A novel Li2TiO3–Li2CeO3 ceramic composite with excellent microwave dielectric properties for low-temperature cofired ceramic applications

A novel low-temperature sinterable (1 ? x)Li₂TiO₃-xLi₂CeO₃ (x = 0.08 ? 0.16 in molar) microwave dielectric ceramic was successfully prepared by a conventional solid-state reaction method. The X-ray diffraction and scanning electron microscopy analysis revealed the coexistence of two phases with different structures owing to their good chemical stability. Their relative content was easily adjusted to achieve near-zero temperature coefficient of the resonant frequency (τ_f) according to the mixing rule of dielectrics. The low-temperature sintering and desirable microwave dielectric properties can be simultaneously achieved by adding Li₂CeO₃ to the Li₂TiO₃ matrix owing to its low-firing characteristic and opposite-sign τ_f. The composite ceramics with x = 0.14 could be well sintered at 850 °C and exhibited excellent microwave dielectric properties of ε_r ～ 21.2, Qxf～ 59,039 GHz and τ_f ～?7.4 ppm/°C. In addition, no chemical reaction was identified between the matrix phase and Ag, suggesting that the Li₂TiO₃-Li₂CeO₃ ceramics might be promising candidates for low-temperature co-fired ceramic applications.     

BaMnV2O7：A novel microwave dielectric ceramic for LTCC applications

A novel low-temperature fired BaMnV₂O₇ ceramic was fabricated with solid-state reaction. Rietveld refinements based on X-ray diffraction data and TEM analysis indicated that BaMnV₂O₇ exhibited a monoclinic structure with a P21/n space group. The dense microstructure of the BaMnV₂O₇ ceramic obtained at 850 °C was examined by scanning electron microscopy. The increasing content of V⁴⁺ affected the quality factor, which was confirmed by X-ray photoelectron spectroscopy. The intrinsic dielectric properties were obtained from far infrared reflectivity spectra. Additionally, the BaMnV₂O₇ ceramic showed good chemical stability with a Ag electrode and desirable microwave dielectric performance at 850 °C: ϵ_r = 11.7, Q × f =20040 GHz and τ_f = −48.2 ppm/°C, which can potentially be applied in LTCC technology.     

A novel fiber–veneer-laminated composite based on tannin resin

Natural nonwoven fiber was impregnated with a tannin resin and laminated with wood veneer for preparation of laminated composites. The tannin resin used showed a good compatibility with the natural fiber, and was easy to assemble with the wood veneers. The tannin resin penetration into the wood veneer was observed by light microscopy. The laminated composite shows very good mechanical properties and water resistance. Shear force–displacement testing demonstrates that the laminated composite had a ductile behavior under wet testing conditions. The laminated composite was prepared using 100% natural biorenewable raw materials and had good properties compared to conventional plywood bonded with synthetic resin.     

Property optimization of Ba0.4Sr0.6TiO3–BaMoO4 composite ceramics for tunable microwave applications

(1 ? x)Ba_0.4Sr_0.6TiO₃–xBaMoO₄ ceramics with x = 5, 10, 20, 30, 40 and 60 wt% were prepared by traditional solid-state reaction method. Two crystalline phases, a cubic perovskite structure Ba_0.4Sr_0.6TiO₃ (BST) and a tetragonal scheelite structure BaMoO₄ (BM) were obtained by XRD analysis. The microwave dielectric properties of Ba_0.4Sr_0.6TiO₃–BaMoO₄ composite ceramics were investigated systematically. The results show that the composite ceramics exhibited promising microwave properties. The dielectric constant can be adjusted in the range from 900 to 78, while maintaining relatively high tunability from 27.3% to 12.8% under a direct current electric field of 60 kV/cm and Q values from 619 to 67 in the gigahertz frequency region.     

Sintered ZrO2–TiO2 ceramic composite and its mechanical appraisal

This work mainly considered the effect of different TiO₂ additions and of sintering temperatures on the structural change, densification and mechanical properties of ZrO₂–TiO₂ ceramic composites obtained by cold compaction and subsequent sintering. The results demonstrated that the structural transformation happens from pristine monoclinic zirconia into tetragonal zirconia, amount of cubic phase in as-obtained ZrO₂–TiO₂ specimens could be distinguished as well. The increasing concentration of TiO₂ addition facilitated lower the sintering temperature and densification of ZrO₂ matrix. The grain growth and bulk density of ZrO₂–TiO₂ ceramic composites varied with the sintering temperatures and dopant concentrations. Full evaluation of the role of TiO₂ addition and sintering temperature on the mechanical properties of ZrO₂–TiO₂ samples was carried out in terms of Vickers hardness, flexural strength and fracture toughness. In particular, the ZrO₂ matrix with a value of 5 wt % TiO₂ generated the desired flexural strength and fracture toughness at the sintering temperature of 1400 °C.     

BaO–TiO2 microwave ceramics

In this paper, the structure and dielectric properties of BaO–TiO₂ system ceramics were studied. By adding ZnO and Nb₂O₅ as sintering agents to the raw materials, the BaO–TiO₂ system ceramics were sintered at a temperature of 1260 °C for 2 h and have superior dielectric properties at 1 GHz: quality factor Q=12,500, relative dielectric constant ε_r≈37, temperature coefficient of dielectric constant α_ε=0±30 ppm/°C. XRD pattern shows that the main crystal phase of the ceramics is Ba₂Ti₉O₂₀, accompanied by a small number of additional phases: BaTi₄O₉, Ba₄Ti₁₃Zn₇O₃₄, Ba₄Ti₁₃O₃₀ and Ti₂Nb₁₀O₂₉, etc. The initial Ba/Ti ratio has a great effect on the dielectric properties of the ceramics, which can be explained by the variance in the formation of phases due to different Ba/Ti ratios.     

Composite materials with ZrO2–TiO2 matrix and ZrO2 containing ceramic fibres

Abstract

The aim of the work reported in the present paper was to obtain composites consisting of a ZrO₂–TiO₂ matrix reinforced with ceramic fibres containing 12 wt-% ZrO₂, which are resistant to temperatures higher than1500°C. The resulting ceramic matrix consisted of 95 wt-% ZrO₂, partially stabilised with CaO, and 5 wt-% rutile TiO₂. A ceramic fibre content of 0·82 vol.-% was used and for the matrix, several grades of ZrO₂ partially stabilised with CaO were explored, prepared by dry and wet grinding for various grinding periods. Composites were prepared by uniaxial die pressing at 350 MPa and sintered at two temperatures: 1360°C for 1 h and 1500°C for 3 h. The resulting composites showed the following range of properties: total drying and firing shrinkage 0·4–3·3%; apparent density 3·51–3·96 g cm^-3; porosity 25–34%; water absorption 6–10%; bend strength 12–43 MPa. The optimum ZrO₂ grades were determined based on physical and mechanical properties, and on structural determinations carried out by thermodifferential and thermogravimetric analyses, X-ray diffraction (XRD), and scanning electron microscopy (SEM). SEM evaluation illustrated the increase in average size of crystallites typical of ZrTiO₄ solid solution as a function of temperature, from 2 μm at 1360 up to 14 μm at 1600°C, and of their tendency to sinter.     

Brazing SiC ceramic using novel B4C reinforced Ag–Cu–Ti composite filler

The development of new composite fillers is crucial for joining ceramics or ceramics to metals because the composite fillers exhibit more advantages than traditional brazing filler metal. In this research, novel B₄C reinforced Ag–Cu–Ti composite filler was developed to braze SiC ceramics. The interfacial microstructure of the joints was characterized by scanning electron microscope (SEM), X-ray diffraction (XRD) and transmission electron microscopy (TEM). The effect of B₄C addition and brazing temperature on the microstructure evolution and mechanical properties of the joints was analyzed. The results revealed that TiB whisker and TiC particles were simultaneously synthesized in the Ag-based solid solution and Cu-based solid solution due to the addition of B₄C particles. As the brazing temperature increased, the thickness of Ti₃SiC₂+Ti₅Si₃ layers adjacent to SiC ceramic increased. Desirable microstructure similar to the metal matrix reinforced by TiB whisker and TiC particles could be obtained at brazing temperature of 950 °C. The maximum bending strength of 140 MPa was reached when the joints brazed at 950 °C for 10 min, which was 48 MPa (~52%) higher than that of the joints brazed using Ag–Cu–Ti filler.     

A novel TiO2/ZrxTi1−xO2 composite photocatalytic films

TiO₂/Zr_xTi_1−xO₂ composite films have been prepared by sol–gel method and their photocatalytic activity and stability have been investigated for the first time. Their surface morphology and average surface roughness are characterized by AFM. TiO₂ P25 and pure sol–gel TiO₂ films have also been prepared and investigated for comparison. Films with smaller crystallite size and larger surface roughness have been obtained by introduction of Zr_xTi_1−xO₂ intermediate layers between TiO₂ layers and substrate in the composite films. The results show that the photocatalytic activity and stability of the composite films are higher than those of pure sol–gel TiO₂ and TiO₂ P25 films.     

Flexural strength of glass–ceramic for structural applications

In order to characterise the design strength of an innovative type of glass–ceramic with a view to structural applications, 4-point-bending and Ring-on-Ring biaxial bending tests have been performed. Strength is comparable with that of tempered glass but remarkably, the material breaks into large pieces like annealed glass. Interpreted through Weibull-type probability distributions, the data show much lower dispersion with respect to glass. Additional tests performed at different load rates have allowed an evaluation of the effects of static fatigue. Using a phenomenological model of equivalent-crack growth, a method is presented to calculate the decay of strength with loading time. As expected, this material is proven to be less sensitive than glass to this type of degradation.     

A novel polyborosilazane for high-temperature amorphous Si–B–N–C ceramic fibres

Polyborosilazane synthesised from BCl₃, HMeSiCl₂, and Me₃SiNHSiMe₃ is easy to cross-link for dehydrogenation of Si–H and N–H, which limits its practical applications for Si–B–N–C fibres on an industrial scale. Therefore, in this context, MeSiCl₃ was used instead of HMeSiCl₂ to synthesise a novel polyborosilazane with limited cross-linking density to fabricate Si–B–N–C fibres. The polyborosilazane synthesised from BCl₃, MeSiCl₃, and Me₃SiNHSiMe₃ exhibits good melt-processability and 1 km long polyborosilazane fibre can be obtained by melt spinning. Prior to pyrolysis, chemical curing with vapour HSiCl₃ at 80 °C was utilised to make the λ green fibres infusible. The as-cured fibres were subsequently pyrolyzed at 1200 °C in nitrogen atmospheres to provide Si–B–N–C ceramic fibres with ca. 1.5 GPa in tensile strength, ca. 160 GPa in Young's modulus, ca. 12 μm in diameter and keeping amorphous up to 1700 °C, which makes them to be promising reinforcements in ceramic matrix composites for high temperature applications.     

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.     

Crystal structure and microwave dielectric properties of Li2Mg0.6− xCoxZn0.4SiO4 ceramic for LTCC applications

In this work, Li₂Mg_0.6−xCo_xZn_0.4SiO₄ ceramics (x = 0–0.4) added with 3 wt% Li₂O–B₂O₃–Bi₂O₃–SiO₂ (LBBS) glass were synthesised using the solid-state reaction method. The effects of substituting Co²⁺ for Mg²⁺in Li₂Mg_0.6−xCo_xZn_0.4SiO₄ ceramics on crystal structure, microstructure, densification, crystallisation and microwave dielectric properties were investigated. X-ray diffraction patterns showed that monoclinic Li₂MgSiO₄, monoclinic Li₂ZnSiO₄ and orthorhombic Li₂CoSiO₄ formed finite solid solution in Li₂Mg_0.6−xCo_xZn_0.4SiO₄ ceramics. Clear grain boundaries were observed via scanning electron microscopy. The substitution of Co²⁺ for Mg²⁺ increased grain size, densification, crystallinity degree and dielectric constant; it also reduced the dielectric loss of the ceramics to a certain extent. The absolute values of τ_f were positively related to the crystallinity degree. Li₂Mg_0.55Co_0.05Zn_0.4SiO₄ ceramic added with 3 wt% LBBS and sintered at 900 °C exhibited considerable microwave dielectric properties of ε_r = 5.8, Q × f = 47,518 GHz and τ_f = −74.8 ppm/°C. Therefore, the ceramic is considered a candidate low-temperature co-fired ceramic material for substrate and filter applications.     

A new type of microwave dielectric ceramic based on K2O–SrO–P2O5 composition with high quality factor and low sintering temperature

A new type of microwave dielectric ceramics with low dielectric loss was fabricated through a traditional solid-phase method. X-ray diffraction and density tests showed that KSrPO₄ ceramics with a single orthorhombic phase could be synthesized and densified at 950 °C, and the crystal structure of KSrPO₄ was further confirmed by Rietveld refinement analysis. The densification temperature of KSrPO₄ was lower than 961 °C, indicating the ceramics could be used in LTCC devices. Additionally, based on the complex chemical bond theory, some internal parameters of KSrPO₄ ceramics were calculated and the effects of these parameters on the properties of KSrPO₄ were systematically analyzed for the first time. Furthermore, the composite dielectric constant and loss of KSrPO₄ ceramics were analyzed by infrared reflectance spectroscopy, and the theoretical loss and the actual loss were compared. Finally, a vector network analyzer was employed to measure the microwave dielectric properties of all samples. The results showed that KSrPO₄ sintered at 950 °C obtain the best microwave dielectric properties, including ε_r = 7.85, Q·f = 34,527 GHz (at 10.43 GHz) and τ_f = ?14.82 ppm/°C.     

Bi1/2Na1/2TiO3–BaTiO3 based thick-film capacitors for high-temperature applications

Thick films with compositions (1 − x)(0.94Bi_1/2Na_1/2TiO₃–0.06BaTiO₃)–x(K_0.5Na_0.5NbO₃) (x = 0, 0.03, 0.09 and 0.18) have been prepared and their structural and electrical properties have been investigated. Dielectric properties show that these films are well suited for high-temperature applications due to their low variance in permittivity (<15%) over large temperature ranges. The thick film with x = 0.18 offers an operational temperature range from room temperature to 350 °C. Films with x = 0.03 and 0.09 also possess a stabile permittivity up to 400 °C. The improvement in the thermal stability of the permittivity is attributed to the addition of K_0.5Na_0.5NbO₃ which leads to breaking of the long-range order in the materials. However, the polarizability of the materials was found to decrease possibly due to the clamping effect of the substrate. The characteristics of each film are discussed based on dielectric and electrical properties.     

A computational analysis of a ZrO2–SiO2 scale for a ZrB2–ZrC–Zr ultrahigh temperature ceramic composite system

The success of a ceramic composite for ultrahigh temperatures (i.e., >1873 K) in an oxidizing atmosphere resides in the protective characteristics of a scale to limit oxygen ingress or to control the oxygen reaction into the substrate. With temperature changes from room temperature to ultrahigh temperatures, the mechanics of the scale and its reactivity becomes critical for ceramic composites to operate under extreme environments. A study was pursued to design computationally a SiO₂–ZrO₂ scale for a ZrB₂/ZrC/Zr–Si composite by using conventional finite element analysis, which was used as a baseline microstructure for the extended finite element method. The model of the Zr boride/carbide composite with a SiO₂/ZrO₂/ZrSi_x scale simulates the development of local strain energetics under a thermal load from 300 to 1700 K. The computational analysis determined that the size of the SiO₂ and ZrSi_x precipitates does not appreciably influence the durability of the microstructure. A simulated annealing optimization algorithm was also developed for an extended finite element program (called XMicro) with the purpose of optimizing the auto re-meshing of XMicro and thus minimizing its combinatorial selection of a composite's reinforcement architecture. After correcting for the overlapping of ZrO₂ precipitates within a matrix, XMicro determined that 1.96 μm as the optimal spacing of precipitates within a cluster and 20 μm between clusters within a silica matrix of the scale interphase. The strategic experimentation determined that porosity developed during oxidation should be incorporated into the simulation of a ceramic composite. To probe into the efficacy of the silica layer for the scale, oxidizing experiments were performed at 1973 K, as well as microstructural analysis of the scale interphase. The computational mechanics coupled with consideration of the thermodynamic stability of phases for the Zr–Si–O system to set the oxygen potentials between layers can design a scale interphase for an ultrahigh-temperature, ceramic composite system. The processing challenge would be to attain the optimal configuration of the microstructure, for example, silicide precipitates developed with the appropriate spacing along a scale/matrix interface or ZrO₂ clusters within a silicate phase.     

A novel porous gel polymer electrolyte based on poly(acrylonitrile–maleic anhydride) composite by polyhedral oligomeric silsesquioxane for lithium-ion batteries

Journal of Applied Electrochemistry - A novel porous polymer membrane based on polyhedral oligomeric silsesquioxane (POSS) composite poly(acrylonitrile–maleic anhydride) (P(AN–MAH)) is...     

Soft magnetic composite based on iron in sintered Mn–Zn ferrite matrix without non-magnetic coating

Low core loss soft magnetic composites based on iron powder particles encapsulated in CoO- and TiO₂-doped sintered Mn–Zn spinel ferrite matrix are fabricated with no additional organic nor inorganic non-magnetic insulating layer. As both the iron and ferrite contribute to the entire effective composite properties with their ferromagnetic and ferrimagnetic nature, respectively, the resulting composites possess improved magnetic performance. The absence of any non-magnetic binder ensures higher ability of iron-matrix magnetic coupling. The temperature-dependent properties are tuned to higher level of operating temperatures of about 200 °C. The magnetic losses are shown to be suppressed thanks to the high electrical resistivity of ferrite insulation and permeability is enhanced because of the collectivization of iron particles and ferrite grains in magnetization process. This unique property descends from mediating the paths for magnetic flux between iron particles by ferrite matrix which, at the same time, mitigates the demagnetizing effects on the scale of composite's microstructure.     

Microwave dielectric materials based on the MgO–SiO2–TiO2 system

Ceramics in the system MgO–SiO₂–TiO₂ were prepared by standard mixed oxide route. By adding ZnO–B₂O₃ to the starting mixtures, the firing temperature of the ceramics could be reduced to 1160 °C. Small additions of MnCO₃ and CaTiO₃ improve microwave dielectric properties leading to an increase in insulation resistance and a decrease in temperature coefficient of capacitance. By adding Co₂O₃ grain growth can be inhibited and the dielectric Qf value greatly increased. The resultant ceramic material exhibited low dielectric constant and low dielectric loss: relative permittivity (ε_r): 20±2; temperature coefficient of capacitance (τ_c): 0±30 ppm/°C; Qf: 100,000 (at 10 GHz); insulation resistance: 10¹³ Ω cm:     

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.