Targeted Ni 2+ doping shifts the Co 3− x Ni x B 2 O 6 –Co 3− x Ni x BO 5 phase boundary and enables reversible switching at Co 3 B 2 O 6 –Co 3− x Ni x BO 5 –Ni 3 B 2 O 6 triple point at x = 1. The precise synthesis control and redox management in cobalt materials are demonstrated.

Cobalt-containing borates are emerging as multifunctional materials for optical devices, Li-ion and Na-ion battery anodes, and rare-earth-free permanent magnets. In particular, the phases Co2B2O5, Co3B2O6 and Co3BO5 - which incorporate Co2+ and Co3+ centers - can all be crystallized from closely related Bi2O3-MoO3-Na2O-B2O3 fluxes with only minimum compositional adjustments. In this study, we elucidate (1) high-temperature crystallization pathways in these multicomponent flux systems and (2) factors that stabilize Co in oxidation states +2 versus +3. By systematically varying the Na2O/MoO3/B2O3 ratio, we tune relative populations of Co2+- and Co3+-bearing species in the flux. We monitor the competitive formation of intermediate phases - Na2MoO4, CoMoO4, Na2B4O7 and putative NaCoO2 - and show how these intermediates direct the ultimate borate phase. Moreover, by incrementally introducing NiO into the flux, we estimate solid solutions of the kotoite type (Co3-xNixB2O6) and ludwigite type (Co3-xNixBO5) and map their phase boundary in unprecedented detail. This compositional "switch" controls whether Co3+-rich borates are formed. We report the first synthesis of Co3-xNixB2O6 solid solutions within the range of 0 < x < 1, which has not been previously explored, revealing a magnetic ordering transition near 35 K. Crystals of Co2B2O5 (pyroborate) and Co3-xNixBO5 ludwigites have also been grown. Comprehensive structural refinements and magnetic measurements of all the phases are presented to substantiate our mechanistic insights.

The cubic Fe2-xMnxO3 is an intriguing material that has recently been investigated for various applications, including lithium-ion battery anodes, catalysts, energy storage media, humidity sensors, and photocatalysts. Despite its wide range of promising applications, the magnetic properties of Fe2-xMnxO3 remain controversial, with different sources reporting conflicting information regarding the type of magnetic ordering, phase transition temperature, and magnetic moment of this compound. This work presents a study of the magnetic state of three Fe2-xMnxO3:Ga solid solutions with varying Mn:Fe:Ga ratios, along with one gallium-free Fe2-xMnxO3 reference sample. We performed a detailed analysis of the actual chemical composition and crystal structure of the synthesized samples using energy-dispersive X-ray spectroscopy (EDX), powder X-ray diffraction (XRD), and X-ray absorption spectroscopy (XAS) to evaluate compositional differences. The magnetic states of the three Fe2-xMnxO3:Ga samples and the gallium-free Fe2-xMnxO3 were investigated using magnetometry and Mossbauer spectroscopy. The low-temperature magnetic anomalies were found to be more consistent with spin-glass-like freezing than with conventional long-range antiferromagnetic ordering. Although variations in magnetic behavior were observed and found to depend on composition and the cooling rate during synthesis, our results demonstrate that these factors do not account for the drastically different magnetic properties reported for similar bixbyite-type oxides. Instead, the apparent room-temperature ferrimagnetism observed in one sample is most likely extrinsic and can be attributed to a trace spinel-type impurity phase, as supported by magnetizations and ESR measurements. Thus, the origin of these discrepancies lies primarily in the chemical purity of the samples and, to a significant extent, in the synthesis technique employed.

Single and polycrystalline samples of Mg2 – xMn1 + xBO5 (x = 0.0, 0.2, 0.4) oxyborates have been obtained for the first time by spontaneous crystallization from the solution–melt and through a solid-state reaction. X-ray diffraction studies have shown that compounds are crystallized with increasing manganese content in the ludwigite (space group Pbam)–hulsite (space group P2/m)–orthopinakiolite (space group Pbam) series and belong to the “3 Å wallpaper” borate family. A common property of materials is the presence of octahedral complexes (walls) consisting of manganese ions with a mixed valence at even crystallographic sites. The dc magnetization and specific heat of the Mg2 – xMn1 + xBO5 (x = 0.0, 0.2, 0.4) compounds have been studied for the first time. These studies have shown that cooling is accompanied by magnetic transitions, which are due to the ordering of several magnetic subsystems.

Copper oxyborate single crystals with a ludwigite structure, Cu 2 MBO 5 (M = Cr, Fe, Mn), containing different substitutes in the trivalent subsystem have been grown from Bi 2 O 3 –MoO 3 –Na 2 O–B 2 O 3 fluxes. The structural properties of grown compounds have been compared in detail using X-ray diffraction and Raman spectroscopy methods. In addition, these methods have been used to determine the degree of cationic ordering in these ludwigites. The temperature and field dependences of the Cu 2 MBO 5 (M = Cr, Fe, Mn) ludwigite magnetization are presented.

To study the dependence of the properties of ternary oxides (Mn,Fe,Ga) 2 O 3 with the bixbyite structure on the composition, the temperature dependences of the magnetization and ac magnetic susceptibility of two single-crystal samples of different compositions obtained using the flux method were analyzed. A detailed study of the structure was carried out using single-crystal X-ray diffraction analysis, and the changes in structural parameters depending on the composition were analyzed. The dc magnetization and ac magnetic susceptibility of Fe 1.1 Mn 0.76 Ga 0.14 O 3 and Fe 0.65 Mn 1.1 Ga 0.26 O 3 bixbyites have been studied. Despite the qualitatively similar behavior of the magnetic properties, significant differences were also found, despite a small difference in the Mn/Fe/Ga ratio in the samples under study. It is shown that both compounds experience two successive low-temperature magnetic phase transitions from the paramagnetic phase at T=20-32 K as the temperature is lowered. Calculations of the Mydosh parameter for the detected phase transitions showed different degrees of ordering in the compounds under study. Keywords: transition metal oxides, magnetic phase transitions, spin glass state, bixbyite.

The effects related to the conversion of magnetic structures of a Cu2MnBO5 ferrimagnet to a Cu2GaBO5 antiferromagnet under the Mn3+→Ga3+ substitution were studied. The properties of four single crystal samples with the gallium concentration x = 0.04, 0.11, 0.17, 0.25 were examined. The chemical composition and valence state of the samples were determined by X-ray absorption spectroscopy element-sensitive technique. Distribution of the 3d metal ions over crystallographic positions was studied using the first principal calculations by Wien2k program. The evolution of the magnetic properties was investigated by the measurements of the temperature and field dependences of magnetization, dc and ac magnetic susceptibility. In agreement with the previous study of the structure evolution of Cu2Mn1-xGaxBO5 solid solutions, the critical concentration upon a change in the magnetic ordering type was found in the range x = 0.17÷0.25. The non-monotonic behavior of magnetization in terms of the gallium content was found in the concentration range of 0.04÷0.17. A complex pattern of magnetic phase transitions belonging to the concentration phase boundary was obtained in the compounds with gallium being within the range x = 0.17÷0.25. One could observe the splitting of the peaks of the real part of ac-susceptibility of the high-temperature phase transition in the Cu2MnBO5-like phase (x = 0.04, 0.11) and that of the low-temperature one at the concentration boundary (x = 0.17, 0.25) with different frequency and orientational dependence. The type and origin of the multiple phase transitions observed in the studied samples were analyzed.

The influence of Bi 2 O 3 –MoO 3 –B 2 O 3 –Na 2 O flux components on the crystallization of the triple oxides (Mn,Fe,Ga) 2 O 3 is studied. 9 single crystal samples of bixbyite, spinel and orthorhombic phase are obtained and characterized.

To study the dependence of the properties of ternary oxides (Mn,Fe,Ga)2O3 with the bixbyite structure on the composition, the temperature dependences of the magnetization and ac magnetic susceptibility of two single-crystal samples of different compositions obtained using the flux method were analyzed. A detailed study of the structure was carried out using single-crystal X-ray diffraction analysis, and the changes in structural parameters depending on the composition were analyzed. The dc magnetization and ac magnetic susceptibility of Fe1.1Mn0.76Ga0.14O3 and Fe0.65Mn1.1Ga0.26O3 bixbyites have been studied. Despite the qualitatively similar behavior of the magnetic properties, significant differences were also found, despite a small difference in the Mn/Fe/Ga ratio in the samples under study. It is shown that both compounds experience two successive low-temperature magnetic phase transitions from the paramagnetic phase at T = 20–32 K as the temperature is lowered. Calculations of the Mydosh parameter for the detected phase transitions showed different degrees of ordering in the compounds under study.

The Cu2MnBO5/Cu2GaBO5 phase boundary was found in grown Cu2Mn1−xGaxBO5 ludwigites at x = 0.15–0.175 using X-ray and vibrational spectroscopy techniques. The polarized Raman spectra of the monoclinic ludwigites were obtained and analyzed for the first time.

To study the gradual change of the structure and the magnetic state of the ludwigite Cu2GaBO5 upon Mn3+ doping, single crystals of Cu2Ga1-xMnxBO5 (x = 0.55, 0.7, 0.8) with the size up to 3 x 3 x 10 mm(3) were grown using the flux technique. The phase homogeneity and crystal structure of the obtained compounds were investigated by the powder and single crystal X-ray diffraction. All the samples possessed the monoclinic distorted ludwigite structure with the P2(1)/c space group. The study of the actual Cu/Ga/Mn composition by the EDX (energy-dispersive X-ray spectroscopy) technique revealed the lower Mn content in all the samples and the refined formulas were Cu2Ga0.47Mn0.53BO5 , Cu1.92Ga0.5Mn0.58BO5 and Cu2Ga0.32Mn0.68BO5 , respectively. Despite the high manganese content, the concentration transition (from Cu2GaBO5 to Cu2MnBO5) and change of the monoclinic angle did not occur, but strong Me-O octahedra distortions exceeding those both in the parent ludwigites Cu2GaBO5 and Cu2MnBO5 were found. The study of the thermodynamic and magnetic properties revealed the low-temperature magnetic phase transition inherited from the parent Cu2GaBO5 in all the samples. However, the nature and ordering type for the compounds with different Mn content were different: there was a complex transformation of the magnetic state from the partially ordered AFM (antiferromagnetically) in Cu2Ga0.47Mn0.53BO5, through the spin glass state, to the combined spin glass/ordered state in Cu2Ga0.32Mn0.68BO5 with the appearance of magnetic anisotropy. The evident dependence of Tc (phase transition temperature) on the magnetic field was found as well as its decrease at the nonzero magnetic field in the samples with x = 0.53 and 0.68. (C) 2022 Elsevier B.V. All rights reserved.

Needle-shape single crystals of Co5/3Nb1/3BO4 warwickite were grown using the flux technique. X-ray diffraction measurements have revealed an orthorhombic structure (Sp. Gr. Pbnm) where the octahedral M1 site is occupied by a mixture of Co2+/Nb5+ ions and the M2 site is exclusively filled by Co2+ ions. Using dc magnetization measurements it was established that the new material undergoes two magnetic transitions: an antiferromagnetic transition at TN1 = 27 K and a ferrimagnetic one at TN2 = 14 K, below which a hysteresis cycle opens. Both magnetic transitions are marked by anomalies in the specific heat. High magnetic anisotropy with c-axis as a hard magnetization direction was detected.

The ludwigite Co2FeBO5 has been studied experimentally using 57Fe Mössbauer spectroscopy and theoretically using DFT + GGA calculations. The room-temperature Mössbauer spectra are composed of four quadrupole doublets corresponding to the high-spin Fe3+ ions in octahedral oxygen coordination. All components undergo splitting below 117 K due to the magnetic hyperfine fields. The DFT + GGA calculations performed for three models of Fe ion distributions have revealed that the ground state corresponds to the "Fe4(HS)" model with the high-spin Fe3+ ions located at the M4 site and the high-spin Co2+ ions located at the M1, M2, and M3 sites. A ferrimagnetic ground state, with the Co and Fe magnetic moments being nearly parallel to the b-axis and a total magnetic moment of circa 1.1μB f.u.-1, was found. The other Fe distributions cause an increase in the local octahedral distortions and transformation of the spin state. The calculated quadrupole splitting values are in good agreement with the experimental values obtained by Mössbauer spectroscopy.

We present the results of a thorough study of the specific heat and magnetocaloric properties of a ludwigite crystal Cu2MnBO5 over a temperature range of 60 - 350 K and in magnetic fields up to 18 kOe. It is found that at temperatures below the Curie temperature (92 K), capacity possesses a linear temperature-dependent behavior, which is associated with the predominance of two-dimensional antiferromagnetic interactions of magnons. The temperature independence of capacity is observed in the temperature range of 95 - 160 K, which can be attributed to the excitation of the Wigner glass phase. The magnetocaloric effect (i.e. the adiabatic temperature change) was assessed through a direct measurement or an indirect method using the capacity data. Owing to its strong magnetocrystalline anisotropy, an anisotropic MCE or the rotating MCE is observed in Cu2MnBO5. A deep minimum in the rotating MCE near the TC is observed and may be associated with the anisotropy of the paramagnetic susceptibility.

X-ray diffraction, heat capacity and magnetic measurements are performed on single crystals of Mn2-xMgxBO4 (x = 0.5, 0.6 and 0.7) with the warwickite structure. The monoclinic symmetry is found for all samples with the space group P21/n. The M1 site is occupied by trivalent Mn ions while the M2 site is occupied by a mixture of divalent Mg and Mn ions. Regular cation and charge distributions are observed, which is unusual for heterometallic warwickites. The local octahedral distortions of M1O6 show the monotonic dependence on the Mg content and are in accordance with the Jahn-Teller distortion. All samples are found to undergo long-range antiferromagnetic ordering with rather low transition temperatures of TN = 16, 14 and 13 K for x = 0.5, 0.6, and 0.7, respectively. The ordering of local octahedral distortions, caused by the strong electron-phonon interaction of the trivalent Mn ions, is proposed to stabilise the cationic ordering and, as a result, the long-range magnetic ordering in the material.

Needle-shape single crystals of Mn2.25Co0.75BO5 ludwigite were synthesized by the flux technique and investigated by means of X-ray diffraction, static magnetic susceptibility and specific heat measurements. Magnetization and specific heat experiments showed the presence of ferrimagnetic ordering near T-N similar or equal to 61K. Below this temperature the magnetic properties demonstrated the angular dependence and the high magnetic hardness in a magnetic field applied perpendicular to the crystallographic c axis, which is similar to other cobalt-containing ludwigites. The effective magnetic moment per magnetic ion 4.8 mu(B) was calculated from the paramagnetic data. Analysis of the phonon contribution to the specific heat allowed to distinguish the magnetic contribution C-M, which has two features. One of which was observed at T(N )and can be attributed to strong exchange interactions between spins of magnetic ions. The second one at T = 11.6 K is due to the effect of the ligands crystal field on a magnetic ion with S > 1/2.

Magnetic structure of the substituted multiferroics-ferroborates Nd0.9Tb0.1Fe3(BO3)(4) and Nd0.8Tb0.2Fe3(BO3)(4) were determined in the framework of a self-consistent refinement of the single crystal neutron diffraction data. The small substitution of Nd for Tb leads to the reorientation of the main antiferromagnetic vector L from the basal plane towards the hexagonal axis. The reorientation takes place via an angular structure for which L does not coincide with the principal crystallographic directions and evolves with temperature due to competing magnetic anisotropies of Fe, Nd, and Tb subsystems. Our refinement at 2 K reveals the existence of distortions in the collinear antiferromagnetic Fe spin arrangement suggested before in other ferroborates. Therefore, besides the main antiferromagnetic vector L, the magnetic structure involves additional fine symmetrized combinations of spin components allowed by symmetry. They coexist with certain L components and could originate from the antisymmetric Dzyaloshinsky-Moriya Fe-Fe exchange interactions. At higher temperatures, the magnetic structure is described by the simple collinear model, where the L vector is deviated from the hexagonal plane.

Исследуемые в данной работе твердые растворы со структурой варвикита представляют значительный интерес с фундаментальной точки зрения, поскольку данные объекты относятся к квази-низкоразмерным магнетикам. В структуре варвикита четыре октаэдра, объединяясь общими гранями, формируют ряд, ряды объединяются в ленты, распространяющиеся вдоль короткой оси. Общая формула соединений со структурой варвикита M2+M3+BO4. В структуре варвикита разновалентные металлические ионы занимают две кристаллографически неэквивалентные октаэдрические позиции 4е: М1 и М2. Марганцевый варвикит Mn2BO4 демонстрирует зарядовое упорядочение: позиция М1 занята ионами Mn3+, позиция M2- ионами Mn2+ . Особый интерес представляет система твердых растворов с замещением в двухвалентной подсистеме на немагнитный ион и сохранением ян-теллеровских ионов Mn3+ в трехвалентной подсистеме. С использованием раствор-расплавного синтеза были получены монокристаллы твердых растворов оксиборатов Mn2-xMgxBO4 (x = 0.91, 1.00, 1.10, 1.14, 1.20) со структурой природного минерала варвикита. Структура и параметры решетки полученных образцов были определены с помощью метода порошкового рентгеноструктурного анализа. Сравнение структурных данных полученных образцов и известных составов позволяет предположить, что концентрации магния для всех синтезированных образцов значительно меньше концентраций «по закладке». При увеличении концентрации магния параметры решетки плавно уменьшаются. При максимальных значениях концентрации магния наблюдается изменение угла моноклинности, хотя структура остается в варвикитной фазе. Вероятно, концентрация хс ≈ 0.76 является критической для стабилизации варвикитной фазы, при дальнейшем увеличении концентрации Mg происходит переход на фазу такеучит или людвигит.