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Directional Solidification and Mechanical Properties of NiAl-NiAlTa Alloys

Directional solidification of eutectic alloys is a promising technique for producing in-situ composite materials exhibiting a balance of properties. Consequently, the microstructure, creep strength and fracture toughness of directionally solidified NiAl-NiAlTa alloys were investigated. Directional solidification was performed by containerless processing techniques to minimize alloy contamination. The eutectic composition was found to be NiAl-15.5 at% Ta and well-aligned microstructures were produced at this composition. A near-eutectic alloy of NiAl-14.5Ta was also investigated. Directional solidification of the near-eutectic composition resulted in microstructures consisting of NiAl dendrites surrounded by aligned eutectic regions. The off-eutectic alloy exhibited promising compressive creep strengths compared to other NiAl-based intermetallics, while preliminary testing indicated that the eutectic alloy was competitive with Ni-base single crystal superalloys. The room temperature toughness of these two-phase alloys was similar to that of polycrystalline NiAl even with the presence of the brittle Laves phase NiAlTa.

Johnson, D. R.↗

Simulating the Effect of Space Vehicle Environments on Directional Solidification of a Binary Alloy

Space microgravity missions are designed to provide a microgravity environment for scientific experiments, but these missions cannot provide a perfect environment, due to vibrations caused by crew activity, on-board experiments, support systems (pumps, fans, etc.), periodic orbital maneuvers, and water dumps. Therefore, it is necessary to predict the impact of these vibrations on space experiments, prior to performing them. Simulations were conducted to study the effect of the vibrations on the directional solidification of a dendritic alloy. Finite element ca!cu!attie?ls were dme with a simd2titcr based on a continuum model of dendritic solidification, using the Fractional Step Method (FSM). The FSM splits the solution of the momentum equation into two steps: the viscous intermediate step, which does not enforce continuity; and the inviscid projection step, which calculates the pressure and enforces continuity. The FSM provides significant computational benefits for predicting flows in a directionally solidified alloy, compared to other methods presently employed, because of the efficiency gains in the uncoupled solution of velocity and pressure. finite differences, arises when the interdendritic liquid reaches the eutectic temperature and concentration. When a node reaches eutectic temperature, it is assumed that the solidification of the eutectic liquid continues at constant temperature until all the eutectic is solidified. With this approach, solidification is not achieved continuously across an element; rather, the element is not considered solidified until the eutectic isotherm overtakes the top nodes. For microgravity simulations, where the convection is driven by shrinkage, it introduces large variations in the fluid velocity. When the eutectic isotherm reaches a node, all the eutectic must be solidified in a short period, causing an abrupt increase in velocity. To overcome this difficulty, we employed a scheme to numerically predict a more accurate value for the rate of change of fraction of liquid as the liquid in an element solidifies. The new method enables us to contrast results of simulations in which the alloy is subjected to no gravity or a steady-state acceleration versus simulations when the alloy is subjected to vibration disturbances; therefore, the effect of vibration disturbances can be assessed more accurately. To assess the impact of these vibration-perturbations, transient accelerometer data from a space shuttle mission are used as inputs for the simulation model. These on-orbit acceleration data were obtained from the Microgravity Science Division at Glenn Research Center (GRC- MSD) and are applied to the buoyancy term of the momentum equation in a simulation of a Pb-5.8 wt. % Sb alloy that solidifies in a thermal gradient of 4000 K/m and a translation velocity of 3 p d s . Figure 2 shows the vertical velocity of a node that begins in the all-liquid region and subsequently solidifies; the vibrations are applied at 5000 seconds in this simulation. An important difficulty, common to all solidification models based on finite elements or 2 The magnitudes of the velocity oscillations that are vibration-induced are very small and acceptable. The biggest concern is whether the concentration of the liquid near the dendrite tips is distorted because of the vibration-induced perturbations. Results for this case show no concentration oscillations present in the all-liquid region.

Westra, D. G.↗

Laboratory micro- and nanoscale X-ray tomographic investigation of Al–7 at.%Cu solidification structures

X-ray computed tomography across multiple length scales provides an opportunity to non-destructively visualize and quantify the micro- to nano-scale microstructural features of solidification structures in three dimensions. Aluminum–7 at.%copper samples were directionally solidified at three cooling rates (0.44, 0.67, and 1.33 °C/s), resulting in systematic changes in the as-solidified microstructure, which are difficult to quantify using traditional microscopic techniques. The cooling rate of a material affects its ultimate microstructure, and characterizing that microstructure is key to predicting and understanding its bulk properties. Here, two different laboratory X-ray computed tomography instruments were used to characterize as-solidified microstructures, including micro-scale computed tomography with approximately 1 mm field-of-view, ∼ 1.7 μm resolution, and nano-scale X-ray computed tomography ∼ 65 μm FOV, 150 nm resolution. Micro-scale X-ray radiography and computed tomography enabled a quantitative investigation of changes in the primary dendritic solidification structure with increasing cooling rate. Nano-scale absorption contrast X-ray computed tomography resolved the distinct phases of the lamellar eutectic structure and three dimensional measurements of the ∼ 1 μm interlamellar spacing. It is found that the lamella eutectic structure thickness is inversely proportional to the cooling rate. Nano-scale Zernike phase contrast was also used to image voids at eutectic colony boundaries. The application and resolution of these two instruments are discussed with respect to the resolvable features of the solidification structures. - Highlights: • Al–Cu eutectic is a model system for studying solidification microstructure. • X-ray computed tomography provides a 3D picture of these complex structures. • Micro-scale tomography images the primary and secondary dendritic structures. • Nano-scale tomography images the eutectic lamella and measures its thickness. • The ∼ 1 micrometer thickness of the eutectic lamella correlates to the cooling rate.

36 MATERIALS SCIENCE↗

Transmission electron microscopy of the rapid solidification microstructure evolution and solidification interface velocity determination in hypereutectic Al-20at.%Cu after laser melting

The evolution of rapid solidification (RS) microstructure and solidification interface velocity has been studied experimentally by in-situ transmission electron microscopy and postmortem characterization for hypereutectic Al-20at.%Cu (37 wt.%Cu) after laser melting. Four morphologically distinct regions formed via growth modes changing from θ-Al 2 Cu phase dendrites to eutectic cell growth, possibly α-Al dendrite growth (α-cell), banded growth, and α-Al plane front growth. Tendency for faceting and low capacity for solute trapping limited the θ-phase dendrite growth to solidification interface velocity v < 0.07 m/s. Consequently, formation of pro-eutectic micro-constituent was suppressed, and RS microstructure formation was dominated by eutectic, α-cell, and banded morphology grains for the Al-20at.%Cu alloy. Eutectic growth operated for interface velocity of 0.1 m/s ≤ v < 0.3 m/s, with a transition from regular lamellar, 2-λ and 1-λ mode to a dense irregular morphology dominated by α-phase at v = 0.3 m/s. Interface temperature calculations indicated feasibility of α-cell growth mode for 0.3 m/s ≤ v < 0.7 m/s. Banded growth occurred for 0.7 m/s ≤ v < 1.3 m/s. Plane front α-phase growth was evident for interface velocities v ≥ 1.3 m/s. Previous work on rapid solidification microstructure development in hypereutectic Al-Cu alloys reported a regime of α-cell growth subsequently to eutectic and prior to transition to banded growth for Al-19at.%Cu (36 wt.%Cu), while for Al-22at.%Cu (40 wt.%Cu) eutectic growth transitioned directly to α-plane front growth without emergence of a banded regime. Finally, based on the current study the disappearance of the banded growth regime occurs for a composition larger than 20at.%Cu.

36 MATERIALS SCIENCE↗

Microstructure and mechanical properties of hypoeutectic Al–6Ce–3Ni-0.7Fe (wt.%) alloy

Here, a hypoeutectic, Fe-modified Al–Ce–Ni alloy (Al–6Ce–3Ni-0.7Fe, wt.%) is studied in terms of microstructure, thermal stability, ambient temperature strengthening, and creep resistance. The as-cast microstructure consists of primary Al dendrites and interdendritic binary eutectic regions (Al–Al11Ce3 and/or Al–Al9(Fe,Ni)2), with micron/submicron lamellar spacing, depending on the location along the height of the ingot. The cast alloy exhibits excellent coarsening resistance at 400 °C, with mostly unchanged microstructure and microhardness after 6 weeks of aging, indicating good thermal stability of Al11Ce3 and Al9(Fe,Ni)2. Orowan strengthening and load transfer are identified as strengthening mechanisms at ambient and elevated temperature. A high volume fraction of the intermetallic phases (providing load transfer) and relatively coarse eutectic spacing (for modest Orowan strengthening) result in a moderate as-cast microhardness of 566 ± 32 MPa. Creep resistance at 300 and 350 °C is similar to a binary Al-12.5Ce eutectic alloy (with twice the Ce content) because of two countering effects: Al–6Ce–3Ni-0.7Fe shows a higher volume fraction of strengthening intermetallic phases, but it also exhibits a large fraction of primary Al dendrites which weaken the alloy. By contrast, the alloy, when laser-remelted at the surface, has a fully eutectic microstructure without primary aluminum dendrites achieved by high undercooling on solidification, with a refined network of eutectic phases that doubles the microhardness as compared to the cast alloy. Whereas coarsening is faster due to the shorter diffusion distances between the eutectic phases, hardness remains ~30% higher than the as-cast alloy after ~6 weeks aging at 400 °C.

36 MATERIALS SCIENCE↗

Coordination and thermophysical properties of select trivalent lanthanides in LiCl–KCl

The coordination chemistry of various fission and decay products, such as actinides and lanthanides, are crucial to the commercial deployment of molten salt reactors as they can affect the thermophysical properties. In this report we examined the structure, coordination environment, and physical properties such as the density and the vibrational density of states for three lanthanide species, namely Ce, Eu, and Sm in the LiCl–KCl eutectic system using a combination of quantum mechanics simulations and spectroscopic experiments. Quantum mechanics molecular dynamics (QM-MD) modelling was employed to determine the physical properties of each system resulting in accurate local coordination of each species. Then, the vibrational density of states (DOS) was determined using a two-phase thermodynamic modelling which was then compared to the experimentally obtained Raman spectra of the species in molten LiCl–KCl having the eutectic composition. We find that Ce 3+ , Eu 3+ and Sm 3+ all adopt octahedral local coordination environments in the eutectic salt composition in good agreement with experimental results. Ce3+ is found to fluctuate between an octahedral six-coordinated and a seven-coordinated structure due to the increased local proximity of Cl in the eutectic salt, resulting in a lower fluidicity/diffusivity than the other trivalent lanthanides studied. The thermophysical properties of the eutectic composition with trivalent lanthanides were not significantly different from the pure eutectic salt composition, but several changes were noted.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Influence of convection on microstructure

The primary motivation for this research was to determine the cause for space processing altering the microstructure of some eutectics, especially the MnBi-Bi eutectic. Four primary hypotheses were to be tested under this current grant: (1) A fibrous microstructure is much more sensitive to convection than a lamellar microstructure, which was assumed in our prior theoretical treatment. (2) An interface with one phase projecting out into the melt is much more sensitive to convection than a planar interface, which was assumed in our prior theoretical treatment. (3) The Soret effect is much more important in the absence of convection and has a sufficiently large influence on microstructure that its action can explain the flight results. (4) The microstructure is much more sensitive to convection when the composition of the bulk melt is off eutectic. These hypotheses were tested. It was concluded that none of these can explain the Grumman flight results. Experiments also were performed on the influence of current pulses on MnBi-Bi microstructure. A thorough review was made of all experimental results on the influence of convection on the fiber spacing in rod eutectics, including results from solidification in space or at high gravity, and use of mechanical stirring or a magnetic field. Contradictory results were noted. The predictions of models for convective influences were compared with the experimental results. Vigorous mechanical stirring appears to coarsen the microstructure by altering the concentration field in front of the freezing interface. Gentle convection is believed to alter the microstructure of a fibrous eutectic only when it causes a fluctuating freezing rate with a system for which the kinetics of fiber branching differs from that for fiber termination. These fluctuations may cause the microstructure to coarsen or to become finer, depending on the relative kinetics of these processes. The microstructure of lamellar eutectics is less sensitive to freezing rate fluctuations and to gentle convection.

Wilcox, William R.↗

Metal Fuel Implications on Severe Accident Scenarios

Superior steady-state irradiation performance of metal fuel has been demonstrated, and metal fuel has been the choice for recent sodium-cooled fast reactor designs, e.g. PRISM, SAFR, 4S, TWR, PGSFR, and so on. Metal fuel also has excellent transient capabilities. The metal fuel itself does not impose any restrictions on transient operations or load-following capabilities. Metal fuel has benign run beyond cladding breach (RBCB) performance characteristics. Because metal fuel is compatible with sodium, there is no reaction product and the fuel loss is practically zero. Metal fuel is expected to be very reliable. However, even if unforeseen fuel pin failure occurs, it will simply release gases and does not cause failure propagation to neighboring pins. The eutectic formation temperature between the fuel and the cladding has been considered a critical parameter for the metal fuel pin design. The onset of fuel-cladding eutectic formation starts in the 700-725 deg. C temperature range, depending on the fuel alloy and cladding types. However, at this onset temperature, not much interaction occurs. In fact, even at 100 deg. C above the eutectic temperature, the eutectic penetration into the cladding is minimal in one hour. Only at much higher temperatures, close to the fuel melting point itself, the eutectic penetration into cladding becomes rapid. Therefore, the eutectic formation is not a primary safety concern during transient overpower conditions. (authors)

21 SPECIFIC NUCLEAR REACTORS AND ASSOCIATED PLANTS↗

Significantly Promoting the Thermal Conductivity and Machinability of Negative Thermal Expansion Alloy via In Situ Precipitation of Copper Networks

Rapid advancements in electronic devices yield an urgent demand for high-performance electronic packaging materials with high thermal conductivity, low thermal expansion, and great mechanical properties. However, it is a great challenge for current design philosophies to fulfill all the requirements simultaneously. Here, an effective strategy is proposed for significantly promoting the thermal conductivity and machinability of negative thermal expansion alloy (Zr,Nb)Fe 2 through eutectic precipitation of copper networks. The eutectic dual-phase alloy exhibits an isotropic chips-matched thermal expansion coefficient and a thermal conductivity enhancement exceeding 200% compared with (Zr,Nb)Fe 2 , along with an ultimate compressive strength of 550 MPa. The addition of copper reorganizes the composition of (Zr,Nb)Fe 2 , which smooths the magnetic transition and shifts it toward higher temperature, resulting in linear low thermal expansion in a wide temperature range. The highly fine eutectic copper lamellae construct high thermal conductivity networks within (Zr,Nb)Fe 2 , serving as highways for heat transfer electrons and phonons. The in situ forming of eutectic copper lamellae also facilitates the mechanical properties by enhancing interfacial bonding and bearing additional stress after yielding of (Zr,Nb)Fe 2 . This work provides a novel strategy for promoting thermal conductivity and mechanical properties of negative thermal expansion alloys via eutectic precipitation of copper networks.

36 MATERIALS SCIENCE↗

The Binary Alkali Nitrate and Chloride Phase Diagrams: NaNO{sub 3}-KNO{sub 3}, LiNO{sub 3}-NaNO{sub 3}, LiNO{sub 3}-KNO{sub 3}, and NaCl-KCl

LiNO{sub 3}-NaNO{sub 3}, LiNO{sub 3}-KNO{sub 3,} NaNO{sub 3}-KNO{sub 3}, and NaCl-KCl phase relations were formulated using the regular solution model to obtain desired compositions for their potential application as a heat transfer fluid. The simultaneous nonlinear equations formed were solved numerically using a contour plot technique in Matlab. An algorithm was developed to determine the real roots of the coupled nonlinear equations and subsequent phase diagrams were constructed. The phase diagrams were compared with those predicted using FactSage thermochemical package and literature data from experimental studies. The calculated NaNO{sub 3}-KNO{sub 3} phase diagram shows that this system has a eutectic point at 0.5 mole fraction of KNO{sub 3} with a eutectic temperature of 220.85 °C, while the LiNO{sub 3}-KNO{sub 3} system was found to have a eutectic point at 0.44 mole fraction LiNO{sub 3} at 137 °C. The LiNO{sub 3}-NaNO{sub 3} system shows a eutectic at 0.524 mole fraction LiNO{sub 3} at 192.8 °C, and finally the NaCl-KCl system has a eutectic point at 0.48 mole fraction NaCl at 634 °C. The liquidus and solidus curves obtained fitted close against values obtained from the quasi-chemical model used in FactSage and experimental values from the literature. This study showed that the regular solution model combined with the contour plots approach can sufficiently describe the liquidus–solidus curves of the alkali binary nitrate and chloride systems and could be a useful method for predicting the phase diagrams for higher order alkali nitrates and chlorides.

36 MATERIALS SCIENCE↗

Influence of the Composition on the Solidification Path, Microstructure Evolution and Mechanical Properties of Al-Cu-Mg Alloys

The influence of the initial composition on the solidification path, microstructure evolution, thermophysical properties and mechanical properties of Al-Cu-Mg alloys was investigated. The solidification paths of the investigated alloys were determined by analyzing the solidification structure, and then the experimentally determined paths were compared with those from the calculated results. Three of the investigated alloys experienced typical ternary eutectic solidification, and the other four alloys experienced quasiperitectic reactions. Due to differences in the initial compositions, different eutectic morphologies were formed during the solidification process. The binary eutectic phases, (α-Al + Al{sub 2}Cu) and (α-Al + Al{sub 6}CuMg{sub 4}), and the (α-Al + Al{sub 6}CuMg{sub 4} + Al{sub 8}Mg{sub 5}) ternary eutectic phase tended to exhibit divorced growth, and the (α-Al + Al{sub 2}CuMg), (α-Al + Al{sub 6}CuMg{sub 4}) and (α-Al + Al{sub 2}Cu + Al{sub 2}CuMg) eutectic phases tended to exhibit coupled growth. The results indicated that the initial composition, solidification path, microstructure and morphology could greatly affect the melting enthalpy, microhardness and compressive strength of the investigated Al-Cu-Mg alloys.

36 MATERIALS SCIENCE↗

Deformation Behavior of Pure Copper Castings with As-Cast Surfaces for Electrical Parts

Herein, the tensile deformation behavior of pure copper castings with as-cast surfaces was investigated. It was found that small and sufficiently large uniform elongation types corresponded, respectively, to the presence or absence of a Cu-Cu{sub 2}O eutectic phase in the microstructure. Fissure defects were observed near the as-cast surfaces when the eutectic phase was present, probably leading to stress concentration. On the other hand, surface pinholes were observed when the eutectic phase was absent, and these were not prevented by directional solidification. Although the as-cast specimens (non-directionally solidified) exhibited a slightly reduced uniform elongation compared to the machined specimens in the absence of the eutectic phase, the directionally solidified as-cast samples exhibited a uniform elongation that was similar to that of the machined specimens. In addition, micropore arrays were formed along the grain boundaries inside the castings when the eutectic phase was absent, whereas almost no micropores were observed inside the directionally solidified as-cast specimens because the solidification process involved a faster cooling rate and/or higher temperature gradient. These results do not only suggest the existence of surface pinholes but also indicate that microporosity can reduce the cross-sectional area of the specimens, thus, affecting their uniform elongation.

36 MATERIALS SCIENCE↗

The microstructure and composition of equilibrium phases formed in hypoeutectic Te-In alloy during solidification

As a key tellurium atoms evaporation source for ultraviolet detection photocathode, the hypoeutectic Te{sub 75}In{sub 25} alloy was prepared by employing a slow solidification speed of about 10{sup −2} K/s. The microstructure and chemical composition of the equilibrium phases formed in the as-prepared alloy were studied in this research work. The experimental results show that the as-prepared Te-In alloy was constituted by primary In{sub 2}Te{sub 5} phase and eutectic In{sub 2}Te{sub 5}/Te phases. The eutectic In{sub 2}Te{sub 5}/Te phases are distributed in the grain boundaries of primary In{sub 2}Te{sub 5} phase. With the slow solidification speed, a pure eutectic Te phase without any excessive indium solute was obtained, where Te content of eutectic Te phase is 100 mass%. Moreover, it can be considered that the stress between the In{sub 2}Te{sub 5} and Te phases plays an important role in reducing the tellurium vapor pressure in Te{sub 75}In{sub 25} alloy. - Highlights: • The microstructure of Te-In alloy as an evaporation source was analyzed. • A pure eutectic Te phase was obtained by using a slow solidification speed method. • The relation between vapor pressure and inner-stress in the alloy was discussed.

36 MATERIALS SCIENCE↗

Effects of boron addition on the morphology of silicon phases in Al-Si casting alloys

Highlights: • The influence of boron on Si phase was studied. • Boron addition reduces the length of eutectic Si plates in Al-11Si alloys. • Boron addition promotes the nucleation temperature of primary Si phases in Al-14Si alloys. • Boron addition increases the twin density in the <112>{sub Si} growth direction of eutectic Si in Al-11Si and Al-14Si alloys. - Abstract: The influence of B elements on the morphology of Si phases in Al-11Si and Al-14Si alloys has been investigated employing Optical Microscope, Scanning Electron Microscopy, Transmission Electron Microscopy and Differential Scanning Calorimetry. In Al-11Si alloy, the addition of B element not only refines the primary Al dendrites, but also reduces the length of eutectic Si plates. In Al-14Si alloys, the addition of B element promotes the nucleation temperature of primary Si phases, but shows weak influence on the nucleation temperature of eutectics. The effects of B element on the morphologies of both primary Si particle and eutectics can be attributed to the interaction between B and Si elements during the solidification process.

36 MATERIALS SCIENCE↗

Interdiffusion Behavior of U{sub 3}Si{sub 2} and FeCrAl via Diffusion Couple Studies

Uranium Silicide (U{sub 3}Si{sub 2}) is in use as a dispersion plate fuel in test reactors, but has not been fully tested in light water reactor (LWR) conditions. U{sub 3}Si{sub 2} pellets have been fabricated for use in commercial LWRs as part of an accident tolerant fuel system U{sub 3}Si{sub 2} has a higher uranium loading density as well as a higher thermal conductivity relative to UO{sub 2}. FeCrAl alloy is a candidate cladding material to replace the industry standard, Zircaloy. FeCrAl has outstanding high-temperature mechanical strength and oxidation resistance under accident conditions. The U{sub 3}Si{sub 2}-FeCrAl system is expected to provide more than double the amount of time from a Scram until failure criteria for the reactor is met, as well as producing roughly half the amount of H{sub 2} in the event of a loss of coolant accident (LOCA). Uranium and iron have well know eutectics that may affect/enhance diffusion of the U{sub 3}Si{sub 2}/FeCrAl fuel system. The interaction of iron with molten uranium has been investigated In the U-Fe system, UFe{sub 2}, which melts congruently at 1235 deg. C, forms a eutectic with iron that melts at 1080 deg. C and has a composition of U-77at% Fe. UFe{sub 2} also forms a eutectic with uranium that melts at 725 deg. C and has a composition of U-34at% Fe. The U-34at% Fe eutectic extended the temperature range down to 740 deg. C. Regular operating temperatures for U{sub 3}Si{sub 2} fuel is expected to be around 300 - 400 deg. C. The eutectics of iron and uranium would nominally only be of concern in accident scenarios.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

Microstructure and strengthening of Al-6Ce-3Ni-0.7Fe (wt%) alloy manufactured by laser powder-bed fusion

In this study, an Al-6Ce-3Ni-0.7Fe (wt%) alloy was fabricated via laser powder-bed fusion and its microstructure, thermal stability, tensile properties, and creep properties are investigated for two rapid-solidification rates with different eutectic spacings. For both faster- and slower-cooled states, the as-fabricated alloy mostly shows elongated grains with very fine eutectic networks (~40 nm lamellar width) comprising a high-volume fraction (~18 %) of intermetallic phases. Faster-cooled samples, however, display a less continuous eutectic network with finer spacing (~100 nm), leading to higher Orowan strengthening and therefore superior microhardness and yield stress up to ~350 °C. Upon aging (300 - 450 °C), micron-size Al 9 (Ni,Fe) 2 needle-like precipitates form within grains, and the Al 11 Ce 3 eutectic network spheroidizes, while retaining a submicron width and spacing, resulting in 33–37 % drop in microhardness after 144 h aging at 400 °C. Limited tensile ductility (~6 %) and creep ductility (~1-2 %) are measured for both faster- and slower-cooled alloys due to an inhomogeneous microstructure, where cavitation preferentially initiates at melt-pool boundaries, precipitate-free zones, and/or denuded zones, eventually leading to local fracture. Denuded zones, induced by stress, form due to diffusional flow with stress-dependent orientations, and are identified as microstructurally weak regions leading to strain localization. The present alloy does not show a significant difference in 300 °C creep resistance between: (i) tensile and compressive loading, (ii) faster- and slower-cooled samples, and (iii) continuous and spheroidized eutectics. Creep resistance at 300 °C is comparable to that of a Ce-richer Al-10.5Ce-3.1Ni-1.2Mn (wt%) alloy, despite the formation of denuded zones and needle-like Al 9 (Ni,Fe) 2 precipitates.

36 MATERIALS SCIENCE↗

Determination of a surrogate for plutonium electrorefining

Conducting research experiments on plutonium electrorefining is difficult due to the significant hazards and regulations associated with nuclear materials. Finding a surrogate for plutonium electrorefining studies would enable more fundamental research to be conducted. Potential surrogates were first identified by determining the physical properties required to conduct electrorefining at the same conditions commonly used in plutonium electrorefining, a molten metal and molten CaCl 2 at 1123 K. Ce-CeCl 3 , In-InCl 3 , and Pb-PbCl 2 were the only potential surrogates identified using these constraints. Sn-SnCl 2 was also tested at these same conditions. More potential surrogates were identified by changing the matrix salt and operating temperature. This expanded the potential surrogate list to also include Zn-ZnCl 2 , Sn-SnCl 2 , and Bi-BiCl 3 . Zn-ZnCl 2 was used with the LiCl-CaCl 2 (65:35 mol%) eutectic at 773 K. Sn-SnCl2 and Bi-BiCl 3 were used with the LiCl-KCl-CaCl 2 (50.5:44.2:5.3 mol%) eutectic at 673–773 K. Ce electrorefining in molten CaCl 2 resulted in a difficult to separate colloid mixture of Ce, Ca and Cl. Electrorefining rates for In in molten CaCl 2 were too slow due to InCl 3 volatilizing out of the molten salt. Only trace amounts of SnCl 2 was retained in the CaCl 2 at 1123 K resulting in impractical electrorefining rates. Zn metal product was successfully collected in the LiCl-CaCl 2 eutectic molten salt, but the metal obtained did not coalesce into one piece. Sn and Bi were successfully electrorefined in the LiCl-KCl-CaCl 2 eutectic molten salt and coalesced into product rings with high yields and coulombic efficiencies. Finally, while a surrogate could not be identified using the same conditions as plutonium electrorefining, two possible surrogates, Sn-SnCl 2 and Bi-BiCl 3 , were found that could imitate the physical configuration (i.e., molten salt on top of molten metal) of plutonium electrorefining at a reduced temperature using the eutectic LiCl-KCl-CaCl 2 salt at 673–773 K in place of CaCl 2 at 1123 K.

36 MATERIALS SCIENCE↗

Influence of convection on microstructure

The influence was studied of convection during directional solidification on the resulting microstructure of eutectics, specifically lead/tin and manganese/bismuth. A theory was developed for the influence of convection on the microstructure of lamellar and fibrous eutectics, through the effect of convection on the concentration field in the melt in front of the growing eutectic. While the theory agrees with the experimental spin-up spin-down results, it predicts that the weak convection expected due to buoyancy will not produce a measurable change in eutectic microstructure. Thus, this theory does not explain the two fold decrease in MnBi fiber size and spacing observed when MnBi-Bi is solidified in space or on Earth with a magnetic field applied. Attention was turned to the morphology of the MnBi-Bi interface and to the generation of freezing rate fluctuations by convection. Decanting the melt during solidification of MnBi-Bi eutectic showed that the MnBi phase projects into the melt ahead of the Bi matrix. Temperature measurements in a Bi melt in the vertical Bridgman-Stockbarger configuration showed temperature variations of up to 25 C. Conclusions are drawn and discussed.

Wilcox, William R.↗