Crystallization behaviour and properties of BaO-CaO-B2O3-SiO2 glasses and glass-ceramics for LTCC applications

The influence of BaO content (up to 15?mol%) on the crystallization behaviour, structure, thermal properties and microwave dielectric properties of the BaO-CaO-B₂O₃-SiO₂ glasses and glass-ceramics system was investigated. The glasses were produced by melting at 1400?°C and quenching into water, and the glass-ceramics were produced via heat treatment at temperatures between 750 and 800?°C. The results of X-ray diffraction analysis showed that increasing the BaO content raised the resistance of the glass against crystallization and favoured the transformation of β-CaSiO₃ and α-CaSiO₃ phases, which crystallized in the Ba-free and in low BaO content compositions, into SiO₂ and Ba₄Si₆O₁₆, which crystallized in compositions with higher concentrations of BaO. The BaO content had little influence on the glass transition temperature (T_g) and the linear coefficient of thermal expansion (CTE), but strongly reduced the softening point (T_s). Even the addition of BaO as minor additives resulted in a dramatic reduction of the T_s; for example, the T_s decreased from 902?°C for the Ba-free composition to 682?°C for the BaO-containing one (5%). Low values of the dielectric constant (5.9?≤?ε_r ≤?6.63) and dielectric loss (1.12?×?10^?3 ≤?tanδ?≤?3.15?×?10^?3) were measured.     

Synthesis and characterization of LTCC compositions with middle permittivity based on CaO-B2O3-SiO2 glass/CaTiO3 system

CaTiO₃ ceramics with the addition of CaO-B₂O₃-SiO₂ (CBS) glass (45–55 wt%) composites were sintered at 830 °C, 850 °C, 875 °C and 900 °C. To illustrate influence mechanism of the different glass contents and sintering temperatures on the properties of the composites, we focused on the multiple performances of the composites by employing different qualitative and quantitative instruments. Composites with 50 wt% glass sintered at 875 °C presented fairly ideal performance: the bulk density was 3.20 g/cm³, the dielectric constant was 25.7 and the dielectric loss was 0.0009 at 7 GHz. Micro-Structure analysis of the composites showed a dense and pore-less microstructure except for few pores with size around 1 μm. In addition, the composite could meet the shrinkage requirement of Ag electrodes and could not possibly react with Ag electrodes any more. This makes them suitable for various dielectric applications at low sintering temperature.     

Manufacturing a high performance film of CaO-B2O3-SiO2 glass-ceramic powder with surface modification for LTCC application

The present work was oriented to develop a high-performance film for LTCC application through using a kind of silane coupling agent (SCA) to modify the CBS (CaO-B₂O₃-SiO₂) glass-ceramic powders in tape casting process. The coupling mechanism of the silane coupling agent interacting with the powders was illustrated in detail, and the optimum amount of additions was determined by the infrared transmittance and contact angle experiment. The rheological properties of suspensions, the compactness and tensile breaking strength of the green tape were texted by using a number of quantitative and qualitative instruments. Furthermore, when the green tapes sintered at 820 °C, the sintering characteristics and microwave properties of sintered body with different SCA additions was also analyzed. Based on the experimental results, it revealed that the powders modified by SCA with 1.5 wt% additions could induce the most excellent performance of film, with the density at 1.57 g/cm³ and the tensile strength at 2.57 MPa, possessing the highest density and best microwave properties of sintered body: the density of sintered body was 2.48 g/cm³, the dielectric constant and dielectric loss was ε_r = 5.93, tanδ=8 × 10^?4 at 12 Hz.     

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.     

Fabrication of a high-performance film based borosilicate glass/Al2O3 ceramics for LTCC application

The present work was initiated aiming at developing a high-performance film for LTCC application using a kind of polymeric dispersant in tape casting process of borosilicate-based glass/Al₂O₃ ceramics. The dispersion mechanism of the polymeric dispersant with the powders was analyzed in detail and the optimal amount of the dispersant addition was also determined through the sedimentation experiment. Its effects on the compactness, tensile strength and surface roughness of the films were analyzed. In addition, the sintering and microwave properties of the composite fired at 850 °C were also determined. For the application of tape technology, the co-firing compatibility between the composite and Ag electrodes at 850 °C was also verified. After testing and verification with different qualitative and quantitative instruments, a flexible film optimized by 1.5 wt% polymeric dispersant achieved the best overall performance.     

Low temperature sintering and microwave dielectric properties of Zn1.8SiO3.8 ceramics with BaCu(B2O5) additive for LTCC applications

The Zn_1.8SiO_3.8 (ZS) ceramics with BaCu(B₂O₅) (BCB) additive were synthesized by the conventional solid-state reaction route and the effect of BCB additive on the microwave dielectric properties of the ceramics was investigated. The results demonstrate that BCB could effectively decrease the sintering temperature from 1300?°C to 930?°C and does not induce obviously degradation of the microwave dielectric properties. The 6.wt% BCB added ZS ceramics exhibited a low sintering temperature (~ 930?°C) and excellent dielectric properties of ε_r =?6.79, Q×f =?33,648?GHz, and τ_f =??30?ppm/°C. To compensate the negative τ_f value of this system, TiO₂ powders were introduced. Particularly when 10.wt% TiO₂ was added, good microwave dielectric properties of ε_r=?8.175, Q×f=?21,252?GHz, and τ_f =?1.2?ppm/°C were obtained for the 6.wt% BCB added ZS ceramic sintered at 930?°C for 3?h. Moreover, BCB added ZS-TiO₂ ceramics have a chemical compatibility with silver, which indicate that the BCB added ZS ceramics are promising candidate for LTCC applications.     

Influence of glass phase on Al2O3 fiber-reinforced Al2O3 composites processed by slip casting

The present work describes the processing of alumina fiber reinforced alumina ceramic preforms consisting of chopped Al₂O₃ fibers (33 wt%) and Al₂O₃ (67 wt%) fine powders by slip casting. The preforms were pre-sintered in air at 1100 °C for 1 h. A lanthanum based glass was infiltrated into these preforms at 1250 °C for 90 min. Linear shrinkage (%) was studied before and after glass infiltration. Pre-sintered and infiltrated specimens were characterized by scanning electron microscopy, energy dispersive X-ray, X-ray diffraction, porosimetry and flexural strength. The alumina preforms showed a narrow pore size distribution with an average pore size of ∼50 nm. It was observed that introducing Al₂O₃ fibers into Al₂O₃ particulate matrix produced warp free preforms with minor shrinkage during pre-sintering and glass infiltration. It was observed that the infiltration process fills up the pores and considerably improves the strength and reliability of alumina preform.     

Microwave dielectric properties of Ba3Ti4−x(Zn1/3Nb2/3)xNb4O21 for low temperature co-fired ceramics

The effects of substitution of (Zn_1/3Nb_2/3) for Ti on the sintering behavior and microwave dielectric properties of Ba₃Ti_4−x(Zn_1/3Nb_2/3)_xNb₄O₂₁ (0 ≤ x ≤ 4) ceramics have been investigated. The dielectric constant (?_r) and the temperature coefficient of the resonant frequency (τ_f) of Ba₃Ti_4−x(Zn_1/3Nb_2/3)_xNb₄O₂₁ ceramics decreased with increasing x. However, the Q × f values enhanced with the substitution of (Zn_1/3Nb_2/3) for Ti. It was found that a small amount of MnCO₃-CuO (MC) and ZnO-B₂O₃-SiO₂ (ZBS) glass additives to Ba₃Ti_4−x(Zn_1/3Nb_2/3)_xNb₄O₂₁ (x = 2) ceramics lowered the sintering temperature from 1250 to 900 °C. And Ba₃Ti_4−x(Zn_1/3Nb_2/3)_xNb₄O₂₁ (x = 2) ceramics with 1 wt% MC and 1 wt% ZBS sintered at 900 °C for 2 h showed excellent dielectric properties: ?_r = 53, Q × f = 14,600 GHz, τ_f = 6 ppm/°C. Moreover, it has a chemical compatibility with silver, which made it as a promising material for low temperature co-fired ceramics technology application.     

Eco-friendly tape casting of borosilicate glass/Al2O3 sheets for LTCC applications

This work reports the innovative development of a borosilicate glass/Al₂O₃ tape for LTCC applications using an eco-friendly aqueous tape casting slurry. Polyvinylpyrrolidone (PVP) and polyacrylic acid (PAA) were the respective dispersants, while carboxymethyl cellulose (CMC) and styrene acrylic emulsion (SA) were the respective binders. The results showed that PVP was more suitable than PAA as the dispersant for the aqueous casting slurry, and that 1.5 wt% PVP would achieve well dispersion of CABS glass/Al₂O₃ powder in the aqueous slurry. Moreover, a small amount of 2.0 wt% CMC binder could yield smooth CABS glass/Al₂O₃ tapes crack free. A high-quality CABS glass/Al₂O₃ tape with a smooth surface was made from an aqueous slurry containing 1.5 wt% PVP dispersant, 2.0 wt% CMC binder, and 2.0 wt% PEG-400 plasticizer. The density, tensile strength, and surface roughness of the green tape were 2.05 g/cm³, 0.87 MPa, and 148 nm, respectively. The resulting CABS glass/Al₂O₃ composites sintered at 875 °C exhibited a bulk density of 3.14 g/cm³, a dielectric constant of 8.09, a dielectric loss of 1.0 × 10^?3, a flexural strength of 213 MPa, a thermal expansion coefficient of 5.30 ppm/^°C, and a thermal conductivity of 3.2 W m^?1 K^?1, thus demonstrating its broad prospects in LTCC applications.     

The effects of La2O3 doping on the photosensitivity,crystallization behavior and dielectric properties of Li2O-Al2O3-SiO2 photostructurable glass

Photostructurable Li₂O-Al₂O₃-SiO₂ glass is a promising material to fabricate complex three-dimensional structure with a high aspect ratio. However, its high dielectric loss at high frequencies has restrained its application in the field of integrated circuits packaging. In this research, La₂O₃, which has a large ionic radius, as well as strong polarization and bonding strength, was used to obstruct mobile ion migration to reduce the dielectric loss. The results indicated that moderate doping with La₂O₃ could effectively reduce the dielectric loss. When the dopant amount was 3%, the dielectric loss was successfully reduced to a minimum of 4?×?10^?3 with a dielectric constant of 6.6 at 1?GHz, and this sample also possessed the optimal dielectric-temperature stability. Additionally, the effects of doping on the photosensitivity and crystallization behavior were also analysed. The results suggested that La₂O₃ doping did not affect the photosensitivity and selective crystallization characteristics. However, La₂O₃ restrained the precipitation of silicate from the [SiO₄] tetrahedron, resulting in a decrease of nucleation rate and a delay of crystallization.     

Fabrication and mechanical properties of Al2O3-Si3N4/ZrO2-Al2O3 laminated composites

In this paper, Al₂O₃-Si₃N₄/ZrO₂-Al₂O₃ laminated composites were fabricated by tape casting and hot press sintering, and the relationships between the process, microstructure, and mechanical properties of Al₂O₃-Si₃N₄/ZrO₂-Al₂O₃ laminated composites were determined. The SiAlON phase was found in the Al₂O₃-Si₃N₄ layer, and liquid-phase sintering was proposed. Nano-scratch tests were carried out to investigate the interface bonding strength of the laminates. The distribution of residual stresses, generated due to the different coefficients of thermal expansion between the different layers, was estimated according to lamination theory and confirmed using Vickers indentation. When the sintering temperature was 1550 °C, the sintered laminated ceramics had good mechanical properties, with a maximum strength and toughness of 413 MPa and 6.2 MPa m^1/2, respectively. The main toughness mechanics of laminated composites was residual stress.     

Microstructural and microwave dielectric properties of LZT (Li2ZnTi3O8) ceramics sintered in presence of bismuth borate glass for LTCC applications

In the present research, the Li₂ZnTi₃O₈(LZT) ceramics were synthesized throughout solid-state ceramic processing, then mixed with bismuth borate (BiBO) glass prepared based on conventional melt quenching method. Wetting behavior of BiBO glass on the LZT ceramic substrate was monitored by hot stage microscopy. Afterward, dielectric LZT ceramics containing different amounts of BiBO glass (0.25–6 wt%) were sintered at various temperatures. X-ray diffraction and electron back scatter diffraction examinations revealed the presence of two crystalline phases of Li₂ZnTi₃O₈ and Bi₂Ti₂O₇. The maximum value of relative density (above 95%) was obtained in the case of specimens contained more than 5 wt% glass. The microwave dielectric properties of the finally sintered BiBO glass containing LZT ceramics were as follows: dielectric constant (ε_r) = 21.44–25.09, quality factor (Q × f) = 10839–54708 GHz and temperature coefficient of resonant frequency (τ_f) = (? 15.58) ? (? 12.86)ppm/°C.     

Enhanced energy storage properties of BaO-K2O-Nb2O5-SiO2 glass ceramics obtained through microwave crystallization

BaO-K₂O-Nb₂O₅-SiO₂ (BKNS) glass ceramics were prepared by microwave crystallization of transparent glass matrices and the effects of microwave treatment temperature on their dielectric performances, phase structure, microstructure and breakdown strength (BDS) were investigated systematically. X-ray diffraction results suggested that microwave treatment had no significant influence on the type of precipitated phases. The microstructure of the glass ceramics was remarkably optimized via microwave treatment. The dielectric constant and breakdown strength of microwave-treated samples were significantly improved as compared with conventional-heated samples at the same temperature. The maximum theoretical energy storage density of microwave-treatment samples at 750?°C reached 12.7?J/cm³, which was larger than that of the conventional-heated samples (8.6?J/cm³).     

Effects of alumina on the crystallization behavior, densification and dielectric properties of BaO–ZnO–SrO–CaO–Nd2O3–TiO2–B2O3–SiO2 glass–ceramics

The alumina addition effects on the crystallization, sintering behaviors and dielectric properties of BaO–ZnO–SrO–CaO–Nd₂O₃–TiO₂–B₂O₃–SiO₂ (Ba–Zn–Sr–Ca–Nd–Ti–B–Si) glass powder were investigated using the differential thermal analyzer (DTA), thermo-mechanical analyzer (TMA), X-ray diffractometer (XRD). The results showed that the addition of alumina powder into Ba–Zn–Sr–Ca–Nd–Ti–B–Si glass changed the crystallization sequence from Nd₂Ti₄O₁₁–Nd_0.66TiO₃ to Nd₂Ti₃O_8.7–Nd₂Ti₂O₇–Nd₂Ti₄O₁₁and increased the densification activation energy due to the dissolution of Al³⁺ ions into the glass structure. Fully densified 30 vol.% alumina-added Ba–Zn–Sr–Ca–Nd–Ti–B–Si glass can be obtained via glass viscous flow before the second and third crystalline phases, Nd₂Ti₂O₇ and Nd₂Ti₄O₁₁crystallization. The 30 vol.% alumina-added Ba–Zn–Sr–Ca–Nd–Ti–B–Si glass–ceramics sintered at 900 °C exhibited a high dielectric constant of 17 and a quality factor of about 820, which provided a promising candidate for LTCC applications.     

Glass transition and crystallization of ZnO-B2O3-SiO2 glass doped with Y2O3

The effect of Y₂O₃ on the glass transition kinetics, crystallization kinetics, phase separation and crystallization behavior of 60ZnO–30B₂O₃–10SiO₂ glass has been investigated by non-isothermal differential thermal analysis, scanning electron microscopy (SEM) and X-ray powder diffraction (XRD). The glass transition activation energies E_g calculated by using both Kissinger and Moynihan model decrease from 668?kJ/mol to 573?kJ/mol for Kissinger model, and 682?kJ/mol to 587?kJ/mol for Moynihan model with the increase of yttrium oxide doping content from 0 to 6?mol%. And the glass crystallization kinetics parameters, crystallization activation energy E_c and Avrami exponent n stands for crystal growth, are also obtained on the basis of several well developed equations. Increase of about 58?kJ/mol in Ec values obtained by different theoretical equations is caused by addition of 6?mol% yttrium oxide into 60ZnO–30B₂O₃–10SiO₂ glass, and the Avrami exponent (n close to 2) suggests that crystal growth in 60ZnO–30B₂O₃–10SiO₂ glass doped with or without yttrium is mainly one-dimensional growth of crystals. The results on the phase separation and crystallization behavior occurred at 893?K and 993?K respectively for base and doped glass, are well consistent with the glass transition and crystallization kinetics results. Hence, addition of yttrium oxide into 60ZnO–30B₂O₃–10SiO₂ glass decrease the glass transition activation energy while increase the crystallization activation energy of glass, thereby the stability of glass structure is improved. Phase separation phenomenon and crystallization behavior occurred at glass surface provide some useful information for preparing glass ceramics with micro- or nano-crystals in surface.     

Tape casting and characterization of Li2.08TiO3-LiF glass free LTCC for microwave applications

Li_2.08TiO₃-LiF Glass-free Low temperature co-fired ceramic (LTCC) green tapes were prepared by tape casing technique. The rheology of the slurry was characterized using rheometer. The slurry exhibited pseudoplastic behavior. The sintering kinetics of the green tape was investigated using heating microscope. The sintering activation energy was determined to be ∼173 kJ/mol. The green tape could be densified at 900 °C/2 h. Microwave dielectric properties of the sintered tape were characterized in a split-post dielectric resonator using a network analyzer. The ceramic sheet with thickness of 0.11 mm demonstrated good microwave dielectric properties: ε_r = 22.4 and Q × f = 35,490 GHz. The cross sectional microstructure of the cofired multilayer stack was observed by scanning electron microscopy (SEM). The green tape demonstrated good chemical and shrinkage compatibilities with Ag electrode during sintering process. The thermal expansion coefficient and thermal conductivity of the ceramic is 22.4 ppm/∘C and 4.75 W m⁻¹ K ⁻¹, respectively.     

Low-temperature sintering and microwave dielectric properties of 3Z2B glass–Al2O3 composites

A potential low temperature co-fired ceramics system based on zinc borate 3ZnO–2B₂O₃ (3Z2B) glass matrix and Al₂O₃ filler was investigated with regard to phase development and microwave dielectric properties as functions of the glass content and sintering temperature. The densification mechanism for 3Z2B–Al₂O₃ composites was reported. The linear shrinkage of 3Z2B glass–Al₂O₃ composites exhibited a typical one-stage densification behavior. XRD patterns showed that a new crystalline phase, ZnAl₂O₄ spinel, formed during densification, indicating that certain chemical reaction took place between the 3Z2B glass matrix and the alumina filler. Meanwhile, several zinc borate phases, including 4ZnO·3B₂O₃, crystallized from the glass matrix. Both of the reaction product phase and crystallization phases played an important role in improving the microwave dielectric properties of composites. The optimal composition sintered at 850–950 °C showed excellent microwave dielectric properties: ?_r = ∼5.0, Q·f₀ = ∼8000 GHz, and τ_f = ∼−32 ppm/°C at ∼7.0 GHz.     

Effects of Al2O3 addition on the sintering behavior and microwave dielectric properties of CaSiO3 ceramics

The effects of Al₂O₃ addition on the densification, structure and microwave dielectric properties of CaSiO₃ ceramics have been investigated. The Al₂O₃ addition results in the presence of two distinct phases, e.g. Ca₂Al₂SiO₇ and CaAl₂Si₂O₈, which can restrict the growth of CaSiO₃ grains by surrounding their boundaries and also improve the bulk density of CaSiO₃-Al₂O₃ ceramics. However, excessive addition (≥2 wt%) of Al₂O₃ undermines the microwave dielectric properties of the title ceramics since the derived phases of Ca₂Al₂SiO₇ and CaAl₂Si₂O₈ have poor quality factor. The optimum amount of Al₂O₃ addition is found to be 1 wt%, and the derived CaSiO₃-Al₂O₃ ceramic sintered at 1250 °C presents improved microwave dielectric properties of ?_r = 6.66 and Q × f = 24,626 GHz, which is much better than those of pure CaSiO₃ ceramic sintered at 1340 °C (Q × f = 13,109 GHz).     

Effects of Al2O3 addition on the microstructure and microwave dielectric properties of Ba4Nd9.33Ti18O54 ceramics

Ba₄Nd_9.33Ti₁₈O₅₄·x wt%Al₂O₃ (BNT-A) ceramics (x=0, 0.5, 1.0, 1.5, 2.0, 2.5) were prepared by the conventional solid state reaction. The effects of Al₂O₃ on the microstructure and microwave dielectric properties of Ba₄Nd_9.33Ti₁₈O₅₄ (BNT) ceramics were investigated. X-ray diffraction and backscatter electronic images showed that the Al₂O₃ additive gave rise to a second phase BaAl₂Ti₅O₁₄ (BAT). The formation mechanism and grain growth of the BAT phase were first discussed. Dielectric property test revealed that the Al₂O₃ additive had improved the dielectric properties of the BNT ceramics: increased the Q×f value from 8270 to 12,180 GHz and decreased the τ_f value from 53.4 to 11.2 ppm/°C. A BNT-A ceramic with excellent dielectric properties: ε_r=70.2, Q×f=12,180 GHz, τ_f=20 ppm/°C was obtained with 2.0 wt% Al₂O₃ added after sintering at 1320 °C for 4 h.     

Low temperature and microwave dielectric properties of TiO2/ZBS glass composites

TiO₂ based ceramic/glass composites were prepared by a non-reactive liquid phase sintering (NLPS) using zinc borosilicate (ZBS) glass having the deformation temperature of 588 °C. The compounds of Zn₂SiO₄ and Zn₄B₆O₁₃ were formed after the sintering process, indicating that the ZBS glass was a non-reactive one in this system. For TiO₂/50 vol% ZBS glass composite, the two-stage sintering behavior was conducted as the sintering temperature increased. The former might be correlated to the NLPS process and the latter appeared to be related to the crystallization. The dielectric constant (?_r) was mainly affected by the porosity and obeyed the logarithmic mixing rule. The quality factor (Q × f₀) showed an increase and then a steep decrease after the maximum at 850 °C. TiO₂/50 vol% ZBS glass composite sintered at 900 °C demonstrated 36 in the dielectric constant (?_r) and 7500 GHz in the quality factor (Q × f₀) for an application to LTCC filters.