RESUMEN
Carbon contamination from graphite molds during spark plasma sintering (SPS) considerably affects the properties of the sintered materials, especially transparent ceramics. Herein, transparent Y3Al5O12 (YAG) ceramics were prepared via SPS using Mo and Ta foils, separately and in tandem, as protective barriers against carbon contamination. The effects of Ta and Mo foils on the transparency and microstructure of the ceramics, and their protection mechanisms were studied. Experimental results show that a reaction layer formed at the Ta-YAG interface with a YTaO4-Al2O3 eutectic composition suppresses carbon penetration into the ceramic, increasing its transparency. By contrast, Mo foils, when used as protective barriers, allow carbon diffusion into the ceramic, resulting in the formation of nonuniform microstructural features. However, it does not form a reactive layer and, hence, is removed easily from the YAG surface. Multilayered Ta-Mo barrier exhibits improved outcomes if the Ta thickness is more than â¼100 µm. This behavior is attributed to the interior diffusion-blocking mechanism of Ta. Similar optical performance was demonstrated by both approaches. The results prove that carbon contamination in SPS-derived samples can be effectively prevented. Additionally, this study reports on a novel strategy of bonding oxide ceramics to metals by adding a Ta layer at the joint interface.
RESUMEN
The synthesis of methanol and dimethyl ether (DME) from carbon dioxide (CO2) and green hydrogen (H2) offers a sustainable pathway to convert CO2 emissions into value-added products. This heterogeneous catalytic reaction often uses copper (Cu) catalysts due to their low cost compared with their noble metal analogs. Nevertheless, improving the activity and selectivity of these Cu catalysts for these products is highly desirable. In the present study, a new architecture of Cu- and Cu/Zn-based catalysts supported on electrospun alumina nanofibers were synthesized. The catalysts were tested under various reaction conditions using high-throughput equipment to highlight the role of the hierarchical fibrous structure on the reaction activity and selectivity. The Cu or Cu/ZnO formed a unique structure of nanosheets, covering the alumina fiber surface. This exceptional morphology provides a large surface area, up to ~300 m2/g, accessible for reaction. Maximal production of methanol (~1106 gmethanolKgCu-1âh-1) and DME (760 gDMEKgCu-1âh-1) were obtained for catalysts containing 7% wt. Cu/Zn with a weight ratio of 2.3 Zn to Cu (at 300 °C, 50 bar). The promising results in CO2 hydrogenation to methanol and DME obtained here point out the significant advantage of nanofiber-based catalysts in heterogeneous catalysis.
RESUMEN
Optically transparent ceramics and MgO in particular are promising materials for a wide range of optical applications. This study introduces exceptionally highly transparent MgO ceramics produced via spark plasma sintering (SPS) at relatively low temperature and pressure by optimal incorporation of LiF as a sintering additive. The effect of LiF content on the microstructural and optical properties is presented with emphasis on its function as a densification aid and an agent for minimizing residual carbon contamination. Fully dense MgO discs, 20 mm in diameter and 2 mm thick, with â¼80% in-line transmission at 800 nm and >85% transmission in the infrared range (2-6 µm), are attained. These results demonstrate outstanding transparency in SPS polycrystalline MgO in the 800 nm range, only 7% below the theoretical value. In addition, this work strengthens our understanding of the LiF action mechanism during MgO sintering and its influence on texture development in the SPS-pressing direction. These findings pave the way for fabrication of large, fully dense samples with nearly theoretical transparency.
RESUMEN
We developed synthetic methods for the doping of metals (M) with metallic nanoparticles (NPs). To the best of our knowledge - unlike oxides, polymers and carbon-based supports - metals were not used so far as supporting matrices for metallic NPs. The composites (denoted M1-NPs@M2) comprise two separate phases: the metallic NPs (the dopant) and the entrapping 3D porous metallic matrix, within which the NPs are intimately held and well dispersed. Two different general synthetic strategies were developed, each resulting in a group of materials with characteristic structure and properties. The first strategy uses pre-prepared NPs and these are entrapped during reductive formation of the metallic matrix from its cation. The second strategy is in situ growth of the doped metallic NPs within the pre-prepared entrapping metallic matrix. These two methods were developed for two types of entrapping metallic matrices with different morphologies: porous aggregated metallic matrices and metallic foams. The leading case in this study was the use of Pt as the NP dopant and Ag as the entrapping matrix, using all of the four combinations - entrapment or growth within aggregated Ag or Ag foam matrices. Full physical and chemical properties analysis of these novel types of materials was carried out, using a wide variety of analytical methods. The generality of the methods developed for these bi-metallic composites was investigated and demonstrated on additional metallic pairs: Au NPs within Ag matrices, Pd NPs within Ni matrices and Ir-NPs within a Rh matrix. As the main application of metallic NPs is in catalysis, the catalytic activity of M1-NPs@M2 is demonstrated successfully for entrapped Pt within Ag for reductive catalytic reactions, and for Pd within Ni for the electrocatalytic hydrogen oxidation reaction.
RESUMEN
Anion-conducting ionomer-based nanofibers mats are prepared by electrospinning (ES) technique. Depending on the relative humidity (RH) during the ES process (RHES), ionomer nanofibers with different morphologies are obtained. The effect of relative humidity on the ionomer nanofibers morphology, ionic conductivity, and water uptake (WU) is studied. A branching effect in the ES fibers found to occur mostly at RHES < 30% is discussed. The anion conductivity and WU of the ionomer electrospun mats prepared at the lowest RHES are found to be higher than in those prepared at higher RHES. This effect can be ascribed to the large diameter of the ionomer fibers, which have a higher WU. Understanding the effect of RH during the ES process on ionomer-based fibers' properties is critical for the preparation of electrospun fiber mats for specific applications, such as electrochemical devices.