Fabrication and performance of dielectric tape based on CaO-B2O3-SiO2 glass/Al2O3 for LTCC applications

A non-aqueous tape-casting process for fabricating CaO-B₂O₃-SiO₂ glass/Al₂O₃ dielectric tape for LTCC applications was investigated. An isopropanol/ethanol/xylene ternary solvent-based slurry was developed by using castor oil, poly(vinyl butyral), and dibutyl phthalate as dispersant, binder, and plasticizer, respectively. The effects of dispersant concentration, binder content, plasticizer/binder ratio, and solid loading, on the properties of the casting slurry and resultant tape were systematically investigated. The results showed that the optimal values for the dispersant and binder contents, plasticizer/binder ratio, and solid loading were 2.0 wt%, 7.5 wt%, 0.6, and 62 wt%, respectively. The resultant flexible and uniform, 120-μm-thick CaO-B₂O₃-SiO₂ glass/Al₂O₃ tape had a density of 1.90 g/cm^?3, tensile strength of 1.66 MPa, and average surface roughness of 310 nm. Laminated tapes sintered at 875 °C for 15 min exhibited excellent properties: relative density of 97.3%, ε_r of 7.98, tan δ of 1.3 × 10^?3 (10 MHz), flexural strength of 205 MPa, and thermal expansion coefficient of 5.47 ppm/°C. The material demonstrated good chemical compatibility with Ag electrodes, indicating a significant potential in LTCC applications.     

Aqueous processing of Ce0.8Sm0.2O1.9 green tapes

An aqueous tape casting of Ce_0.8Sm_0.2O_1.9 (SDC) ceramics was developed using poly(acrylic acid) (PAA) as dispersant, poly(vinyl alcohol) (PVA) as binder, poly(ethylene glycol) (PEG) as plasticizer, and deionized water as solvent. Surface properties of SDC powder with and without PAA dispersant were characterized by electrokinetic measurements. The rheology of the SDC slurries was evaluated with a rotary viscometer. The zeta potential measurement showed that the isoelectric point (IEP) for SDC powders in the absence of dispersant corresponds to a pH value of 3.66. The experimental results showed that the pH value greatly affects the rheology of the slurry. The optimum content to get a stable dispersed slurry is 2 wt% PAA in pH value range of 9–10. In presence of 2 wt% PAA dispersant, 55 wt% SDC powders exhibited shear thinning behavior, indicating that SDC slurry was homogenous and well stabilized. Homogeneous, smooth, and defect-free green tapes were successfully obtained by an appropriate slurry formula.     

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.     

Aqueous tape casting and crystallization kinetics of Ce0.8La0.2O1.9 powder

An aqueous tape casting of Ce_0.8La_0.2O_1.9 (LDC) ceramics was developed using PAA as dispersant, PVA as binder, PEG as plasticizer, and deionized water as solvent. Surface properties of LDC powder with and without PAA dispersant were characterized by electrokinetic measurements. The rheology of the LDC slurries was evaluated with a rotary viscometer. The zeta potential measurement showed that the isoelectric point for LDC powders in the absence of dispersant corresponds to a pH value of 4.02. The experimental results showed the pH value greatly affects the rheology of the slurry. The optimum content to get a stable dispersed slurry is 1.5 wt% PAA at pH value of 9–10. In presence of 1.5 wt% PAA dispersant, 5 wt% PVA binder, 5 wt% PEG plasticizer, and 55 wt% LDC powders exhibited shear thinning behavior, indicating that LDC slurry was homogenous and well stabilized. With an appropriate formulation homogeneous, smooth, and defect-free green tapes were successfully obtained. Moreover, the crystallization kinetics of LDC powders prepared by coprecipitation process also has been investigated in this study. The activation energy of crystallization was calculated on the basis of differential scanning calorimetry (DSC) at different heating rates. From non-isothermal DSC data presented values in the range of 343.3–379.1 kJ/mol and 2.282–2.030 for the activation energy of crystallization and the Avrami exponent, respectively, at specific temperatures ranging from 280 to 285 °C.     

Li2ZnTi3O8 based High κ LTCC tapes for improved thermal management in hybrid circuit applications

A low temperature co-fired ceramic based on Li₂ZnTi₃O₈ (LZT), that possess auspicious thermal and dielectric properties is reported. In order to achieve the low sintering temperature suitable for LTCC applications (875 °C), 1 wt% of 20:Li₂O-20: MgO-20: ZnO-20:B₂O₃-20: SiO₂ (LMZBS) glass was added to LZT ceramics. The post-milled powder had an average particle size of 450 nm with an effective surface area of 0.812 m²g⁻¹. A well dispersed tape casting slurry was prepared using xylene/ethanol mixture as solvent and fish oil as dispersant. The crystal structure and microstructure of the tapes were analyzed through XRD and scanning electron microscopy (SEM). The microwave dielectric properties of the green as well as sintered tapes were measured at different frequencies (5, 10 and 15 GHz). The Li₂ZnTi₃O₈+1 wt% LMZBS has shown excellent thermal conductivity of 5.8 W/mK, thermal expansivity (11.97 ppm/°C) closer to silver electrode, low temperature coefficient of dielectric constant (−29 ppm/°C) and ultralow dielectric losses (tanδ~10⁻⁴).     

Rheological behavior and curing deformation of paste containing 85 wt% Al2O3 ceramic during SLA-3D printing

The preparation of high solids loading Al₂O₃ paste is of great significance for improving the properties of ceramics formed by UV-curing. However, the solid contents of alumina slurry used by digital light processing (DLP) and traditional alumina paste for stereolithography (SLA) are both less than 80 wt%. With increase in solid content, the viscosity of paste increases sharply, and rheological property deteriorates. In this study, ceramic paste containing 85 wt% (62 vol%) Al₂O₃ was prepared for SLA-3D printing of ceramics, and more than 85 wt% solid content was achieved by dispersant and other additives. Effects of different dispersants on rheological and curing properties of Al₂O₃ ceramic paste were studied. At room temperature, the viscosity of 85 wt% Al₂O₃ ceramic paste was 51733 mPa s at shear rate of 30 s^?1. A novel method was proposed to control curing deformation of parts during printing. As-manufactured ceramic did not show any cracks by naked eye and exhibited excellent mechanical properties, with three-point bending strength of 540 MPa, fracture toughness of 4.19 MPa m^1/2, Vickers hardness of 16 GPa, surface roughness of 0.463 μm, and density of 3.86 g/cm³.     

Investigation on properties of Al2O3–SiO2 complex shaped refractory fabricated by layered extrusion forming

As one of the 3D printing methods, layered extrusion forming (LEF) has distinct advantages to form complex configuration ceramics directly. The feasibility of using LEF to make refractory products with complex shapes was explored by this work, using water-based Al₂O₃–SiO₂ ceramic slurry and specially equipped device. By measuring rheological parameters, the effects of binder addition, dispersant addition and volume proportion of the solid portion composed of α-Al₂O₃ ultrafine powder (92 wt%) and silica fume (8 wt%) on rheological behavior of the slurry were investigated. The green body specimens prepared by the LEF were fired at 1400°C–1600 °C for 3h. The influence of firing temperature on phase composition, microstructure, sintering degree and comprehensive properties of the specimens was investigated. At 2.5 wt% addition of aluminum dihydrogen phosphate as binder, 0.2 wt% addition of sodium hexametaphosphate as dispersant and with solid portion between 56 vol% and 58 vol%, required pseudoplastic behavior of the slurry can be achieved, suitable for the LEF. With the increase of heating temperature, mullitization by the reaction between the α-Al₂O₃ ultrafine powder and silica fume becomes stronger and sintering gets enhanced, leading to improved comprehensive properties of the specimens. Fired at 1600 °C, properties in terms of bulk density 3.03g/cm³, cold compressive strength 190.5 MPa and refractoriness under load 1598 °C are achieved. Crucible slag test shows a good resistance to the glass melt corrosion. Good feasibility of fabricating some complex shaped refractory products by LEF as a novel forming approach has been confirmed by the present work.     

Effect of Polyacrylic Acid Addition on Rheology of SiC‐Al2O3‐ZrO2(3Y) Mixed Suspensions

A suspension with good rheology and high stability is crucial for slip casting and gelcasting technology. However, a mixed suspension from two or more different powders usually has bad rheology because of the easy agglomeration of mixed powders caused by the attractive force between the powders with heterocharges. We studied the surface modification of the each single‐component powders (SiC, Al₂O₃, ZrO₂(3Y) powders) and the SiC‐Al₂O₃‐ZrO₂(3Y) mixed powders to increase the repulsive force by adjusting the pH value and adding polyacrylic acid (PAA) as dispersant. The PAA addition effects on the SiC‐Al₂O₃‐ZrO₂(3Y) mixture were investigated in terms of zeta potential, pH range for heterocharge region, dispersion of the mixed powders and rheology of the mixed slurry based on the study of each unary suspensions. The results show that before surface modification the SiC‐Al₂O₃‐ZrO₂(3Y) mixed powders were agglomerated severely because they were in the heterocharge region with a broad pH range from 3.5 to 8.25, while after surface modification (pH = 10.5, PAA = 0.8wt%) the heterocharge region was narrowed with a relatively narrower pH range from 2.6 to 3.7. The mixed powders with homocharges were dispersed well because of the great electrostatic repulsive force and steric hindrance offered by PAA and the mixed suspensions had favorable rheology.     

YAG ceramic processed by slip casting via aqueous slurries

Stable YAG (Y₃Al₅O₁₂) aqueous slurry with ammonium polyacrylate (NH₄PAA) polyelectrolytes as dispersant was prepared by ball mill method. The effects of polyelectrolyte concentration and pH value on the stability of the suspension is described here, and the stability maps are constructed at different pH value and polymer concentration. The rheological behavior of YAG slips of different solid loading (60–70%) has been studied by measuring their viscosity and shear stress as a function of shear rate and pH of the slurry. An optimal amount of dispersant and pH value for the suspension was found. YAG suspension displays a maximum in zeta potential values and a minimum viscosity in pH range of 9–11. Slips behaved as near Newtonian at the pH value up to a solid loading of 60 wt% and as non-Newtonian with thixotropic behaviors above this solid loading value. The density and the green as well as sintered microstructure of the cast products bear a direct relationship to the state of this slips induced by the alternation in the pH and the concentration of the dispersant as well as solid loading.     

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.     

High-performance and high-precision Al2O3 architectures enabled by high-solid-loading,graphene-containing slurries for top-down DLP 3D printing

To date, obtaining the high-solid-loading Al₂O₃ slurry and overcoming the trade-off between high solid loading and printing accuracy and strength of printed green bodies to achieve high-performance and precision Al₂O₃ ceramic parts by DLP 3D printing remain challenging. In this study, an Al₂O₃ slurry with high solid loading of 60 vol% was developed through dispersant optimisation for top-down DLP 3D printing. Graphene was innovatively introduced during slurry fabrication to decouple the printing accuracy and strength of green bodies from such high solid loading. Simultaneously, graphene addition could considerably reduce slurry fluidity, thereby facilitating its coordination with top-down DLP. With 0.07 wt% graphene addition, the dimension deviations of printed green bodies improved from 90 to 880 µm to ≤ 70 µm, and the bending strength increased by 17.75%. High-performance and precise Al₂O₃ ceramic components with low sintering shrinkages were prepared. The density and microhardness were 99.7% and 18.61 GPa, respectively.     

Microstructure and strengthening behavior in high content SiC nanowires reinforced SiC composites

In this study, the high-content SiC_nw reinforced SiC ceramic matrix composites (SiC_nw/SiC CMC) were successfully fabricated by hot pressing β-SiC and sintering additive (Al₂O₃-Y₂O₃) with boron nitride interphase modification SiC_nw. The effects of sintering additive content and mass fraction (5–25 wt%) of SiC_nw on the density, microstructure, and mechanical properties of the composites were investigated. The results showed that with the increase of sintering additives from 10 wt% to 12 wt%, the relative density of the SiC_nw/SiC CMC increased from 97.3% to 98.9%, attributed to the generated Y₃Al₅O₁₂ (YAG) liquid phase from the Al₂O₃-Y₂O₃ that promotes the rearrangement and migration of SiC grains. The comprehensive performance of the obtained composite with 15 wt% SiC_nw possessed the optimal flexural strength and fracture toughness of 524 ± 30.24 MPa and 12.39 ± 0.49 MPa·m^1/2, respectively. Besides, the fracture mode of the composites with 25 wt% SiC_nw content revealed a pseudo-plastic fracture behavior. It concludes that the 25 wt% SiC_nw/SiC CMC was toughened by the fiber pull-outs, debonding, bridging, and crack deflection that can consume plenty of fracture energy. The strategy of SiC nanowires worked as a main bearing phase for the fabrication of SiC/SiC CMC providing critical information for understanding the mechanical behavior of high toughness and high strength SiC nanoceramic matrix composites.     

High solid loading,low viscosity photosensitive Al2O3 slurry for stereolithography based additive manufacturing

Photosensitive Al₂O₃-resin slurries with high solid loading, low viscosity used for stereolithography based additive manufacturing were prepared in this paper. The dispersion behavior and rheological behavior of the Al₂O₃-resin slurries were studied by rheology observation and sedimentation tests. The dispersant type, concentration and solid loading had significant effects on the rheological behavior and stability of the photosensitive Al₂O₃-resin slurries. A long term stability and homogeneity slurry was obtained when the dispersant and concentration were KOS110 and 5?wt%, respectively. The Al₂O₃ slurry prepared with a high solid loading up to 60?vol%, low viscosity of 15.4?Pa?s at 200?s^?1 was chosen for stereolithography based additive manufacturing.     

Fabrication of transparent yttria ceramics by alcoholic slip-casting

Y₂O₃ transparent ceramics were prepared from alcoholic slurries of Y₂O₃ nanopowders via a slip-casting method to avoid the hydrolysis issue. Polyvinyl pyrrolidone (PVP), polyethylene glycol (PEG) and polyethylenimine (PEI) were used as dispersants to improve the rheological properties of the slurries. It was found that PEI is the most effective dispersant in ethanol. The adsorbed amount of PEI was evaluated by infrared absorption and rheology measurements. Y₂O₃ slurry with a solid loading of 20.8 vol% and a viscosity of <0.1 Pa s at the shear rate of 10 s⁻¹ was obtained using 1.5 wt% PEI. The slurry yielded a homogeneous green body, and finally resulted in a high-quality Y₂O₃ ceramic with the in-line transmittance of 80% at 800 nm.     

0.73ZrTi2O6–0.27MgNb2O6 microwave dielectric ceramics modified by Al2O3 addition

0.73ZrTi₂O₆–0.27MgNb₂O₆ ceramics with various Al₂O₃ contents (0‐2.0 wt%) were prepared by conventional ceramic route. The effects of Al₂O₃ on the phase composition, microstructure, conductivity, and microwave dielectric properties were systematically investigated. The coexistence of a disordered α–PbO₂‐type phase and a rutile second phase was found in all compact ceramics with low Al₂O₃ contents (x = 0, 0.5, and 1.0 wt%), while a corundum phase was detected when Al₂O₃ additive increased to 1.5 and 2.0 wt% based on X‐ray diffraction results. With the addition of Al₂O₃, the decreased grain size of the matrix phase was observed using field‐emission scanning electron microscope, accompanied with increased resistivity and band‐gap energy. Additionally, Al₂O₃ additives efficiently improved the quality factor of the ceramics. After sintering at 1360°C for 3 hours, the ceramic with 1.0 wt% Al₂O₃ exhibited excellent microwave dielectric properties: a dielectric constant of 43.8, a quality factor of 33 900 GHz (at 6.6 GHz), and a near‐zero temperature coefficient of resonant frequency (3.1 ppm/^°C).     

Additive manufacturing of SiC-Sialon refractory with excellent properties by direct ink writing

Additive manufacturing of SiC-Sialon refractory with complex geometries was achieved using direct ink writing processes, followed by pressureless sintering under nitrogen. The effects of particle size of SiC powders, solid content of slurries and additives on the rheology, thixotropy and viscoelasticity of ceramic slurries were investigated. The optimal slurry with a high solid content was composed of 81 wt% SiC (3.5 µm+0.65 µm), Al₂O₃ and SiO₂ powders, 0.2 wt% dispersant, and 2.8 wt% binder. Furthermore, the accuracy of the structure of specimens was improved via adjustment of the printing parameters, including nozzle size, extrusion pressure, and layer height. The density and flexural strength of the printed SiC-Sialon refractory sintered at 1600 °C were 2.43 g/cm³ and 85 MPa, respectively. In addition, the printed SiC-Sialon crucible demonstrated excellent corrosion resistance to iron slag. Compared to the printed crucible bottom, the crucible side wall was minimally affected by molten slag.     

Carbon nanotube/graphene oxide‐added CaO‐B2O3‐SiO2 glass/Al2O3 composite as substrate for chip‐type supercapacitor

A CaO‐B₂O₃‐SiO₂ (CBS) glass/40 wt% Al₂O₃ composite sintered at 900°C exhibited a dense microstructure with a low porosity of 0.21%. This composite contained Al₂O₃ and anorthite phases, but pure glass sintered at 900°C has small quantities of wollastonite and diopside phases. This composite was measured to have a high bending strength of 323 MPa and thermal conductivity of 3.75 W/(mK). The thermal conductivity increased when the composite was annealed at 850°C after sintering at 900°C, because of the increase in the amount of the anorthite phase. 0.25 wt% graphene oxide and 0.75 wt% multi‐wall carbon nanotubes were added to the CBS/40 wt% Al₂O₃ composite to further enhance the thermal conductivity and bending strength. The specimen sintered at 900°C and subsequently annealed at 850°C exhibited a large bending strength of 420 MPa and thermal conductivity of 5.51 W/(mK), indicating that it would be a highly effective substrate for a chip‐type supercapacitor.     

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.     

LTCC system with new high-ɛr and high-Q material co-fired with conventional low-ɛr base material for wireless communications

The authors have developed a new LTCC material with characteristics of high dielectric constant (ɛ_r), high quality factor (Q) and low temperature coefficient of capacitance (TCC). This material can be co-fired with a conventional base LTCC material and buried resistors with low temperature coefficient of resistance (TCR). The base material which consists of Al₂O₃ filler and glass, has low ɛ_r of 8.7 at 3 GHz. The newly developed LTCC material, which consists of Ba–(Re)–Ti–O filler, Al₂O₃ filler, and glass, has the following characteristics of ɛ_r of 15.1, Q of 900 at 3 GHz, and TCC of −10 ppm/K. The buried resistors consist of RuO₂ and glass. Two different LTCC materials, a resistor material and a silver electrode paste can be co-fired as multi-layer substrates and are regarded as a new LTCC system.Constrained sintering could be applied to this LTCC system and the dimensions of substrates could be controlled with quite high accuracy. This LTCC system is expected to contribute to further miniaturization of RF circuits and the reduction of electrical loss.     

Low leakage rate of silicate glass modified with Al2O3 for solid oxide fuel cell

The gas tightness of glass sealing materials is a big challenge for the solid oxide fuel cell (SOFC) stacks operating at high temperature. Thermal, sintering, crystallization behavior and gas tightness properties of the glass-based with two different Al₂O₃ contents sealants are evaluated and discussed. The study showed that the sealants avoid cracks at the interface on NiO-YSZ (NiO-yttria stabilized zirconia) and SUS430 stainless steel interconnect substrates. The Al₂O₃ embedded in the glass matrix as a second phase, and promoted crystallization of K[AlSi₃O₈] at the early stage. This may because some ultrafine Al₂O₃ particles whose structure is destroyed by prolonged high temperature treatment according XRD and TEM analysis. Especially, the sealant containing 5 wt% Al₂O₃ undergoes a thermal cycle and maintains a stable leakage rate below 10^?4 sccm?cm^?1 for about 1000 h at 750 °C. The above results prove the possibility of using the Al₂O₃-doped sealing glass for SOFC stacks.