Si-based polymer-derived ceramics for energy conversion and storage

Since the 1960s, a new class of Si-based advanced ceramics called polymer-derived ceramics (PDCs) has been widely reported because of their unique capabilities to produce various ceramic materials (e.g., ceramic fibers, ceramic matrix composites, foams, films, and coatings) and their versatile applications. Particularly, due to their promising structural and functional properties for energy conversion and storage, the applications of PDCs in these fields have attracted much attention in recent years. This review highlights the recent progress in the PDC field with the focus on energy conversion and storage applications. Firstly, a brief introduction of the Si-based polymer-derived ceramics in terms of synthesis, processing, and microstructure characterization is provided, followed by a summary of PDCs used in energy conversion systems (mainly in gas turbine engines), including fundamentals and material issues, ceramic matrix composites, ceramic fibers, thermal and environmental barrier coatings, as well as high-temperature sensors. Subsequently, applications of PDCs in the field of energy storage are reviewed with a strong focus on anode materials for lithium and sodium ion batteries. The possible applications of the PDCs in Li-S batteries, supercapacitors, and fuel cells are discussed as well. Finally, a summary of the reported applications and perspectives for future research with PDCs are presented.

Thermal Qualification of the UHTCMCs Produced Using RF-CVI Technique with VMK Facility at DLR

Ultra high-temperature ceramic matrix composites (UHTCMCs) based on carbon fibre (Cf) have been shown to offer excellent temperature stability exceeding 2000 °C in highly corrosive environments, which are prime requirements for various aerospace applications. In C3Harme, a recent European Union-funded Horizon 2020 project, an experimental campaign has been carried out to assess and screen a range of UHTCMC materials for near-zero ablation rocket nozzle and thermal protection systems. Samples with ZrB2-impregnated pyrolytic carbon matrices and 2.5D woven continuous carbon fibre preforms, produced by slurry impregnation and radio frequency aided chemical vapour infiltration (RF-CVI), were tested using the vertical free jet facility at DLR, Cologne using solid propellants. When compared to standard CVI, RFCVI accelerates pyrolytic carbon densification, resulting in a much shorter manufacturing time. The samples survived the initial thermal shock and subsequent surface temperatures of >2000 °C with a minimal ablation rate. Post-test characterisation revealed a correlation between surface temperature and an accelerated catalytic activity, which lead to an understanding of the crucial role of preserving the bulk of the sample.

Chemical Supercritical Fluid Infiltration of Pyrocarbon with Thermal Gradients: Deposition Kinetics and Multiphysics Modeling

The chemical supercritical fluid infiltration process is a recent variation of the chemical vapor infiltration (CVI) process that allows rapid and efficient manufacturing of ceramic-matrix composites (CMCs), albeit still needing optimization. This article proposes a quantitative assessment of the process dynamics through experiments and modeling. The kinetics of carbon deposition were determined through two sets of experiments: CVD on a single filament at pressures between 10 and 50 bar and infiltration at pressures ranging between 50 and 120 bar. The CVI experiments were conducted under important thermal gradients and were interpreted using a model-based reconstitution of these gradients. We found that (i) the kinetic law has to incorporate the potential effect of the reverse reaction (i.e., etching of C by H2); (ii) the activation energy and pre-exponential factor both decrease with pressure up to 50 bar, then remain roughly constant, and (iii) although the apparent activation energy is modest, a favorable situation occurs in which an infiltration front builds up and travels from the hottest to the coldest part of the preform due to the presence of sufficient heat flux. A numerical simulation of the process, based on the solution of momentum, heat, and mass balance equations, fed with appropriate laws for the effective transfer properties of the porous medium and their evolution with infiltration progress, was performed and validated by comparing the simulated and actual infiltration profiles.