Novel Low‐Firing Microwave Dielectric Ceramic LiCa3MgV3O12 with Low Dielectric Loss

Novel low temperature firing microwave dielectric ceramic LiCa₃MgV₃O₁₂ (LCMV) with garnet structure was fabricated by the conventional solid‐state reaction method. The phase purity, microstructure, and microwave dielectric properties were investigated. The densification temperature for the LCMV ceramic is 900°C. LCMV ceramic possessed ε_r = 10.5, Q_u × f = 74 700 GHz, and τ_f = ?61 ppm/°C. Furthermore, 0.90LiCa₃MgV₃O₁₂–0.10CaTiO₃ ceramic sintered at 925°C for 4 h exhibited good properties of ε_r = 12.4, Q_u × f = 57 600 GHz, and τ_f = 2.7 ppm/°C. The LCMV ceramic could be compatible with Ag electrode, which makes it a promising ceramic for LTCC technology application.     

Preparation of an environment-friendly LTCC material by using waste soda-lime glass and natural volcanic ash

Glass/ceramic composites applied in the field of low-temperature co-fired ceramics (LTCC) were successfully prepared at 670–710 °C by using waste soda-lime glass (WG) as a binder and natural volcanic ash as a ceramic raw material. Based on the theories of suppression and supplementary network effects, alkaline-earth metal ions (R²⁺, R = Mg, Ca, Sr, and Ba) and B₂O₃ were applied to improve the dielectric properties of WG and composites, respectively. The influence of R²⁺ on the crystal phase evolution, microstructure, mechanical, dielectric, and thermal properties of WG-volcanic ash-based composites were systematically investigated. By doping 2.5 wt% Ba²⁺ to the environment-friendly LTCC composites, physical properties i.e., ε_r of 4.86 at 1 MHz, tan δ of 6.32 × 10^?3, coefficient of thermal expansion of 8.72 × 10^?6/°C, and thermal conductivity of 1.04 W/(m·K) are obtained. It is worth mentioning that the environment-friendly LTCC composite uses WG with a low glass transition temperature to reduce the sintering temperature and a tiny amount of a modifier to adjust the dielectric performance instead of synthesizing specific crystals by adding lots of chemical reagents. These, in turn, do not only have the potential to be used in the LTCC packaging technology but also have significance for sustainable development. Additionally, because of good chemical compatibility between aluminum and the composites, the environment-friendly LTCC composites with ultra-low sintering temperature have the potential ability to lower the cost of LTCC packaging materials.     

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.     

Cold sintered LiMgPO4 based composites for low temperature co-fired ceramic (LTCC) applications

Cold sintered, Li₂MoO₄-based ceramics have recently been touted as candidates for electronic packaging and low temperature co-fired ceramic (LTCC) technology but MoO₃ is an expensive and endangered raw material, not suited for large scale commercialization. Here, we present cold sintered temperature-stable composites based on LiMgPO₄ (LMP) in which the Mo (and Li) concentration has been reduced, thereby significantly decreasing raw material costs. Optimum compositions, 0.5LMP-0.1CaTiO₃-0.4K₂MoO₄ (LMP-CTO-KMO), achieved 97% density at <300°C and 600 MPa for 60 minutes. Raman spectroscopy, X-ray diffraction, scanning electron microscopy, and energy dispersive X-ray mapping confirmed the coexistence of end-members, LMP, CTO, and KMO, with no interdiffusion and parasitic phases. Composites exhibited temperature coefficient of resonant frequency ~ –6 ppm/°C, relative permittivity ~9.1, and Q × f values ~8500 GHz, properties suitable for LTCC technology and competitive with commercial incumbents.     

Integration of High‐Frequency M‐Type Hexagonal Ferrite Inductors in LTCC Multilayer Modules

Monolithic hexagonal BaCo_1,3Ti_1,3Fe_9,4O₁₉ ferrite multilayers sintered at 900°C exhibit a fine‐grained microstructure with permeability of μ′ = 16 and a resonance frequency f_r ≥ 1GHz. Co‐firing of hetero‐laminates of ferrite with CT700 glass–ceramic LTCC tapes and with polycrystalline zinc titanate (ZT) LTCC tapes was studied. Co‐firing at 900°C of ferrite/CT700 leads to multilayers with cracks caused by substantial thermal expansion mismatch. Co‐fired ferrite/ZT multilayer laminates exhibit a permeability of μ′ = 16 and do not show any defects. Hexagonal ferrite multilayer inductor elements were integrated into ZT‐based multilayer LTCC modules and co‐fired at 900°C with Ag metallization.     

A Novel Low‐Firing and Low Loss Microwave Dielectric Ceramic Li2Mg2W2O9 with Corundum Structure

The crystal structure and microwave dielectric properties of a novel low‐firing compound Li₂Mg₂W₂O₉ were investigated in this study. The phase purity and crystal structure were investigated using X‐ray diffraction analyses and Rietveld refinement. The best microwave dielectric properties of the ceramic with a low permittivity (ε_r) ~11.5, a quality factor (Q × f) ~31 900 GHz (at 10.76 GHz) and a temperature coefficient of the resonant frequency (τ_f) ~ ?66.0 ppm/°C were obtained at the optimum sintering temperature (920°C). CaTiO₃ was added into the Li₂Mg₂W₂O₉ ceramic to obtain a near zero τ_f, and 0.93Li₂Mg₂W₂O₉–0.07CaTiO₃ ceramic exhibited improved microwave dielectric properties with a near‐zero τ_f ~ ?1.3 ppm/°C, a ε_r ~21.6, a high Q_u × f value ~20 657 GHz. The low sintering temperature and favorable microwave dielectric properties make it a promising candidate for LTCC applications.     

Ultralow-permittivity glass /Al2O3 composite for LTCC applications

In the field of low temperature co-fired ceramic (LTCC), it remains a challenge to design the performance of LTCC with low permittivity less than 5. Here, a novel glass mixture of K-Al-B-Si-O (KABS) and Zn-B-Si-O (ZBS) is introduced as a sintering aid of alumina to obtain ultralow-permittivity glass/Al₂O₃ composite. Meanwhile, the factors of glass mixture component on microstructure, phase structure and dielectric properties of the composites are considered systematically. The crystal structure measured by X-ray diffraction (XRD) shows that pure crystalline phase of ZnAl₂O₄ spinel can be attained by tailoring the component of the glass mixture. In case of mass ratio of KABS: ZBS equal to 6:4, it favors to efficiently increase the sintering densification of composite, and significantly benefit the low dielectric loss, good mechanical and thermal performances. In detail, the optimal glass/ceramic composites sintered at 850 °C for 2 h exhibit the bulk density of 2.89 g/cm3, ε_r of 4.92 at 14 GHz and Q × f of 6873 GHZ, flexural strength of 202 MPa, thermal expansion coefficient of 5.5 ppm/°C. The above study provides an effective approach for preparing the novel composites as a promising candidate for LTCC applications.     

Effect of processing route on thermomechanical properties of low temperature firing ceramic for electronic packaging

Abstract

Mechanical properties and thermal expansivities of two compositionally identical ceramics intended for use in 'low temperature cofired ceramic' (LTCC) technology were investigated. Both were based on a commercial MgCaTiO₃ dielectric ceramic with the sintering temperature reduced by addition of ZnO-B₂O₃-SiO₂, either in the glassy state or as separate glass forming oxides. Although in each case the additions were accompanied by decreases in elastic modulus, flexural strength, hardness, fracture toughness, and linear thermal expansivity, the values remained close to those for commercial LTCC materials. The route which involved mixing the separate oxides produced a slightly tougher material, which also had a thermal expansivity closer to the optimum value. The study demonstrates that an acceptable LTCC ceramic can be produced starting from glass forming oxides as sintering aids, thus avoiding the need for glass melting and comminution steps.     

Phase formation and microwave dielectric properties of BiMVO5 (M = Ca,Mg) ceramics potential for low temperature co-fired ceramics application

Two low-firing BiMVO₅ (M = Ca, Mg) ceramics were prepared in the sintering temperature range of 760-850°C. Their differences in phase formation, sintering behavior, and dielectric performances were investigated. BiCaVO₅ formed a single phase with an orthorhombic structure, while BiMgVO₅ crystallized in a monoclinic structure that needs longer dwelling time to obtain single phase. The optimized microwave dielectric properties were obtained with ε_r = 15.70, Q × f = 55 000 GHz (at 10.6 GHz), and τ_f = −71 ppm/°C for BiCaVO₅, ε_r = 18.55, Q × f = 86 860 GHz (at 9.63 GHz), and τ_f = −65 ppm/°C for BiMgVO₅. In addition, the large negative τ_f values of BiMVO₅ (M = Ca, Mg) ceramics were successfully adjusted by forming composite ceramics with CaTiO₃ and near-zero τ_f values of +2 ppm/°C and −3 ppm/°C were obtained in 0.92BiCaVO₅-0.08CaTiO3 and 0.94BiMgVO₅-0.06CaTiO₃, respectively. Both ceramics exhibited good chemical compatibility with Ag electrode. The results demonstrate BiMVO₅ (M = Ca, Mg) ceramics to be attractive candidates in LTCC technology.     

Densification,flexural strength and dielectric properties of CaO-MgO-ZnO-SiO2/Al2O3 glass ceramics for LTCC applications

Novel glass ceramics for LTCC applications with high flexural strength can be achieved by CaO-MgO-ZnO-SiO₂(CMSZ) glass cofiring with Al₂O₃. The sintering shrinkage behavior, crystalline phases, mechanical and dielectric properties, and thermal expansion of the CMZS/Al₂O₃ glass ceramic were determined. The X-ray diffraction results revealed that multiphases (CaMgSi₂O₆, Al₂Ca(SiO₄)₂ and ZnAl₂O₄) formed in the sintering process of the CMZS/Al₂O₃ glass ceramic. The flexural strength of CMZS/Al₂O₃ glass ceramics first increases and then decreases with increasing Al₂O₃ content. The CMZS/Al₂O₃ glass ceramic with 50 wt % Al₂O₃ sintered at 890 °C for 2 h achieved the best performance, with a maximum flexural strength of 256 MPa, dielectric constant (ε_r) of 7.89, dielectric loss (tan δ) of 3.41 × 10⁻³ (12 GHz), temperature coefficient of resonance frequency (τ_f) of −29 ppm/°C, and the CTE value of 7.93 × 10⁻⁶/°C.     

The modification of surface,size and shape of barium zirconate powder via salt flux

The “top-down” process via direct conversion of the micro (μm)-to-submicroscale (sub-μm) particle was applied in this work by using eutectic chloride salts to prepare BaZrO₃. The particle size at optimum condition could be decreased by more than 10 times from 2.1 ± 0.9 μm to 168 ± 23 nm without destroying the 1:1 of Ba:Zr stoichiometry. The uniform sub-μm-BaZrO₃ powder was sintered in order to obtain ~98% dense ceramic at 1400°C/10 h, which is significantly lower than the 1650°C in normal cases. The microwave dielectric constant, tan δ, and quality factor were also determined. Furthermore, this method also was applied to lead-free piezoelectric material in the 0.87BaTiO₃–0.13BaZrO₃–CaTiO₃ (0.87BT–0.13BZ–CT) system. The particle size of 0.87BT–0.13BZ–CT was reduced greatly from >10 µm to 2.8 ± 0.4 µm. It can be proved that salt flux dissolution method enables high-purity with uniform sub-micro/nanometer powder production in one step by using simple laboratory equipment and low-cost raw materials.     

Influence of particle size on densification and abnormal expansion of LTCC multilayer substrate

Abstract

Two series of LTCC (low temperature cofired ceramic) multilayer substrates were fabricated using glass powders with different particle sizes. The series with finer particle size always showed better densification properties. Abnormal expansion was found in the experimental samples as a result of the emergence and growth of a second crystalline phase, Al₃Si₂O₁₃.     

Influence of LaMgAl11O19 On Solid Particle Impact Erosion Wear Behavior of 3YSZ Ceramic at Elevated Temperatures

To study the improvement in solid particle impact erosion wear resistances of 3 mol% yttria‐stabilized zirconia (3YSZ) ceramic at elevated temperatures up to 1400°C, 2 wt% LaMgA1₁₁O₁₉ was added into 3YSZ to prepare LaMgA1₁₁O₁₉‐3YSZ ceramic for erosion resistance tests with angular corundum abrasive particles. The testing results show that the volume erosion rates of 3YSZ and LaMgA1₁₁O₁₉‐3YSZ ceramic were similar in the temperature range from room temperature to 600°C, then exhibited a sharp increase from 600°C to 1200°C, and dropped again at 1400°C. It was mainly caused by the change in material removal mechanisms from plastic deformation below 600°C to the interaction of transverse cracks in the temperature range from 600°C to 1400°C. The solid particle impact erosion wear properties of 3YSZ ceramic in the temperature range from 600°C to 1400°C were successfully improved by the addition 2 wt% LaMgA1₁₁O₁₉ platelets. Comparing with the volume erosion rate of pure 3YSZ ceramic (0.687 mm³/g) at 1200°C, the value of LaMgA1₁₁O₁₉‐3YSZ ceramic (0.551 mm³/g) has been decreased by 20%.     

Chemical Processes During Energy‐Saving Preparation of Lightweight Ceramics

Lightweight glass‐ceramic material similar to foam glass was obtained at 700°C–800°C directly from alkali‐activated silica clay and zeolitized tuff without preliminary glass preparation. It was characterized by low bulk density of 100–250 kg/m³ and high pore size homogeneity. Chemical processes occurring in alkali‐activated silica clay and zeolitized tuff were studied using X‐ray diffraction, thermal gravimetry, IR‐spectroscopy, and scanning electron microscopy. Pore formation in both compositions is caused by dehydration of hydrated sodium polysilicates (Na₂O·mSiO₂·nH₂O), formed during alkali activation. Additional pore‐forming gas source in alkali‐activated zeolitized tuff is trona, Na₃(CO₃)(HCO₃)·2H₂O, formed during interaction between unbound NaOH and CO₂ and H₂O from air. Influence of mechanical activation of raw materials on chemical processes occurring in alkaline compositions was also studied.     

Sintering kinetics of a 18.8Li2O 8.3ZrO2 64.2SiO2 8.7Al2O3 glass ceramic

The LZSA (Li₂O-ZrO₂-SiO₂-Al₂O₃) glass ceramic system has shown high potential as low temperature co-fired ceramics, the so called LTCC, for several applications, such as screen-printed electronic components, due to its low sintering temperature (< 1000 °C). However, a good microstructural control must be achieved in order to obtain a low porosity material. The 18.8Li₂O 8.3ZrO₂ 64.2SiO₂ 8.7Al₂O₃ LZSA glass ceramic composition was prepared by melting, quenching in water, and grinding in order to obtain a very fine powder (3.78 μm mean particle size). Subsequently, compacted bodies were obtained by uniaxial pressing (40 MPa) and drying. Sintering kinetics was investigated by optical dilatometry measurements and scanning electron microscopy (SEM) observations. The activation energy for sintering was found to be 314 kJ.mol⁻¹, whilst a maximum linear shrinkage of 22% and porosity of 3.5% were obtained with 10 min swelling time at 800 °C.     

New Sintered Li2O–Al2O3–SiO2 Ultra‐Low Expansion Glass‐Ceramic

We developed a new Li₂O–Al₂O₃–SiO₂ (LAS) ultra‐low expansion glass‐ceramic by nonisothermal sintering with concurrent crystallization. The optimum sintering conditions were 30°C/min with a maximum temperature of 1000°C. The best sintered material reached 98% of the theoretical density of the parent glass and has an extremely low linear thermal expansion coefficient (0.02 × 10^?6/°C) in the temperature range of 40°C–500°C, which is even lower than that of the commercial glass‐ceramic Ceran^® that is produced by the traditional ceramization method. The sintered glass‐ceramic presents a four‐point bending strength of 92 ± 15 MPa, which is similar to that of Ceran^® (98 ± 6 MPa), in spite of the 2% porosity. It is white opaque and does not have significant infrared transmission. The maximum use temperature is 600°C. It could thus be used on modern inductively heated cooktops.     

Silver Co‐Firable Li2ZnTi3O8 Microwave Dielectric Ceramics with LZB Glass Additive and TiO2 Dopant

New dielectric ceramics are prepared by the conventional solid‐state ceramic route. Effects of LZB glass on sintering, phase purity, microstructure, and dielectric properties of Li₂ZnTi₃O₈ ceramics have been investigated. Adding LZB lowers sintering temperature from 1050°C to 875°C, and does not induce much degradation of dielectric properties. The 1.0 wt% LZB glass‐added ceramic has better properties of ε_r = 23.9, Q × f = 31,608 GHz, τ_f = ?14.3 ppm/°C. Additions of TiO₂ markedly improve microwave properties. Typically, the Li₂ZnTi₃O₈ + 1 wt%LZB + 3.5 wt%TiO₂ sintered at 900°C shows ε_r = 26.1, Q × f = 45,168 GHz, τ_f = ?4.1 ppm/°C. Compatibility with Ag electrode indicates that this material may be applied to LTCC devices.     

Pt-V2O5-WO3/TiO2 catalysts supported on SiC filter for NO reduction at low temperature

The catalytic filter, V₂O₅-WO₃-TiO₂ supported on a ceramic filter, is known as a promising material for treating particulates and NO _x simultaneously at optimum temperatures around 320°C. In order to improve its catalytic activity at low temperatures, the effect of Pt addition on the catalytic filter has been investigated. Catalytic filters, Pt-V₂O₅-WO₃-TiO₂/SiC, were prepared by co-impregnation of Pt, V, and W precursors on TiO₂ coated-SiC filter by vacuum aided-dip coating. The Pt-added catalytic filter shifted the optimum working temperature from 280–330°C (for the non Pt-impregnated filter) to 180–230°C, providing N _x slip concentration less than 20 ppm for the treatment of 700 ppm NO at a face velocity of 2 cm/s with the same value over the non Pt-added catalytic filters. The promotional effect following the addition of Pt is believed to result from electrical modification of the catalyst maintaining a high electron transfer state. Ammonia oxidation was also observed to be dominant above the optimal temperature for SCR.     

Synthesis of Complex Lanthanum and Calcium Titanates with a Perovskite Structure and Their Electric Properties Studied at High Temperatures

Phase formation in the CaTiO₃ – La₂O₃ system in the concentration range 0 – 40 mol.% La₂O₃ is revisited. Conductivity, dielectric constant, and dielectric loss are measured in the temperature range of 5 – 600°C, and electric strength and the temperature coefficient for dielectric constant (TCε) of perovskite phases in the CaTiO₃ – La₂O₃ system are determined. The ceramic materials studied have a low dielectric loss depending but slightly on temperature [tan d = (1 – 6) × 10^–4], a high dielectric constant (ε = 30 – 120), and a TCε varying from – 1480 × 10^–6 deg^–1 to + 10,500 × 10^–6 deg^–1 with composition; the zero point for TCε is identified at 23 mol.% La₂O₃.     

Effect of PSO and TiB2 content on the high temperature adhesion strength of SiBCNO ceramic

In the present work, SiBCNO-based ceramic as high temperature adhesives are fabricated by polymer derived ceramic route. The effect of polysiloxane (PSO) and TiB₂ on the microstructure and high temperature strength is studied, and the toughing effect of TiB₂ is discussed. The highest adhesion strength of the joint (S12) reached up to 18.95?MPa at room temperature and 12.3?MPa at 1000?°C in vacuum after pyrolysis at 1000?°C in air for 2?h. It is interesting to find that the crystallization of nano-SiO₂ reinforces the strength and thermal stability of glass phase with the addition of PSO, besides, the TiB₂ plays the important role in improving adhesion strength by bearing load and facilitating the formation of stable SiO₂-B₂O₃-TiO₂ glass.