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Experiments and simulations on solidification microstructure for Inconel 718 in powder bed fusion electron beam additive manufacturing

Previous research on the powder bed fusion electron beam additive manufacturing of Inconel 718 has established a definite correlation between the processing conditions and the solidification microstructure of components. However, the direct role of physical phenomena such as fluid flow and vaporization on determining the solidification morphology have not been investigated quantitatively. In this work, we investigate the transient and spatial evolution of the fusion zone geometry, temperature gradients, and solidification growth rates during pulsed electron beam melting of the powder bed with a focus on the role of key physical phenomena. The effect of spot density during pulsing, which relates to the amount of heating of the build area during processing, on the columnar-to-equiaxed transition of the solidification structure was studied both experimentally and theoretically. Predictions and the evaluation of the role of heat transfer and fluid flow were established using existing solidification theories combined with transient, three-dimensional numerical heat transfer and fluid flow modeling. Metallurgical characteristics of the alloy’s solidification are extracted from the transient temperature fields, and microstructure is predicted and validated using optical images and electron backscattered diffraction data from the experimental results. Simulations show that the pure liquid region solidified quickly, creating a large two-phase, mushy region that exists during the majority of solidification. While conductive heat transfer dominates in the mushy region, both the pool geometry and the solidification parameters are affected by convective heat transfer. Lastly, increased spot density during processing is shown to increase the time of solidification, lowering temperature gradients and increasing the probability of equiaxed grain formation.

36 MATERIALS SCIENCE↗

Influence of alloy solidification path on melt pool behavior in additive manufacturing

Numerical models used to study transport phenomena in laser-powder bed fusion processes often rely on assumptions and simplifications to reduce their computational expense. One common simplification is in the description of latent heat evolution during the solid-liquid phase change (i.e., the solidification pathway), justified by the fact that the mushy zone thickness is similar to the numerical grid spacing used for continuum transport models. The lack of resolution of transport phenomena in the mushy zone motivates the use of computationally convenient solidification paths such as linear or sigmoidal relationships over pathways derived from fundamental solidification theory such as equilibrium or Scheil models. In the present work, an uncertainty quantification (UQ) framework is used to analyze the influence of solidification pathway selection on the solidification dynamics and melt pool geometries in laser based additive manufacturing (AM) of IN625. Results show the solidification pathway has a quantifiable influence on the cooling rate at the liquidus isotherm, mushy zone thickness, and solidification time. Due to similarities in the latent heat evolution at the beginning of solidification, the equilibrium and Scheil models predict similar cooling rates near the liquidus isotherm, however the wider freezing range of Scheil leads to a wider mushy zone compared to equilibrium. The non-physical latent heat release profiles of sigmoidal and linear paths lead to significant overpredictions of cooling rates at the liquidus isotherm compared to equilibrium and Scheil. Finally, these results indicate that careful consideration should be given to the choice of solidification pathway to ensure reliable model predictions.

36 MATERIALS SCIENCE↗

Cadarache LOR (liquides organiques radioactifs) treatment by a solidification process using NOCHAR polymers

In France, two options can be considered to handle the Very Low Level Waste (VLLW) and the Low Level Waste (LLW). The first one is the incineration at CENTRACO facility and the second one is the disposal at ANDRA sites. The waste acceptance in these two channels is dependent upon the adequacy between the waste characteristics (physical chemistry and radiological) and the channel specifications. If the waste characteristics and the channel specifications (presence of significant quantities of halogens, complexing agents, organic components... or/and high activity limits) are incompatible, an alternative solution have to be identify. It consists of a waste pre-treatment process. For Cadarache LOR (Liquides Organiques Radioactifs) waste streams, two radioactive scintillation cocktails have to be treated. They are composed of a mix of organic liquids and water: for the first one, 19 % of organic compounds (xylene, mesitylene, diphenyloxazole, TBP...) and 86.9 % of water, and for the second one, 23 % of organic compounds (TBP...) and 77 % of water. They contain halogens (chlorine and fluorine), complexants agents (nitrate, sulphate, oxalate and formate) and have got αβγ spectra with mass activities equal to some 100 Bq/g. Therefore, tritium is also present. As a consequence, in order for storage acceptance at the ANDRA site, it is necessary to pre-treat the waste. An adequate solution seems to be a solidification process using NOCHAR polymers. Indeed, NOCHAR polymers correspond to an important variety of products applied to the treatment of radioactive aqueous and organic liquids (solvent, oil, solvent/oil mixing ...) and sludge through a mechanical and chemical solidification process. For Cadarache LOR, N910 and N960 respectively dedicated to the organic and aqueous liquids solidification are considered. With the N910, the organic waste solidification occurs in two steps. As the organic liquid travels moves through the polymer strands, the strands swell and immobilize the liquid. Then as the polymer-organic cure, over time, the polymer continues to collapse on the organic to create a permanent chemical bond. The N960 has the ability to absorb aqueous waste up to 100 times its own weight. It creates a strong mechanical bond which permanently traps the contamination imbedded in the aqueous liquids. Therefore, these two NOCHAR polymers seem to be able to constitute a suitable solidification matrix for a final acceptance in storage on ANDRA sites. In order to validate the solidification process using NOCHAR polymers as an acceptable solution for Cadarache LOR treatment, some solidification tests realised with N910 and N960, have been carried out for different Waste/Polymer ratios. To determine the best Waste/Polymer ratio and the optimal experimental parameters, exudation tests have been made. Indeed, the process prevents leaching and it results in the absence residual free organic or aqueous liquid which is forbidden in storage by ANDRA specifications. With these results, the obtained scientific data constitute a fundamental basis of an ANDRA agreement. As a conclusion, the aim of this study is to demonstrate that the pre-treatment by solidification using NOCHAR polymers can constitute a solution for Cadarache LOR handling and more generally, for various organic and mixed organic/aqueous waste which can not be directly acceptable at CENTRACO facility or at ANDRA storage sites. So then, this study is a solid background to demonstrate the feasibility of the waste pre-treatment by solidification with NOCHAR polymer and to encourage this process development. (authors)

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

NOCHAR Polymers: An Aqueous and Organic Liquid Solidification Process for Cadarache LOR (Liquides Organiques Radioactifs) - 13195

To handle the Very Low Level Waste (VLLW) and the Low Level Waste (LLW) in France, two options can be considered: the incineration at CENTRACO facility and the disposal facility on ANDRA sites. The waste acceptance in these radwaste routes is dependent upon the adequacy between the waste characteristics (physical chemistry and radiological) and the radwaste route specifications. If the waste characteristics are incompatible with the radwaste route specifications (presence of significant quantities of chlorine, fluorine, organic component etc or/and high activity limits), it is necessary to find an alternative solution that consists of a waste pre-treatment process. In the context of the problematic Cadarache LOR (Liquides Organiques Radioactifs) waste streams, two radioactive scintillation cocktails have to be treated. The first one is composed of organic liquids at 13.1 % (diphenyloxazol, mesitylene, TBP, xylene) and water at 86.9 %. The second one is composed of TBP at 8.6 % and water at 91.4 %. They contain chlorine, fluorine and sulphate and have got alpha/beta/gamma spectra with mass activities equal to some kBq.g{sup -1}. Therefore, tritium is present and creates the second problematic waste stream. As a consequence, in order for disposal acceptance at the ANDRA site, it is necessary to pre-treat the waste. The NOCHAR polymers as an aqueous and organic liquid solidification process seem to be an adequate solution. Indeed, these polymers constitute an important variety of products applied to the treatment of radioactive aqueous and organic liquids (solvent, oil, solvent/oil mixing etc) and sludge through a mechanical and chemical solidification process. For Cadarache LOR, N910 and N960 respectively dedicated to the organic and aqueous liquids solidification are considered. With the N910, the organic waste solidification occurs in two steps. As the organic liquid travels moves through the polymer strands, the strands swell and immobilise the liquid. Then as the polymer-organic cure, over time, the polymer continues to collapse on the organic to create a permanent bond. The N960 has the ability to absorb aqueous waste up to 100 times its own weight. It creates a strong mechanical bond which permanently traps the contamination imbedded in the aqueous liquids. As a consequence, these two polymers seem to be able to constitute a suitable solidification matrix for a final acceptance in storage on ANDRA sites. In order to validate the polymers as an acceptable aqueous and organic solidification process for Cadarache LOR, some solidification tests realized with N910 and N960, have been carried out for different Waste/Polymer ratios. The determination of the best Waste/Polymer ratio and of the optimal experimental parameters has been made through an exudation test. Indeed, the process prevents leaching and it results in the absence of residual free organic or aqueous liquid which is forbidden in storage by ANDRA specifications. With these test results, we generated scientific data which are fundamental to obtain an ANDRA agreement. As a conclusion, the aim of this study is to demonstrate that the solidification by polymers can constitute a pre-treatment solution for Cadarache LOR and more generally, for various organic and mixed organic/aqueous waste which can not be directly acceptable at CENTRACO facility or at ANDRA storage sites. This work is, therefore, a solid background to demonstrate the feasibility of the waste pre-treatment by solidification with polymers and to encourage the development of this process. (authors)

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Application of SIAL{sup R} Solidification Technology for Processing of Problematic Waste Streams - 18267

SIAL{sup R} is a proven, safe, cost-effective and licensed waste solidification technology that has been used successfully for 20 years in Slovakia and the Czech Republic for processing of various problematic radioactive waste streams. This abstract presents and summarises the most interesting performance records of the SIAL{sup R} geopolymer solidification technology, the applied mobile devices as well as the characteristics of final products. Radioactive waste solidification into matrix SIAL{sup R} is based on polycondensation of inorganic aluminosilicate components with chemical composition similar to average cement. The main components of matrix SIAL{sup R} are natural inorganic raw materials containing SiO{sub 2}, Al{sub 2}O{sub 3}, CaO, MgO, Na{sub 2}O, K{sub 2}O, Fe{sub 2}O{sub 3}, and TiO{sub 2}. The treatment/solidification process is modified for individual radioactive streams with different compositions. To determine the most appropriate composition, the SIAL{sup R} application technology is laboratory tested on real samples of each individual waste stream identified for solidification. Then an appropriate mixture of aluminosilicate composition and other inorganic compounds is defined for a given solidification application. When determining the most appropriate mixture, other requirements are taken into consideration: maximum dose rate on the drum with solidified product, mass, volume, alpha radionuclide content in the final product, need for a waste's dewatering before solidification, dry matter content in the solidification product as well as other specific waste acceptance criteria (i.e., compressive strength, leachability, diffusion coefficients, radiation stability, biodegradability of matrix, distribution and partition coefficients, influence of frost and water presence to the product stability including long term physical stability in water, dustiness, flammability, time dependence of compression strength and water reduction, product homogeneity and also radiolytic G-value for hydrogen release, GH{sub 2}). The Amec Foster Wheeler baseline approach to implementing the SIAL{sup R} waste treatment process is structured on three steps - waste characterization, waste retrieval and pre-treatment and at last the solidification of pre-treated waste itself. The equipment used for the solidification process is relatively small, lightweight and designed for the specific application on site, directly 'in situ' or local to the tanks storing the sludge's/resins/other waste streams. This mitigates the problems normally experienced by transferring sticky, tight waste through long pipes. The equipment is normally 'tailor-made' to take into account the real space conditions and other existing facility requirements. At Bohunice and Dukovany sites, the facilities for encapsulation were designed to occupy existing areas of the plants in close proximity to the tanks where the waste was being stored. This allowed for the removal of the waste using Remote Operated Vehicles and for the waste to be immediately treated on site without the need for transportation thus saving both, time and resource. To date, SIAL{sup R} has been used successfully to immobilize approximately 2 x 10{sup 6} kg of waste which includes sludge, resin, crystalline borates and contaminated organic waste from Bohunice and Mochovce, Slovakia and approximately 300 m{sup 3} of spent ion exchange resins and sludge from tanks on site at the Dukovany NPP (Nuclear Power Plant) in the Czech Republic. The technology now has a track record of over 20 years which includes on-going research and development. The International missions WANO (the World Association of Nuclear Operators) and OSART (the Operational Safety Review Team) evaluated the SIAL{sup R} matrix technology at Dukovany NPP as an example of good practice. (authors)

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Macrosegregation Resulting from Directional Solidification Through an Abrupt Change in Cross-Sections

Simulations of the directional solidification of two hypoeutectic alloys (Al-7Si alloy and Al-19Cu) and resulting macrosegregation patterns are presented. The casting geometries include abrupt changes in cross-section from a larger width of 9.5 mm to a narrower 3.2 mm width then through an expansion back to a width of 9.5 mm. The alloys were chosen as model alloys because they have similar solidification shrinkages, but the effect of Cu on changing the density of the liquid alloy is about an order of magnitude greater than that of Si. The simulations compare well with experimental castings that were directionally solidified in a graphite mold in a Bridgman furnace. In addition to the simulations of the directional solidification in graphite molds, some simulations were effected for solidification in an alumina mold. This study showed that the mold must be included in numerical simulations of directional solidification because of its effect on the temperature field and solidification. For the model alloys used for the study, the simulations clearly show the interaction of the convection field with the solidifying alloys to produce a macrosegregation pattern known as "steepling" in sections with a uniform width. Details of the complex convection- and segregation-patterns at both the contraction and expansion of the cross-sectional area are revealed by the computer simulations. The convection and solidification through the expansions suggest a possible mechanism for the formation of stray grains. The computer simulations and the experimental castings have been part of on-going ground-based research with the goal of providing necessary background for eventual experiments aboard the ISS. For casting practitioners, the results of the simulations demonstrate that computer simulations should be applied to reveal interactions between alloy solidification properties, solidification conditions, and mold geometries on macrosegregation. The simulations also presents the possibility of engineering the mold-material to avoid, or mitigate, the effects of thermosolutal convection and macrosegregation by selecting a mold material with suitable thermal properties, especially its thermal conductivity.

Lauer, M.↗

Effect of Processing Parameters and Shape of Blade on the Solidification of Single-Crystal CMSX-4 Ni-Based Superalloy

The effect of mold withdrawal velocity, heater and pouring temperatures and the thickness of blade root on the solidification parameters and shape of the liquidus isotherm as well as microstructure of single-crystal CMSX-4 nickel-based superalloy, manufactured by the Bridgman method, has been analyzed in the article. The temperature gradient G, solidification rate v and location of the liquidus isotherm were determined in relation to the radiation baffle on the basis of temperature measurements conducted in nine test points along the height of castings (140 mm) with different thicknesses of root (27, 15 and 7 mm) and withdrawal velocities of 3 and 5 mm/min. The increase of root thickness, relative to the airfoil, resulted in the rise of inhomogeneity of solidification parameters as well as the primary dendrite arm spacing and unsteady state solidification along the whole blade height. However, in the case of blade with constant thickness, the steady-state solidification was created at the distance of 65 to 130 mm from its base. The increase of mold withdrawal velocity caused the decrease of temperature gradient. However, the solidification rate was different from the mold withdrawal velocity, especially in the root and middle part of the airfoil. The increase of heater temperature resulted in a rise of temperature gradient and reduction of the curvature of the liquidus isotherm, whereas the pouring temperature did not affect the solidification parameters in the blade. Particularly unfavorable conditions of the solidification process could occur in the middle part of the airfoil and root because of the lowest value of G/v and the largest primary dendrite arm spacing.

36 MATERIALS SCIENCE↗

Determination of Location-Specific Solidification Cracking Susceptibility for a Mixed Dissimilar Alloy Processed by Wire-Arc Additive Manufacturing

Solidification cracking is a major obstacle when joining dissimilar alloys using additive manufacturing. In this work, location-specific solidification cracking susceptibility has been investigated using an integrated computational materials engineering (ICME) approach for a graded alloy formed by mixing P91 steel and Inconel 740H superalloy. An alloy mixture of 26 wt.% P91 and 74 wt.% Inconel 740H, with high configurational and total entropy, was fabricated using wire arc additive manufacturing. Microstructure characterization revealed intergranular solidification cracks in the FCC matrix, which increased in length along with the enrichment of Nb (~27 to 56 wt.%) and Cu (~87 wt.%) in the middle and top regions. DICTRA simulations to model location-specific solidification cracking susceptibility showed that the top region with the highest cooling rate (270 K/s) has the highest solidification cracking susceptibility in comparison with the middle and bottom regions. This is in good agreement with the experimentally observed varying crack length. From Scheil simulations, it was deduced that enrichment of Nb and Cu affected the solidification range as high as ~77%, in comparison with the matrix composition. The overall solidification cracking susceptibility and freezing range was highest for the 26 wt.% P91 alloy amongst the mixed compositions between P91 steel and 740H superalloy, proving that solidification characteristics play a major role in alloy design for additive manufacturing.

20 FOSSIL-FUELED POWER PLANTS↗

Numerical Study of Solidification Crack Susceptibility in Novel Refractory Alloy Systems

Calculation of Phase Diagrams (CALPHAD) -based solidification computa­tions, such as Scheil or equilibrium computations, have been utilized to propose crack solidification susceptibility indices (CSSIs) of cracking. These CSSIs have been proposed in order to predict the cracking susceptibility of an alloy in the solidification range, as a function of its solidification frac­tion and as dependent upon its wt.% elemental composition through the CALPHAD computation & via comparative methods between one composition & the next. Recently Kou at al. have proposed a novel CSSI where the gradient of the e.x. Scheil solidification curve is obtained in the critical solidification cracking region of greater than 0.95 fraction of solid. Therefore, a direct Temperature dependent metric is now available for the prediction, and presumably the control, of solidification cracking. In this TM, the researchers apply this Kou gradient method to refractory alloys for the first time & discuss justification for the approach via Spearman rank correlation with Varestraint cracking test data as well as by comparisons with Thermocalc based vulnerability time CSSI calculations. A Python Pycalphad module example of the approach is provided & can be utilized as an open-source resource that utilizes also open-source available thermodynamical databases, making the CSSI quantitative aspect of ICME more available and freely available to practitioners.

ICME integrated computational materials engineerin↗

Oxygen Effects on Solidification Behavior of Gas Tungsten Arc–Welded Laser Powder Bed Fusion–Fabricated 304L Stainless Steel

ct The laser – powder bed fusion (L-PBF) process inherently accumulates interstitial gas elements during powder fabrication and laser deposition processes. Such elements can lead to localized variations in the weld pool and affect the solidification behavior (when compared with its wrought equivalent), in addition to chemical micro-segregation within the fabricated material. This study was conducted to characterize the solidification behavior of gas tungsten arc welds made on L-PBF 304L stainless steel. The effect of surface active elements on the local solidification rates was studied. An emphasis was placed on the role local solidification rates and temperature gradients throughout the weld play on the resultant weld solidification structure and micro-segregation. It was determined that gas tungsten arc welds on L-PBF 304L stainless steel exhibited a vermicular ferrite solidification structure compared to a mix of vermicular and lathy ferrite structure in wrought 304L. The varying thermal gradients affected the solidification modes and partitioning of elements leading to fluctuations of micro-segregation in the L-PBF 304L. Macroscopically, such partitioning affected the surface tension within the weld pool, producing asymmetric weld pool geometries. The compositional differences between wrought and L-PBF fabricated 304L stainless steels resulted in irregular solidification behaviors during welding affecting the final weld microstructure.

36 MATERIALS SCIENCE↗

Experimental Verification of Solidification Stress Theory

A research program is being conducted to develop a crack-free ceramic waste form (CWF) to be used for long term encasement of fission products and actinides resulting from processing spent nuclear fuel. Cracking usually occurs in the cooldown phase of the glass or ceramic formations. A crack-free formation should have more resistance to leaching than one with many cracks. In the research leading up to producing a CWF, a model was developed that proposes a permanent stress develops when the melt solidifies and that this stress can cause failure as the CWF nears room temperature. This paper reports on how the formation, CWF2, confirms the existence of this stress. The solidification stress is in addition to and of opposite sign of the thermal stress. Its derivation is reported on in Ref. 1. Cracking of the CWF would occur at low temperatures if solidification stress exists but at high temperatures if it doesn’t. If solidification stress occurs, then the cooldown rate during solidification should be reduced. If not, it should be reduced when the thermal stresses are highest. Recording cracking sounds confirm the existence of this solidification stress since cracking occurred during the low temperature phase of the cooldown. As a side purpose of this paper, a cooldown rate is proposed that should eliminate cracking in the next experiment, CWF3. CWF2 is a prototype vertical ceramic waste cylinder formed over a period of 10 days by heating a mixture of 75% zeolite, 25% glass frit in an argon atmosphere furnace through melting to 925 C and then cooling through solidification to room temperature. It is approximately 1 m high, 0.5 m in diameter, weighs about 400 kg, and is formed in a stainless steel can 0.5 cm thick. This cylinder developed many cracks on cooldown. At least 15 loud cracks were recorded over a period of 4 days at the end of cooldown when the temperatures were below 400 C. The CWF2 surface and centerline temperatures at mid height were measured which allowed the stress to be calculated. The timing of the cracks was compared to the time the calculated total stress exceeded the tensile stress limit and verified that the cause of the cracking was solidification stress and not thermal stress. Since the CWF is encased in a can in a furnace, the cracks cannot be easily observed but can be detected with sound measurements. Similarly, the stress cannot be measured but only estimated with analysis. Destructive examination of the CWF after cooldown was used to determine the pattern of the cracking which appeared to be initiated mainly in the inner region which is evidence the cracking is due to solidification stress.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

Modeling of Detached Solidification

Our long term goal is to develop techniques to achieve detached solidification reliably and reproducibly, in order to produce crystals with fewer defects. To achieve this goal it is necessary to understand thoroughly the physics of detached solidification. It was the primary objective of the current project to make progress toward this complete understanding. 'Me products of this grant are attached. These include 4 papers and a preliminary survey of the observations of detached solidification in space. We have successfully modeled steady state detached solidification, examined the stability of detachment, and determined the influence of buoyancy-driven convection under different conditions. Directional solidification in microgravity has often led to ingots that grew with little or no contact with the ampoule wall. When this occurred, crystallographic perfection was usually greatly improved -- often by several orders of magnitude. Indeed, under the Soviet microgravity program the major objective was to achieve detached solidification with its resulting improvement in perfection and properties. Unfortunately, until recently the true mechanisms underlying detached solidification were unknown. As a consequence, flight experiments yielded erratic results. Within the past three years, we have developed a new theoretical model that explains many of the flight results. This model gives rise to predictions of the conditions required to yield detached solidification.

Regel, Liya L.↗

Improved Crystal Quality by Detached Solidification in Microgravity

The goals of our work on detached solidification have been to: Develop a complete understanding of all of the phenomena of detached solidification; Make it possible to achieve detached solidification reproducibly; Increase crystallographic perfection through detached solidification. Specifically, we aimed in this project to: Identify a system and develop methods that would allow viewing of the melt surface and convection in the melt during detached solidification in microgravity; Improve understanding of the origination and evolution of detachment through experiments and theoretical treatments; Achieve detachment on earth. The project resulted in 14 publications, 15 presentations, completion of 2 Ph.D. theses, and completion of 2 M.S. theses. Two additional papers are currently being reviewed for publication. Copies of most of the papers are attached as appendices. Among the accomplishments are: Achievement of detached solidification of InSb on earth and determination of the conditions favoring detachment on earth. Development of a new method for coating the interior of silica growth ampoules with transparent boron nitride, which yields the high contact angles for semiconductor melts that favor detachment. Development of a new coating for the interior of Pyrex ampoules yielding very high contact angles for water and molten organic compounds. Development of a material-balance model for steady detached solidification that provides greatly improved insight into the process, both in microgravity and on earth. Dimensionless parameters were found that clarify the role of operating conditions and physical properties. The reason for the occurrence of two steady states was clarified, along with their relative stability. Observation of periodic gas tubes during directional solidification of water and organic compounds. Gas bubbles did not propagate around the periphery to yield full detachment. Failure to obtain detachment is attributed to the ready plastic deformation of these materials, so that the frozen material continues to adhere to the ampoule wall during cooling.

Regel, Liya L.↗

In Situ Observation of Growth Dynamics in DECLIC Directional Solidification Insert Onboard ISS: DSI-R Flight Campaign

The study of solidification microstructure formation is of utmost importance for materials design and processing, as solid-liquid interface patterns largely govern mechanical and physical properties. Pattern selection occurs under dynamic conditions of growth in which the initial morphological instability evolves nonlinearly and undergoes a reorganization process. The dynamic and nonlinear nature of this instability renders in situ observation of the interface an invaluable tool to gain knowledge on the time-evolution of the interface pattern. Transparent organic analogs, which solidify like metallic alloys, allow direct visualization of interface dynamics. Extensive ground-based studies of both metallic and organic bulk samples have established the presence of significant convection during solidification processes that alters the formation of interfacial microstructures. A reduced-gravity environment is therefore mandatory for fluid flow elimination in bulk samples. In the framework of the CNES project MISOL3D (MIcrostrutures de SOLidification 3D) and the NASA projects DSIP (Dynamical Selection of 3D Interface Patterns), SPADES (SPAtiotemporal Evolution of three-dimensional DEndritic array Structures) and CAMUS (ComputAtional Studies of MicrostrUcture Formation During Alloy Solidification in Microgravity), we participated in the development of the Directional Solidification Insert (DSI) of the DEvice for the study of Critical Liquids and Crystallization (DECLIC). The DECLIC-DSI is dedicated to in situ and real-time characterization of solid-liquid interface patterns during directional solidification of transparent alloys in diffusive transport regime. Between April 2010 and March 2011, the first ISS campaign (DSI) explored the entire range of microstructures resulting in unprecedented observations. A second campaign (DSI-R), performed between October 2017 and December 2018, in which the insert contained an alloy of higher solute concentration, allowed to complete the benchmark database. The increase of solute concentration resulted in well-developed dendritic patterns at lower velocities (lower interface curvature and larger tip radius). The microstructure resulting from dendritic growth is dominant in metallurgy so that it is fundamental to understand the mechanisms of its formation. The main aims of this experimental campaign are to understand: the mechanisms of the cell to dendrite transition, the fundamental mechanisms of sidebranching formation, the dependence of dendrite tip shapes on growth conditions, the interaction of primary array and secondary sidebranches, and the influence of subgrain boundaries on the spatiotemporal organization of the array structure. Preparation, analysis and interpretation of the experiments performed onboard ISS are considerably enhanced by experiments performed on ground using thin-samples (Pr. Trivedi’s group) and phase-field simulations of microstructure formation in a diffuse growth regime (Pr. Karma’s group). In this summary, we will present an initial assessment of the results obtained during the DSI-R campaign. Nomenclature Vp: pulling velocity G: thermal gradient L: solidified length rtip: tip curvature radius Acronyms/Abbreviations CADMOS: Centre d'Aide au Développement des activités en Micro-pesanteur et des Opérations Spatiales CNES: Centre National d’Études Spatiales DECLIC: Device for the study of Critical LIquids and Crystallization DSI: Directional Solidification Insert DSI-R: Directional Solidification Insert - Refurbish ISS: International Space Station NASA: National Aeronautics and Space Administration PF: phase-field SCN: Succinonitrile 3D: three-dimensional

Mota, F.L.↗

Formation Mechanism and Nucleation Effect of Ti{sub 2}O{sub 3}–TiN Complex Nucleus at Solidification Front of 18Cr Ferritic Stainless Steel

Formation mechanism of Ti{sub 2}O{sub 3}–TiN complex nucleus and its nucleation effect on δ-Fe at solidification front of Fe-18Cr ferritic stainless steel was investigated through experimental and theoretical methods. According to the equilibrium calculation, Ti{sub 2}O{sub 3} will crystallize in the molten steel before solidification and TiN will not form until the solid phases appear. However, complex nucleus and equiaxed grains exist in the edge of Ti-bearing ingot, where the solidification velocity and temperature gradient are high. Therefore, complex nucleus is indicated to be formed at solidification front and a non-equilibrium solidification model for multi-component alloy was established to investigate the dendrite tip interface phenomenon. The calculation results exhibit an element enrichment at solidification front and explain well with the formation of complex nucleus before solidification. It is also found that there is approximate lattice matching between TiN, and Ti{sub 2}O{sub 3}, δ-Fe on the basis of disregistry theory. These results are consistent with the observed complex nucleus and the increased equiaxed zone ratio (EZR) of Ti-bearing ferritic stainless steel.

36 MATERIALS SCIENCE↗

Relationships Between Solidification Parameters in A319 Aluminum Alloy

The design of high-performance materials depends on a comprehensive understanding of the alloy-specific relationships between solidification and properties. However, the inconsistent use of a particular solidification parameter for presenting materials characterization in the literature impedes inter-study comparability and the interpretation of findings. Therefore, there is a need for accurate expressions relating the solidification parameters for each alloy. In this study, A319 aluminum alloy castings were produced in a permanent mold with various preheating temperatures in order to control metal cooling. Analysis of the cooling curve for each casting enabled the identification of its liquidus, Al-Si eutectic, and solidus temperatures and times. These values led to the calculation of the primary solidification rate, total solidification rate, primary solidification time, and local solidification time for each casting, which were related to each other as well as to the average casting SDAS and material hardness. Expressions for each of their correlations have been presented with high coefficients of determination, which will aid in microstructural prediction and casting design.

36 MATERIALS SCIENCE↗

Solidification modes during additive manufacturing of steel revealed by high-speed X-ray diffraction

Solidification during fusion-based additive manufacturing (AM) is characterized by high solidification velocities and large thermal gradients, two factors that control the solidification mode of metals and alloys. Using two synchrotron-based, in situ setups, we perform high-speed X-ray diffraction measurements to investigate the impact of the solidification velocities and thermal gradients on the solidification mode of a hot-work tool steel over a wide range of thermal conditions of relevance to AM of metals. The solidification mode of primary δ-ferrite is observed at a cooling rate of 2.12x10 4 K/s, and at a higher cooling rate of 1.5x10 6 K/s, δ-ferrite is sup-pressed, and primary austenite is observed. The experimental thermal conditions are evaluated and linked to a Kurz-Giovanola-Trivedi (KGT) based solidification model. The modelling results show that the predictions from the multicomponent KGT model agree with the experimental observations. This work highlights the role of in situ XRD measurements for a fundamental understanding of the microstructure evolution during AM and for vali-dation of computational thermodynamics and kinetics models, facilitating parameter and alloy development for AM processes.

36 MATERIALS SCIENCE↗

Solidification and grain formation in alloys: a 2D application of the grand-potential-based phase-field approach

Solidification is a significant step in the forming of crystalline structures during various manufacturing and material processing techniques. Solidification characteristics and the microstructures formed during the process dictate the properties and performance of the materials. Hence, understanding how the process conditions relate to various microstructure formations is paramount. In this work, a grand-potential-based multi-phase, multi-component, multi-order-parameter phase-field model is used to demonstrate the solidification of alloys in 2D. This model has several key advantages over other multi-phase models such as it decouples the bulk energy from the interfacial energy, removes the constraints for the phase concentration variable, and prevents spurious third-phase formation at the two phase interfaces. Here, the model is implemented in a finite-element-based phase-field modeling code. The role of various modeling parameters in governing the solidification rate and the shape of the solidified structure is evaluated. It is demonstrated that the process conditions such as temperature gradient, thermal diffusion, cooling rate, etc, influence the solidification characteristics by altering the level of undercooling. Furthermore, the capability of the model to capture directional solidification and polycrystalline structure formation exhibiting various grain shapes is illustrated. In both these cases, the process conditions have been related to the growth rate and associated shape of the dendritic structure. As a result, this work serves as a stepping stone towards resolving the larger problem of understanding the process–structure–property–performance correlation in solidified materials.

36 MATERIALS SCIENCE↗