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The complex synthesis and solid state chemistry of ceria-lanthana solid solutions prepared via a hexamethylenetetramine precipitation

Mixed oxide solid solutions are becoming ever more commercially important across a range of applications. However, their synthesis can be problematical. Here, we show that ceria-lanthana solid solutions can be readily prepared via simple precipitation using hexamethylenetetramine. However, the solution chemistry can be complex, which results in the precipitated particles having a complex structure and morphology. Great care must be taken in both the synthesis and characterisation to quantify the complexity of the product. Even very high heat treatments were not able to produce highly homogeneous materials and X-ray diffractions reveals the non-equilibrium form of particles prepared in this way. Unexpected crystal structures are revealed including a new metastable cubic La{sub 2}O{sub 3} phase. - Graphical abstract: The suggested mechanism for the formation of dual fluorite phase particles, where Step 1 corresponds to room temperature aging, Step 2; heating the solution to 90 deg. C, Step 3; cooling of the solution to room temperature, Step 4; calcination to 500 deg. C, Step 5; calcination to 700 deg. C and Step 6; calcination to 1300 deg. C. The terminology of e.g. La{sub 1-x}Ce{sub x}(OH){sub 3} is used to indicate the formation of a mixed oxy-hydroxy participate rather than a definitive assignment of stoichiometry. Similarly, La{sub 1-y}Ce{sub y}O{sub 2} only implies a mixed solid solution. Highlights: > Mol% of prepared Ce-La oxides did not follow that of reactant mol%. > Complex reaction pathway found to be dependent on metal solution concentrations. > At certain concentrations core shell particles were found to form. > A reaction model was produced based on cationic solubility. > Report lanthana solubility higher than previously reported in CeO{sub 2}.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Synthesis of GaN:ZnO solid solution by solution combustion method and characterization for photocatalytic application

GaN-ZnO solid solution has emerged as a successful and reproducible photocatalyst for overall water splitting by one-step photoexcitation, with a bandgap in visible region. When the solid solution is formed, some of the Zn and O ions are replaced by Ga and N ions respectively and there is a narrowing of bandgap which is hypothesized as due to Zn3d-N2p repulsion. The traditional method of synthesis of GaN-ZnO solid solution is by nitridation of the starting oxides under constant ammonia flow. Here we report a solution combustion technique for the synthesis of the solid solution at a temperature about 500 ° C in a muffle furnace with metal nitrates as precursors and urea as the fuel. The as prepared samples showed change in color with the increased concentration of ZnO in the solution. The structural, microstructural, morphological and optical properties of the samples were realized by Powder X ray diffraction, Scanning electron microscopy, Energy dispersive X ray analysis, Transmission electron microscopy and Photoluminescence. Finally the hydrogen production efficiency of the GaN-ZnO nanopowders by water splitting was found, using methanol as a scavenger. The apparent quantum yield (AQY) of 0.048% is obtained for GaN-ZnO solid solution.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Synthesis, structure, and transport properties of Ba 8 Cu 16 – x Au x P 30 clathrate solid solution

In this work, a new clathrate solid solution Ba 8 Cu 16 – x Au x P 30 ( x = 4, 8, 12) was synthesized by a high-temperature solid-state annealing method. The crystal structures of Ba 8 Cu 16 – x Au x P 30 were determined by single crystal x-ray diffraction. This clathrate solid solution crystallizes in the orthorhombic superstructure of clathrate-I type with 23 crystallographically independent framework sites, eight of them are occupied by Au/Cu and 15 are exclusively occupied by P atoms. The distribution of Au and Cu atoms over these eight framework sites is not random with a clear preference for Au to occupy the largest (Au/Cu)P 4 tetrahedra in the framework. The thermal stability and thermoelectric properties of the Ba 8 Cu 16 – x Au x P 30 solid solution were evaluated. Low thermal conductivity was achieved for Ba 8 Cu 16 – x Au x P 30 due to the combination of the host–guest crystal structure with rattling Ba atoms with the presence of heavy Au atoms and substitutional Cu/Au disorder in the clathrate framework.

36 MATERIALS SCIENCE↗

A study of room-temperature Li x Mn 1.5 Ni 0.5 O 4 solid solutions

Understanding the kinetic implication of solid-solution vs. biphasic reaction pathways is critical for the development of advanced intercalation electrode materials. Yet this has been a long-standing challenge in materials science due to the elusive metastable nature of solid solution phases. The present study reports the synthesis, isolation, and characterization of room-temperature Li x Mn 1.5 Ni 0.5 O 4 solid solutions. In situ XRD studies performed on pristine and chemically-delithiated, micron-sized single crystals reveal the thermal behavior of Li x Mn 1.5 Ni 0.5 O 4 (0 ≤ x ≤ 1) cathode material consisting of three cubic phases: LiMn 1.5 Ni 0.5 O 4 (Phase I), Li 0.5 Mn 1.5 Ni 0.5 O 4 (Phase II) and Mn 1.5 Ni 0.5 O 4 (Phase III). A phase diagram capturing the structural changes as functions of both temperature and Li content was established. In conclusion, the work not only demonstrates the possibility of synthesizing alternative electrode materials that are metastable in nature, but also enables in-depth evaluation on the physical, electrochemical and kinetic properties of transient intermediate phases and their role in battery electrode performance.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Solid state synthesis, crystal growth and optical properties of urea and p-chloronitrobenzene solid solution

Urea is an attractive material for frequency conversion of high power lasers to UV (for wavelength down to 190 nm), but its usage is hindered due to its hygroscopic nature, though there is no alternative organic NLO crystal which could be transparent up to 190 nm. The hygroscopic character of urea has been modified by making the solid solution (UCNB) of urea (U) and p-chloronitrobenzene (CNB). The formation of the solid solution of CNB in U is explained on the basis of phase diagram, powder XRD, FTIR, elemental analysis and single crystal XRD studies. The solubility of U, CNB and UCNB in ethanol solution is evaluated at different temperatures. Transparent single crystals of UCNB are grown from its saturated solution in ethanol. Optical properties e.g., second harmonic generation (SHG), refractive index and the band gap for UCNB crystal were measured and their values were compared with the parent compounds. Besides modification in hygroscopic nature, UCNB has also shown the higher SHG signal and mechanical hardness in comparison to urea crystal. - Highlights: • The hygroscopic character of urea was modified by making the solid solution • Solid solution formation is support by elemental, powder- and single crystal XRD • Crystal of solid solution has higher SHG signal and mechanical stability. • Refractive index and band gap of solid solution crystal have determined.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Thermodynamics of copper‐manganese and copper‐iron spinel solid solutions

Abstract High‐temperature oxide melt solution calorimetry has been performed to investigate the energetics of spinel solid solutions in the Mn 3 O 4 ‐CuMn 2 O 4 and Fe 3 O 4 ‐CuFe 2 O 4 systems. The spinel solid solutions were synthesized by a ceramic route and calcined at appropriate temperatures to obtain single phase samples. The drop solution enthalpies of the solid solutions in the Mn 3 O 4 ‐CuMn 2 O 4 system are the same within experimental error as the enthalpies of drop solution of mechanical mixtures of the end‐members, indicating a zero heat of mixing, i.e., ideal mixing in terms of enthalpy. In Fe 3 O 4 ‐CuFe 2 O 4 , the drop solution enthalpy of the solid solutions shows a positive deviation from those of the mechanical mixture of the end‐members, suggesting negative mixing enthalpy. The formation enthalpies of the spinel solid solutions from their constituent oxides plus oxygen and from the elements were also determined.

Sahu, Sulata K.↗

Analysis of solid solutions stability in scheelite-type molybdates and tungstates

Mutual solubility of bivalent metal molybdates and tungstates with scheelite structure was theoretically estimated by calculating formation enthalpies and the maximal decomposition temperatures of solid solutions at different temperatures. The theoretical stability of continuous solid solutions in binary systems of bivalent metal molybdates and tungstates was found to be higher than reported literature data. After cooling down continuous substitution solid solution should remain in following systems: CaMoO{sub 4}-CdMoO{sub 4}, SrMoO{sub 4}-MMoO{sub 4} (M=Ba, Pb), BaMoO{sub 4}-PbMoO{sub 4}, SrWO{sub 4}-MWO{sub 4} (M=Ca, Pb), and BaWO{sub 4}-PbWO{sub 4}. There is a probability that at room temperature in systems CaMoO{sub 4}-SrMoO{sub 4,} CaWO{sub 4}-PbWO{sub 4}, and BaWO{sub 4}-SrWO{sub 4} the single homogeneity region may decompose to limited solid solutions. It was shown experimentally that a continuous series of scheelite-structure solid solutions M{sub 1-x}M{sup I}{sub x}TO{sub 4} can be formed via citrate synthesis at temperatures below 500 deg. S. - Graphical abstract: Calculated boundaries of solid solutions in BaWO{sub 4}-CaWO{sub 4} (1) and PbMoO{sub 4}-CaMoO{sub 4} (2) systems. Highlights: > Stability of solid solutions molybdates and tungstates has been investigated. > The ionic model for isovalent substitutions was used. > In 'polyhedral substitution model' enthalphies of mixing were calculated. > Most of the examined series of solid solutions is stable at room temperatures. > Solid solutions M{sub 1-x}M{sup I}{sub x}Mo(W)O{sub 4} (x=0-1) were formed via citrate synthesis below 500 S.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

The thermodynamic stability of intermediate solid solutions in LiFePO 4 nanoparticles

Theoretical predictions from first principles and recent advances in in situ electrochemical characterization techniques have confirmed the presence of solid-solution states during electrochemical (de)lithiation of LiFePO 4 nanoparticles. Surprisingly, however, such thermodynamically unfavorable solid solution states have been observed at rates as low as 0.1C. Given the high diffusivity of Li in LiFePO 4 and the thermodynamic instability of homogeneous solid solution states, spinodal decomposition to a thermodynamically favorable two-phase state is expected to occur on time scales as rapid as 1–100 ms. Here, we resolve this apparent paradox by demonstrating that, given the symmetry of the low-energy solid-solution Li/Va orderings and the 1D character of Li diffusion, spinodal decomposition from a solid solution preferentially leads to the formation of a diffuse ac interface with a large intermediate solid-solution region, as opposed to the commonly assumed bc interface. Our first principles predictions not only rationalize the persistence of solid-solution states at low-to-moderate C-rates in high-rate LiFePO 4 electrodes, but also explain the observations of large intermediate solid-solution regions at an ac interface in single Li x FePO 4 particles quenched from a high-temperature solid solution.

36 MATERIALS SCIENCE↗

A solid solution series of atacamite type Ni{sub 2x}Mg{sub 2−2x}Cl(OH){sub 3}

For the first time a complete solid solution series Ni{sub 2x}Mg{sub 2−2x}Cl(OH){sub 3} of an atacamite type alkaline main group metal chloride, Mg{sub 2}Cl(OH){sub 3}, and a transition group metal chloride, Ni{sub 2}Cl(OH){sub 3}, was prepared and characterized by chemical and thermal analysis as well as by Raman and IR spectroscopy, and high resolution laboratory X-ray powder diffraction. All members of the solid solution series crystallize in space group Pnam (62). The main building units of these crystal structures are distorted, edge-linked Ni/MgO{sub 4}Cl{sub 2} and Ni/MgO{sub 5}Cl octahedra. The distribution of Ni{sup 2+}- and Mg{sup 2+}-ions among these two metal-sites within the solid solution series is discussed in detail. The crystallization of the solid solution phases occurs via an intermediate solid solution series, (Ni/Mg)Cl{sub 2x}(OH){sub 2−2x}, with variable Cl: OH ratio up to the 1:3 ratio according to the formula Ni{sub 2x}Mg{sub 2−2x} Cl(OH){sub 3}. For one isolated intermediate solid solution member, Ni{sub 0.70}Mg{sub 0.30}Cl{sub 0.58}(OH){sub 1.42}, the formation and crystal structure is presented as well. - Graphical abstract: For the first time a complete solid solution series, Ni{sub 2x}Mg{sub 2−2x} Cl(OH){sub 3}, was synthesized and characterized. Structure solution by revealed that Ni{sup 2+} prefers to occupy the Jahn–Teller-like distorted hole, out of two available cation sites. Substitution of Ni{sup 2+} by Mg{sup 2+} in atacamite type Ni{sub 2}Cl(OH){sub 3} results in systematic band shifts in Raman and IR spectra as well as in systematic changes in thermal properties. The α-polymorphs M{sub 2}Cl(OH){sub 3} with M=Mg{sup 2+}, Ni{sup 2+} and other divalent transition metal ions, as described in literature, were identified as separate compounds. - Highlights: • First synthesis of solid solution series between main and transition metal chloride. • Ni{sup 2+} prefers to occupy Jahn–Teller-like distorted octahedral holes. • Substitution of Ni{sup 2+} by Mg{sup 2+} results in systematic Raman and IR band shifts. • α-Polymorphs M{sub 2}Cl(OH){sub 3} with M=Mg{sup 2+}, Ni{sup 2+}, … as described in literature do not exist.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

NaCu(Ta{sub 1-y}Nb{sub y}){sub 4}O{sub 11} solid solution: A tunable band gap spanning the visible-light wavelengths

The new solid-solution NaCu(Ta{sub 1-y}Nb{sub y}){sub 4}O{sub 11} (0{<=}y{<=}0.7) was synthesized by solid-state methods in the form of bulk powders that ranged from light-yellow to brown colored and were characterized by powder X-ray diffraction techniques (Space group R-3c (no. 167); Z=6; a=6.214(1)-6.218(1) Angstrom-Sign and c=36.86(1)-36.94(1) Angstrom-Sign ). Full-profile Rietveld refinements confirmed a site-differentiated ordering of the Cu(I) and Na cations, i.e., occupying the 12c (linear environment) and 18d (seven-coordinate environment) crystallographic sites respectively. Conversely, a statistical mixture of Ta(V) and Nb(V) cations occurred over the 6b (octahedral environment) or the 18e (pentagonal-bipyramidal environment) crystallographic sites, without any preferential segregation. The UV-Vis diffuse reflectance spectra showed a significant red-shift of the optical bandgap size (indirect) from {approx}2.70 eV to {approx}1.80 eV across the solid solution with increasing Nb(V) content. Electronic-structure calculations using the tight-binding linear-muffin-tin-orbital approach showed that the reduction in bandgap size arises from the introduction of the lower-energy Nb 4d{sup 0} orbitals into the conduction band and consequently a lower energy of the conduction band edge. The lowest-energy bandgap transitions were found to be derived from electronic transitions between the filled Cu(I) and the empty Nb(V) d-orbitals, with a small amount of mixing with the O 2p orbitals. The resulting conduction and valence band energies are found to approximately bracket the redox potentials for water reduction and oxidation, and meeting the thermodynamic requirements for photocatalytic water-splitting reactions. - Graphical Abstract: The NaCu(Ta{sub 1-y}Nb{sub y}){sub 4}O{sub 11} (0{<=}y{<=}0.7) solid solution shows a statistical occupancy of the Ta(V) and Nb(V) cations in both octahedral and pentagonal bipyramidal environments. An increasing Nb(V) content also causes a significant red-shift of the bandgap size from {approx}2.70 eV to {approx}1.80 eV. Highlights: Black-Right-Pointing-Pointer Double solid-solution of M(I) (=Cu, Na) and M(V) (=Nb, Ta) crystallographic sites. Black-Right-Pointing-Pointer Increasing Nb content leads to tunable bandgap size from {approx}2.70 eV to {approx}1.80 eV across the solid solution. Black-Right-Pointing-Pointer Layers of MO{sub 7} (M=Ta, Nb) pentagonal bipyramids and isolated MO{sub 6} octahedra.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Enhanced photocatalytic degradation of 2-propanol over macroporous GaN/ZnO solid solution prepared by a novel sol-gel method

Macroporous GaN/ZnO solid solution photocatalyst is synthesized through a novel sol-gel method under mild conditions. The performance of as-synthesized solid solution photocatalyst is evaluated for decomposition of gaseous 2-propanol (IPA). It is found that due to enhancement in both the adsorption to gaseous IPA and the absorbance to visible light, the porous GaN/ZnO solid solution exhibits a good photocatalytic performance for IPA decomposition. Moreover, the mechanism for photocatalytic degradation IPA over porous GaN/ZnO solid solution is also investigated in comparison with those for the two end materials ZnO and GaN. The trapping effects with different scavengers prove that both the photoexcited electrons and holes affect the IPA photodegradation process, simultaneously.

36 MATERIALS SCIENCE↗

Metal Structural Environment in Zn x Ni 1-x O Macroscale and Nanoscale Solid Solutions

The metal structural environments in macroscale and nanoscale Zn x Ni 1–x O solid solutions were examined using X-ray diffraction (XRD), X-ray absorption spectroscopy (XAS), and X-ray photoelectron spectroscopy (XPS). XRD demonstrates that solid solutions form for both macroscale (bulk) and nanoscale crystallites, and that the lattice parameter increases linearly as the amount of zinc increases, an indication of a homogeneous solid solution. XAS for both the bulk material and the nanoparticles reveals that the zinc atoms are incorporated into the rocksalt lattice and do not form zinc oxide clusters. The X-ray absorption near edge spectroscopy (XANES) of the Zn k-edge region in the solid solution is similar to the Ni k-edge region of NiO, and not the Zn k-edge region of ZnO. XPS confirms that solid solutions are formed; Auger parameters for zinc are consistent with a different geometry than the tetrahedral coordination of wurtzite ZnO. Nanoscaled solid solutions show evidence of a lattice contraction relative to macroscale solutions of the same concentration. While the contraction persists across the entire concentration range, the nanoparticle lattice parameter approaches the bulk Zn x Ni 1–x O value as the concentration of zinc increases to predict ZnO rocksalt lattice parameters that are in agreement with observed ZnO data.

Peck, Matthea A.↗

Thermodynamic non-ideality and disorder heterogeneity in actinide silicate solid solutions

Non-ideal thermodynamics of solid solutions can greatly impact materials degradation behavior. We have investigated an actinide silicate solid solution system (USiO 4 –ThSiO 4 ), demonstrating that thermodynamic non-ideality follows a distinctive, atomic-scale disordering process, which is usually considered as a random distribution. Neutron total scattering implemented by pair distribution function analysis confirmed a random distribution model for U and Th in first three coordination shells; however, a machine-learning algorithm suggested heterogeneous U and Th clusters at nanoscale (~2 nm). The local disorder and nanosized heterogeneous is an example of the non-ideality of mixing that has an electronic origin. Partial covalency from the U/Th 5f–O 2p hybridization promotes electron transfer during mixing and leads to local polyhedral distortions. The electronic origin accounts for the strong non-ideality in thermodynamic parameters that extends the stability field of the actinide silicates in nature and under typical nuclear waste repository conditions.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Multicomponent pyrochlore solid solutions with uranium incorporation – A new perspective of materials design for nuclear applications

Multicomponent pyrochlore solid solutions with and without uranium incorporation were fabricated and their thermal-mechanical properties were characterized. Multicomponent pyrochlore solid solutions without uranium exhibit comparable thermal conductivity and higher mechanical strength compared to baseline single component rare-earth titanate pyrochlore (A 2 Ti 2 O 7 ). Uranium incorporation reduces hardness as compared with single component compositions. High entropy pyrochlore with uranium displays the highest thermal conductivity within multicomponent pyrochlore solid solutions with significantly better mechanical properties than UO 2 . The measured thermal conductivity correlates well with A-site cation mixing entropy and a modified size disorder parameter, and thus the size disorder and mixing entropy could be good indicators for predicting thermal conductivity of multicomponent pyrochlore solid solutions. This work opens up the possibility of designing multicomponent oxide solid solutions by controlling their chemical disorder/mixing entropy to achieve acceptable thermal-mechanical properties, desired radiation and corrosion performance for potential nuclear waste form and inert matrix fuel applications.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Irradiation responses and defect behavior of single-phase concentrated solid solution alloys

Single-phase concentrated solid solution alloys (SP-CSAs) are newly emerging advanced structural materials, which are defined as multiprincipal element solid solutions. SP-CSAs with more than four components in equimolar or near-equimolar ratios are also referred to as high-entropy alloys due to their high configurational entropy. SP-CSAs are potential structural materials in advanced nuclear energy systems due to their attractive mechanical properties. Therefore many investigations have been carried out to study the irradiation-induced structural damage and defect behavior in SP-CSAs. This paper reviews recent experimental results on the irradiation responses of various SP-CSAs, focusing on the accumulation of irradiation-induced structural damage, void swelling resistance, and solute segregation behavior. In addition, the characteristic defect behavior in SP-CSAs derived from ab initio and molecular dynamics simulations, as well as the challenges in the applications of SP-CSAs for the nuclear energy systems are briefly discussed.

36 MATERIALS SCIENCE↗

Ion mobility and conductivity in the M{sub 0.5–x}Pb{sub x}Bi{sub 0.5}F{sub 2+x} (M=K, Rb) solid solutions with fluorite structure

Ionic mobility and conductivity in the K{sub 0.5–x}Pb{sub x}Bi{sub 0.5}F{sub 2+x} and Rb{sub 0.5–x}Pb{sub x}Bi{sub 0.5}F{sub 2+x} (x=0.05, 0.09) solid solutions with the fluorite structure have been investigated using the methods of {sup 19}F NMR, X-ray diffraction and impedance spectroscopy. Types of ionic motions in the fluoride sublattice of solid solutions have been established and temperature ranges of their realization have been determined (150–450 K). Diffusion of fluoride ions is a dominating type of ionic motions in the fluoride sublattice of solid solutions under study above 350 K. Due to high ionic conductivity, above 10{sup –3} S/cm at 450 K, these solid solutions can be used as solid electrolytes in various electrochemical devices and systems. - Graphical abstract: Temperature dependence of the concentration of mobile (2, 4) and immobile (1, 3) F ions in the K{sub 0.5–x}Pb{sub x}Bi{sub 0.5}F{sub 2+x} solid solutions. - Highlights: • Studied the ion mobility, conductivity in M{sub 0.5–x}Pb{sub x}Bi{sub 0.5}F{sub 2+x} solid solutions (M=K, Rb). • An analysis of {sup 19}F NMR spectra made it possible to identify types of ion mobility. • The main type of ion motion above 300 K in solid solutions is a diffusion of ions F{sup –}. • The ionic conductivity of the solid solutions studied more than 10{sup –3} S/cm at 450 K.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Local-environment dependence of stacking fault energies in concentrated solid-solution alloys

Concentrated solid-solution alloys (CSAs) based on 3d transition metals have demonstrated extraordinary mechanical properties and radiation resistance associated with their low stacking fault energies (SFEs). Owing to the intrinsic disorder, SFEs in CSAs exhibit distributions depending on local atomic configurations. In this work, the distribution of SFEs in equiatomic CSAs of NiCo, NiFe, and NiCoCr are investigated based on empirical potential and first-principles calculations. We show that the calculated distribution of SFEs in chemically disordered CSAs depends on the stacking fault area using empirical potential calculations. Based on electronic structure calculations, we find that local variations of SFEs in CSAs correlate with the charge density redistribution in the stacking fault region. We further propose a bond breaking and forming model to understand and predict the SFEs in CSAs based on the local structure alone. It is shown that the perturbation induced by a stacking fault is localized in the first-nearest planes for NiCo, but extends up to the third nearest planes for NiFe and NiCoCr because of partially filled d electrons in Fe and Cr.

36 MATERIALS SCIENCE↗