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Using the technique of fluorescence piezospectroscopy, we determine the distribution of thermal residual stresses across the edges of three laminated alumina/zirconia composites. We develop a methodology for separating the measured stress state into microstresses that result from grain-to-grain thermal mismatch and macrostresses that result from lamination-induced thermal mismatch between individual plies. Comparison between the measured edge-stress distributions and those calculated based on a simple force-superposition model shows good agreement, indicating that the laminate system is well approximated as linear elastic. Given the experimental confirmation of significant edge stresses in multi-ply laminates, the possibility of failure initiating at composite edges must be considered in the design of surface-compressed laminate structures with the aim of mediating the detrimental effect of surface flaws.

Samples of strontium hexaluminate (SrAl12O19), both pure and mixed with different amounts of ceria-stabilized zirconia (CE-TZP), have been prepared via a chemical route. The fluorescence spectrum of SrAl12O19 is similar to that of ruby and yttrium aluminium garnet (YAG); consequently, this similarity has been attributed to the presence of a trace impurity of Cr3+ ions. The most-intense fluorescence peak of SrAl12O19 exhibits a dependence on stress that is given by the average uniaxial piezospectroscopic coefficient ( = 1.5 cm-1·GPa-1). The piezospectroscopic coefficient has been used to convert to stress the fluorescence frequency shift of SrAl12O19 mixed with zirconia (ZrO2). The stress, as a function of the volume fraction of ZrO2, resides between the Hashin-Shtrikman bounds but is best reproduced by an effective medium approximation.

The stresses of laminate structures obtained by joining single layers of pure alumina (A), pure yttria-stabilized tetragonal zirconia, 3Y-TZP (Z), and an intimate mixture of alumina and zirconia (AZ) have been determined by fluorescence (in alumina) and Raman (in zirconia) piezospectroscopy. Three symmetrical stacking sequences were examined, namely, A/Z/A, A/AZ/A, and AZ/Z/AZ, with the aim of designing structures where the higher coefficient of thermal expansion (CTE) of zirconia could be used to induce compressive stress in the external layers (and ensuing tensile stress in the central layer). Two experimental sessions, 6 years apart, were conducted on the same samples, also taking care to record the spectra from the same locations; during the time elapsed between the two sessions, the samples were kept at room temperature and humidity. The stress values in alumina obtained during the more recent session were markedly different from those observed in the first session. Monoclinic zirconia (m-zirconia) was absent in all samples in the first session, whereas up to 25 vol% zirconia could be observed during the second session. m-Zirconia could only be observed in AZ layers and not in Z layers, irrespective of the position in the stacking sequence. It was concluded that 3Y-TZP underwent spontaneous tetragonal-to-monoclinic (t–m) transformation, that is, “aging,” when mixed with alumina at the grain-size level. Aging occurred only where pristine t-zirconia was subject to tensile stresses larger than ∼400 MPa.

Raman spectroscopy has been used to obtain Raman spectra of yttria-stabilized tetragonal zirconia subject to surface nitridation induced by contact with zirconium nitride. Raman spectra recorded from regions at increasing distance from the source of nitridation have been used to obtain diffusion profiles from samples treated at different times and temperatures. The coupling of X-ray diffraction data previously taken and of the Raman spectra shows that in the samples there is a two-phase region (tetragonal + cubic) near the nitrided surface and that, at larger distance inside the samples, there is only one phase (tetragonal). Fitting of the diffusive profiles in the single-phase tetragonal region with an appropriate diffusion function allows the determination of the diffusion coefficient of nitrogen in tetragonal zirconia which is expressed in terms of the preexponential factor, D0= (3.98 ± 0.5) × 10−3 cm2/s, and the activation energy, Q= 170 ± 10 kJ/mol.

Observations are reported of the room-temperature propagation of a spalling failure mode of a thermal barrier coating (TBC) from its bond coat after oxidation. The coating is a Y2O3-stabilized ZrO2 coating formed by electron-beam deposition on a Ni-Co-Cr-Al-Y bond coat. The spall shape evolution and stress redistribution as the spall propagates are reported. The failure propagates primarily as an interface crack between the bond coat and the thermally grown aluminum oxide (TGO) formed on the underside of the TBC during oxidation. The observations are consistent with subcritical propagation of an interface crack between the TGO and bond coat assisted by the presence of moisture. An estimate of 9 J/m2 is made of the fracture resistance in air of the interface.

A stress-induced aging phenomenon is observed to occur at room temperature in deformation bands introduced into a 8.5 mol% ceria-stabilized tetragonal zirconia/alumina (Ce-TZP/Al{sub 2}O{sub 3}) composite by flexural loading. The aging occurs with time after unloading and in laboratory air. Over a period of 100 days, the concentration of monoclinic zirconia within a deformation band increases and, in addition, the wedge-shaped deformation band grows with time. Accompanying these two changes are an increase in the tensile stress in the remaining tetragonal zirconia within the deformation band and a consequential increase in the overall compressive stress within the band. The average value of the monoclinic concentration within the deformation band is found to increase parabolically with time, suggesting the mechanism responsible for the observed aging is diffusion limited. Away from the deformation bands, no aging is observed to occur, suggesting aging is stress dependent. Although a water-vapor-mediated mechanism cannot be ruled out, it is proposed that the observed aging is in fact due to a tensile stress assisted chemical reduction of Ce{sup 4+} to Ce{sup 3+} whose rate is controlled by the indiffusion of oxygen vacancies driven by the tensile stress gradient. It is further proposed that the deformation band growsmore » with time the region ahead of the band is under tension a subject to an enhanced rate of reduction.« less

Alumina/ceria-stabilized zirconia bars tested in four-point bending exhibited deformation bands on the tensile side due to localized tetragonal-to-monoclinic transformation. These bands became increasingly darker and were fully visible some weeks after the bending experiment. XPS spectra revealed that the darker regions are characterized by a higher concentration of cerium in the + 3 oxidation state, as opposed to other undeformed regions, in which + 4 is the predominant oxidation state. A numerical calculation established that residual stresses exist in the deformation bands. It is suggested that these stresses facilitate the reduction of cerium with the gradient in stress motivating the diffusion of oxygen vacancies.