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Fine Structure of Levels and Piezospectroscopy of A{sup +} Centers in GaAs/AlGaAs Quantum Wells

Experimental and theoretical piezospectroscopic investigation of A{sup +} centers in GaAs/AlGaAs quantum wells doped with beryllium is presented. Spectra of linearly polarized photoluminescence are studied experimentally depending on applied uniaxial pressure. A model of the A{sup +} center in the quantum well in the presence of uniaxial deformation in the plane of the quantum well has been constructed. Analytical expressions for the level energy, optical transition intensities, and polarization ratio have been obtained. In the framework of the proposed theory, the experimentally observed change in the polarization ratio depending on pressure and the shift of the line maximum towards short waves are explained.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

The Effect of HVOF Bond Coating with APS Flash Coating on TBC Performance

To study the benefit of ~ 50-µm-thick air-plasma-sprayed (APS) ‘flash’ bond coatings, NiCoCrAlYHfSi high-velocity oxygen fuel (HVOF) bond coatings were deposited on alloy 247 disk substrates with APS yttria-stabilized zirconia topcoatings. Using 1-h cycles at 1100 °C in air with 10% H 2 O and HVOF-only bond coatings as a baseline, APS flash coatings extended the average coating lifetime by > 10% using NiCoCrAlYHfSi and > 70% using NiCoCrAlY powder. Coatings were characterized after 0, 100 and 300 cycles and after failure. Residual stress in the thermally grown alumina scale was mapped every 100 cycles using photo-stimulated luminescence piezospectroscopy. The flash coating created an interlocked metal–alumina layer that appeared to inhibit critical crack formation, and the underlying HVOF layer prevented further internal oxidation and appeared to supply the APS flash coating with Al. Furthermore, the addition of Hf and Y to the flash coating increased internal oxidation and accelerated Al consumption, thereby reducing the benefit of the flash coating.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

APS TBC performance on directionally-solidified superalloy substrates with HVOF NiCoCrAlYHfSi bond coatings

Directionally-solidified (DS) superalloy components with advanced thermal barrier coatings (TBC) to lower the metal operating temperature have the potential to replace more expensive single crystal superalloys for large land-based turbines. In order to assess relative TBC performance, furnace cyclic testing was used with superalloys 1483, X4 and Hf-rich DS 247 substrates and high velocity oxygen fuel (HVOF)-NiCoCrAlYHfSi bond coatings at 1100 °C with 1-h cycles in air with 10% H 2 O. With these coating and test conditions, there was no statistically-significant effect of substrate alloy on the average lifetime of the air plasma sprayed (APS) yttria-stabilized zirconia (YSZ) top coatings on small coupons. Using photo-stimulated luminescence piezospectroscopy maps at regular cycling intervals, the residual compressive stress in the α-Al 2 O 3 scale underneath the YSZ top coating and on a bare bond coating was similar for all three substrates and delaminations occurred at roughly the same rate and frequency. As a result, x-ray fluorescence (XRF) measurements collected from the bare bond coating surface revealed higher Ti interdiffusion occurring with the 1483 substrate, which contained the highest Ti content.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Effect of APS flash bond coatings and curvature on TBC performance on rod specimens

The addition of an air plasma sprayed (APS) “flash” bond coating layer on top of a high velocity oxy-fuel (HVOF) bond coating greatly extended the lifetime of APS yttria stabilized zirconia (YSZ) thermal barrier coatings (TBC) on rod specimens of superalloy 247 tested using 100-h cycles in air+10%H 2 O at 1100 °C. The flash bond coatings of both NiCoCrAlY and NiCoCrAlYHfSi powder were compared to an HVOF-only and a vacuum plasma sprayed (VPS) NiCoCrAlYHfSi bond coating. Here, the flash coatings appear to form a mixed oxide-metal zone, which likely inhibits crack formation and therefore extends lifetime compared to conventional bond coatings. The underlying dense HVOF layer appeared to act as a source of Al for this intermixed zone and prevented the oxide from penetrating deeper into the bond coating. Residual stress in the thermally-grown Al 2 O 3 scale was measured using photo-luminescence piezospectroscopy (PLPS) as a function of time for each coating variation, including a comparison of concave and convex surfaces on a specially designed rod.

36 MATERIALS SCIENCE↗

Three-dimensional characterization of modifications in sapphire exposed to laser-induced damage using multimodal spectral microimaging

Sapphire (Al 2 O 3 ) is a commonly used dielectric material with many applications in lasers and optical systems. Owing to its high resistivity to laser induced damage, it is particularly suitable for use in high power laser systems. This work focuses on developing techniques to characterize material modifications in sapphire. These techniques were applied following localized laser induced ablation, commonly referred to as laser-damage, resulting from exposure to single 100-ps and 6-ns pulses. Measurements of fluorescence-based piezospectroscopy and confocal Raman microscopy were performed with spatial resolution on the order of 1 μ m. Raman microscopy reveals that the relaxation of material exposed to the rapid laser heating, elastic and viscoplastic deformation, melting, and solidification leads to the formation of a polycrystalline material phase. In addition, narrowband fluorescence lines, referred to as R 1 and R 2 , exhibit pressure-sensitive changes to their spectral profiles, allowing 3D internal stresses to be recorded with spatial resolution of the order of a few micrometers.

Laser-damage↗

3D Microscopy to Assess the Effect of High Temperature Cyclic Oxidation on the Deformation of Cast and ODS FeCrAlY Alloys

Specimen deformation, oxide scale growth, and scale cracking were monitored for cyclic oxidation exposures at 1200 °C of three cast FeCrAlY(Hf) alloys and two oxide dispersion strengthened (ODS) FeCrAl alloys. Evolution of both the specimen geometry and surface deformation was quantified using 3D optical microscopy. The stress in the alumina scale was also measured using photo-stimulated luminescence piezospectroscopy. The goal was to examine the effect of stress generation and stress relaxation on scale spallation for FeCrAl materials with drastic differences in terms of high temperature strengths. After 1000, 1-h cycles, the cast alloys exhibited significant deformation with a convoluted oxide scale, leading for the two Hf-free FeCrAlY alloys to undergo crack formation and spallation. For the Hf-containing FeCrAlY, limited spallation was observed due to the localization of spallation at grain boundaries, the large grain structure, and the beneficial effect of Hf on scale adhesion. On the other hand, limited deformation was measured for the ODS FeCrAl alloys, with minimal cracking and scale spallation for alloy PM2000 after 1000 h. A higher spallation rate was observed for ODS MA956, which was attributed to a high defect concentration in the alumina scale that formed. The mechanisms leading to spallation during cyclic oxidation for the cast and ODS FeCrAlY alloys are described.

36 MATERIALS SCIENCE↗

The Effect of APS-HVOF Bond Coating Thickness Ratio on TBC Furnace Cycle Lifetime

In this work, combinations of NiCoCrAlY APS and high-velocity oxygen fuel (HVOF) bond coatings were deposited on alloy 247 disk substrates with APS yttria-stabilized zirconia (YSZ) top coatings to assess the benefit of air plasma sprayed (APS) ‘flash’ bond coatings. Using 1-h cycles at 1100 °C in air with 10% H 2 O and HVOF-only and APS-only bond coatings as a baseline, it was found that APS flash coatings extended the average coating lifetime by 16% to 35% with the thicker flash coating performing best. Principal component analysis and energy dispersive spectroscopy (EDS) compositional mapping on coatings characterized after 0, 100, 300 and 500 cycles and after failure showed that the Al in the bond coatings was depleted due to both oxidation and back diffusion into the substrate. The APS-only bond coating had significant oxidation throughout the bond coating and was so depleted in Al, that Al diffused from the substrate to the coating. Residual stress maps of the thermally-grown alumina scale were obtained every 100 cycles using photo-stimulated luminescence piezospectroscopy (PLPS) revealing that the Thick Flash coating had the slowest rate of damage accumulation in the oxide scale.

alumina scale↗

Role of bond coat processing methods on the durability of plasma sprayed thermal barrier systems

Metallic alloy bond coats are used as an interlayer to promote adhesion of ceramic Thermal Barrier Coatings (TBCs) to the superalloy substrates. These bond coats can be applied through a variety of processing means such as Air Plasma Spray (APS), High-Velocity Oxy Fuel spray (HVOF), and Vacuum Plasma Spray (VPS). While widely adopted in the industry, some uncertainties remain as to the specific microstructural attributes which are influenced by the processing routes and their implications on durability. This paper seeks to elucidate these subtleties between bond coat deposition processing routes through an integrated study of processing to connect to furnace cycle durability on a single bond coat chemistry of NiCoCrAlYHfSi. A standard porous APS TBC top coating based on yttria stabilized zirconia (7YSZ) was consistently applied on these distinct bond coats and tested for durability in cyclic furnace testing at 1100 °C. The results point to substantial differences in durability which are not readily explained only by the variances in coating roughness. Detailed assessment of deposited bond coat properties (modulus, thermal expansion, chemistry) provided some explanation relative to durability. Here, the results suggest a complex interplay among roughness, compliance, aluminum diffusion pathway, and thermal expansion mismatch. Photo-stimulated luminescence piezospectroscopy (PLPS) provided additional insights enabling a comprehensive assessment of processing-performance linkages.

36 MATERIALS SCIENCE↗

Control of deviatoric stress in the diamond anvil cell through thermal expansion mismatch stress in thin films

Elastic and plastic properties of materials and phase transitions at extreme conditions vary with both hydrostatic pressure and deviatoric stress. To generate and measure controlled deviatoric stress at pressures beyond those accessible with large volume differential and rotational presses and optical access for spectroscopy, experiments tested the combination of diamond anvil cell and thin film technology. Thin films of polycrystalline Cr-doped Al 2 O 3 ruby were prepared using pulsed laser deposition on single-crystal substrates of either Al 2 O 3 sapphire or yttria-stabilized cubic zirconia for contrasting initial film stress, and loaded in diamond anvil cells for confining stress. The piezospectroscopic response of the ruby films demonstrates consistently higher deviatoric stress in the film on zirconia relative to the film on the control sapphire, and an increase in deviatoric stress with applied load. Complementary synchrotron X-ray diffraction of the zirconia substrate confirmed that no pressure-induced phase transitions impacted the stress state of the ruby film, but differences in compressibility of film and substrate result in changes in film stress analogous to thermal expansion mismatch. Furthermore, this technique may be applied to evaluate elastic and plastic response of thin films of a variety of materials under extreme stress.

36 MATERIALS SCIENCE↗