Crystallization kinetics of atomic crystals revealed by a single-shot and single-particle X-ray diffraction experiment

Crystallization is a fundamental natural phenomenon and the ubiquitous physical process in materials science for the design of new materials. So far, experimental observations of the structural dynamics in crystallization have been mostly restricted to slow dynamics. We present here an exclusive way to explore the dynamics of crystallization in highly controlled conditions (i.e., in the absence of impurities acting as seeds of the crystallites) as it occurs in vacuum. We have measured the early formation stage of solid Xe nanoparticles nucleated in an expanding supercooled Xe jet by means of an X-ray diffraction experiment with 10-fs X-ray free-electron laser (XFEL) pulses. We found that the structure of Xe nanoparticles is not pure face-centered cubic (fcc), the expected stable phase, but a mixture of fcc and randomly stacked hexagonal close-packed (rhcp) structures. Furthermore, we identified the instantaneous coexistence of the comparably sized fcc and rhcp domains in single Xe nanoparticles. The observations are explained by the scenario of structural aging, in which the nanoparticles initially crystallize in the highly stacking-disordered rhcp phase and the structure later forms the stable fcc phase. The results are reminiscent of analogous observations in hard-sphere systems, indicating the universal role of the stacking-disordered phase in nucleation.

Investigation of Sulfate Attack by Experimental and Thermodynamic Means

Wolfgang Kunther

This work investigates sulfate attack in complex sulfate environments by exposing different binder types to various sulfate solutions and comparing predicted phase and volume changes with experimental data. The most important aspects of this work can be grouped in three topics: The comparison of the predicted volume increase with the experimentally observed length changes. This part of the work shows that volume increase cannot be linked directly to the observed expansions. Additionally, the volume increase model does not provide an explanation for the driving force for the space filling to overcome mechanical constraints. A more plausible explanation of expansion lies in the theory of crystallization pressure, in which crystals forming from a supersaturated solution seem to be a more applicable explanation for the deterioration differences. However, this is difficult to verify directly as it is impossible to measure the solution concentration or individual crystals exert pressure on their surroundings. It is observed that expansion occurs in systems where thermodynamic modelling predicts the co-existence of ettringite with gypsum. In such a case, if monosulfate and gypsum are both present locally, the solution can be highly supersaturated with respect to ettringite within the exposed materials. An increase of sulfate contents in the C-S-H phase has been observed for these cases, indicating increased sulfate concentrations in the pore solution while providing the necessary confinement for the crystals in intimate phase mixtures to exceed pressure. The presence of bicarbonate ions in the sulfate solution reduces the expansion significantly for the CEM I and CEM III/B binders, and reduced the sulfate uptake in the phase assemblage. The CEM III/B mortars showed a highly leached zone at the surface in which also calcite was observed, this is attributed to the destabilisation of ettringite in the presence of high concentrations of bicarbonate ions. The microstructural characterization combined with the information from thermodynamic modelling suggests that conditions of high supersaturation with respect to ettringite are unlikely to occur in samples exposed to solutions containing bicarbonate ions. Degradation of mortars exposed to complex magnesium containing sulfate solutions showed that the presence of sodium, potassium and calcium in a magnesium solution reduce the deterioration symptoms significantly for the CEM I and CEM III/B mortars. The experimental observations suggest that sulfate attack in natural environments is not only less severe, due to reduced sulfate concentrations in the field, but are likely to be affected by the presence of bicarbonate anions and the common occurrence of different cations. Both of these aspects reduce the deterioration significantly and can be assumed to occur in most natural waters.

EPFL2012

Microstructure of single crystal Ni-based superalloys during blade manufacturing process and creep deformation

Stéphane Pierret

The aim of the thesis is to obtain more understanding about the influence of plastic deformation on the microstructural changes observed in single crystal (SX) Ni-based superalloys using diffraction techniques. This work was organised around two main problematics: (1) rafting in turbine blades after the manufacturing process and (2) rafting and mosaicity evolution in two SX alloys with different composition during creep deformation. SX Ni-based superalloys are first choice materials for turbine blade application in land-based gas turbines and aero-engines. Superior mechanical properties of these materials at high temperatures are achieved due to the optimisation of the alloying composition and the microstructure. SX Ni-based superalloy turbine blades solidify by dendritic solidification with dendrites aligned along the directions of lowest Young modulus (interdendritic spacing around 300μm). At the end of the manufacturing process, the microstructure consists of high volume fraction of cubic γ’ precipitates (around 500nm) coherently embedded in the γ matrix. However specific parts of engine-ready turbine blades exhibit directionally coarsened γ’ precipitates in a preferred direction (rafting) without the influence of an applied load. It is of prime importance to understand the origin of rafting prior to the introduction of the blades in the engine since rafting can alter the mechanical properties of the alloy. Chemical segregations and the introduction of plastic deformation prior to thermal treatments were identified as potential driving force for rafting during load-free high temperature annealing. Most of the SX Ni-based superalloys used in the current blade production in Alstom contain significant amount of refractory elements which are expensive and increase the density of the alloy. To answer the demand of cheaper and lighter components, Alstom launched a development program to design novel SX superalloys. One of these projects led to the production of a Re-free superalloy, so-called MD2. Extensive mechanical investigations on MD2 are on-going and compared to the behaviour of the MK4HC alloy (3wt% Re) currently used in turbine blade production. One of the major differences in terms of mechanical properties between Re-containing and Re-free SX alloys is the faster kinetics of coarsening and rafting during creep deformation at high temperature in the latter alloys. It prevented so far their application in the hottest areas in gas turbines. It is therefore of utmost importance to acquire more knowledge about the mechanisms associated with the microstructure evolution during creep of the new MD2 SX alloy in comparison with the MK4HC alloy. The evolution of the lattice parameter misfit in different directions with respect to the applied load during creep deformation was associated with the evolution of the microstructure from cubic to elongated γ’ precipitates It could be shown that rafting occurs after the cooling stage following the solution heat treatment (SHT) during the manufacturing of the blade with investigations of the microstructure. The influence of chemical segregations on rafting was excluded with the investigation of the blade alloy composition in different parts of the blade cooled from the SHT and diffraction measurements in stress-relieved combs prepared from the same blade. The formation of a rafted microstructure during the manufacturing process was associated with the formation of plastic strains during cooling after the SHT. This was confirmed after gathering results from investigations of the microstructure, simulation of the cooling stage and neutron diffraction measurements on the blade. The investigations of the microstructure performed on the engine-ready blade revealed an inversion of the γ’ raft orientation below (parallel to [001]) and above the platform of the blade (perpendicular to [001]). This was attributed to an inversion of the sign of residual strain between the previously mentioned positions as revealed by neutron diffraction measurements performed along the airfoil of the blade cooled after the SHT. Microscopy also showed that the rafted microstructure was more pronounced below the platform (long γ’ rafts) than above the platform (shorter γ’ rafts with retained cubic precipitates). The concept of the threshold plastic strain necessary to induce rafting during annealing subsequent to plastic deformation was used to describe the difference in rafted microstructure. It is suggested that plastic strains largely exceed the threshold below the platform leading to fully formed rafted microstructure. On the other side, plastic strains of the order to the threshold strain are suggested above the platform in order to explain the partially formed rafted microstructure Neutron diffraction measurements revealed that the lattice parameter misfit was larger in the MK4HC than in the MD2 alloy at 20°C in the unloaded state. The larger misfit in the MK4HC alloy was attributed to the larger concentration of elements dissolving in the γ phase and to the presence of Re. During creep deformation, coherency stresses are relieved at the γ/γ’ interface in the γ channels perpendicular to the applied load by dislocations. On the other hand, dislocations increase the internal stress at the γ/γ’ interface in the γ channels parallel to the applied load. This leads to the rafting of the γ’ precipitates perpendicular to the applied load. This was observed in the MK4HC. The absence of clear misfit evolution in the MD2 alloy was attributed to the anomalous microstructure at the beginning of the creep deformation. The mosaicity of the MK4HC and MD2 alloys revealed crystallographic misorientation between neighbouring dendrites up to 0.5°. The misorientation was associated with the presence of dislocations in the regions between the dendrites formed during the dendritic solidification of the alloys from existing work. It was shown that the composition of the SX alloys and short periods at high temperature in the unloaded state had only little influence on the misorientation between neighbouring dendrites. Upon creep loading to 180MPa, the mosaicity markedly changed in the two SX alloys independent of the creep temperature. In particular, the number of single misoriented domains measured by X-ray diffraction decreased. This was attributed to the fast propagation of the dislocations present in the interdendritic structure inducing a rotation of the individual dendrites. During creep deformation, the mosaicity increased as visible from the broadening of the maximum spread in misorientation. The formation of inhomogeneous plastic strain fields in the γ/γ’ microstructure is believed to create new mosaic blocks in the dendritic structure of the alloys leading to the observed broadening of the mosaicity. The influence of plastic deformation on the evolution of the mosaicity was demonstrated. The mosaicity significantly changed during creep of the MD2 at 1050°C/180MPa and 1000°C/180MPa whereas no significant evolution could be measured during creep at 950°C/180MPa. This was attributed to a temperature dependence of the yield strength of the MD2 alloy. It therefore induces difference in dislocation propagation at 950°C compared to 1050°C and 1000°C which retards the broadening of the mosaicity during creep at 950°C. Furthermore, the mosaicity formed during creep deformation was retained upon unloading and cooling of the SX samples to room temperature.

EPFL2012

Energy-selective neutron imaging for materials science

Steven Luc X Peetermans

Common neutron imaging techniques study the attenuation of a neutron beam penetrating a sample of interest. The recorded radiograph shows a contrast depending on traversed material and its thickness. Tomography allows separating both and obtaining 3D spatial information about the material distribution, solving problems in numerous fields ranging from virtually separating fossils from surrounding rock to water management in fuel cells. It is nowadays routinely performed at PSI¿s neutron imaging facilities. Energy-selective neutron imaging studies the wavelength-dependency of the cross-section by using a beam of reduced wavelength bandwidth instead of averaging out the cross-section over the incident beam spectrum. The range of observed contrasts/image information is than extended and can largely be understood in the context of the Bragg law. Different types of monochromator (mechanical neutron velocity selector, double crystal monochromator, filter materials) are characterized for use in neutron imaging. In polycrystalline samples, sharp Bragg edges are observed as coherent elastic scattering at the (hkl) plane can occur for all wavelengths up to 2dhkl, after which a sharp increase in transmission intensity is observed. Much like diffraction peaks, they contain information on e.g. crystal phase or projected strain. The absence of coherent elastic scattering past the last Bragg edge (Bragg cut-off) allows for quantification. In samples with few grains or even single crystals, all orientations w.r.t. the beam are no longer present and rather than Bragg edges, the cross section now exhibits distinct peaks, the ensemble of which holds information on the crystallite¿s phase, orientation and shape. A spatial variation in contrast appears across the sample, between those grains fulfilling the Bragg condition ¿ scattering and decreasing the transmitted beam intensity ¿ and those that do not. After initial qualitative assessments, recent advances on the quantitative grain orientation mapping are made based on time-of-flight measurements of high energy resolution recorded at the ISIS pulsed neutron source. But where do these scattered neutrons go to? A new set-up was developed to permit simultaneous transmission and diffractive neutron imaging. Capturing the neutrons diffracted by a grain also yields a projection of that grain, with the position on the detector indicative of the orientation. These projections can in turn be used for algebraic reconstruction, which yields a grain volume as well. After feasibility studies on an iron single crystal cube the recent push towards polycrystalline samples will is illustrated with a neutron diffraction contrast tomography (nDCT) of a coarse-grained aluminium strain sample.

EPFL2015

Energy-selective neutron imaging for materials science

Steven Luc X Peetermans

EPFL2015

Microstructure of single crystal Ni-based superalloys during blade manufacturing process and creep deformation

Stéphane Pierret

EPFL2012

Investigation of Sulfate Attack by Experimental and Thermodynamic Means

Wolfgang Kunther

EPFL2012