Synthesis, crystal structure and thermal behavior of Sr3B2SiO8 borosilicate

Single crystals of Sr₃B₂SiO₈ were obtained by solid-state reaction of stoichiometric mixture at 1200 °C. The crystal structure of the compound has been solved by direct methods and refined to R1=0.064 (wR=0.133). It is orthorhombic, Pnma, a=12.361(4), b=3.927(1), c=5.419(1) Å, V=263.05(11) Å³. The structure contains zigzag pseudo-chains running along the b axis and built up from corner sharing (Si,B)−O polyhedra. Boron and silicon are statistically distributed over one site with their coordination strongly disordered. Sr atoms are located between the chains providing three-dimensional linkage of the structure.The formation of Sr₃B₂SiO₈ has been studied using annealing series in air at 900-1200 °C. According powder XRD, the probe contains pure Sr₃B₂SiO₈ over 1100 °C. The compound is not stable below 900 °C. In the pseudobinary Sr₂B₂O₅-Sr₃B₂SiO₈ system a new series of solid solutions Sr_3−xB₂Si_1−xO_8−3x (x=0-0.9) have been crystallized from melt. The thermal behavior of Sr₃B₂SiO₈ was investigated using powder high-temperature X-ray diffraction (HTXRD) in the temperature range 20-900 °C. The anisotropic character of thermal expansion has been observed: α_a= −1.3, α_b=23.5, α_c=13.9, and α_V=36.1×10⁻⁶ °C⁻¹ (25 °C); α_a= −1.3, α_b=23.2, α_c=5.2, and α_V=27.1×10⁻⁶ °C⁻¹ (650 °C). Maximal thermal expansion of the structure along of the chain direction [0 1 0] is caused by the partial straightening of chain zigzag. Hinge mechanism of thermal expansion is discussed.     

Structure and phase composition of nanocrystalline Ce1−xLuxO2−y

The microstructure and phase stability of nanocrystalline mixed oxide Lu_xCe_1−xO_2−y (x=0-1) are described. Nano-sized (3-4 nm) oxide particles were prepared by the reverse microemulsion method. Morphological and structural changes upon heat treatment in an oxidizing atmosphere were studied by transmission electron microscopy (TEM), X-ray diffraction (XRD), Raman and Yb³⁺ emission spectroscopy, the latter ion being present as an impurity in the Lu₂O₃ starting material. Up to 950 °C, the samples were single phase, with structure changing smoothly with Lu content from fluorite type (F) to bixbyite type (C). For the samples heated at 1100 °C phase separation into coexisting F- and C-type structures was observed for 0.35<x<0.7. It was also found that addition of Lu strongly hinders the crystallite growth of ceria during heat treatment at 800 and 950 °C.     

Preparation, crystal structure and thermal expansion of a new bismuth barium borate, BaBi2B4O10

Single crystals of a new compound, BaBi₂B₄O₁₀ were grown by cooling a melt with the stoichiometric composition. The crystal structure of the compound has been solved by direct methods and refined to R₁=0.049 (wR=0.113) on the basis of 1813 unique observed reflections (|F_o|>4σ|F_o|). It is monoclinic, space group P2₁/c, a=10.150(2), b=6. 362(1), c=12.485(2) Å, β=102.87(1)^o, V=786.0(2) Å³, Z=4. The structure is based upon anionic thick layers that are parallel to (001). The layers can be described as built from alternating novel borate [B₄O₁₀]⁸⁻_∞ chains and bismuthate [Bi₂O₅]⁴⁻_∞ chains extended along b-axis. The borate chains are composed of [B₃O₈]⁷⁻ triborate groups of three tetrahedra and single triangles with a [BO₂]⁻ radical. The borate chains are interleaved along the c-axis with rows of the Ba²⁺ cations so that the Ba atoms are located within the layers. The layers are connected by two nonequivalent Ba-O bonds as well as by two equivalent Bi-O bonds with bond valences in the range of 0.2-0.3 v.u.Thermal expansion of BaBi₂B₄O₁₀ studied by high-temperature X-ray powder diffraction in the temperature range of 20-700 °C (temperature step 30-35 °C) is highly anisotropic. While the b and c unit-cell parameters increase almost linearly on heating, temperature dependencies of a parameter and β monoclinic angle show nonlinear behavior. As a result, on heating orientation of thermal expansion tensor changes, and bulk thermal expansion increases from 20×10⁻⁶ °C⁻¹ at the first heating stage up to 57×10⁻⁶ °C⁻¹ at 700 °C that can be attributed to the increase of thermal mobility of heavy Bi³⁺ and Ba²⁺ cations.     

Thermal behaviour and fragility of Sb<Subscript>2</Subscript>O<Subscript>3</Subscript>-containing zinc borophosphate glasses

Thermal behaviour of the glass series (100-x)[50ZnO-10B₂O₃-40P₂O₅]·xSb₂O₃ (x=0-42 mol%) and (100-y)[60ZnO-10B₂O₃-30P₂O₅]·ySb₂O₃ (y=0-28 mol%) was investigated by DSC and TMA. The addition of Sb₂O₃ results in a decrease of the glass transition temperature and crystallization temperature in both compositional series. All glasses crystallize on heating in the temperature range of 522–632°C. Thermal expansion coefficient of the glasses monotonously increases with increasing Sb₂O₃ content in both series and varies within the range of 6.6–11.7 ppm °C⁻¹. From changes of thermal capacity within the glass transition region it was concluded that with increasing Sb₂O₃ content the ‘fragility’ of the studied glasses increases.     

LiB3O5 crystal structure at 20, 227 and 377 °C

Crystal structure of LiB₃O₅ (a framework of [B₃O₅]⁻ rings and Li atoms located in interspaces) was refined at high temperatures using single-crystal X-ray diffraction, MoKα-radiation, anharmonic approximation, orthorhombic; Pna2₁; Z=4; 20 °C (a=8.444, b=7.378, c=5.146 Å, 1411 F(hkl), R=0.022); 227 °C (a=8.616, b=7.433, c=5.063 Å, 1336 F(hkl), R=0.026), 377 °C (a=8.746, b=7.480, c=5.013 Å, 1193 F(hkl), R=0.035). A high mobility of Li atoms and their highly asymmetric vibrations are revealed. Ellipsoid of Li thermal vibrations is oviform. Li is shifted on heating to 0.26 Å mainly along a-axis causing high thermal expansion in this direction; Li temperature factors are multiplied by 4 on heating. Rigid boron-oxygen groups in LiB₃O₅ remain practically stable on heating similar to α-Na₂B₈O₁₃ and α-CsB₅O₈. At the same time these groups rotate relative to each other like hinges leading to extremely anisotropic thermal expansion (α_a=101, α_b=31, α_c=−71, α_v=60×10⁻⁶ °C⁻¹, 20-530 °C, HTXRPD data).     

Thermal analysis and calorimetry in the study of materials and processes for fundamental sciences and various applications in Central and Eastern Europe

We investigated the influence of B substitution for Al₂W₃O₁₂ on thermal changes of UV–Vis and Raman spectra, and colors. First, B-substituted Al₂W₃O₁₂ powder was synthesized by a solid-state reaction method. Single-phase Al_2?xB_xW₃O₁₂ powders with x = 0, 0.10 and 0.20 were successively prepared. B substitution promoted thermal changes of the UV–Vis spectra, resulting in a more pronounced color change of Al₂W₃O₁₂ in the range of 30–150 °C. Raman spectra of the Al_2?xB_xW₃O₁₂ powders with x = 0 and 0.20 indicated that the lattice vibrations of Al_2?xB_xW₃O₁₂ with x = 0.20 were larger than those of Al₂W₃O₁₂. The thermal change of the color phase (ΔE) in the range 30–150 °C of Al₂W₃O₁₂ was increased by B substitution. The color of the B-substituted Al₂W₃O₁₂ powders changed reversibly from pale white at 30 °C to light yellowish green at 150 °C.     

The effect of ball-milling on the thermal behavior of anatase-doped hematite ceramic system

High energy ball-milling methods were employed in the synthesis of anatase-doped hematite xTiO₂(a) · (1−x)α-Fe₂O₃ (x = 0.1, 0.5, and 0.9) ceramic system. The thermal behavior of as obtained ceramic system was characterized by simultaneous DSC–TG. The pure anatase phase was found to be stable below 800 °C, but there is a 10.36% mass loss due to the water content. Two exothermic peaks on DSC curves of pure anatase indicate the different crystallization rates. The pure hematite partially decomposed upon heating under argon atmosphere. Ball-milling has a strong effect on the thermal behaviors of both anatase and hematite phases. For x = 0.1 and 0.5, there is gradual Ti substitution of Fe in hematite lattice, and the decomposition of hematite is enhanced due to the smaller particle size after ball-milling. The crystallization of hematite was suppressed as the enthalpy values decreased due to the anatase-hematite solid–solid interaction. For x = 0.9, most of the anatase phase converted to rutile phase after long milling time. The thermal behavior of xTiO₂(a) · (1−x)α-Fe₂O₃ showed smaller enthalpy value of the hematite transformation to magnetite and anatase crystallization due to the small fraction of hematite phase in the system and hematite–anatase interaction, while the mass loss upon heating increased as a function of milling time due to more water content absorbed by the smaller particle size.     

Thermal investigation by simultaneous TG/DTG-DTA and IR spectroscopy of new lanthanide complexes with salicylhydroxamic acid

Summary The reaction of a hydrated nitrate salt of lanthanide (Ln=Pr, Nd, Gd, Dy, Er) with the polyfunctional ligand salicylhydroxamic acid (H₃sha), in the presence of base, afforded solid compounds, insoluble in common organic solvents and in water. The new complexes characterized by means of elemental analyses (C, H, N, Ln), magnetic moment determinations and spectroscopic data (IR, MS). It is proposed that they are neutral, with a possible polymeric structure of the general type: [Ln₂(Hsha)₂(H₂sha)(DMF)_x(CH₃O)(H₂O)]_n×2H₂O Their thermal decomposition was studied in nitrogen and/or oxygen atmosphere, between 25-1000°C by using simultaneous TG/DTG-DTA technique. The IR spectroscopy used to determine the intermediates and the final products. The intermediates at 180°C suggest the formation of N-hydroxylactam complex, which upon further heating gives a carbonaceous residue of Ln₂O₃ at 1000°C in nitrogen, while in oxygen the stable oxides are formed at 600°C.     

La3TaO7 derivatives with Weberite structure type: Possible electrolytes for solid oxide fuel cells and high temperature electrolysers

In this study, with the aim to enhance the ionic conduction of known structures by defect chemistry, the La₂O₃-Ta₂O₅ system was considered with a focus on the La₃TaO₇ phase whose structure is of Weberite type. In order to predict possible preferential substitution sites and substitution elements, atomistic simulation was used as a first approach. A solid solution La_3−xSr_xTaO_7−x/2 was confirmed by X-ray diffraction and Raman spectroscopy; it extends for a substitution ratio up to x = 0.15. Whereas La₃TaO₇ is a poor oxide ion conductor (σ_700 °C = 2 × 10⁻⁵S.cm⁻¹), at 700 °C, its ionic conductivity is increased by more than one order of magnitude when 3.3% molar strontium is introduced in the structure (σ_700 °C = 2 × 10⁻⁴S.cm⁻¹).     

Formation, sintering, and electrical conductivity of perovskite Sm(Cr1−xMgx)O3 (0?x?0.23) prepared by the hydrazine method

The presence of SmCrO₄ is experimentally established. In Mg²⁺-substituted SmCrO₃, single-phase perovskite Sm(Cr_1−xMg_x)O₃, where x=0-0.23, are formed at ∼830°C by decomposition of Sm(Cr_1−xMg_x)O₄ which crystallizes at 530-570°C from amorphous materials prepared by the hydrazine method. Sm(Cr_1−xMg_x)O₃ solid solution powders consisting of submicrometer-size particles are sinterable; dense materials can be fabricated by sintering for 2 h at 1700°C in air. The relative densities, grain sizes, and electrical conductivities increase with increased Mg²⁺ content. Sm(Cr_0.77Mg_0.23)O₃ materials exhibit an excellent direct current electrical conductivity of 2.2×10³ S m⁻¹ at 1000°C.     

Stability and oxygen-storage characteristics of Al-substituted YBaCo4O7+δ

A series of Al-substituted YBa(Co_1−xAl_x)₄O_7+δ samples was synthesized and characterized with respect to the capability to store large amounts of oxygen at low temperatures (at 200-400 °C) and the phase decomposition upon heating under oxidizing conditions at higher temperatures (above 550 °C). It was revealed that increasing the Al-substitution level up to x≈0.10 boosts up the phase-decomposition temperature from ∼550 to ∼700 °C, while the unique oxygen absorption/desorption characteristics remain nearly the same as those of the pristine YBaCo₄O_7+δ phase. The maximum amount of excess oxygen absorbed by the Al-substituted YBa(Co_1−xAl_x)₄O_7+δ samples was determined to be as large as δ≈1.45 for x=0.10 (in 100 atm O₂ at 320 °C). Isothermal annealing experiments carried out for the same x=0.10 phase at 300 °C revealed that it could be reversibly charged and discharged with 1.2 oxygen atoms per formula unit by switching the gas flow from N₂ to O₂ and vice versa.     

Structural investigation in the TiB2-(Na2O·B2O3·Al2O3) system

Composites in the TiB₂-Na₂O·B₂O₃·Al₂O₃ systems, TiB₂-MBA (MB stands for sodium metaborate and A is Al₂O₃), were prepared by self-propagating high-temperature synthesis (SHS), in simultaneous mode. Selection of these compositions was ruled by the interesting properties of both TiB₂ and double borates of alkali metal and aluminum. The structure of the obtained materials was evaluated by micro-Raman spectroscopy, from room temperature up to 600 °C, and X-ray photoelectron spectroscopy (XPS). Formation of the TiB₂ and TiO_2−xB_x phases along with TiO₂ as rutile were identified as titanium speciation in the grain phase embedded in a sodium aluminum borate matrix. Integration of the Raman spectra of the grain phases revealed a TiB₂ content of 16.99% and 23.32% for the two composite investigated 2TiB₂·2MBA and 3TiB₂·5MBA. A constrained-width model for the spectral deconvolution of the high-frequency Raman band was forwarded to calculate the proportion of tetrahedral boron atoms (7.424%) in the blank borate matrix Na₂B₂O₄·Al₂O₃ in solid phase.     

Sol-gel synthesis and characterization of LiNO3-Al2O3 composite solid electrolyte

Composite solid electrolytes in the system (1 − x)LiNO₃-xAl₂O₃, with x = 0.0-0.5 were synthesized by sol-gel method. The synthesis carried out at low temperature resulted in voluminous and fluffy products. The obtained materials were characterized by X-ray diffraction, differential scanning calorimetry, scanning electron microscopy/energy dispersive X-ray, Fourier transform infrared spectroscopy and AC impedance spectroscopy. Structural analysis of the samples showed base centred cell type of point lattice of LiNO₃ for the composite samples with x = 0.1-0.2 and body centred cell for the sample with x = 0.3. A trace amount of α-LiAlO₂ crystal phase was also present in these composite samples. The thermal analysis showed that the samples were in a stable phase between 48 °C and 230-260 °C. Morphological analysis indicated the presence of amorphous phase and particles with sizes ranging from micro to nanometre scale for the composite sample with x = 0.1. The conductivities of the composites were in the order of 10⁻³ and 10⁻² S cm⁻¹ at room temperature and 150 °C, respectively.     

Approach to thermal properties and electronic polarizability from average single bond strength in ZnOBi2O3B2O3 glasses

The glass transition temperature (T_g), density, refractive index, Raman scattering spectra, and X-ray photoelectron spectra (XPS) for xZnO-yBi₂O₃-zB₂O₃ glasses (x=10-65, y=10-50, z=25-60 mol%) are measured to clarify the bonding and structure features of the glasses with large amounts of ZnO. The average electronic polarizability of oxide ions (α_O2−) and optical basicity (Λ) of the glasses estimated using Lorentz-Lorenz equation increase with increasing ZnO or Bi₂O₃ content, giving the values of α_O2−=1.963 Å³ and Λ=0.819 for 60ZnO-10Bi₂O₃-30B₂O₃ glass. The formation of BOBi and BOZn bridging bonds in the glass structure is suggested from Raman and XPS spectra. The average single bond strength (B_MO) proposed by Dimitrov and Komatsu is applied to the glasses and is calculated using single bond strengths of 150.6 kJ/mol for ZnO bonds in ZnO₄ groups, 102.5 kJ/mol for BiO bonds in BiO₆ groups, 498 kJ/mol for BO bonds in BO₃ groups, and 373 kJ/mol for BO bonds in BO₄ groups. Good correlations are observed between T_g and B_MO, Λ and B_MO, and T_g and Λ, proposing that the average single bond strength is a good parameter for understanding thermal and optical properties of ZnOBi₂O₃B₂O₃ glasses.     

Structural characterization and catalytic properties of bis(1,1,3,3-tetramethylguanidinium) dichromate

The structure of bis(1,1,3,3-tetramethylguanidinium) dichromate was determined from powder X-ray diffraction data. The compound crystallizes in the monoclinic system (space group P2₁/n) with a = 10.79714 (15) Å, b = 11.75844 (16) Å, c = 8.15097 (11) Å, β = 109.5248 (6)°. The structure consists of dichromate anions (Cr₂O₇²⁻) stabilized by tetramethylguanidinium cations ([H₂NC(N(CH₃)₂)₂]⁺ or [TMGH]⁺). Phase transitions of [TMGH]₂Cr₂O₇ were determined by differential scanning calorimetry, thermal gravimetric analysis and in situ Raman spectroscopy, where the decomposition of the matrix into CrO_x was found at 171-172 °C. Further heat treatment to above 400 °C resulted in formation of the thermodynamically stable Cr₂O₃, most likely with the [TMGH]⁺ cation as reductant. The catalytic activity of [TMGH]₂Cr₂O₇ supported on TiO₂ anatase in the selective catalytic reduction (SCR) of nitrogen oxide was also investigated, however only moderate activity was observed in the temperature range 100-400 °C compared to the activity of e.g., vanadia supported on titania.     

Investigation of Ba fully occupied A-site BaCo0.7Fe0.3−xNbxO3−δ perovskite stabilized by low concentration of Nb for oxygen permeation membrane

BaCo_0.7Fe_0.3−xNb_xO_3−δ (BCFN, x = 0–0.2) were prepared by the conventional solid state reaction process. The crystal structure, electrical conductivity and oxygen desorption property were studied by X-ray diffraction (XRD), different thermal analysis (DTA), four-terminal direct current conductivity and oxygen temperature programmed desorption (O₂-TPD), respectively. At x = 0.08–0.20, BCFN have a cubic perovskite structure, while it exhibits the hexagonal structure for x = 0.00 and the mixed phases of cubic perovskite with trace amount of hexagonal for x = 0.05. BCFN shows good structure stability in 5%H₂ + Ar reducing atmosphere, and it is enhanced with the increased Nb-doping content. The electrical conductivity of BCFN increases with increasing temperature and decreases with the Nb substitution content for iron. BCFN exhibits a p-type semiconductor and obeys the thermally activated small polarons hopping mechanism. The oxygen fluxes increase with the working temperature and the COG flow rate, but decrease with increasing Nb content. The flux of BCFN (x = 0.08) with 1.0 mm thickness membrane reaches 25.77 ml min⁻¹ cm⁻² at 875 °C, higher than most of the reported materials.     

Thermal Conversion of Gels Prepared by the Complex Sol-Gel Process (CSGP) from Li+-Me2+-CH3COO−-Ascorbic Acid (ASC)-NH4 +-OH−-H2O Systems to LiMn2O4 and LiNi x Co1 − x O2

The spinel LiMn₂O₄ and layered oxides LiNi _x Co_{1 – x} O₂ (x = 1; 0.75; 0) have been prepared by Complex Sol-gel Process (CSGP). The appropriate sol compositions were obtained from acetate aqueous solution of metals containing ascorbic acid by alkalizing it with aqueous ammonia. Gels were produced from the systems by evaporation of water and other volatilies at elevated temperatures. A very intense foaming was observed during the heating at the temperatures higher than 140°C. To avoid foaming in the course of the final thermal treatment, a very long (lasting several days) soaking step was found necessary. However pretreated materials exhibit self-ignition at temperature range 320–500°C dependent on socking conditions. The dependence of self-ignition temperature on carbon content in bed as well as on specific surface has not been proved. Final thermal transformation of gel to solid was studied by TG, DTA, XRD, and IR methods. It was observed that final compounds are formed faster from precursors which did not contain Ni (e.g. LiMn₂O₄ and LiCoO₂), while Li carbonate is not formed in these systems. In contrast, in Li-Ni(Co)-O the formation of Li(or Ni)CO₃ was always proved. In addition, during the thermal treatment Ni species are partially reduced even to metallic phase. This effect evidently restrains the formation of pure layered oxides phase. Electrochemical properties of carbonate free compounds are definitely better than of those containing CO₃.     

Structural and conductivity studies of Y10−xLaxW2O21

The aim of this work was to determine structural parameters of the Y_10−xLa_xW₂O₂₁ (x=0-10) solid solution series and investigate their electric properties. Crystallographic data shows a gradual increase in symmetry with increasing La content, as the structure evolves from orthorhombic, Y₁₀W₂O₂₁, towards the pseudo-cubic structure of Y₅La₅W₂O₂₁. The solubility limit of La₂O₃ was found to be 50% (x=5). Above this level two phases were observed, La₆W₂O₁₅ and (La,Y)_10+xW_2−xO_21−δ. The conductivity of Y rich samples was very low, with σ of the order 2×10⁻⁵-5×10⁻⁵ S cm⁻¹ at 1000 °C, whilst ionic conductivity was observed for most La rich doped samples. The highest conductivity was observed for La₁₀W₂O₂₁ and its doped analogues, at 1×10⁻³-5×10⁻³ S cm⁻¹ at 1000 °C. Unit cell parameters were determined as a function of temperature from 0 to 1000°C, and thermal expansion of these materials was determined from temperature studies carried out at the Australian Synchrotron facility in Melbourne, Victoria, Australia.     

Crystal growth, crystal structure of new polymorphic modification, β-Bi2B8O15 and thermal expansion of α-Bi2B8O15

Single crystals of α- and β-polymorphs of Bi₂B₈O₁₅ were grown by Czochralski method from a charge of the stoichiometric composition. The crystal structure of β-Bi₂B₈O₁₅ was solved by direct methods from a twinned crystal and refined to R1=0.081 (wR=0.198) on the basis of 1584 unique observed reflections (I>2σ(I)). The compound is triclinic, space group , a=4.3159(8), b=6. 4604(12), c=22.485(4) Å, α=87.094(15)°, β=86.538(15)°, γ=74.420(14)°, V=602.40(19) Å³, Z=2. The B-O layered anion of β-Bi₂B₈O₁₅ is topologically identical to the anion of α-Bi₂B₈O₁₅ but the orientation of neighboring layers is different. Thermal expansion of α-Bi₂B₈O₁₅ has been investigated by X-ray powder diffraction in air in temperature range from 20 to 700 °C. It is strongly anisotropic, which can be explained by the hinge mechanism applied to chains of Bi-O polyhedra. While the anisotropy of thermal expansion is rather high, the volume thermal expansion coefficient α_V=40×10⁶ °C⁻¹ for α-Bi₂B₈O₁₅ is close to those of other bismuth borates.     

X-ray powder diffraction studies and thermal behaviour of NaK2B9O15, Na(Na.17K.83)2B9O15, and (Na.80K.20)K2B9O15

The crystal structures of NaK₂B₉O₁₅ (, , , β=94.080(1)°, R_p=0.047, R_wp=0.059, R_B=0.026), Na(Na_.17K_.83)₂B₉O₁₅ (, , , β=94.228(2)°, R_p=0.053, R_wp=0.068, R_B=0.026), and (Na_.80K_.20)K₂B₉O₁₅ (, , , β=94.071(1)°, Z=4, R_p=0.041, R_wp=0.052, R_B=0.023) were refined in the monoclinic space groups P2₁/c(Z=4) using X-ray powder diffraction data and the Rietveld method. These nonaborates are isostructural to K₃B₉O₁₅. Their crystal structure consists of a three-dimensional open framework built up from three crystallographically independent triborate groups. The alkali metal cations are located on three different sites in the voids of the framework. High-temperature X-ray diffraction studies show that NaK₂B₉O₁₅ decomposes at about 700 °C in accordance with the peritectic reaction NaK₂B₉O₁₅↔K₅B₁₉O₃₁+liquid. The thermal expansion of NaK₂B₉O₁₅ and Na(Na_.17K_.83)₂B₉O₁₅ is highly anisotropic. A similarity of the thermal and compositional (Na-K substitution) deformations of NaK₂B₉O₁₅ is revealed: heating of NaK₂B₉O₁₅ by 1 °C leads to the same deformations of the crystal structure as increasing the amount of K atoms in (Na_1−xK_x)₃B₉O₁₅ by 0.04 at% K.