Dr. Ir. Loïc Malet

• Transmission Electron Microscopy
• Electron Backscatterd Diffraction

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• Supervision of BA2, MA1 Projects and Master Thesis

Articles dans des revues avec comité de lecture

2024

Effects of aging on the microstructure and mechanical properties of metastable β-type Ti-23.6Nb-5.1Mo-6.7Zr alloy with low elastic modulus

In this study, the influence of thermomechanical treatments on the microstructure and mechanical properties of a new metastable β-titanium Ti-23.6Nb-5.1Mo-6.7Zr alloy was assessed. The objective was to determine if the alloy is a potential candidate for a future fabrication of orthopedic implants, in particular prosthetic hip stems with a functional gradient of mechanical properties. Two thermomechanical processing routes were investigated: (a) 90% cold-rolled, (b) 90% cold-rolled, followed by annealing at 950 °C for 1 h. After these initial processing steps, samples were aged between 300 °C and 500 °C from 0.5 h to 4 h. Microstructural characterization was conducted by optical microscopy, transmission electron microscopy and x-ray diffraction. Young's modulus and microhardness were measured. Young's modulus of the sample annealed after cold rolling is lower than that after the cold rolled one. Aging was effective at increasing hardness but also increasing Young's modulus. The hardening during aging resulted from fine ωiso and α precipitation. The transmission electron microscopy investigations indicated that an aging treatment at 500 °C leads to a fine (α + β) microstructure, avoiding brittle ωiso precipitation. For these reasons, this alloy is a potential candidate for the manufacture of a hybrid hip prosthetic stem by employing localized aging treatment at 500 °C in the neck region, creating a functional strength gradient and maintaining a low Young's modulus in the distal part, which is needed to mitigate the stress shielding of the bone.

Atomic scale mechanism of reorientation induced plasticity in titanium alloys - experimental and first principles investigation of the mobile {134‾1} interfaces

Recent experiments identified a new type of stress induced structural transformation allowing to combine high strength, great work hardening and good ductility in multiphase Ti alloys. These properties are achieved through reorientation of the α′ martensite plates being in specific self accommodating 〈54‾1‾3〉 type II twin relation, i.e. under applied load one martensite variant reconfigure to its twinned configuration with visible motion of the {134‾1} twin boundary. This mechanism of plastic deformation was never observed before thus, its current understanding is fragmentary. In this article we present the results of experimental observations and ab initio calculations of 〈54‾1‾3〉 type II twins determining the crystallography of twin formation, structure and energy of the {134‾1} interface as well as mobility of the corresponding twinning disconnections. It was found that the investigated boundary has one of the lowest energies among known twinning modes in hexagonal Ti. Moreover, the 〈54‾1‾3〉{134‾1} disconnections have the smallest Burgers vector and step height in comparison to other active twinning systems. As a result, these disconnections are highly mobile which rationalize migration of the {134‾1} twin boundaries at straining. Furthermore, energy of the twin boundary and mobility of disconnections can be adjusted by particular alloying elements enabling the conscious development of new alloys exhibiting reorientation induced plasticity.

Influence of Austenite Grain Size on the Variant Configurations of Martensite in a Fe-30.5Ni-0.155C Alloy

A Fe-30.5wt%Ni-0.155wt%C alloy was annealed at two different temperatures to produce two different austenite grain sizes. In the coarse-grained specimen, hierarchical configurations of variants are formed and carefully analyzed using EBSD. These typical patterns result from the alternate formation of two perpendicular plate groups of variants over several length scales, and two distinct types of mechanical couplings are shown to occur sequentially in the process of the transformation of an austenitic grain. In the fine-grained specimen, the martensite start temperature is depressed below liquid nitrogen temperature, and the martensitic transformation can only occur under stress assistance. Grain size reduction brings about a dramatic change in the morphology of martensite and its configurations. Martensite is fully twinned, and martensite variants arrange themselves into self-accommodating configurations involving all four variants of the same plate group. Those specific configurations share striking similarities with those usually encountered in conventional shape memory alloys. The reversion of such microstructures upon heating is believed to be at the origin of the observed shape memory effect.

Revisiting the Crystallography of {225}γ Martensite: How EBSD Can Help to Solve Long-Standing Controversy

Explaining the crystallography of iron alloys martensite with a {225}γ habit plane remains a challenging task within the phenomenological theory of martensite crystallography. The purpose of this study is to re-examine the martensite formed in a Fe-8Cr-1.1C alloy using EBSD, which has a better angular resolution than the conventional transmission electron diffraction techniques previously used. The results show that the single morphological plates, which hold a near {225}γ habit plane, are bivariant composites made up of two twin-related variants. It is shown that a {113}γ plane is systematically parallel to one of the three common (Formula presented.) planes between the two twin-related crystals. This observation suggests that the lattice invariant strain of transformation occurs through a dislocation glide on the {113}γ 〈110〉γ system, rather than through twinning as is commonly accepted. Based on this assumption, the predictions of Bowles and Mackenzie's original theory are in good agreement with the crystallographic features of {225}γ martensite. Unexpectedly, it is the high shear solution of the theory that gives the most accurate experimental predictions.

Design rules to develop solute lean α+β titanium alloys exhibiting high work-hardening by reorientation induced plasticity

While work-hardening is typically considered in Ti as a prerogative of the β-metastable alloys, this paper introduces a novel perspective, presenting a set of alloy design rules to develop solute lean α + β titanium alloys exhibiting increased work-hardening capabilities. More specifically, reaching this goal is made possible through the development of α + α′ microstructures exhibiting Reorientation Induced Plasticity (RIP) within the α′ martensitic phase. The microstructural requirements for activating RIP and maximizing mechanical properties (i.e., combining high work-hardening, yield strength and ductility levels) are derived from an analysis of the microstructures/mechanical property relationships of various α + α′ samples. A set of design rules is provided. Emphasis is laid on the pivotal role of the chemistry of the α′ martensitic phase in RIP activation and a Molybdenum equivalent chemical criterion is proposed. The α phase is here suggested as a mean to reduce the prior β grain size and the resulting size of the martensite plates. This approach reveals that the versatile thermal treatments leading to α+α' structures broaden the mechanical property landscape, achieving large work-hardening capabilities (typically over 500 MPa) that can be combined with high yield strength (over 800 MPa).

2023

Influence of the Chemical Composition on the Phase Stability and Mechanical Properties of Biomedical Ti-Nb-Mo-Zr Alloys

A new generation of titanium alloys with non-toxic, non-allergenic elements and lower Young's modulus (YM) have been developed, presenting modulus values close to that of bone. In titanium alloys, the value of the Young's modulus is strongly dependent on the chemical composition. Young's modulus also depends on the present phases and on the crystallographic texture related to the thermomechanical processing. A lower YM is normally attributed to the formation of the α″ phase into the β matrix, but there is no consensus for this assumption. In the present work, four alloys were designed and melted, based on the Ti-Nb-Mo-Zr system and heat-treated to favor the formation of the β phase. The alloys were produced by arc melting under argon atmosphere and heat-treated at 1000 °C for 24 h under high vacuum, being subsequently quenched in water to room temperature. Alloys were then characterized by optical microscopy (OM), X-ray diffraction (XRD) and transmission electron microscopy (TEM). Young's modulus was determined by the impulse excitation technique and Vickers microhardness. The purpose of the study was to define an optimal chemical composition for the further production on a semi-industrial scale of a new Ti-Nb-Mo-Zr alloy for orthopedic implant manufacturing. The results showed that all of the four studied alloys are potential candidates for biomedical applications. Among them, the Ti-24Nb-4Mo-6Zr alloy has the lowest Young's modulus and the highest microhardness. So, this alloy presents the highest HV/YM ratio, which is a key indicator in order to evaluate the mechanical performance of metallic biomaterials for orthopedic implants.

Reorientation Induced Plasticity (RIP) in high-strength titanium alloys: An insight into the underlying mechanisms and resulting mechanical properties

The present paper aims at providing a fine-scale analysis of the Ti-4.5Al-2.5Fe-0.25Si α+α'+βretained microstructures to give insight into the link between the microstructural characteristics of the alloy (phase fraction and chemistry, grain size, etc.) and the deformation mechanisms at play. These microstructures were found to exhibit outstanding work-hardening capabilities that have the great potential to be obtained simultaneously with a high yield strength when the microstructural features are carefully optimized. Ex-situ analyses coupled with TEM revealed the simultaneous occurrence of Reorientation Induced Plasticity (RIP) into the self-accommodated Fe-enriched α' martensite, TRansformation Induced Plasticity (TRIP) of the βretained phase and TWinning Induced Plasticity (TWIP) of the α phase that add to dislocation glide. The Fe-enriched martensite has the remarkable capability to induce reorientation through two distinctive mechanisms: by the motion upon deformation of the intervariant boundary associated to the [45¯13¯]α′ Type II twin, a rather classical mechanism although not often reported into α'; but more surprisingly into such a fine phase, by the creation and growth upon deformation of {101¯2}1¯011α′ twins. A 3-scale mechanical contrast is proposed to explain the remarkable work-hardening rates achieved. Reorientation is shown to be a key microstructural feature for the development of Ti alloys with superior mechanical properties.

2022

Influence of Nb Addition on α″ and ω Phase Stability and on Mechanical Properties in the Ti-12Mo-xNb Stoichiometric System

Metastable β-Ti alloys have become one of the most attractive implant materials due to their high biocorrosion resistance, biocompatibility, and mechanical properties, including lower Young's modulus values. Mechanical properties of these alloys are strongly dependent on the final microstructure, which is controlled by thermomechanical treatment processing, in particular the Young's modulus and hardness. The aim of this work was to analyze the influence of phase precipitations in heat-treated Ti-12Mo-xNb (x = 0, 3, 8, 13, 17, and 20) alloys. The alloys were prepared via arc melting and treated at 950 °C/1 h, and then quenched in water. The microstructures were analyzed by optical microscopy, transmission electron microscopy, and X-ray diffraction. Mechanical properties were based on Vickers microhardness tests and Young's modulus measurements. Microstructural characterization showed that α″ and ω stability is a function of Nb content for the Ti-12Mo base alloy. Nb addition resulted in the suppression of the α″ phase and decrease in the ω phase volume fraction. Although the ω phase decreased with higher Nb contents, ω particles with ellipsoidal morphology were still observed in the Ti-12Mo-20Nb alloy. The α″ phase suppression by Nb addition caused a marked increase in the Young's modulus, which decreased back to lower values with higher Nb concentrations. On other hand, the decrease in the ω phase continuously reduced alloy hardness. The study of the effect of chemical composition in controlling the volume fraction of these phases is an important step for the development of β-Ti alloys with functional properties.

Effect of yttrium addition on phase transformations in alloy 718

The nickel-base alloy 718 is widely used due to its superior performance at high temperatures, combining properties such as high strength, high corrosion and oxidation resistances and good formability and weldability. Its properties can be further improved by controlled additions of alloying elements such as Ce, W, Mo, P, B and Y. The present work aims to evaluate the effect of the yttrium alloying on the phase transformation in alloy 718. Thermodynamic calculation, scanning electron microscopy, electron backscattered diffraction, hardness measurements and differential scanning calorimetry tests were conducted. The Ni17Y2 phase was observed in two situations: associated with the Nb-rich particles or as single particles. The addition of yttrium has a remarkable effect on grain size control. The differential scanning calorimetry tests indicated that the alloy with the high Y content showed earlier precipitation of the γ"phase (Ni3Nb), which is the main hardening contributor, resulting in an increase in hardness.

2021

Effect of the Concentration and the Type of Dispersant on the Synthesis of Copper Oxide Nanoparticles and Their Potential Antimicrobial Applications

The bactericidal properties of copper oxide nanoparticles have growing interest due to potential application in the medical area. The present research investigates the influence of sodium dodecyl sulfate (SDS) and poly(vinylpyrrolidone) (PVP) on the production of copper oxide nanoparticles prepared from copper sulfate (CuSO4) and sodium borohydride (NaBH4) solutions. Different analytical techniques were used to determine the crystal nature, mean size diameter, and surface morphology of the copper oxide nanoparticles. The X-ray diffraction (XRD) patterns showed formation of nanoparticles of cuprite (Cu2O) and tenorite (CuO) when PVP and SDS were added at the beginning of the reaction. In fact, when the Cu/PVP ratio was 1.62, Cu2O nanoparticles were obtained. In addition, nanoparticles of CuO were synthesized when the Cu/PVP ratios were 0.54 and 0.81. On the other hand, a mixture of copper oxides (CuO and Cu2O) and cuprite (Cu2O) was obtained when PVP (Cu/PVP = 0.81 and 1.62) and SDS (Cu/SDS = 0.90) were added 30 min after the beginning of the reaction. Transmission electron microscopy (TEM) images show agglomerated nanoparticles with a size distribution ranging from 2 to 60 nm, while individual particles have sizes between 4.1 ± 1.9 and 41.6 ± 12.8 nm. The Kirby-Bauer method for the determination of antibacterial activity shows that small CuO (4.1 ± 1.9 nm) and Cu2O (8.5 ± 5.3 nm) nanoparticles inhibit the growth of Escherichia coli, Staphylococcus aureus MRSA, S. aureus and Pseudomonas aeruginosa bacteria. The antibacterial test of cotton fabric impregnated with nanoparticles shows positive results. The determination of the optimal ratio of copper oxide nanoparticles per cm2 of fabric that are able to exhibit a good antibacterial activity is ongoing.

2020

Crystallography and reorientation mechanism upon deformation in the martensite of an α-α' Ti-6Al-4V dual-phase microstructure exhibiting high work-hardening rate

The present study provides a fundamental understanding of the crystallography and the microscale behavior of the V-enriched and Al-depleted α' martensite taking place during the microstructure formation and the deformation of the dual phase α + α' microstructure produced in Ti-6Al-4V. This particular microstructure exhibits much larger work-hardening capabilities than the conventional wrought product. The as-quenched structure of the martensite is analyzed using the Phenomenological Theory of the Martensite Crystallography (PTMC) coupled with EBSD analyses. This approach sheds new light on the microstructure configuration obtained during the dual-phase treatment and its fine-scale mechanical behavior. The martensite preferentially forms into parallel groups of 3 self-accommodating variants separated by a misorientation of 63.26∘/[10¯553¯]α'. TEM analyses additionally show that the variants of a same group are separated by a hitherto unobserved {134¯1}α' type twin plane. Postmortem analyses after tensile testing demonstrate that this twinning plane is mobile under deformation. This allows the martensitic microstructure to exhibit the remarkable property to reorient under uniaxial tension. This unique property is shown to be intimately related to the mobility of the {134¯1}α' twinning plane thereby evidencing for the first time that twin boundary motion is not uniquely associated to the orthorhombic α'' martensite but can also occur in hexagonal α' martensite. Quantification of the Interaction Energy (IE) appears relevant to rationalize and predict the reorientation of the martensite. The critical influence of the parent β grains texture on the reorientation is evidenced, while the impact of this deformation mechanism on the ductility of the martensite is debated.

Skeletal integrity of a marine keystone predator (Asterias rubens) threatened by ocean acidification

The current increase in atmospheric CO2 concentration induces changes in the seawater carbonate system resulting in decreased pH and calcium carbonate saturation state, a phenomenon called ocean acidification (OA). OA has long been considered as a major threat to echinoderms because their extensive endoskeleton is made of high-magnesium calcite, one of the most soluble forms of calcium carbonate. Numerous studies addressed this question in sea urchins, but very few questioned the impact of OA on the sea star skeleton, although members of this taxon do not compensate their extracellular pH, contrary to most sea urchins. In the present study, adults of the common sea star, Asterias rubens from Kiel Fjord, a site experiencing natural acidification events exceeding pCO2 levels of 2500 µatm, were chronically exposed to different levels of simulated ocean acidification (pHT-SW 8.0, 7.4, 7.2), encompassing present and future conditions, for the duration of 109 days. Corrosion and mechanical properties of skeletal elements were studied using scanning electron microscopy, three-point bending tests as well as nanoindentation. The spines were significantly corroded at pHT-SW 7.4 and below while the ambulacral plates were only affected at pHT-SW 7.2. Nanoindentation of newly formed spines and ambulacral plates did not reveal significant CO2-induced differences in skeleton hardness or elasticity across treatments. Results of three-point bending tests revealed significantly reduced characteristic strength and fracture force of ambulacral plates from the median arm segment at pHT-SW 7.4 and below. These plates are those supporting the tube feet involved in the opening of bivalves during feeding and in the animal attachment to the substrate. Under reduced seawater pH, this might result in fracture of sea star plates during predation on mussel. The present results predict a possible impact of ocean acidification on the skeletal integrity of a marine keystone predator.

An integrated investigation of the effects of ocean acidification on adult abalone (Haliotis tuberculata)

Ocean acidification (OA) and its subsequent changes in seawater carbonate chemistry are threatening the survival of calcifying organisms. Due to their use of calcium carbonate to build their shells, marine molluscs being particularly vulnerable. This study investigated the effect of CO2-induced OA on adult European abalone (Haliotis tuberculata) using a multi- parameter approach. Biological (survival, growth), physiological (pHT of haemolymph, phagocytosis, metabolism, gene expression) and structural responses (shell strength, nanoindentation measurements, SEM imaging of microstructure) were evaluated throughout a 5-month exposure to ambient (8.0) and low (7.7) pH conditions. During the first two months, the haemolymph pH was reduced, indicating that abalone do not compensate for the pH decrease of their internal fluid. Overall metabolism and immune status were not affected, suggesting that abalone maintain their vital functions when facing OA. However, after four months of exposure, adverse effects on shell growth, calcification, microstructure and resistance were highlighted, whereas the haemolymph pH was compensated. Significant reduction in shell mechanical properties were revealed at pH 7.7, suggesting that OA altered the biomineral architecture leading to a more fragile shell. It is concluded that under lower pH, abalone metabolism is maintained at a cost to growth and shell integrity. This may impact both abalone ecology and aquaculture.

2019

Characterization of a Cast Duplex Stainless Steel with 3.0%Cu and Modeling of Precipitation Hardening

Duplex stainless steels (DSSs) are corrosion-resistant alloys extensively used in aggressive environments. Cast DSSs may be selected for pipes, valves and pumps in chemical, petrochemical and nuclear industries. The grade steel ASTM A890 1B is an example of cast DSS with 2.7-3.3%Cu addition. Copper increases the resistance to many types of corrosion, especially in non-oxidizing environments. When the copper content is higher than 2%, the steel can be precipitation-hardened. In this work, the precipitation hardening of a DSS ASTM A890 1B steel with 3.0%Cu was studied and modeled for aging temperatures in the 450-600 °C range. Copper precipitates in the ferrite phase, but remains in solid solution in the austenite. The age hardening curves were modeled by ΔH = K(t) n model, where ΔH is the increase in hardness, t is the aging time, and K and n are constants to be determined. The microstructure and substructure were investigated by scanning electron and transmission electron microscopes.

Effect of Zn on the grain boundary precipitates and resulting alkaline etching of recycled Al-Mg-Si-Cu alloys

The Zinc level in many 6000 Al alloys (Al-Mg-Si-type) was set to a maximum of 0.03 wt% as common industrial practice. Concentrations above 0.03 wt% can modify the alkaline etching mechanism causing the surface to go from a desired smooth look associated with a grain boundary attack (GBA), into an undesired speckled appearance due to preferential grain etching (PGE), visible after anodizing. This significantly limits the ambition of reducing the carbon footprint of Aluminum by increasing the amount of recycled material in the production process. Because Cu has been reported to counteract this negative effect of Zn, the present study is dedicated to contribute to the understanding of this interaction and is focused on Zn and Cu in peak aged AlMgSi alloys. The chemical composition of the various precipitates formed in two Al6063 alloys was studied by means of TEM and EDX, whereby Zn was found in the Q phase (AlMgSiCu) grain boundary precipitates. Two alloys, with different content of Cu and Zn were studied. The Zn/Cu ratio in the bulk was similar for both alloys, but the level of Zn in the Cu containing Q particles in the grain boundaries was different. The increased Zn concentration in Q phase precipitates is believed to decrease the potential of the precipitates with respect to the surrounding matrix. Thus, the Cu/Zn ratio in these alloys is extremely important as it defines the potential differences that in turn cause either GBA or PGE.

Influence of thermo-mechanical processing on structure and mechanical properties of a new metastable β Ti-29Nb-2Mo-6Zr alloy with low Young's modulus

A low Young's modulus is required for titanium alloys used in orthopedic implants, such as hip prosthetic stems, in order to avoid stress shielding due to a large difference in Young's modulus between the prosthetic stem and the cortical bone. The low Young's modulus has been observed to occur in metastable β-Ti alloys by precipitation of a stress-induced α″ martensite during cold deformation. Under this context, the Influence of thermo-mechanical processing on the microstructure and mechanical properties of the metastable β Ti-29Nb-2Mo-6Zr alloy was studied as well as the influence of the degree of deformation by cold rolling with subsequent annealing after homogenization heat treatment. The alloy presents a β microstructure after solution heat treatment at 1000 °C for 24h, followed by water quenching, while posterior cold rolling induces the precipitation of α” martensite. Young's modulus decreases and hardness increases with the degree of deformation. The annealed samples showed higher hardness and Young's modulus than the cold rolled samples. A thickness reduction of 90% maximizes the hardness/Young's modulus ratio and optimizes the required mechanical properties for orthopedic implants. The results indicate that the alloy is a promising alternative for the widely used Ti-6Al-4V.

2018

Micro and nanoscale characterization of complex multilayer-structured white etching layer in rails

Micro-to nano-scale characterization of the microstructures in the white etching layer (WEL), observed in a Dutch R260 Mn grade rail steel, was performed via various techniques. Retained austenite in the WEL was identified via electron backscatter diffraction (EBSD), automatic crystallographic orientation mapping in transmission electron microscopy (ACOM-TEM), and X-ray diffraction (XRD). EBSD and ACOM-TEM methods were used to quantify grains (size range: 50 nm-4 µm) in the WEL. Transmission electron microscopy (TEM) was used to identify complex heterogeneous microstructural morphologies in the WEL: Nano-twinning substructure with high dislocation density in the WEL close to the rail surface and untransformed cementite and dislocations in the WEL close to the pearlite matrix. Furthermore, atom probe tomography (APT) revealed a heterogeneous through-thickness distribution of alloying elements in the WEL. Accordingly, the WEL is considered a multi-layered martensitic microstructure. These findings are supported by the temperature calculations from the shape analysis of the manganese profile from APT measurements, related to manganese diffusion. The deformation characteristics of the WEL and the pearlite beneath the WEL are discussed based on the EBSD measurements. The role of deformation in the martensitic phase transformation for WEL formation is discussed.

Humidity dependence of transport properties of composite materials used for thermochemical heat storage and thermal transformer appliances

Water sorption thermochemical heat storage is a promising way to provide dwellings with renewable central heating. It requires the use of several cubic meters of materials per dwelling. Depending on the design of the heating system, specific heat and mass transfer issues occur. For instance, the heat transfer rate in reactive medium and the kinetics of sorption process determine the system thermal power. In addition, the moisture propagation during inter-seasonal storage must be understood. In this paper, the influence of the water mass uptake on the apparent thermal conductivity and apparent mass diffusivity of solid material were studied. The studied material was a composite of calcium chloride (CaCl2) encapsulated in mesoporous silica with a salt content of 40-43 wt.%. The thermal conductivity was measured by the transient hot bridge method and varied from 0.13 to 0.16 W m−1 K−1, having a threshold at 0.14 g/g of water mass uptake. The apparent water mass diffusivity was studied using a diffusion column. The water diffusivity - concentration dependency was established by using the modified Hall method. The apparent diffusion coefficient ranged from 3 × 10−10 to 2 × 10−8 m2 s−1 in experimental conditions.

Influence of Heat Treatments on Microstructure and Magnetic Domains in Duplex Stainless Steel S31803

The influence of heat treatments on microstructure and magnetic domains in duplex stainless steel S31803 is studied using an innovative structural characterization protocol. Electron backscatter diffraction (EBSD) maps as well as magnetic force microscopy (MFM) images acquired on the same region of the sample, before and after heat treatment, are compared. The influence of heat treatments on the phase volumetric fractions is studied, and several structural modifications after heat treatment are highlighted. Three different mechanisms for the decomposition of ferrite into sigma phase and secondary austenite are observed during annealing at 800 °C. MFM analysis reveals that a variety of magnetic domain patterns can exist in one ferrite grain.

On the effect of Q&P processing on the stretch-flange-formability of 0.2C ultra-high strength steel sheets

Quenching and Partitioning (Q&P) has been proposed as a novel heat treatment to produce cold rolled sheets with excellent strength and sufficient formability for cold stamping. The impact of Q&P processing on microstructure and tensile properties has been extensively studied in contrast to the lower attention devoted to its effect on stretch-flange-formability. In this study, the stretch-flange-formability of Q&P microstructures is investigated by means of hole expansion tests carried out on punched holes. The balance between tensile properties and hole expansion ratios (HER) is discussed and compared to three model microstructures: biphasic dual-phase (DP), single phase quenched & tempered (Q&T) and quenched & austempered (QAT). It is shown that Q&P microstructures exhibit a better combination of tensile ductility and stretch-flange-formability than fully martensitic (excellent HER but poor tensile ductility) and austempered microstructures (good ductility but poor HER). The study of the impact of the Q&P parameters demonstrates that stretch-flange-formability is further promoted by choosing low quench temperatures and long partitioning times. The hole expansion properties are linked to the hardness gradients in the microstructure, evaluated by nanohardness mapping. The narrower nanohardness distribution in the Q&P microstructure leads to better hole expansion ratios compared to bainitic microstructures obtained by austempering, where the presence of hard M/A blocks is unavoidable.

Chemical, morphological and structural characterisation of electroless duplex NiP/NiB coatings on steel

Duplex electroless nickel coatings constituted of one layer of nickel-phosphorous and one of nickel-boron are a promising solution to provide combined wear and corrosion resistance to parts. Duplex systems were compared to systems of similar thickness constituted of only one material, in one or two layers. Duplex coatings present intermediate surface texture, but each layer keeps its typical cross-section morphology and structural features, even after heat treatment. The interfaces between the separate layers are sharp in the as-deposited state but not as much after heat treatment. When nickel-boron is deposited first, it influences slightly the grain growth of the subsequent nickel-phosphorous layer, but no influence can be observed when nickel-phosphorous is deposited first.

Production, microstructure and mechanical properties of cold-rolled Ti-Nb-Mo-Zr alloys for orthopedic applications

The microstructure and mechanical properties of two new metastable β Ti alloys were studied and the influence of the degree of deformation by cold rolling after homogenization heat treatment was also investigated. Both Ti-29Nb-2Mo-6Zr and Ti-24Nb-4Mo-3Zr alloys present a β microstructure after solution heat treatment at 1000 °C for 24 h followed by water quenching whereas ulterior cold rolling induces the precipitation of α” martensite. The results indicate that both alloys are promising alternatives to the widely used Ti-6Al-4V. Young's modulus decreases and hardness increases with the degree of deformation. A thickness reduction of 90% maximizes the hardness/Young's modulus ratio and optimizes the required mechanical properties for orthopedic implants.

Synthesis and characterization of zinc oxide nanoparticles for application in the detection of fingerprints

Stable zinc oxide nanoparticles were prepared by chemical process. Zinc oxide nanoparticles were synthesized using a modified method with zinc nitrate and sodium hydroxide at 60° C. The synthesized nanopowders were characterized in terms of chemical composition (EDS), structure FTIR and XRD, particle size and morphology by TEM. The XRD results confirm that ZnO nanoparticles were obtained with hexagonal arrangement (Wurtzite). The nanoparticles showed sizes between 10 to 30 nm and semispherical forms. The luminescent properties of the synthesized nanoparticles were measured in a photoluminescence assay on a Raman instrument. The samples were irradiated with two laser beams of different wavelengths. The application of the fingerprints on different surfaces was done using deferments surfaces.

2017

On the relationship between the multiphase microstructure and the mechanical properties of a 0.2C quenched and partitioned steel

In the present work, Quenching and Partitioning (Q&P) heat treatments were carried out in a quench dilatometer on a 0.2 wt% carbon steel. The microstructure evolution of the Q&P steels was characterized using dilatometry, SEM, EBSD and XRD. The martensitic transformation profile was analyzed in order to estimate the fraction of martensite formed at a given temperature below the martensite start temperature Ms. Q&P was shown to be an effective way to stabilize retained austenite at room temperature. However, the measured austenite fractions after Q&P treatments showed significant differences when compared to the calculated values considering ideal partitioning conditions. Indeed, the measured austenite fractions were found to be less sensitive to the quench temperature and were never larger than the ideal predicted maximum fraction. Competitive reactions such as austenite decomposition into bainite and carbide precipitation were found to occur in the present work. Furthermore, a broad range of mechanical properties was obtained when varying the quenching temperatures and partitioning times. The direct contributions between Q&P microstructural constituents -such as retained austenite as well as tempered/fresh martensite- and resulting mechanical properties were scrutinized. This was critically discussed and compared to quenching and austempering (QAT) which is a more conventional processing route of stabilizing retained austenite at room temperature. Finally, Q&P steels were shown to exhibit an interesting balance between strength and ductility. The achievement of this interesting combination of mechanical properties was reached for much shorter processing times compared to QAT steels.

Galvanostatic anodizing of additive manufactured Al-Si10-Mg alloy

The galvanostatic anodizing behavior of additive manufactured (AM) Al-Si10-Mg alloy was studied in H2SO4 electrolyte. The analysis of the voltage vs time response was complemented with a systematic characterization of the anodic oxide layer using a variety of techniques. In addition, a cast alloy of approximately the same chemical composition as that of theAMspecimens was used as a reference in this study. Significant differences were found in the voltage-time characteristics of the samples analyzed. Besides, an anisotropic anodizing behavior was observed in the additive manufactured specimens. Due to the fine silicon microstructure present in the additive manufactured samples, the anodic oxide growth was much more obstructed than for the cast alloy. Nevertheless, even though the oxide layer was generally thinner in the AM samples for the same conditions and anodizing time, a much more continuous and uniform oxide layer was found in the additive manufactured specimens compared to the cast alloy. The porous structure was found to be greatly affected by the fine distribution of the silicon phase in the AM parts.

Microstructure and mechanical properties of Ti-12Mo-8Nb alloy hot swaged and treated for orthopedic applications

Metastable β-type Ti alloys with non-toxic addition elements such as Mo, Zr, Sn, Ta and Nb were developed as an alternative to the widely used Ti-6Al-4V alloy for biomedical applications. These alloys possess enhanced biocompatibility and reduced elastic modulus in comparison with Ti-6Al4V. Moreover, for orthopedic implants, low Young's modulus is required in order to avoid the stress shielding phenomenon. This study analyzes the microstructure and mechanical properties of a new Ti-12Mo-8Nb alloy after hot swaging, annealing at 950 ºC for 1h and water quenching. The alloy was characterized by X-ray diffraction, optical microscopy and transmission electron microscopy. Tensile tests were performed at room temperature. Young's modulus and hardness values were also measured. The structural characterization reveals a metastable β structure containing only a small amount of α and ω phases. Exhibiting a lower Young's modulus than Ti-6Al-4V and other previously studied Ti-Mo-Nb alloys, the Ti-12Mo-8Nb alloy can be a promising alternative for orthopedic application.

2016

Dislocation/hydrogen interaction mechanisms in hydrided nanocrystalline palladium films

The nanoscale plasticity mechanisms activated during hydriding cycles in sputtered nanocrystalline Pd films have been investigated ex-situ using advanced transmission electron microscopy techniques. The internal stress developing within the films during hydriding has been monitored in-situ. Results showed that in Pd films hydrided to β-phase, local plasticity was mainly controlled by dislocation activity in spite of the small grain size. Changes of the grain size distribution and the crystallographic texture have not been observed. In contrast, significant microstructural changes were not observed in Pd films hydrided to α-phase. Moreover, the effect of hydrogen loading on the nature and density of dislocations has been investigated using aberration-corrected TEM. Surprisingly, a high density of shear type stacking faults has been observed after dehydriding, indicating a significant effect of hydrogen on the nucleation energy barriers of Shockley partial dislocations. Ab-initio calculations of the effect of hydrogen on the intrinsic stable and unstable stacking fault energies of palladium confirm the experimental observations.

2015

Pt(Ni) electrocatalysts for methanol oxidation prepared by galvanic replacement on TiO<inf>2</inf> and TiO<inf>2</inf>-C powder supports

Pt(Ni) catalysts were prepared by electroless deposition of Ni on TiO<inf>2</inf> and mixed TiO<inf>2</inf>-C powder supports, followed by partial galvanic replacement of Ni by Pt in a chloroplatinate solution. Pt(Ni)/TiO<inf>2</inf> and Pt(Ni)/TiO<inf>2</inf>-C catalysts were characterized by transmission electron microscopy (TEM), energy-dispersive spectrometry (EDS), X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS) and anomalous small-angle X-ray scattering (ASAXS). XPS and ASAXS results showed no detectable alloying between Pt and Ni. In accordance with ASAXS analysis, the size of the Pt particles of the two samples is practically similar (2.1 and 1.5 nm). The electrocatalytic activity of the catalysts towards methanol oxidation and poisonous CO removal was assessed by cyclic voltammetry and chronoamperometry experiments and compared to commercial Pt/C catalysts. Despite the fact that the specific mass activity of the prepared catalysts is lower than that of the commercial material (as a result of their smaller surface area), both Pt(Ni)/TiO<inf>2</inf> and Pt(Ni)/TiO<inf>2</inf>-C electrodes showed superior intrinsic catalytic activity (per Pt electroactive area) than the Pt/C catalyst. This is attributed to a synergistic effect of TiO<inf>2</inf> on facile CO poison removal from Pt sites.

On the relation between orientation relationships predicted by the phenomenological theory and internal twins in plate martensite

The phenomenological theory of martensite crystallography predicts two equivalent solutions for a particular habit plane in the case of a Fe-Ni-C alloy. Those two solutions differ in the magnitude of the inhomogeneous shear and in the orientation relationship (OR) they hold with austenite. Only the OR associated to the low shear solution has been observed experimentally so far. In the present study, the orientation relationship associated to the high shear solution is assessed experimentally using TEM measurements.

On the relation between orientation relationships predicted by the phenomenological theory and internal twins in plate martensite

The phenomenological theory of martensite crystallography predicts two equivalent solutions for a particular habit plane in the case of a Fe-Ni-C alloy. Those two solutions differ in the magnitude of the inhomogeneous shear and in the orientation relationship (OR) they hold with austenite. Only the OR associated to the low shear solution has been observed experimentally so far. In the present study, the orientation relationship associated to the high shear solution is assessed experimentally using TEM measurements.

Dislocation-mediated relaxation in nanograined columnar palladium films revealed by on-chip time-resolved HRTEM testing.

The high-rate sensitivity of nanostructured metallic materials demonstrated in the recent literature is related to the predominance of thermally activated deformation mechanisms favoured by a large density of internal interfaces. Here we report time-resolved high-resolution electron transmission microscopy creep tests on thin nanograined films using on-chip nanomechanical testing. Tests are performed on palladium, which exhibited unexpectedly large creep rates at room temperature. Despite the small 30-nm grain size, relaxation is found to be mediated by dislocation mechanisms. The dislocations interact with the growth nanotwins present in the grains, leading to a loss of coherency of twin boundaries. The density of stored dislocations first increases with applied deformation, and then decreases with time to drive additional deformation while no grain boundary mechanism is observed. This fast relaxation constitutes a key issue in the development of various micro- and nanotechnologies such as palladium membranes for hydrogen applications.

2014

Crystallographic Reconstruction Study of the Effects of Finish Rolling Temperature on the Variant Selection During Bainite Transformation in C-Mn High-Strength Steels

The effect of finish rolling temperature on the austenite-(γ) to-bainite (α) phase transformation is quantitatively investigated in high-strength C-Mn steels using an alternative crystallographic γ reconstruction procedure, which can be directly applied to experimental electron backscatter diffraction mappings. In particular, the current study aims to clarify the respective contributions of the γ conditioning during the hot rolling and the variant selection during the phase transformation to the inherited texture. The results confirm that the sample finish rolled at the lowest temperature [1102 K (829 °C)] exhibits the sharpest transformation texture. It is shown that this sharp texture is exclusively due to a strong variant selection from parent brass {110}〈112〉, S {213}〈364〉 and Goss {110}〈001〉 grains, whereas the variant selection from the copper {112}〈111〉 grains is insensitive to the finish rolling temperature. In addition, a statistical variant selection analysis proves that the habit planes of the selected variants do not systematically correspond to the predicted active γ slip planes using the Taylor model. In contrast, a correlation between the Bain group to which the selected variants belong and the finish rolling temperature is clearly revealed, regardless of the parent orientation. These results are discussed in terms of polygranular accommodation mechanisms, especially in view of the observed development in the hot-rolled samples of high-angle grain boundaries with misorientation axes between 〈111〉γ and 〈110〉γ.

Mechanical characterization of cruciate and collateral ligaments of human knee

An alternative to the crystallographic reconstruction of austenite in steels

An alternative crystallographic austenite reconstruction programme written in Matlab is developed by combining the best features of the existing models: the orientation relationship refinement, the local pixel-by-pixel analysis and the nuclei identification and spreading strategy. This programme can be directly applied to experimental electron backscatter diffraction mappings. Its applicability is demonstrated on both quenching and partitioning and as-quenched lath-martensite steels. © 2014 Elsevier Inc.

Formation of Nanostructures in Severely Deformed High-Strength Steel Induced by High-Frequency Ultrasonic Impact Treatment

Surface modification by the generation of a nanostructured surface layer induced via ultrasonic impact treatment was performed at the weld toe of a welded high-strength quenched and tempered structural steel, S690QL1 (Fe-0.16C-0.2Si-0.87Mn-0.33Cr-0.21Mo (wt pct)). Such high-frequency peening techniques are known to improve the fatigue life of welded components. The nanocrystallized structure as a function of depth from the top-treated surface was characterized via a recently developed automated crystal orientation mapping in transmission electron microscopy. Based on the experimental observations, a grain refinement mechanism induced by plastic deformation during the ultrasonic impact treatment is proposed. It involves the formation of low-angle misoriented lamellae displaying a high density of dislocations followed by the subdivision of microbands into blocks and the resulting formation of polygonal submicronic grains. These submicronic grains further breakdown into nano grains. The results show the presence of retained austenite even after severe surface plastic deformation. The average grain size of the retained austenite and martensite is (Formula presented).35 nm, respectively. The in-grain deformation mechanisms are different in larger and smaller grains. Larger grains show long-range lattice rotations, while smaller grains show plastic deformation through grain rotation. Also the smaller nano grains exhibit the presence of short-range disorder. Surface nanocrystallization also leads to an increased fraction of low angle and low energy coincident site lattice boundaries especially in the smaller grains ((Formula presented). nm).

2012

Variant selection and texture in an AISI 301LN stainless steel

There has recently been significant interest in the problem of variant selection in the strain-induced transformation of austenite to α'-martensite in metastable austenitic stainless steels. Previous work has highlighted our poor understanding of the mechanisms leading to this transformation, in particular the role that the macroscopic stress plays in the transformation. In this work, we have sought to perform detailed experiments aimed at developing a statistical grain level view of variant selection in one particular grade of austenitic stainless steel. EBSD measurements made over a large number of grains as well as macroscopic texture measurements made at different levels of imposed plastic strain allow for comparison against various approaches for predicting variant selection based on the Patel-Cohen interaction energy. © (2012) Trans Tech Publications, Switzerland.

2011

Grain scale analysis of variant selection during the gamma-epsilon-alpha phase transformation in austentic steels

Grain scale analysis of variant selection during the gamma-epsilon-alpha' phase transformation in austenitic steels

Austenitic steels can exhibit a complex transformation sequence during deformation. Indeed, the austenitic phase transforms first into bands of ε (HCP) martensite. This transformation is then followed by the formation of α' (BCC) martensite. In this study, the crystallography of the transformation together with the occurrence of variant selection is studied at the scale of individual austenite grains. About ten prior austenite grains deformed at different strain levels in uniaxial tension were analysed by means of EBSD techniques. One of the classical approaches to predict the variant selection phenomenon is based on the calculation of the interaction energy between the macroscopic stress and the shape deformation associated with the formation of the product phase. The formation of the α' variants was observed to lead to a very strong variant selection that cannot be fully explained by energetic criterion. It is suggested that the crystallography of the transformation sequence can account for the unexpected variants. © (2011) Trans Tech Publications.

2010

Microstructural evolution during spheroidization annealing of eutectoid steel : effect of interlamellar spacing and cold working

Eutectoid steels present a wide range of interesting mechanical properties (high strength, wear resistance, ductility and toughness) and could be a cheaper alternative to high strength low-alloyed steels (HSLA) in applications where weldability is not a critical requirement. The mechanical properties of pearlite are mainly dictated by the interlamellar spacing and the spheroidization of cementite. In this work, the spheroidization kinetics during annealing of a fully pearlitic steel produced in an electric arc furnace (EAF) is investigated. More specifically, the influence of a prior cold deformation and of the interlamellar spacing is studied using image analysis and hardness tests. It is shown that spheroidization is faster in fine pearlite than in coarse pearlite. Prior cold deformation strongly accelerates the spheroidization kinetics in fine and coarse pearlite. The tensile properties corresponding to different pearlite microstructure were measured and are compared to the hardness evolution during annealing. © (2010) Trans Tech Publications.

Quantitative analysis of variant selection and orientation relationships during the γ-to-α phase transformation in hot-rolled TRIP steels

2009

Variant selection during the γ-to-αb phase transformation in hot-rolled bainitic TRIP-aided steels

The variant selection phenomenon during the austenite to bainite phase transformation in hot-rolled TRIP-aided steels was quantitatively characterized at the level of individual austenite grains. The reconstruction of the electron backscatter diffraction maps provided evidence that bainite grows by packets of laths sharing a common {1 1 1}γ plane in the austenite. The affect of hot deformation is to reduce the number of packets that form. It is suggested that slip activity is important in understanding this effect. © 2009 Acta Materialia Inc.

Communications publiées lors de congrès ou colloques nationaux et internationaux

2015

The zig-zag pattern revisited in Fe-31Ni-0.155C

Thèses et mémoires

2015

The formation of plate martensite in a Fe-High Ni alloy

Mainly two different morphologies of martensite can be obtained in steels depending on the amount of alloying elements. The first morphology, referred to as lath martensite, forms in low alloy, low carbon steels. It is, by far, the most extensively studied form of martensite due to its industrial applications. The second morphology of martensite, referred to as plate martensite, forms in highly alloyed and in high carbon steels and in particular in Fe-High Ni alloys. In this case, the transformation product is disc shaped and internally twinned. This morphology is the only form of martensite that has the potential to exhibit shape memory properties. It is therefore of great interest to understand the mechanisms of its formation. This is investigated in the present dissertation through the study of the martensitic transformation occurring in a Fe-30.5%Ni-0.155%C alloy. More precisely, the influence of stress and grain size on the crystallography of plate martensite is discussed in the general framework of the phenomenological theory of martensite crystallography. This theory allows associating a unique shape deformation to each orientational variant. In this way, the experimental observations carried out at different length scales by means of optical microscopy, EBSD and TEM can be used to infer the transformation path followed under different conditions. Firstly, the burst configurations of variants observed in coarse-grained austenite under stress free conditions are rationalized by considering the mechanical couplings between the variants. It is shown that self-accommodating and autocatalytic couplings are responsible for the formation of hierarchical configurations of variants. More precisely, the transformation is shown to occur through the alternate formation of perpendicular plate groups of variants. Self-accommodation is the dominant coupling between variants of the same plate group while autocatalytic couplings are responsible for the transfer of the transformation from one generation to the next. It is suggested that the plastic accommodation of the shape deformation plays a dominant role in propagating the transformation to a lower length scales. Secondly, the influence of a uniaxial stress state on the transformation is studied. It is seen experimentally that only the most favoured variants are systematically formed in coarse Cube grains while coarse non-Cube grains generally transform into plate groups of variants that are only moderately favoured by the stress. These observations are well explained by considering the interaction energy between the applied stress and the shape deformation associated with the transformation. Thirdly, the influence of the austenitic grain size on the transformation is also studied. A decrease in grain size is seen to decrease the martensite start temperature. For a grain size below about 10µm, the thermal transformation in liquid nitrogen is indeed suppressed in the present alloy. This observation is related to the increasing yield strength of austenite as the grain size is reduced. A noticeable change in the morphology of martensite also accompanies the decrease in grain size. Indeed, martensite forming in coarse-grained austenite is mostly lens shaped and partially twinned while it appears plate shaped and fully twinned in smaller grains. Furthermore, martensite forming in fine-grained austenite develops self-accommodating configurations suggesting that most of the transformation deformations are elastically accommodated in this case. This is believed to be related to the observance of a shape memory effect in the present alloy in its fine-grained condition.