Claudia Fasel

Silazane derived ceramics and related materials

This review highlights the synthesis, processing and properties of non-oxide silicon-based ceramic materials derived from silazanes and polysilazanes. A comprehensive summary of the preparation of precursor compounds containing Si–N–Si units, including commercially available materials, is followed by the discussion of various processing techniques. The fabrication of dense bulk ceramics in the Si/E/C/N systems is reported which involves cross-linking of the polymeric ceramic precursor followed by a polymer-to-ceramic transformation step. The cross-linked precursor can be milled, compacted and pyrolysed to form dense, additive-free, amorphous silicon carbonitride monoliths or polycrystalline composites which withstand oxidation in air at 1600°C. Furthermore, an overview is given on the fabrication of silazane derived powders and coatings involving chemical vapour deposition (CVD) methods utilising volatile precursors. Fibre spinning and fibre properties, as well as other processing techniques like infiltration of preforms, the preparation of porous ceramics and joining are briefly discussed. A state of the art of the mechanical properties of polymer derived amorphous Si/C/N and Si/B/C/N ceramics with respect to hardness as well as high-temperature creep and oxidation resistance is summarised. Finally, some important aspects of industrial applications will be considered. The review is in part based on our own work related to the polysilazane derived ceramics, but will also cover a comprehensive state of the art including the published literature in this field.

Visible Light Photocatalysis with c-WO3–x/WO3×H2O Nanoheterostructures In Situ Formed in Mesoporous Polycarbosilane-Siloxane Polymer

In recent years, there have been significant efforts to find novel photocatalytic materials with improved properties. Thus, there is an active ongoing search for new materials that can operate at a broad range of wavelengths for photocatalytic reactions. Among photocatalytically active semiconductors, considerable attention has been given to tungsten oxide with a band gap of E(g) ≈ 2.6 eV, which provides the opportunity to harvest visible light. In the present work, we report on a one-step synthesis of c-WO(3-x)/WO3×H2O nanowhiskers dispersed in a hydrolytically stable mesoporous polycarbosilane-siloxane ([-Si(O)CH2-]n) matrix. The as-synthesized nanocomposites possess high photocatalytic activity for the degradation of methylene blue (MB) under visible light irradiation. The enhanced photocatalytic activity is due to (i) the reduction in the electron-hole recombination rate because of the reduced dimensions of nanowhiskers, (ii) more efficient consumption of photogenerated electrons and holes as a result of the high surface-to-bulk-ratio of the nanowhiskers, and (iii) better electron-hole pair separation due to the formation of c-WO(3-x)/WO3×H2O nanoheterostructures.

Dense Silicon Carbonitride Ceramics by Pyrolysis of Cross-linked and Warm Pressed Polysilazane Powders

This study reports on the pyrolysis and densifaction behavior of cross-linked poly(hydridomethylsilazane) powders. The influence of the cross-linking procedure such as temperature and annealing time of the polymer powders on the compaction behavior under cold and warm pressing conditions is discussed. The degree of cross-linking is determined by thermal mechanical analysis (TMA). In addition to particle sliding which is assumed to be the compaction mechanism obtained by cold-pressing, the polymer powder consolidates by plastic deformation applying warm-pressing. A continuous 3-dimensional polysilazane network is formed after a dwelling time under these conditions. Pyrolysis of the cross-linked and compacted polysilazane powder in argon at 1100°C gives crack-free amorphous silicon carbonitride Si3+xCx+yN4 with compositions ranging from x=1·47 and y=0·88 for cold pressed samples to x=1·47 and y=1·86 for warm pressed materials. The residual open porosity is significantly reduced from 10–15 vol% in the cold pressed specimens to 1·3–5 vol% by the warm pressing procedure. The weight loss during pyrolysis between room temperature and 1300°C is about 5 wt% lower than that for cold pressed specimens. This result is explained by a reduced methane evolution during the polymer-to-ceramic conversion and is in accordance with the enhanced carbon content of the warm pressed material.

Investigation of the wear mechanism of cubic boron nitride tools used for the machining of compacted graphite iron and grey cast iron

Various experiments were performed to investigate the wear mechanism of cubic boron nitride (cBN) tools used for the machining of compacted graphite iron (CGI). Comparative studies for tools used to machine grey cast iron (CI) were also performed in order to find out why in this case the tool lifetime is significantly higher. Two main effects were found that are responsible for tool wear, namely: (1) oxidation of the tool, and (2) interdiffusion of constituting elements between tool and CGI. These wear mechanisms are more or less the same for the machining of CGI and grey CI. The difference in tool lifetime can be explained by the formation of a MnS layer on the tool surface in the case of grey CI. This layer is missing in the case of CGI. The MnS layer acts as a lubricant and as a diffusion barrier and is the reason for the reduced wear in the case of grey CI.

Single-Source-Precursor Synthesis of Hafnium-Containing Ultrahigh-Temperature Ceramic Nanocomposites (UHTC-NCs)

Amorphous SiHfBCN ceramics were prepared from a commercial polysilazane (HTT 1800, AZ-EM), which was modified upon reactions with Hf(NEt2)4 and BH3·SMe2, and subsequently cross-linked and pyrolyzed. The prepared materials were investigated with respect to their chemical and phase composition, by means of spectroscopy techniques (Fourier transform infrared (FTIR), Raman, magic-angle spinning nuclear magnetic resonance (MAS NMR)), as well as X-ray diffraction (XRD) and transmission electron microscopy (TEM). Annealing experiments of the SiHfBCN samples in an inert gas atmosphere (Ar, N2) at temperatures in the range of 1300-1700 °C showed the conversion of the amorphous materials into nanostructured UHTC-NCs. Depending on the annealing atmosphere, HfC/HfB2/SiC (annealing in argon) and HfN/Si3N4/SiBCN (annealing in nitrogen) nanocomposites were obtained. The results emphasize that the conversion of the single-phase SiHfBCN into UHTC-NCs is thermodynamically controlled, thus allowing for a knowledge-based preparative path toward nanostructured ultrahigh-temperature stable materials with adjusted compositions.

Crystallization Behavior and Controlling Mechanism of Iron-Containing Si−C−N Ceramics

The crystallization behavior and controlling mechanism of the Si-Fe-C-N system based on polymer-derived SiCN ceramic filled with iron metal powder has been studied. The composite preparation conditions allow the formation of a random distribution of metallic particles in the polymer matrix volume for the Si-C-N system. Pyrolysis of the composite material at 1100 degrees C indicates the presence of one crystalline phase Fe(3)Si. While the sample pyrolyzed at 1200 degrees C reveals the formation of both Fe(3)Si and Fe(5)Si(3) phases, a crystallization of beta-SiC is additionally observed by increasing the temperature up to 1300 degrees C. The propensity for the formation of SiC is due to the presence of Fe(5)Si(3), where a solid-liquid-solid (SLS) growth mechanism was suggested to occur. X-ray diffraction (XRD), scanning electron microscopy (SEM), differential thermal analysis (DTA), and thermal gravimetric analysis with mass spectroscopic detection (TGA-MS) were employed to investigate the crystallization behavior of the Si-Fe-C-N system.

CsEuBr3: Crystal structure and its role in the photostimulation of CsBr:Eu2+

CsBr:Eu2+ has recently been investigated as a photostimulable x-ray storage phosphor with great potential for application in high-resolution image plates. In a recent paper Hackenschmied et al. [J. Appl. Phys. 93, 5109 (2003)] suggested that segregations of CsEuBr3 or Cs4EuBr6 formed within CsBr:Eu2+ during annealing are responsible for an increase in the photostimulated luminescence (PSL) yield. In this work single crystals of CsEuBr3 were prepared by a one step synthesis and identified by x-ray diffraction (XRD) analysis as single phase perovskites. It was concluded that, after preparation, CsEuBr3 degrades in normal atmosphere into at least two phases, one of which is the orthorhombic structure of Cs2EuBr5∙10H2O. The XRD powder diffraction pattern of this compound is very similar to that of the segregations observed within CsBr:Eu2+ and reported by Hackenschmied et al. However, the increased PSL yield in CsBr:Eu2+ after annealing cannot be due to the segregations, because the trivalent nature of the eu...

Structure and magnetic properties of iron nanoparticles stabilized in carbon

Nanoparticles composed of iron and carbon have been produced by chemical vapor synthesis. A detailed structural, electronic, and magnetic characterization has been performed by several methods. The atomic arrangement in the as-prepared particles is strongly affected and stabilized by excess carbon. Small clusters of different ferrous phases are the building blocks of the particles. Due to the in situ formation of a carbonaceous shell the particles are stable against oxidation at ambient conditions. The magnetic properties are influenced by the exceptionally small particle size. The particles exhibit superparamagnetic behavior with a blocking temperature of 30K and the temperature dependence of the magnetization is governed by the finite size of the system.

In situ formation of tungsten oxycarbide, tungsten carbide and tungsten nitride nanoparticles in micro- and mesoporous polymer-derived ceramics

We present a facile approach to design micro- and mesoporous ceramic nanocomposites, which avoids the sintering of nanoparticles even at high synthesis temperatures and in situ forms nanoparticles in high temperature stable porous silicon oxycarbonitride (SiOC(N)) matrices. Our case study includes the synthesis of micro- and mesoporous polymer nanocomposites (c-WO3−x/WO3×H2O/[–Si(O)CH2–]n) which contain cubic tungsten oxide and tungsten oxide monohydrate (c-WO3−x/WO3×H2O) nanowhiskers in highly micro- and mesoporous polycarbosilane–siloxane matrices. The thermolysis of c-WO3−x/WO3×H2O/[–Si(O)CH2–]n nanocomposites under a suitable atmosphere and temperature leads to the in situ formation of well-dispersed nanoparticles of cubic tungsten oxide (c-WO3−x), tungsten oxycarbide (W2CO), tungsten carbide (WC) and tungsten nitride (WN) in micro- and mesoporous matrices.

Synthesis and functionality of the storage phosphor BaFBr:Eu2+

The present paper relates to a method for synthesizing the photostimulable storage phosphor BaFBr:Eu2+ that features high stimulation characteristics for use in image plates. All previous synthesis routes consist of a multistep process whereas the presented route is a one-step synthesis. Starting compounds are BaCO3, NH4F, and NH4Br, as well as EuF3 where the ammonium compounds are highly volatile at temperatures below 300°C. Their reaction products initiate the decomposition of BaCO3 and form BaFBr. The incorporation of F-centers and europium ions occurs at temperature exceeding 550°C. The individual reaction steps are monitored by simultaneous thermal analysis (thermogravimetry/differential thermal analysis) and the gaseous reaction products are detected by in situ mass spectroscopy. Intermediate and final products are characterized by x-ray diffraction techniques to determine the involved phases. Photoluminescence spectra reveal the typical emission peak of Eu2+ accompanied by a redshifted emission ban...