Papers by Author: Fritz Aldinger

Abstract: The present contribution reports two different approaches to achieve a good dispersion of single-walled carbon nanotubes (SWCNTs) in a precursor-derived Si-C-N matrix, which represents an important prerequisite for attaining a high-performance material. The first approach involves the use of SWCNTs covalently functionalized by disilazane groups, aiming at enhanced interfacial interaction between the nanotube surface and the matrix. Within the second approach, the effect of an electrical field applied in the cross-linking step during the nanocomposite synthesis was studied toward the task of dispersing and simultaneously aligning the SWCNTs in the Si-C-N matrix.

Abstract: A nano-sized CeO2 powder was synthesized by a modified glycine nitrate process (MGNP). The synthesized powder was characterized by X-ray diffraction (XRD), the Brunauer Emmett Teller (BET) method, and transmission electron microscopy (TEM). The lattice parameter and crystallite size were determined by the Rietveld refinement of X-ray diffraction patterns. The shrinkage kinetics of the green body was continuously monitored in air and in oxygen atmospheres using a high temperature dilatometer up to 1500°C. During the high temperature sintering in air a redox reaction occurred (Ce4+ was partially reduced to Ce3+, and oxygen gas was released). The redox reaction influenced the sintering behaviour of CeO2, resulting in a decrease in density. On the basis of shrinkage kinetics data in oxygen atmosphere a master sintering curve for CeO2 was constructed. Using the concept of the master sintering curve, the densification behaviour in oxygen atmosphere was successfully predicted from early to final stages of sintering. During sintering of CeO2 at lower temperature in air atmosphere a significant contribution of the surface diffusion was observed.

Abstract: Bipolar electric fatigue in ferroelectric niobium-doped lead zirconate titanate stannate ceramics was investigated. Variations in the polarization and strain hysteresis loops as well as microstructural modifications of the material due to the electric cycling were analyzed. Compared with ferroelectric PZT ceramics cycled under similar conditions, the material exhibited a higher resistance to electric fatigue. Properties of the specimens showed significant decays above 106.5 cycles. Asymmetric suppression of strain hysteresis loop was monitored. At 108 cycles, the remanent polarization, the right maximum strain and the left maximum strain decreased to 70%, 58% and 44% of their initial values, respectively. The color of the material was changed from pale yellow to dark grey with cycling. The properties and color of the fatigued samples were recovered almost fully to those of the virgin state after a heat treatment at 500oC for 1 h. The pinning of domain walls, probably by oxygen vacancies, was concluded to be the predominant fatigue mechanism for the material.

Abstract: Aqueous freeze casting is an alternative wet shaping technique where water-based ceramic suspensions containing a cryoprotectant are cast in molds, frozen and dried. The method can be applied to various ceramic systems depending mainly on the ability to produce high solid loading in aqueous ceramic slurries. Against this background, aqueous aluminum nitride (AlN) suspensions were developed for the application in freeze casting. The results show that the applied process additives are most effective not only in chemically protecting AlN against hydrolysis but also in obtaining colloidally stable slurries with solid loadings in excess of 50 vol.-%. After optimization of the viscosity, the freeze cast green samples exhibit homogeneous microstructures without cracks and warpage. Besides, the systematic control of the freezing step and the solid loading allow the preparation of sintered samples with defined density.

Abstract: Consolidation of pyrolyzed powders has been tried by hot isostatic pressing (HIP) without sintering additives, in order to obtain dense non-oxide ceramic bulk materials derived from polymer precursors. Si1.0C1.6N1.3 ceramic powders were derived from a polyvinylsilazane polymer. The polymer was thermally crosslinked at 250oC and pyrolyzed at 1050oC under Ar atmosphere. The pyrolyzed powders were die-pressed into rectangular bars at room temperature and densified by HIP at 1400oC-900 MPa and 1500oC-950 MPa. Dense ceramic monolith, in which pores were not observed by optical microscopy, was obtained by the HIP consolidation at 1500oC-950 MPa. The microstructure of the ceramic monolith was a nano-composite structure consisted of α-Si3N4 and graphite phases. In the compression tests of the HIP-treated sample, slight plastic deformation was observed at 1400 and 1500oC in spite of high compressive stress over 1000 MPa. On the other hand, the sample showed a compressive strain of about 7% at 1000 MPa at 1600oC. The compressive strain of about 11% was achieved at 1700oC.

Abstract: In the present contribution, the electrophoretic deposition (EPD) of nanocrystalline SiC powders will be discussed. In order to avoid the electrolysis of water during deposition as well as oxygen uptake of the nanocrystalline SiC by hydrolysis reactions, nonaqueous solvents were tested including ethanol and diethyl formamide. The solvents were compared regarding their effect on particle size distributions and sedimentation tests. Auxiliary information on the surface conditions as a function of the acidity of the suspension was drawn from aqueous zeta-potential measurements. The influence of dispersants, binders and the type of powder on the suspension properties was studied, and EPD was performed. For promising solvent-dispersant systems, the film thickness, current and deposition time at a given voltage were monitored during EPD.

Abstract: One of the methods for powder synthesis that is both cost and time effective is the selfpropagating room temperature synthesis. We applied this method to synthesize rare earth doped ceria nanopowders. Since they exhibit very high ionic conductivity at intermediate temperatures these compositions are attractive for a new generation of nanostructured ceramics applicable in solid oxide fuel cells as electrolytes. In this paper we paid our attention to the reaction based on methathetical pathway, whereby solid solution nanopowders of rare earth elements with ceria were obtained at room temperature. Compositions of Ce1-xRexO2-δ (Re = Y , Nd) were synthesized with x ranging from 0 to 0.20. The reaction course is discussed and the properties of the obtained powders are presented.

Abstract: The stoichiometric compound Cu2PbO2 has been synthesized by solid-state reaction from Cu2O and PbO in a sealed quartz ampoule. The optimum synthesis conditions are 910 K and 260 h. The enthalpy of formation of Cu2PbO2 has been measured with the use of high-temperature calorimeter. The enthalpy of reaction Cu2O + PbO = Cu2PbO2 is – 25.4 ± 1 kJ·mol-1 at temperature 968 ± 5 K. Standard enthalpy and Gibbs energy of formation of the Cu2PbO2 compound from elements and its entropy at 298.15 K are DfH° = – 413.086 kJ·mol-1, DfG° = – 353.165 kJ·mol-1 and S° = 135.165 J·mol-1·K-1. The eutectic reaction L → Cu2O + PbO was found to occur at 1017 ± 5 K. Using the thermodynamic database for Cu-Pb-O system the revised Cu2O-PbO phase diagram is proposed.

Abstract: Bipolar electric fatigue in antiferroelectrics of the lead zirconate titanate stannate ceramics family was investigated. Variations in strain hysteresis loops and damages in microstructure of the materials due to the electric cycling were analyzed. The materials showed symmetric or asymmetric suppression of strain hysteresis loop, normal or diffuse AFE-FE phase transition and intact or damaged microstructure after 5×10-7 cycles, indicating a strong composition dependent fatigue effect and the corresponding mechanism. In general, the antiferroelectric materials exhibited much higher fatigue resistance than ferroelectric ceramics reported previously.