Selective synthesis of 3-picoline via the vapor-phase methylation of pyridine with methanol over Ni1-x Co x Fe2O4 (x = 0, 0.2, 0.5, 0.8 and 1.0) type ferrites

A series of Ni–Co ferrites with the general formula Ni_1-x Co _x Fe₂O₄ (x = 0, 0.2, 0.5, 0.8 and 1.0) was prepared by a low-temperature hydroxide coprecipitation route. The catalyst systems were characterized by adopting various physico-chemical techniques. Alkylation of pyridine with methanol was carried out in a down-flow vapor-phase reactor. The influence of surface acid–base properties, cation distribution in the spinel lattice and various reaction parameters are discussed. It was observed that the systems possessing x values 0.5 are selective for 3-picoline formation, whereas the ones with x values 0 and 0.2 give a mixture of 2- and 3-picolines. Pyridine conversion increased with the progressive substitution of Ni²⁺ ions by Co²⁺ ions. Cation distribution in the spinel lattice influences their acidic and basic properties, and these factors have been adequately considered as helpful to evaluate the activity of the systems.     

Improvement of microwave dielectric properties of the LiNb0.6Ti0.5O3 M-phase by doping with (Co1/3Nb2/3)4+

Structural evolution and microwave dielectric properties of LiNb_0.6(Ti_1-x[Co_1/3Nb_2/3]_x)_0.5O₃ (.05≤x≤.2) ceramics have been studied in this paper. Although the doped compositions maintain the M-phase solid solutions, compositional fluctuation due to nonuniform dispersion of minor dopants could be observed as x < .05, and trace amount of Li₂TiO₃-based solid solution (Li₂TiO₃ss) secondary phase presents in the x > .05 compositions. The microwave dielectric properties could be remarkably improved by the doping of (Co_1/2Nb_1/2)⁴⁺ in comparison to the undoped counterpart. Optimized microwave dielectric properties with Q × f = ∼6500 GHz, ε_r = ∼74 and τ_f = +8.2 ppm/°C could be obtained at x = .10 after sintering at 1050°C/2 h. The sintering temperature could be further reduced to 900°C/2 h by adding .2 wt% B₂O₃ without affecting significantly its microwave dielectric properties: ε_r = 73, Q × f = 6000 GHz, τ_f = +8.5 ppm/°C. The LiNb_0.6(Ti_1-x[Co_1/3Nb_2/3]_x)_0.5O₃ ceramics obtained in this case exhibit large dielectric permittivity coupled with much improved Q × f values, near zero τ_f, and low sintering temperature simultaneously, which makes it a promising high-k microwave dielectric material for low temperature cofired ceramic applications.     

Microwave dielectric properties and vibrational spectra of (Na0.5xLa1–0.5x)(Nb1−xMox)O4 ceramics with scheelite structures

In this study, (Na_0.5xLa_1–0.5x)(Nb_1?xMo_x)O₄ (0.0 ≤ x ≤ 1.0) ceramics were synthesized by the traditional solid-state reaction method. All the (Na_0.5xLa_1–0.5x)(Nb_1?xMo_x)O₄ samples could be densified well at 1120–1200 °C. Solid solutions with tetragonal scheelite structures were obtained in the (Na_0.5xLa_1–0.5x)(Nb_1?xMo_x)O₄ ceramics when 0.4 ≤ x < 1.0. A temperature-stable microwave dielectric ceramic with a near-zero temperature coefficient of resonant frequency (TCF) of approximately 2.4 ppm/°C was obtained for the (Na_0.25La_0.75)(Nb_0.5Mo_0.5)O₄ sample, along with a high Q×f value of approximately 45,600 GHz and a low permittivity of approximately 14.5. Introducing the fergusonite phase into the scheelite phase proved effective in obtaining a near-zero TCF.     

(1-x)BaTiO3-xLiNbO3陶瓷的制备及性能研究

采用复合溶胶凝胶法制粉技术结合传统陶瓷制备工艺，制备了（1-x）BaTiO3-xLiNbO3陶瓷，并对其晶相特征、介电及压电、铁电性能进行了研究。在1250℃下烧结的陶瓷形成了单一相的钙钛矿结构固溶体，该固溶体在20-40℃之间存在二级相变，介电常数及介电损耗出现异常变化。陶瓷的铁电、压电性能随LiNbO3的加入得到显著提高。LiNbO3加入量为0．005mol的陶瓷压电常数d33为121pC／N，剩余极化强度为2．8μC／cm^2。     

(1-x)Ba(Mg1/3Nb2/3)O3-xBaSnO3陶瓷的微波介电性能

用传统陶瓷制备方法制备了(1-x)Ba(Mg1/3Nb2/3)O3-xBaSnO3[0.0≤x≤0.3,(1-x)BMN-xBS]体系微波介质陶瓷,研究了该陶瓷的微观结构和微波介电性能.用X射线衍射仪研究陶瓷的晶体结构.用扫描电镜观察陶瓷的显微结构.用网络分析仪测试陶瓷的微波介电性能.结果表明:晶格常数c和a均随x值的增加而增加;晶格常数比(c/a)随x值的增加而减小.当x≥0.1时,1∶2有序衍射峰消失.陶瓷的平均晶粒尺寸在0.7～2 μm之间.随x值的增加,陶瓷的相对介电常数(εr)和谐振频率温度系数(τr)呈线性减小;品质因数与谐振频率的乘积(Qf)呈非线性变化.当x=0.15时,Qf达到最大值,为86 200 GHz.当x=0.3时,在此体系中可以获得τf接近零的微波介质陶瓷Ba(Sn0.3Mg0.233Nb0.467)O3,其微波介电性能如下:εr=26.1;Qf=42 500GHz;τr=4.3×10-6/℃.     

Magnetoelectric,magnetodielectric effect and dielectric,magnetic properties of microwave-sintered lead-free x(Co0.9Ni0.1Fe2O4)-(1-x)[0.5(Ba0.7Ca0.3TiO3)-0.5(BaZr0.2Ti0.8O3)] particulate multiferroic composite

Materials with two distinct (magnetostrictive-ferroelectric) phases, i.e., x (Co_0·9Ni_0·1Fe₂O₄) -(1-x) [0.5 (Ba_0·7Ca_0·3TiO₃) −0.5 (BaZr_0·2Ti_0·8O₃)], combined at ratios of 10:90, 20:80, 30:70, and 40:60 were prepared using a hydroxide coprecipitation method. These multiferroic composites were subjected to sintering via the hybrid microwave sintering technique at 1200 °C for 20 min. Ni-substituted CFO exhibited excellent magnetic properties at room temperature, with Ms ≈ 80 emu/g, μB ≈ 3.37, Mr ≈ 19.05 emu/g, and Hc ≈ 599 Oe, as well as a high value of the magnetostriction coefficient (λ12 ≈ −118 ppm). The magnetostrictive-ferroelectric crystal phases in each composite were confirmed via X-ray diffraction analysis. The highest value of the linear magneto-electric coefficient was α = 21.6 mV/cm-Oe at a frequency of 1 kHz for the 40CNFO-60(BCT-BZT) composite, and a similar sample had the highest value of the magnetodielectric coefficient, which was approximately 3.3% at f = 1 kHz with an applied magnetic field of 1 T. The typical ferromagnetic and ferroelectric nature of each composite was confirmed by M − H and P–E hysteresis loops, respectively at room temperature. Two anomalies were observed in the temperature-dependent dielectric permittivity one at ~140 °C and another above 500 °C confirming the coexistence of two materials with distinct transition points, i.e., BCT-BZT and CNFO, respectively.     

Structure,microstructure, dielectric and piezoelectric properties of (1-x-y)BiFeO3-xPbFe0.5Nb0.5O3-yPbTiO3 ceramics

Ceramics of seven quasi-binary concentration sections of the ternary solid solution system (1-x-y)BiFeO₃-xPbFe_0.5Nb_0.5O₃-yPbTiO₃ were prepared by the conventional solid-phase reaction method in the range of 0.05 ≤ x ≤ 0.325; 0.05 ≤ y ≤ 0.325. By using x-ray diffraction technique, the phase diagram of the system was constructed which was shown to contain the regions of tetragonal and rhombohedral symmetry and the morphotropic phase boundary between them. Grain morphology, dielectric and piezoelectric properties of selected solid solutions were investigated. The highest piezoelectric coefficient d₃₃ = 50 pC/N was obtained. Dielectric characteristics of ceramics revealed ferroelectric relaxor behavior and region of diffuse phase transition from the paraelectric to ferroelectric phase in the temperature range of 600–800 K.     

Influence of the stoichiometry,microstructure, and metallization method on the dielectric properties of 0.94 Na0.5Bi0.5TiO3-0.06 BaTiO3

The morphotropic composition of the lead-free solid solution between Na_0.5Bi_0.5TiO₃ and BaTiO₃ (0.94 Na_0.5Bi_0.5TiO₃-0.06 BaTiO₃ or NBT-6BT) is of particular interest for the next generation of high-temperature capacitors but remains plagued by the diversity of dielectric properties reported in the literature. In order to explain the apparent inconsistencies among the reported dielectric properties of NBT-6BT, we examine the influence of stoichiometry, phase separation, and metallization method. We show that the nominal stoichiometry has a crucial effect, since increasing the nominal Na/Bi ratio increases conductivity and dielectric losses (tan δ). It also increases the real part of the permittivity (ε’) and the frequency dispersion of both ε’ and tan δ, thereby altering the shape of the evolution with temperature of the dielectric properties. Moreover it increases the depolarization temperature (T_d) and decreases the temperature of maximum permittivity (T_m). Phase separation also occurs during the synthesis of NBT-6BT as Na evaporation leads to the formation of secondary Ba-containing phases. We report that these phases can have a positive impact on the dielectric properties: a moderate volume fraction (2.5 to 3.0%) and average grain surface (0.9 to 3.0 µm²) of these secondary Ba-containing phases increase the relative permittivity, decrease the dielectric losses, and increase the insulation resistance. We also show that the metallization method impacts the dielectric properties and therefore may contribute to the differences between various reports. The dielectric properties of NBT-6BT samples are measured during successive heating/cooling cycles and reveal that the permittivity value is lower during the first heating when silver paste, even cured, is used. These three components contribute to explaining the diversity of the reported dielectric properties of NBT-6BT.     

Microwave dielectric properties of low loss microwave dielectric ceramics: A0.5Ti0.5NbO4 (A = Zn,Co)

The microwave dielectric properties of low-loss A_0.5Ti_0.5NbO₄ (A = Zn, Co) ceramics prepared by the solid-state route had been investigated. The influence of various sintering conditions on microwave dielectric properties and the structure for A_0.5Ti_0.5NbO₄ (A = Zn, Co) ceramics were discussed systematically. The Zn_0.5Ti_0.5NbO₄ ceramic (hereafter referred to as ZTN) showed the excellent dielectric properties, with ɛ_r = 37.4, Q × f = 194,000 (GHz), and τ_f = −58 ppm/°C and Co_0.5Ti_0.5NbO₄ ceramic (hereafter referred to as CTN) had ɛ_r = 64, Q × f = 65,300 (GHz), and τ_f = 223.2 ppm/°C as sintered individually at 1100 and 1120 °C for 6 h. The dielectric constant was dependent on the ionic polarizability. The Q × f and τ_f are related to the packing fraction and oxygen bond valence of the compounds. Considering the extremely low dielectric loss, A_0.5Ti_0.5NbO₄ (A = Zn and Co) ceramics could be good candidates for microwave or millimeter wave device application.     

Novel B-site scheelite structure ceramic Bi(Ge0.5Mo0.5)O4 and its dielectric properties

Scheelite structure phase inorganic oxides show their irreplaceable role in numerous application areas due to their clear structure and superior properties, especially in dielectrics. Scheelite structure phase BiVO₄ has been permanently studied but substitutions, modifications, and explorations of novel phases persist hitherto and inspire more interest. In this work, we report a novel Scheelite structure phase of Bi(Ge_0.5Mo_0.5)O₄ and a detailed study of both structural analysis and dielectric properties investigation. Bi(Ge_0.5Mo_0.5)O₄ adopts the monoclinic Scheelite structure, identical to BiVO₄, with a dielectric permittivity of ∼ 35, Qf value of ∼20 000 GHz, and TCF value of ‒46 ppm/°C. No secondary ferroelastic transition was seen in Bi(Ge_0.5Mo_0.5)O₄ till 600°C, close to its synthetical temperature. The results indicate the success of discovering a new Scheelite structure phase and its prior engineering potential in modifying and substituting BiVO₄ over the dielectric area, photocatalyst, ion conductor, and so forth.     

Structural evolution,sintering behavior and microwave dielectric properties of Al(1-x)(Si0.5Zn0.5)xPO4 ceramics

Al_(1-x)(Si_0.5Zn_0.5)_xPO₄ (0 ≤x≤0.6) ceramics were prepared via solid state reaction process. Their structural evolution, sintering behavior and microwave dielectric properties were investigated by X-ray diffraction (XRD), scanning electron microscopy (SEM) and with a network analyzer. Phase pure AlPO₄ could not be obtained for the undoped composition. However, microscopically homogeneous single phase solid solution formed within the compositional range of 0 < x ≤ 0.05. Immiscibility with two-phase structure within apparently single phase solid solution could be observed for other doped compositions (0.1 ≤ x ≤ 0.6). Small level of doping with (Si_0.5Zn_0.5)³⁺ (x≤0.4) stabilized the orthorhombic cristobalite-like AlPO₄ (C-AlPO₄) phase; while further doping led to the transformation from orthorhombic α-C-AlPO₄ into cubic β-C-AlPO₄ phase. The doping with (Si_0.5Zn_0.5)³⁺ considerably improved the sinterability and reduced the sintering temperature to ?900 °C when x = 0.6. The dielectric permittivity slightly increases and the Q × f value decreases with the increasing doping concentration. All composition demonstrate low permittivity (?_r ?4) and negative value of τ_f. Good combined microwave dielectric properties with ?_r ?3.9, Q × f?25,000 GHz and τ_f ? -25 ppm/^oC could be obtained for the x = 0.2 composition after sintering at 1200 °C/2h.     

Na~+掺杂对尖晶石型Co_(1-x)Na_xFe_2O_4的结构及光催化性能的影响

采用溶胶-凝胶法制备了尖晶石型铁氧体Co1-xNaxFe2O4的系列样品,通用XRD,SEM对颗粒的结构、形貌进行了分析。结果表明,所合成的样品均为尖晶石型铁氧体;未掺杂样品CoFe2O4的形貌呈立方颗粒状,粒径均匀,边长约为1μm,掺杂后的样品Co0.8Na0.2Fe2O4颗粒为圆球状,尺寸大约在100~200nm,且有明显团聚的现象。通过对亚甲基蓝的降解情况对其光催化活性进行了研究。结果表明,经过A位Na+掺杂的CoFe2-xCrxO4样品,光催化活性明显提高。     

Enhancement of magnetic properties of Ni0.5Zn0.5Fe2O4 nanoparticles prepared by the co-precipitation method

Nano crystalline Ni–Zn ferrites of composition Ni_0.5Zn_0.5Fe₂O₄have been prepared by a chemical co-precipitation method. The powdered samples were sintered at a temperature of 800 °C and 900 °C for three hours. X-ray Diffraction (XRD), Field Emission Scanning Electron Microscopy (FESEM) and Fourier Transform Infrared (FTIR) Spectroscopy were used to study their structural and morphological changes. The enhanced magnetic properties were investigated by using a Vibrating Sample Magnetometer (VSM). The saturation magnetization was found to increase from 73.88 to 89.50 emu/g as a function of sintering temperature making this material useful for high frequency applications. Electromagnetic studies showed sustained values of permittivity up to 1 GHz. These results have been explained on the basis of various models and theories.     

Structure and microwave dielectric properties of Li(Al1-xLix)SiO4-x ceramics

Li(Al_1-xLi_x)SiO_4-x (x = 0.005, 0.01, 0.015, and 0.02) ceramics were synthesized via a traditional solid phase reaction method with different sintering temperatures. To determine the positions occupied by Li⁺ in the lattice, the defect formation energies and total energies of various sites of LiAlSiO₄ (LAS) occupied by Li⁺ were examined, and the energy of LAS systems were calculated using density functional theory of first-principle with the CASTEP module. The results demonstrated that the Al-sites occupied by Li⁺ had the lowest formation energies and total energy, so Li ⁺ should substitute Al³⁺. The impacts of replacing Al³⁺ with Li⁺ on the bulk density, sintering properties, phase composition, microstructure, and microwave dielectric properties of Li(Al_1-xLi_x)SiO_4-x (0 = x ≤ 0.02) ceramics were thoroughly studied. With Li⁺-doping, the sintering temperature decreased from 1300 °C (x = 0) to 1175 °C (x = 0.02), while the Q × f and τ_f values of LAS ceramics significantly increased. The Li(Al_0.99Li_0.01)SiO_3.99 ceramic was fully sintered at 1250 °C for 10 h to obtain excellent microwave dielectric properties: ε_r = 3.49, Q × f = 51,358 GHz, and τ_f = ?51.48 × 10^?6 °C^?1.     

Investigation of dielectric and piezoelectric properties in aliovalent Eu3+-modified Pb(Mg1/3Nb2/3)O3-PbTiO3 ceramics

Rare earth (Eu³⁺)-modified Pb(Mg_1/3Nb_2/3)O₃-PbTiO₃ (PMN-PT) polycrystalline ferroelectric ceramics were fabricated by high-temperature solid-state sintering, the phase structure, dielectric and piezoelectric properties were investigated. Eu³⁺ addition was found to significantly improve dielectric and piezoelectric properties of PMN-PT, where the optimized properties were achieved for the composition of 2.5 mol%Eu: 0.72PMN-0.28PT, with the piezoelectric d₃₃ = 1420 pC/N, dielectric ε_r = 12 200 and electromechanical k₃₃ = 0.78, respectively. All these results indicate that the Eu³⁺-doped PMN-PT ceramics are promising candidates for high-performance room-temperature piezoelectric devices.     

添加剂对Ba(Zn1/3Nb2/3)O3-Sr(Zn1/3Nb2/3)O3陶瓷介电性能的影响

研究了MnCO3,BaZrO3对0.35Ba(Zn1/3Nb2/3)O3(BZN)-0.65Sr(Zn1/3Nb2/3)O3(SZN)陶瓷介电性能的影响.研究表明:添加MnCO3,BaZrO3时,对陶瓷的烧结均起促进作用,增大介电常数.加入1%(质量分数)的MnCO3可使陶瓷具有较小的介质损耗,同时MnCO3对陶瓷的介电常数温度系数具有正向调整作用.加入BaZrO3后通过生成液相而减少了第二相Ba5Nb4O15,BaNb2O6的生成.所制备的(0.35BZN0.65SZN)+0.1%MnCO3陶瓷的εr≈43.6,αe≈-8×10-6/K,tanδ＝0.6×10-4,且烧结温度低于1 300℃.     

Weak ferroelectricity and low-permittivity microwave dielectric properties of Ba2Zn(1+x)Si2O(7+x) ceramics

Ba₂Zn_(1+x)Si₂O_(7+x) ceramics were prepared using the conventional solid-state method at 1200 °C for 3 h in air. Apart from the previously reported Ba₂Zn_(1+x)Si₂O_(7+x) (x = 0) with a monoclinic structure (C 2/c), the end-member compositions at x = −1 and 1 exhibit single-phase β-BaSiO₃ with an orthorhombic structure (P2₁2₁2₁) and BaZnSiO₄ with a hexagonal structure (P6₃), and possess a coexistence of weak ferroelectricity and low-permittivity microwave dielectric properties. A reduction in Zn²⁺ content mainly decreases the intensity of the ε_r anomaly peak at lower temperature and increases the ε_r (or frequency) stability against temperature. The Zn²⁺-rich BaZnSiO₄ phase has a τ_f value of −181 ppm/°C, whereas the τ_f value of Zn²⁺-free BaSiO₃ phase decreases to −35.4 ppm/°C. The Zn²⁺ deficiency in Ba₂ZnSi₂O₇ composition could inhibit the presence of BaZnSiO₄ phase and improve the τ_f value, whereas excessive Zn²⁺ cations prompt the formation of the BaZnSiO₄ phase to deteriorate significantly the τ_f value.     

Low-fire processing and microwave dielectric properties of LB glass-doped Ba3.75Nd9.5Ti17.5(Cr0.5Nb0.5)0.5O54 ceramic

The effects of LB glass on the sintering behavior, structure, and dielectric properties for the Ba_3.75Nd_9.5Ti_17.5(Cr_0.5Nb_0.5)_0.5O₅₄ (BNTCN) ceramic were investigated. The results showed that the LB glass, as an effective sintering aid, successfully lowered the sintering temperature of BNTCN ceramic by formation of the liquid phase. Furthermore, the change of the structure and decrease in grain size had influences on the electrical conductivity, thermal stability, and microwave dielectric properties for the BNTCN ceramics doped LB glass. Finally, the excellent microwave dielectric properties with ε_r = 73.4, Q × f = 5277 GHz, and τ_f = +7.1 ppm/°C were obtained for samples sintered at 950°C when x = 5, indicating the BNTCN ceramic doped with 5 wt% LB glass is a promoting LTCC material.     

Temperature-insensitive dielectric and piezoelectric properties in (1-x)K0.5Na0.5Nb0.997Cu0.0075O3-xSrZrO3 ceramics

Systematic investigation on phase transition, dielectric and piezoelectric properties of (1-x)K_0.5Na_0.5Nb_0.997Cu_0.0075O₃-xSrZrO₃ (x = 0, 0.03, 0.06, 0.09, 0.12, 0.15, abbreviated as KNNC-100xSZ) ceramics was carried out. Due to the coexistence of orthorhombic and tetragonal phase in a wide temperature range, a diffused polymorphic phase transition (PPT) region was achieved in KNNC with x ≥ 0.06. KNNC-12SZ ceramics exhibited high dielectric permittivity (∼1679), low dielectric loss (∼0.02) and small variation (Δe'/ε'_25 °C ≤ 15%) in dielectric permittivity from −78 °C to 237.3 °C. KNNC-6SZ ceramic possessed a high level of unipolar strain (∼0.15%) and maintained a smaller variation of ±12% under the corresponding electric field of 60 kV cm⁻¹ at 10 Hz from 25 °C to 175 °C. d₃₃^*, which was calculated according to the unipolar strain at 60 kV cm⁻¹, was 230 pm V⁻¹ and remained stable below 100 °C. Therefore, our work provided a new promising candidate for temperature-insensitive capacitors and piezoelectric actuators.