Structural,magnetic and electric properties of ZrO2 tapes decorated with magnetic nanoparticles

We produced ZrO₂ ceramic tape decorated with magnetic nanoparticles through tape casting technique. The green and sintered magnetic tapes were characterized by XRD, SEM, EDS, magnetic measurements, and I–V curves. We investigated the changes in the structural, magnetic and electrical properties, after the sintering process, and discussed the connections between them. The magnetic properties, performed in a wide range of external magnetic field and temperature, show magnetite phase for the magnetic nanoparticles governing the magnetic and electric properties of the green tape. On the other hand, for the sintered tape, the increase in the hematite phase led to remarkable changes in the magnetic and electrical properties. The electrical characterization reflects the observed changes in the structural properties after the sintering process. Additionally, the main advantages of the ceramic tapes decorated with magnetic nanoparticles reside in the possibility of producing functional thin ceramic materials that are easily moldable for electronic devices applications.     

Effect of pore orientation on anisotropic shrinkage in tape-cast products

During tape casting, an anisotropic shrinkage can be observed, which is attributed to particle alignment during the casting process. The understanding of the relationship between green body microstructure and shrinkage anisotropy is of great importance for further miniaturization of multilayer ceramics. In the current study, four alumina powders with different particle shape (spherical, standard, plate-like and extreme plate-like) were used to cast green tapes. The sintering shrinkage behavior and the microstructure were analyzed. In particular, the pore orientation was determined quantitatively by using a modified linear intercept method. The relationship between pore alignment and anisotropic sintering shrinkage of cast green tapes is discussed in all three spatial directions. The shrinkage anisotropy could be correlated quantitatively with the pore anisotropy. Furthermore, this correlation was verified by mathematical modeling based on elongated particles and pores.     

Effect of powder,binder and process parameters on anisotropic shrinkage in tape cast ceramic products

The effect of powder, binder and process parameters on the properties of cast alumina tapes and their anisotropic shrinkage were investigated. Three alumina powders with different particle shapes (platelets, spherical, standard) and three PVB binders with different chain lengths were used. In addition, casting velocity and blade gap height were varied. The orientation of the particles in the tape was detected quantitatively by image analysis of micrographs. The shrinkage anisotropy is more than 12% for the platelet shaped powder and 8% for the standard powder, whereas the spherical particles lead to almost isotropic shrinkage. The influence of the organic binder chain length proved to be minor compared to the influence of the particle morphology. The variation of casting speed and blade gap height has no effect on anisotropic shrinkage in the investigated parameter range. This is explained by theoretical considerations of particle rotation in a sheared fluid.     

Preparation and electrical properties of multilayer ZnO varistors with water-based tape casting

Multilayer ZnO varistors were prepared by water-based tape casting with water-soluble acrylic as binders. Zeta potentials of the doped ZnO suspensions as a function of pH with and without dispersant were measured. Viscosity measurements were used to find the optimum dispersant concentration needed to prepare a stable slurry. Viscosity properties of the tape casting slurry were investigated. The results showed that aqueous acrylic binders have shear thinning properties suitable for tape casting of ceramic powders. Scanning electron microscopy (SEM) studies revealed that the green sheets have a smooth defect-free surface and that the multilayer varistor (MLV) ceramics prepared by water-based tape casting have a fine grain microstructure with a uniform grain size and dopant distribution. The multilayer ZnO varistors prepared by water-based tape casting display comparable good electrical properties to those prepared by solvent-based tape casting. This is believed to be attributed to the well dispersed water-based slurry, which makes more uniform dopant distribution throughout the multilayer ZnO varistors. Therefore, water-based tape casting is suitable for the manufacture of high performance multilayer ZnO varistors.     

Verfahrenstechnische Fortschritte für die Herstellung neuer Materialien – Foliengießen aus Nanopartikeln

It is shown by the example of a ceramic tape casting process, how advances in the field of process engineering lead to improved material properties. One great advance is the possibility of producing nanoparticles in stirred media mills. The nano‐sized particle suspensions can be directly processed to ceramic tapes. The processing of nanoparticles requires specifically adjusted process conditions, but leads to a drastic improvement of the final product properties. Hence, dense and crack‐free ceramic tapes with a higher mechanical strength, a lower surface roughness and a translucent character compared to tapes from micro‐sized powders can be obtained.     

Factors Influencing the Green Body Properties and Shrinkage Tolerance of LTCC Green Tapes

Low-temperature co-fired ceramics (LTCC) is a powerful technology for the manufacture of integrated electronic devices. To fulfill the needs of miniaturization, the applied materials must be of constant quality and the manufacturing processes must be well controlled. The reproducibility in shrinkage is one of the most important quality issues of LTCC tapes. To guarantee the customer a narrow shrinkage tolerance, the tape producer must know the important influencing factors of tape manufacturing on shrinkage. In this work, the effects of slurry composition, tape-casting parameters like casting speed and opening of the blades, and tape handling on the sintering shrinkage behavior were investigated by using design of experiments. The investigation showed that the green density and therefore the shrinkage values of tapes depend considerably on the variation of the solvent mixture. Furthermore, significant interactions were quantified between the tape-casting velocity as well as the particle size and the shrinkage behavior. The shrinkage values were also influenced by mechanical deformations of the tapes before firing.     

Manufacturing porous ceramic materials by tape casting—A review

Tape casting is a well-established technique to fabricate ceramic tapes. This technique has been usually applied to produce dense substrates for electronic applications, but recently there are increasing efforts regarding the production of porous cast tapes. The aim of this paper is to present the latest strategies and achievements to manufacture porous ceramic materials by tape casting. The pores morphology can be manipulated by adjusting particle size, sacrificial pore formers, sintering conditions, and combined techniques (phase inversion and freeze casting). Moreover, tape casting enables adjusting the thickness of the product, which is a key property in separation applications using membranes and/or support materials with tailorable structure.     

Functionally Graded Ceramics Fabricated with Side‐by‐Side Tape Casting for Use in Magnetic Refrigeration

Functionally graded ceramic tapes have been fabricated by a side‐by‐side tape casting technique. This study shows the possibility and describes the main principles of adjacent coflow of slurries resulting in formation of thin plates of graded ceramic material. Results showed that the small variations of solvent and binder system concentrations have a substantial effect on slurry viscosity. Varying these parameters showed that side‐by‐side tape casting with a well‐defined interface area is possible for slurries with viscosities above 3500 mPa s at a casting shear rate of 3.3 s^?1. As it was expected, the choice of de‐bindering and sintering regimes significantly influences crack formation, and a three‐step heating programme was found to result in tapes of the highest quality. The interface regions of green graded tapes were investigated structurally by scanning electron microscopy; for a distinct identification of the interface region and analysing the degree of cross‐interface diffusion, the isothermal entropy change was measured by a vibrating sample magnetometer as the magnetic transition temperature (Curie temperature) is very sensitive to the dopant level in ceramics. Also the purpose of developing this graded ceramic tape casting was applications of these specific magnetocaloric properties within the magnetic refrigeration technology.     

Influence of Green Formulation and Pyrolyzable Particulates on the Porous Microstructure and Sintering Characteristics of Tape Cast Ceramics

Porous morphology and total porosity produced in sintered ceramic tapes was controlled by the amount and distribution of pyrolyzable graphite particles added to a colloidal suspension during a tape casting operation. A conceptual model of the green tape microstructure was used to explain the influence of graphite and tape formulation on sintering characteristics. The creation of a connected, open porous network in the sintered body was the result of graphite particle percolation within the green body. Additional voidage introduced by particle bridging was the source of excess porosity and also resulted in a bimodal pore size distribution. Sintering shrinkage was determined by the ceramic packing density, which was primarily determined by the tape formulation.     

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.     

Zero Shrinkage of LTCC by Self-Constrained Sintering

Low shrinkage in x and y direction and low tolerances of shrinkage are an indispensable precondition for high-density component configuration. Therefore, zero shrinkage sintering technologies as pressure-assisted sintering and sacrificial tapes have been introduced in the low-temperature co-fired ceramics (LTCC) production by different manufacturers. Disadvantages of these methods are high costs of sintering equipment and an additional process step to remove the sacrificial tapes. In this article, newly developed self-constrained sintering methods are presented. The new technology, HeraLock^®, delivers LTCC modules with a sintering shrinkage in x and y direction of less than 0.2% and with a shrinkage tolerance of ±0.02% without sacrificial layers and external pressure. Each tape is self-constrained by integration of a layer showing no shrinkage in the sintering temperature range of the LTCC. Large area metallization, integration of channels, cavities and passive electronic components are possible without waviness and camber. Self-constrained laminates are an alternative way to produce zero shrinkage LTCC. They consist of tapes sintering at different temperature intervals. Precondition for a successful production of a self-constrained LTCC laminate is the development of well-adapted material and tapes, respectively. This task is very challenging, because sintering range, high-temperature reactivity and thermal expansion coefficient have to be matched and each tape has to fulfill specific functions in the final component, which requires the tailoring of many properties as permittivity, dielectric loss, mechanical strength, and roughness. A self-constrained laminate is introduced in this article. It consists of inner tapes sintering at especially low-temperature range between 650°C and 720°C and outer tapes with an as-fired surface suitable for thin-film processes.     

Production of Si3N4/Glass Composites for LTCC Substrate by Aqueous Tape Casting Process

In this work, Si₃N₄/glass sheets were prepared by aqueous tape casting, and the preparation process and properties of green and sintered tapes were discussed thoroughly. The effect of Si₃N₄ content on the rheological behavior of the slurries was investigated, and the results showed that the viscosity of the slurry increased with the solid loading and all the slurries exhibited shear‐thinning behavior within the entire range of shear rate. Green tapes were fabricated successfully by aqueous tape casting which have excellent properties such as uniform pore distribution, low porosity, and high bulk density. The sintered samples exhibited low shrinkage, and low dielectric constant and loss.     

Tape Casting and Dielectric Properties of Zn2Te3O8-Based Ceramics with an Ultra-Low Sintering Temperature

The suitability of dielectric ceramics made of zinc tellurate (Zn₂Te₃O₈) and titanium dioxide (TiO₂) with an ultra-low sintering temperature (650°C) for tape casting and thus for the multimodule technique with Al electrodes was investigated. The properties of the tape before and after sintering as well as the amount of organic additives for the casting process and a thermal analysis of the tape up to 1000°C are reported. In addition, electrodes on a multilayer module made on stacked tapes were prepared using Al paste and postfiring, followed by relative permittivity and loss tangent measurements to verify the electrical performance of the whole structure. The dielectric properties of the stacked module without any electrodes were also measured. The results show that the composition is well suited for the tape process but extra care should be taken especially with the proper sintering temperature for optimized electrical performance.     

Tape casting of multilayer YAG-Nd:YAG transparent ceramics for laser applications: Study of green tapes properties

In this study, the mechanical properties of ceramic green tapes elaborated by tape casting were determined. The influence of slurry formulation (i.e. organic content and binder-to-plasticiser volume ratio) on these properties was studied. In the studied formulation domain with polyvinyl butyral (PVB) and benzyl butyl phthalate (BBP) as binder (B) and plasticiser (P) respectively, it was shown that maximum elongation, maximum stress and Young’s modulus are increased for higher organic content and B/P ratio. This work also shows the possibility to manufacture multi-layered transparent ceramics for waveguide applications by the tape casting process. In that case, a compromise has been identified between good mechanical properties and low organic content that can alter the transparency of the material.     

BNT-based multilayer device with large and temperature independent strain made by a water-based preparation process

A piezoelectric multilayer device based on bismuth-sodium-titanate ceramics (BNT) co-fired with Ag/Pd inner electrodes is described and its dielectric and piezoelectric properties are measured. The ceramic powder and tape was made by a water-based preparation process. After printing with Ag/Pd paste for inner electrodes these tapes were stacked to a multilayer device with 50 active layers. This device exhibited a large and temperature independent strain around 0.19% between 25 °C and 150 °C. The large strain is due to a field-induced phase transition. The low temperature dependence results from the broadening of the nonpolar phase by doping.     

流延成型法制备Mn掺杂Ba_(0.6)Sr_(0.4)TiO_3/MgO陶瓷及其介电性能

用流延成型法制备Mn掺杂钛酸锶钡(BaxSr1-xTiO3,BST)/MgO复相陶瓷厚膜,介绍从制粉、流延浆料制备到厚膜的脱脂及烧结的整个工艺流程。通过差热-热重测试曲线分析Mn掺杂BST/MgO流延膜的脱脂特性,制定膜片的脱脂工艺。用扫描电镜观察不同温度烧结样品的微观结构,确定最佳厚膜烧结工艺,在1320℃和1350℃烧结的陶瓷厚膜样品的相对密度达到96.1%。分析研究不同温度烧结陶瓷厚膜的介电性能的结果表明:1350℃烧结样品的室温相对介电常数为108,介电损耗低于0.002,Curie温度在-70℃左右,介电常数可调率为25.15%。     

Influence of Low-Temperature Co-Fired Ceramics Green Tape Characteristics on Shrinkage Behavior

To establish a better understanding of the complex densification and shrinkage processes of low-temperature co-fired ceramics (LTCC) and to improve the dimensional control in the manufacture of LTCC multilayer devices, the influence of glass, composite, and microstructural green tape characteristics on the densification and shrinkage behavior of LTCC materials, with special focus on the development of anisotropy, was investigated. To study the influence of these factors, a commercial LTCC system was analyzed regarding chemical and microstructural composition as well as sintering behavior. The results of the analysis showed that the commercial LTCC system is composed of alumina as a ceramic filler and a CaO–SiO₂–B₂O₃–Al₂O₃ glass. Based on these results, a similar glass was produced. To understand the mechanisms of densification, its wetting behavior and viscosity as a function of temperature were investigated. As developed glass was mixed with an alumina powder and milled down to average grain sizes of 1, 2, and 3 μm, respectively. From these composite powders, slurries were prepared and tape cast. The sintering kinetics including onset temperature, development of viscous flow as well as phase development of both commercial and internally developed LTCC tapes LTCC tapes in relation to their modified composition and green tape structures were analyzed in situ by means of optical dilatometry, thermo-mechanical analysis (TMA), and high-temperature-X-ray diffraction. The viscous behavior of the glass-filler composites was determined by means of cyclic dilatometry in a TMA device.     

Impact of bio-based binders on rheological properties of aqueous alumina slurries for tape casting

This work describes the preparation of concentrated alumina suspensions based on bio-sourced additives with a low environmental impact and with the rheological properties adapted to the tape casting process. Natural polysaccharides extracted from plants and fruits (pectin, psyllium…) were characterized (molar weight) and identified as promising binders for substituting the classical organic binders from petrochemical industry. The rheological behavior of the additives and of the suspensions containing these bio-sourced additives was studied in flow and in oscillations. The mechanical properties of the green tapes obtained with the different bio-sourced binders were determined from tensile experiment. This paper studies the relations between the nature of the binder, the rheological behavior of the suspension, the ability to tape cast the suspensions and the final properties of the green and sintered tapes.     

UV Curable Systems for Tape Casting

The substitution of solvents by photopolymerizable binders in the tape casting process allows to achieve high ceramic loading and to eliminate the drying stage which is a critical step of the tape casting process. After the rapid UV polymerization of the resin, the high strength green tapes can be debinded and sintered. Ceramic suspensions containing alumina or zirconia powder, dispersant, UV curable binder and photoinitiator have been prepared. The use of a low viscosity organic vehicle allows to prepare low viscosity ceramic suspensions, containing about 50 vol% powder, which have a shear thinning behaviour. Because of the rapid attenuation of the incident light in UV curing systems containing ceramic particles it is important to estimate the thickness of the tape that can be treated. The effect of incident energy, of photoinitiator concentration and of powder volume fraction was studied. There is an optimal photoinitiator concentration which maximizes the cured depth and which depends on the volume fraction of solid. A theoretical model based on the Beer–Lambert’s law enables the prediction of cured depth for any volume fraction of solid. To prove the ability to manufacture ceramic sheets by tape casting, some suspensions were tape cast.     

Critical analysis of aqueous tape casting,sintering, and characterization of planar Yttria‐Stabilized Zirconia electrolytes for SOFC

Tape casting is an established forming technique for several industries, however, researches focus more on slurry composition. In this work, the combined use of design of experiment and materials characterization techniques showed tape casting process parameters have great influence on the microstructure and mechanical properties of green tapes. Formulation and processing optimization allowed obtaining YSZ green tapes with good mechanical characteristics and homogeneous microstructure without laminating step. The optimized sintering schedule and sintering load allowed obtaining planar electrolytes with high density, tensile strength, and electrical conductivity. This work provides an environmental friendly procedure for large‐scale production of SOFCs planar electrolytes.