Enhanced negative thermal expansion of (KMg)3+-substituted Fe2Mo3O12 ceramics

Herein, we report the solid-state synthesis of (KMg)_xFe_2-xMo₃O₁₂ (0 = x ≤ 1.5) ceramics. Phase composition, crystal structure, morphology, phase transition and thermal expansion behavior of the (KMg)_xFe_2-xMo₃O₁₂ ceramics were investigated by XRD, Raman, XPS, HRTEM, EDX, SEM, TMA and high-temperature XRD. Results indicate that (KMg)³⁺ dual-cations have successfully replaced Fe³⁺ in Fe₂Mo₃O₁₂ ceramics and single-phase monoclinic (KMg)_xFe_2-xMo₃O₁₂ ceramics were prepared for 0.25 = x ≤ 1. (KMg)³⁺ introduction can increase the density of (KMg)_xFe_2-xMo₃O₁₂ ceramics and effectively improve their negative thermal expansion (NTE) performance. In addition, the phase transition temperature (Tc) of Fe₂Mo₃O₁₂ was reduced from 508.1 °C to room temperature with the increase of (KMg)³⁺-substitution. Monoclinic KMgFeMo₃O₁₂ ceramics was observed to show stronger NTE in a wider temperature range of 30–700 °C for the first time. Its corresponding coefficient of thermal expansion (CTE) is as high as ?17.21 × 10^?6 °C^?1. The distortion of [FeO₆/MgO₆] polyhedra in (KMg)_xFe_2-xMo₃O₁₂ caused by (KMg)³⁺-substitution contributed to the stronger NTE.     

Flower-like Sc2Mo3O12 nanosheet clusters: Synthesis,thermal expansion and photocatalytic properties

In this work, Sc₂Mo₃O₁₂ has been synthesized via one-pot hydrothermal reaction. The effects of process conditions on the crystal structure, morphology, photocatalytic activity and negative thermal expansion (NTE) behaviors of flower-like Sc₂Mo₃O₁₂ were systematically investigated. Results indicate that orthorhombic flower-like Sc₂Mo₃O₁₂ assembled by nano-size flaky crystal grains can be synthesized by one-pot hydrothermal reaction at a temperature as low as 120 °C for 2 h. The hydrothermal reaction temperature and time have no obvious effects on the crystal structure and morphology. However, the photocatalytic property of synthesized Sc₂Mo₃O₁₂ is sensitive to the above parameters. The sample synthesized at 200 °C for 2 h shows the best photocatalytic degradation of methyl orange, and the degradation rate is 73.32% in 2 h ¹The coefficient of thermal expansion (CTE) of Sc₂Mo₃O₁₂ is ?1.99 × 10^?6 °C^?1 in 50–500 °C tested using TMA. The high-temperature XRD analysis reveals that Sc₂Mo₃O₁₂ exhibits anisotropic NTE and the intrinsic CTE is measured to be ?2.09 × 10^?6 °C^?1 in 25–800 °C.     

Effect of isovalent substitution on phase transition and negative thermal expansion of In2−xScxW3O12 ceramics

Solid solutions of In_2−xSc_xW₃O₁₂ (0≤x≤2) were successfully synthesized using the solid state reaction method. Effects of substituted scandium content on the phase composition, microstructure, phase transition temperatures and thermal expansion behaviors of the resulting In_2−xSc_xW₃O₁₂ (0≤x≤2) samples were investigated using X-ray diffraction (XRD), field emission scanning electron microscopy (FESEM), and thermal mechanical analyzer (TMA). Results indicate that the obtained In₂W₃O₁₂ ceramic undergoes a structure phase transition from monoclinic to orthorhombic at 248 °C. This phase transition temperature of In₂W₃O₁₂ can be easily shifted to a lower temperature by partly substituting the In³⁺ with Sc³⁺. When the x value increased from 0 to 1, the phase transition temperatures of In_2−xSc_xW₃O₁₂ (0≤x≤2) samples decreased from 248 to 47 °C. All the In_2−xSc_xW₃O₁₂ (0≤x≤2) ceramics show fine negative thermal expansion below their corresponding phase transition temperatures. The negative thermal expansion coefficients of the In_2−xSc_xW₃O₁₂ (0≤x≤2) ceramics change in the range from −1.08×10⁻⁶ °C⁻¹ to −7.13×10⁻⁶ °C⁻¹.     

Synthesis and thermal expansion behaviors of spin-coated Sc2Mo3O12 thin films

Orthorhombic Sc₂Mo₃O₁₂ films have been successfully prepared via spin coating technique followed by annealing at 500–750 °C. The phase composition, microstructure, morphology and negative thermal behavior of the synthesized Sc₂Mo₃O₁₂ films were investigated. XRD and XPS analysis indicate that as-deposited film is amorphous. Orthorhombic Sc₂Mo₃O₁₂ films can be prepared after post-annealing at 500–750 °C for 1 h. The crystallinity of Sc₂Mo₃O₁₂ films gradually improved with the increase of post-annealing temperature. SEM analysis shows as-deposited film is smooth and compact, and the grain size of Sc₂Mo₃O₁₂ film grows up as the post-annealing temperature increases. Variable temperature XRD analysis demonstrates that the synthesized orthorhombic Sc₂Mo₃O₁₂ films show stable thermo-chemical and anisotropic NTE property in 25–700 °C. The corresponding coefficients of thermal expansion (CTEs) of the orthorhombic Sc₂Mo₃O₁₂ film in a, b and c directions are ?6.68 × 10^?6 °C^?1, 5.08 × 10^?6 °C^?1 and ?4.76 × 10^?6 °C^?1, respectively. The whole unit cell of the orthorhombic Sc₂Mo₃O₁₂ film shrinks and the volumetric CTE of the Sc₂Mo₃O₁₂ thin film is ?6.36 × 10^?6 °C^?1, and the linear CTE is about ?2.12 × 10^?6 °C^?1 (α_v = 3α_l).     

Effects of Yb and Sc co-doping on the thermal properties and CMAS corrosion of garnet-type (Y3-xYbx)(Al5-xScx)O12 ceramics

Thermal barrier coatings with excellent thermal performance and corrosion resistance are essential for improving the performance of aero-engines. In this paper, (Y_3-xYb_x)(Al_5-xSc_x)O₁₂ (x = 0, 0.1, 0.2, 0.3) thermal barrier coating materials were synthesized by a combination of sol-gel method and ball milling refinement method. The thermal properties of the (Y_3-xYb_x)(Al_5-xSc_x)O₁₂ ceramics were significantly improved by increasing Yb and Sc doping content. Among designed ceramics, (Y_2.8Yb_0.2)(Al_4.8Sc_0.2)O₁₂ (YS-YAG) showed the lowest thermal conductivity (1.58 Wm^?1K^?1, at 800 °C) and the highest thermal expansion coefficient (10.7 × 10^?6 K^?1, at 1000 °C). In addition, calcium-magnesium- aluminum -silicate (CMAS) corrosion resistance of YS-YAG was further investigated. It was observed that YS-YAG ceramic effectively prevented CMAS corrosion due to its chemical inertness to CMAS as well as its unique and complex structure. Due to the excellent thermal properties and CMAS corrosion resistance, YS-YAG is considered to be prospective material for thermal barrier coatings.     

Double cation (KMg)3+ co-substitution to regulate negative thermal expansion property of ln2W3O12

To improve the negative thermal expansion (NTE) performance of ln₂W₃O₁₂, a novel series of NTE (KMg)_xln_2-xW₃O₁₂ ceramics were fabricated via the solid-state method. The effects of (KMg)³⁺ substitution on the phase composition, microstructure and thermal expansion property of the ln₂W₃O₁₂ ceramics were characterized using X-ray diffraction (XRD), Raman spectrometer (Raman), X-ray photoelectron spectrometer (XPS), scanning electron microscopy (SEM), transmission electron microscope (TEM) and thermal mechanical analyzer (TMA). Results indicate that (KMg)³⁺ can partially replace In³⁺ in In₂W₃O₁₂ and form a new phase K_xMg_xln_2-xW₃O₁₂ with monoclinic symmetry. For x = 0.5, pure monoclinic (KMg)_0.5ln_1.5W₃O₁₂ ceramics is prepared and shows strong NTE. Its coefficient of thermal expansion is −7.89 × 10⁻⁶ °C⁻¹ in 30–700 °C, in addition, no phase transition was observed over the entire testing temperature range. These research results indicate that double cations co-substitution is an effective strategy to improve the NTE property of ln₂W₃O₁₂ through crystal structure modulation. This strategy could be extended to the performance modulation of other NTE materials.     

Negative thermal expansion coefficient of Sc-doped indium tungstate ceramics synthesized by co-precipitation

Co-precipitation was successfully applied to synthesize the Sc³⁺ doped In_2-xSc_x (WO₄)₃ (x = 0, 0.3, 0.6, 0.9 and 1.2) compounds. The composition- and temperature-induced structural phase transition and thermal expansion behaviors of Sc³⁺ doped In₂(WO₄)₃ were investigated. Results indicate that In_2-xSc_x (WO₄)₃ crystalizes in a monoclinic structure at 300 °C for x ≤ 0.3 and changes into hexagonal structure for x ≥ 0.6. Hexagonal In_1.1Sc_0.9(WO₄)₃ displays negative thermal expansion (NTE) with an average linear coefficient of thermal expansion (CTE) of −1.85 × 10⁻⁶ °C ⁻¹. After sintering at 700 °C and above, a phase transition from hexagonal to orthorhombic phase was observed in In_2-xSc_x (WO₄)₃ (x ≥ 0.6). Sc³⁺ doping successfully reduce the temperature-induced phase transition temperature of In_2-xSc_x (WO₄)₃ ceramics from 250 °C (x = 0) to room temperature (x = 0.9). When x = 0.9 and 1.2, the average linear CTEs of In_2-xSc_x (WO₄)₃ ceramics are −5.45 × 10⁻⁶ °C⁻¹ and -4.43 × 10⁻⁶ °C⁻¹ in a wider temperature range of 25–700 °C, respectively.     

Preparation of In0.5Sc1.5Mo3O12 nanofibers and its negative thermal expansion property

Orthorhombic In_0.5Sc_1.5Mo₃O₁₂ nanofibers were prepared by electrospinning followed by a heat treatment. The effects of post-annealing temperatures on the phase composition, microstructure and morphology were investigated by XRD, SEM, HRTEM and XPS. Negative thermal expansion (NTE) behaviors of the In_0.5Sc_1.5Mo₃O₁₂ nanofibers were analyzed by high-temperature XRD. Results indicate that the as-prepared In_0.5Sc_1.5Mo₃O₁₂ nanofibers show an amorphous structure with smooth and homogeneous shape. The average diameter of the as-prepared In_0.5Sc_1.5Mo₃O₁₂ nanofibers is around 515 nm. Well crystallized orthorhombic In_0.5Sc_1.5Mo₃O₁₂ nanofibers could be prepared after post-annealing at 550 °C for 2 h with an average diameter of about 192 nm. The crystallinity of In_0.5Sc_1.5Mo₃O₁₂ nanofibers gradually improved with the increase of annealing temperature. However, too high post-annealing temperature leads to a damage of sample's fiber structure. The high-temperature XRD results reveal that In_0.5Sc_1.5Mo₃O₁₂ nanofibers show an anisotropic NTE, and the coefficients of thermal expansion (CTEs) along a-axis and c-axis were −5.95 × 10⁻⁶ °C⁻¹ and -3.54 × 10⁻⁶ °C⁻¹, while the one along b-axis is 5.61 × 10⁻⁶ °C⁻¹. The volumetric CTE of In_0.5Sc_1.5Mo₃O₁₂ nanofibers is −3.90 × 10⁻⁶ °C⁻¹ and the linear one is 1.3 × 10⁻⁶ °C⁻¹ in 25–700 °C.     

Synthesis and tunable thermal expansion properties of Sc2−xYxW3O12 solid solutions

A new series of rare earth solid solutions Sc_2−xY_xW₃O₁₂ was successfully synthesized by the conventional solid-state method. Effects of doping ion yttrium on the crystal structure, morphology and thermal expansion property of as-prepared Sc_2−xY_xW₃O₁₂ ceramics were investigated by X-ray diffraction (XRD), thermogravimetric analysis (TG), field emission scanning electron microscope (FE-SEM) and thermal mechanical analyzer (TMA). Results indicate that the obtained Sc_2−xY_xW₃O₁₂ samples with Y doping of 0≤x≤0.5 are in the form of orthorhombic Sc₂W₃O₁₂-structure and show negative thermal expansion (NTE) from room temperature to 600 °C; while as-synthesized materials with Y doping of 1.5≤x≤2 take hygroscopic Y₂W₃O₁₂·nH₂O-structure at room temperature and exhibit NTE only after losing water molecules. It is suggested that the obvious difference in crystal structure leads to different thermal expansion behaviors in Sc_2−xY_xW₃O₁₂. Thus it is proposed that thermal expansion properties of Sc_2−xY_xW₃O₁₂ can be adjusted by the employment of Y dopant; the obtained Sc_1.5Y_0.5W₃O₁₂ ceramic shows almost zero thermal expansion and its average linear thermal expansion coefficient is −0.00683×10⁻⁶ °C⁻¹ in the 25–250 °C range.     

High configurational entropy for low phase transition temperature and thermal expansion of A2M3O12 oxide ceramics

Transverse vibrations of bridging atoms in framework structure oxides contribute to negative thermal expansion (NTE), increasing the configurational entropy. Herein, the configurational entropy of NTE (Al_1/3Fe_1/3Cr_1/3)₂Mo₃O₁₂ (AFCM) is tuned by introducing ZrMg and W to AlFeCr and Mo sites to lower NTE. The NTE of ((Zr_1/2Mg_1/2)_x(Al_1/3Fe_1/3Cr_1/3)_(1-x))₂Mo₃O₁₂ (ZMAFCM) reduce obviously with increasing the content of ZrMg and also the phase transition temperatures (PTTs) (x = 0∼0.5). For ((Zr_1/2Mg_1/2)_x(Al_1/3Fe_1/3Cr_1/3)_(1-x))₂(Mo_1/2W_1/2)₃O₁₂ (ZMAFCMW), the NTE and PTTs reduce at a faster rate than that of ZMAFM. The configurational entropy increases with the content of ZrMg firstly (x = 0∼0.4) and then decreases. The possible mechanism of thermal expansion change is related to the enhanced lattice configuration, high entropy. The inconsistent transverse vibrations of bridging oxygen atoms could reduce their contribution to NTE, especially for high entropy. The PTT of high configurational entropy oxides is reduced obviously due to the influenced on the effective electronegativity. The investigation paves a high entropy way to lower thermal expansion and PTT of A₂M₃O₁₂ oxide ceramics and explores the further mechanism of NTE.     

Expanding negative thermal expansion range of ZrMnMo3O12 to cover room temperature by introducing V5+

Solid solutions of Zr_1+xMn_1-xMo_3-2xV_2xO₁₂ (0 ≤ x ≤ 0.5) are developed with reduced phase transition temperature (from 362 to 160 K) by introducing V⁵⁺ into ZrMnMo₃O₁₂. Zr_1+xMn_1-xMo_3-2xV_2xO₁₂ adopt monoclinic (P2₁/a) and orthorhombic (Pbcn) structure at room temperature (RT) for x ≤ 0.1 and x ≥ 0.2, respectively. The formation of bond V–O induces a larger average effective negative charge on oxygen to enhance the repulsive force between them and then strengthens the bond of Mo–O, which reduces the phase transition temperature due to the reduction in effective electronegativity and expands negative thermal expansion (NTE) range covering RT. NTE property in a wide temperature range (from 160 to 673 K) for Zr_1.5Mn_0.5Mo₂VO₁₂ is realized, implying great potential for applications. The NTE property of the materials is induced by low-frequency phonons.     

Improvement on thermophysical and mechanincal properties of LaMgAl11O19 magnetoplumbite by Nd2O3 and Sc2O3 co-doping

LaMgAl₁₁O₁₉-type magnetoplumbite holds great promise to be used above 1300 °C as thermal barrier coatings (TBCs), but its practical application has been restricted because of inferior thermophysical properties. Herein, we focus on optimizing the thermophysical properties of LaMgAl₁₁O₁₉ by simultaneously substituting La³⁺ and Al³⁺ ions with Nd³⁺ and Sc³⁺ ions, respectively. Results show that the effects of co-substitution on reducing thermal conductivity are pronounced. The thermal conductivities of La_1-xNd_xMgAl_11-xSc_xO₁₉ (x = 0, 0.1, 0.2, 0.3) ceramics decrease progressively with dopant concentration and a lowest thermal conductivity of 2.04 W/(m·K) is achieved with x = 0.3 at 1000 °C, which is a value superior to pure LMA and even lower than YSZ. The mechanisms behind the lowered thermal conductivity are investigated. Increase of the thermal expansion coefficient is also realized (8.53 × 10⁻⁶ K⁻¹ for pure LMA, 9.07 × 10⁻⁶ K⁻¹ for x = 0.3, 1300 °C). Most importantly, Nd³⁺ and Sc³⁺ combination doping indeed facilitates mechanical properties of La_1-xNd_xMgAl_11-xSc_xO₁₉ solid solutions as well. It should be noted that Sc³⁺ doping at Al³⁺ site plays more effective role in improving thermal properties than Nd³⁺ does at La³⁺ site. This work provides a path to simultaneously integrate low thermal conductivity, good phase stability, moderate thermal expansion behavior and excellent mechanical properties on LMA for the next generation TBCs.     

Thermal enhancement of up-conversion luminescence in Lu2W2.5Mo0.5O12: Er3+, Yb3+ phosphors

Lu₂W_2.5Mo_0.5O₁₂: Er³⁺/Yb³⁺ phosphors were synthesized through high temperature solid state method. Under 980 nm laser excitation, the Lu₂W_2.5Mo_0.5O₁₂: Er³⁺/Yb³⁺ compounds show thermal enhancement of up-conversion luminescence (UCL), which is attributed to the lattice contraction and distortion from negative thermal expansion (NTE) of Lu₂W_2.5Mo_0.5O₁₂ host enhancing the energy transfer of Yb³⁺ to Er³⁺, eliminating the energy transfer of Er³⁺ to Er³⁺ through Er³⁺ single-doped Lu₂W_2.5Mo_0.5O₁₂ phosphors without thermal enhancement of UCL. The green luminescence intensities at 693 K of the Lu_1.98-xW_2.5Mo_0.5O₁₂: 0.02Er³⁺, xYb³⁺ (x = 0.2, 0.3, 0.4) samples are 4.6, 4.3 and 7.0 times as that of 302 K, respectively. And through fluorescence intensity ratio (FIR) technique, the corresponding maximum absolute sensitivities are 0.00741, 0.00744 and 0.00723, respectively. The green monochromaticity of UCL spectra in Er³⁺/Yb³⁺ co-doped samples increase with the increasing of temperature, and the possible UCL mechanism with temperature was discussed. The results indicate that the Lu₂W_2.5Mo_0.5O₁₂: Er³⁺/Yb³⁺ phosphors can be applied at a high temperature as optical thermometer with a good green monochromaticity.     

Synthesis and negative thermal expansion properties of solid solutions Yb2−xLaxW3O12 (0 ≤ x ≤ 2)

A new series of rare earth solid solutions Yb_2?xLa_xW₃O₁₂ were successfully synthesized by the solid-state method. Effects of substituted ion lanthanum on the microstructures and thermal expansion properties in the resulting Yb_2?xLa_xW₃O₁₂ ceramics were investigated by X-ray diffraction (XRD), thermogravimetric analyzer (TGA), field emission scanning electron microscope (FESEM) and thermal mechanical analyzer (TMA). Results indicate that the structural phase transition of the Yb_2?xLa_xW₃O₁₂ changes from orthorhombic to monoclinic with increasing substituted content of lanthanum. The pure phases can form in the composition range of 0 ≤ x < 0.5 with orthorhombic structure and 1.5 < x ≤ 2 with monoclinic one. High lanthanum content leads to a low hygroscopicity of Yb_2?xLa_xW₃O₁₂. Negative thermal coefficients of the Yb_2?xLa_xW₃O₁₂ (0 ≤ x ≤ 2) also vary from ?7.78 × 10^?6 K^?1 to 2.06 × 10^?6 K^?1 with increasing substituted content of lanthanum.     

Influence of Ta doping on the structural stability and conductivity of Sr11Mo4O23 electrolyte

Sr₁₁Mo₄O₂₃(SMO) material has a double-layer perovskite superstructure, which exhibits unusual structural flexibility and oxygen ion mobility. However, the Sr₁₁Mo₄O₂₃ cubic phase will transform into SrMoO₄ tetragonal phase at 400 °C, which leads to a sharp decrease in conductivity. In order to solve this problem, Ta doped Sr₁₁Mo_4-xTa_xO_23-δ (SMTO, 0 ≤ x ≤ 1.25) electrolytes were synthesized by a route combining the Pechini method and solid-state reaction. The effects of acceptor-type Ta⁵⁺ doping on the structural stability, micro-scale structure and ionic conductivity of SMO are characterized by X-ray diffraction, thermogravimetric analysis, differential scanning calorimetry, scanning electron microscopy, and electrochemical impedance spectroscopy. All Sr₁₁Mo_4-xTa_xO_23-δ powders are single-phase and no secondary phase is detected. Moreover, the phase transition of Sr₁₁Mo₄O₂₃ to SrMoO₄ is highly inhibited by partially replacing Mo with Ta (x ≥ 0.50) during the heat treatment, and the Sr₁₁Mo₄O₂₃ cubic phase with high conductivity may be maintained for a long time at 800 °C. The total ionic conductivity of Sr₁₁Mo_4-xTa_xO_23-δ samples increases with increasing the Ta concentration, and then declines at higher doping content (x = 1.25). The ionic conductivity of Sr₁₁Mo₃TaO_23-δ (SMTO100) pellet is the highest, reaching 1.44 × 10^?2 S/cm at 800 °C. More remarkably, the conductivity of STMO100 pellet remains at its peak during the 100 h annealing test at the temperature of 800 °C.     

Complex Effect of Sm3+/W6+ Codoping on α‐β Phase Transformation and Phonon Scattering of Oxygen‐Deficient La2Mo2O9

Lanthanum molybdate, La₂Mo₂O₉, has been attracted considerable attention owing to its high concentration of intrinsic oxygen vacancies, which could be reflected by enhanced phonon scattering and low thermal conductivity. A new series of La₂Mo₂O₉‐based oxides of the general formula La_2?xSm_xMo_2?xW_xO₉, where x ≤ 0.2, were synthesized by citric acid sol–gel process. The variation in thermal conductivity with Sm³⁺and W⁶⁺ fractions was analyzed based on structure information provided by X‐ray diffraction and Raman spectroscopy. The fully dense La_2?xSm_xMo_2?xW_xO₉ ceramics showed a minimum thermal conductivity value [κ = 0.84 W·(m·K)^?1,T = 1073 K] at the composition of La_1.8Sm_0.2Mo_1.8W_0.2O₉, which stems from the multiple enhanced phonon scatterings due to mass and strain fluctuations at the La³⁺ and Mo⁶⁺ sites as well as the high concentration of intrinsic oxygen vacancies embedded in the crystal lattice. The thermal conductivities present an abrupt decrease at the structural transition, which is due to the phase transformation from a low‐temperature ordered form (monoclinic α‐La₂Mo₂O₉) to a high‐temperature disordered form (cubic β‐La₂Mo₂O₉₎.     

Near‐Zero Thermal Expansion in In(HfMg)0.5Mo3O12

In(HfMg)_0.5Mo₃O₁₂, which can be considered as a 1:1 mole ratio solid solution of the low‐positive thermal expansion material HfMgMo₃O₁₂ and the low‐negative thermal expansion (NTE) material In₂Mo₃O₁₂ was prepared. From DSC and XRPD results, we show that In(HfMg)_0.5Mo₃O₁₂ exists in a monoclinic (P2₁/a) structure at low temperature and undergoes a phase transition at ~425 K to an orthorhombic phase (Pnma), with an associated enthalpy change of 0.89 kJ mol^?1. Thermal expansion is large and positive in the low‐temperature monoclinic phase (average α_? = 16 × 10^?6 K^?1 and 20 × 10^?6 K^?1, from dilatometry and XRPD, respectively). Remarkably, this material has a near‐zero thermal expansion (ZTE) coefficient over the temperature range ~500 to ~900 K in the high‐temperature orthorhombic phase, both intrinsically and for the bulk sample. The average linear intrinsic (XRPD) value is α_? = ?0.4 × 10^?6 K^?1, and the average bulk (dilatometric) value is α_? = 0.4 × 10^?6 K^?1 with an uncertainty of ± 0.2 × 10^?6 K^?1. The slight difference between intrinsic and bulk thermal expansion is attributed to microstructural effects. XRPD results show that the thermal expansion is more isotropic than for the parent compounds HfMgMo₃O₁₂ and In₂Mo₃O₁₂.     

Crystal structure,vibration characteristics and microwave dielectric properties of low loss MgMo1-xWxO4 solid solution ceramics

Solid-phase method was used to synthesize MgMo_1-xW_xO₄ (x = 0–0.15) ceramics. The influences of substitution Mo⁶⁺ with W⁶⁺ on crystal structure, vibration characteristics and microwave dielectric properties of MgMo_1-xW_xO₄ ceramics were comprehensively studied. X-Ray diffraction illustrated all samples exhibit single-phase monoclinic wolframite structure when x = 0–0.15, in which W⁶⁺ replaces Mo⁶⁺ sites formed solid solution. W⁶⁺ effectively improves sintering properties of the MgMoO₄, the average grain size and relative density were increased. Raman characterization reveals that suitable W⁶⁺ substitution amount leads to reduction of v₁ A_g peaks FWHM and the enhancement of specific v₃ A_g peak for Mo/WO₄ tetrahedron, which improves the ordered distribution of the crystal structure. The above combined effect results in the increased Q × f value, but has little influence of W⁶⁺ substitution on ε_r and τ_f for MgMoO₄. When x = 0.09, MgMo_0.91W_0.09O₄ ceramic sintered at 1050 °C has optimal microwave dielectric performance: ε_r = 7.21, Q×f = 90,829 GHz, τ_f = ?67 ppm/°C.     

Phase transition and negative thermal expansion properties in isovalently substituted In2−xScx(MoO4)3 ceramics

Sc-substituted In_2−xSc_x(MoO₄)₃ (0 ≤ x ≤ 2) ceramics were successfully synthesized by the solid state reaction method with the goal of tuning the phase transition temperature. Effects of Sc³⁺ substitution on the phase composition, microstructure, phase transition temperature and thermal expansion behavior of the In_2−xSc_x(MoO₄)₃ (0 ≤ x ≤ 2) ceramics were investigated using XRD, FESEM, EDX, XPS and TMA, respectively. The results indicate that all samples are single phase. The relative densities of the In_2−xSc_x(MoO₄)₃ ceramics increased gradually with increasing Sc³⁺ content. Investigations on thermal expansion properties of the In_2−xSc_x(MoO₄)₃ ceramics reveal that the temperature-induced phase transition from monoclinic to orthorhombic symmetry is strongly correlated to the Sc³⁺ content. The obtained In₂(MoO₄)₃ ceramics undergoes a structural phase transition from monoclinic to orthorhombic around 355.3 °C. The phase transition temperature can be significantly shifted from 355.3 °C (x = 0) to 31.9 °C (x = 1.5) by partially replacing In³⁺ cations with less electronegative Sc³⁺ cations. All In_2−xSc_x(MoO₄)₃ (0 ≤ x ≤ 2) ceramics exhibit strong negative thermal expansion above the phase transition temperature. In_0.5Sc_1.5(MoO₄)₃ exhibits linear NTE over the 100–700 °C temperature range with a linear coefficient of thermal expansion of −3.99 × 10⁻⁶ °C ⁻¹.     

Improving room temperature negative thermal expansion performance of Fe2-xScx(MoO4)3

Negative thermal expansion (NTE) performance of Fe₂(MoO₄)₃ is only found in a high-temperature range due to its monoclinic-to-orthorhombic (M-O) phase transformation temperature (PTT) at 503.5°C. To stabilize the orthorhombic phase of Fe₂(MoO₄)₃ at room temperature, a series of Fe_2-xSc_x(MoO₄)₃ (0≤x≤1.5) (abbreviated as F_2-xS_xM) were fabricated via solid-state reaction. Results indicate that the M-O PTT of Fe₂(MoO₄)₃ is successfully reduced from 503.5°C to 34.5°C by A-site cation substitution of Sc³⁺. The regulation mechanism is considered to be the decrease in electronegativity of (Fe_2-xSc_x)⁶⁺ in F_2-xS_xM. Both variable temperature X-ray diffraction (XRD) and thermal mechanical analysis (TMA) analysis results indicate that F_0.5S_1.5 M exhibits anisotropic NTE in 100–700°C. The results indicate that it can effectively improve the densification of Sc-substituted F_0.5S_1.5 M ceramics by two-step calcination process. Furthermore, higher second-step calcination temperature is beneficial for the formation of single-phased orthorhombic F_0.5S_1.5 M. The NTE response temperature range of F_0.5S_1.5 M ceramics second-step sintered at 1000°C is broadened to 30–600°C, and the corresponding coefficient of thermal expansion is -5.74 × 10⁻⁶°C⁻¹. The ease in the proposed design and preparation method makes NTE F_0.5S_1.5 M potential for a wide range of applications in precision mechanical, electronic, optical, and communication instruments.