Modulation of electrical transport in calcium cobaltite ceramics and thick films through microstructure control and doping

Ca₃Co₄O₉ is a promising p-type thermoelectric oxide material having intrinsically low thermal conductivity. With low cost and opportunities for automatic large scale production, thick film technologies offer considerable potential for a new generation of micro-sized thermoelectric coolers or generators. Here, based on the chemical composition optimized by traditional solid state reaction for bulk samples, we present a viable approach to modulating the electrical transport properties of screen-printed calcium cobaltite thick films through control of the microstructural evolution by optimized heat-treatment. XRD and TEM analysis confirmed the formation of high-quality calcium cobaltite grains. By creating 2.0 at% cobalt deficiency in Ca_2.7Bi_0.3Co₄O_9+δ, the pressureless sintered ceramics reached the highest power factor of 98.0 μWm^?1 K^-2 at 823 K, through enhancement of electrical conductivity by reduction of poorly conducting secondary phases. Subsequently, textured thick films of Ca_2.7Bi_0.3Co_3.92O_9+δ were efficiently tailored by controlling the sintering temperature and holding time. Optimized Ca_2.7Bi_0.3Co_3.92O_9+δ thick films sintered at 1203 K for 8 h exhibited the maximum power factor of 55.5 μWm^?1 K^-2 at 673 K through microstructure control.     

Enhancement in the osteogenesis and angiogenesis of calcium phosphate cement by incorporating magnesium-containing silicates

Based on the good osteogenic and angiogenic effects of silicon and magnesium elements, three types of micro-nano magnesium-containing silicates (MS), including akermanite (Ake, Ca₂MgSi₂O₇), diopside (Dio, CaMgSi₂O₆) and forsterite (For, Mg₂SiO₄), were incorporated into calcium phosphate cement (CPC) to improve its osteogenic and angiogenic performances for clinical application. In this present work, the physicochemical properties, osteogenesis and angiogenesis of MS/CPCs (Ake/CPCs, Dio/CPCs and For/CPCs) were investigated systematically and comparatively. The results showed that all MS/CPCs had good biomineralization and significantly stimulated the osteogenic differentiation of mBMSCs and angiogenic differentiation of HUVECs, respectively. Besides, the stimulating effects were related to not only the category of MS, but also the content of MS. The For/CPCs had a good angiogenic property but their initial setting times were beyond 60 min. The Dio/CPCs showed the lowest biological performance among the three groups of MS/CPCs due to the lower ion release (Si and Mg). The Ake was the ideal modifier that could provide CPC with appropriate physicochemical properties, better osteogenesis and angiogenesis. Simultaneously, a higher addition (10 wt%) of akermanite resulted in the best potential to bone regeneration. Taken together, this research provides an effective approach to improve the overall performance of CPC, and 10Ake/CPC is of great promising prospect in bone repair.     

Corrosion behavior of T24, T92, VM12, and AISI 304 steels exposed to KCl–NaCl–K2SO4–Na2SO4 salt mixtures

The corrosion mechanisms of T24, T92, VM12, and AISI 304 steels are studied under the influence of NaCl–KCl, NaCl–Na₂SO₄, and KCl–K₂SO₄ salt mixtures in a dry air atmosphere at 650°C for 15 days. NaCl–KCl was the most aggressive deposit and AISI 304 stainless steel exhibited the highest corrosion resistance. There was no relation between the Cr content of the ferritic steels and their corrosion resistance in NaCl–KCl. In contrast, the resistance of high-Cr steels was better when exposed to NaCl–Na₂SO₄ and KCl–K₂SO₄. The high-Cr and the low-Cr steels were more susceptible to NaCl–Na₂SO₄ and to KCl–K₂SO₄, respectively.     

Thermal behaviour and phases evolution during the sintering of porous inorganic membranes

Anorthite-based highly porous membranes were successfully produced using calcined oyster shell to enhance the pore network. The calcined oyster shells produce CaO responsible for the crystallisation of gehlenite and anorthite at relatively low temperature. While the crystallisation produced nano and meso size of intergranular pores, vitrification of feldspar is responsible for development of the capillary porosities. The increasing sintering temperature from 1200 °C to 1300 °C implies the increase in average pores radius from 1.2 μm to 14.3 μm due to the formation of spherical pores from vitrification. The combination of different class of porosities in the matrices results in the interconnection with improvement of the permeability of the porous network. Porosity, permeability and chemical stability were improved with 20 wt.% of calcined oyster shell addition allowing the possible development of high strength porous network which is promising for the membranes support and other applications including liquid separation as well as liquid filtration where high pressure is used.     

Performance characteristics of concrete based on a ternary calcium sulfoaluminate–anhydrite–fly ash cement

This paper reports an assessment of the performance of concrete based on a calcium sulfoaluminate–anhydrite–fly ash cement combination. Concretes were prepared at three different w/c ratios and the properties were compared to those of Portland cement and blast-furnace cement concretes. The assessment involved determination of mechanical and durability properties. The results suggest that an advantageous synergistic effect between and ettringite and fly ash (Ioannou et al., 2014) was reflected in the concrete’s low water absorption rates, high sulfate resistance, and low chloride diffusion coefficients. However, carbonation depths, considering the dense ettringite-rich microstructure developed, were higher than those observed in Portland cement concretes at a given w/c ratio. It was concluded that the amount of alkali hydroxides present in the pore solution is as important factor as the w/c ratio when performance of this type of concrete is addressed.     

Effect of nanosilica addition on bioactivity and in vivo properties of calcium aluminate cement

This study aims at assessing the influence of nanosilica on the bioactivity and mechanical properties of calcium aluminate cement. For this purpose, nanosilica was applied as a replacement for calcium aluminate cement at 0, 2, 5 and 8 wt%. The main components were analyzed by scanning electron microscope coupled with surface imaging and elemental analysis, fourier transform infrared spectroscopy and X-ray diffraction analysis. To estimate the bioactivity of specimens, hydroxyapatite formation on the surface of cement paste was investigated in the simulated body fluid solution. In addition, in vivo evaluation of calcium aluminate cement was performed in subcutaneous tissue of rats. To investigate the mechanical properties, both compressive and flexural strengths were also measured. The results revealed that by increasing nanosilica up to 8 wt%, the strength enhanced. Moreover all cement paste samples with various amounts of nanosilica represented good bioactivity because of formation of bonelike apatite layer on the surface of specimens within 28 days after soaking in simulated body fluid. In vivo experiments indicated that the cement sample was absorbed by the tissue and there was no infection at the implant site. Based on the in vitro and in vivo results, the specimen with 2 wt% nanosilica represented the highest bioactivity.     

High-temperature stability of Mg(Al,Cr)2O4 spinel co-existing with calcium aluminates in air

Cr₂O₃ is a well-known corrosion resistant oxide used in refractory applications. However, it can oxidize into toxic and water-soluble Cr(VI) compounds upon reaction with calcium aluminate cement phases in the presence of oxygen, which subsequently causes disposal problems after use. This study describes the extent to which chromium in the spinel Mg(Al,Cr)₂O₄ phase can be oxidized to Cr(VI) when it reacts with the calcium aluminate cement phases C₁₂A₇, CA, CA₂ and free CaO at 1300 °C in air, using XRD, XPS and leaching tests (TRGS 613 standard) as analytical tools. On reaction with CaO, the Mg(Al,Cr^III)₂O₄ spinel mainly transformed into hauyne (Ca₄Al₆Cr^VIO₁₆) and Ca₅Cr₃O₁₂ which contains both Cr(IV) and Cr(VI). The reaction of C₁₂A₇ and CA with the spinel phase also resulted in the formation of Ca₄Al₆CrO₁₆. Conversely, the reaction of Mg(Al,Cr^III)₂O₄ spinel with CA₂ resulted in the formation of only a trace amount of Cr(VI). Water-soluble Cr(VI) leached in large quantities (>100 mg/L) from samples where the Mg(Al,Cr^III)₂O₄ reacted with either C₁₂A₇ or CA. Almost no Cr(VI) leached from the sample when Mg(Al,Cr^III)₂O₄ reacted with CaO, using the standard TRGS 613 leach test, but a significant amount of Cr(VI) was released into solution when leached with a HCl solution for 12 h. Both Cr(IV) and Cr(VI) present in the Ca₅Cr₃O₁₂ dissolved into acidic solution. Only a small amount of Cr(VI) leached from the sample that resulted when spinel was reacted with CA₂, even after a prolonged HCl leach. Cr(III) in spinel Mg(Al,Cr)₂O₄ is very stable and does not leach in either distilled water or acidic solution.     

Optimised phase compositions and improved microwave dielectric properties based on calcium tin silicates

The Ca_(1+2y)Sn_(1-x)Si_(1+y)O_(5-2x+4y) low-permittivity microwave dielectric ceramics were prepared through solid-state reaction at 1350–1450 °C for 5 h. The relations between microwave dielectric properties and phase compositions for non-stoichiometric Ca_(1+2y)Sn_(1-x)Si_(1+y)O_(5-2x+4y) ceramics have been investigated. A single CaSnSiO₅ phase with abnormally positive temperature coefficient of resonant frequency (τ_f = + 62.5 ppm/°C) was synthesised at 1450 °C. This composition was an effective τ_f compensator of CaSiO₃ and Ca₃SnSi₂O₉ phases with typically negative τ_f value. The CaSiO₃ second phase was related to the Sn deficiency in the CaSn_(1-x)SiO_(5-2x) (0 < x < 1.0) composition, whereas the Ca₃SnSi₂O₉ second phase was obtained by controlling the Ca:Sn:Si ratios on the basis of the Ca_(1+2y)SnSi_(1+y)O_(5+4y) (0 < y < 1.0) composition. A promising low-permittivity millimetre-wave ceramic with most excellent microwave dielectric properties (ε_r = 10.2, Q×f = 81,000 GHz and τ_f = −4.8 ppm/°C) was produced from the Ca_(1+2y)SnSi_(1+y)O_(5+4y) (y = 0.4) ceramic.     

Calcium phosphates grown on bacterial cellulose template

Bacterial cellulose membranes were employed as templates for calcium phosphates deposition by successive immersion in solutions of Ca(NO₃)₂·4H₂O and (NH₄)₂HPO₄, under ultrasonication. During the wet chemical reaction, mineral phases were loaded on bacterial cellulose fibrils, leading to precursor hybrid composites. These were subjected to a lyophilisation procedure in order to preserve the 3D porous aspect and afterwards to a thermal treatment with the aim of removing the polymeric phase and generating well crystallized structures. Different types of morphologies were achieved by varying the heating rate, as well as the calcination temperature and period. The as-prepared samples and the final ones were investigated from compositional and structural point of view through X-ray diffraction and Fourier-transform infrared spectroscopy and morphologically concerning by scanning electron microscopy. The magnetic properties were also evaluated in order to demonstrate the suitability of the obtained materials for the development of magnetic scaffolds dedicated to hard tissue applications.