Surface Modifications for Oxidation Resistance

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The Performance of Ce Surface Treated Ferritic Stainless Steels for Solid Oxide Fuel Cell Interconnects

This research deals with the effect of a Ce surface treatment on the behavior of Fe-Cr-Mn ferritic stainless steels which may have application in SOFC technology. This treatment consisted of applying a slurry of CeO2 and a halide activator to the surface of coupons. After the slurry dried the coupons were heated to 900C in a controlled atmosphere furnace for 12 hours. The effectiveness of the treatment on commercial (Type 409 (12Cr), Type 430 (18Cr), Crofer 22APU (22Cr), Type 446(26Cr)) and experimental (NETL F9 (12Cr) and NETL F5 (22Cr)) alloys as a function of Cr content will be presented. The oxidation behavior of the alloys was assessed by exposing coupons (untreated and treated) to moist air at 800C. Area specific resistance (ASR) was measured at 800C. In general, the rare earth treatment effectively reduced the oxidation rate, resulting in thinner oxide scales and less internal oxidation

Influence of alloy content and a cerium surface treatment on the oxidation behavior of Fe-Cr ferritic stainless steels

The cost of solid oxide fuel cells (SOFC) can be significantly reduced by using interconnects made from ferritic stainless steels. In fact, several alloys have been developed specifically for this application (Crofer 22APU and Hitachi ZMG323). However, these steels lack environmental stability in SOFC environments, and as a result, degrade the performance of the SOFC. A steel interconnect can contribute to performance degradation through: (i) Cr poisoning of electrochemically active sites within the cathode; (ii) formation of non-conductive oxides, such as SiO2 or Al2O3 from residual or minor alloying elements, at the base metal-oxide scale interface; and/or (iii) excessive oxide scale growth, which may also retard electrical conductivity. Consequently, there has been considerable attention on developing coatings to protect steel interconnects in SOFC environments and controlling trace elements during alloy production. Recently, we have reported on the development of a Cerium surface treatment that improves the oxidation behavior of a variety alloys, including Crofer 22APU [1-5]. Initial results indicated that the treatment may improve the performance of Crofer 22APU for SOFC application by: (i) retarding scale growth resulting in a thinner oxide scale; and (ii) suppressing the formation of a deleterious continuous SiO2 layer that can form at the metal-oxide scale interface in materials with high residual Si content [5]. Crofer 22 APU contains Fe-22Cr-0.5Mn-0.1Ti (weight percent). Depending on current market prices and the purity of raw materials utilized for ingot production, Cr can contribute upwards of 90 percent of the raw materials cost. The present research was undertaken to determine the influence of Cr content and minor element additions, especially Ti, on the effectiveness of the Ce surface treatment. Particular emphasis is placed on the behavior of low Cr alloys

Discovery of a Luminous Quasar in the Nearby Universe

In the course of the Pico dos Dias survey (PDS), we identified the stellar like object PDS456 at coordinates alpha = 17h 28m 19.796s, delta = -14deg 15' 55.87'' (epoch 2000), with a relatively nearby (z = 0.184) and bright (B = 14.69) quasar. Its position at Galactic coordinates l_II = 10.4deg, b_II = +11.2deg, near the bulge of the Galaxy, may explain why it was not detected before. The optical spectrum of PDS456 is typical of a luminous quasar, showing a broad (FWHM ~ 4000 km/s) H_\beta line, very intense FeII lines and a weak [OIII]\lambda5007 line. PDS456 is associated to the infrared source IRAS 17254-1413 with a 60 \mum infrared luminosity L_{60} = 3.8 x 10^{45} erg/s. The relatively flat slopes in the infrared (\alpha(25,60) = -0.33 and \alpha(12,25) = -0.78) and a flat power index in the optical (F_{\nu} \propto \nu^{-0.72}) may indicate a low dust content. A good match between the position of PDS456 and the position of the X-ray source RXS J172819.3-141600 implies an X-ray luminosity L_x = 2.8 x 10^{44} erg/s. The good correlation between the strength of the emission lines in the optical and the X-ray luminosity, as well as the steep optical to X-ray index estimated (\alpha_{ox} = -1.64) suggest that PDS456 is radio quiet. A radio survey previously performed in this region yields an upper limit for radio power at ~ 5 GHz of ~ 2.6 x 10^{30} erg/s/Hz. We estimate the Galactic reddening in this line-of-sight to be A_B \simeq 2.0, implying an absolute magnitude M_B = -26.7 (using H_0 = 75 km s^{-1} Mpc^{-1} and q_0 = 0). In the optical, PDS456 is therefore 1.3 times more luminous than 3C 273 and the most luminous quasar in the nearby (z \leq 0.3) Universe.Comment: 12 pages, LaTeX (aasms4.sty) + 3 figures; accepted for publication in the Astrophysical Journal Letter

Discovery of optical pulsations in V2116 Ophiuchi/GX 1+4

We report the detection of pulsations with $\sim 124$ s period in V2116 Oph, the optical counterpart of the low-mass X-ray binary GX 1+4. The pulsations are sinusoidal with modulation amplitude of up to 4% in blue light and were observed in ten different observing sessions during 1996 April-August using a CCD photometer at the 1.6-m and 0.6-m telescopes of Laborat\'orio Nacional de Astrof\'{\i}sica, in Brazil. The pulsations were also observed with the $UBVRI$ fast photometer. With only one exception the observed optical periods are consistent with those observed by the BATSE instrument on board the Compton Gamma Ray Observatory at the same epoch. There is a definite correlation between the observability of pulsations and the optical brightness of the system: V2116~Oph had $R$ magnitude in the range $15.3-15.5$ when the pulsed signal was detected, and $R = 16.0-17.7$ when no pulsations were present. The discovery makes GX 1+4 only the third of $\sim 35$ accretion-powered X-ray pulsars to be firmly detected as a pulsating source in the optical. The presence of flickering and pulsations in V2116 Oph adds strong evidence for an accretion disk scenario in this system. The absolute magnitude of the pulsed component on 1996 May 27 is estimated to be $M_V \sim -1.5$. The implied dimensions for the emitting region are 1.1 R_{\sun}, 3.2 R_{\sun}, and 7.0 R_{\sun}, for black-body spectral distributions with $T = 10^5$ K, $2 \times 10^4$ K, and $1 \times 10^4$ K, respectively.Comment: 9 pages, 3 figures in PostScript, latex, accepted for publication on the Astrophysical Journal Letter

Materials Performance in USC Steam

The proposed steam inlet temperature in the Advanced Ultra Supercritical (A-USC) steam turbine is high enough (760 °C) that traditional turbine casing and valve body materials such as ferritic/martensitic steels will not suffice due to temperature limitations of this class of materials. Cast versions of several traditionally wrought Ni-based superalloys were evaluated for use as casing or valve components for the next generation of industrial steam turbines. The full size castings are substantial: 2-5,000 kg each half and on the order of 100 cm thick. Experimental castings were quite a bit smaller, but section size was retained and cooling rate controlled to produce equivalent microstructures. A multi-step homogenization heat treatment was developed to better deploy the alloy constituents. The most successful of these cast alloys in terms of creep strength (Haynes 263, Haynes 282, and Nimonic 105) were subsequently evaluated by characterizing their microstructure as well as their steam oxidation resistance (at 760 and 800 °C)

Cast Alloys for Advanced Ultra Supercritical Steam Turbines

The proposed steam inlet temperature in the Advanced Ultra Supercritical (A-USC) steam turbine is high enough (760 °C) that traditional turbine casing and valve body materials such as ferritic/martensitic steels will not suffice due to temperature limitations of this class of materials. Cast versions of several traditionally wrought Ni-based superalloys were evaluated for use as casing or valve components for the next generation of industrial steam turbines. The full size castings are substantial: 2-5,000 kg each half and on the order of 100 cm thick. Experimental castings were quite a bit smaller, but section size was retained and cooling rate controlled to produce equivalent microstructures. A multi-step homogenization heat treatment was developed to better deploy the alloy constituents. The most successful of these cast alloys in terms of creep strength (Haynes 263, Haynes 282, and Nimonic 105) were subsequently evaluated by characterizing their microstructure as well as their steam oxidation resistance (at 760 and 800 °C)

Microstructural Stability and Oxidation Resistance of 9-12 Chromium Steels at Elevated Temperatures

Various martensitic 9-12 Cr steels are utilized currently in fossil fuel powered energy plants for their good elevated temperature properties such as creep strength, steam side oxidation resistance, fire side corrosion resistance, and thermal fatigue resistance. Need for further improvements on the properties of 9-12 Cr steels for higher temperature (>600oC) use is driven by the environmental concerns (i.e., improve efficiency to reduce emissions and fossil fuel consumption). In this paper, we will discuss the results of the research done to explore new subsitutional solute solution and precipitate hardening mechanisms for improved strength of 9-12 Cr martensitic steels. Stability of the phases present in the steels will be evaluated for various temperature and time exposures. A comparison of microstructural properties of the experimental steels and commercial steels will also be presented. The influence of a Ce surface treatment on oxidation behavior of a commercial (P91) and several experimental steels containing 9 to 12 weight percent Cr was examined at 650ºC in flowing dry and moist air. The oxidation behavior of all the alloys without the Ce modification was significantly degraded by the presence of moisture in the air during testing. For instance the weight gain for P91 was two orders of magnitude greater in moist air than in dry air. This was accompanied by a change in oxide scale from the formation of Cr-based scales in dry air to the formation of Fe-based scales in moist air. The Ce surface treatment was very effective in improving the oxidation resistance of the experimental steels in both moist and dry air. For instance, after exposure to moist air at 650ºC for 2000 hours, an experimental alloy with the cerium surface modification had a weight gain three orders of magnitude lower than the alloy without the Ce modification and two orders of magnitude lower than P91. The Ce surface treatment suppressed the formation of Fe-based scales and promoted the formation of more protective Cr-based scales. However, the Ce surface treatment was not effective in improving the resistance of P91. The results are discussed in terms of synergistic effects of constituent alloying elements