Mechanical properties of MC multimetallic carbides in steel

Carbides constitute a class of materials used for many applications, where excellent mechanical properties, such as stiffness, hardness and fracture toughness, are required. The machining industry is a typical example where carbide are crucial materials. Whether it be in tool steels or in cermets, the most performant machining alloys are actually composed of ternary carbides, i.e. contain two different metallic elements in addition to carbon, present as a reinforcement in a metallic matrix. Ternary carbides constitute better reinforcements providing enhanced mechanical properties in comparison with binary carbides; however, our knowledge of ternary carbides per se is insufficient, and only the properties of the alloys have been characterized. The main reason explaining such a lack of data is the relative small size of these particles, in the micro-range, which complicate the measurement of their mechanical properties. This thesis aims to contribute towards filling this gap by means of micromechanical methods able to measure locally the main properties of individual microscopic carbide particles. This is now possible thanks to the recent developments of experimental techniques such as nanoindentation and FIB. The challenges of this thesis are then to be able to 1) produce carbides particles embedded in iron with tailored compositions, 2) test mechanically individual particles and 3) explain the evolution of the properties with changes in composition, in order to find an optimal composition characterized by enhanced mechanical properties. The main challenges come from the small dimension of the particles (< 40 µm) and the fact that such particles are embedded in a steel matrix, more compliant than the particles, which can then bias the measurement of elastic properties. Standard nanoindentation techniques cannot measure accurately the mechanical properties of such matrix/particle combinations and new methods have been developed in this thesis in order to overcome this problem. Carbide particles have been grown in situ by arc-melting cast iron with transition metal high purity chips, in order to properly tune the composition. Three mechanical properties have been measured: elastic modulus, hardness and fracture toughness, by indenting a polished surface, or by bending up to fracture notched micro-cantilever beams. This trio of properties is essential in order to characterize properly a material in view of an application in machining industry. By using binary carbide compositions as references, we have characterized five ternary carbide systems, namely (Ti,W)C, (Ti,V)C, (Ti,Ta)C, (Ti,Nb)C and (Ta,V)C, as well as the quaternary (Ti,Ta,V)C system. The ratio of the metallic elements has been varied in order to cover the entire range of compositions. For the ternary systems, we found compositions that exhibited both a higher hardness and modulus than the two corresponding binary carbides, enhancing the properties by ~15-20%. By investigating the filling of atomic bonds involving d-orbitals, we can provide a partial explanation to the elastic modulus and hardness evolution with composition, the maxima in hardness corresponding to a valence electron concentration between 8.4 and 8.6. The quaternary system aims to further improve mechanical response of the ternary carbides: it allows to highlight a very promising quaternary composition, characterized by the combination of both a very high modulus and hardness of respectively 636 and 41 GPa.

On the relationship between the microstructure and the mechanical properties of an ODS ferritic/martensitic steel

Amuthan Ramar

In the quest of materials for the first wall of the future fusion reactor, it has been shown that oxide dispersion strengthened (ODS) ferritic / martensitic (F/M) steels appear to be promising candidates. The inherent good mechanical properties supported by a good thermal conductivity, swelling resistance and low radiation damage accumulation of the base material, such as EUROFER97, are further enhanced by the presence of a fine dispersion of nanometric oxide particles. They would allow in principle for a higher operating temperature of the fusion reactor, above 550°C, which improves its thermal efficiency. In effect, their strength remains higher than the base material at high temperatures. There are however limitations to their application in the reactor, which relate to the intimate link between the microstructure and the mechanical properties. These limitations, such as an increased ductile to brittle transition temperature above room temperature relative to the base material, come directly from the role played by the oxide particles but also from their indirect impact on the overall microstructure, stemming from the procedure of elaboration of these materials. In addition, there is a lack of knowledge on their response to irradiation, which, even though it appears to be promising with a reduced irradiation induced hardening, is not very well understood. In this work we have developed and evaluated ferritic/martensitic steel, EUROFER97, strengthened by a dispersion of yttria particles. (1) The powder metallurgical process used to obtain it was optimized, (2) the basic mechanisms of hardening were identified and (3) the impact of irradiation on its microstructure and mechanical properties were investigated. In order to understand the behaviour of this class of material other oxide dispersion strengthened (ODS) ferritic/martensitic steels based on EUROFER97 and model alloys were also investigated. For the elaboration of the ODS steel the powders of atomized EUROFER97 and yttria are ball milled in a planetary ball mill and the material is compacted by hot isostatic pressing (HIP). The mechanical properties are evaluated by uniaxial tensile test, Charpy test and micro-indentation while the microstructure is investigated by optical microscopy, scanning electron microscopy and transmission electron microscopy. The focused ion beam (FIB) technique is also used. In the study of the ball milling it appears that the optimal time is 20 hours, as the X-ray peak broadening, crystallite size and hardness of the particles remain unchanged at longer times. Yttria nanoparticles clusters are no more detectable by X-ray after 2 hrs of milling, which is attributed here to their incorporation in the matrix, as opposed to dissolution in the matrix as is often suggested in the open literature. HR-TEM performed on the yttria particles before and after incorporation in the steel by ball milling shows that the yttria maintain its bcc equilibrium structure throughout the process. This could suggest that they are not dissolved during ball milling. We have clarified this point by a cross sectional examination of the EUROFER97 ball milled particles with 0.3wt% of yttria in an FIB. By X-ray EDS analysis it shows nanometric regions reach in yttrium and oxygen, which are the yttria particles embedded in the EUROFER97 particles, proving that they are not dissolved by ball milling. The mechanism at the origin of the alloy compaction during HIP was elaborated. The alloy compaction was done through HIPing at 1150°C for 2.5 hrs at a pressure of 190 MPa. This condition is shown to provide the highest bulk density, to a value close to 99.9%. In the optimization process, it is found that temperature plays a larger role than pressure for alloy compaction. The compaction appears to be mainly due to diffusion. Also, it appears that the ball milled particle size plays a major role in the alloy compaction. It is shown that smaller particles size induces better compaction, provided that the densification proceeds through diffusion flow. This further suggests to terminate the ball milling process by 20 hrs as the particles size reaches its minimum. The impact of the ball milling process on the mechanical properties was evaluated. EUROFER97 with and without ball milling, with and without oxide addition presents an average density around 99.8%. In the as received state, casted EUROFER97, atomized EUROFER97, ball milled EUROFER97 and ODS Yttria present microstructure morphology typical of tempered martensite, whereas ODS Ti presents a nano sized grain microstructure with an average grain size of 200 nm. Ball milling and HIPping does have a slight influence up to 400°C, due to the higher dislocation density induced by ball milling relative to casted EUROFER97. It becomes negligible above 400°C, since both casted and ball milled EUROFER97 present similar hardness and microstructure. In ODS Yttria, yttria presents an average particle size of 25 nm. In ODS Ti, Y-Ti-O presents an average particle size of 7 nm. In the following the identification of the hardening mechanisms in ODS F/M steels. A new model was developed to quantify the collective hardening due to different obstacles, assuming that they provide independent hardening mechanisms. The model helped identifying the dominating source of hardening in ODS F/M steels. The base of the model is the dispersion barrier strengthening model, which is given by Δσsparticle or defects = Mαμb(Nd)1/2 for the hardening due small defects or oxide particles and is given by Δσd-d = Mαμb(ρ)1/2 for the hardening due to dislocations. In this approximation, the total hardening is then given by Δσtotal = {(Δσd-d)2 + (Δσparticle or defects)2}1/2 . The model is used to explain the hardening due to oxides, dislocations and irradiation induced defects. It appears that dispersed oxides is dominating hardness up to 800°C, while following a heat treatment at 1000°C it is the dislocations that then dominate the hardness. Deformation mechanisms were investigated using differential strain rate experiments. The activation parameters, i.e. the activation volume and activation energy, were calculated. It appears that there is a decrease in the activation volume from room temperature to 400°C, which is less than 3%. At about 500°C there is a sudden drop in the activation volume that reaches a minimum at 600°C. With further increase in temperature, there is a significant raise in the activation volume. This abrupt decrease between 400°C and 600°C hints at a change in dislocation-rate controlling mechanism, marking two regimes, a low temperature one and a high temperature one. In situ TEM observations show that at low temperature the deformation is mainly due to the formation of the Orowan loops around the particle. At high temperature the activation energy is about 3.4 eV for ODS, whereas it is 1.3 eV for EUROFER97. The calculated activation energy corresponds well to the one of dislocation climb mechanism. This indicates that at high temperature the yttria particles could be overcome by climb, while at low temperature they are overcome by the Orowan mechanism. The peculiar response of the yield stress to irradiation for this class of material was rationalized using the total hardening model we developed. At a dose of 2 dpa, irradiation induced defects are higher in number density than the dispersed yttria particles, which although they are weaker than the yttria particles they can explain the significant hardening observed in the material. Conversely, the shallow impact of irradiation on ODS F/M steels at low doses, relative to base F/M steels, is explained by the fact that the amount of dispersoid is found to be higher than the density of irradiation induced defects.

EPFL2008

Probing the local strength and toughness of microscopic hard second phases in metals and composites

Marco Cantoni, Raphaël Charvet, Cyril Dénéréaz, Willy Dufour, Marta Fornabaio, Lionel Michelet, Andreas Mortensen, Martin Guillermo Mueller, Václav Pejchal, Goran Zagar

Many engineering alloys and composites combine a ductile matrix with discrete microscopic reinforcing phases, e.g. silicon particles in aluminium alloys, carbides in steels or ceramic particles in metal matrix composites. It is well understood that the mechanical properties of such alloys and composites are strongly influenced by those of their reinforcing particles; yet not much is known of the nature and size of strength-limiting flaws within such microscopic second phases. To investigate the strength and fracture toughness of these microscopic particles directly, we have developed test methods that combine focused ion beam (FIB) milling with microtesting techniques and bespoke finite element simulation. Local strength is probed by micromachining individual reinforcing particles in such a way that tensile stresses are produced in a volume of material free of FIB and polishing artifacts upon the application of a load via nanoindenter. Fracture toughness is measured by the chevron-notch fracture test technique adapted for microscopic samples. Testing methods are established using nanocrystalline alumina fibers as the testbench material, so as to compare data thus obtained with known fiber properties from tensile tests on long sections of the fibers. These test methods are currently being transposed towards the microscopic testing of more irregularly shaped and anisotropic brittle second phases, with the objective to measure their local mechanical properties and identify microstructural flaws that govern the strength of such particles, using in-depth electron microscopy characterization combined with microtesting.

2015

On the relationship between the microstructure and the mechanical properties of an ODS ferritic/martensitic steel

Amuthan Ramar

EPFL2008