High-density YSZ tapes fabricated via the multi-folding lamination process

A new method of ceramic processing to obtain high green and fully sintered yttria-stabilized zirconia (YSZ) ceramic parts has been studied. The procedure involved slip casting, multi-folding lamination, and sintering. A rheological study revealed correlation between compositional parameters and densities. A particular method of folding and lamination we named multi-folding lamination was proved to be an appropriate route to obtain dense, homogeneous green bodies, reaching density values of ca. 61%. Further studies on the sintered parts were performed in this work, obtaining YSZ sintered tapes suitable for the use in high temperature solid-state devices. This tapes, sintered at 1550 °C, reached values of 98% of theoretical density and average particle sizes within 1.7–12 μm.     

Low-pressure,thermo-compressive lamination

Lamination of green ceramic tapes is one of the most important technological processes in multilayer ceramic technology. Lamination affects the quality of all 3D structures (e.g., channels, chambers, membranes, etc.). Novel chemical methods of lamination reduce the deformation of 3D structures. However, these methods are useless in the fabrication of thin membranes and structures with thick-film electronic components or electric vias. Therefore, thermo-compressive lamination is still the best solution for the lamination of green ceramic tapes. Low-pressure thermo-compressive lamination with an insert material is presented in this paper. The influence of pressure and Low Temperature Cofired Ceramics (LTCC) material on the compressibility and shrinkage of LTCC, as well as the influence of the insert material on deflection and distortion of the membranes are presented and discussed in this paper.     

Manufacture of 3D structures by cold low pressure lamination of ceramic green tapes

3D multilayer devices were generated by Laminated Object Manufacturing (LOM), a well-known rapid-prototyping technology. Divergent from this method, commercial ceramic green tapes were used which were laminated by Cold Low Pressure Lamination (CLPL). In contrast to thermo-compression, which works at pressures and elevated temperatures, CLPL allows to join particularly fine, complex structures with cavities or undercuts, because no mass flow occurs. This technique is based on gluing the adjacent tapes by means of an adhesive film at room temperature under a low pressure. After binder burnout and sintering the ceramic laminate has a homogenous and dense microstructure free of interfaces. This modified LOM technique is particularly suitable for the production of Micro Electro Mechanical Systems (MEMS).In the given paper commercial Low Temperature Co-fired Ceramic (LTCC) green tapes were used, which were structured by means of a high-frequency milling plotter and laminated by using CLPL. Various 3D devices of different shape with inlying cavities were manufactured. The quality of the fired and unfired structures of the devices were characterised by different methods and show a high quality surface of the multilayer structures. Process aspects of the CLPL technique are discussed. The results demonstrate the advantages of this method for the fabrication of MEMS.     

Low-Sintering High-k Materials for an LTCC Application

High-k LTCC tapes with ultralow sintering temperatures were developed from lead-free perovskite powders. Lowering of the sintering temperature from 1250°C down to 900°C has been achieved by means of ultrafine ceramic powders in combination with suitable sintering aids. The tape-casting process has been optimized for ultrafine powders with an enhanced sintering activity. Low-sintering high-k tapes of a thickness down to 40 μm, suitable for LTCC processing, were obtained. The sintering behavior of these high-k tapes has been studied and compared with other LTCC materials. Dielectric properties of the high-k material have been investigated on a multilayer test structure consisting of up to 20 dielectric layers. After metallization with an Ag conductor, the green tapes were stacked and laminated. Sintering of these multilayer stacks at 900°C gives dense ceramic samples. Permittivities up to 2000 have been obtained, together with low dielectric losses. Material compatibility with several Ag/Au-thick-film-paste systems has been tested.     

PZT components derived from polysulphone spinning process

The present paper deals with the development of lead zirconate titanate (PZT) fibres, pearls and fibre fragments, for their use as active phase in piezocomposites. As new a approach, the green ceramic components are shaped by polysulphone spinning, allowing for effective and flexible forming over a wide range of different geometries and sizes. The correlation between processing parameters, e.g. the slurry composition, nozzle size and operation velocity, and the resultant shape of ceramic components is analysed. Sintered piezoceramic parts show a dense microstructure. Performance data are evaluated on PZT/epoxy composites. Measurement results of strain, polarisation and piezoelectric coupling are given and discussed. The developed PZT components are seen as key for the creation of smart and lightweight structural components. Further, free formed PZT components open new design approaches for sensing and actuating devices and ultrasound transducers.     

Cold chemical lamination of ceramic green tapes

The cold chemical lamination (CCL) is a new technique of bonding ceramic green tapes into one 3D structure. Instead of a standard thermo-compression method, new solvent-based lamination is presented. A film of a special chemical agent is put on the green tape surface. The solvent melts the surface. Then the tapes are stacked. The bonding of the green tapes is made at a room temperature. The new method is used for joining green tapes of the low temperature co-fired ceramics (LTCC). A quality of the bonding depends on the solvent type. The cold chemical lamination is examined on two types of the LTCC tapes: DuPont 943 and DuPont 951. Six types of the solvents are analyzed in the paper. The bonding quality and geometry of the test structures are examined. The lamination quality is investigated by the scanning electron microscope.     

Effects of microwave heating on dielectric and piezoelectric properties of PZT ceramic tapes

Commercial lead zirconate titanate (PZT) perovskite powders were used to fabricate ceramic tape and then sintered by microwave and conventional methods. Both dielectric and piezoelectric properties of PZT ceramic tapes were studied in terms of sintering process. X-ray diffraction analysis (XRD) and scanning electron microscopy (SEM) show the PZT perovskite phase with smaller grain size and dense microstructure can be obtained at a lower sintering temperature by microwave process. It was also observed that shrinkage ratio and bulk density of the tapes sintered at 800 °C were obtained about 19% and 7.46 g/cm³ by the microwave heating method, respectively, that is corresponding to those values of sintered PZT tapes at 950 °C by conventional process. Moreover, the dielectric constant and maximum permittivity are increased about 30% as compared with conventional processing method. The experimental results demonstrated that the characteristics of the PZT tapes could be significantly improved by microwave heating method. These results demonstrate that such a simple approach can upswing the piezoelectric and dielectric properties of these tapes by using microwave process with a short heating time.     

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.     

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 nanocrystalline ceria gadolinia powder

A ceramic ceria gadolinia solid solution membrane for solid oxide fuel cells was fabricated by tape casting using a nanopowder of 37 nm average particle size. A novel combination of solvent and dispersant was used to disperse the nanoparticles. The polymer was added in a dilute stage to guarantee a homogeneous distribution. After casting a remarkable densification of the cast tape suspension from a solid loading of 20 up to 42 vol.% was observed during drying. The green tape was sintered to >92% theoretical density and was dense towards perfusion. The resulting grain size in the sintered specimen still was <200 nm.     

Optimization of borosilicate glass/CaTiO3-TiO2 composite via altering prefiring temperature and particle size

Low-temperature co-fired ceramic (LTCC) with middle permittivity is very crucial to the miniaturization of components. Based on our previous study on the glass/CaTiO₃-TiO₂ composite, prefiring temperature and particle size of CaTiO₃-TiO₂ ceramic were optimized in this study to promote the performance of the composites. Comparing with our previous study, after being sintered with 50 wt% glass at 875°C, CaTiO₃-TiO₂ ceramic prefired at 1275°C with particle size of 3.38 μm showed excellent properties of sintering density = 3.33 g/cm³, ε_r = 30.2, tan δ = 0.0005 (7 GHz). In addition, surface roughness of green tapes was also improved after optimization. The material has a good chemical stability and shrinkage matching with silver, making it a very promising candidate material for LTCC applications.     

The effect of laminating factors on the thermal properties of unfired multilayer glass-ceramic and alumina substrates

This paper presents experimental data on heat capacities and thermal conductivities of two ceramic tapes measured using standard ASTM methods. The two ceramic tapes were prepared using alumina and a glass ceramic of aluminum-magnesium silicate with poly(vinyl butyral) binder, and laminated at pressures of 208E5 to 620E5 Pa at two laminating temperatures and times. The measured properties showed that laminating pressures have a greater effect, and that thermal conductivities are affected more than heat capacities. Empirical models have been developed to fit the experimental data. A correlation is developed to express the density of laminated green sheets in terms of the laminating variables—time, temperature, and pressure.     

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.     

Prediction and Explanation of Aging Shrinkage in Tape-Cast Ceramic Green Sheets

A simple test to predict linear shrinkage of tape-cast green sheets as a function of time was developed. Shrinkage was found to correlate inversely with the amount of organic phase bound to ceramic particle surfaces. The test was developed for alumina green tapes with acrylic binder. The correlation was found to be independent of the medium used for the two slurry systems evaluated, water and toluene/ethanol. Treatments developed to dimensionally stabilize green sheets reduced shrinkage after 35 days of aging to less than 0.15%. Stabilization treatments involved heating and/or polymer swelling which facilitated the binding of organic phase to alumina particles, causing the tape to be in a more relaxed state.     

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.     

Tape casting of ferroelectric,dielectric, piezoelectric and ferromagnetic materials

Tape casting is a feasible method for preparing ceramic tapes with different electrical and magnetic properties for multilayer ceramic devices. This paper describes the tape casting process for several different electroceramic materials (BST, PZT, NZF and ZSB) utilising similar organic additive and solvent systems. The properties of tapes with different ceramic compositions before and after sintering are investigated, including surface roughness, shrinkage and microstructures. The parameters affecting the casting, shrinkage, lamination, thickness and tensile strength of green tape are also presented. This enables process design for tape which can be used in devices with true integration of dielectric and piezoelectric, ferroelectric and ferromagnetic layers in 3-dimensional multilayer structures.     

PVA/PVAc复合黏结剂制备Li1.075Nb0.625Ti0.45O3水基流延膜

采用PVA/PVAc复合黏结剂制备Li_1.075Nb_0.625Ti_0.45O₃微波介质陶瓷基片。研究了PVAc用量和固相含量对浆料流变性能以及流延膜片力学性能的影响。结果表明,随着PVAc添加量的增加,浆料的黏度和屈服应力不断下降,膜片的断裂方式由韧性断裂转变为脆性断裂。随着浆料固相含量的增大,浆料的流变模型从Bingham型转变为Casson型。SEM观察表明,膜片的微观结构非常均匀。     

Processing, Microstructure, and Properties of Laminated Silicon Nitride Stacks

By lamination of silicon nitride tapes, components with complex geometries can be produced. Unstructured tapes can be laminated by common thermal compression. Structured tapes, however, have to be joined by pressureless processes using e.g. pastes as lamination aids because deformation of the structures would occur. These pastes usually contain a binder for maintaining the mechanical contact between the tapes during processing. To prevent the high mass loss of typical organic binders during burnout, pre-ceramic polymers were used in this work. These ceramic precursors convert partly into an inorganic material during heat treatment with a significant reduced mass loss compared with common organic binders. Thus, the porosity in the interlayer of a laminated stack is strongly decreased, which should be favorable for the mechanical and thermal properties. This work discusses the resulting microstructure, strength, and thermal diffusivity data of stacks laminated with pastes containing various precursor contents. These results are compared with those obtained by samples prepared by compression of green tapes. It is found that except for some large pores, the microstructure of the precursor-derived interlayers is qualitatively the same as in the tape material. For stacks made by both lamination methods, strength measurements reveal that the properties parallel and perpendicular to the layers are different. It is shown that the same strength level can be obtained both by using the pressureless route and by the compression method. Unlike the strength, the thermal conductivity does not change with the direction of measurement.     

Tape casting system for ULTCCs to fabricate multilayer and multimaterial 3D electronic packages with embedded electrodes

A 3D multilayer structure built by two ultra‐low temperature co‐fired ceramic (ULTCC) compositions with silver embedded electrodes are co‐fired at a temperature of 450°C. The 3D multilayer module is prepared by laminating the ULTCC green tapes with a new binder system, which organics can be completely burned out at temperature of 250°C before the sintering of the ULTCC 3D modulus. High‐density microstructures are achieved for the sintered module. In this study, the ULTCC feasible binder system is introduced. Also, ULTCC multilayers and multimaterial structures with surface and embedded silver electrodes are fabricated. This research opens up a new horizon for fabrication of electroceramic devices with embedded electrodes in multimaterial devices.     

Cold Chemical Lamination—New Bonding Technique of LTCC Green Tapes

The low-temperature co-fired ceramic (LTCC) technology enables fabrication of sensors, actuators, microfludic devices² and fuel cells. The structures consist of screen-printed components, gas/liquid channels, reactive chambers and mixers. The lamination process determines the quality of such devices. Thermo-compression is the most popular bonding method. The LTCC green tapes are joined together at high temperature (up to 80°C) and high pressure (up to 30 MPa) for 2 to 15 minutes. The method allows good encapsulation of the LTCC structures, but the channels geometry is strongly affected by elevated temperature and pressure. Cold Chemical Lamination (CCL) is a new LTCC green tapes bonding technique, which allows for fabrication of 3D modules. A solvent-based method is used in the CCL lamination instead of the thermo-compression process. A special liquid agent is screen-printed on the green tape in the CCL method. The liquid melts the tape surface. Then the tapes are stacked and compressed at room temperature by a printing roll. The influence of the CCL and the thermo-compression methods on the chamber's geometry quality as well as basic electrical properties of screen-printed resistors (sheet resistance R_φ standard deviation of sheet resistance σ_R, variability coefficient of sheet resistance V_R, and long-term stability) are analyzed and compared in this paper. The bonding quality is examined by a scanning electron microscope (SEM).