Relationships between crystal structure and microwave dielectric properties of Li2(Mg1−xCox)3TiO6 (0 ≤ x ≤ 0.4) ceramics

Li₂(Mg_1−xCo_x)₃TiO₆ (x = 0, 0.1, 0.2, 0.3, 0.4) ceramics were prepared using the conventional solid-state reaction method. Effects of Co-substitution on the crystal structure, sintering characteristics, micro–structures, microwave dielectric properties and Raman spectra were investigated. Co-substitution would affect the crystal structure and further influence the microwave dielectric properties. On the basis of the chemical bond theory and Rietveld refinement, some intrinsic factors such as the lattice energy, bond ionicity were calculated to explain the variations of the microwave dielectric properties. Ti–O and Li–O bonds played major role in influencing intrinsic factors and correlations between intrinsic factors of Ti–O, and Li–O bonds and microwave dielectric properties were established. With the increase of x values, the dielectric constant (ε_r) gradually increased, which could be explained by the variations of the polarizability, bond ionicity of Ti–O bonds, and Raman vibration modes. The decrease of the quality factor (Q·f) could be predicted by the decrease of the bond valence, packing fraction and lattice energy of Ti–O bonds. The temperature coefficient of resonant frequency (τ_ƒ) significantly correlated with the bond energy of Li–O bonds and thermal expansion coefficient of Ti–O bonds.     

Effects of Ti-substitution on the crystal structures,micro-structures and microwave dielectric properties of Li2Mg3Zr1-xTixO6 (0 ≤ x ≤ 1) ceramics

Li₂Mg₃Zr_1?xTi_xO₆ (x = 0, 0.2, 0.4, 0.6, 0.8, 1) ceramics were prepared via a solid-state reaction method. Crystal structures, sintering behaviors, micro-structures and microwave dielectric properties of Li₂Mg₃Zr_1?xTi_xO₆ (0 ≤ x ≤ 1) ceramics were investigated by XRD, SEM and chemical bond theory. XRD results showed that a single phase with the rock-salt structure was formed in all ranges. On the basis of the Rietveld refinement and chemical bond theory, several intrinsic parameters were calculated and connections between intrinsic parameters and microwave dielectric properties were investigated. The substitutions of Ti⁴⁺ for Zr⁴⁺ obviously increased the relative density and improved the quality factors. Variations of ε_r could be explained by changes of the polarizability. Q·f values showed the similar trend with the packing fractions, average bond valences and lattice energy of Zr–O bonds. τ_? values significantly correlated with the bond energy of Zr–O bonds.     

Intrinsic dielectric properties of columbite ZnNb2O6 ceramics studied by P–V–L bond theory and Infrared spectroscopy

In this study, intrinsic dielectric properties of ZnNb₂O₆ ceramics were investigated using P–V–L chemical bond theory and far-infrared reflectivity spectra. The largest bond ionicity and bond susceptibility of Nb–O bonds suggest that the dielectric polarizability is mainly determined by Nb–O bonds. Relative permittivity, calculated via P–V–L bond theory, is close to experimental value determined using TE₀₁₁ mode. The Nb–O bonds are also crucial for the structural stability. According to far-infrared reflectivity spectra and complex dielectric function analysis, a relatively consistent result between calculated and measured dielectric properties, fit using classical damped oscillator mode, indicate that the B_1u mode at 168.87 cm⁻¹ provides majority contribution to the dielectric properties.     

Crystal structure,chemical bond characteristics,and microwave dielectric properties of novel Sr2CaMoO6 ceramic at different sintering temperatures

This work prepared a novel Sr₂CaMoO₆ (SCM) ceramic through the conventional solid-state process. The crystal structure, chemical bond characteristics, and microwave dielectric properties of SCM ceramic were investigated for the first time. The X-ray diffraction patterns and Rietveld refinement indicate that SCM ceramic formed an orthorhombic phase with the space group Pmm2 (25) at temperatures above 1300 °C. The lattice vibrational modes of SCM ceramic were obtained through the Fourier transformed infrared spectrum (FTIR). The measured dielectric constant and dielectric loss of SCM ceramic is close to the theoretical values obtained by FTIR. According to the P–V–L theory, the chemical bond characteristics of SCM ceramic were calculated. The high ionicity and lattice energy of the Mo–O bond positively affect the properties of SCM ceramic. The outstanding microwave dielectric properties of ε_r = 19.37, Q·f = 32,970 GHz (at 5.96 GHz), and τ_f = ?32.56 ppm/°C were obtained in SCM ceramic sintered at 1450 °C. This work reveals the crystal structure of SCM ceramic, establishes the relationship between the properties and chemical bonds of the ceramic, and lays a foundation for studying the dielectric properties of related ceramic systems.     

Pseudo Phase Diagram and Microwave Dielectric Properties of Li2O–MgO–TiO2 Ternary System

Li₂O–MgO–TiO₂ ternary system is an important microwave dielectric ceramic material with excellent properties and prospect in both scientific research and application. A phase diagram of the Li₂O–MgO–TiO₂ ternary system was established in this article, based on earlier research results and our present work. Microwave dielectric properties with compositions in different regions of the phase diagram have been analyzed. We found that the 0.33 Li₂MgTi₃O₈–0.67 Li₂TiO₃ ceramics sintered at 1200°C exhibited excellent dielectric properties: Q × f value = 80 476 GHz (at 7.681 GHz), ε_r = 24.7, τ_f = +3.2 ppm/°C. We also designed two ceramic systems in the Li‐rich region of the Li₂O–MgO–TiO₂ ternary system, which received little attention in the past decades, because many excellent single‐phase ceramics, such as Li₂MgTiO₄, Li₂MgTi₃O₈ and MgTiO₃, have been found in the Ti‐rich region. The ceramic systems have low sintering temperatures but also relatively poor dielectric properties.     

Broad sintering temperature range and stable microwave dielectric properties of Mg2TiO4–CeO2 composite ceramics

There has been extensive research on microwave dielectric materials considering their application in 5G and 6G communication technologies. In this study, the sintering temperature range of Mg₂TiO₄–CeO₂ (MT-C) ceramics was broadened using a composite of CeO₂ and Mg₂TiO₄ ceramics, and their microwave dielectric performance was stabilized. Low-loss MT-C composite ceramics were prepared using the solid-phase reaction method, and their microwave dielectric properties, microscopic morphologies, and phase structures were investigated. The proposed MT-C ceramics contained Mg₂TiO₄ and CeO₂ phases; their average grain size was maintained at 2–4 μm in the sintering temperature range of 1275–1425 °C, and the samples were uniformly dense without porosity. The cross-distribution of Mg₂TiO₄ and CeO₂ grains in the samples inhibited the growth of ceramic grains, providing uniform and dense surfaces. The dielectric loss of MT-C ceramics remained constant in the temperature range of 1300–1425 °C at 9 × 10^?4 (8.45 ≤ f ≤ 8.75 GHz). As opposed to the base material, MT-C ceramics are advantageous owing to their wide sintering temperature range and the stable microwave dielectric properties, and there are suitable substrate materials for further industrial applications.     

Photocatalysis,microstructure, and surface characterization of TiO2‐loaded wooden‐activated carbon fibers

In this study, TiO₂‐loaded wooden‐activated carbon fibers (TiO₂/WACFs) were prepared by sol–gel method. TiO₂/WACFs were detected by scanning electron microscopy, X‐ray diffraction, Fourier transform infrared spectroscopy, and X‐ray photoelectron spectroscopy. The results showed that TiO₂ was deposited on almost each WCAF with a coating thickness. All the TiO₂ films on the surface of WACFs were composed of anatase with high photocatalytic property. The characteristic adsorption peaks of nano‐TiO₂ emerged at 1,402 and 471 cm⁻¹ on the infrared spectrum of TiO₂/WACFs. It was also found that Ti was in the binding state of Ti⁴⁺ (TiO₂) in the TiO₂/WACFs. As the calcination temperature increased, the content of elements Ti and Ti O bond of lattice oxygen on the surface of TiO₂/WACFs increased and then decreased, but the loaded nano‐TiO₂ did not affect the formation of graphite structure of WACFs. It is suggested that TiO₂/WACFs obtained at 450°C have the best photocatalytic property. POLYM. COMPOS., 36:62–68, 2015. © 2014 Society of Plastics Engineers     

Effects of TiO2 additive on ultra-low-loss MgO–LiF microwave dielectric ceramics

MgO ceramics have good microwave dielectric properties, but the high sintering temperatures limit its application. The effects of TiO₂ additive on the phase composition and microwave dielectric properties of MgO ceramics with 4mol%LiF were investigated by solid state reaction method. TiO₂ and MgO form Mg₂TiO₄ in a magnesium-rich environment with 4mol%LiF at about 900 °C, which as a solid solution or second phase had a huge impact on MgO ceramic with 4mol % LiF. When the content of TiO₂ less than 2mol %, Mg₂TiO₄ as a solid solution in MgO ceramics, which made the grain of MgO larger. When the content of TiO₂ more than 2mol %, Mg₂TiO₄ as a second phase in MgO ceramics, which made the microwave dielectric properties of MgO ceramics bad. Typically, the MgO-4mol%LiF-0.5mol%TiO₂ ceramic sintered at 1075 °C for 6 h acquired the best dielectric properties: ε_r = 9.7, Qf = 617,000 GHz and τ_f = −59.49 ppm/°C.     

Novel temperature stable NiSnTa2O8 microwave dielectric ceramics with trirutile structure

A novel low-loss and temperature stable NiSnTa₂O₈ ceramic with trirutile structure was prepared using traditional solid-state method. The structure-performance relationships were investigated by Rietveld refinement, chemical bond theory and far-infrared spectrum. The results show that the relative densities play a dominant role in the change of dielectric constant. Theoretical dielectric constant calculated via bond theory, Clausius-Mossotti equation and fitted result of far-infrared spectrum are close to experimental value. Ta–O bonds with greatest bond ionicity and bond energy have the primary contributions to dielectric polarizabilities and dielectric loss. The optimal microwave dielectric performances of NiSnTa₂O₈ ceramics were obtained: ε_r ∼21.04, Q×f ∼31328 GHz and τ_f = −2.63 ppm/^°C at 1425 °C.     

Chemical bond characteristics and infrared reflectivity spectrum of a novel microwave dielectric ceramic CaIn2O4 with near-zero τf

Orthorhombic-structured CaIn₂O₄ ceramics with a space group Pca2₁ were synthesized via a solid-state reaction method. A high relative density (95.6 %) and excellent microwave dielectric properties (ε_r ～11.28, Qf = 74,200 GHz, τ_f ～ ?4.6 ppm/°C) were obtained when the ceramics were sintered at 1375 °C for 6 h. The dielectric properties were investigated on the basis of the Phillips–Van Vechten–Levine chemical bond theory. Results indicated that the dielectric properties were mainly determined by the InO bonds in the CaIn₂O₄ ceramics. These bonds contributed more (74.65 %) to the dielectric constant than the CaO bonds (25.35 %). Furthermore, the intrinsic dielectric properties of the CaIn₂O₄ ceramics were investigated via infrared reflectivity spectroscopy. The extrapolated microwave dielectric properties were ε_r ～10.12 and Qf = 112,200 GHz. Results indicated that ion polarization is the main contributor to the dielectric constant in microwave frequency ranges.     

Effect of Mn2+ doping on the lattice and the microwave dielectric properties of MgTa2O6 ceramics

A series of Mn²⁺-doped Mg_1-xMn_xTa₂O₆ (x = 0.02, 0.04, 0.06, 0.08, 0.10, 0.12) ceramics were synthesized by solid-state reaction method. The influence of introducing Mn–O bonds as a partial replacement for Mg–O bonds on the lattice and microwave dielectric properties was systematically investigated. XRD and Rietveld refinement confirm that Mn²⁺ occupies the 2a Wyckoff position and forms a pure trirutile phase. Moreover, based on the chemical bond theory, the dielectric constant is mainly affected by the ionicity of the Ta–O bond. The lattice and dielectric properties remain relatively stable with Mn²⁺ doping below 0.1, but excessive Mn²⁺ doping leads to pronounced distortion of the lattice, which is not beneficial for lattice stability and microwave dielectric properties. Introducing an appropriate amount of Mn–O bonds with high bond dissociation energy facilitates MgO6 octahedron stability, which improves the thermal stability of the lattice. Accordingly, the microwave dielectric properties for 0.06 Mn²⁺-doped MgTa₂O₆ ceramics were determined: ε_r = 28, Q × f = 105,000 GHz (at 7.5 GHz), τ_f = 19.5 ppm/^°C.     

Ferroelectric–Dielectric Composites Model of Ba0.5Sr0.5TiO3/Mg2AO4(A = Ti,Si) for Tunable Application

The correspondence between the theoretical model and the experimental results of the dielectric response in two‐phase composites of Ba_0.5Sr_0.5TiO₃ and Mg₂AO₄ (A = Ti, Si)was studied. The Ba_0.5Sr_0.5TiO₃ (BST50)/Mg₂AO₄ composites in 2‐2 model structure consisting of BST50 layers and Mg₂AO₄ layers were fabricated by tape casting and multilayer technique. The 3‐0 model of the two‐phase composites is fabricated by conventional ball mill mixing and solid‐state reaction process. The ceramics samples with dense structure were obtained because the coefficient of thermal expansion (CTE) of Mg₂SiO₄ (12.84 ppm/°C) and Mg₂TiO₄ (12.11 ppm/°C) ceramic specimens are close to the pure BST50(13.15 ppm/°C) ceramic. The microstructure, dielectric, and tunable properties of 2‐2 and 3‐0 model composites were investigated. The experimental results agree well with the theoretical prediction in 2‐2 model. An important feature of 2‐2 model composites is that the DC field is efficiently applied to the high‐permittivity ferroelectric phase. With the increase in Mg₂AO₄ volume fraction q, the tunability of the composite remains almost unchanged whereas the permittivity greatly reduced in the 2‐2‐//model. These results show that the 2‐2‐//model sample is good candidates for the tunable devices.     

Crystal structure and temperature dependence of permittivity in barium aluminate based solid solutions

This study systematically investigated the structural, dielectric, and ferroelectric properties of BaAl_(2−2x)(Mg_0.5Ti_0.5)_2xO₄ ceramics in the 0 ≤ x ≤ 0.04 range. Single-phase solid solutions in the P6₃ space group with hexagonal crystal symmetry were confirmed in the composition range of 0 ≤ x ≤ 0.03. The bond lengths of Al1/(Mg,Ti)–O, Al₂/(Mg,Ti)–O, and Al₃/(Mg,Ti)–O increased with the increase in x, as confirmed through the Rietveld refinement and evolutions of corresponding modes in Raman spectra. The temperature stability of dielectric properties improved at a composition around x = 0.03, and the dielectric constant ε_r ascended with the increase in x. Ultrabroad temperature stability (−100°C to 700°C) was obtained, and an optimal combination (ε_r = 18.5, tan δ < 10⁻³, −22 ppm/°C ≤ TCC ≤ +20 ppm/°C, resistivity ~4.5 × 1014 Ω·cm) was achieved for the x = 0.03 ceramic sintered at 1260°C in air for 6 hours. The increase in stability was ascribed to the variations in axial bonds, and lattice distortions were determined through high-resolution transmission electron microscopy. The x = 0.03 ceramic could be a promising candidate for C0G or NP0 multilayer ceramic capacitors because of its low loss, high reliability, superior insulating properties and comparatively low-cost raw materials.     

The Impact of Composite Effect on Dielectric Constant and Tunability in Ferroelectric–Dielectric System

A theoretical study was carried out to analyze the impact of composite effect on dielectric constant and tunability in the ferroelectric–dielectric system. Models of Ba_0.5Sr_0.5TiO₃–Mg₂TiO₄, Ba_0.45Sr_0.55TiO₃–MgO and Ba_0.5Sr_0.5TiO₃–MgO–Mg₂SiO₄ system were constructed. The corresponding dielectric constant, tunability, and electric field distribution were obtained from the finite element analysis and the connections between these parameters were analyzed. The effects of the relative relationship between the dielectric constant of ferroelectric and dielectric on the whole dielectric properties were also analyzed by constructing a series of models with different dielectrics.     

Anomalous Correlation between Dielectric Constant and Tunability in (Ba,Sr)TiO3–MgO–Mg2SiO4 Composite Ceramics

(Ba, Sr)TiO₃–MgO–Mg₂SiO₄ composite ceramics were prepared by a solid‐state reaction method. The microstructures, microwave dielectric characteristics, and tunability of composite ceramics were investigated. An anomalous correlation between tunability and dielectric constant was observed: with the increase in Mg₂SiO₄ content and the decrease in MgO content, the dielectric constant of (Ba, Sr)TiO₃–MgO–Mg₂SiO₄ composite ceramics decreases, but the tunability increases. The anomalous increased tunability is beneficial for tunable microwave applications and can be attributed to the redistribution of the electric field. For 50Ba_0.5Sr_0.5TiO₃–(50?x)MgO–xMg₂SiO₄, the dielectric constant was decreased from 164.2 to 126.5 by increasing Mg₂SiO₄ content from 5 to 45 wt% and the tunability at 3.9 kV/mm increased from 11.5% to 15.2%.     

Crystal structural refinement of corundum-structured A4M2O9 (A = Co and Mg,M = Nb and Ta) microwave dielectric ceramics by high-temperature X-ray powder diffraction

The microwave dielectric properties and crystal structure of corundum-structured Mg₄Nb₂O₉ (MN), Co₄Nb₂O₉ (CN) and Mg₄Ta₂O₉ (MT) compounds were investigated in this study. The crystalline phases of the ceramics were characterized by using the high-temperature X-ray powder diffraction and the crystal structures of the compounds were refined in terms of Rietveld analysis. The temperature coefficient of resonant frequency (τ_f) varied from −70 to −10 ppm/°C with increasing the composition x when Mg was substituted by Co. From the calculation of covalency of cation–oxygen bonds, it is found that the covalency of CoO bond is lower than that of MgO bond and the difference in the covalency of these cation–oxygen bonds influences on the temperature dependence of dielectric constant on the compounds. As for the dielectric constant (ɛ_r) and the quality factor (Q·f) of the ceramics, these values ranged from 10 to 16 and from 210,000 to 5000 GHz, depending on the composition x.     

High quality factor microwave dielectric ceramics in the (Mg1/3Nb2/3)O2–ZrO2–TiO2 ternary system

Novel high quality factor microwave dielectric ceramics (1?x)ZrTiO₄?x(Mg_1/3Nb_2/3)TiO₄ (0.325≤x≤0.4) and (ZrTi)_1?y(Mg_1/3Nb_2/3)_yO₄ (0.2≤y≤0.5) with the addition of 0.5 wt% MnCO₃ in the (Mg_1/3Nb_2/3)O₂–ZrO₂–TiO₂ ternary system were prepared, using solid‐state reaction method. The relationship between the structure and microwave dielectric properties of the ceramics was studied. The XRD patterns of the sintered samples reveal the main phase belonged to α‐PbO₂‐type structure. Raman spectroscopy and infrared reflectivity (IR) spectra were employed to evaluate phonon modes of ceramics. The 0.65ZrTiO₄?0.35(Mg_1/3Nb_2/3)TiO₄?0.5 wt% MnCO₃ ceramic can be well densified at 1240°C for 2 hours and exhibits good microwave dielectric properties with a relative permittivity (ε_r) of 42.5, a quality factor (Q×f) value of 43 520 GHz (at 5.9 Ghz) and temperature coefficient of resonant frequency (τ_f) value of ?5ppm/°C. Furthermore, the (ZrTi)_0.7(Mg_1/3Nb_2/3)_0.3O₄?0.5 wt% MnCO₃ ceramic sintered at 1260°C for 2 hours possesses a ε_r of 31.8, a Q×f value of 35 640 GHz (at 6.3 GHz) and a near zero τ_f value of ?5.9 ppm/°C. The results demonstrated that the (Mg_1/3Nb_2/3)O₂–ZrO₂–TiO₂ ternary system with excellent properties was a promising material for microwave electronic device applications.     

Bi-modified SrTiO3-based ceramics for high-temperature energy storage applications

Dielectric capacitors with high energy storage performance are in great demand for emerging advanced energy storage applications. Relaxor ferroelectrics are one type dielectric materials possessing high energy storage density and energy efficiency simultaneously. In this study, 0.9(Sr_0.7Bi_0.2)TiO₃–0.1Bi(Mg_0.5Me_0.5)O₃ (Me = Ti, Zr, and Hf) dielectric relaxors are designed and the corresponding energy storage properties are investigated. The excellent recoverable energy density of 3.1 J/cm³ with a high energy efficiency of 93% is achieved at applied electric field of 360 kV/cm for 0.9(Sr_0.7Bi_0.2)TiO₃–0.1Bi(Mg_0.5Hf_0.5)O₃ (0.9SBT–0.1BMH) ceramic. High breakdown strength of 460 kV/cm in 0.9SBT–0.1BMH ceramic is obtained by Weibull distribution with satisfied reliability. In addition, 0.9SBT–0.1BMH shows outstanding thermal stability of energy storage performance up to 200°C, with the variation being less than 5%, together with satisfying cycling stability and high charge-discharge rate, making the 0.9SBT–0.1BMH ceramic a potential lead-free candidate for high power energy storage applications at elevated temperature.     

Evolution of TiOx-SiOx nano-composite during annealing of ultrathin titanium oxide films on Si substrate

This paper discusses the formation of the TiO_x-SiO_x nano-composite phase during annealing of ultrathin titanium oxide films (~27 nm). The amorphous titanium oxide films are deposited on silicon substrates by sputtering. These films are important for high-k dielectrics and sensing applications. Annealing of these films at 750 °C in the O₂ environment (for 15–60 min) resulted in the polycrystalline rutile phase. The films exhibit Raman peaks at 150 cm⁻¹ (B_1g), 435 cm⁻¹ (E_g), and 615 cm⁻¹ (A_1g) confirming the rutile phase. The signature TO (1078 cm⁻¹) and LO (1259 cm⁻¹) infrared active vibrational modes of Si–O–Si bond confirms the presence of silicon-oxide. The X-ray photoelectron spectra of the TiO_x films show multiple peaks corresponding to Ti metal (453.8 eV); Ti⁴⁺ state (458.3 eV (Ti 2p_3/2) and 464 eV (Ti 2p_1/2)); and Ti³⁺ state (456.4 eV (Ti 2p_3/2) and 460.8 eV (Ti 2p_1/2)). The O1s XPS spectra peaks at 530–533 eV can be attributed to Ti–O and Si–O bonds of the TiO_x-SiO_x nano-composite phase in the annealed films. The depth profiling XPS study shows that the top surface of the annealed film is mainly TiO_x and the amount of SiO_x increases with the depth.     

Ultrasound Synthesis of Polyindole–TiO2 Nanocomposite and Evaluation of Antibacterial Activity

The present work reports the synthesis and evaluation of antimicrobial activity of polyindole–TiO₂ nanocomposite. Polyindole–TiO₂ nanocomposite was synthesized by aqueous in situ chemical polymerization of indole using ammonium persulfate as an oxidant under ultrasonic condition. The synthesized polyindole and polyindole–TiO₂ nanocomposites were characterized by ultraviolet-visible spectroscopy, Fourier transform infrared spectroscopy, scanning electron microscope, thermogravimetric analysis, and X-ray diffraction techniques. A sharp peak at ～1,402?cm^?1 is due to the stretching vibrations of O?Ti?O bond in polyindole–TiO₂ nanocomposite. The X-ray diffraction pattern shows the major diffraction peaks at 25°C and 48°C, indicating TiO₂ in anatase form. Polyindole–TiO₂ shows maximum activity against gram-positive Staphylococcus aureus and Bacillus subtilis as compared to gram-negative Escherichia coli.