TY - CONF A1 - Bresch, Sophie A1 - Mieller, Björn A1 - Rabe, Torsten T1 - Influence of solid-state-synthesis conditions on properties of oxide thermoelectric materials N2 - Calcium cobaltite and calcium manganate are promising oxide thermoelectric materials for applications between 600 °C and 900 °C in air to convert waste heat directly into electrical power. The solid state reaction, well known for large scale powder synthesis of functional materials, is used for the production of thermoelectric oxides. As a high temperature process, the powder synthesis consumes a lot of energy. In different studies, different synthesis conditions were used for the preparation of calcium cobaltite and calcium manganate powder. To the author’s knowledge, a systematic study of the synthesis conditions of calcium cobaltite and calcium manganate has not yet been published. Therefore, the synthesis conditions for calcium cobaltite (temperature, dwell time, and particle size of raw materials) were studied with a statistical design of experiments (2³) and investigated regarding phase composition (XRD), densification and thermoelectric properties. The gained knowledge was used to optimize the solid state reaction of calcium manganate. This study showed that a higher energy input (elevated temperatures, longer dwell times, or repeated calcinations) during powder synthesis does not improve but deteriorate the thermoelectric properties of calcium cobaltite. The same correlation was determined for the densification. As a higher energy input during powder synthesis leads to a larger grain size and therefore to a reduced sinter activity the densification at a given sinter profile is minimize as well as the thermoelectric properties. These results can be used to minimize the energy demand for the powder synthesis of oxide thermoelectric materials. T2 - 92. DKG Jahrestagung & Symposium Hochleistungskeramik 2017 CY - Berlin, Germany DA - 19.03.2017 KW - Thermoelectrics KW - Solid-state-reaction KW - Calcium cobaltite KW - Calcium maganate PY - 2017 AN - OPUS4-39520 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Bresch, Sophie T1 - Druckunterstützte Sinterung von Calciumcobaltitfolien N2 - Calcium cobaltite Ca3Co4O9 is a promising p-type oxide thermoelectric material for applications between 600 °C and 900 °C in air. The properties and the morphology of Ca3Co4O9 are strongly anisotropic because of its layered crystal structure. By aligning the plate-like grains, the anisotropic properties can be assigned to the component. Hot-pressing of tablets is a well-known technology for grain alignment of Ca3Co4O9 and increases the thermoelectric properties in a/b-direction remarkably [1-3]. However, hot-pressing of tablets is limited by the tablet size. An interesting alternative for larger components is the pressure assisted sintering of panels from tape casted layers. Tape casting already leads to grain orientation during green body forming. By combining tape casting and pressure assisted sintering (50 kN maximum force) of Ca3Co4O9, high densities and high thermoelectric properties can be reached for large components up to 200 mm edge length. The morphology of Ca3Co4O9-grains can be designed by doping as well as by varying the powder synthesis conditions. For example Bi-doping increases the anisotropy of the grains, and reaction sintering of uncalcined powder leads to a fine grained microstructure and increases the electrical conductivity for pressure-less sintered specimens. Doped and undoped Ca3Co4O9 powders were successfully tape cast with the doctor blade technique. Several layers of tape were stacked and laminated to 7 cm x 7 cm panels. These panels were sintered in a LTCC sintering press with combined in-situ shrinkage measurement. Pressure-less sintered panels from undoped powder have a 2.5 times higher electrical conductivity at room temperature than dry-pressed test bars with randomly orientated particles. By applying a uniaxial pressure of 10 MPa during sintering, the electrical conductivity (σ25°C=15000 S/m) increases by the factor of 6 compared to the pressure-less sintered panels, which is in good accordance to the values reported in literature for conventional hot pressing [1, 3]. It is not possible to assign the increased anisotropy of Ca2.7Bi0.3Co4O9 to the pressure-assisted sintered panels, as Bi leads to an abnormal grain growth (up to 500 µm) with randomly oriented grains. This decreases the electrical conductivity (σ25°C=5000 S/m). Such an abnormal grain-growth is reported for Bi over-doped Ca3Co4O9 [4] but not because of hot-pressing. N2 - Calciumcobaltit ist eines der vielversprechendsten thermoelektrischen Oxide, welche zur direkten Wärmerückgewinnung genutzt werden können. Calciumcobaltit weist sowohl eine anisotrope Partikelform als auch anisotrope thermoelektrische Eigenschaften auf. Durch gezielte Ausrichtung der Partikel mittels Foliengießens und druckunterstützter Sinterung kann diese Anisotropie gezielt auf ein Bauteil übertragen werden. Die Partikelmorphologie kann durch Dotierung und Kalzinierung beeinflusst werden. Verschiedene Calciumcobaltitpulver wurden druckgesintert und das Gefüge sowie die thermoelektrischen Eigenschaften untersucht. Die Dotierung mit Bismut führte zu einer Verschlechterung der elektrischen Leitfähigkeit bei druckgesinterten Proben im Gegensatz zu undotierten Pulvern. T2 - Funktionsmaterialien - Lehrstuhlseminar CY - Bayreuth, Germany DA - 02.06.2017 KW - Thermoelectrics KW - Calcium cobaltite KW - Pressure assisted sintering KW - Druckunterstützte Sinterung KW - Calciumcobaltit KW - Thermoelektrika PY - 2017 AN - OPUS4-40467 LA - deu AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Bresch, Sophie A1 - Mieller, Björn A1 - Moos, Ralf A1 - Rabe, Torsten T1 - Pressure-assisted sintering of tape cast calcium cobaltite Ca3Co4O9 with varied powder compositions N2 - Calcium cobaltite Ca3Co4O9 is a promising p-type oxide thermoelectric material for applications between 600 °C and 900 °C in air. The properties and the morphology of Ca3Co4O9 are strongly anisotropic because of its layered crystal structure. By aligning the plate-like grains, the anisotropic properties can be assigned to the component. Hot-pressing of tablets is a well-known technology for grain alignment of Ca3Co4O9 and increases the thermoelectric properties in a/b-direction remarkably. However, hot-pressing of tablets is limited by the tablet size. An interesting alternative for larger components is the pressure assisted sintering of panels from tape casted layers. Tape casting already leads to grain orientation during green body forming. By combining tape casting and pressure assisted sintering (50 kN maximum force) of Ca3Co4O9, high densities and high thermoelectric properties can be reached for large components up to 200 mm edge length. The morphology of Ca3Co4O9-grains can be designed by doping as well as by varying the powder synthesis conditions. For example Bi-doping increases the anisotropy of the grains, and reaction sintering of uncalcined powder leads to a fine grained microstructure and increases the electrical conductivity for pressure-less sintered specimens. Doped and undoped Ca3Co4O9 powders were successfully tape cast with the doctor blade technique. Several layers of tape were stacked and laminated to 7 cm x 7 cm panels. These panels were sintered in a LTCC sintering press with combined in-situ shrinkage measurement. Pressure-less sintered panels from undoped powder have a 2.5 times higher electrical conductivity at room temperature than dry-pressed test bars with randomly orientated particles. By applying a uniaxial pressure of 10 MPa during sintering, the electrical conductivity (σ25°C = 15000 S/m) increases by the factor of 6 compared to the pressure-less sintered panels, which is in good accordance to the values reported in literature for conventional hot pressing [1, 3]. It is not possible to assign the increased anisotropy of Ca2.7Bi0.3Co4O9 to the pressure-assisted sintered panels, as Bi leads to an abnormal grain growth (up to 500 µm) with randomly oriented grains. This decreases the electrical conductivity (σ25°C = 5000 S/m). Such an abnormal grain-growth is reported for Bi over-doped Ca3Co4O9 but not because of hot-pressing. T2 - European Conference on Thermoelectrics (ECT) 2017 CY - Padua, Italy DA - 25.09.2017 KW - Thermoelectrics KW - Pressure assisted sintering KW - Grain growth PY - 2017 AN - OPUS4-42283 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Bresch, Sophie A1 - Mieller, Björn A1 - Moos, Ralf A1 - Rabe, Torsten T1 - Pressure assisted sintering of tape cast calcium cobaltite N2 - Thermoelectric materials can convert waste heat directly into electrical power by utilizing the Seebeck effect. Calcium cobaltite Ca3Co4O9 is a promising p-type oxide thermoelectric material for applications between 600 °C and 900 °C in air. The properties and morphology of Ca3Co4O9 are strongly anisotropic because of its crystal structure of alternating layers of CoO2 and Ca2CoO3. The electrical conductivity is for example 13.5 times higher in a/b-direction than in c-direction. By aligning the plate-like grains, the anisotropic properties can be assigned to the component. Hot-pressing of tablets is a well-known technology for grain alignment of Ca3Co4O9 and increases the thermoelectric properties in a/b-direction remarkably. It also increases the relative density. However, hot-pressing of tablets is limited by the tablet size. An interesting alternative for larger components is the pressure assisted sintering of panels from tape casted layers. Tape casting already leads to a grain alignment during green body forming. By combining tape casting and pressure assisted sintering (50 kN maximum force) of Ca3Co4O9, high densities and high thermoelectric properties can be reached for large components up to 200 mm edge length. Ca3Co4O9 was successfully tape casted with the doctor blade technique (binder: polyvinyl butyral, organic solvent). Several layers of tape were stacked and laminated to 5 cm x 5 cm panels. These panels were sintered with different applied pressures in a LTCC sintering press with combined in-situ shrinkage measurement. Pressure-less sintered panels have a 2.5 times higher electrical conductivity at room temperature than test bars with randomly orientated particles. By applying a uniaxial pressure of 10 MPa during sintering, the electrical conductivity increases by the factor of 6 compared to the pressure-less sintered panels. About 40 % linear shrinkage are reached in pressing direction. The Seebeck coefficient (S25 °C=146 μV/K) and the electrical conductivity (σ25 °C=15100 S/m) are in good agreement with the values published in literature for hot-pressed tablets. T2 - 15th Conference & Exhibition of the European Ceramic Society CY - Budapest, Hungary DA - 09.07.2017 KW - Thermoelectrics KW - Pressure assisted sintering PY - 2017 AN - OPUS4-41026 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Bresch, Sophie A1 - Mieller, Björn A1 - Delorme, F. A1 - Chen, C. A1 - Bektas, M. A1 - Moos, R. A1 - Rabe, Torsten T1 - Influence of Reaction-Sintering and Calcination Conditions on Thermoelectric Properties of Sm-doped Calcium Manganate CaMnO3 JF - Journal of Ceramic Science and Technology N2 - A wide range of solid-state synthesis routes for calcium manganate is reported in the literature, but there is no systematic study about the influence of the solid-state synthesis conditions on thermoelectric properties. Therefore, this study examined the influence of calcination temperature and calcination cycles on the Seebeck coefficient, electrical conductivity, and thermal conductivity. Higher calcination temperatures and repeated calcination cycles minimized the driving force for sintering of the synthesized powder, leading to smaller shrinkage and lower densities of the sintered specimens. As the electrical conductivity increased monotonously with increasing density, a higher energy input during calcination caused deterioration of electrical conductivity. Phase composition and Seebeck coefficient of sintered calcium manganate were not influenced by the calcination procedure. The highest thermoelectric properties with the highest power factors and figures of merit were obtained by means of reaction-sintering of uncalcined powder. KW - Thermoelectric oxides KW - Calcination KW - Solid-state-synthesis KW - Power factor KW - Reaction-sintering PY - 2018 DO - https://doi.org/10.4416/JCST2018-00017 SN - 2190-9385 VL - 9 IS - 3 SP - 289 EP - 300 PB - Göller Verlag AN - OPUS4-46224 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Bresch, Sophie A1 - Stargardt, Patrick A1 - Moos, Ralf A1 - Mieller, Björn T1 - Co‐Fired Multilayer Thermoelectric Generators Based on Textured Calcium Cobaltite JF - Advanced Electronic Materials N2 - Thermoelectric generators are very attractive devices for waste heat energy harvesting as they transform a temperature difference into electrical power. However, commercially available generators show poor power density and limited operation temperatures. Research focuses on high‐temperature materials and innovative generator designs. Finding the optimal design for a given material system is challenging. Here, a theoretical framework is provided that allows appropriate generator design selection based on the particular material properties. For high‐temperature thermoelectric oxides, it can be clearly deduced that unileg multilayer generators have the highest potential for effective energy harvesting. Based on these considerations, prototype unileg multilayer generators from the currently best thermoelectric oxide Ca3Co4O9 are manufactured for the first time by industrially established ceramic multilayer technology. These generators exhibit a power density of 2.2 mW/cm² at a temperature difference of 260 K, matching simulated values and confirming the suitability of the technology. Further design improvements increase the power density by a factor of 22 to facilitate practicable power output at temperature differences as low as 7 K. This work demonstrates that reasonable energy harvesting at elevated temperatures is possible with oxide materials and appropriate multilayer design. KW - Optical and Magnetic Materials KW - Electronic PY - 2023 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-596306 DO - https://doi.org/10.1002/aelm.202300636 SN - 2199-160X VL - 10 IS - 3 SP - 1 EP - 12 PB - Wiley VHC-Verlag AN - OPUS4-59630 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Bresch, Sophie A1 - Höhne, Patrick A1 - Lindemann, Franziska A1 - Koppert, Ralf A1 - Mieller, Björn T1 - Chemical resistance of commercial LTCC against thin film etching media N2 - Low-temperature co-fired ceramics (LTCC) are used to fabricate robust multilayer circuits. Typically, thick-film technology is applied for metallization. For specific sensor applications, thin films are deposited directly on the as-fired LTCC-surface. These deposited thin films are structured either by lift-off or by etching. The latter is less error-prone and thus preferred in industry provided the selected materials allow it. 200 nm Ni-thin films were deposited on three different commercial constrained-sintered LTCC (CT708, CT800 and DP951) by electron beam physical vapour deposition. The thin-films were structured by covering corresponding sections with a UV-curable photo resisn and subsequent etching of the uncovered surface, leaving behind the desired structure. The etched Ni-thin film showed high difference in failure rate and sheet resistance regarding the used LTCC-material. DP951 had the lowest sheet resistance and no failure, whereas the CT800 had a failure rate of 40 %. The LTCC with high failure rate showed a strong chemical attack by the used etching medium. To address this phenomenon, the chemical resistance of the three different commercial LTCC (CT708, CT800 and DP951) against four different commonly used etching media (sulphuric acid, phosphoric acid, aqua regia, and hydrofluoric acid) is investigated. The dissolved ions are analyzed by ICP-OES to correlate the LTCC-composition and its chemical resistance. T2 - KERAMIK 2023 / 98. DKG-Jahrestagung CY - Jena, Germany DA - 27.03.2023 KW - Glass-ceramics KW - Hydrogen sensors KW - Acids PY - 2023 AN - OPUS4-57273 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Bresch, Sophie A1 - Höhne, Patrick A1 - Koppert, R. A1 - Mieller, Björn T1 - Thin-film capability of commercial LTCC N2 - Low-temperature co-fired ceramics (LTCC) are used to fabricate multilayer circuits which are robust in harsh environments. Thick-film technology is well established for the metallization of circuit boards and microsystems. For specific sensor applications, the combination of LTCC and thin-film technology is advantageous to reach higher structure resolutions. Due to the high roughness of as-fired LTCC surfaces compared with silicon-wafers, the deposition of low-defect- films with narrowly specified properties is challenging. The deposited thin-films are structured either by lift-off or by etching. The latter is less error-prone and thus preferred in industry provided the selected materials allow it. There is spare literature about thin films on commercial LTCC comparing different material systems or sintering techniques. For developing thin-film sensors on multilayer circuits it is crucial to identify thin-film-compatible commercial LTCC material as well as the crucial surface properties. In this work we evaluate the thin-film capability of different LTCC compositions and surface qualities. To evaluate the influence of the material composition on the thin film capability, 200 nm Ni-thin films were deposited on three different constrained-sintered LTCC (CT708, CT800 and DP951) by electron beam physical vapour deposition. The effect of surface quality was assessed by thin-film deposition on free-sintered, pressure-assisted sintered, and polished DP951. The thin-films were structured by covering corresponding sections with a UV-curable photo resin and subsequent etching of the uncovered surface, leaving behind the desired structure. The etched Ni-thin films showed high difference in failure rate and sheet resistance regarding the used LTCC-material. DP951 had the lowest sheet resistance and no failure, whereas CT800 had a high sheet resistance and a failure rate of 40 %. These results are correlated with surface roughness of the LTCC, scanning electron micrographs of the deposited thin-films, and the chemical resistance of the LTCC against commonly used etching media. Contrary to the expectations, no correlation between roughness and thin-film capability was found. The LTCC with high failure rate showed a strong chemical attack by the used etching medium. Additionally, the adhesion of thin-films on DP951 is better than on CT708 and CT800. T2 - XVIII EcerS Conference & Exhibition CY - Lyon, France DA - 02.07.2023 KW - Glass-ceramics KW - Etching KW - Resistance PY - 2023 AN - OPUS4-58019 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Stargardt, Patrick A1 - Bresch, Sophie A1 - Falkenberg, Rainer A1 - Mieller, Björn T1 - Effect of Reaction Layers on Internal Stresses in Co‐Fired Multilayers of Calcium Manganate and Calcium Cobaltite JF - physica status solidi (a) N2 - A widespread recovery of waste heat requires a cost‐effective production of thermoelectric generators. Thermoelectric oxides are predestined for use at high temperatures. For manufacturing reasons, a multilayer generator design will be easily scalable and cost‐effective. To evaluate the potential of ceramic multilayer technology for that purpose, a multilayer of the promising thermoelectric oxides calcium cobaltite (Ca3Co4O9), calcium manganate (CMO, CaMnO3), and glass–ceramic insulation layers is fabricated. Cracks and reaction layers at the interfaces are observed in the microstructure. The compositions of these reaction layers are identified by energy‐dispersive X‐ray spectroscopy and X‐ray diffraction. Mechanical and thermal properties of all layers are compiled from literature or determined by purposeful sample preparation and testing. Based on this data set, the internal stresses in the multilayer after co‐firing are calculated numerically. It is shown that tensile stresses in the range of 50 MPa occur in the CMO layers. The reaction layers have only a minor influence on the level of these residual stresses. Herein, it is proven that the material system is basically suitable for multilayer generator production, but that the co‐firing process and the layer structure must be adapted to improve densification and reduce the tensile stresses in the CMO. KW - Ceramic multilayers KW - Co-firings KW - Internal stresses PY - 2024 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-601626 DO - https://doi.org/10.1002/pssa.202300956 SP - 1 EP - 9 PB - Wiley VHC-Verlag AN - OPUS4-60162 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER -