Thermodynamic properties of the La2 O3 -ZrO2 system by Knudsen effusion mass spectrometry at high temperature.
RATIONALE
Zirconia doped with a lanthanum oxide system is of high interest due to its exceptional thermal stability for the development of high-performance ceramics. It possesses the beneficial properties of pure zirconia, such as heat resistance, mechanical strength and inertness, but also eliminates its main disadvantage, i.e. brittleness. At high temperatures, components of such systems may vaporize selectively, leading to significant change in composition, and hence, the thermal resistance, phase stability and performance of the ceramic materials. Therefore, information on the vaporization processes and thermodynamic properties of the La2 O3 -ZrO2 system is of great importance.


METHODS
Knudsen effusion mass spectrometry was used to study the vaporization processes and thermodynamic properties of solid solutions in the La2 O3 -ZrO2 system at 2110 K. Pure La2 O3 was used as a reference substance. Comprehensive characterization of the precursors and ceramics was performed via SEM, STA, XRD and PSD analysis.


RESULTS
Zirconia-doped lanthania precursor powders and ceramics with La2 O3 of 33.3, 50, 70 and 90 mol.% content were manufactured by solid-state synthesis and the original cryochemical technique. La, LaO, ZrO and ZrO2 were found to be the main vapor species over the samples studied. The activities and thermodynamic properties of La2 O3 were calculated. Via XRD analysis it was shown that the phase composition of xLa2 O3 -(100-x)ZrO2 powders (x = 0.33, 0.5, 0.7 and 0.9 mol. fraction) significantly depends on the synthesis technique chosen.


CONCLUSIONS
According to the XRD results combined with Rietveld refinement of the patterns, 33.3 La2 O3 -66.7 ZrO2 ceramics after solid-state synthesis are composed of well-formed cubic pyrochlore-type La2 Zr2 O7 with 5 wt.% admixture of monoclinic and cubic ZrO2 whereas 33.3 La2 O3 -66.7 ZrO2 precursor powders after cryochemical synthesis correspond to low-crystalline La(OH)3 . The components of the La2 O3 -ZrO2 system evaporate separately: there is no temperature range where lanthanum and zirconium gaseous species are present together. It was found that the activities of lanthania have low negative deviation from the ideal case.
The Rapid Formation of La(OH)3 from La2O3 Powders on Exposureto Water Vapor
The reactivity of various lanthana powders in air was studied. The materials rapidly hydroxylate to form a stable hydroxide, La(OH)3, at room temperature. Smaller amounts of an oxycarbonate species (La2O2CO3) are also observed following air exposure. This oxycarbonate phase is stable to hydroxylation. All oxide materials synthesized here show rapid reactions so that 24 h of exposure to atmosphere is generally sufficient to cause complete hydroxylation at room temperature. The rate of reaction was related to the crystallite size as determined by XRD. The reaction was found to follow a two-stage kinetic process, a relatively slow surface reaction followed by a rapid bulk reaction. The relevance of the reactivity of these powders is discussed.
Physical Ageing of the Research Reactor Core Structural Materials Due to Neutron Irradiation Exposure: a Review
A research reactor (RR) is a  nuclear reactor that has function to generate and utilize neutron flux and radiation ionization for  research purposes and industrial applications. More than 60% of current operating RRs have  been operated for 30 years or more. As the time passes, the functional capabilities of structures,  systems and components (SSCs) of those RRs deteriorate by physical ageing, which can be  caused by neutron irradiation exposure such as irradiation induced dislocation and  microstructural changes. To extend the lifetime and/or to avoid unplanned outages, ageing on  the safety related SSCs of RRs need to be properly managed. An ageing management is a  strategy to engineer, operate, maintenance, and control SSC degradation within acceptable limits. The purpose of this study is to review physical ageing of the core structural materials of  the RRs caused by neutron irradiation exposure. In order to achieve this objective, a wide range  of literatures are reviewed. Comprehensive discussions on irradiation behaviors are limited only  on reactor vessel and core support structure materials made from zirconium and beryllium as  well as their alloys, which are widely used in RRs. It is found that the stability of the mechanical  properties of zirconium and beryllium as well as their alloys was mostly affected by the neutron  fluences and temperatures.