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At least 973 records · Page 54
All sourcesNASA NTRSDOE OSTI
DOE OSTI2026

Determining the Solubility Behavior of Kogarkoite in Simulated Nuclear Waste

Kogarkoite (Na 3 FSO 4 ) is a sparingly soluble fluoride–sulfate double salt that has been identified in high level nuclear waste sludge at the Hanford Site and, more recently, in sludge batch compilation samples at the Savannah River Site (SRS). Due to its complex dissolution behavior, which exhibits an inverse dependence on sodium ion activity, the presence of this mineral poses significant challenges to waste retrieval and processing. Incomplete dissolution during sludge washing can lead to the retention of fluoride and sulfate in the high-level waste feed, potentially causing the formation of corrosive, immiscible molten salt layers, known as "glass gall,” in vitrification melters. Current efforts to optimize flowsheet parameters and wash-water volumes are hindered by the absence of a commercially available, certified reference material, which prevents the accurate calibration of analytical methods and the verification of dissolution kinetics. To address this critical gap, this research focuses on the laboratory synthesis of pure Kogarkoite to serve as a standard for comprehensive solubility and washing performance testing. A coupled synthesis and simulant campaign was executed using an evaporative crystallization protocol designed to replicate the dynamic concentration effects observed in tank farm operations. Thirteen simulant matrices were prepared by dissolving systematically varied ratios of sodium fluoride (NaF) and sodium sulfate (Na 2 SO 4 ) in deionized water under three distinct caustic regimes: 0.0 g (control), 4.0 g (~1 M), and 12.0 g (~3 M) sodium hydroxide (NaOH). While thermodynamic equilibrium models suggest that high-caustic environments should favor the stability of the double salt7, results from this evaporative study at 25 0 C revealed a distinct kinetic divergence. Simulants with high hydroxide loading predominantly yielded large, blocky crystals of sodium sulfate decahydrate (Na 2 SO 4 .10H 2 O). Successful synthesis of pure Kogarkoite was achieved exclusively in specific NaOH-free compositional windows, where the precipitate manifested as fine, opaque granular aggregates. Ion chromatography (IC) analysis confirmed phase purity through the simultaneous stoichiometric depletion of both fluoride and sulfate from the supernatant. This successful synthesis establishes a reproducible route to generate bulk Kogarkoite, enabling the subsequent phase of quantitative dissolution testing using inhibited water to optimize sludge-batch assembly.

Sarker, Md Sharif [Florida International Univ. (FI↗
DOE OSTI2023

Dose and dose rate effects on the microstructural and mechanical stability of long-range ordered precipitates in Inconel 718

Nickel-based alloys offer exceptional mechanical properties and corrosion resistance for various applications in extreme environments such as high neutron flux, temperature, and stress. Precipitates, resulting from thermal treatments, increase the strength and creep resistance of these alloys. Here, heavy ion irradiation is shown to destabilize the γ' and γ" precipitates in Inconel 718 nickel-based alloy by disordering and dissolution processes. Transmission electron microscopy and atom probe tomography reveal that the disordering and dissolution rates of the precipitates are proportional to both irradiation dose and dose rate. Irradiation induced disordering occurs at a higher rate than the dissolution. From analyzing the hardening contributions, microscale mechanical results suggest radiation-induced disordering is responsible for the majority of the softening response at low dose. In addition, low dose radiation-induced disordering results in strain localization and is believed to be the primary cause for the drastic degradation of uniform elongation and toughness in irradiated Inconel 718.

36 MATERIALS SCIENCE↗
DOE OSTI2021

Employing the Dynamics of the Electrochemical Interface in Aqueous Zinc-Ion Battery Cathodes

Intrinsically stable materials are desirable for constructing energy storage devices, which aim to demonstrate durability under the harsh electrochemical conditions that are detrimental to their lifespan. However, in this study it is demonstrated that the intrinsic instability of an electrochemical interface can be converted from an obstacle into an advantage. In aqueous zinc-ion batteries, manganese oxide (MnO 2 ) exhibits considerable dissolution even in electrolyte containing Mn 2+ salt. Balancing with redeposition alleviates the harmful impact of dissolution on performance and alters the trajectory of the active phase. Inclusion of Mn 2+ salt in the electrolyte induces MnO 2 deposition on all conductive surfaces, requiring that distracting side reactions be eliminated to isolate the dynamics of the active phase. Under conditions favoring dissolution, capacity decreases dramatically and a highly crystalline tetragonal ZnMn 2 O 4 phase forms, while redeposition helps maintain capacity and promotes a disordered cubic Zn-rich phase. Ultimately, this work aims to illuminate a path forward to unlock the potential of batteries made with materials that are fundamentally unstable in their operating environment.

25 ENERGY STORAGE↗
DOE OSTI2025

Mitigating Cyclable Li‐Ion Inventory Loss in Full Cells with Mn‐Rich Disordered Rocksalt Cathodes

Lithium (Li)- and manganese (Mn)-rich disordered rock salt (DRX) materials are promising cathode materials for next-generation Li-ion batteries. Although these cathode materials are Li-ions rich in their pristine state, their incorporation into full cells results in challenges with maintaining Li-ion inventory during cycling. Herein, the degradation mechanisms of DRX materials in different DRX||Graphite full cells are reported. It is found that DRX electrodes contain Li impurities, primarily due to the environmental sensitivity of mechanochemically synthesized DRX materials during sample transfer and storage. In addition, the structural instability of DRX triggers Mn dissolution. Dissolved Mn ions react with exposed Li x C y compounds and induce electrolyte decomposition on the anode, further depleting Li-ion inventory. Control experiments involving the pre-addition of Mn 2+ provide clear evidence of the impact of Mn dissolution on Li-ion inventory. The electrochemical activation process can stabilize DRX, alleviate Mn dissolution and thus mitigate the loss of Li-ion inventory. These mechanistic insights inform the development of chemical pre-lithiation and electrolyte additive strategies to collectively passivate interfaces, mitigate the effects of trace dissolved Mn ions, and preserve Li-ion inventory. Ultimately, the DRX||Graphite full cell achieves highly reversible electrochemical reactions with a high capacity retention. This study fills a research gap in DRX-based full cells and provides insights into degradation mechanisms and optimization strategies for their practical use.

36 MATERIALS SCIENCE↗
DOE OSTI2021

Computational Approach for Rapidly Predicting Temperature–Dependent Polymer Solubilities Using Molecular–Scale Models

One promising approach to recycle multicomponent plastic waste (e. g., multilayer plastic films) is selective dissolution. Selective dissolution is a solvent-mediated process in which differences in polymer solubility in a carefully chosen solvent system are exploited to recover a target polymer. Here, a computational approach was developed that rapidly predicts temperature-dependent polymer solubilities to guide the design of solvent systems for solvent-mediated polymer recycling. Polymer conformations were obtained from molecular dynamics simulations by modeling the polymer as a short oligomer and then used as input to the conductor-like screening model for real solvents (COSMO-RS) for solubility predictions. Using polyethylene (PE) and ethylene vinyl alcohol (EVOH) as representative polymers, the effect of simulation parameters was systematically studied, and predicted solubilities were found to be in good agreement with experimental measurements. Furthermore, the applicability of the approach was demonstrated by identifying selective solvents for PE and EVOH dissolution from a library of 524 solvents.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2017

Secondary structure and dynamics study of the intrinsically disordered silica-mineralizing peptide P 5 S 3 during silicic acid condensation and silica decondensation

The silica forming repeat R5 of sil1 from Cylindrotheca fusiformis was the blueprint for the design of P5S3, a 50-residue peptide which can be produced in large amounts by recombinant bacterial expression. It contains five protein kinase A target sites and is highly cationic due to 10 lysine and 10 arginine residues. In the presence of supersaturated ortho silicic acid P5S3 strongly enhances silica-formation whereas it retards the dissolution of amorphous silica (SiO2) at globally undersaturated concentrations. The secondary structure of P5S3 during these different functions was studied by circular dichroism (CD), complemented by nuclear magnetic resonance (NMR) studies of the peptide in the absence of silicate. The NMR studies of dual-labeled (13C, 15N) P5S3 revealed a disordered structure at pH 2.8 and 4.5. Within the pH range of 4.5 to 9.5, the CD data verified the disordered secondary structure but also suggested the presence of some polyproline II character in the absence of silicic acid. Upon silicic acid polymerization and during dissolution of preformed silica, the CD spectrum of P5S3 indicated partial transition into an α-helical conformation which was transient during silica-dissolution. Consequently, the secondary structural changes observed for P5S3 correlate with the presence of oli-gomeric/polymeric silicic acid, presumably due to P5S3-silicic acid interactions. These interactions appear, at least in part, ionic in nature since dodecylsulfate micelles, which are negatively charged, cause similar conformational shifts to P5S3 in the absence of silica while ß-D-dodecyl maltoside micelles, which are neutral, do not. Thus, P5S3 influences both the condensation of silicic acid into silica and its decondensation back to silicic acid. Moreover, the dynamics of these pro-cesses may be indirectly monitored by following structural changes to P5S3 with CD spectroscopy.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2019

Direct Observation of Pure Cu and Cu-Ag Anode Passivation in H{sub 2}SO{sub 4}-CuSO{sub 4} Aqueous Solution by Channel Flow Double Electrode and Optical Microscopy

The dissolution and passivation of pure Cu and Cu-5 wt pct Ag anodes in H{sub 2}SO{sub 4}-CuSO{sub 4} electrolyte were investigated by a direct observation method that combined the techniques of optical microscopy and channel flow double electrode. Linear sweep voltammetry of the anodes showed that the dissolution of Cu transited from the charge transfer-controlled reaction to the mass transfer-controlled reaction, followed by the passivation of the electrodes. The direct observation of the pure Cu anode revealed that Cu particles were generated on the surface and the particles fell away during passivation. On the other hand, a slime layer of Ag particles that adhered to the surface was generated during the dissolution of the Cu-5 wt pct Ag anode. The Cu-5 wt pct Ag anode was passivated with a lower current density than the pure Cu anode, which suggested that the morphology and adhesive characteristics of the slime on the anode affected the passivation. The direct observation method described herein is useful for understanding reactions on electrodes that undergo drastic changes in their surface morphology. Information obtained from this method can help with the development of new processes for the effective utilization of limited natural resources and energy, such as the recycling of Cu by electrorefining.

36 MATERIALS SCIENCE↗
DOE OSTI2019

Thermo-chemical Fluid Flow Simulation in Hot-Dip Galvanizing: The Evaluation of Dross Build-Up Formation

This paper presents a new computational framework to investigate the driving force for the formation of intermetallic dross particles in the zinc bath and dross build-up on the bath hardware. This is a major problem in continuous hot-dip galvanizing lines. The Computational Fluid Dynamics (CFD) model calculates the turbulent thermo-chemical flow conditions within the liquid melt. A detailed modeling of the steel strip–liquid interface enhances this approach, by means of a conjugated heat transfer calculation and a spatially resolved, temperature- and concentration-dependent iron dissolution and aluminum uptake. The heart of the computational framework is a thermodynamic model, which assesses the driving force for the formation or dissolution of dross particles in the bath and dross build-up on stationary and rotating equipment. The simulation results are validated with temperature and species depth profile measurements. The applicability of the CFD model is shown by investigating the locally resolved aluminum uptake and iron dissolution at the steel-strip surface, and the multi-physics conditions in the region near the roll. The novel approach of evaluating the thermodynamic driving force enables the assessment of the formation of dross build-up at the roll surface.

36 MATERIALS SCIENCE↗
DOE OSTI2014

In-situ early-age hydration study of sulfobelite cements by synchrotron powder diffraction

Eco-friendly belite calcium sulfoaluminate (BCSA) cement hydration behavior is not yet well understood. Here, we report an in-situ synchrotron X-ray powder diffraction study for the first hours of hydration of BCSA cements. Rietveld quantitative phase analysis has been used to establish the degree of reaction (α). The hydration of a mixture of ye'elimite and gypsum revealed that ettringite formation (α ∼ 70% at 50 h) is limited by ye'elimite dissolution. Two laboratory-prepared BCSA cements were also studied: non-active-BCSA and active-BCSA cements, with β- and α′{sub H}-belite as main phases, respectively. Ye'elimite, in the non-active-BCSA system, dissolves at higher pace (α ∼ 25% at 1 h) than in the active-BCSA one (α ∼ 10% at 1 h), with differences in the crystallization of ettringite (α ∼ 30% and α ∼ 5%, respectively). This behavior has strongly affected subsequent belite and ferrite reactivities, yielding stratlingite and other layered phases in non-active-BCSA. The dissolution and crystallization processes are reported and discussed in detail. -- Highlights: •Belite calcium sulfoaluminate cements early hydration mechanism has been determined. •Belite hydration strongly depends on availability of aluminum hydroxide. •Orthorhombic ye’elimite dissolved at a higher pace than cubic one. •Ye’elimite larger reaction degree yields stratlingite formation by belite reaction. •Rietveld method quantified gypsum, anhydrite and bassanite dissolution rates.

36 MATERIALS SCIENCE↗
DOE OSTI2016

Effect of retarders on the early hydration of calcium-sulpho-aluminate (CSA) type cements

The retardation of calcium-sulpho-aluminate (CSA) type cements by three common retarders—sodium gluconate, sodium–potassium tartrate and borax is investigated at a 2% addition rate. Each of the retarders has a different effect on the early-age hydrate assemblage, as shown by quantitative X-ray diffraction, thermogravimetric analysis, scanning electron microscopy and pore solution analysis. Regardless of the retarder used, the hydration starts with mainly the dissolution of ready soluble (calcium) alkali sulphates and ye'elimite, followed by the formation of ettringite and aluminium hydroxide, whereby the specific clinker mineral dissolution as well as ettringite-forming reaction is delayed in different ways depending on the retarder used. The results showed that the retardation is mainly caused by preventing hydrates formation in the case of tartrate and gluconate. Contrary, borax retards the hydration by preventing to a certain extent the dissolution of ye'elimite and lowers the initial pH. Furthermore, the morphology of ettringite is altered depending on the type of the retarder used.

36 MATERIALS SCIENCE↗
DOE OSTI2018

Modelling of the sulfuric acid attack on different types of cementitious materials

A chemical-reactive transport model is used to simulate the sulfuric acid attack of cement pastes based on ordinary Portland cement (CEM I), blended Portland cements (CEM III, CEM IV, and CEM V), and calcium aluminate cement (CAC). This model accounts for the dissolution of cement hydrates (portlandite, C-S-H, hydrogarnet), and the precipitation of deterioration products (ettringite and gypsum). Moreover, diffusion of the aqueous species in the pore space of the material is considered. With this model, the hydrate contents, the porosity, and the deterioration phase contents throughout a sulfuric acid attack are determined. Two indicators are defined to predict the service life of the cementitious materials: the deterioration depth and the dissolved calcium content. These two indicators show that calcium aluminate cement has a better resistance to sulfuric acid attack than that of Portland cements. This better resistance is mainly due to the partial dissolution of CAC hydrate as opposed to the total dissolutions of CH and C-S-H.

36 MATERIALS SCIENCE↗
DOE OSTI2018

Synchrotron X-ray nanotomographic and spectromicroscopic study of the tricalcium aluminate hydration in the presence of gypsum

The rheology of modern Portland cement (PC) concrete critically depends on the correct dosage of gypsum (calcium sulfate hydrate) to control the hydration of the most reactive phase - tricalcium aluminate (C{sub 3}A). The underlying physio-chemical mechanism, however, remains unsolved mainly due to the lack of high-spatial-resolved and chemistry-sensitive characterization of the C{sub 3}A dissolution frontier. Here, we fill this gap by integrating synchrotron-radiation based crystallographic, photon-energy-dependent spectroscopic and high-resolution morphological studies of the C{sub 3}A hydration product layer. We propose that ettringite (6CaO·Al{sub 2}O{sub 3}·SO{sub 3}·32H{sub 2}O) is the only hydration product after the initial reaction period and before complete gypsum dissolution. We quantify the 2D and 3D morphology of the ettringite network, e.g. the packing density of ettringite at various surface locations and the surface dissolution heterogeneity. Our results show no trace of a rate-controlling diffusion barrier. We expect our work to have significant impact on modeling the kinetics and morphological evolution of PC hydration.

36 MATERIALS SCIENCE↗
DOE OSTI2025

Corrosion of 316 L stainless steel under the natural circulation of molten NaCl-MgCl 2 salt

The corrosion behavior of 316 L stainless steel (SS) was studied via the natural circulation of molten eutectic NaCl-MgCl 2 salt through a microloop. The post-corrosion tested 316 L SS microloop sections were characterized with microscopy techniques to determine the microstructural and microchemical changes that occurred at the alloy/salt interface. It was found that 316 L SS showed heterogeneous dissolution at the hot-leg, whereas deposition of corrosion products occurred at the cold-leg. For the first time, experimentally obtained molten salt flow-induced corrosion of 316 L SS results were combined with computational thermodynamic-kinetic models to validate the dissolution and deposition in terms of elemental compositional changes at the alloy/salt interface. The thermodynamic-kinetic modeling predicted that the heterogeneous dissolution of Cr and Fe from the hot-leg section of 316 L SS persisted throughout the salt circulation. The model also estimated that, despite Cr deposition starting earlier than Fe, the total redeposition of Fe is expected to be significantly greater than that of Cr over the circulation of salt. Furthermore, the modeling accurately predicted the subsurface enrichment of Mo which is attributed to the reduced Cr activity and the relatively higher diffusion rate of Mo within the alloy matrix. Here, the agreement between modeling and experimental results confirms that Fe chlorides dissolve at the hot-leg and subsequently deposit at the cold-leg due to activity changes driven by the thermal gradient. By contrast, Cr was not detected in the cold-leg deposits, which is attributed to its weaker temperature dependence on activity, limiting its redeposition under these conditions.

36 - MATERIALS SCIENCE↗
DOE OSTI2023

Mastering the synergy between Na 3 V 2 (PO 4 ) 2 F 3 electrode and electrolyte: A must for Na-ion cells

Sodium-ion batteries are emerging as suitable energy storage devices for special applications such as high-power devices with the advantages of being cheaper and more sustainable than the Li-ion equivalents. The sodium ion cells consisting of polyanionic Na 3 V 2 (PO 4 ) 2 F 3 - hard carbon electrodes exhibit high power rate capabilities but limited cycle life, especially at high temperatures. To circumvent this drawback we herein conducted in-depth analyses of the origins of structural degradations occurring in Na 3 V 2 (PO 4 ) 2 F 3 electrodes upon long cycling. Vanadium dissolution with associated parasitic reactions is identified as one of the major reasons for cell failure. Its amount varies depending on the electrolyte, with NaTFSI-based electrolyte showing the least vanadium dissolution as the TFSI - anion decomposes without producing acidic impurities, in contrast to the NaPF 6 -based electrolyte. The dissolved vanadium species undergoes oxidation and reduction processes at the Na 3 V 2 (PO 4 ) 2 F 3 and HC electrodes, respectively, with the electrochemical signature of these processes being used as a fingerprint to identify state of health of the 18650 cells. Here, having found that surface reactivity is the primary cause of vanadium dissolution we provide methods to mitigate it by combining surface coating and optimized electrolyte formulation.

25 ENERGY STORAGE↗
DOE OSTI2011

Inner-Helmholtz potential development at the hematite (α-Fe2O3) (001) surface

Electric potentials of the (001) plane of hematite were measured as a function of pH and ionic strength in solutions of sodium nitrate and oxalic acid using the single-crystal electrode approach. The surface is predominantly charge-neutral in the pH 4-14 range, and develops a positive surface potential below pH 4 due to protonation of μ-OH 0 sites (pK 1,1,0 int = -1.34). This site is resilient to deprotonation up to at least pH 14 (-pK -1,1,0 int >> 21). The associated Stern layer capacitance of 0.62 F/m 2 is smaller than typical values of powders, and possibly arises from a lower degree of surface solvation. Acid-promoted dissolution under elevated concentrations of HNO 3 etches the (001) surface, yielding a convoluted surface populated by OH 2 0.5+ sites. The resulting surface potential was therefore larger under these conditions than in the absence of dissolution. Oxalate ions also promoted (001) dissolution. Associated electric potentials were strongly negative, with values as large as -0.5 V, possibly from metal-bonded interactions with oxalate. The hematite surface can also acquire negative potentials in the pH 7-11 range due to surface complexation and/or precipitation of iron species (0.003 Fe/nm 2 ) produced from acidic conditions. Oxalate-bearing systems also result in negative potentials in the same pH range, and may include ferric-oxalate surface complexes and/or surface precipitates. All measurements can be modeled by a thermodynamic model that can be used to predict inner-Helmholtz potentials of hematite electrodes.

58 GEOSCIENCES↗
DOE OSTI2018

Recycling Glass Fiber Thermoplastic Composites from Wind Turbine Blades

We report that thermoplastic resin systems have long been discussed for use in large-scale composite parts but have yet to be exploited by the energy industry. The use of these resins versus their thermosetting counterparts can potentially introduce cost savings due to non-heated tooling, shorter manufacturing cycle times, and recovery of raw materials from the retired part. Because composite parts have high embedded energy, recovery of their constituent materials can provide substantial economic benefit. This study determines the feasibility of recycling composite wind turbine blade components that are fabricated with glass fiber reinforced Elium (R) thermoplastic resin. Several experiments are conducted to tabulate important material properties that are relevant to recycling, including thermal degradation, grinding, and dissolution of the polymer matrix to recover the constituent materials. Dissolution, which is a process unique to thermoplastic matrices, allows recovery of both the polymer matrix and full-length glass fibers, which maintain their stiffness (190 N/(mm g)) and strength (160 N/g) through the recovery process. Injection molded regrind material is stiffer (12 GPa compared to 10 GPa) and stronger (150 MPa compared to 84 MPa) than virgin material that had shorter fibers. An economic analysis of the technical data shows that recycling thermoplastic-glass fiber composites via dissolution into their constituent parts is commercially feasible under certain conditions. This analysis concludes that 50% of the glass fiber must be recovered and resold for a price of $0.28/kg. Furthermore, 90% of the resin must be recovered and resold at a price of $2.50/kg.

17 WIND ENERGY↗
DOE OSTI2011

Direct Observation of Ion-irradiation-induced Chemical Mixing

Irradiation-induced dissolution of particles and mixing at heterogeneous interfaces in materials is of importance for ion beam processing and radiation materials sciences. Modeling has predicted dissolution of particles and homogenization at sharp chemical interfaces; imaging and depth profiling techniques have also been used to observe damage and mixing resulting from ion or neutron bombardment. Analytical scanning transmission electron microscopy has been used to directly observe the ion-irradiation induced elemental mixing and dissolution of {approx}25-50 nm titanium oxycarbonitrides in a nanostructured ferritic alloy irradiated at 173 K. The magnitude of the mixed zone is consistent with radiation damage theory.

72 PHYSICS OF ELEMENTARY PARTICLES AND FIELDS↗
DOE OSTI2014

Origin of the solid solution in the LiInSe{sub 2}–In{sub 2}Se{sub 3} system

Techniques of bulk and local analyses were used to characterize the melt-grown single crystals of LiInSe{sub 2}, where yellow matrix coexists together with extended red areas distributed irregularly. Bulk chemical analysis showed that the average stoichiometry of yellow matrix is close to ideal 1:1:2, but red areas are enriched with In{sub 2}Se{sub 3}. An excess In{sub 2}Se{sub 3} is incorporated coherently into the crystal lattice of LiInSe{sub 2}, forming the substitution solid solution with the general formula (Li{sub 1−3x}In{sub x}⎕{sub 2})InSe{sub 2} and changing the color from yellow to red. The test crystals with the 50–55% content of In{sub 2}Se{sub 3} were found by the X-ray analysis to be single phase. The differential dissolution technique, measuring the spatial variation of the composition with high resolution, demonstrated that the single phase crystals in the LiInSe{sub 2}–In{sub 2}Se{sub 3} system might be grown only in a very narrow range close to stoichiometric. Being supersaturated, the heterovalent solid solution phases decompose in the course of cooling, and the concentration micro-heterogeneity occurs in the matrix as the coherent (or incoherent) inclusions of two different types, practically pure selenides of lithium and indium. The origin and scale of the micro-heterogeneity determining the physical properties of LiInSe{sub 2} are discussed as a starting point for the development of physicochemical foundations for growing high quality optical crystals. - Graphical abstract: Differential dissolution technique applied for detection of dispersive precipitates in as-grown LiInSe{sub 2} single crystals: kinetic curves of the phase dissolution: F is the main phase Li{sub 0.96}In{sub 1.01}Se{sub 2} (98.9%), secondary minor phases Li{sub 2}Se (0.1%), In{sub 2}Se{sub 3} (0.9%). - Highlights: • Phase purity of crystals Li{sub 1−3x}In{sub 1+x}Se{sub 2} was examined by a new stoichiographic method. • Breakup of the metastable solid solution with temperature drop was detected. • Dispersive precipitates Li–Se and In–Se of low content result from the breakup. • A crucial role of the precipitates in optical properties of the crystals is shown. • Conditions are given how to grow stoichiometric and single-phase crystals.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗