic-bainitic (acicular) microstructure in both the CGHAZ and in the base plate. In this way, the sub-zones subjected to intercritical thermal cycles (the ICCGHAZ and the ICHAZ) develop evenly distributed M-A constituents between ferrite and bainite laths. These favourable microstructures can be achieved by using titanium killing or by avoiding niobium microalloying by using copper plus nickel alloying instead. In the laboratory experiments titanium killed steel, containing titanium-manganese oxide/manganese sulphide inclusions with a number density of 300–750 particles/mm2, develops a largely acicular ferritic microstructure in the base plate provided the austenite grain size is greater than about 120 μm and the cooling rate is in the range 6–11 °C/s down to 500 °C. Under plate mill conditions, no significant amount of acicular ferrite could be obtained, because it was not possible to achieve austenite grain sizes larger than about 70 μm after rolling. However, a significant fraction of acicular ferritic-bainitic microstructure was achieved in the CGHAZ, when the austenite grain size exceeded 90 μm. When achieved, a uniform distribution of M-A particles in an acicular ferritic-bainitic microstructure improves toughness. Cracks nucleate at numerous sites on M-A/ferrite boundaries or bainite packet interfaces, but they are initially arrested in the acicular matrix. Crack growth finally occurs by linking of the numerous arrested microcracks.

L’industrie automobile cherche constamment à augmenter la part des pièces fabriquées à partir de tôles minces en aciers plus résistants et à plus bas coût. Le parallèle entre les diagrammes de phases Fe-N et Fe-C montre qu’il est possible de développer des aciers similaires dans le système Fe-N. Les objectifs de cette étude étaient l’élaboration des aciers binaires Fe-N et le développement des structures équivalentes à celles dans les aciers au carbone. Les approches envisagées s’articulent autour de : Elaboration : la nitruration gazeuse en phase austénitique suivie de traitements d’homogénéisation ont permis de charger des tôles minces de fer pur en concentrations importantes d’azote. Une simulation de la diffusion de l’azote a été proposée. Genèse des microstructures : Le refroidissement lent de l’austénite Fe-N conduit à des structures perlitiques lamellaires et globulaires, constituées de ferrite et du nitrure non-stoechiométrique Fe4N. Une structure aciculaire particulière a été identifiée. Il s’agit de la ferrite se développant dans le nitrure Fe4N. Le refroidissement lent de la ferrite Fe-N sursaturée conduit à la précipitation des nitrures stables Fe4N et métastable Fe16N2. Des microstructures multiphasées [alpha+alpha'+gamma] ont été obtenues par des maintiens dans le domaine intercritique suivis de trempe. Le domaine intercritique a été réexaminé en utilisant le modèle des sous-réseaux. Des essais in-situ en MET ont relevé l’évolution des précipités de Fe16N2 dans la ferrite au cours du vieillissement à 85 °C. Des proportions importantes de l’austénite résiduelle ont été relevées, ce qui serait à la base du développement des aciers TRIP à l’azote / Car designers are seeking ways to increase the proportion of parts made of sheet steels of higher strength and lower cost. The parallel between the Fe-N and Fe-C phase diagrams shows that it is possible to develop similar steels in the Fe-N system. The objective of this study was to prepare binary Fe-N steels and to develop structures equivalent to those in carbon steels. Approaches to meet the objectives are considered: Preparations of Fe-N steels: gas nitriding in austenite domain followed by homogenization treatments allowed to introduce high amount of nitrogen in pure iron sheet. A simulation of the nitrogen diffusion was proposed to describe the weight increase during nitriding. Genesis of microstructures: The slow cooling of the Fe-N austenite led to lamellar and globular pearlitic structures composed of ferrite and nitrideFe4N. An acicular microstructure, which is the consequence of the precipitation of the ferrite in the nitride Fe4N, was also identified. The slow cooling of the supersaturated Fe-N ferrite led to the precipitation of the stable nitride Fe4N and the metastable nitride Fe16N2, which witnessed a rapid diffusion of nitrogen in ferrite at low temperature, comparable to that of carbon. The multiphase microstructures [alpha+alpha'+gamma] were obtained by intercritical treatments followed by quenching. The intercritical domain was reviewed using the sub-lattice model. In-situ TEM investigations have identified the precipitation of Fe16N2 nitride in the ferrite during the aging at 85 °C. High amount of the residual austenite have been identified, which would be the basis for development of TRIP nitrogen steels

The Chatham Islands are located in the SW Pacific Ocean, approximately 850 km to the east of the South Island of New Zealand. This small group of islands is situated near the eastern margin of the Chatham Rise, an elongated section of submerged continental crust that represents part of the Late Paleozoic-Mesozoic Gondwana accretionary margin. The location and much of the geology of the Chatham Islands are attributed to intra-plate basaltic volcanism, initiated during the Late Cretaceous, in association with development of a failed rifting system to the south of the Chatham Rise. Despite the volcanic nature of much of the geology, the majority of the Cenozoic sedimentary stratigraphic record on the islands comprises non-tropical skeletal carbonate deposits whose deposition was often coeval with submarine volcanics and volcaniclastic deposits. This has resulted in complex stratigraphic relationships, with the volcanic geology exerting a strong influence on the geometry and distribution of the carbonate deposits. These limestones, despite some general field descriptions, have been little studied and are especially poorly understood from a petrographic and diagenetic perspective. The carbonate geology in detail comprises eleven discrete limestone units of Late Cretaceous through to Pleistocene age which were studied during two consecutive field expeditions over the summers of 2005 and 2006. These limestone occurrences are best exposed in scattered coastal outcrops where they form prominent rugged bluffs. While many of the younger (Oligocene to Pliocene) outcrops comprise of poorly exposed, thin and eroded limestone remnants (it;5 m thick), older (Late Paleocene to Early Oligocene) exposures can be up to 100 m in thickness. The character of these limestones is highly variable. In outcrop they display a broad range of textures and skeletal compositions, often exhibit cross-bedding, display differing degrees of porosity occlusion by cementation, and may include rare silicified horizons and evidence of hardground formation. Petrographically the limestones are skeletal grainstones and packstones with a typical compositional makeup of about 70% skeletal material, 10% siliciclasts, and 20% cement/matrix. Localised increases in siliciclastics occur where the carbonates are diluted by locally-derived volcaniclastics. The spectrum of skeletal assemblages identified within the Chatham Island limestones is diverse and appears in many cases to be comparable to the bryozoan dominant types common in mainland New Zealand and mid-latitude Australian cool-water carbonates in general. However, some key departures from the expected cool-water carbonate skeletal makeup have been identified in this study. The occurrence of stromatolitic algal mats in Late Cretaceous and Early Eocene carbonate deposits indicates not cool-temperate, but certainly warm-temperate paleoclimatic conditions. A change to cool-temperate conditions is recorded in the limestone flora/fauna from the mid-Late Miocene times following the development and later northward movement of the Subtropical Front. An uncharacteristic mix of shallow-shelf (bryozoans) and deeper water fauna (planktic foraminifera), together with their highly fragmented and abraded nature, is indicative of the likely remobilisation and redistribution of carbonate, primarily during episodic storm events. The Chatham Islands limestones formed within the relative tectonic stability of an oceanic island setting, which was conducive to ongoing carbonate accumulation throughout much of the Cenozoic. This contrasts markedly with other mainland New Zealand shelf carbonates which formed over sporadic and short-lived geological periods, experiencing greater degrees of burial cementation controlled by a relatively more active tectonic setting. As a consequence of the tectonically stable setting, the Chatham Islands limestones have experienced little burial and exhibit a paucity of burial cementation effects. They remain commonly soft and friable. Detailed petrographic investigations have shown the limestones are variably cemented by rare uneven acicular spar fringes, poorly to well-developed syntaxial rim cements about echinoderm fragments, and equant/blocky microsparite. Staining of thin sections and cathodoluminescence petrography show these spar cement generations are non-ferroan and their very dull- to non-luminescent nature supports precipitation from Mn-poor oxygenated waters, likely of an either meteoric or combined marine/shallow burial origin. Micrite is the dominant intra- and inter-particle pore fill and occurs both as a microbioclastic matrix and as precipitated homogenous and/or micropeloidal cement. The rare fringing cements often seen in association with homogenous and/or micropeloidal micrite may be indicative of true early marine (seafloor) cement precipitation and localised hardground development. An interesting feature of the geology of the Chatham Islands is the occurrence of carbonate material within sedimentary dykes. The locations of the dykes are in association with volcanic and volcaniclastic deposits. Similarities between dyke characteristics at Red Bluff on Chatham Island with mainland occurrences from East Coast and Canterbury Basins (North and South Islands, respectively) on mainland New Zealand have been recognised. They show complex structures including sidewall striations, internal flow structures as revealed by grain sorting, and extra-clast inclusions of previous fill lithologies which are characteristic of carbonate injection. This is in contrast to other dykes which are known to be of a passive fill origin. Multiple phases of carbonate sediment injection can be recognised by crosscutting relationships enabling the determination of a parasequence of events. Possible injection mechanisms are most likely associated with sediment overloading or hydrothermal pressurisation associated with emplacement of submarine volcanics. The Chatham Islands provide an exciting example of a geologically unique and complex non-tropical carbonate depositional setting. The production of carbonates is controlled by volcanic and volcaniclastic sediment input with the types of carbonate deposits and water depth variations related to thermal uplift/subsidence in association with global eustatic sealevel and temperature changes associated with development of Southern Ocean water fronts from the Late Cretaceous-Cenozoic. Carbonate deposition on the Chatham Islands is considered to relate to a rather variable and small scale oceanic, high energy, cool-water carbonate ramp setting whose geometry was continually evolving/changing as a consequence of periodic volcanic episodes.

Des nuances d’aciers à moyen carbone, microalliés au vanadium, ont été élaborées avec l’objectif d’obtenir de nouvelles microstructures, majoritairement constituées de ferrite aciculaire (FA). Le contrôle de la composition chimique (0.1-0.3 % V) et la vitesse de refroidissement (2.0 °Cs-1) conduit à des fractions de FA atteignant 80 %. Un paramètre empirique, le pouvoir ferritisant, P, a été introduit pour évaluer l’effet combiné de la composition chimique et de la vitesse de refroidissement sur la fraction de FA. Les caractérisations par MEB et MET montrent que la FA se développe à partir de la ferrite proeutectoïde recouvrant les inclusions de MnS. Une précipitation interphase de carbonitrures de vanadium, V(C,N), serait à l’origine d’un appauvrissement local en carbone de la matrice austénitique autour des aiguilles de FA, favorisant une germination autocatalytique. Le caractère fractal de la FA a été mis en évidence par des caractérisations morphologiques. Les dimensions fractales, D, et les longueurs de coupure ont été déterminées par la méthode de comptage de boîtes à partir d’images MEB. Des essais mécaniques isothermes-quasistatiques révèlent des propriétés mécaniques équivalentes à celles des microstructures bainitiques. Les courbes contrainte-déformation montrent un comportement mécanique de type Hollomon. Les structures de ces aciers présentent des taux de consolidation qui augmentent avec l’accroissement de la fraction de FA. Une corrélation entre les propriétés mécaniques et la dimension fractale a été établie. Ce lien s’exprime par des relations de type exponentiel : [delta]M = c exp [[alpha](D -2)] où M représente? les propriétés mécaniques (Re, Rm, etc.) et c? et ?[alpha] des constantes / Medium carbon vanadium microalloyed steels have been developed to obtain new microstructures, mainly formed of acicular ferrite (AF). Controlling the chemical composition and (0.1-0.3 % V) and the cooling rates (2.0 °Cs-1) lead to AF fractions up to 80 %. An empirical parameter, the ferritisant power, P, has been introduced to evaluate the combined effect of chemical composition and cooling conditions. Scanning (SEM) and transmission (TEM) electron microscopy investigations indicate that AF develops from proeutectoid ferrite enveloping MnS inclusions. An interphase precipitation of vanadium carbo-nitrides, V(C,N) has been identified. It is suggested that this precipitation is at the origin of carbon depletion in the austenitic matrix surrounding the AF plates. The formation of the AF is then enhanced by an autocatalytic effect. The fractal nature of AF has been determined by SEM and TEM characterisations. Fractal dimensions, D, and cut off lengths have been derived by the counting box method applied to SEM images. Mechanical tests conducted in isothermal and quasistatic conditions reveal that mechanical properties of AF are of the same grade of that of bainitic microstructures. Experimental strain-stress curves are described by the Hollomon law. The work hardening of the studied microstructures increases with the AF fraction. The mechanical properties have been linked to the fractal dimension by the following exponential relation : [delta]M = c exp [[alpha] (D -2)], where M represents the mechanical property (Re, Rm, etc.) and c and [alpha] are constants parameters

En perspective de la prolongation de la durée de vie en service des REPs, il est de plus en plus important d’obtenir une évaluation fiable de l’évolution de la microstructure des aciers constituant la cuve des REPs et de leurs propriétés correspondantes. Un mécanisme de fragilisation non-durcissante, dû à la ségrégation intergranulaire du P qui affaiblirait la cohésion des joints de grains, pourrait contribuer à la fragilisation et doit donc être étudié. Les présents travaux ont pour objectifs d’étudier la ségrégation intergranulaire du P dans un acier de cuve de réacteur afin (i) de connaître l’influence du type de joint de grain sur la ségrégation du P, (ii) de clarifier l’influence des conditions de vieillissement (vieillissement thermique et irradiation ionique) sur la ségrégation du P et (iii) de faire une comparaison avec les modèles disponibles et proposés ici.Pour cela, une méthodologie corrélative -Diffraction des Électrons Rétrodiffusés (EBSD), Diffraction de Kikuchi en Transmission (TKD) et Sonde Atomique Tomographique (APT) -a été adoptée pour étudier la ségrégation intergranulaire. Les informations cristallographiques (5 paramètres) et la composition chimique ont été collectées et systématiquement corrélées. Les aciers ont une microstructure complexe de ferrite aciculaire et de carbures intergranulaires. La ségrégation des solutés aux joints des grains (joints des grains faiblement désorientés (LAGB), joints des grains fortement désorientés généraux (HAGB) et Σ3HAGBs) et aux interfaces (interfaces carbure-ferrite M2.0-3.2C et interfaces cémentite-ferrite) a été quantifiée. Il existe une ségrégation évidente d'un élément ou de plusieurs espèces chimiques (C, P, Mn, Mo, Cr, Si et Ni) pour tous ces types de défauts plans. Tenant compte de la nature des éléments ségrégants et de la cristallographie du joint de grain, les ségrégations interstitielles et substitutionnelles ont été quantifiées et discutées. Sur la base d’un grand nombre de données, il apparaît que les niveaux moyens des segrégations en P sont plus élevés dans les HAGBs généraux ou les LAGBs que les autres types d'interfaces quel que soit le vieillissement envisagé. Par ailleurs, les résultats expérimentaux ont été comparés avec les résultats prévus par des modèles analytiques pour des systèmes binaires, ternaires et multi-composants. Bien qu'ayant un niveau de ségrégation du P prédit plus élevé, le modèle ternaire Fe-P-C se rapproche le plus des résultats expérimentaux. / With expectations for extending the service lifespans of PWRs, it is of great importance to get a reliable evaluation of the microstructural evolution and the corresponding property changes of RPV steels. A non-hardening mechanism, due to intergranular P segregation that impairs the grain boundary (GB) cohesion, may contribute to the embrittlement and thus needs to be studied. The present work aims to investigate the intergranular P segregation behavior in a RPV steel in order to (i) determine the influence of GB type on P segregation behavior, (ii) clarify the influence of ageing conditions (thermal ageing and ion irradiation) on P segregation behavior and (iii) make a comparison with the existing analytical models. To reach these objectives, a correlative - Electron Backscatter Diffraction (EBSD), Transmission Kikuchi Diffraction (TKD) and Atom Probe Tomography (APT) - methodology was adopted to study the GB segregation behavior. The crystallographic information (5 parameters) and chemical composition were collected simultaneously. The steels have a complex microstructure of acicular ferrite and intergranular carbides. The solute segregation at GBs (Low Angle Grain Boundaries (LAGBs), general High Angle Grain Boundaries (HAGBs) and Σ3 HAGBs) and interfaces (M2.0-3.2C carbide-ferrite interfaces and cementite-ferrite interfaces) were quantified. There is an obvious segregation of one element or several chemical species (C, P, Mn, Mo, Cr, Si and Ni) at all boundary types. Taking into account the nature of segregants and the five-parameter GB crystallography, both interstitial and substitutional segregation behaviors were discussed. Based on a large dataset, it appears that the average P segregation levels are higher in general HAGBs or LAGBs than in other boundary types. Besides, the experimental results were compared to the predicted ones from analytical models for binary, ternary and multicomponent systems. Though with a higher predicted P segregation level, the Fe-P-C ternary model seems to better fit the experimental results in all ageing conditions.