Influence of processing on stability,microstructure and thermoelectric properties of Ca3Co4 − xO9 + δ

Due to high figure of merit, Ca₃Co_4 ? xO_9 + δ (CCO) has potential as p-type material for high-temperature thermoelectrics. Here, the influence of processing including solid state sintering, spark plasma sintering and post-calcination on stability, microstructure and thermoelectric properties is reported. By a new post-calcination approach, single-phase materials were obtained from precursors to final dense ceramics in one step. The highest zT of 0.11 was recorded at 800 °C for CCO with 98 and 72% relative densities. In situ high-temperature X-ray diffraction in air and oxygen revealed a higher stability of CCO in oxygen (～970 °C) than in air (～930 °C), with formation of Ca₃Co₂O₆ which also showed high stability in oxygen, even at 1125 °C. Since achievement of phase pure high density CCO by post-calcination method in air is challenging, the phase stability of CCO in oxygen is important for understanding and further improvement of the method.     

Transverse thermoelectric multilayer generator with bismuth-substituted calcium cobaltite: Design optimization through variation of tilt angle

Sintering of Ca_2.7Bi_0.3Co₄O₉ pellets and multilayer laminates at 920 °C results in a ceramic microstructure with low density with a pronounced anisotropy. The electrical conductivity of multilayers is 56 S/cm at 400 K (perpendicular to pressing direction). The Seebeck coefficient is positive, and the power factor increases from 60 μW/(K²m) at 400 K to 200 μW/(K²m) at 900 K. The thermal conductivity (parallel to pressing direction) is 0.65 W/(mK). Transverse multilayer thermoelectric generators (TMLTEG) were fabricated by stacking layers of Ca_2.7Bi_0.3Co₄O₉ green tapes, screen-printing of AgPd stripes at various tilt angle φ relative to the heat flux direction (20°, 45°, and 65°), and co-firing at 920 °C. For φ = 65° the power output is 8 mW at ΔT = 200 K with room temperature at the cold side. FEM modelling as well as analytical calculations agree well with measurements, and the optimum tilt angle is found to be φ = 58°.     

Fabrication of a transversal multilayer thermoelectric generator with substituted calcium manganite

The sintering behavior and thermoelectric performance of Ca_0.99Gd_0.01Mn_0.99W_0.01O₃ was studied, and a multilayer thermoelectric generator was fabricated. The addition of CuO as sintering additive was found to be effective for the reduction in the sintering temperature from 1300°C to about 1000°C‐1050°C. Dense samples were obtained after firing at 1050°C, whereas some porosity remained after firing at 1000°C. Samples sintered at reduced temperature exhibit lower electrical conductivity, whereas the Seebeck coefficient S = ?150 μV/K at 100°C is not affected by lowering the sintering temperature. The figure of merit is ZT = 0.12 at 700°C for samples sintered at 1300°C; ZT = 0.08 and 0.03 were obtained for multilayer laminates sintered at 1050°C and 1000°C, respectively. A transversal multilayer thermoelectric generator (TMLTEG) was built by stacking layers of substituted CaMnO₃ green tapes, and printing AgPd conductor stripes onto the thermoelectric layers at an angle of 30° relative to the direction of the heat flow. The multilayer stack was co‐fired at 1000°C. The TMLTEG has a power output of 2.5 mW at ?T= 200 K in the temperature interval of 25°C‐300°C. A meander‐like generator with larger power output comprising six TMTEGs is also presented.     

Synthesis of single-phase Ca3Co4O9 ceramics and their processing for a microstructure-enhanced thermoelectric performance

Single-phase Ca₃Co₄O₉ with a high porosity, having a ZT of 0.09 at 627 °C, was successfully prepared by a simple solid-state reaction using fine powders of CaCO₃ and Co₃O₄ after a calcination at 760 °C for 12 hours. It was excellent either for the preparation of the starting powder for the processing of the Ca₃Co₄O₉ ceramics or for direct processing. The influence of already-reported processing methods (classic sintering, hot pressing, free-edge spark-plasma sintering (SPS) of a sintered pellet) and new methods, such as free-edge SPS of a pellet from just-compacted powder, cold pressing of a sintered pellet without post annealing, and free-edge cold pressing of a sintered pellet with post-annealing, on the preparation of Ca₃Co₄O₉ ceramics was studied. The results showed how the density, the grain morphology and the microstructural anisotropy can all influence the thermoelectric characteristics of Ca₃Co₄O₉ ceramics measured in directions parallel and perpendicular to the applied pressure. While the fully dense (99%) and perfectly textured ceramics prepared by the free-edge SPS of a pellet from just-compacted powder had a ZT of 0.17, the highest ZT of 0.31 was obtained for the free-edge cold-pressed and annealed ceramics with modest texturing and low density (65%), having a very low κ of 0.47 W/mK. The results also showed that thin and irregular-shaped plate-like grains with sharp edges are preferred, while their thickening accompanied by rounding of their shape resulted in a reduced thermoelectric performance. The study revealed both the possibilities and the limitations for enhancing the TE characteristics of Ca₃Co₄O₉ ceramics just through microstructure optimisation.     

Oxide multilayer thermoelectric generators

Oxide multilayer thermoelectric generators (MLTEG) were fabricated, using the standard multilayer technology. Green tapes of p‐type La₂CuO₄ and n‐type Nd₂CuO₄ thermoelectric oxides were stacked with intermediate insulating glass layers. Electrical contacts between thermoelectric oxides were applied, using screen‐printing of AgPd paste, and multilayers were cofired at 1000°C. However, cofiring of four different materials turned out to be very challenging, and contact resistance problems frequently led to device malfunctions. We developed a new concept of a transversal multilayer thermoelectric generator (TMLTEG), which is characterized by a simple design. This generator is build up by stacking layers of a p‐ or n‐type thermoelectric oxide and printing stripes of AgPd paste onto the thermoelectric layers at an angle with respect to the temperature gradient. Transversal multilayer thermoelectric generators were fabricated using p‐type La₂CuO₄, or n‐type substituted CaMnO₃; cofiring of the multilayer stacks was performed at 1000°C. The TMLTEG based upon p‐type lanthanum cuprate exhibits a power output of 7.8 mW at ?T= 200 K in the low temperature range of 25‐135°C. Materials issues, cofiring characteristics, design and the thermoelectric performance of multilayer TEGs will be discussed.     

Electrical conductivity and thermoelectric power studies of solution-combustion-processed Ca2.76Cu0.24Co4O9

Nanocrystalline Ca_2.76Cu_0.24Co₄O₉ powders (25 nm in crystallite size) are synthesized by the solution combustion method, using aspartic acid as the combustion fuel. In this study, we discuss the effect of sintering temperature on the microstructure and thermoelectric properties of Ca_2.76Cu_0.24Co₄O₉. The density and grain size increase with an increase in sintering temperature. The Ca_2.76Cu_0.24Co₄O₉ sintered at 900 °C shows the largest value of electrical conductivity and Seebeck coefficient, resulting in the largest power factor (3.8×10^?4 W m^?1 K^?2 at 800 °C). This value is more than 22 times larger than that of the Ca_2.76Cu_0.24Co₄O₉ sintered at 940 °C (1.7×10^?5 W m^?1 K^?2 at 800 °C).     

Promising high temperature thermoelectric properties of dense Ba2Co9O14 ceramics

Layered cobalt oxides have shown high thermoelectric properties. The n = 1 member of the Ba_n+1Co_nO_3n+3(Co₈O₈) family, Ba₂Co₉O₁₄, a new layered cobalt oxides family with Co(II) and Co(III) in the CdI₂ layers, has been synthesized by solid state reaction and sintered as dense ceramics (relative density ∼ 93%) by Spark Plasma Sintering. It presents promising p-type thermoelectric properties at high temperature. The dimensionless figure of merit ZT is 0.032 at 660 K and 0.04 at 1000 K, which is about one quarter to one third of the ZT value of Ca₃Co₄O₉ ceramics.     

Microstructure and mechanical properties of ZTA composites fabricated by oscillatory pressure sintering

The influence of sintering temperature on the microstructure and mechanical properties of Al₂O₃?20 wt% ZrO₂ composites fabricated by oscillatory pressure sintering (OPS) was investigated by means of X-ray diffraction, scanning electron microscopy, three-point bending test and Vickers indentation. Results were compared to specimens obtained by conventional hot pressing (HP) under a similar sintering schedule. The optimum oscillatory pressure sintering temperature was found to be 1600 °C; almost fully dense materials (99.94% of theoretical density) with homogeneous microstructure could be achieved. The highest flexural strength, fracture toughness and hardness of such composites reached 1145 MPa, 5.74 MPa m^1/2 and 19.08 GPa when sintered at 1600 °C, respectively. Furthermore, the oscillatory pressure sintering temperature could be decreased by more than 50 °C as compared with the HP method, OPS favouring enhanced grain boundary sliding, plastic deformation and diffusion in the sintering process.     

Effects of microstructure evolution on transport properties of thermoelectric nickel-doped zinc oxide

We investigate the effects of microstructure evolution on transport properties of nickel-doped ZnO for thermoelectric waste heat recovery at high temperatures. A 3 at.% supersaturated Ni-alloyed ZnO solid solution was prepared by sintering at 1400 °C followed by controlled nucleation and growth of sub-micrometer size NiO-precipitates by aging at 750, 800, and 900 °C for different durations. Minimum thermal conductivity as low as 8.0 W m⁻¹ K⁻¹ at 700 °C is obtained for samples aged at 750 °C for 16 h due to precipitates with high number density of 1.3·10²⁰ m⁻³, which initiate phonon scattering. In turn, as-quenched samples exhibit the highest electrical conductivity, ca. 17.9 S cm⁻¹ at 700 °C. Further nucleation and growth of precipitates taking place for longer annealing durations reduce electrical conductivity and increase Seebeck coefficients, which is associated with dilution of the ZnO-matrix from Ni-atoms. This study provides us with guidelines for optimization of thermoelectric Ni-doped ZnO.     

Microstructure and thermoelectric properties of La0.1Dy0.1SrxTiO3 ceramics

La_0.1Dy_0.1Sr_xTiO₃ (x=0.80, 0.78, 0.75, 0.70) powders were synthesized via a sol-gel method, followed by sintering at 1550 °C in a reducing atmosphere of 5 vol% hydrogen in nitrogen. The microstructure and thermoelectric properties of the Sr-deficient La and Dy co-doped SrTiO₃ were investigated. The result of XRD revealed that La_0.1Dy_0.1Sr_xTiO₃ consisted of SrTiO₃ with a cubic crystal structure as the main phase and of a small amount of Dy₂Ti₂O₇ as the second phase. All the Sr-deficient samples exhibited a step-like microstructure. As the nominal Sr deficient content increased, the electrical conductivity of the Sr-deficient La_0.1Dy_0.1Sr_xTiO₃ ceramics enhanced due to the increasing Sr and oxygen vacancies, the absolute value of the Seebeck coefficient increased a little, and the thermal conductivity decreased to ~3.0 W m⁻¹ K⁻¹, leading to a high ZT value of 0.19 for La_0.1Dy_0.1Sr_0.75TiO₃ at 500 °C.     

Direct preparation of La-doped SrTiO3 thermoelectric materials by mechanical alloying with carbon burial sintering

Thermoelectric Sr_1-xLa_xTiO₃ (x = 0, 0.02, 0.05, 0.08) nanoparticles were directly prepared by mechanical alloying, followed by carbon burial sintering to produce the bulk counterparts, for the purpose of obtaining pure phase and fine microstructures in a facile process. Electrical and thermal transport properties have been measured over the temperature range from 300 K to 1100 K. La was successfully doped into the SrTiO₃ during the milling process and acted as an n-type dopant. Core structure and superstructure in bulk samples, leads to a relatively high absolute Seebeck coefficient. The dimensionless figure-of-merit ZT changes with the increasing of La content and temperature, and the maximum ZT value can reach 0.06 at 300 K for x = 0.02 and 0.20 at 1000 K for x = 0.08. This strategy for bulk thermoelectric materials is simple, cost-effective and has great potential in large-scale industrial applications.     

High-temperature thermoelectric properties of Sm3+-doped Ca3Co4O9+δ fabricated by spark plasma sintering

Ca_3-xSm_xCo₄O_9+δ (0 ≤ x ≤ 0.3) samples were fabricated by the sol-gel method followed by spark plasma sintering in vacuum. The high-temperature thermoelectric properties of the Ca_3-xSm_xCo₄O_9+δ were also studied, with an emphasis placed on the partial substitution of Sm³⁺ for Ca²⁺. The sintered Ca_3-xSm_xCo₄O_9+δ formed a monoclinic Ca₃Co₄O₉ phase and exhibited fine lamellar grains and dense morphology. With increased Sm³⁺ content, the electrical and thermal conductivities decreased, whereas the Seebeck coefficient significantly increased. Of the prepared samples, Ca_2.7Sm_0.3Co₄O_9+δ had the largest dimensionless figure-of-merit (0.175) at 800 °C. The results showed that the partial substitution of Sm³⁺ for Ca²⁺ in Ca₃Co₄O_9+δ is effective for enhancing its thermoelectric properties.     

Structural characterization of YSZ/Al2O3 nanostructured composite coating fabricated by electrophoretic deposition and reaction bonding

Suspension of YSZ and Al particles in acetone in presence of 1.2 g/l iodine as dispersant was used for electrophoretic deposition of green form YSZ/Al coating. Results revealed that applied voltage of 6 V and deposition time of 3 min were appropriate for deposition of green composite form coating. After deposition, a nanostructured dense YSZ/Al₂O₃ composite coating was fabricated by oxidation of Al particles at 600 °C for 2 h and subsequently sintering heat treatment at 1000 °C for 2 h. Melting and oxidation of Al particles in the green form composite coating not only caused reaction bonding between the particles but also lowered the sintering temperature of the ceramic coating about 200 °C. The EDS maps confirmed that the composition of fabricated coating was uniform and Al₂O₃ particles were dispersed homogenously in YSZ matrix.     

Sintering process optimization for multi-layer CGO membranes by in situ techniques

The sintering of asymmetric CGO bi-layers (thin dense membrane on a porous support; Ce_0.9Gd_0.1O_1.95?δ = CGO) with Co₃O₄ as sintering additive has been optimized by combination of two in situ techniques. Optical dilatometry revealed that bi-layer shape and microstructure are dramatically changing in a narrow temperature range of less than 100 °C. Below 1030 °C, a higher densification rate in the dense membrane layer than in the porous support leads to concave shape, whereas the densification rate of the support is dominant above 1030 °C, leading to convex shape. A flat bi-layer could be prepared at 1030 °C, when shrinkage rates were similar. In situ van der Pauw measurements on tape cast layers during sintering allowed following the conductivity during sintering. A strong increase in conductivity and in activation energy E_a for conduction was observed between 900 and 1030 °C indicating an activation of the reactive sintering process and phase transformation of cobalt oxide.     

CuAlO2 thermoelectric compacts by SPS and thermoelectric performance improvement by orientation control

We fabricated CuO/Al₂O₃ green compacts from plate-like Al₂O₃ and granular CuO powders by multi-press forming and investigated the alumina orientation using Lotgering's method. The results showed that Al₂O₃ particles preferentially aligned perpendicular to the pressure direction and the orientation degree increased as the forming pressure was increased. We proposed a model describing the movement of the alumina particles to explain the pressure effect on their orientation. The orientation calculation was in good agreement with those by Lotgering's method. Furthermore, we prepared the CuAlO₂ compacts by regular or spark plasma sintering (SPS). However, the compacts sintered by SPS exhibited higher orientation degree and density than those produced by regular sintering. The electrical conductivity values of the orientation-controlled compacts sintered by SPS reached 770 S m⁻¹ at 928 K, which was close to that of CuAlO₂ single crystal. The power factor of the CuAlO₂ compacts with highest orientation degree is as high as 5.95 × 10⁻⁵ W m⁻¹ K⁻¹ at 928 K. Therefore, we can conclude that orientation control is an effective method to enhance the thermoelectric performance of compact polycrystalline CuAlO₂ bulks.     

Process-tolerant pressureless-sintered silicon carbide ceramics with alumina-yttria-calcia-strontia

Process-tolerant SiC ceramics were prepared by pressureless sintering at 1850–1950 °C for 2 h in an argon atmosphere with a new quaternary additive (Al₂O₃-Y₂O₃-CaO-SrO). The SiC ceramics can be sintered to a > 94% theoretical density at 1800–1950 °C by pressureless sintering. Toughened microstructures consisting of relatively large platelet grains and small equiaxed grains were obtained when SiC ceramics were sintered at 1850–1950 °C. The presently fabricated SiC ceramics showed little variability of the microstructure and mechanical properties with sintering within the temperature range of 1850–1950 °C, demonstrating process-tolerant behavior. The thermal conductivity of the SiC ceramics increased with increasing sintering temperature from 1800 °C to 1900 °C due to decreases of the lattice oxygen content of the SiC grains and residual porosity. The flexural strength, fracture toughness, and thermal conductivity of the SiC ceramics sintered at 1850–1950 °C were in the ranges of 444–457 MPa, 4.9–5.0 MPa m^1/2, and 76–82 Wm^?1 K^?1, respectively.     

Continuous functionally graded material to improve the thermoelectric properties of ZnO

Functionally graded material (FGM) in terms of grain size gradation is fabricated from ZnO with a combination of modified Spark Plasma Sintering (SPS) graphite tooling, water sintering enhancements through transient liquid phase surface transport, and strategic SPS mechanical loading. The grain size gradation of the ZnO FGM spans from 180 nm grains to 1.2 micrometers in a fully dense material. This is the first semiconductor or ceramic to be graded microstructurally to this extent. Predictions of the microstructure with a Master Sintering Curve (MSC) approach were done with a series of isothermal experiments on two different FGM conditions revealing a slight offset due to a constrained mechanism. The mechanical properties were tested with Vickers micro hardness across the sample, showing a gradient in hardness from 2.6 GPa to 4.2 GPa. In addition, the thermoelectric properties of the FGM were measured and show a zT of 2 × 10⁻⁵ at 100 °C compared to uniform small- and large-grained samples of 1 × 10⁻⁶. This is an order of magnitude difference making a new path for improvements of bulk thermoelectric material.     

Phase formation,microstructure development and thermoelectric properties of (ZnO)kIn2O3 ceramics

The (ZnO)_kIn₂O₃ system is interesting for applications in the fields of thermoelectrics and opto-electronics. In this study we resolve the complex homologous phase evolution with increasing temperature in polycrystalline ceramics for k = 5, 11 and 18 and its influence on the microstructural development and thermoelectric properties. The phase formation at temperatures above 1000 °C is influenced by the local ZnO-to-In₂O₃ ratio in the starting-powder mixture. While the Zn₅In₂O₈ equilibrium phase for k = 5 is formed directly after sintering at 1200 °C, the formation of the k = 11 and k = 18 equilibrium phases proceeds at higher temperatures by diffusion between the initially formed phases, the lower k Zn₅In₂O₈/Zn₇In₂O₁₀ and the higher k Zn_kIn₂O_k+3 (9 < k < ∞). Such phase formation affects the sintering and grain growth, and consequently, with the degree of structural and compositional homogeneity, also the thermoelectric characteristics of the (ZnO)_kIn₂O₃ ceramics.     

Preparation of high-performance Ca3Co4O9 thermoelectric ceramics produced by a new two-step method

High-performance Ca₃Co₄O₉ thermoelectric ceramic has been prepared from a Ca_1?xCo_xO/Ca_yCo_1?yO divorced eutectic structure produced by a directional melt-grown using the laser floating zone technique. This material has been grown at very high solidification rate in order to produce a very fine microstructure to reduce the necessary annealing time to recover the Ca₃Co₄O₉ thermoelectric phase as the major one. As-grown and annealed samples were microstructurally characterized to determine the phases and estimate the extent of Ca₃Co₄O₉ formation with time and related with their thermoelectric performances. The optimum annealing time, 72 h, has been determined by the maximum power factor value (about 0.42 mW K^?2m^?1), which is around the best values reported in textured materials (～0.40 mW K^?2m^?1). This high power factor outcome from the high Ca₃Co₄O₉ phase content, apparent density and Co³⁺/Co⁴⁺ relationship determinations performed in the present work.     

High temperature thermoelectric properties of Ca3Co4O9+δ by auto-combustion synthesis and spark plasma sintering

A rapid method for the synthesis of Ca₃Co₄O_9+δ powder is introduced. The procedure is a modification of the conventional citric-nitrate sol–gel method where an auto-combustion process is initiated by a controlled thermal oxidation–reduction reaction. The resulting powders inherit the advantages of a wet chemical synthesis, such as morphological and compositional homogeneity, and fine, well-defined particle sizes coming from the controlled nature of the auto-combustion. Optimized spark plasma sintering (SPS) processing conditions were determined and used to fabricate dense and highly c-axis oriented samples. The microstructure and thermoelectric transport properties were determined both parallel (||) and perpendicular (⊥) to the SPS pressure axis in order to investigate any possible anisotropy variations in the transport properties. At 800 °C, power factors of 506 μW/m K² (⊥) and 147 μW/m K² (||), thermal conductivities values of 2.53 W/m K (⊥) and 1.25 W/m K (||), and resulting figures-of-merit, ZT, of 0.21 (⊥) and 0.13 (||) were observed.