Tape Casting of Lanthanum Chromite

The effects of process additives, ball milling, and solids loading were evaluated for tape casting suspensions of glycinenitrate-synthesized La_0.7Ca_0.31CrO₃ powder. An optimized formulation was obtained based on rheological characterization, electrokinetic sonic amplitude measurements, qualitative examination of green tapes, and the sintered microstructure. The tape casting formulation incorporated 66:34 methyl ethyl ketone/ethyl alcohol solvent, an aliphatic phosphate ester dispersant, and 80 wt% (35 vol%) solids. The best binder/plasticizer system was 12 wt% (15 vol%) poly(isobutyl methacrylate) and 5 wt% (6.3 vol%) benzyl butyl phthalate plasticizer (binder:plasticizer = 2.3). Cast tapes were sintered at 1300°C for 2 h, producing a bulk density of 96.2% theoretical, with linear shrinkage of 22% and an approximate grain size of 1.3 μm.     

Tape casting of non-aqueous silicon nitride slips

Tape casting is a powerful method for the manufacturing of flat, large area ceramic components. Silicon nitride is a reference material for high temperature structural applications. Between them, thick film/coating technologies and ceramic–ceramic joining are receiving an increased attention. In this work, the rheological behavior on non-aqueous silicon nitride slips for tape casting was investigated considering different solvent and binding systems, by controlling the total binder and plasticizer content and the binder to plasticizer ratio. A phosphate ester was used as dispersant. The characteristics of the green tapes obtained in different conditions were studied in terms of density, thickness and microstructure and related with the rheological properties of the slips. Once the slip properties were adjusted, manufacturing parameters, such as the casting speed and the gap between the blades and the carrier substrate, were also analyzed in order to improve the green tape properties and the process reliability. In order to obtain sinterable compacts, Al₂O₃ and Y₂O₃ were used as sintering aids. The effect of the sintering aids in both the rheological behavior and the green characteristics was also studied.     

The preparation of SiCP/Ag–Cu–Ti hybrid tapes and application in the joining of silicon carbide ceramics

Abstract

A novel method of tape casting to fabricate ceramic-particulate-reinforced composite filler alloy tapes with low organics (no more than 6?wt.%) was developed, with which SiC_P/Ag–Cu–Ti hybrid tapes were successfully prepared and used in joining of sintered silicon carbide ceramics. The stress rheometer, scanning electron microscopy and energy dispersive spectrometer were used to characterize the rheological properties of slurry and microstructure of green tapes and joints. The slurry for tape casting consists of dispersant, binder, solvent, a mixture of ceramics particulates and metal powders, and no plasticizer was added. Castor oil phosphate was proven the suitable dispersant for the slurry, and the content of dispersant, binder, solid loading was optimized as 3?wt.%, 2.6?wt.% and 26?vol.%, respectively. The fabricated hybrid tapes possess good ductility and uniform thickness. The SiC particulates were homogeneously distributed in the metal powders matrix in both sides of the green tapes, and the distribution was retained in the SiC/SiC joints.     

Cardanol as a dispersant plasticizer for an alumina/toluene tape casting slip

Cardanol, a naturally occurring C₁₅ alkyl chain substituted phenol obtained from cashew nut shell liquid (CNSL), is used as a dispersant and plasticizer for PMMA binder based alumina tape casting slips in toluene medium. The best dispersion of an alumina powder with BET surface area of 10.4 m²/g occurs at a cardanol concentration 2 wt.% of the powder at which the cardanol molecules form a monolayer on the particles with an end-on-adsorbed configuration through phenolic hydroxyl anchored on the surface. Cardanol added in excess of the dispersing agent acts as a plasticizer for PMMA, as revealed by significant decrease in the T_g of the polymer, reduction in the slurry viscosity and increase in the tape flexibility. Green tapes with good flexibility (failure strain, 10–20%) and strength (5.7–7 MPa) were obtained using a binder content 12 wt.% of alumina and employing a plasticizer to binder ratio in the range 0.66–0.82 by weight. The green tapes were thermally debinded with or without extraction of the plasticizer with methanol. The solvent extraction of the plasticizer prior to thermal debinding, however, did not show any effect on the density (97% TD) of the tapes sintered at 1500°C.     

Corrosion of a Dense, Low-additive Si3N4 in High Temperature Combustion Gases

The oxidation/corrosion resistance of silicon nitride is determined by a number of factors, most notably the amount and chemical composition of the grain boundary phases produced as a result of adding oxides to promote densification during sintering/hot pressing. The intergranular material may be very active during high temperature exposure, producing a deleterious effect on the oxidation/corrosion processes. A method for producing silicon nitride with low levels of additives (only 0·59% Al₂O₃ and 1·22% Y₂O₃) and the benefits in terms of corrosion behaviour are described in this paper. The results of tests in combustion gases, where the concentration of sulphur in the fuel and contaminants in the ingested air have particular effects on the rate of corrosion, are reported.     

Aqueous tape casting of silicon nitride

Slurries consisting of a low cost silicon nitride powder, sintering aids yttria and alumina, dispersants, binders, defoamers and water as a solvent were optimised for tape casting by electroacoustic and viscosity measurements and by casting experiments. The slurries exhibit shear-thinning behaviour due to the highly shear-thinning binder emulsion. Crack free tapes with a maximum thickness of approx. 250 μm and a binder content of 13–15 wt.% could be obtained. The green tapes with a high flexibility and green strength could be laminated easily by compression at room temperature. After sintering a dense microstructure developed. A significant shrinkage anisotropy parallel and perpendicular to the cast direction was observed.     

High performance porous Si3N4 ceramics prepared by coated pore-forming agent method

Coated pore-forming agent method (CPFAM) was introduced to improve the pore-forming agent method (PFAM) for the preparation of porous silicon nitride ceramics. Using SEM in combination with measurements of porosity and flexural strength, it has been found that the flexural strength of the porous silicon nitride ceramics produced with the CPFAM method is significantly higher than those without the coating process: a 100% increase in flexural strength for samples with a porosity of 50%. The porous silicon nitride ceramics also have a very low dielectric constant, which is ideal for applications in wave-transmitting systems. The enhanced mechanical strength of the silicon nitride made by the CPFAM method is a result of a more uniform distribution of the spherical pores and the formation of a dense layer of rod-like microstructures near the surface of the pores.     

氮化硅流延膜的制备

流延成型是一种制备高质量陶瓷基片的成型方法.氮化硅是一种高热导率的材料,有望在电子基片领域获得应用.本文利用流延成型制备了具有较好柔韧性和一定强度的氮化硅流延素坯膜.研究了无水乙醇、无水乙醇/丁酮作为溶剂时对浆料粘度的影响.通过优化流延浆料添加剂的各种配比,得出了适合氮化硅粉体(SN-E10)流延的最佳配方.     

Optimization of non-aqueous tape casting of high solid loading slurry for aluminum nitride ceramic substrates

Aluminum nitride (AlN) ceramic substrates have been fabricated using non-aqueous tape casting and pressureless densification under flowing N₂ atmosphere. Considering the economic and environmental impact, a new strategy of solvent and dispersant system was adopted to prepare AlN slurries with high solid loading. According to the viscosity characteristics of AlN slurries, dispersant content was adjusted to be 0.5 wt% of AlN powder in order to optimize the rheological behavior of AlN slurries. The addition contents of binder and plasticizer were both optimized as 5 wt% of AlN powders by combining the viscosity of slurries and tensile strength of green tapes. Green AlN tapes were fabricated with an optimized tape casting process such as dry temperature. The exclusion process of organic additives was investigated by employing thermogravimetric analysis. Flat and dense AlN ceramic substrates with a relative bulk density over 99.75 % were achieved after being sintered under 1800°C for 6 hours, which had a maximum size of 110 × 110 mm. The thermal conductivity of the AlN substrate could reach 145 Wm⁻¹K⁻¹.     

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.     

Role of organic additives on non-aqueous tape casting of SiAlON ceramics

Suspensions consisting of precursor α/β SiAlON forming powders, azeotropic solvent mixture of 60 MEK/40E, dispersant, binder, and plasticizer were optimized for tape casting by rheological measurements and tape properties. Sodium tripolyphosphate (STPP) was introduced as a dispersant for low temperature applications of α/β-SiAlONs. Optimum STPP amount was determined as 0.012 g/m² (of the particle surface) for stable α/β-SiAlON suspensions. Different amounts of binder/plasticizer mixtures were added to the slurries and the effects on rheological and green tape properties were investigated. Green tapes with dibutyl phthalate (DBP), and plasticizer mixture, poly(ethylene glycol) (PEG) and DBP, exhibited centered cracks with high plasticity, on the other hand, polyvinyl butral (PVB) and PEG showed no crack but low plasticity. Therefore, many different parameters were found to be effective on final tape properties. In addition, tapes were prepared with 6 vol% PVB + PEG, sintered at 1800 °C for 2 h and exhibited almost 97%TD in room temperature applications of α/β SiAlONs.     

In situ preparation of SiC/Si3N4-NW composite powders by combustion synthesis

Large-scale composite powders containing silicon carbide (SiC) particles and silicon nitride nanowires (Si₃N₄-NWs) were synthesized in situ by combustion synthesis (CS). In this process, a mixture of silicon, carbon black, polytetrafluoroethylene (PTFE) and a small amount of iron powders was used as the precursor. The products were characterized by XRD, SEM, EDS and TEM. The particles are equiaxed with diameters in the micron range, and the in situ formed nanowires are straight with uniform diameters of 20-350 nm and lengths of tens of microns. The Si₃N₄-NWs are characterized to be α-phase single crystals grown along the [1 0 1] or [1 0 0] direction. VLS and SLGS processes are proposed as the growth mechanisms of the nanowires. The as-synthesized powders have great potential for use in the preparation of high-performance SiC/Si₃N₄-NW composites.     

Crack propagation and residual stress in laminated Si3N4/BN composite structures

The level of residual stress and crack propagation in a new generation of laminates, based on silicon nitride (Si₃N₄) layer and a mixture of boron nitride (BN) and alumina (Al₂O₃) interlayer, was presented. The structure consists of alternated concentric rings of Si₃N₄ separated by the weak BN interlayer possessing no planes of easy crack propagation and fracture resistance much larger than that of any classical planar laminates. The results on direction of crack propagation and residual stress in relation to inter-layer composition, the number of layers, and their thickness are investigated and reported. The effect of residual stress on crack propagation was studied by using Vicksrs intentation. The highest compressive residual stress of ∼170 MPa was found in samples with five layers possessing an average layer thickness of ∼310 × 10⁻⁶ m.     

In-situ formation of BN layers by nitriding boron powders in BN/Si3N4-based composite ceramics

Boron nitride/silicon nitride (BN/Si₃N₄) composite ceramics were fabricated via the in-situ nitridation of boron (B) and silicon (Si) powders in forming gas (95%N₂/5%H₂) at 1390?°C. The effect of the B content on the phase composition, microstructure, density/porosity, machinability as well as mechanical properties of nitridized BN/Si₃N₄ composite ceramics was investigated. The addition of B slightly increased the nitridation degree of the Si and B powders mixture, and improved the ratio of the β-Si₃N₄ phase significantly at low B contents. B powders may have acted as a nucleating agent to promote the formation of β-Si₃N₄ crystals. A core-shell Si₃N₄/BN structure was revealed by the TEM technique, and the number of BN layers increased with the increase of the B content. The in-situ BN formed by the nitridation of B played a similar role with the BN directly added in enhancing the machinability of the BN/Si₃N₄ composite ceramics. The method of the in-situ nitridation of B is also effective to prepare SiC fiber-reforced BN/Si₃N₄ ceramic matrix composites.     

Low toxicity binder systems for tape cast Ce0.9Gd0.1O1.95 laminates

Conventional binder systems for tape casting contain toxic phthalate plasticizers and butanone (MEK) as part of the solvent. The effects of exchanging the phthalate with a non-toxic alternative, and butanone with ethanol, were studied on laminates of high-green density CGO (Ce_0.9Gd_0.1O_1.95) tapes. Samples were prepared with a binder system containing DBP (dibutyl phthalate) plasticizer and MEK solvent, and with a binder system based on a non-toxic non-phthalate plasticizer and ethanol. In both systems, the weight ratio of plasticizer to the PVB (polyvinyl butyral) binder was varied between 0.4 and 0.7. Substitution to the less toxic binder system had no adverse impacts on the microstructure. In fact, denser packing and improved homogeneity were observed with the non-phthalate-based system at ratio 0.5 indicating improved dispersion in this system. The denser packing also coincided with a maximum in z-shrinkage and molecular weight of the binder system, which could be related to the distribution of the binder system.     

Bilayered coatings of BN/diamond grown on Si3N4 ceramic substrates

Cubic boron nitride (c-BN) is a well known material to be used in machining of ferrous metallic alloys, namely as a coating. However, in most practical cases, there is a lack of adhesion to the substrate material. In this work, BN coatings were deposited by magnetron sputtering on silicon nitride (Si₃N₄) ceramic substrates using an intermediate layer of CVD microcrystalline (MCD) or nanocrystalline diamond (NCD). The goal was to improve the c-BN content by using diamond interlayers, and to optimize film adhesion to the substrate by employing such ceramic, which is known to provide very high adhesion strength to CVD diamond. The BN/NCD/Si₃N₄ combination demonstrated to be unique regarding the absence of delamination at both the BN/diamond and diamond/substrate interfaces, also providing the highest c-BN phase content.     

Fabrication and characterization of Li1+x−yNb1−x−3yTix+4yO3 substrates using aqueous tape casting process

An aqueous system for tape casting Li_1+x−yNb_1−x−3yTi_x+4yO₃ (LNT) ceramics was developed using poly(vinyl alcohol) (PVA) binder, ethylene alcohol (EG) plasticizer and ammonium salt of polycarboxylate (PCA-NH₄) dispersant. The zeta potential measurement showed that the isoelectric point of the LNT particles moved slightly toward more acid region after the dispersant absorbed on the particles, while the zeta potential increased significantly. The rheological test indicated that the ceramic slurry exhibited a typical pseudoplastic behavior without thixotropy. The effect of solid loading on the properties of the green tapes was investigated. The increase in the solid loading increased the tensile strength and the green density of the tapes. TGA analysis indicated that the organic additives in the green tapes can be completely removed by heat treatment at 600 °C. SEM micrographs showed that the microstructure of the green and sintered tapes was homogeneous.     

Porous Si3N4 ceramics prepared via slip casting of Si and reaction bonded silicon nitride

Slip casting process combined with reaction bonded silicon nitride (RBSN) was used to prepare porous Si₃N₄ ceramic with near-net and complex shape. A butyl stearate (BS) coated process was introduced to restrain the hydrolysis of Si, and ammonium polyacrylate (NH₄PAA) was used to enhance the dispersion of coated Si. The measured oxygen content showed that the hydrolysis of Si was strongly prohibited by BS coating, and relatively low viscosity was obtained with the addition of 0.25-1.5 wt% NH₄PAA to the 60 wt% solid load slurry. 40-60 wt% solid load slurries were used for slip casting in the experiment. After vacuum degassing, slip casting, debindering and nitridation, a density of 1.57-1.92 g/cm³ (porosity 50.9-40%) and a flexural strength of 47-108 MPa were obtained. The samples without vacuum degassing showed a large number of nanowires grown in the large pores.     

Tape casting of UV-curable aluminium nitride-based slurries

Aluminium nitride (AlN) is one of the materials used for the preparation of substrates for electronic circuits. Such substrates can be prepared via tape casting method. Until now, only non-aqueous and aqueous tape casting was developed and studied for AlN. In this work, the development of UV-curable tape casting for AlN, including the use of photopolymerisable binder, is shown. Two different dispersing agents, BYK-W 9010 and glycerol trioleate, were used to stabilize and homogenize AlN dispersions. In order to modify the powder surface, a pre-treatment step was used, where the powder was first mixed with the dispersing agent in an azeotropic solvent mixture, followed by the evaporation of the solvents and the redispersing of the pre-conditioned powder into the reactive binder. The effective concentration of the dispersants, the impact of the solid loading on the viscosity and slurry behaviour, as well as the effect of the powder pre-conditioning, were studied by means of rheological measurements. Green tapes were optimised by evaluating the effect of the casting gap and the photo- and co-initiator concentrations. Finally, FTIR measurements were used to estimate the polymer conversion degree as a function of exposure time for the green tapes.     

Shrinkage of Tape Cast Products During Binder Burnout

During sintering of tape cast products, anisotropic shrinkage occurs, which can be attributed to an anisotropic green tape structure concerning particle and pore orientation. Little is known about the shrinkage during binder burnout (BBO) and its relation to the microstructure of green tapes including the binder–plasticizer phase. Therefore, the article determines the shrinkage behavior of green tapes derived from alumina powders with different particle shape during binder burnout and prefiring in all spatial directions. The shrinkage after prefiring relative to the green and the debindered states is also discussed. The interrelation between shrinkage behavior and microstructure is investigated in dependence on different process parameters and specifically on the thermal behavior of the binder–plasticizer phase in the green tapes. It is shown that the subtraction of the BBO shrinkage from the total shrinkage results in completely different data for the sintering shrinkage anisotropy in z direction.