Deformation behavior of nanoporous polycrystalline silver layers sintered by low temperature bonding: experiment and simulation

Integrated circuit packaging technology has become a prime design consideration for the develop-ment of electronic system concepts. One key issue is the bonding layer between chip and substrate. Currently, high-lead solder materials are being used, which apart from their environmental problem, limit the reliable operation temperature of devices to temperatures lower than 175ºC. Low-temperature bonding by sintering nanograin sized silver is emerging as a promising replacement in power electronics modules working at high temperatures. Although silver has been studied as bonding material since three decades, it has not been widely used in the packaging industry which might be ascribed to the limited knowledge on its mechanical behavior. In this work, the microstructure of thin layers of nanoporous silver sintered under different conditions are studied and linked to the mechanical behavior (at room temperature) using X-ray diffraction in-situ deformation tests and finite element simulations. First the microstructure of several samples such as grain size distribution, defect structures, porosity, pore morphology and ligament size distribution are investigated and are related to the corresponding sintering conditions. Electron microscopy, high resolution X-ray imaging, and X-ray diffraction techniques are the employed characterization methods. We found a strong dependency of the microstructure on the sintering conditions. Afterward, series of X-ray diffraction in-situ continuous, load-unload and stress relaxation tensile tests are performed to study the deformation mechanisms at room temperature. All samples exhibit small elongation and a large hysteresis in the stress-strain curve. From the change in the peak position upon unloading the residual elastic strain inside the sample is calculated while the evolution of the peak broadening provides information on the recovery mechanisms and induced dislocations. A significant recovery in the peak position and peak broadening after unloading and during relaxation is observed for all specimens. This is attributed to the presence of the pores. We found that the density of generated dislocations during tensile deformation depends on the porous structure. The results suggest that there exist two contributions to deformation: one related to the pores and other to intra-granular dislocations. The competition between both mechanisms is discussed in terms of porosity and grain size. Finally, 3D FE microstructure-based simulations are performed to allow a better correlation between the porous morphology and mechanical behavior. The 3D reconstructed images of nanoporous silver obtained from X-ray ptychography are used as an input to create finite element meshes of the actual porous morphology. For homogenization purpose, a representative volume element approach is chosen. The apparent elastoplastic response of the bulk silver is extracted from the porous samples using inverse homogenization method. The simulations allow distinguishing between the interplay and role of the ligament size, pore morphology and porosity, and provide a better comprehension on the experimental observations. We show that the proposed model has a predictive character for general nanoporous silver microstructures.

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

Nanocrystalline metals: transient testing during in situ X-ray diffraction and molecular dynamics

Zhen Sun

Nanocrystalline (NC) metals have attracted widespread interest in materials science due to their high strength compared to coarse-grained counterparts. It is well know that during uniaxial deformation, the stress-strain behaviour exhibits an extraordinary work-hardening followed by an early observation of constant flow stress. Information on possible deformation mechanisms have been gathered by extensive research combining in situ deformation experiments, electron microscopy observations and computational modelling. Generally, these mechanisms are categorized into two types: dislocation slip and grain boundary (GB) accommodation processes, as for instance, GB sliding based mechanisms and GB migration eventually coupled to the shear stress. However, the interplay between these mechanisms resulting in the constant deformation resistance is not fully understood. Transient testing has proven to be a suitable tool to gather information on the rate limiting deformation mechanisms that are activated during the deformation path. In particular in stress reduction experiments, after an intermediate/large stress drop thermally activated dislocation slip is suppressed so that other underlying mechanisms are brought into foreground during subsequent transient creep. Those mechanisms may play a minor role in the determination of the flow stress but might still be essential to the development of a constant deformation resistance. Within this thesis, transient testing is combined with in situ X-ray diffraction at the Swiss Light Source. Therefore, the transient responses are captured in terms of evolution of macrostrain as well as diffraction peak broadening. Since dislocation slip and GB accommodation have an opposite footprint on the peak broadening, the presence of these two types of mechanisms can be distinguished. Three electrodeposited NC materials with different grain sizes are investigated: two NC Ni batches and one NC Ni50Fe50 batch. The results reveal that the constant flow stress reached during uniaxial deformation of electrodeposited NC metals reflects a quasi-stationary balance between dislocation-based mechanisms and GB-mediated accommodation. The latter plays an important role in producing plastic strain and recovering the defects and internal stress. Depending on the magnitude of the stress drop, a non-monotonic behaviour of the diffraction peak width is observed, suggesting an alternation of mechanisms. Also, by comparing transient responses among different NC materials, the relative contributions of dislocation slip and GB accommodation mechanisms are discussed in terms of grain size and alloying. Finally, different magnitudes of stress reduction are carried out by molecular dynamics (MD) simulations with the aim to verify in situ experimental results and explore the mechanisms responsible for GB accommodation. MD simulations confirm that dislocation slip is reduced after a moderate stress drop, however can continue to operate after adaption of the GB structures by a variety of GB accommodation mechanisms explaining the non-monotonic behaviour of the peak broadening during transient creep.

EPFL2016

Contribution to the Production and Characterization of W-Y, W-Y2O3 and W-TiC Materials for Fusion Reactors

Lyubomira Veleva

This PhD Thesis work was aimed at investigating the potentiality of tungsten-base materials as structural materials for the future thermonuclear fusion reactors in attempting to develop reduced activation tungsten-base materials with high strength and sufficient ductility, especially in terms of fracture toughness and ductile-to-brittle transition temperature, on the basis of the following ideas: (1) nano-grained materials are expected to show an improved ductility with respect to normal grain-sized materials, and (2) nano-grained materials and materials reinforced with either oxide or carbide particles are expected to show improved strength and radiation resistance, as (i) the particles should act as obstacles for the propagation of mobile dislocations, (ii) the numerous grain boundaries and interfaces between the matrix and the particles should act as sinks for the irradiation-induced defects, and (iii) the particles should also help stabilizing the numerous grain boundaries upon thermal annealing and/or irradiation. A variety of W-base materials, namely W-(0.3-1.0-2.0)Y2O3, W-(0.3-1.0-2.0)Y and W-(0.3-0.9-1.7)TiC materials (in weight percent), have been successfully produced at the laboratory scale by powder metallurgy techniques including mechanical alloying followed by either cold pressing and sintering or hot isostatic pressing (HIPping). X-ray diffractometry and scanning and transmission electron microscopy observations combined with density and microhardness measurements as well as with tensile, Charpy impact, fracture toughness and non-standard three point bending tests allowed the identification of optimal chemical compositions and manufacturing conditions, among those investigated and on the basis of the experimental devices at disposal. Microscopic investigations showed that the materials produced at the laboratory scale are composed of small grains, with sizes between a few tens and a few hundreds nanometers, and contain a high density of small Y2O3 or TiC particles, with sizes between 1 and 50 nm. In the case of W-Y materials, all the Y transformed into Y2O3 during mechanical alloying, due to the high amount of O (around 1 wt.%) present in the milled powders, which is beneficial for reducing the excess O content in the materials. All materials also contain a residual porosity of a few percents, which is typical of materials compacted by HIPping. Macroscopic investigations showed that the HIPped materials exhibit high strength values and a promising resistance to irradiation but poor fracture properties up to a very high temperature of about 1100 °C, due mostly to air contamination of the mechanically alloyed powders and to residual porosity of the compacted materials. The materials produced entirely at the laboratory scale by mechanical alloying and HIPping are of better quality than a W-2Y material that was produced by mechanical alloying at the laboratory scale and compacted by sintering and forging at the Plansee company (Austria). Further studies should focus on reducing the O content in the mechanically alloyed powders and the residual porosity of the compacted materials. The grain size should be also optimized as well as the size distribution, number density and crystallographic features of the oxide and carbide particles.

EPFL2011