Effects of Fe doping on structure,negative thermal expansion,and magnetic properties of antiperovskite Mn3GaN compounds

We synthesized antiperovskite Mn₃Ga_1−xFe_xN (0 ≤ x ≤ 0.30) compounds and investigated their negative thermal expansion (NTE) behavior, structure, and magnetic properties. A high-resolution transmission electron microscopy analysis and a selected-area electron diffraction (SAED) pattern indicate that the samples have high crystallinity with a single-phase cubic structure. Tunable NTE behavior appears below room temperature, and the NTE operation temperature range (△T) is broadened while increasing the Fe doping. Furthermore, introducing Fe in Mn₃Ga_1−xFe_xN can efficiently adjust the NTE coefficient from −232.57 × 10⁻⁶/K (x = 0) to −12.57 × 10⁻⁶/K (x = 0.20), and the corresponding △T can be broadened from △T = 22 K to 51 K. Besides, the total entropy change (ΔS_total) at the phase transitions continuously decreases from 9.2 to 4.7 J/(kg K) while increasing the Fe content from x = 0.05 to 0.10. With increasing Fe into Ga sites, the magnetic ordering varies from antiferromagnetic (AFM) to ferromagnetic (FM), the AFM to paramagnetic (PM) phase transition temperature decreases, whereas the FM to PM transition temperature increases when increasing the Fe content. The present study indicates that magnetic element doping can efficiently tune the NTE and the correlated physical features of the antiperovskite compounds.     

Phase evolution and chemical durability of Zr1‐xCexO2 (0 ≤ x ≤ 1) ceramics

Ce‐doped zirconia ceramics with general stoichiometry of Zr_1‐xCe_xO₂ (0 ≤ x ≤ 1) have been obtained by substitution of Ce⁴⁺ for Zr⁴⁺ in ZrO₂. The phase and microstructure evolutions of the ceramics were investigated, and the effects of composition, temperature, and pH value on the chemical durability of the ceramics were also studied. The results show that the phase transformation from monoclinic to tetragonal takes place at about x = 0.2, and from tetragonal to cubic at about x = 0.6. It is found that the increase in Ce content and/or sinter temperature promote the phase transformation. The leaching studies show that the normalized leaching rates of Ce (LR_Ce) increase with increasing Ce content. Moreover, LR_Ce in acid solution are higher than those in neutral and alkaline solution. After 42 days, LR_Ce is 10^?5 ~ 10^?7 g m^?2 d^?1 under all different leaching conditions, exhibiting their excellent chemical durability.     

Electrical transport and thermoelectric properties of Ca0.8Y0.2−xDyxMnO3−δ (0 ≤ x ≤ 0.2)

Ca_0.8Y_0.2?xDy_xMnO_3?δ (0≤x≤0.2) samples were fabricated by the solid‐state reaction method, and their thermoelectric properties were studied from 500°C to 800°C. Upon the substitution of Dy³⁺ for Y³⁺ in the Ca_0.8Y_0.2?xDy_xMnO_3?δ, the electrical and thermal conductivities gradually decreased with increasing Dy³⁺ concentration, whereas the absolute value of the Seebeck coefficient significantly increased. The Ca_0.8Dy_0.2MnO_3?δ showed the largest value of dimensionless figure of merit (0.180) at 800°C as a result of the combination of the largest absolute value of the Seebeck coefficient and the lowest thermal conductivity. We believe that the Ca_0.8Dy_0.2MnO_3?δ is a promising thermoelectric material at high temperatures.     

Structure and microwave dielectric properties of the Li2/3(1−x)Sn1/3(1−x)MgxO systems (x = 0‐4/7)

In this paper, the Li_2/3(1?x)Sn_1/3(1?x)Mg_xO (LSMxO) ceramic systems were prepared by solid‐state reaction using novel atmosphere‐controlled sintering (x = 0‐4/7). Pure Li₂SnO₃ was observed for x = 0, the Li₂Mg₃SnO₆ and Li₂SnO₃ coexisted for x = 1/7, and the coexistence of three kinds of phases was detected for x = 1/5 and 1/4, including Li₄MgSn₂O₇ impurity phase. Pure Li₂Mg₃SnO₆‐like phase with cubic rock salt structure in Fm‐3m space group was obtained in the range of 1/3‐4/7. All samples showed well‐dense and smooth microstructures. The microwave dielectric properties highly depended on the phase composition, bond valence, FWHM of Raman spectrum, Raman shift, average grain sizes, and octahedral distortion. The LSMxO ceramics sintered at 1250°C for 5 hours possessed excellent comprehensive properties of ε_r = 15.43, Q×f = 80 902 GHz and τ_f = +5.61 ppm/°C for x = 1/7. Typically, the LSMxO ceramics sintered at 1350°C for 5 hours showed a maximum Q × f of 168 330 GHz for x = 1/2.     

Synthesis and Electrical Properties of New Lead‐free (100−x)(Li0.12Na0.88)NbO3–xBaTiO3 (0 ≤ x ≤ 40) Piezoelectric Ceramics

New lead‐free (100?x)Li_0.12Na_0.88NbO₃‐xBaTiO₃ (0 ≤ x ≤ 40) piezoelectric ceramics have been synthesized using conventional ceramics processing route. Structural analysis revealed an existence of morphotropic phase boundary (MPB), separating orthorhombic and tetragonal phases, between the BaTiO₃ content, x = 10–12.5. A partial phase diagram has been established based on temperature‐dependent permittivity data for this new system and a almost vertical temperature‐independent MPB is observed. Improvement in electrical properties near MPB (e.g., for x = 12.5; ε_r = 8842 at T_m and 795 at room temperature, d₃₃ = 30 pC/N, k_p = 12.0%, Q_m = 162, P_r = 11.2 μC/cm², E_c = 19.2 kV/cm, = 174 pm/V) is observed, and is attributed to the ease of polarization rotation due to coexistence of orthorhombic and tetragonal phases. The results show that these materials could be suitable for piezoelectric vibrators and ultrasonic transducer applications. The sample with x = 25, also exhibited high dielectric permittivity, ε_r = 2400, and low dielectric loss, tanδ = 0.033 at room temperature which could be suitable for capacitor (X7R/Z5U) applications.     

Anti-thermal quenching of Eu3+ luminescence in negative thermal expansion Zr(WO4)2

Thermal quenching of luminescence is the most critical problem for rare earth doped phosphors used in light-emitting diodes (LEDs). Herein, we demonstrate that thermal quenching can be considerably suppressed via the negative thermal expansion effect in Zr(WO₄)₂ that serves as host for Eu³⁺ red emission. The photoluminescence (PL) intensity is surprisingly enhanced by 130% when the temperature is raised from room temperature to 100 °C. As temperature further increases to 160 °C, the PL intensity turns to reduce, which is still 1.4 times of that at room-temperature. Moreover, Zr(WO₄)₂:15%Eu phosphor has good durability, which still exhibits strong red luminescence (only 13% loss) after being kept in 85 °C/85% relative humidity chamber for 240 h. The anti-thermal quenching of Eu³⁺ luminescence can be ascribed mainly to the following two factors: first one is the thermal-enhanced energy transfer between Eu³⁺ ions induced by the contraction of Zr(WO₄)₂ unit-cell volume that leads to the strong structural rigidity of host lattice; second one would be electron traps in the host that favors the increase of electrons on the excited energy levels. This important anti-thermal quenching effect induced from the negative thermal expansion of the host matrix may stimulates a novel and efficient approach to design highly thermal stable phosphors for next-generation LEDs.     

Negative thermal expansion of (Al1/3Fe1/3Cr1/3)2(Mo1/2W1/2)3O12 (AFCMW) and low thermal expansion of AFCMW-(Co1/2Ni1/2)(Mo1/2W1/2)O4 with high entropy

A₂Mo₃O₁₂ (A-Al, Fe, Cr) have large negative thermal expansion (NTE) coefficients and structural stability but high phase-transition temperatures (PTTs). Herein, we prepared (Al_1/3Fe_1/3Cr_1/3)₂(Mo_1/2W_1/2)₃O₁₂ (AFCMW), and found it to have a low NTE coefficient and a low PTT. Furthermore, combination of AFCMW with (Co_1/2Ni_1/2)(Mo_1/2W_1/2)O₄ (CNMW) afforded an AFCMW–CNMW composite with a low thermal expansion (LTE). We determined that the PTT reductions in A₂Mo₃O₁₂ are largely due to the high-entropy effect resulting from the introduction of different ions into its A and M sites. Moreover, we found that the low LTE of the AFCMW–CNMW composite is attributable to the opposite thermal expansion behaviours of AFCMW and CNMW. We suggest that the suppressed thermal expansion during the phase transition process of the AFCMW–CNMW composite could be derived from the high-entropy effect resulting from its increased diversity of polyhedra, the influence of Co²⁺ and Ni²⁺ dopants, and CNMW-induced lattice distortion.     

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.     

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.     

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.     

K_2xBa_(1-x)Zr_4(PO_4)_6系统的合成及热膨胀行为

用固相反应法合成了属于NZP结构的K2xBa1-xZr4(PO4)6固溶体系统,采用逐步推进的最小二乘法对各组成的高温X射线衍射图作了仔细的指标化和精密点阵常数测定,精确计算了晶格常数随温度的变化。由轴向膨胀系数αa和αc计算得出的平均线膨胀系数α与由顶杆法热膨胀仪测得的陶瓷样品热膨胀系数基本吻合。     

Structural and Dielectric Properties in (1−x)BaTiO3–xBi(Mg1/2Ti1/2)O3 Ceramics (0.1 ≤ x ≤ 0.5) and Potential for High‐Voltage Multilayer Capacitors

Structural and dielectric properties of (1?x)BaTiO₃–xBi(Mg_1/2Ti_1/2)O₃ (x = 0.1–0.5) were investigated to understand the binary system and utilize it for high‐voltage, high energy density capacitors. The solubility limit for Bi(Mg_1/2Ti_1/2)O₃ in a BaTiO₃ perovskite was between x = 0.4 and x = 0.5. A phase with pseudocubic symmetry was formed for x = 0.1–0.4; a secondary phase developed at x = 0.5. Dielectric measurements showed highly diffusive and dispersive relaxor‐like characteristics from 10 to 40 mol% of Bi(Mg_1/2Ti_1/2)O₃. These compositions also showed high relative permittivity with low‐temperature coefficients of permittivity over a wide range of temperatures ?100°C–600°C. Relaxation behavior was quantitatively investigated using the Vogel–Fulcher model, which revealed the activation energy of 0.17–0.22 eV. Prototyped multilayer capacitors of 18 mm × 17 mm × 4 mm dimensions with a capacitance of 12.5 nF at 1 kHz were successfully constructed and demonstrated multiple charge–discharge characteristics up to 10 kV.     

Ferroelectric and magnetic properties in (1−x)BiFeO3–x(0.5CaTiO3–0.5SmFeO3) ceramics

Multiferroic ceramics were prepared and characterized in (1?x)BiFeO₃–x(0.5CaTiO₃–0.5SmFeO₃) system by a standard solid‐state reaction process. The structure evolution was investigated by X‐ray diffraction and Raman spectrum analyses. The refinement results confirmed the different phase assemblages with varying amounts of polar rhombohedral R3c and nonpolar orthorhombic Pbnm as a function of the substitution content. In the compositions range of 0.2≤x≤0.5, polar R3c and nonpolar Pbnm coexisted, which was referred to polar‐to‐nonpolar morphotropic phase boundary (MPB). According to the dielectric and DSC analysis results, the ceramics with x≤0.2 changed to diffused ferroelectric, and the ferroelectric properties were enhanced significantly. Two dielectric relaxations were detected in the temperature range of 200‐300 K and 500‐700 K, respectively. The high‐temperature dielectric relaxation was attributed to the grain‐boundary effects. While the low temperature dielectric relaxation obtained in the samples with x=0.3‐0.5 was related to the charge transfer between Fe²⁺ and Fe³⁺. The magnetic hysteresis loops measured at different temperature indicated the enhanced magnetic properties in the present ceramics, which could be attributed to the suppressed cycloidal spin magnetic structure by Ti ions. In addition, the rare‐earth Sm spin moments might also affect the magnetic properties at relatively lower temperature.     

Effects of Nonstoichiometry and Cocatalyst Loading on the Photocatalytic Hydrogen Production with (Y1.5Bi0.5)1−xTi2O7−3x and (YBi)1−xTi2O7−3x Pyrochlores

By adjusting the Ti/(Y+Bi) ratios during synthesis, nonstoichiometric pyrochlores of (Y_1.5Bi_0.5)_{1 ? x}Ti₂O_{7 ? 3x} and (YBi)_{1 ? x}Ti₂O_{7 ? 3x} were prepared by an aqueous sol–gel method and annealed at different temperatures. The materials were characterized by X‐ray diffraction and UV–vis reflectance spectroscopy. The samples were tested for photocatalytic hydrogen production in the presence of methanol as sacrificial agent after being loaded with nanoparticles of rhodium or platinum acting as cocatalysts. It was found that materials being completely inactive in a stoichiometric composition can be tuned to good photocatalysts by optimizing the Ti/(Y+Bi) ratio. The increase in activity is supposed to derive from an optimization of the TiO₆‐octahedral geometry due to the generation of vacancies inside the structure. Increasing the Bi loading shifts the absorption edge into the visible, but unfortunately, an increase of the bismuth content in the structure also leads to stability issues during photocatalysis, which can be suppressed or at least weakened by a higher cocatalyst loading.     

[Mn（IMI）6]（ClO4）2的合成、晶体结构及感度

利用咪唑的水溶液和高氯酸锰水溶液反应制备高氯酸六咪唑合锰(II),培养出该配合物的单晶.用元素分析、红外光谱、DSC、TG-DTG和X射线单晶衍射等方法对该化合物进行了表征.结果表明,该晶体属于单斜晶系,空间群为P2(1)/n,晶胞参数a=11.721(2) nm, b=7.2191(13) nm, c=16.402(3) nm, β=90.064(3)°,V=1387.9(4) nm~3; Dc=1.585 g/cm~3; Z=2;F(000)=678, μ=0.160 mm, R_1=0.036 7, ωR2_=0.137 2.该化合物的分子式为[Mn(IMI)_6](ClO_4) _2,是由6个咪唑分子直接与二价锰离子配位、与高氯酸根离子结合形成的配合物.热分析结果表明,在10 K/min的升温速率下,该配合物的热分解过程由1个吸热峰和1个放热峰组成,剩余残渣量在9.9%左右.感度测试结果表明,该配合物为不敏感型的含能配合物.     

Chemical expansion in BaZr0.9−xCexY0.1O3−δ (x = 0 and 0.2) upon hydration determined by high‐temperature X‐ray diffraction

Understanding the strain from chemical expansion of proton‐conducting ceramics is crucial to prevent their failure under operating conditions. BZY10 (BaZr_0.9Y_0.1O_3?δ) and BZCY72 (BaZr_0.7Ce_0.2Y_0.1O_3?δ) were studied using high‐temperature X‐ray diffraction (HT‐XRD) in moist and dry reducing atmosphere in order to prevent the competition with the oxidation reaction. Both powder and dense specimens were investigated and similar lattice parameters were obtained, demonstrating that the data were recorded on samples that were in equilibrium with the surrounding environment. Two sets of experiments were performed. In the first one, the sample was hydrated in situ in the XRD chamber at high temperature and diffraction data were collected during cooling. For the second set, the samples were pre‐hydrated ex situ in an autoclave and the XRD patterns were recorded during heating under dry conditions. As expected, lattice parameters were larger for the hydrated samples, due to hydration chemical expansion. The chemical expansion was also found to be larger with the presence of Ce. Finally, larger concentrations of protonic defects were present in the lattice of the ex situ pre‐hydrated samples compared with the in situ hydrated samples.     

Structural,optical, thermoelectrical,and magnetic study of Zn1‐xCoxO (0 ≤ x ≤ 0.10) nanocrystals

In this work, we have prepared Co‐doped ZnO nanocomposites by zinc nitrate and cobalt sulfate as new precursors via the coprecipitation method and the samples were followed to identify the morphological, optical, structural, and magnetic properties. The XRD patterns revealed the crystalline nature of nanoparticles with hexagonal wurtzite structures, which meant that Co impurity did not disturb the structure of pure ZnO and the minimum crystallite size of nanoparticles was calculated to be around 37 nm. The XRD patterns also showed the lattice parameter increase owing to the incorporation of a Co dopant. The TEM results revealed the sphere‐like particles whose size varied between 56 and 88 nm in diameter at a 4% level of impurity. DRS analysis identified that the band gap energy decreased from 3.18 eV for the pure substance to 2.36 eV for the 10% impure substance. VSM analysis exhibited that the saturation magnetization value increased to 8.4 × 10^?3 emu/g for the highest Co content of 10%, which indicated the ferromagnetic behavior of NPs.     

Polyol Synthesis and Investigation of Ce1−xRExO2−x/2 (RE = Sm,Gd, Nd,La, 0 ≤ x ≤ 0.25) Electrolytes for IT‐SOFCs

In this study, we aimed to examine the effect of dopant type and concentration on the ionic conductivity of ceria‐based electrolytes. Ceria electrolytes doped with samarium (SDC), gadolinium (GDC), neodymium (NDC), and lanthanum (LDC) for solid oxide fuel cells were prepared through the polyol process. Acetate compounds of cerium and dopants were used as starting materials, and triethylene glycol was used as a solvent. Prepared powders and pellets were characterized by TG/DTA, XRD, FTIR, SEM, EIS, and EDS techniques. The results of the TG/DTA and XRD indicated that a single‐phase fluorite structure formed at the relatively low calcination temperature of 500°C. The relative densities of the pellets were higher than 90% and these finding were supported by the SEM images. The lattice parameters of the samples increased with the dopant concentration. According to the electrochemical analysis results, the samples with maximum conductivity values were SDC‐20, GDC‐15, NDC‐15, and LDC‐15. The results of the impedance spectroscopy revealed that the SDC‐20 sample exhibited the highest ionic conductivity with a value of 4.29 × 10^?2 S/cm at 800°C in air.     

Nanostructured high‐energy xLi2MnO3·(1‐x)LiNi0.5Mn0.5O2 (0.3 ≤ x ≤ 0.6) cathode materials

Nanostructured lithium‐manganese‐rich nickel‐manganese‐oxide xLi₂MnO₃·(1‐x)LiNi_0.5Mn_0.5O₂ (0.3 ≤ x ≤ 0.6) composite materials were synthesized via spray pyrolysis using mixed nitrate precursors. All the materials showed a composite structure consisting of Li₂MnO₃ (C2/m) and LiNi_0.5Mn_0.5O₂ components, and the amount of Li₂MnO₃‐phase appeared to increase with x, as observed from XRD analysis. These composite materials showed a high‐discharge capacity of about 250 mAhg^?1. In the range of x considered, the layered 0.5Li₂MnO₃·0.5LiNi_0.5Mn_0.5O₂ materials displayed the highest capacity and superior cycle stability. Nonetheless, voltage suppression from a layered‐spinel phase transition was observed for all the composites produced. This voltage suppression was dependent of the amount of Li₂MnO₃ phase present in the composite structure. © 2013 American Institute of Chemical Engineers AIChE J 60: 443–450, 2014