X-radiography front tracking gradient furnace for directional solidification of bulk Al-alloys.

A unique gradient furnace for directional solidification experiments with bulk Al-alloy samples developed at German Aerospace Center is presented. It allows for in situ process control in solidifying samples by using x-radiography, and further insight into the solidification process is gained in combination with x-ray computational tomography on the solidified samples. Tracking of interfaces during directional solidification of bulk samples via in situ x-radiography (TIREX) enables the investigation of the melting process and observation of the movement of the entire mushy zone through the sample, tracing the solid-liquid interface during directional solidification and correlating the observations with the microstructure of the samples. Monitoring the temperature profile inside the sample by in situ observation of the length of the mushy zone is particularly important because the temperature gradient G and the rate of interfacial growth v determine the microstructure of solidification. The x-radiography setup offers temporal and spatial resolutions of 0.5 s and 70 µm, respectively, with a field of view of 10 × 50 mm2. Constant solidification velocities of up to 0.15 mm s-1 at a temperature gradient of up to 8 K mm-1 can be achieved in a temperature range of 537-1373 K. A flat solid-liquid interface inside a rod-like sample with 5 mm diameter is achieved by surrounding the sample by thermal isolating graphite foam. Performance tests with hypoeutectic Al-10 wt. % Cu alloy samples show the functionality of the furnace facility.

In-situ X-ray monitoring of solidification and related processes of metal alloys.

X-ray radioscopy enables the in-situ monitoring of metal alloy processes and then gives access to crucial information on the dynamics of the underlying phenomena. In the last decade, the utilisation of this powerful imaging technique has been adapted to microgravity platforms such as sounding rockets and parabolic flights. The combination of microgravity experimentation with X-ray radioscopy has resulted in a leap in the understanding of fundamental science and has opened new paths in the fields of materials science. The present review focuses on the short history of this research, which includes facility developments, microgravity experiments and results obtained by partners of the XRMON (In-situ X-Ray MONitoring of advanced metallurgical processes under microgravity and terrestrial conditions) research project in the framework of the MAP (Microgravity Application Promotion) programme of the European Space Agency. Three illustrative research topics that were advanced significantly through the use of X-ray radioscopy will be detailed: solidification of metal alloys, metallic foam formation and diffusion in melts.

Isothermal furnace for long-term in situ and real-time X-radiography solidification experiments.

A new x-ray isothermal furnace has been developed, suitable for in situ observations of semi-solid processes including the transition from dendritic to globulitic grain morphology and grain coarsening in metallic samples. A homogeneous, isothermal temperature field is achieved using a novel heater concept. The furnace structure is sandwich-like with heating elements positioned in the beam line and parallel to the sample. Planar heat transfer to the sample enables measurements with low cooling rates and a minimized temperature gradient. Cooling rates from 0.1 to 15 K min-1 can be controlled in the temperature range 1170-670 K. The furnace setup is integrable in the existing rotatable laboratory x-ray facility (X-RISE) at the German Aerospace Center (DLR). In this setup, an effective pixel size of 3 µm and a field of view of 8 mm in diameter can be achieved. Preliminary solidification and semi-solid experiments in the hypo-eutectic alloy systems Al-Ge and Al-Cu, inoculated with Al-5Ti-1B grain refiner, are presented. They indicate a very uniform temperature distribution in the sample.

Gas-loading furnace for deuterium-charged alloy-casting.

A furnace was developed and characterized to allow for safe and controlled gas-loading or degassing of alloys. This oven is able to process samples under varying atmospheres, such as high vacuum or nitrogen containing 10 vol. % deuterium, as well as for pressures up to 800 hPa. Thermal desorption spectroscopy and scanning electron microscopy demonstrate the enhancing effects of high loading-gas concentration, high pressures, high temperatures above liquidus (50-150 K above the liquidus temperature of the cast hypoeutectic aluminum-copper model-alloy), and long holding times (up to 60 min) on the amount of retained gas in the solidified sample. Lack of copper segregation in the casting is confirmed by energy dispersive x-ray diffraction and Rutherford backscattering spectroscopy. It is shown that the facility allows for the controlled generation of distinct amounts of gas pores, down to a nil amount (only shrinkage porosity appearing in the sample).

XRISE-M: X-radiography facility for solidification and diffusion studies of alloys aboard sounding rockets.

A compact fully protected microfocus X-radiography facility (XRISE-M) is presented for the study of microstructure evolution during the solidification of thin liquid alloy samples and chemical diffusion in liquid binary alloys in situ and in real-time aboard a sounding rocket. XRISE-M presently enables the simultaneous processing of either two near-isothermal solidification furnaces or a combination of a linear-shear cell diffusion furnace and a near-isothermal solidification furnace. For optimal detector calibration shortly before flight, the furnaces can be rotated around the central beam axis and calibration images can be recorded. The facility allows preheating the samples into the liquid state prior to lift-off without leakage during the ascent phase at accelerations of up to 27 g. Macrosegregation on remelting of thin metal samples for microstructure evolution investigations is prevented by an inclinable furnace metric. The use of ion-getter pumps for vacuum generation enables us to exploit the entire available time of reduced gravity for image recording and data acquisition. With the device and currently available sample environments, microstructure formation upon solidification and chemical diffusion under purely diffusive conditions in alloys can be investigated. The facility can be used equally for other investigations such as granular matter dynamics or metal foaming, provided that suitable experiment inserts are developed in the future.

Self- and interdiffusion in dilute liquid germanium-based alloys.

Self- and inter-diffusion coefficients in liquid Ge and dilute Ge-based Ge-Si, Ge-Au, Ge-In, Ge-Ce and Ge-Gd alloys-containing 2 at% additions, respectively, are measured using a comprehensive approach of measuring techniques: quasi-elastic neutron scattering, in situ long-capillary experiments combined with x-ray radiography, and a long-capillary experiment under microgravity conditions. Resulting inter- and Ge self-diffusion coefficients are equal within error bars for each investigated alloy. The interdiffusion coefficients are smaller for the alloys containing Ce and Gd, However, no dependence of the atomic mass of the minor additions, that varies by about a factor of seven between Si and Au, on the diffusion coefficients could be observed. This demonstrates that in a loosely-packed metallic liquid with fast diffusive dynamics the diffusion mechanism is highly collective in nature.

Iron self diffusion in liquid pure iron and iron-carbon alloys.

With incoherent quasielastic neutron scattering self-diffusion coefficients [Formula: see text] in pure iron, and iron-carbon alloys containing 8.7 at% and 16.9 at% carbon have been measured. At the melting point [Formula: see text] in liquid iron is [Formula: see text] m2 s-1. For the close-to-eutectic Fe83.1C16.9 composition [Formula: see text] m2 s-1 at T[Formula: see text] K. Contradicting conclusions drawn from literature values of tracer diffusion experiments the addition of carbon has only a minor effect on the iron mobility: at a given temperature the self-diffusion coefficient in Fe83.1C16.9 is only 10% larger than in liquid iron, although mixing has a drastic effect on liquidus temperature and phase behavior.

In situ Measurement of Thermodiffusion in Liquid Alloys.

Temperature gradients can change the concentration distribution in multicomponent materials. This cross-coupling effect of heat and mass transfer is difficult to measure in liquid alloys. We present a new method using x-ray radiography in combination with a high temperature furnace to measure thermodiffusion in melts time and space resolved. This greatly improves the process control and allows us to determine diffusion and thermodiffusion simultaneously. In a first experiment we demonstrate that in liquid Al_{78.5}Ni_{21.5} the component nickel diffuses to the cold end of the sample with a Soret coefficient on the order of 10^{-3} K^{-1}.

Near-isothermal furnace for in situ and real time X-ray radiography solidification experiments.

In this paper, we present a newly developed near-isothermal X-ray transparent furnace for in situ imaging of solidification processes in thin metallic samples. We show that the furnace is ideally suited to study equiaxed microstructure evolution and grain interaction. To observe the growth dynamics of equiaxed dendritic structures, a minimal temperature gradient across the sample is required. A uniform thermal profile inside a circular sample is achieved by positioning the sample in the center of a cylindrical furnace body surrounded by a circular heater arrangement. Performance tests with the hypo-eutectic Al-15wt.%Cu and the near-eutectic Al-33wt.%Cu alloys validate the near-isothermal character of the sample environment. Controlled cooling rates of less than 0.5 K min(-1) up to 10 K min(-1) can be achieved in a temperature range of 720 K-1220 K. Integrated in our rotatable laboratory X-ray facility, X-RISE, the furnace provides a large field of view of 10.5 mm in diameter and a high spatial resolution of ∼4 µm. With the here presented furnace, equiaxed dendrite growth models can be rigorously tested against experiments on metal alloys by, e.g., enabling dendrite growth velocities to be determined as a function of undercooling or solutal fields in front of the growing dendrite to be measured.

Aerodynamic levitator furnace for measuring thermophysical properties of refractory liquids.

The development of novel contactless aerodynamic laser heated levitation techniques is reported that enable thermophysical properties of refractory liquids to be measured in situ in the solid, liquid, and supercooled liquid state and demonstrated here for alumina. Starting with polished crystalline ruby spheres, we show how, by accurately measuring the changing radius, the known density in the solid state can be reproduced from room temperature to the melting point at 2323 K. Once molten, by coupling the floating liquid drop to acoustic oscillations via the levitating gas, the mechanical resonance and damping of the liquid can be measured precisely with high-speed high-resolution shadow cast imaging. The resonance frequency relates to the surface tension, the decay constant to the viscosity, and the ellipsoidal size and shape of the levitating drop to the density. This unique instrumentation enables these related thermophysical properties to be recorded in situ over the entire liquid and supercooled range of alumina, from the boiling point at 3240 K, until spontaneous crystallization occurs around 1860 K, almost 500 below the melting point. We believe that the utility that this unique instrumentation provides will be applicable to studying these important properties in many other high temperature liquids.

Equivalence of the boson peak in glasses to the transverse acoustic van Hove singularity in crystals.

We compare the atomic dynamics of the glass to that of the relevant crystal. In the spectra of inelastic scattering, the boson peak of the glass appears higher than the transverse acoustic (TA) singularity of the crystal. However, the density of states shows that they have the same number of states. Increasing pressure causes the transformation of the boson peak of the glass towards the TA singularity of the crystal. Once corrected for the difference in the elastic medium, the boson peak matches the TA singularity in energy and height. This suggests the identical nature of the two features.

In situ studies of mass transport in liquid alloys by means of neutron radiography.

When in situ techniques became available in recent years this led to a breakthrough in accurately determining diffusion coefficients for liquid alloys. Here we discuss how neutron radiography can be used to measure chemical diffusion in a ternary AlCuAg alloy. Neutron radiography hereby gives complementary information to x-ray radiography used for measuring chemical diffusion and to quasielastic neutron scattering used mainly for determining self-diffusion. A novel Al(2)O(3) based furnace that enables one to study diffusion processes by means of neutron radiography is discussed. A chemical diffusion coefficient of Ag against Al around the eutectic composition Al(68.6)Cu(13.8)Ag(17.6) at.% was obtained. It is demonstrated that the in situ technique of neutron radiography is a powerful means to study mass transport properties in situ in binary and ternary alloys that show poor x-ray contrast.

Dynamics of a protein and its surrounding environment: a quasielastic neutron scattering study of myoglobin in water and glycerol mixtures.

In this quasielastic neutron scattering (QENS) study we have investigated the relation between protein and solvent dynamics. Myoglobin in different water:glycerol mixtures has been studied in the temperature range of 260-320 K. In order to distinguish between solvent and protein dynamics we have measured protonated as well as partly deuterated samples. As commonly observed for bulk as well as for confined water, the dynamics of the surrounding solvent is well described by a jump diffusion model. The intermediate scattering function I(Q,t) from the protein (partly deuterated samples) was analyzed by fitting a single Kohlrausch-Williams-Watts (KWW) stretched exponential function to the data. However, due to the limited experimental time window, two different curve fitting approaches were used. The first one was performed with the assumption that I(Q,t) decays to zero at long times, i.e., it was assumed that all protein relaxations that are observed on the experimental time scale, as well as would be observed on longer time scales, can be described by a single KWW function. In the second approach we instead assumed that both the protein relaxation time tau(p) and the stretching parameter beta(KWW) were Q-independent, i.e., we assumed that the protein dynamics is dominated by more local motions. Advantages and disadvantages of both approaches are discussed. The first approach appears to work best at higher Q-values, indicating a power law relation of the Q-dependent protein dynamics for all samples and temperatures, whereas the second approach seems to work at lower Q-values, where the expected confined diffusion of hydrogen atoms in the protein gives the assumed Q-independent relaxation time. Independent of the chosen approach we find a significant correlation between the average relaxation time of the protein and the diffusion constant (or in this case the related relaxation time) of the solvent. However, the correlation is not perfect since the average relaxation time of the protein is more strongly dependent on the total amount of solvent than the diffusion constant of the solvent itself. Thus, the average relaxation time of the protein decreases not only with increasing solvent mobility, but also with increasing solvent content.

Detection of first-order liquid/liquid phase transitions in yttrium oxide-aluminum oxide melts.

We combine small-angle x-ray scattering (SAXS) and wide-angle x-ray scattering (WAXS) with aerodynamic levitation techniques to study in situ phase transitions in the liquid state under contactless conditions. At very high temperatures, yttria-alumina melts show a first-order transition, previously inferred from phase separation in quenched glasses. We show how the transition coincides with a narrow and reversible maximum in SAXS indicative of liquid unmixing on the nanoscale, combined with an abrupt realignment in WAXS features related to reversible shifts in polyhedral packing on the atomic scale. We also observed a rotary action in the suspended supercooled drop driven by repetitive transitions (a polyamorphic rotor) from which the reversible changes in molar volume (1.2 +/- 0.2 cubic centimeters) and entropy (19 +/- 4 joules mole(-1) kelvin(-1)) can be estimated.

Solvent and lipid dynamics of hydrated lipid bilayers by incoherent quasielastic neutron scattering.

The microscopic dynamics of the planar, multilamellar lipid bilayer system 1,2-dimyristoyl-sn-glycero-3-phosphocholine (DMPC) has been investigated using quasielastic neutron scattering. The DMPC was hydrated to a level corresponding to approximately nine water molecules per lipid molecule. Selective deuteration has been used to separately extract the dynamics of the water, the acyl chains, and the polar head groups from the strong incoherent scattering of the remaining hydrogen atoms. Furthermore, the motions parallel and perpendicular to the bilayers were probed by using two different sample orientations relative to the incident neutron beam. For both sample orientations, the results showed an onset of water motions at 260 K on the experimental time scale of about 100 ps. From lack of wave-vector dependence of the onset temperature for water motions, it is evident that the observed water dynamics is of mainly rotational character at such low temperatures. At 290 K, i.e., slightly below the gel-to-liquid transition around 295 K, the nature of the water dynamics had changed to a more translational character, well described by a jump-diffusion model. On the limited experimental time and length (about 10 A) scales, this jump-diffusion process was isotropic, despite the very anisotropic system. The acyl chains exhibited a weak onset of anharmonic motions already at 120 K, probably due to conformational changes (trans-gauche and/or syn-anti) in the plane of the lipid bilayers. Other anharmonic motions were not observed on the experimental time scale until temperature had been reached above the gel-to-liquid transition around 295 K, where the acyl chains start to show more substantial motions.

Zeolite collapse and polyamorphism.

The phenomenology of zeolite collapse is outlined, drawing on recent synchrotron x-ray diffraction experiments and computer simulations of low density cage structures like zeolite A and zeolite Y. Attention is drawn to the importance of polyamorphism in destabilizing this type of microporous crystal and its role in order-disorder as well as amorphous-amorphous transitions, together with associated differences in entropy and density between polyamorphic phases and the precursor zeolite. Magic angle spinning NMR and inelastic x-ray scattering are used to highlight changes in structural order and mechanical rigidity between the starting zeolite and the final high density polyamorph. In conclusion, two-level systems detected with inelastic neutron scattering are described and their involvement in dictating the dynamics of the collapse of zeolitic cage structures.

The dynamics of water in hydrated white bread investigated using quasielastic neutron scattering.

The dynamics of water in fresh and in rehydrated white bread is studied using quasielastic neutron scattering (QENS). A diffusion constant for water in fresh bread, without temperature gradients and with the use of a non-destructive technique, is presented here for the first time. The self-diffusion constant for fresh bread is estimated to be Ds = 3.8 × 10-10 m2 s-1 and the result agrees well with previous findings for similar systems. It is also suggested that water exhibits a faster dynamics than previously reported in the literature using equilibration of a hydration-level gradient monitored by vibrational spectroscopy. The temperature dependence of the dynamics of low hydration bread is also investigated for T = 280-350 K. The average relaxation time at constant momentum transfer (Q) shows an Arrhenius behavior in the temperature range investigated.

Channel formation and intermediate range order in sodium silicate melts and glasses.

We use inelastic neutron scattering and molecular dynamics simulation to investigate the interplay between the structure and the fast sodium ion diffusion in various sodium silicates. With increasing temperature and decreasing density the structure factors exhibit an emerging prepeak around 0.9 A(-1). We show that this prepeak has its origin in the formation of sodium rich channels in the static structure. The channels serve as preferential ion conducting pathways in the relative immobile Si-O matrix. On cooling below the glass transition this intermediate range order is frozen in.