Solubility Of Indium Research Articles

Synthesis-Controlled Cation Solubility in Solid Sodium Ion Conductors Na2+xZr1–xInxCl6

Mechanochemically synthesized sodium halide solid solutions with the general formula Na2+xZr1–xMxCl6, as a class of potential catholytes, show promising ionic transport in comparison to their parental materials such as Na3YCl6. However, the influence of subsequent heat treatment protocols on the structure and transport properties of these materials is still not fully understood. In this work, a series of Na2+xZr1–xInxCl6 solid solutions are prepared by ball milling with subsequent annealing at different temperatures. X-ray diffraction analyses show a full indium solubility in Na2+xZr1–xInxCl6 when synthesized at low temperatures and crystallizing in the P21/n phase. In contrast, at higher heat treatment temperatures, exsolution is observed as the indium-rich Na2+xZr1–xInxCl6 compound tends to partially transform to the trigonal P3̅1c phase. By assessing the ionic conductivity of the differently synthesized Na2+xZr1–xInxCl6 series, we can show the synergistic effect of the Na+/vacancy ratio and crystallinity on sodium ion transport in this class of materials.

ВЗАЄМОДІЯ КОМПОНЕНТІВ У СИСТЕМАХ R2T2In1-xGax (R = La, Ce; T = Ni, Cu)

This work is devoted to the study of R2T2In1-xGax (R = La, Ce; T = Ni, Cu) systems at 870 K, namely the solubility of the fourth component in compounds with the composition 2:2:1 and structural characteristics of the solid solutions. Samples for the investigation were synthesized by arc-melting of metals (purities better than 0.998) with subsequent annealing at 870 K for one month in the electric muffle furnace SNOL with automatic temperature control. The phase compositions of the alloys were characterized by means of X-ray powder diffraction (DRON-2.0M, Fe Kα-radiation, HZG 4a, Cu Kα-radiation and Guinier camera Fujifilm BAS–1800, Cu Kα-radiation) and energy dispersive X-ray analysis (scanning electron microscope Leica 420i). According to the results of experimental studies, the solubility of Gallium in the La2Ni2In and Ce2Ni2In compounds is not more than 4 at. %. The unit cell parameters of the solid solutions with Mo2FeB2-type structure are: a = 0.7627–0.7609(4), c = 0.3905–0.3898(3) nm, V = 0.2272–0.2257(1) nm3 for La2Ni2In1-0.8Ga0-0.2 and a = 0.7530–0.7503(3), c = 0.3722–0.3718(2) nm, V = 0.2110–0.2093(1) nm3 for Ce2Ni2In1-0.8Ga0-0.2. Significant solubility of indium in ternary gallides with Mo2NiB2-type structure under the conditions of the study was not detected. During the investigation of the components interaction in the R2Cu2In1-xGax (R = La, Ce) systems less 7 at.% of Gallium solubility in the ternary La2Cu2In and Ce2Cu2In compounds at 870 K was detected. The solid solutions with the Mo2FeB2-type structure can be described by formulas: La2Cu2In1-0.65Ga0-0.35 (a = 0.7737–0.7709(4), c = 0.3924–0.3936(3) nm, V = 0.2349–0.2339(1) nm3) and Ce2Cu2In1-0.65Ga0-0.35 (a = 0.7797–0.7774(3), c = 0.3991–0.3999(3) nm, V = 0.2426–0.2417(1) nm3). The peculiarities of the interaction of components in the studied and related systems are briefly discussed.

Microstructural and electrical features of highly conducting indium co‐doped ZnO‐based ceramics

AbstractIn this work, we developed experimental approaches on indium co‐doped ZnO‐based ceramics from the synthesis to the characterizations and analysis of physical features in the aim to achieve the formation of highly conducting ceramics with controlled nonlinearity. Different doping molar ratios of indium were used and the synthesis of the ceramics was realized by the conventional solid‐state reaction method which was then followed by a sintering under air (A), nitrogen (N), or a mixture of nitrogen and carbon monoxide (NC) atmosphere with different reduction capabilities. The structure, morphology, electrical investigations, and the electronic transport analysis were conducted on the different ZnO co‐doped ceramics as functions of the indium incorporation and the used sintering atmosphere, A, N, or NC. Suitable indium doping of 0.3 mol% and the use of highly reducing sintering atmosphere (NC) ensure the formation of ZnO‐based ceramics with an electrical conductivity up to (103 S/cm) and a quasi‐linear behavior on the electrical characteristic I–V. We discussed the obtained performances by correlating the charge transport with the microstructure of the ceramics, the composition, and the structure of grain boundaries as well as the solubility of indium in the host ZnO ceramic grains.

Phase Separation in Liquid Metal Nanoparticles

Nanoparticles produced from gallium-based liquid metal alloys have been explored for developing applications in the fields of electronics, catalysis, and biomedicine. Nonetheless, physical properties, such as phase behavior at micro-/nanosize scale, are still significantly underexplored for such nanoparticles. Here, we conduct an in situ investigation of phase behavior for gallium-based liquid metal nanoparticles and discover the unprecedented coexistence of solid particles in spherical liquid metal shells without the support of a crystalline substrate. The particles can also transform into solid Janus nanoparticles after temperature cycling. In addition, we investigate the optical properties of the nanoparticles before and after phase separation using in situ electron energy-loss spectroscopy. Most importantly, we discover that increasing the content of indium within the nanoparticle can stabilize the solid-core/liquid-shell structure at room temperature. This study provides a foundation to engineer liquid metal nanoparticles for developing new applications in nanoscale optical platforms and shape-configurable transformers.Although various electronic, chemical, and biomedical applications have been demonstrated for nanoparticles made from gallium-based liquid metal alloys, fundamental physical properties such as phase behavior of such nanoparticles are still significantly underexplored. Here, Tang and coworkers present the in situ investigation of phase separation in binary and ternary spherical liquid metal nanoparticles upon cooling, and demonstrate the coexistence of solid core/liquid shell without the support of a crystalline substrate. This study provides insight into engineering such nanoparticles for the development of new applications.Despite gallium-based liquid metal alloys attracting extensive attention for various applications, their phase behavior at the nanoscale is still underexplored. Understanding the impact of phase separation in nanoparticles can be extremely useful for developing new structures and exploring suitable applications. Here, we report on the investigation of phase behavior for spherical nanoparticles made from gallium-based liquid metal alloys upon cooling. We discover the thermally stable coexistence of solid cores in spherical liquid metal shells without the support of a crystalline substrate at room temperature. Given the unique properties of liquid metal, together with the facile process for producing core-shell and Janus nanoparticles, this work will encourage further investigation of the properties of such nanoparticles for developing applications in the fields of electronics, catalysis, nanomedicine, and beyond.

Образование высокоэнтропийных октаэдрических кристаллов в многокомпонентных оксидных системах

In the context of the project covering formation of high-entropy crystal phases with the magnetoplumbite structure the chemical composition, crystal structure, and formation conditions have been analyzed for multicomponent crystals with the spinel structure, obtained as by-products or experiment failures, including crystals with the composition not described in the literature previously. The list of chemical elements, which can be major components of phases with such structures, has been determined. Specifically, it has been found that the composition of the obtained spinel crystals can be expressed by the empirical formulas (Ni,Co,Mn 2+ )(Al,Cr,Fe,Ti,Ga,Mn 3+ ) 2 O 4 and (Co,Fe 2+ ,Mn 2+ )(Al,Cr,Ti,V,Ga,Fe 3+ ,Mn 3+ ) 2 O 4 . At that Ba, Sr, Ca, K, Pb, La, and Bi in such phases can exist in the form of minor admixtures; their addition in all probability does not affect stabilization of the spinel-structured phase. Solubility of indium, In, judging from the obtained data, in solid solutions of the described kind can be limited. Important conclusions of great practical significance have been made, concerning the conditions to be created in the process of crystal growing from high-entropy melts. In particular, it has been shown that allowance must be made for additional oxidation during growing a monocrystal from a melt, compared to the level that can be ensured from the composition of the melt and the air atmosphere, in which the experiments were carried out. It is related to the fact that increasing synthesis temperature (specifically, from 1400 to 1600 °С) leads to reduction of the greater part of iron and manganese atoms to oxidation number +2, which favors formation of octahedral phase in great quantities and has a negative impact on formation of crystals with the magnetoplumbite structure.

Effect of indium addition on interfacial IMC growth and bending properties of eutectic Sn–0.7Cu solder joints

The microstructure and growth behaviors of interfacial IMCs between the Sn–0.7Cu–xIn (x = 0–5.0 wt%) solder and Cu substrate under solid aging were investigated. Bending test was conducted to evaluate the mechanical properties of Cu/Sn–0.7Cu–xIn/Cu solder joints. The needle-like Cu6(Sn,In)5 IMCs formed at interface instead of Cu6Sn5 in as-soldered In-containing solder joints. During solid aging, indium addition had little influence on the growth of Cu6Sn5 IMCs, but strongly suppressed the growth of Cu3Sn IMCs. In Sn–0.7Cu–5.0In/Cu couple, the maximum solubility of indium in Cu6Sn5 and Cu3Sn was about 4.9 and 3.1 at.% respectively which was independent of aging temperature. The average composition of Cu6(Sn,In)5 and Cu3(Sn,In) were given as Cu6(Sn0.89,In0.11)5 and Cu3(Sn0.88,In0.12). After indium addition, the diffusion coefficients were found to be lower than that of Sn–0.7Cu/Cu couple and the activation energy for the growth of Cu3Sn increased with the increase of indium content. Doping indium into Sn–0.7Cu solder improved the bending properties of solder joints. Interfacial cracks were suppressed effectively after long time aging with indium addition.

Partial indium solubility induces chemical stability and colossal thermoelectric figure of merit in Cu2Se

Thermoelectric figure of merit, ZT, exceeding 2.6 at 850 K and copper electromigration inhibition have been demonstrated in indium modified Cu2Se.

Low Thermal Conductivity and High Thermoelectric Performance in In4Se3−x with Phase-Separated Indium Inclusions

We report the thermoelectric properties of undoped hot-pressed In4Se3−x (x = 0.05). Stoichiometric imbalance due to selenium deficiency in In4Se3 was found to create a secondary phase of elemental indium in the host material. Heat treatment drove grain growth and increased the indium solubility in In4Se3. Indium-rich domains at grain surfaces/boundaries in untreated samples were found to redistribute inside the grains and their junctions after heat treatment. Due to enhanced phonon scattering by secondary phase of indium, very low values of thermal conductivity were observed for all samples, leading to a maximum thermoelectric figure of merit (zT) of 1.13 at 723 K along the hot-pressing direction for the heat-treated sample.

Thermodynamics of Indium Dissolution Behavior in FeO-Bearing Metallurgical Slags

Indium solubility in the FeO-SiO2-Al2O3-5CaO-MgOsat slag system was measured at 1573 K (1300 °C) to confirm the thermodynamic dissolution behavior of indium at \( {\text{p}}_{{\text{O}_{2} }} = 10^{ - 11} \) atm. The indium solubility in FeO-bearing slags increased with increasing oxygen partial pressure and decreased with increasing basicity which is in proportion to the activity of FeO. The dissolution of indium in FeO-bearing slags was confirmed to progress according to the following reaction: $$ \text{In} (\text{s} ) + \frac{1}{4}\text{O}_{2} (\text{g} ) = (\text{In}^{ + } ) + \frac{1}{2}(\text{O}^{2 - } ) $$ The enthalpy change for the dissolution of indium in FeO-bearing slag was about −181 kJ/mol, indicating that indium dissolution is exothermic. The indium solubility in the FeO-SiO2-Al2O3-5CaO-MgOsat slag system was minimized as a function of alumina content at a given FeO/SiO2 ratio, which can be explained by the amphoteric behavior of Al2O3 in the slag system. To improve indium recovery by lowering indium loss to the slag phase during the pyro-recycling of In-containing materials using FeO-bearing metallurgical slags, a lower oxygen potential and lower silica content are highly favorable.

Flotation Separation of Soluble and Colloidal Indium from Aqueous Solution

This work investigated the speciation and solubility of indium (In) and its flotation separation from aqueous solution. Lowest theoretical In solubility was predicted for pH 5.5–8.5, and the solubility increased as it became more acidic or more alkaline. Experimentally, 20 mg/L of In completely dissolved at pH < 3.0, which agreed with theoretical prediction. At pH 3.6–9.9, In showed slightly higher solubility than predictions. There was good agreement at pH > 9.9. Flotation reaction was described by pseudo-first-order kinetic model and its reaction rate increased with increasing nitrogen flow rate. The results indicated that pH played a key for the flotation process. As pH increased from 4.0 to 6.8, removal efficiency rose from 65.0% to 95.8% when applying surfactant SDS as collector. The efficiency decreased to 56.7% at pH 9.9. Lower removal efficiency was found once using CTAB. Electrostatic interaction between collector with both soluble and colloidal In was the main mechanism for In flotation.

Phase diagram of In–Co–Sb system and thermoelectric properties of In-containing skutterudites

In-containing skutterudites have long attracted much attention and debate partly due to the solubility limit issue of indium in CoSb3. The isothermal section of the equilibrium phase diagram for the In–Co–Sb system at 873 K is proposed using knowledge of the related binary phase diagrams and experimental data, which explains the debated indium solubility that depends on Sb content. In this paper, a series of In-containing skutterudite samples (InxCo4Sb12−x/3 with x varying from 0.075 to 0.6 and In0.3Co4−ySb11.9+y with y changing from −0.20 to 0.20) are synthesized and characterized. X-ray analysis and scanning electron microscopy images indicate that, up to x = 0.27, single-phase skutterudites are obtained with lattice constant increasing with In fraction x. A fixed-composition skutterudite In0.27±0.01Co4Sb11.9 was determined for the Co-rich side of In–CoSb3 which is in coexistence with liquid InSb and CoSb2. Indium, like Ga, is expected, from DFT calculations, to form compound defects in In-containing skutterudites. However, relatively higher carrier concentrations of In-containing skutterudites compared to Ga-containing skutterudites indicate the existence of not fully charge-compensated compound defects, which can also be explained by DFT calculations. The net n-type carrier concentration that naturally forms from the complex defects is close to the optimum for thermoelectric performance, enabling a maximum zT of 1.2 for the fixed skutterudite composition In0.27Co4Sb11.9 at 750 K.

In y Co4Sb12 Skutterudite: Phase Equilibria and Crystal Structure

Phase relations were investigated for the In-Co-Sb system in the temperature range from 375°C to 800°C using as-cast and annealed alloys. Phase equilibria in the CoSb-InSb-(Sb) composition triangle are presented by a series of isothermal sections and solidus and liquidus surfaces, accompanied by a Schulz–Scheil reaction scheme. The indium-filled skutterudite InyCo4Sb12 already forms an equilibrium with liquid at 484°C, which might limit high-temperature applications of In-Co-Sb-based skutterudites. The maximal solubility of indium in InyCo4Sb12 (y = 0.22) remains almost constant in the temperature range from 475°C to 700°C and corresponds to the equilibrium with CoSb2 and InSb. The solubility of indium in the skutterudite phase is reduced to y = 0.09 when it coexists in equilibrium with InSb and (Sb), and this decrease of the solubility might be responsible for the formation of InSb precipitates. Temperature-dependent x-ray single-crystal and specific heat data for InyCo4Sb12 were employed to determine the rattling behavior of In atoms in the skutterudite lattice.

The Solubility of Indium in Liquid Gallium Supercooled to 12 K

The method of perturbed angular correlation (PAC) was used to determine lattice locations of 111In impurity probe atoms present in extreme dilution in the intermetallic compound FeGa3. In slightly Ga-poor samples, probes were found to strongly prefer one of two inequivalent Ga-sites. In slightly Ga-rich samples at room temperature, 293 K, the PAC spectrum exhibited an unperturbed quadrupole interaction signal that is consistent with indium probes dissolved in small liquid pools of the excess Ga. A myriad of such pools are probably located along grain boundaries in the sample. Cooling from 293 K down to 12 K, the site fraction of indium in liquid decreased, being offset by the increase in a signal attributed to indium solutes in precipitates with other impurities at the sides of the Ga pools. However, these changes were completely reversible upon heating, and no crystallization of the liquid gallium pools was observed down to 12 K. This is attributed to the extraordinarily small volumes for the pools, which, while not measured directly, are orders of magnitude smaller than cubic microns. The measured temperature dependence of the site fraction of indium in the liquid was used to extend the metastable solubility curve for indium in liquid gallium down to a temperature of 150 K, much lower than the eutectic temperature of Ga-In at 288.5 K.

Dissolution Mechanism of Indium in CaO-Al2O3-SiO2 Slag at Low Silica Region

The solubility of indium was measured in the low-silica region (<20 mass pct SiO2) of the CaO-Al2O3-SiO2 system by a thermochemical equilibration technique. The dissolution mechanism of indium into the CaO-Al2O3-SiO2 slag at 1773 K (1500 °C) under a reducing atmosphere was elucidated. The indium solubility increases in the calcium silicate-based flux and decreases in the calcium aluminate-based flux with increasing oxygen partial pressure. Also, the solubility was found to decrease initially with increasing slag basicity until the basicity reached a critical level after which the solubility increases. This behavior is believed to indicate that the indium dissolution mechanism changes according to the basicity of the slag.

Dissolution Behavior of Indium in CaO-SiO2-Al2O3 Slag

The solubility of indium in a molten CaO-SiO2-Al2O3 system was measured at 1773 K (1500 °C) to establish the dissolution mechanism of indium under a highly reducing atmosphere. The solubility of indium increases with increasing oxygen potential, whereas it decreases with increased activity of basic oxide. Therefore, a dissolution mechanism of indium can be constructed according to the following equation: $$ {\text{In}}({\text{s}}) + \frac{1}{4}{\text{O}}_{2} ({\text{g}}) = ({\text{In}}^{ + } ) + \frac{1}{2}({\text{O}}^{2 - } ) $$

Thermoelectric properties of indium-filled In xRh 4Sb 12 skutterudites

This study reports the synthesis and characterization of polycrystalline indium-filled In x Rh 4Sb 12 (0 ≤ x ≤ 0.2) skutterudites. The structural response to indium filling was monitored by whole pattern fitting of the powder X-ray diffraction data. Indium occupation of the oversized void-sites was verified by its unusually large thermal displacement parameter. The indium solubility limit approached 0.15. The principal thermoelectric properties were measured from 300 to 600 K. All samples are semiconducting. Indium void-site occupation reduced the lattice thermal conductivity of In 0.15Rh 4Sb 12 30% at 300 K; however, the effect was subverted at elevated temperatures due to a coincident increase in bipolar thermal diffusion. The high-temperature thermoelectric figure of merits ( ZT's) are low compared to the isostructural indium-filled In x Co 4Sb 12 skutterudites due to a striking sign change in the Seebeck coefficients at 400 K and relatively high thermal conductivities.

The Yb–Zn–In system at 400 °C: Partial isothermal section with 0–33.3 at.% Yb

The phase relations in the ternary system Yb–Zn–In have been established for the partial isothermal section in the 0–33.3 at.% ytterbium concentration range at 400 °C, by researching of more than forty alloys. X-ray powder diffraction (XRPD), optical microscopy (OM) and scanning electron microscopy (SEM), complemented with energy dispersive X-ray spectroscopy (EDS), were used to study the microstructures, identify the phases and characterize their crystal structures and compositions. The phase equilibria of this Yb–Zn–In partial section at 400 °C are characterized by the presence of three extended homogeneity ranges, indium solubility in Yb 13Zn 58 and YbZn 2 and of zinc solubility in YbIn 2, and the existence of one ternary intermetallic compound, YbZn 1− x In 1+ x , x = ∼0.3. This new compound crystallizes in the UHg 2 structure type (space group P6/mmm), with a = 4.7933(5) Å, c = 3.6954(5) Å. The studied partial isothermal section has eight ternary phase fields at 400 °C.

Experimental investigation and thermodynamic description of the In–Sb–Sn ternary system

Phase equilibria in the In–Sb–Sn ternary system have been studied experimentally and calculated by the CALPHAD method. Solubility of indium in the SbSn phase was experimentally established. Our own SEM–EDX results were used together with the literature data for thermodynamic modeling of the Gibbs energy of the SbSn intermediate phase. Optimized phase diagrams of the isothermal sections at 100 °C and 300 °C were compared with the experimental results from this work and literature. Three calculated vertical sections were compared with the DTA results from this work and with available thermal analysis data reported in the literature. Some calculated thermodynamic functions are compared with experimental values reported in the literature. Reasonable agreement between calculations and experimental data was observed in all cases.

Effects of temperature on interfacial reactions in γ–InSn4/Ni couples

Interfacial reactions in γ–InSn4(Sn–20 at.% In)/Ni couples at 130, 140, 150, and 160 °C were investigated. Ni3Sn4phase with significant indium solubility was formed in the couple reacted at 130 and 140 °C, and the reaction path was γ–InSn4/Ni3Sn4/Ni. For the couples reacted at 150 and 160 °C, even though both γ–InSn4and Ni were solid phases, the liquid phase was formed in the couples. A distinguished feature was the nickel substrates becoming nonplanar with spikes at various locations and the Ni3Sn4phase layer on top of the nickel spikes. Except at regions near the nickel spikes, the reaction layer consisted of precipitates and was not a homogeneous phase. The reaction path is γ–InSn4/Ni3Sn4/Ni at the location with Ni3Sn4phase growing on Ni. However, if the Ni3Sn4phase does not nucleate, the liquid phase forms at the interface with accumulation of indium atoms, and the reaction path is γ–InSn4/ liquid/liquid + Ni3Sn4/Ni.

Tunable work function in fully nickel-silicided polysilicon gates for metal gate MOSFET applications

The work function of fully nickel-silicided polysilicon was investigated. The midgap work function (4.7 eV) was obtained for undoped mononickel-silicide (NiSi). It was shown that the implantation of both arsenic and antimony into the polysilicon before silicidation reduces the NiSi work function, and the change in work function is greater for antimony than for arsenic. The pile-up of these species at the oxide interface during the nickel silicidation is demonstrated to be the physical mechanism responsible for the work function shift. Both species activations before silicidation and silicidation conditions were found to affect the NiSi work function shift significantly. The nonactivated species have minimum effect and incomplete silicidation can have maximum work function shift. The doping effect of indium on the NiSi work function is reported for the first time. A shift of /spl sim/0.14 eV toward the valence band was obtained for 2.6-nm oxide capacitors. It was found that the work function shift caused by the indium doping is saturated at a relatively low dose, which may be related to the low solid solubility of indium in polysilicon.