Characterization of oxide scales grown on alloy 310S stainless steel after long term exposure to supercritical water at 500 °C

DOE Office of Scientific and Technical Information (OSTI.GOV)

Behnamian, Yashar, E-mail: behnamia@ualberta.ca

The oxide scale grown of static capsules made of alloy 310S stainless steel was investigated by exposure to the supercritical water at 500 °C 25 MPa for various exposure times up to 20,000 h. Characterization techniques such as X-ray diffraction, scanning/transmission electron microscopy, energy dispersive spectroscopy, and fast Fourier transformation were employed on the oxide scales. The elemental and phase analyses indicated that long term exposure to the SCW resulted in the formation of scales identified as Fe{sub 3}O{sub 4} (outer layer), Fe-Cr spinel (inner layer), Cr{sub 2}O{sub 3} (transition layer) on the substrate, and Ni-enrichment (chrome depleted region) inmore » the alloy 310S. It was found that the layer thickness and weight gain vs. exposure time followed parabolic law. The oxidation mechanism and scales grown on the alloy 310S stainless steel exposed to SCW are discussed. - Highlights: •Oxidation of alloy 310S stainless steel exposed to SCW (500 °C/25 MPa) •The layer thickness and weight gain vs. exposure time followed parabolic law. •Oxide layers including Fe{sub 3}O{sub 4} (outer), Fe-Cr spinel (inner) and Cr{sub 2}O{sub 3} (transition) •Ni element is segregated by the selective oxidation of Cr.« less

Impedance spectroscopy of the oxide films formed during high temperature oxidation of a cobalt-plated ferritic alloy

NASA Astrophysics Data System (ADS)

Velraj, S.; Zhu, J. H.; Painter, A. S.; Du, S. W.; Li, Y. T.

2014-02-01

Impedance spectroscopy was used to evaluate the oxide films formed on cobalt-coated Crofer 22 APU ferritic stainless steel after thermal oxidation at 800 °C in air for different times (i.e. 2, 50, 100 and 500 h). Impedance spectra of the oxide films exhibited two or three semicircles depending on the oxidation time, which correspond to the presence of two or three individual oxide layers. Coupled with scanning electron microscopy/energy-dispersive spectroscopy (SEM/EDS) and X-ray diffraction (XRD), the individual oxide layer corresponding to each semicircle was determined unambiguously. Impedance spectrum analysis of the oxide films formed on the sample after thermal exposure at 800 °C in air for 2 h led to the identification of the low-frequency and high-frequency semicircles as being from Cr2O3 and Co3O4, respectively. SEM/EDS and XRD analysis of the 500-h sample clearly revealed the presence of three oxide layers, analyzed to be Co3-xCrxO4, CoCr2O4, and Cr2O3. Although the SEM images of the 50-h and 100-h samples did not clearly show the CoCr2O4 layer, impedance plots implied their presence. The oxide scales were assigned to their respective semicircles and the electrical properties of Co3-xCrxO4, CoCr2O4 and Cr2O3 were determined from the impedance data.

Oxidation kinetics of Haynes 230 alloy in air at temperatures between 650 and 850 °C

NASA Astrophysics Data System (ADS)

Jian, Li; Jian, Pu; Bing, Hua; Xie, Guangyuan

Haynes 230 alloy was oxidized in air at temperatures between 650 and 850 °C. Thermogravimetry was used to measure the kinetics of oxidation. The formed oxides were identified by the thin film (small angle) X-ray diffraction technique. Cr 2O 3 and MnCr 2O 4 were found in the oxide scale. Multi-stage oxidation kinetics was observed, and each stage follows Wagner's parabolic law. The first slow oxidation stage corresponded to the growth of an Cr 2O 3 layer, controlled by Cr ions diffusion through the dense Cr 2O 3 scale. The faster second stage was a result of rapid diffusion of Mn ions passing through the established Cr 2O 3 scale to form MnCr 2O 4 on top of the Cr 2O 3 layer. A duplex oxide scale is expected. The third stage, with a rate close to that of the first stage, only appeared for oxidation in the intermediate temperature range, i.e., 750-800 °C, which can be explained by the interruption of the Mn flux that forms MnCr 2O 4.

The General Isothermal Oxidation Behavior of Cu-8Cr-4Nb

NASA Technical Reports Server (NTRS)

Thomas-Ogbuji, L. U.; Gray, Hugh R. (Technical Monitor)

2002-01-01

Oxidation kinetics of Cu-8Cr-4Nb was investigated by TGA (thermogravimetric) exposures between 500 and 900-C (at 25-50 C intervals) and the oxide scale morphologies examined by microscopy and micro-analysis. Because Cu-8Cr-4Nb is comprised of fine Cr2Nb precipitates in a Cu matrix, the results were interpreted by comparison with the behavior of copper (OFHC) and 'NARloy-Z' (a rival candidate material for thrust cell liner applications in advanced rocket engines) under the same conditions. While NARloy-Z and Cu exhibited identical oxidation behavior, Cu-8Cr-4Nb differed markedly in several respects: below approx. 700 C its oxidation rates were significantly lower than those of Cu; At higher temperatures its oxidation rates fell into two categories: an initial rate exceeding that of Cu, and a terminal rate comparable to that of Cu. Differences in oxide morphologies paralleled the kinetic differences at higher temperature: While NARloy-Z and Cu produced a uniform oxide scale of Cu2O inner layer and CuO outer layer, the inner (Cu2O) layer on Cu-8Cr-4Nb was stratified, with a highly porous/spongy inner stratum (responsible for the fast initial kinetics) and a dense/blocky outer stratum (corresponding to the slow terminal kinetics). Single and spinel oxides of Nb and Cr were found at the interface between the oxide scale and Cu-8Cr-4Nb substrate and it appears that these oxides were responsible for its suppressed oxidation rates at the intermediate temperatures. No difference was found between Cu-8Cr-4Nb oxidation in air and in oxygen at 1.0 atm.

High-temperature oxidation of advanced FeCrNi alloy in steam environments

NASA Astrophysics Data System (ADS)

Elbakhshwan, Mohamed S.; Gill, Simerjeet K.; Rumaiz, Abdul K.; Bai, Jianming; Ghose, Sanjit; Rebak, Raul B.; Ecker, Lynne E.

2017-12-01

Alloys of iron-chromium-nickel are being explored as alternative cladding materials to improve safety margins under severe accident conditions. Our research focuses on non-destructively investigating the oxidation behavior of the FeCrNi alloy "Alloy 33" using synchrotron-based methods. The evolution and structure of oxide layer formed in steam environments were characterized using X-ray diffraction, hard X-ray photoelectron spectroscopy, X-ray fluorescence methods and scanning electron microscopy. Our results demonstrate that a compact and continuous oxide scale was formed consisting of two layers, chromium oxide and spinel phase (FeCr2O4) oxides, wherein the concentration of the FeCr2O4 phase decreased from the surface to the bulk-oxide interface.

Oxidation behavior of TD-NiCr in a dynamic high temperature environment

NASA Technical Reports Server (NTRS)

Tenney, D. R.; Young, C. T.; Herring, H. W.

1974-01-01

The oxidation behavior of TD-NiCr has been studied in static and high-speed flowing air environments at 1100 and 1200 C. It has been found that the stable oxide morphologies formed on the specimens exposed to the static and dynamic environments were markedly different. The faceted crystal morphology characteristic of static oxidation was found to be unstable under high-temperature, high-speed flow conditions and was quickly replaced by a porous NiO 'mushroom' type structure. Also, it was found that the rate of formation of CrO3 from Cr2O3 was greatly enhanced by high gas velocity conditions. The stability of Cr2-O3 was found to be greatly improved by the presence of an outer NiO layer, even though the NiO layer was very porous. An oxidation model is proposed to explain the observed microstructures and overall oxidation behavior of TD-NiCr alloys.

Oxidation behaviour and electrical properties of cobalt/cerium oxide composite coatings for solid oxide fuel cell interconnects

NASA Astrophysics Data System (ADS)

Harthøj, Anders; Holt, Tobias; Møller, Per

2015-05-01

This work evaluates the performance of cobalt/cerium oxide (Co/CeO2) composite coatings and pure Co coatings to be used for solid oxide fuel cell (SOFC) interconnects. The coatings are electroplated on the ferritic stainless steels Crofer 22 APU and Crofer 22H. Coated and uncoated samples are exposed in air at 800 °C for 3000 h and oxidation rates are measured and oxide scale microstructures are investigated. Area-specific resistances (ASR) in air at 850 °C of coated and uncoated samples are also measured. A dual layered oxide scale formed on all coated samples. The outer layer consisted of Co, Mn, Fe and Cr oxide and the inner layer consisted of Cr oxide. The CeO2 was present as discrete particles in the outer oxide layer after exposure. The Cr oxide layer thicknesses and oxidations rates were significantly reduced for Co/CeO2 coated samples compared to for Co coated and uncoated samples. The ASR of all Crofer 22H samples increased significantly faster than of Crofer 22 APU samples which was likely due to the presence of SiO2 in the oxide/metal interface of Crofer 22H.

Enhancing the Oxidation Performance of Wrought Ni-Base Superalloy by Minor Additions of Active Elements

NASA Astrophysics Data System (ADS)

Tawancy, H. M.

2016-12-01

We show that the oxidation performance of Cr2O3-forming superalloy based upon the Ni-Cr-W system is significantly improved by the presence of minor concentrations of La, Si and Mn, which outweigh the detrimental effect of high W concentration in the alloy. Although Cr2O3 is known to transform into volatile CrO3 at temperatures ≥950 °C, the respective protection is extended to temperatures reaching 1150 °C, which has also been correlated with the beneficial effects of La, Si and Mn. During high-temperature oxidation, an inner protective La- and Si-modified layer of α-Cr2O3 in contact with the superalloy substrate is developed and shielded by an outermost layer of MnCr2O4. The distribution of La and Si in the inner oxide layer has been characterized down to the scale of transmission electron microscopy, and the possible mechanisms underlying their beneficial effects are elucidated.

High-temperature oxidation of advanced FeCrNi alloy in steam environments

DOE PAGES

Elbakhshwan, Mohamed S.; Gill, Simerjeet K.; Rumaiz, Abdul K.; ...

2017-07-04

Alloys of iron-chromium-nickel are being explored as alternative cladding materials to improve safety margins under severe accident conditions. Here, our research focuses on non-destructively investigating the oxidation behavior of the FeCrNi alloy “Alloy 33” using synchrotron-based methods. The evolution and structure of oxide layer formed in steam environments were characterized using X-ray diffraction, hard X-ray photoelectron spectroscopy, X-ray fluorescence methods and scanning electron microscopy. In conclusion, our results demonstrate that a compact and continuous oxide scale was formed consisting of two layers, chromium oxide and spinel phase (FeCr 2O 4) oxides, wherein the concentration of the FeCr 2O 4 phasemore » decreased from the surface to the bulk-oxide interface.« less

Effect of surface state on the oxidation behavior of welded 308L in simulated nominal primary water of PWR

NASA Astrophysics Data System (ADS)

Ming, Hongliang; Zhang, Zhiming; Wang, Jiazhen; Zhu, Ruolin; Ding, Jie; Wang, Jianqiu; Han, En-Hou; Ke, Wei

2015-05-01

The oxidation behavior of 308L weld metal (WM) with different surface state in the simulated nominal primary water of pressurized water reactor (PWR) was studied by scanning electron microscopy (SEM) equipped with energy dispersive X-ray spectroscopy (EDS), X-ray diffraction (XRD) analyzer and X-ray photoelectron spectroscopy (XPS). After 480 h immersion, a duplex oxide film composed of a Fe-rich outer layer (Fe3O4, Fe2O3 and a small amount of NiFe2O4, Ni(OH)2, Cr(OH)3 and (Ni, Fe)Cr2O4) and a Cr-rich inner layer (FeCr2O4 and NiCr2O4) can be formed on the 308L WM samples with different surface state. The surface state has no influence on the phase composition of the oxide films but obviously affects the thickness of the oxide films and the morphology of the oxides (number & size). With increasing the density of dislocations and subgrain boundaries in the cold-worked superficial layer, the thickness of the oxide film, the number and size of the oxides decrease.

Microstructure and Oxidation of (La,Sr)CrO3-Added Ti3SiC2 Composites.

PubMed

Lee, Dong Bok

2015-11-01

Composites of Ti3SiC2-(10, 20, 40)wt% La0.8Sr0.2CrO3 were synthesized by hot pressing powders of Ti3SiC2 and La0.8Sr0.2CrO3. These powders reacted to form stable TiC carbides and LaTiO3, Cr2Ti4O11, La2O3, and SrCrO4 oxides during hot pressing. The composites consisted primarily of a fine TiC-rich matrix phase and coarse Ti3SiC2 dispersoids. The addition of oxidation-immune La0.8Sr0.2CrO3 into Ti3SiC2 increased the oxidation rate because TiC formed during hot pressing. During oxidation of the composites at 800-1000 degrees C for 100 h in air, Ti diffused outward to form an outer rutile-TiO2 layer, and oxygen transported inward to form an inner oxide layer.

Tribological Behavior of Al-Cr Coating Obtained by Dgpsm and IIP Composite Technology

NASA Astrophysics Data System (ADS)

Luo, Xixi; Yao, Zhengjun; Zhang, Pingze; Zhou, Keyin; Chen, Yu; Tao, Xuewei

An Al-Cr composite alloyed layer composed of an Al enriched layer, a Cr enriched layer and a transition layer from the surface to the bulk along the cross-section was deposited on a 45# steel substrate by composite technology, where Cr was deposited using double glow plasma surface metallurgy (DGPSM), and Al was then implanted by ion implantation (IIP) to achieve higher micro-hardness and excellent abrasive resistance. The composite alloyed layer is approximately 5μm, and as metallurgical adherence to the substrate. The phases are Al8Cr5, Fe2AlCr, Cr23C6, Cr (Al) and Fe (Cr, Al) solid solution. The wear resistance tests were performed under various rotational speed (i.e. 280, 560 and 840r/min) with silicon nitride balls as the counterface material at ambient temperature. The Al-Cr composite alloyed layer exhibits excellent wear resistance when the speed is 280r/min with a friction coefficient as low as 0.3, which is attributed to Al8Cr5 in the Al implanted layer that withstands abrasive wear. Better wear resistance (friction coefficient: 0.254) at 560r/min is resulted from the formation of a high micro-hardness zone, and an oxidation layer with lubrication capacity. In addition, the composite alloyed layer suffers severe oxidative wear and adhesive wear at 840r/min due to the increment of the frictional heating. When compared to the 45# steel substrate, the enhanced wear resistance of the Al-Cr composite alloyed layer demonstrates the viable method developed in this work.

Corrosion resistance of high-Cr oxide dispersion strengthened ferritic steels in super-critical pressurized water

NASA Astrophysics Data System (ADS)

Cho, H. S.; Kimura, A.

2007-08-01

The effects of alloying elements, such as Cr and Al, on corrosion resistance in super critical pressurized water (SCPW) have been investigated to develop corrosion resistant oxide-dispersion-strengthened (ODS) steels. Corrosion tests were performed in a SCPW (783 K, 25 MPa) environment. Weight gain was measured after exposure to the SCPW, and then oxide layers were analyzed by low angle X-ray diffraction and SEM microscopy. The weight gains of all high-Cr ODS steels are smaller than an austenitic stainless steel (SUS316L). More uniform and thinner oxidation layers were observed on the ODS steels after corrosion compared to those on 9Cr martensitic steel and SUS316L.

Effect of surface etching on the oxidation behavior of plasma chromizing-treated AISI440B stainless steel

NASA Astrophysics Data System (ADS)

Meng, T. X.; Guo, Q.; Xi, W.; Ding, W. Q.; Liu, X. Z.; Lin, N. M.; Yu, S. W.; Liu, X. P.

2018-03-01

Double glow plasma surface alloying was applied to prepare chromizing layer in the surface of AISI440B stainless steel. Prior to chromizing, the stainless steel was etched by microwave plasma chemical vapor deposition to change the surface morphology and composition, and then heated for chromizing at 950 °C for 3 h. The cyclical oxidation of steel after chromizing was carried out at 900 °C for 100 h. Scanning electron microscopy, glow discharge optical emission spectrometer and X-ray diffractometer were used to characterize microstructure, composition and phase structure of alloyed and oxidized samples. The results show that the surface was composed of the Cr-rich top layer and Cr23C6, Cr7C3 and {Cr,Fe}7C3 below layer after chromizing. The bonding between the chromizing layer and the substrate after etching treatment was obviously strengthened. AISI440B steel shows a poor oxidation resistance and the weight gain oxidized for 100 h was up to 31.1 mg/cm2. Weight gains for chromizing and etching + chromizing treated samples were 0.67 mg/cm2 and 8 mg/cm2, respectively. Both oxidized surfaces of chromizing and etching + chromizing were composed of Cr2O3, but the oxide scale of etching + chromizing treated samples was more compact than that of samples without etching.

Corrosion Behavior of FBR Structural Materials in High Temperature Supercritical Carbon Dioxide

NASA Astrophysics Data System (ADS)

Furukawa, Tomohiro; Inagaki, Yoshiyuki; Aritomi, Masanori

A key problem in the application of a supercritical carbon dioxide (CO2) turbine cycle to a fast breeder reactor (FBR) is the corrosion of structural material by supercritical CO2 at high temperature. In this study, corrosion test of high-chromium martensitic steel (12Cr-steel) and FBR grade type 316 stainless steel (316FR), which are candidate materials for FBRs, were performed at 400-600°C in supercritical CO2 pressurized at 20MPa. Corrosion due to the high temperature oxidation in exposed surface was measured up to approximately 2000h in both steels. In the case of 12Cr-steel, the weight gain showed parabolic growth with exposure time at each temperature. The oxidation coefficient could be estimated by the Arrhenius function. The specimens were covered by two successive oxide layers, an Fe-Cr-O layer (inside) and an Fe-O layer (outside). A partial thin oxide diffusion layer appeared between the base metal and the Fe-Cr-O layer. The corrosion behavior was equivalent to that in supercritical CO2 at 10MPa, and no effects of CO2 pressure on oxidation were observed in this study. In the case of 316FR specimens, the weight gain was significantly lower than that of 12Cr-steel. Dependency of neither temperature nor exposed time on oxidation was not observed, and the value of all tested specimens was within 2g/m2. Nodule shape oxides which consisted of two structures, Fe-Cr-O and Fe-O were observed on the surface of the 316FR specimen. Carburizing, known as a factor in the occurrence of breakaway corrosion and/or the degradation of ductility, was observed on the surface of both steels.

The influence of Cr and Al pack cementation on low carbon steel to improve oxidation resistance

NASA Astrophysics Data System (ADS)

Prasetya, Didik; Sugiarti, Eni; Destyorini, Fredina; Thosin, Kemas Ahmad Zaini

2012-06-01

Pack chromizing and aluminizing has been widely used for many years to improve hot temperature oxidation and corrosion resistance of metals. The coating process involves packing the steel in a powder mixture which contain aluminum and chromium source, and inert filler (usually alumina), and halide activator NH4Cl. Al and Cr were deposited onto carbon steel by pack cementation process using elemental Al and Cr powder as Al and Cr source, whereas NiCo alloys codeposited by electrodeposition. The position of Al and Cr could be under or over Ni-Co alloys deposited. Pack cementation was heated on dry inert gas at temperature 800 °C about 5 hours and 20 minute for Cr and Al respectively. Al and Cr was successfully deposited. Laying down effect of Al and Cr onto carbon steel whether up and down toward NiCo alloys coating have affected to oxidation resistance. The pack aluminizing as top layer given best resitance to restrain excessive oxide scale, in contrast pack chromizing reveal bad oxidation resistance, moreover occured spallation on layer.

Characterization of corrosion resistant on NiCoCr coating layer exposed to 5%NaCl

NASA Astrophysics Data System (ADS)

Sugiarti, E.; Sundawa, R.; Desiati, R. D.; Zaini, K. A.

2018-03-01

Highly corrosion resistant of carbon steel coated NiCoCr was applied in corrosive of marine environtment. Carbon steel coated NiCoCr was prepared by a two step technique of NiCo electro-deposition and Cr pack cementation. The samples were exposed to 5 wt.% NaCl for 48 and 168 hours. The microstructure and corrosion product were characterized by scanning electron microscopy (SEM), X-ray diffraction (XRD), and transmission electron microscopy (TEM). The corrosion resistance of carbon steel coated NiCoCr was found to be better than that of carbon steel substrate without coating. The results showed the microstructure of 48 h corroded sample has duplex layer composed of inner α-(Ni,Co), α-Cr and outer Cr2O3, while a quite thin and continues protective oxide of Cr2O3 was observed in outer layer of 168 h corroded sample. The formation of oxide scale rich in Cr2O3 has contributed for the better corrosion resistance of carbon steel coated NiCoCr, whereas the formation of non protective oxide of iron might caused low corrosion resistance of carbon steel substrate.

Response of Cr and Cr-Al coatings on Zircaloy-2 to high temperature steam

NASA Astrophysics Data System (ADS)

Zhong, Weicheng; Mouche, Peter A.; Heuser, Brent J.

2018-01-01

The oxidation behavior of chromium (Cr) and chromium-aluminum (CrAl) coatings with various compositions deposited on Zircaloy-2 to 700 °C high-temperature steam (HTS) exposure has been investigated. CrAl coatings with higher Al compositions demonstrate lower oxidation weight gain. A layer of γ-alumina developed on the CrAl coatings with Al composition over 43 at%, while Al2O3 and Cr2O3 developed on CrAl coatings with Al composition below 33 at%. Oxidation of Zircaloy-2 substrate was inhibited by the 1um coatings to 20 h HTS exposure. Coating constituent elements diffused into the substrate and formed intermetallic phases with the Zircaloy substrate. Thicker layers of intermetallic phases developed on the coatings with higher Al composition. The intermetallic phases included Fe and Ni, indicating the dissolution of second phase particles (SPPs) during HTS exposure.

Oxidation mechanism of T91 steel in liquid lead-bismuth eutectic: with consideration of internal oxidation

PubMed Central

Ye, Zhongfei; Wang, Pei; Dong, Hong; Li, Dianzhong; Zhang, Yutuo; Li, Yiyi

2016-01-01

Clarification of the microscopic events that occur during oxidation is of great importance for understanding and consequently controlling the oxidation process. In this study the oxidation product formed on T91 ferritic/martensitic steel in oxygen saturated liquid lead-bismuth eutectic (LBE) at 823 K was characterized at the nanoscale using focused-ion beam and transmission electron microscope. An internal oxidation zone (IOZ) under the duplex oxide scale has been confirmed and characterized systematically. Through the microscopic characterization of the IOZ and the inner oxide layer, the micron-scale and nano-scale diffusion of Cr during the oxidation in LBE has been determined for the first time. The micron-scale diffusion of Cr ensures the continuous advancement of IOZ and inner oxide layer, and nano-scale diffusion of Cr gives rise to the typical appearance of the IOZ. Finally, a refined oxidation mechanism including the internal oxidation and the transformation of IOZ to inner oxide layer is proposed based on the discussion. The proposed oxidation mechanism succeeds in bridging the gap between the existing models and experimental observations. PMID:27734928

Oxidation behaviors of porous Haynes 214 alloy at high temperatures

DOE Office of Scientific and Technical Information (OSTI.GOV)

Wang, Yan, E-mail: wangyan@csu.edu.cn; Liu, Yong, E-mail: yonliu@csu.edu.cn; Tang, Huiping, E-mail: hptang@c-nin.com

The oxidation behaviors of porous Haynes 214 alloy at temperatures from 850 to 1000 °C were investigated. The porous alloys before and after the oxidation were examined by optical microscopy, scanning electron microscopy (SEM) and energy dispersive spectroscopy (EDS), X-ray diffraction (XRD) analyses, and X-ray photoelectron spectroscopy (XPS). The oxidation kinetics of the porous alloy approximately follows a parabolic rate law and exhibits two stages controlled by different oxidation courses. Complex oxide scales composed of Cr{sub 2}O{sub 3}, NiCr{sub 2}O{sub 4} and Al{sub 2}O{sub 3} are formed on the oxidized porous alloys, and the formation of Cr{sub 2}O{sub 3} onmore » its outer layer is promoted with the oxidation proceeding. The rough surface as well as the micropores in the microstructures of the porous alloy caused by the manufacturing process provides fast diffusion paths for oxygen so as to affect the formation of the oxide layers. Both the maximum pore size and the permeability of the porous alloys decrease with the increase of oxidation temperature and exposure time, which may limit its applications. - Highlights: • Two-stage oxidation kinetics controlled by different oxidation courses is showed. • Oxide scale mainly consists of Cr{sub 2}O{sub 3}, NiCr{sub 2}O{sub 4} and Al{sub 2}O{sub 3}. • Rough surface and micropores lead to the formation of uneven oxide structure. • Content of Cr{sub 2}O{sub 3} in the outer layer of the scale increases with time at 1000 °C. • Maximum pore size and permeability decrease with increasing temperature and time.« less

High-temperature oxidation behavior and mechanism of a new type of wrought Ni-Fe-Cr-Al superalloy up to 1300 C

DOE Office of Scientific and Technical Information (OSTI.GOV)

Huang, J.; Fang, H.; Fu, X.

The oxidation behavior of a new type of wrought Ni-Fe-Cr-Al superalloys has been investigated systematically in the temperature range of 1,100 to 1,300 C. Results are compared with those of alloy 214, Inconel 600, and GH 3030. It is shown that the oxidation resistance of the new superalloys is excellent and much better than that of the comparison alloys. Scanning electron microscopy (SEM), electron probe microanalysis (EPMA), and X-ray diffraction (XRD) experiments reveal that the excellent oxidation resistance of the new superalloy is due to the formation of a dense, stable and continuous Al{sub 2}O{sub 3} and Cr{sub 2}O{sub 3}more » oxide layer at high temperatures. Differential thermal analysis (DTA) shows that the formation of Cr{sub 2}O{sub 3} and Al{sub 2}O{sub 3} oxide layers on the new superalloy reaches a maximum at 1,060 and 1,356 C, respectively. The Cr{sub 2}O{sub 3} layer peels off easily, and the single dense Al{sub 2}O{sub 3} layer remains, giving good oxidation resistance at temperatures higher than 1,150 C. In addition, the new superalloy possesses high mechanical strength at high temperatures. On-site tests showed that the new superalloy has ideal oxidation resistance and can be used at high temperatures up to 1,300 C in various oxidizing and corrosion atmospheres, such as those containing SO{sub 2}, CO{sub 2} etc., for long periods.« less

Effect of CrO3 Sealing Time on Anodized A12024-T3

NASA Astrophysics Data System (ADS)

Korda, Akhmad A.; Hidayat, R. Z.

2016-08-01

The effect of CrO3 sealing time on anodized aluminum alloy has been investigated. A1 2024-T3 were used as substrate. Anodizing was carried out using chromic acid. CrO3 sealing was conducted in CrO3 solution for 30, 60, 90, 120 and 150 minutes. As comparison, other specimens were also prepared as anodized and boiled water sealing. Thickness of the coating was observed by optical microscope. Anodized and sealing layer was analyzed by X- ray diffraction. The hardness of as anodized, boiled water sealing and CrO3 sealing were compared. The highest hardness is achieved by CrO3 sealed specimen and followed by boiled water sealing and as anodized specimens. The longer the processes of CrO3 sealing the higher layer thickness and therefore the higher hardness of the oxide layer. The best resistance to electrolyte penetration is achieved by the CrO3 sealed specimen followed by boiled water sealed and as anodized specimens. The higher thickness of oxide layer, the higher the resistance against electrolyte penetration.

Hafnium influence on the microstructure of FeCrAl alloys

NASA Astrophysics Data System (ADS)

Geanta, V.; Voiculescu, I.; Stanciu, E.-M.

2016-06-01

Due to their special properties at high temperatures, FeCrAl alloys micro-alloyed with Zr can be regarded as potential materials for use at nuclear power plants, generation 4R. These materials are resistant to oxidation at high temperatures, to corrosion, erosion and to the penetrating radiations in liquid metal environments. Also, these are able to form continuously, by the self-generation process of an oxide coating with high adhesive strength. The protective oxide layers must be textured and regenerable, with a good mechanical strength, so that crack and peeling can not appear. To improve the mechanical and chemical characteristics of the oxide layer, we introduced limited quantities of Zr, Ti, Y, Hf, Ce in the range of 1-3%wt in the FeCrAl alloy. These elements, with very high affinity to the oxygen, are capable to stabilize the alumina structure and to improve the oxide adherence to the metallic substrate. FeCrAl alloys microalloyed with Hf were prepared using VAR (Vacuum Arc Remelting) unit, under high argon purity atmosphere. Three different experimental alloys have been prepared using the same metallic matrix of Fe-14Cr-5Al, by adding of 0.5%wt Hf, 1.0%wt Hf and respectively 1.5%wt Hf. The microhardness values for the experimental alloys have been in the range 154 ... 157 HV0.2. EDAX analyses have been performed to determine chemical composition on the oxide layer and in the bulk of sample and SEM analyze has been done to determine the microstructural features. The results have shown the capacity of FeCrAl alloy to form oxide layers, with different texture and rich in elements such as Al and Hf.

Chromium Vaporization Reduction by Nickel Coatings For SOEC Interconnect Materials

DOE Office of Scientific and Technical Information (OSTI.GOV)

Michael V. Glazoff; Sergey N. Rashkeev; J. Stephen Herring

2014-09-01

The vaporization of Cr-rich volatile species from interconnect materials is a major source of degradation that limits the lifetime of planar solid oxide devices systems with metallic interconnects, including Solid Oxide Electrolysis Cells, or SOECs. Some metallic coatings (Ni, Co, and Cu) significantly reduce the Cr release from interconnects and slow down the oxide scale growth on the steel substrate. To shed additional light upon the mechanisms of such protection and find a suitable coating material for ferritic stainless steel materials, we used a combination of first-principles calculations, thermodynamics, and diffusion modeling to investigate which factors determine the quality ofmore » the Ni metallic coating at stainless steel interconnector. We found that the Cr migration in Ni coating is determined by a delicate combination of the nickel oxidation, Cr diffusion, and phase transformation processes. Although the formation of Cr2O3 oxide is more exothermic than that of NiO, the kinetic rate of the chromia formation in the coating layer and its surface is significantly reduced by the low mobility of Cr in nickel oxide and in NiCr2O4 spinel. These results are in a good agreement with diffusion modeling for Cr diffusion through Ni coating layer on the ferritic 441 steel substrate.« less

Auger electron spectroscopy study of oxidation of a PdCr alloy used for high-temperature sensors

NASA Technical Reports Server (NTRS)

Boyd, Darwin L.; Zeller, Mary V.; Vargas-Aburto, Carlos

1993-01-01

A Pd-13 wt. percent Cr solid solution is a promising high-temperature strain gage alloy. In bulk form it has a number of properties that are desirable in a resistance strain gage material, such as a linear electrical resistance versus temperature curve to 1000 C and stable electrical resistance in air at 1000 C. However, unprotected fine wire gages fabricated from this alloy perform well only to 600 C. At higher temperatures severe oxidation degrades their electrical performance. In this work Auger electron spectroscopy was used to study the oxidation chemistry of the alloy wires and ribbons. Results indicate that the oxidation is caused by a complex mechanism that is not yet fully understood. As expected, during oxidation, a layer of chromium oxide is formed. This layer, however, forms beneath a layer of metallic palladium. The results of this study have increased the understanding of the oxidation mechanism of Pd-13 wt. percent Cr.

Observations on the oxidation of Mn-modified Ni-base Haynes 230 alloy under SOFC exposure conditions

DOE Office of Scientific and Technical Information (OSTI.GOV)

Yang, Z Gary; Xia, Gordon; Stevenson, Jeffry W.

2005-07-01

The commercial Ni-base Haynes 230 alloy (Ni-Cr-Mo-W-Mn) was modified with two increased levels of Mn (1 and 2 wt per cent) and evaluated for its oxidation resistance under simulated SOFC interconnect exposure conditions. Oxidation rate, oxide morphology, oxide conductivity and thermal expansion were measured and compared with commercial Haynes 230. It was observed that additions of higher levels of Mn to the bulk alloy facilitated the formation of a bi-layered oxide scale that was comprised of an outer M3O4 (M=Mn, Cr, Ni) spinel-rich layer at the oxide – gas interface over a Cr2O3-rich sub-layer at the metal – oxide interface.more » The modified alloys showed higher oxidation rates and the formation of thicker oxide scales compared to the base alloy. The formation of a spinel-rich top layer improved the scale conductivity, especially during the early stages of the oxidation, but the higher scale growth rate resulted in an increase in the area-specific electrical resistance over time. Due to their face-centered cubic crystal structure, both commercial and modified alloys demonstrated a coefficient of thermal expansion that was higher than that of typical anode-supported and electrolyte-supported SOFCs.« less

New Creep-Resistant Cast Alloys with Improved Oxidation Resistance in Water Vapor at 650–800°C

DOE PAGES

Dryepondt, Sebastien; Pint, Bruce A.; Maziasz, Philip J.

2015-08-13

Cast stainless steel CF8C-Plus (19wt%Cr/12%Ni) has excellent creep properties, but limited oxidation resistance above 700 C in environments containing H 2O. One strategy to improve the alloy oxidation performance is to increase the Cr and Ni concentration. Two new alloys, with, respectively, 21wt%Cr 15wt%Ni and 22wt%Cr 17.5wt%Ni were therefore developed and their long-term oxidation behaviors in humid air were compared with the oxidation behavior of five other cast alloys. Also, at 650 C and 700 C, all the alloys formed internal Cr-rich nodules, and outer nodules or layers rich in Fe and Ni, but they grew a protective Cr-rich innermore » layer over time. At 750 C, the lower alloyed steels such as CF8C-Plus showed large metal losses, but the two new alloys still exhibited a protective oxidation behavior. The 21Cr 15Ni alloy was severely oxidized in locations at 800 C, but that was not the case for the 22Cr 17.5Ni alloy. Thus, the two new modified alloys represent a potential operating temperature gain of, respectively, 50 C and 100 C in aggressive environments compared with the CF8C-Plus alloy.« less

Effects of iron content in Ni-Cr-xFe alloys and immersion time on the oxide films formed in a simulated PWR water environment

NASA Astrophysics Data System (ADS)

Ru, Xiangkun; Lu, Zhanpeng; Chen, Junjie; Han, Guangdong; Zhang, Jinlong; Hu, Pengfei; Liang, Xue

2017-12-01

The iron content in Ni-Cr-xFe (x = 0-9 at.%) alloys strongly affected the properties of oxide films after 978 h of immersion in the simulated PWR primary water environment at 310 °C. Increasing the iron content in the alloys increased the amount of iron-bearing polyhedral spinel oxide particles in the outer oxide layer and increased the local oxidation penetrations into the alloy matrix from the chromium-rich inner oxide layer. The effects of iron content in the alloys on the oxide film properties after 500 h of immersion were less significant than those after 978 h. Iron content increased, and chromium content decreased, in the outer oxide layer with increasing iron content in the alloys. Increasing the immersion time facilitated the formation of the local oxidation penetrations along the matrix/film interface and the nickel-bearing spinel oxides in the outer oxide layer.

Anomalous temperature dependence of training effect in specular spin valve using ultrathin Cr2O3-nano-oxide layer with magnetoelectric effect

NASA Astrophysics Data System (ADS)

Sawada, Kazuya; Shimomura, Naoki; Doi, Masaaki; Sahashi, Masashi

2010-05-01

Exchange bias from antiferromagnetic (AFM) oxides with a magnetoelectric (ME) effect has been studied for controlling ferromagnetic (FM) magnetizations by an applying electric field. However, thick ME oxides are needed for realizing the electrically controlled exchange biasing. Therefore, in this study the temperature dependencies of the training effect for the Cr2O3-nano-oxide-layer (NOL) are investigated for confirming the ME effect of the Cr2O3-NOL. The anomalous temperature tendencies of system dependent constant for exchange bias and magnetoresistance (MR), κHex and κMR, were observed, which are probably originated from the ME effect of the Cr2O3-NOL because (1) these anomalous temperature tendencies could not be obtained in the CoO-NOL spin valve and (2) the κHex and κMR are defined as the strength of the coupling between FM and AFM spins. It is remarkable result for us to confirm the possibility of the ME effect from the ultrathin Cr2O3 layer (less than 1 nm) because the ME effect was observed in only thick ME materials.

Composite oxygen transport membrane

DOEpatents

Lu, Zigui; Plonczak, Pawel J.; Lane, Jonathan A.

2016-11-08

A method is described of producing a composite oxygen ion membrane and a composite oxygen ion membrane in which a porous fuel oxidation layer and a dense separation layer and optionally, a porous surface exchange layer are formed on a porous support from mixtures of (Ln.sub.1-xA.sub.x).sub.wCr.sub.1-yB.sub.yO.sub.3-.delta. and a doped zirconia. Preferred materials are (La.sub.0.8Sr.sub.0.2).sub.0.95Cr.sub.0.7Fe.sub.0.3O.sub.3-.delta. for the porous fuel oxidation layer, (La.sub.0.8Sr.sub.0.2).sub.0.95Cr.sub.0.5Fe.sub.0.5O.sub.3-.delta. for the dense separation layer, and (La.sub.0.8Sr.sub.0.2).sub.0.95Cr.sub.0.3Fe.sub.0.7O.sub.3-.delta. for the porous surface exchange layer. Firing the said fuel activation and separation layers in nitrogen atmosphere unexpectedly allows the separation layer to sinter into a fully densified mass.

Critical temperature determination of detectable Cr diffusion enhancement by nanostructure through structural evolution analysis of the oxide films at 25-450 °C on 304 stainless steel

NASA Astrophysics Data System (ADS)

Gui, Y.; Meng, X. B.; Zheng, Z. J.; Gao, Y.

2017-10-01

The structural evolution of the oxide films at 25-450 °C on nanocrystalline (NC) and coarse crystalline (CC) 304 stainless steels (SS) was investigated. The structure of the oxide film on both NC and CC SSs was observed to undergo transient processes from a bi-layer to a single-layer and then back to a bi-layer when the temperature changed from the low range (25-150 °C) to the medium range (150-300 °C) and subsequently to the high range (300-450 °C), respectively. These formation mechanisms of the oxide films on SS were attributed to the different diffusion properties of Cr and Fe in the three temperature ranges. The thickness of the oxide films was similar between the NC and CC SSs below 300 °C due to their similar Crox/Feox concentration ratios in their oxide films at this temperature. Above 300 °C, Cr diffusion enhancement in the NC matrix led to a higher Crox/Feox ratio and better compactness of the oxide film, which resulted in a slower atomic diffusion rate in the oxide film and a thinner oxide film. Therefore, the temperature of 300 °C was concluded to be the critical temperature of the detectable Cr diffusion enhancement in the NC SS compared to the CC SS.

Stability domain of alumina thermally grown on Fe-Cr-Al-based model alloys and modified surface layers exposed to oxygen-containing molten Pb

NASA Astrophysics Data System (ADS)

Jianu, A.; Fetzer, R.; Weisenburger, A.; Doyle, S.; Bruns, M.; Heinzel, A.; Hosemann, P.; Mueller, G.

2016-03-01

The paper gives experimental results concerning the morphology, composition, structure and thickness of the oxide scales grown on Fe-Cr-Al-based bulk alloys during exposure to oxygen-containing molten lead. The results are discussed and compared with former results obtained on Al-containing surface layers, modified by melting with intense pulsed electron beam and exposed to similar conditions. The present and previous results provide the alumina stability domain and also the criterion of the Al/Cr ratio for the formation of a highly protective alumina layer on the surface of Fe-Cr-Al-based alloys and on modified surface layers exposed to molten lead with 10-6 wt.% oxygen at 400-600 °C. The protective oxide scales, grown on alumina-forming Fe-Cr-Al alloys under the given experimental conditions, were transient aluminas, namely, kappa-Al2O3 and theta-Al2O3.

Nucleation of graphene layers on magnetic oxides: Co 3O 4(111) and Cr 2O 3(0001) from theory and experiment

DOE Office of Scientific and Technical Information (OSTI.GOV)

Beatty, John; Cheng, Tao; Cao, Yuan

We report directly grown strongly adherent graphene on Co 3O 4(111) by carbon molecular beam epitaxy (C MBE) at 850 K and density functional theory (DFT) findings that the first graphene layer is reconstructed to fit the Co 3O 4 surface, while subsequent layers retain normal graphene structure. This adherence to the Co 3O 4 structure results from partial bonding of half the carbons to top oxygens of the substrate. This structure is validated by X-ray photoelectron spectroscopy and low-energy electron diffraction studies, showing layer-by-layer graphene growth with ~0.08 electrons/carbon atom transferred to the oxide from the first graphene layer,more » in agreement with DFT. In contrast, for Cr 2O 3 DFT finds no strong bonding to the surface and C MBE on Cr 2O 3(0001) yields only graphite formation at 700 K, with C desorption above 800 K. As a result, strong graphene-to-oxide charge transfer aids nucleation of graphene on incommensurate oxide substrates and may have implications for spintronics.« less

Nucleation of graphene layers on magnetic oxides: Co 3O 4(111) and Cr 2O 3(0001) from theory and experiment

DOE PAGES

Beatty, John; Cheng, Tao; Cao, Yuan; ...

2016-12-14

We report directly grown strongly adherent graphene on Co 3O 4(111) by carbon molecular beam epitaxy (C MBE) at 850 K and density functional theory (DFT) findings that the first graphene layer is reconstructed to fit the Co 3O 4 surface, while subsequent layers retain normal graphene structure. This adherence to the Co 3O 4 structure results from partial bonding of half the carbons to top oxygens of the substrate. This structure is validated by X-ray photoelectron spectroscopy and low-energy electron diffraction studies, showing layer-by-layer graphene growth with ~0.08 electrons/carbon atom transferred to the oxide from the first graphene layer,more » in agreement with DFT. In contrast, for Cr 2O 3 DFT finds no strong bonding to the surface and C MBE on Cr 2O 3(0001) yields only graphite formation at 700 K, with C desorption above 800 K. As a result, strong graphene-to-oxide charge transfer aids nucleation of graphene on incommensurate oxide substrates and may have implications for spintronics.« less

Performance evaluation of several commercial alloys in a reducing environment

NASA Astrophysics Data System (ADS)

Liu, Y.

Several commercial alloys including Ebrite, Crofer 22 APU, Haynes 230 and Haynes 242, which are candidates for intermediate-temperature solid oxide fuel cell (SOFC) interconnect materials, were isothermally and cyclically oxidized at 900 °C in the reducing atmosphere of Ar + 5 vol.% H 2 + 3 vol.% H 2O corresponding to the SOFC anode environment. Results indicate that these alloys exhibited good scale spallation resistance with the Ni-base alloys possessing better oxidation resistance over the Fe-base alloys. Both Mn-Cr spinel and Cr 2O 3 were formed in the oxide scales of these alloys. For Crofer 22 APU and Haynes 242, a continuous protective MnO and Mn-Cr spinel layer formed outside on the inner layer of Cr 2O 3. The increase in scale ASR after longer-term thermal exposure in the reducing environment was relatively slower for the Ni-base alloys than for the Fe-base alloys.

Corrosion Characteristics of Ni-Based Hardfacing Alloy Deposited on Stainless Steel Substrate by Laser Cladding

NASA Astrophysics Data System (ADS)

Awasthi, Reena; Abraham, Geogy; Kumar, Santosh; Bhattacharyya, Kaustava; Keskar, Nachiket; Kushwaha, R. P.; Rao, Ramana; Tewari, R.; Srivastava, D.; Dey, G. K.

2017-06-01

In this study, corrosion characteristics of a nickel-based Ni-Mo-Cr-Si hardfacing alloy having 32Mo, 15Cr, and 3Si (wt pct) as alloying elements, deposited on stainless steel SS316L substrate by laser cladding, have been presented. Corrosion behavior of the laser clad layer was evaluated in reducing (0.1 M HCl) and oxidizing (0.5 M HNO3) environments, in comparison with the reference substrate SS316L, using electrochemical potentiodynamic technique at room temperature. The corrosion mechanisms have been evaluated on the basis of microstructural and microchemical analysis using scanning electron microscopy attached with energy-dispersive spectrometry. Passivity behavior of the laser clad layer was studied in 0.5 M H2SO4, using the potentiostatic technique and analyzing the passive layer by X-ray photoelectron spectroscopy. Laser clad layer of Ni-Mo-Cr-Si exhibited higher pitting corrosion resistance in chloride (reducing) environment, indicated by much higher breakdown potential ( 0.8 VSCE) and the absence of pitting as compared to substrate SS316L ( 0.3 VSCE). However, in oxidizing (0.5 M HNO3) environment, both the laser clad layer and substrate SS316L showed excellent and similar corrosion resistance exhibiting high breakdown potential ( 0.85 VSCE) and wide passivation range ( 0.8 VSCE) with low passive current density ( 4 to 7 × 10-6 A/cm2). The stable passive layer formed on laser clad layer of Ni-Mo-Cr-Si after exposure in 0.5 M H2SO4 solution at constant potential 0.6 VSCE (within the passive range), consisted oxides of Mo as Mo+4 (MoO2) and Mo+6 (MoO4)-2, Cr as Cr3+ (mixture of both Cr2O3 and Cr (OH)3), and Si as Si4+(SiO2), which have contributed to passivation and repassivation and therefore excellent corrosion behavior.

Control of substrate oxidation in MOD cerawwwmic coating on low-activation ferritic steel with reduced-pressure atmosphere

NASA Astrophysics Data System (ADS)

Tanaka, Teruya; Muroga, Takeo

2014-12-01

An Er2O3 ceramic coating fabricated using the metal-organic decomposition (MOD) method on a Cr2O3-covered low-activation ferritic steel JLF-1 substrate was examined to improve hydrogen permeation barrier performance of the coating. The Cr2O3 layer was obtained before coating by heat treating the substrate at 700 °C under reduced pressures of <5 × 10-3 Pa and 5 Pa. The Cr2O3 layer was significantly stable even with heat treatment at 700 °C in air. This layer prevented further production of Fe2O3, which has been considered to degrade coating performance. An MOD Er2O3 coating with a smooth surface was successfully obtained on a Cr2O3-covered JLF-1 substrate by dip coating followed by drying and baking. Preprocessing to obtain a Cr2O3 layer would provide flexibility in the coating process for blanket components and ducts. Moreover, the Cr2O3 layer suppressed hydrogen permeation through the JLF-1 substrate. While further optimization of the coating fabrication process is required, it would be possible to suppress hydrogen permeation significantly by multilayers of Cr2O3 and MOD oxide ceramic.

Effects of alloy heat treatment on oxidation kinetics and scale morphology for Crofer 22 APU

NASA Astrophysics Data System (ADS)

Magdefrau, Neal J.; Chen, Lei; Sun, Ellen Y.; Aindow, Mark

2013-11-01

The effect of alloy heat treatment on the oxidation kinetics and oxide scale microstructure of Crofer 22 APU has been studied. Parabolic oxidation rate constants were measured for the as-received alloy and after pre-oxidation heat treatment in argon at 1050 °C for 1 and 4 h. The oxide scale microstructure was investigated using scanning electron microscopy, focused ion beam milling and transmission electron microscopy. It was found that the alloy forms a two-layer scale with a continuous chromia layer and a discontinuous MnCr2O4 overlayer. Two forms of internal oxides were also formed: subscale pockets of spinel and isolated TiOx precipitates in the underlying alloy. The pre-oxidation heat treatment had a profound effect on the grain size and morphology of the Cr2O3 and MnCr2O4 layers in the scale. The heat-treated samples exhibit a 3.5× lower parabolic oxidation rate constant than the as-received Crofer 22 APU. This improvement in oxidation resistance is attributed to the dramatic differences in the morphology of the oxide scale that forms during the earliest stages of oxidation (<5 h). The implications of these findings for oxidation mechanisms and long-term SOFC performance are discussed.

Preparation and Oxidation Performance of Y and Ce-Modified Cr Coating on open-cell Ni-Cr-Fe Alloy Foam by the Pack Cementation

NASA Astrophysics Data System (ADS)

Pang, Q.; Hu, Z. L.; Wu, G. H.

2016-12-01

Metallic foams with a high fraction of porosity, low density and high-energy absorption capacity are a rapidly emerging class of novel ultralight weight materials for various engineering applications. In this study, Y-Cr and Ce-Cr-coated Ni-Cr-Fe alloy foams were prepared via the pack cementation method, and the effects of Y and Ce addition on the coating microstructure and oxidation performance were analyzed in order to improve the oxidation resistance of open-cell nickel-based alloy foams. The results show that the Ce-Cr coating is relatively more uniform and has a denser distribution on the surface of the nickel-based alloy foam. The surface grains of the Ce-Cr-coated alloy foam are finer compared to those of the Y-Cr-coated alloy foam. An obvious Ce peak appears on the interface between the coating and the alloy foam strut, which gives rise to a "site-blocking" effect for the short-circuit transport of the cation in the substrate. X-ray diffraction analysis shows that the Y-Cr-coated alloy foam mainly consists of Cr, (Fe, Ni) and (Ni, Cr) phases in the surface layer. The Ce-Cr-coated alloy foam is mainly composed of Cr and (Ni, Cr) phases. Furthermore, the addition of Y and Ce clearly lead to an improvement in the oxidation resistance of the coated alloy foams in the temperature range of 900-1000 °C. The addition of Ce is especially effective in enhancing the diffusion of chromium to the oxidation front, thus, accelerating the formation of a Cr2O3 layer.

Behavior of an improved Zr fuel cladding with oxidation resistant coating under loss-of-coolant accident conditions

NASA Astrophysics Data System (ADS)

Park, Dong Jun; Kim, Hyun Gil; Jung, Yang Il; Park, Jung Hwan; Yang, Jae Ho; Koo, Yang Hyun

2016-12-01

This study investigates protective coatings for improving the high temperature oxidation resistance of Zr fuel claddings for light water nuclear reactors. FeCrAl alloy and Cr layers were deposited onto Zr plates and tubes using cold spraying. For the FeCrAl/Zr system, a Mo layer was introduced between the FeCrAl coating and the Zr matrix to prevent inter-diffusion at high temperatures. Both the FeCrAl and Cr coatings improved the oxidation resistance compared to that of the uncoated Zr alloy when exposed to a steam environment at 1200 °C. The ballooning behavior and mechanical properties of the coated cladding samples were studied under simulated loss-of-coolant accident conditions. The coated samples showed higher burst temperatures, lower circumferential strain, and smaller rupture openings compared to the uncoated Zr. Although 4-point bend tests of the coated samples showed a small increase in the maximum load, ring compression tests of a sectioned sample showed increased ductility.

Process for depositing Cr-bearing layer

DOEpatents

Ellis, Timothy W.; Lograsso, Thomas A.; Eshelman, Mark A.

1995-05-09

A method of applying a Cr-bearing layer to a substrate, comprises introducing an organometallic compound, in vapor or solid powder form entrained in a carrier gas to a plasma of an inductively coupled plasma torch or device to thermally decompose the organometallic compound and contacting the plasma and the substrate to be coated so as to deposit the Cr-bearing layer on the substrate. A metallic Cr, Cr alloy or Cr compound such as chromium oxide, nitride and carbide can be provided on the substrate. Typically, the organometallic compound is introduced to an inductively coupled plasma torch that is disposed in ambient air so to thermally decompose the organometallic compound in the plasma. The plasma is directed at the substrate to deposit the Cr-bearing layer or coating on the substrate.

Process for depositing Cr-bearing layer

DOEpatents

Ellis, T.W.; Lograsso, T.A.; Eshelman, M.A.

1995-05-09

A method of applying a Cr-bearing layer to a substrate, comprises introducing an organometallic compound, in vapor or solid powder form entrained in a carrier gas to a plasma of an inductively coupled plasma torch or device to thermally decompose the organometallic compound and contacting the plasma and the substrate to be coated so as to deposit the Cr-bearing layer on the substrate. A metallic Cr, Cr alloy or Cr compound such as chromium oxide, nitride and carbide can be provided on the substrate. Typically, the organometallic compound is introduced to an inductively coupled plasma torch that is disposed in ambient air so to thermally decompose the organometallic compound in the plasma. The plasma is directed at the substrate to deposit the Cr-bearing layer or coating on the substrate. 7 figs.

Suppressing the chromium disproportionation reaction in O3-type layered cathode materials for high capacity sodium-ion batteries

DOE Office of Scientific and Technical Information (OSTI.GOV)

Cao, Ming -Hui; Wang, Yong; Shadike, Zulipiya

Chromium-based layered cathode materials suffer from the irreversible disproportionation reaction of Cr 4+ to Cr 3+ and Cr 6+, which hinders the reversible multi-electron redox of Cr ions in layered cathodes, and limits their capacity and reversibility. To address this problem, a novel O3-type layer-structured transition metal oxide of NaCr 1/3Fe 1/3Mn 1/3O 2 (NCFM) was designed and studied as a cathode material. A high reversible capacity of 186 mA h g –1 was achieved at a current rate of 0.05C in a voltage range of 1.5 to 4.2 V. X-ray diffraction revealed an O3 → (O3 + P3) →more » (P3 + O3'') → O3'' phase-transition pathway for NCFM during charge. X-ray absorption, X-ray photoelectron and electron energy-loss spectroscopy measurements revealed the electronic structure changes of NCFM during Na + deintercalation/intercalation processes. It is confirmed that the disproportionation reaction of Cr 4+ to Cr 3+ and Cr 6+ can be effectively suppressed by Fe 3+ and Mn 4+ substitution. Lastly, these results demonstrated that the reversible multi-electron oxidation/reduction of Cr ions can be achieved in NCFM during charge and discharge accompanied by CrO 6 octahedral distortion and recovery.« less

Suppressing the chromium disproportionation reaction in O3-type layered cathode materials for high capacity sodium-ion batteries

DOE Office of Scientific and Technical Information (OSTI.GOV)

Cao, Ming-Hui; Wang, Yong; Shadike, Zulipiya

Chromium-based layered cathode materials suffer from the irreversible disproportionation reaction of Cr4+ to Cr3+ and Cr6+, which hinders the reversible multi-electron redox of Cr ions in layered cathodes, and limits their capacity and reversibility. To address this problem, a novel O3-type layer-structured transition metal oxide of NaCr1/3Fe1/3Mn1/3O2 (NCFM) was designed and studied as a cathode material. A high reversible capacity of 186 mA h g-1 was achieved at a current rate of 0.05C in a voltage range of 1.5 to 4.2 V. X-ray diffraction revealed an O3 → (O3 + P3) → (P3 + O3'') → O3'' phase-transition pathway formore » NCFM during charge. X-ray absorption, X-ray photoelectron and electron energy-loss spectroscopy measurements revealed the electronic structure changes of NCFM during Na+ deintercalation/intercalation processes. It is confirmed that the disproportionation reaction of Cr4+ to Cr3+ and Cr6+ can be effectively suppressed by Fe3+ and Mn4+ substitution. These results demonstrated that the reversible multi-electron oxidation/reduction of Cr ions can be achieved in NCFM during charge and discharge accompanied by CrO6 octahedral distortion and recovery.« less

Suppressing the chromium disproportionation reaction in O3-type layered cathode materials for high capacity sodium-ion batteries

DOE PAGES

Cao, Ming -Hui; Wang, Yong; Shadike, Zulipiya; ...

2017-02-14

Chromium-based layered cathode materials suffer from the irreversible disproportionation reaction of Cr 4+ to Cr 3+ and Cr 6+, which hinders the reversible multi-electron redox of Cr ions in layered cathodes, and limits their capacity and reversibility. To address this problem, a novel O3-type layer-structured transition metal oxide of NaCr 1/3Fe 1/3Mn 1/3O 2 (NCFM) was designed and studied as a cathode material. A high reversible capacity of 186 mA h g –1 was achieved at a current rate of 0.05C in a voltage range of 1.5 to 4.2 V. X-ray diffraction revealed an O3 → (O3 + P3) →more » (P3 + O3'') → O3'' phase-transition pathway for NCFM during charge. X-ray absorption, X-ray photoelectron and electron energy-loss spectroscopy measurements revealed the electronic structure changes of NCFM during Na + deintercalation/intercalation processes. It is confirmed that the disproportionation reaction of Cr 4+ to Cr 3+ and Cr 6+ can be effectively suppressed by Fe 3+ and Mn 4+ substitution. Lastly, these results demonstrated that the reversible multi-electron oxidation/reduction of Cr ions can be achieved in NCFM during charge and discharge accompanied by CrO 6 octahedral distortion and recovery.« less

Nitridation of a Super-Ferritic Stainless Steel for PEMFC Bipolar Plate

DOE Office of Scientific and Technical Information (OSTI.GOV)

Wang, H.; Turner, J. A.; Brady, M. P.

2007-01-01

AL29-4C alloy nitrided in pure nitrogen resulted in a nitrogen-modified oxide surface, which is the same as AISI446 nitrided under identical conditions. When the alloy was nitrided 24h at 900 C in N2-4H2, XRD and XPS analysis indicated that the surface layer consisted of a nitride outer layer ({approx}0.20 {micro}m) and an oxide inner layer ({approx} 0.82 {micro}m). According to XPS, the nitride outer layer is composed of CrN and [Cr(N),Fe]2N1-x, with much more Cr2N than Fe2N. Mn is migrated and enriched in the oxide inner layer and combined with chromium oxide.AL29-4C alloy nitrided in N2-4H2 resulted in low ICRmore » and excellent corrosion resistance in simulated PEMFC environments. Current was at ca. -3.0 {micro}A/cm2 in the PEMFC anode environment, and at ca. 0.3 {approx} 0.5 {micro}A/cm2 in the cathode environment. This is considered to be rather stable. After being polarized in a PEMFC environment, the ICR increased slightly compared with the as-nitrided sample, but was still rather low.« less

Thermochemical Compatibility and Oxidation Resistance of Advanced LWR Fuel Cladding

DOE PAGES

Besmann, T. M.; Yamamoto, Y.; Unocic, K. A.

2016-06-21

We assessed the thermochemical compatibility of potential replacement cladding materials for zirconium alloys in light water reactors. Considered were FeCrAl steel (similar to Kanthal APMT), Nb-1%Zr (similar to PWC-11), and a hybrid SiC-composite with a metallic barrier layer. The niobium alloy was also seen as requiring an oxidation protective layer, and a diffusion silicide was investigated. Metallic barrier layers for the SiC-composite reviewed included a FeCrAl alloy, Nb-1%Zr, and chromium. Thermochemical calculations were performed to determine oxidation behavior of the materials in steam, and for hybrid SiC-composites possible interactions between the metallic layer and SiC. Additionally, experimental exposures of SiC-alloymore » reaction couples at 673K, 1073K, and 1273K for 168 h in an inert atmosphere were made and microanalysis performed. Whereas all materials were determined to oxidize under higher oxygen partial pressures in the steam environment, these varied by material with expected protective oxides forming. Finally, the computed and experimental results indicate the formation of liquid phase eutectic in the FeCrAl-SiC system at the higher temperatures.« less

Effect of Layer-Graded Bond Coats on Edge Stress Concentration and Oxidation Behavior of Thermal Barrier Coatings

NASA Technical Reports Server (NTRS)

Zhu, Dongming; Ghosn, Louis J.; Miller, Robert A.

1998-01-01

Thermal barrier coating (TBC) durability is closely related to design, processing and microstructure of the coating Z, tn systems. Two important issues that must be considered during the design of a thermal barrier coating are thermal expansion and modulus mismatch between the substrate and the ceramic layer, and substrate oxidation. In many cases, both of these issues may be best addressed through the selection of an appropriate bond coat system. In this study, a low thermal expansion and layer-graded bond coat system, that consists of plasma-sprayed FeCoNiCrAl and FeCrAlY coatings, and a high velocity oxyfuel (HVOF) sprayed FeCrAlY coating, is developed to minimize the thermal stresses and provide oxidation resistance. The thermal expansion and oxidation behavior of the coating system are also characterized, and the strain isolation effect of the bond coat system is analyzed using the finite element method (FEM). Experiments and finite element results show that the layer-graded bond coat system possesses lower interfacial stresses. better strain isolation and excellent oxidation resistance. thus significantly improving the coating performance and durability.

Transmission Electron Microscopy (TEM) Study of the Oxide Layers Formed on Fe-12Cr-4Al Ferritic Alloy in an Oxygenated Pb-Bi Environment at 800°C

NASA Astrophysics Data System (ADS)

Popovic, M. P.; Yang, Y.; Bolind, A. M.; Ozdol, V. B.; Olmsted, D. L.; Asta, M.; Hosemann, P.

2018-06-01

Liquid lead-bismuth eutectic (LBE) can serve as a heat transfer fluid for advanced nuclear applications as well as concentrated solar power but poses corrosion challenges for the structural materials at elevated temperatures. Oxide passivation of the surfaces of these materials during exposure to liquid LBE can inhibit such material degradation. In this study, transmission electron microscopy of oxides formed on Fe-Cr-Al alloy during exposure to low-oxygenated LBE at 800°C has been performed. A complex structure of the oxide film has been revealed, consisting of a homogeneous inner layer of mostly Al2O3 and a heterogeneous outer layer.

Stability of Fe-Cr alloy interconnects under CH 4-H 2O atmosphere for SOFCs

NASA Astrophysics Data System (ADS)

Horita, Teruhisa; Xiong, Yueping; Yamaji, Katsuhiko; Sakai, Natsuko; Yokokawa, Harumi

The chemical stability of Fe-Cr alloys (ZMG232 and SUS430) was examined under humidified CH 4 gases at 1073 K to simulate the real anode atmosphere in SOFC operation. Surface microstructure change and oxide scale layer formation were observed on the oxidized Fe-Cr alloy surfaces. The main reaction products were Mn-Cr-(Fe) spinels for both alloys. Secondary ion mass spectrometry (SIMS) was applied to measure the elemental distribution of minor and major elements around the oxide scale/alloy interface. A high concentration of Mn on the oxide scale surface suggested the fast diffusion of Mn in the oxide scale to form the spinels. Annealing in CH 4-H 2O made the oxide scale thicker with duration time on the alloy surface. The parabolic growth rates ( kp) of oxide scale layer were evaluated from the thickness of oxide scales by secondary ion mass spectrometry (SIMS) depth profiles, which were calculated to the following: kp=6.25×10 -6 μm 2/s for SUS430 and kp=4.42×10 -6 μm 2/s for ZMG232. The electrical conductivity of oxidized alloys showed the semi-conductor temperature dependence for both alloys. The electrical conductivity of oxidized ZMG232 alloy was higher than that of oxidized SUS430.

Composite oxygen transport membrane

DOEpatents

Christie, Gervase Maxwell; Lane, Jonathan A.

2014-08-05

A method of producing a composite oxygen ion membrane and a composite oxygen ion membrane in which a porous fuel oxidation layer and a dense separation layer and optionally, a porous surface exchange layer are formed on a porous support from mixtures of (Ln.sub.1-xA.sub.x).sub.wCr.sub.1-yB.sub.yO.sub.3-.delta. and a doped zirconia. In the porous fuel oxidation layer and the optional porous surface exchange layer, A is Calcium and in the dense separation layer A is not Calcium and, preferably is Strontium. Preferred materials are (La.sub.0.8Ca.sub.0.2).sub.0.95Cr.sub.0.5Mn.sub.0.5O.sub.3-.delta. for the porous fuel oxidation and optional porous surface exchange layers and (La.sub.0.8Sr.sub.0.2).sub.0.95Cr.sub.0.5Fe.sub.0.5O.sub.3-.delta. for the dense separation layer. The use of such materials allows the membrane to sintered in air and without the use of pore formers to reduce membrane manufacturing costs. The use of materials, as described herein, for forming the porous layers have application for forming any type of porous structure, such as a catalyst support.

Composite oxygen transport membrane

DOEpatents

Christie, Gervase Maxwell; Lane, Jonathan A.

2016-11-15

A method of producing a composite oxygen ion membrane and a composite oxygen ion membrane in which a porous fuel oxidation layer and a dense separation layer and optionally, a porous surface exchange layer are formed on a porous support from mixtures of (Ln.sub.1-xA.sub.x).sub.wCr.sub.1-yB.sub.yO.sub.3-.delta. and a doped zirconia. In the porous fuel oxidation layer and the optional porous surface exchange layer, A is Calcium and in the dense separation layer A is not Calcium and, preferably is Strontium. Preferred materials are (La.sub.0.8Ca.sub.0.2).sub.0.95Cr.sub.0.5Mn.sub.0.5O.sub.3-.delta. for the porous fuel oxidation and optional porous surface exchange layers and (La.sub.0.8Sr.sub.0.2).sub.0.95Cr.sub.0.5Fe.sub.0.5O.sub.3-.delta. for the dense separation layer. The use of such materials allows the membrane to sintered in air and without the use of pore formers to reduce membrane manufacturing costs. The use of materials, as described herein, for forming the porous layers have application for forming any type of porous structure, such as a catalyst support.

Preparation and performances of Co-Mn spinel coating on a ferritic stainless steel interconnect material for solid oxide fuel cell application

NASA Astrophysics Data System (ADS)

Zhang, H. H.; Zeng, C. L.

2014-04-01

Ferritic stainless steels have become the candidate materials for interconnects of intermediate temperature solid oxide fuel cell (SOFC). The present issues to be solved urgently for the application of ferritic stainless steel interconnects are their rapid increase in contact resistance and Cr poisoning. In the present study, a chloride electrolyte suspension has been developed to electro-deposit a Co-Mn alloy on a type 430 stainless steel, followed by heat treatment at 750 °C in argon and at 800 °C in air to obtain Co-Mn spinel coatings. The experimental results indicate that an adhesive and compact Co-Mn alloy layer can be deposited in the chloride solution. After heat treatment, a complex coating composed of an external MnCo2O4 layer and an inner Cr-rich oxide layer has been formed on 430SS. The coating improves the oxidation resistance of the steel at 800 °C in air, especially in wet air, and inhibits the outward diffusion of Cr from the Cr-rich scale. Moreover, a low contact resistance has been achieved with the application of the spinel coatings.

In-depth evolution of chemical states and sub-10-nm-resolution crystal orientation mapping of nanograins in Ti(5 nm)/Au(20 nm)/Cr(3 nm) tri-layer thin films

NASA Astrophysics Data System (ADS)

Zhu, Xiaoli; Todeschini, Matteo; Bastos da Silva Fanta, Alice; Liu, Lintao; Jensen, Flemming; Hübner, Jörg; Jansen, Henri; Han, Anpan; Shi, Peixiong; Ming, Anjie; Xie, Changqing

2018-09-01

The applications of Au thin films and their adhesion layers often suffer from a lack of sufficient information about the chemical states of adhesion layers and about the high-lateral-resolution crystallographic morphology of Au nanograins. Here, we demonstrate the in-depth evolution of the chemical states of adhesive layers at the interfaces and the crystal orientation mapping of gold nanograins with a lateral resolution of less than 10 nm in a Ti/Au/Cr tri-layer thin film system. Using transmission electron microscopy, the variation in the interdiffusion at Cr/Au and Ti/Au interfaces was confirmed. From X-ray photoelectron spectroscopy (XPS) depth profiling, the chemical states of Cr, Au and Ti were characterized layer by layer, suggesting the insufficient oxidation of the adhesive layers. At the interfaces the Au 4f peaks shift to higher binding energies and this behavior can be described by a proposed model based on electron reorganization and substrate-induced final-state neutralization in small Au clusters supported by the partially oxidized Ti layer. Utilizing transmission Kikuchi diffraction (TKD) in a scanning electron microscope, the crystal orientation of Au nanograins between two adhesion layers was non-destructively characterized with sub-10 nm spatial resolution. The results provide nanoscale insights into the Ti/Au/Cr thin film system and contribute to our understanding of its behavior in nano-optic and nano-electronic devices.

Intermediate coating layer for high temperature rubbing seals for rotary regenerators

DOEpatents

Schienle, James L.; Strangman, Thomas E.

1995-01-01

A metallic regenerator seal is provided having multi-layer coating comprising a NiCrAlY bond layer, a yttria stabilized zirconia (YSZ) intermediate layer, and a ceramic high temperature solid lubricant surface layer comprising zinc oxide, calcium fluoride, and tin oxide. Because of the YSZ intermediate layer, the coating is thermodynamically stable and resists swelling at high temperatures.

Role of Y in the oxidation resistance of CrAlYN coatings

NASA Astrophysics Data System (ADS)

Domínguez-Meister, S.; El Mrabet, S.; Escobar-Galindo, R.; Mariscal, A.; Jiménez de Haro, M. C.; Justo, A.; Brizuela, M.; Rojas, T. C.; Sánchez-López, J. C.

2015-10-01

CrAlYN coatings with different aluminum (4-12 at.%) and yttrium (2-5 at.%) contents are deposited by d.c. reactive magnetron sputtering on silicon and M2 steel substrates using metallic targets and Ar/N2 mixtures. The influence of the nanostructure and chemical elemental distribution on the oxidation resistance after heating in air at 1000 °C is studied by means of cross-sectional scanning electron microscopy (X-SEM), energy dispersive X-ray analysis (EDX), X-ray diffraction (XRD) and glow discharge optical emission spectroscopy (GD-OES). The sequential exposure to the metallic targets during the synthesis leads to a multilayer structure where concentration of metallic elements (Cr, Al and Y) is changing periodically. A good oxidation resistance is observed when Al- and Y-rich regions are separated by well-defined CrN layers, maintaining crystalline coherence along the columnar structure. This protective behavior is independent of the type of substrate and corresponds to the formation of a thin mixed (Al, Cr)-oxide scale that protects the film underneath. The GD-OES and XRD analysis have demonstrated that Y acts as a reactive element, blocking the Fe and C atoms diffusion from the steel and favoring higher Al/Cr ratio in the passivation layer after heating. The coating with Y content around 4 at.% exhibited the best performance with a thinner oxide scale, a delay in the CrN decomposition and transformation to Cr2N, and a more effective Fe and C blocking.

The effect of chloride ions on the corroded surface layer of 00Cr22Ni5Mo3N duplex stainless steel under cavitation.

PubMed

Wan, Tong; Xiao, Ning; Shen, Hanjie; Yong, Xingyue

2016-11-01

The effects of Cl(-) on the corroded surface layer of 00Cr22Ni5Mo3N duplex stainless steel under cavitation in chloride solutions were investigated using nanoindentation in conjunction with XRD and XPS. The results demonstrate that Cl(-) had a strong effect on the nano-mechanical properties of the corroded surface layer under cavitation, and there was a threshold Cl(-) concentration. Furthermore, a close relationship between the nano-mechanical properties and the cavitation corrosion resistance of 00Cr22Ni5Mo3N duplex stainless steel was observed. The degradation of the nano-mechanical properties of the corroded surface layer was accelerated by the synergistic effect between cavitation erosion and corrosion. A key factor was the adsorption of Cl(-), which caused a preferential dissolution of the ferrous oxides in the passive film layer on the corroded surface layer. Cavitation further promoted the preferential dissolution of the ferrous oxides in the passive film layer. Simultaneously, cavitation accelerated the erosion of the ferrite in the corroded surface layer, resulting in the degradation of the nano-mechanical properties of the corroded surface layer on 00Cr22Ni5Mo3N duplex stainless steel under cavitation. Copyright © 2016. Published by Elsevier B.V.

Contact Sensor Attachment to Titanium Metal Composites

NASA Technical Reports Server (NTRS)

Vargas-Aburto, Carlos

1997-01-01

A Pd-13wt%Cr solid solution is a promising high-temperature strain gage alloy. In bulk form it has a number of properties that are desirable in a resistance strain gage material, such as a linear electrical-resistance-versus-temperature curve to 1000 C and stable electrical resistance in air at 1000 C. However, unprotected fine wire gages fabricated from this alloy perform well only to 600 C. At higher temperatures severe oxidation degrades their electrical performance. In this work Auger electron spectroscopy has been used to study the oxidation chemistry of the alloy wires and ribbons. Results indicate that the oxidation is caused by a complex mechanism that is not yet fully understood. As expected, during oxidation, a layer of chromium oxide is formed. This layer, however, forms beneath a layer of metallic palladium. The results of this study have increased the understanding of the oxidation mechanism of Pd-13wt%Cr.

Influence of Bond Coat on HVOF-Sprayed Gradient Cermet Coating on Copper Alloy

NASA Astrophysics Data System (ADS)

Ke, Peng; Cai, Fei; Chen, Wanglin; Wang, Shuoyu; Ni, Zhenhang; Hu, Xiaohong; Li, Mingxi; Zhu, Guanghong; Zhang, Shihong

2017-06-01

Coatings are required on mold copper plates to prolong their service life through enhanced hardness, wear resistance, and oxidation resistance. In the present study, NiCr-30 wt.%Cr3C2 ceramic-metallic (cermet) layers were deposited by high velocity oxy-fuel (HVOF) spraying on different designed bond layers, including electroplated Ni, HVOF-sprayed NiCr, and double-decker Ni-NiCr. Annealing was also conducted on the gradient coating (GC) with NiCr bond layer to improve the wear resistance and adhesion strength. Coating microstructure was investigated by scanning electron microscopy and x-ray diffraction analysis. Mechanical properties including microhardness, wear resistance, and adhesion strength of the different coatings were evaluated systematically. The results show that the types of metallic bond layer and annealing process had a significant impact on the mechanical properties of the GCs. The GCs with electroplated Ni bond layer exhibited the highest adhesion strength (about 70 MPa). However, the GC with HVOF-sprayed NiCr bond layer exhibited better wear resistance. The wear resistance and adhesion strength of the coating with NiCr metallic bond layer were enhanced after annealing.

The reactive element effect of yttrium and yttrium silicon on high temperature oxidation of NiCrAl coating

NASA Astrophysics Data System (ADS)

Ramandhany, S.; Sugiarti, E.; Desiati, R. D.; Martides, E.; Junianto, E.; Prawara, B.; Sukarto, A.; Tjahjono, A.

2018-03-01

The microstructure formed on the bond coat affects the oxidation resistance, particularly the formation of a protective oxide layer. The adhesion of bond coat and TGO increased significantly by addition of reactive element. In the present work, the effect of yttrium and yttrium silicon as reactive element (RE) on NiCrAl coating was investigated. The NiCrAl (without RE) and NiCrAlX (X:Y or YSi) bond coating were deposited on Hastelloy C-276 substrate by High Velocity Oxygen Fuel (HVOF) method. Isothermal oxidation was carried out at 1000 °C for 100 hours. The results showed that the addition of RE could prevent the breakaway oxidation. Therefore, the coating with reactive element were more protective against high temperature oxidation. Furthermore, the oxidation rate of NiCrAlY coating was lower than NiCrAlYSi coating with the total mass change was ±2.394 mg/cm2 after 100 hours of oxidation. The thickness of oxide scale was approximately 1.18 μm consisting of duplex oxide scale of spinel NiCr2O4 in outer scale and protective α-Al2O3 in inner scale.

Pulsed Laser Deposited Ferromagnetic Chromium Dioxide thin Films for Applications in Spintronics

NASA Astrophysics Data System (ADS)

Dwivedi, S.; Jadhav, J.; Sharma, H.; Biswas, S.

Stable rutile type tetragonal chromium dioxide (CrO2) thin films have been deposited on lattice-matched layers of TiO2 by KrF excimer laser based pulsed laser deposition (PLD) technique using Cr2O3 target. The TiO2 seed layer was deposited on oxidized Si substrates by the same PLD process followed by annealing at 1100 °C for 4 h. The lattice-matched interfacial layer is required for the stabilization of Cr (IV) phase in CrO2, since CrO2 behaves as a metastable compound under ambient conditions and readily converts into its stable phase of Cr (III) oxide, Cr2O3. Analyses with X-ray diffraction (XRD), Glancing-angle XRD (GIXRD), Raman spectroscopy and grazing-angle Fourier transform infra-red (FTIR) spectroscopy confirm the presence of tetragonal CrO2 phase in the as-deposited films. Microstructure and surface morphology in the films were studied with field emission scanning electron microscope (FESEM) and atomic force microscope (AFM). Electrical and magnetic characterizations of the films were performed at room temperature. Such type of stable half-metallic CrO2 thin films with low field magnetoresistive switching behaviour are in demand for applications as diverse as spin-FETs, magnetic sensors, and magneto-optical devices.

The Influence of Plasma-Based Nitriding and Oxidizing Treatments on the Mechanical and Corrosion Properties of CoCrMo Biomedical Alloy

NASA Astrophysics Data System (ADS)

Noli, Fotini; Pichon, Luc; Öztürk, Orhan

2018-04-01

Plasma-based nitriding and/or oxidizing treatments were applied to CoCrMo alloy to improve its surface mechanical properties and corrosion resistance for biomedical applications. Three treatments were performed. A set of CoCrMo samples has been subjected to nitriding at moderate temperatures ( 400 °C). A second set of CoCrMo samples was oxidized at 395 °C in pure O2. The last set of CoCrMo samples was nitrided and subsequently oxidized under the experimental conditions of previous sets (double treatment). The microstructure and morphology of the layers formed on the CoCrMo alloy were investigated by X-ray diffraction, Atomic Force Microscopy, and Scanning Electron Microscopy. In addition, nitrogen and oxygen profiles were determined by Glow Discharge Optical Emission Spectroscopy, Rutherford Backscattering Spectroscopy, Energy-Dispersive X-ray, and Nuclear Reaction Analysis. Significant improvement of the Vickers hardness of the CoCrMo samples after plasma nitriding was observed due to the supersaturated nitrogen solution and the formation of an expanded FCC γ N phase and CrN precipitates. In the case of the oxidized samples, Vickers hardness improvement was minimal. The corrosion behavior of the samples was investigated in simulated body fluid (0.9 pct NaCl solution at 37 °C) using electrochemical techniques (potentiodynamic polarization and cyclic voltammetry). The concentration of metal ions released from the CoCrMo surfaces was determined by Instrumental Neutron Activation Analysis. The experimental results clearly indicate that the CoCrMo surface subjected to the double surface treatment consisting in plasma nitriding and plasma oxidizing exhibited lower deterioration and better resistance to corrosion compared to the nitrided, oxidized, and untreated samples. This enhancement is believed to be due to the formation of a thicker and more stable layer.

Strain-tolerant ceramic coated seal

DOEpatents

Schienle, James L.; Strangman, Thomas E.

1994-01-01

A metallic regenerator seal is provided having multi-layer coating comprising a NiCrAlY bond layer, a yttria stabilized zirconia (YSZ) intermediate layer, and a ceramic high temperature solid lubricant surface layer comprising zinc oxide, calcium fluoride, and tin oxide. An array of discontinuous grooves is laser machined into the outer surface of the solid lubricant surface layer making the coating strain tolerant.

Physical properties of spin-valve films grown on naturally oxidized metal nano-oxide surfaces

NASA Astrophysics Data System (ADS)

Mao, Ming; Cerjan, Charlie; Kools, Jacques

2002-05-01

The physical properties of spin-valve films NiFe 25 Å/CoFe 10 Å/Cu(tCu)/CoFe 30 Å/IrMn 70 Å/Ta 20 Å with graded Cu layer thickness (tCu=18-45 Å) grown on the surface of metal nano-oxide layers (NOLs) were studied. The NOLs were formed from ultrathin Al, Cr, Cu, Nb, Ta, CoFe, NiFe, and NiFeCr layers by natural oxidation. The growth of the spin-valve films on NOLs has led to an enhancement in giant magnetoresistance value by up to 48%. A corresponding reduction in minimum film resistance by over 10% confirms that this enhancement originates from an increase in the mean free path of spin-polarized electrons due to the resultant specular reflection at the nano-oxide surfaces. A wide spectrum of oscillatory interlayer exchange coupling dependence on tCu for these NOL-bearing films suggests that a specular nano-oxide surface does not necessarily result in a smoother multilayer structure. The observation of an enhanced exchange biasing among these spin-valve films appears in contradiction to the observed deterioration of their crystallographic quality. As an important application, TaOx, CrOx, and NbOx could be employed as an alternative to AlOx as the barrier layer for magnetic tunnel junctions.

Stability of Phosphonic Self Assembled Monolayers (SAMs) on Cobalt Chromium (Co-Cr) Alloy under Oxidative conditions

PubMed Central

Bhure, Rahul; Abdel-Fattah, Tarek M.; Bonner, Carl; Hall, Felicia; Mahapatro, Anil

2011-01-01

Cobalt Chromium (Co-Cr) alloys has been widely used in the biomedical arena for cardiovascular, orthopedic and dental applications. Surface modification of the alloy allows us to tailor the interfacial properties to address critical challenges of Co-Cr alloy in medical applications. Self assembled monolayers (SAMs) of Octadecylphosphonic acid (ODPA) have been used to form thin films on the oxide layer of the Co-Cr alloy surface by solution deposition technique. The SAMs formed were investigated for their stability to oxidative conditions of ambient laboratory environment over periods of 1, 3, 7 and 14 days. The samples were then characterized for their stability using X-ray Photoelectron Spectroscopy (XPS), Atomic Force Microscopy (AFM) and Contact Angle Measurements. Detailed high energy XPS elemental scans confirmed the presence of the phosphonic monolayer after oxidative exposure which suggested that the SAMs were firmly attached to the oxide layer of Co-Cr alloy. AFM images gave topographical data of the surface and showed islands of SAMs on Co-Cr alloy surface, before and after SAM formation and also over the duration of the oxidative exposure. Contact angle measurements confirmed the hydrophobicity of the surface over 14 days. Thus the SAMs were found to be stable for the duration of the study. These SAMs could be subsequently tailored by modifying the terminal functional groups and could be used for various potential biomedical applications such as drug delivery, biocompatibility and tissue integration PMID:21603056

Long term high temperature oxidation characteristics of La and Cu alloyed ferritic stainless steels for solid oxide fuel cell interconnects

NASA Astrophysics Data System (ADS)

Swaminathan, Srinivasan; Lee, Young-Su; Kim, Dong-Ik

2016-09-01

To ensure the best performance of solid oxide fuel cell metallic interconnects, the Fe-22 wt.% Cr ferritic stainless steels with various La contents (0.006-0.6 wt.%) and Cu addition (1.57 wt.%), are developed. Long-term isothermal oxidation behavior of these steels is investigated in air at 800 °C, for 2700 h. Chemistry, morphology, and microstructure of the thermally grown oxide scale are examined using XPS, SEM-EDX, and XRD techniques. Broadly, all the steels show a double layer consisting of an inner Cr2O3 and outer (Mn, Cr)3O4. Distinctly, in the La-added steels, binary oxides of Cr, Mn and Ti are found at the oxide scale surface together with (Mn, Cr)3O4. Furthermore, all La-varied steels possess the metallic Fe protrusions along with discontinuous (Mn, Cr)3O4 spinel zones at the oxide scale/metal interface and isolated precipitates of Ti-oxides in the underlying matrix. Increase of La content to 0.6 wt.% is detrimental to the oxidation resistance. For the Cu-added steel, Cu is found to segregate strongly at the oxide scale/metal interface which inhibits the ingress of oxygen thereby suppressing the subscale formation of (Mn, Cr)3O4. Thus, Cu addition to the Fe-22Cr ferritic stainless steels benefits the oxidation resistance.

Interfaces in Oxides Formed on NiAlCr Doped with Y, Hf, Ti, and B

DOE Office of Scientific and Technical Information (OSTI.GOV)

Boll, Torben; Unocic, Kinga A.; Pint, Bruce A.

Abstract This study applies atom probe tomography (APT) to analyze the oxide scales formed on model NiAlCr alloys doped with Hf, Y, Ti, and B. Due to its ability to measure small amounts of alloying elements in the oxide matrix and its ability to quantify segregation, t he technique offers a possibility for detailed studies of the dopant’s fate during high-temperature oxidation. Three model NiAlCr alloys with different additions of Hf, Y, Ti, and B were prepared and oxidized in O 2at 1,100°C for 100 h. All specimens showed an outer region consisting of different spinel oxides with relativelymore » small grains and the protective Al 2O 3-oxide layer below. APT analyses focused mainly on this protective oxide layer. In all the investigated samples segregation of both Hf and Y to the oxide grain boundaries was observed and quantified. Neither B nor Ti were observed in the alumina grains or at the analyzed interfaces. The processes of formation of oxide scales and segregation of the alloying elements are discussed. The experimental challenges of the oxide analyses by APT are also addressed.« less

Interfaces in Oxides Formed on NiAlCr Doped with Y, Hf, Ti, and B

DOE PAGES

Boll, Torben; Unocic, Kinga A.; Pint, Bruce A.; ...

2017-03-20

Abstract This study applies atom probe tomography (APT) to analyze the oxide scales formed on model NiAlCr alloys doped with Hf, Y, Ti, and B. Due to its ability to measure small amounts of alloying elements in the oxide matrix and its ability to quantify segregation, t he technique offers a possibility for detailed studies of the dopant’s fate during high-temperature oxidation. Three model NiAlCr alloys with different additions of Hf, Y, Ti, and B were prepared and oxidized in O 2at 1,100°C for 100 h. All specimens showed an outer region consisting of different spinel oxides with relativelymore » small grains and the protective Al 2O 3-oxide layer below. APT analyses focused mainly on this protective oxide layer. In all the investigated samples segregation of both Hf and Y to the oxide grain boundaries was observed and quantified. Neither B nor Ti were observed in the alumina grains or at the analyzed interfaces. The processes of formation of oxide scales and segregation of the alloying elements are discussed. The experimental challenges of the oxide analyses by APT are also addressed.« less

[Study on high temperature oxidation of Ni-Cr ceramic alloys. Effects of Cr and Mo].

PubMed

Mizutani, M

1990-03-01

The effects of Cr and Mo addition to Ni-Cr alloys on high temperature oxidation were investigated. The alloys were prepared with the composition of Cr ranging from 5 to 40 wt%. Also 2, 4 and 9 wt% of Mo was added to both Ni-5% Cr and Ni-20% Cr binary alloys. The alloys were heated at 800 degrees C, 900 degrees C and 1000 degrees C for 15 minutes in air, and the weight change after heat treatment was measured by electric automatic balance. The weight change during heating was measured by thermogravimetric measurement (TG). The products after heat treatment were characterized by X-ray diffraction and scanning electron microscopy (SEM). The results are summarized as follows: The Ni-Cr binary alloys were classified into three types of Cr ranging from 5 to 20 wt%, Cr 25% and Cr from 30 wt% to 40 wt% according to the weight gains with oxidation. In the case of the more than 25 wt% Cr content of the Ni-Cr binary alloys, the weight gain was extremely low and the heating temperature effects on the weight change were also small. X-ray diffraction study showed that NiO, NiCr2O4 and Cr2O3 formed on the surface of the Ni-Cr binary alloys whose composition of Cr ranged from 5 to 25 wt%, whereas NiO and NiCr2O4 rarely formed on the Ni-Cr binary alloys whose composition of Cr ranged from 30 to 40 wt%. This suggests that the formation of Cr2O3 prevents the formation of NiO on the alloy with a high Cr content. The weight gain of the Ni-Cr-Mo ternary alloys was smaller than that of the Ni-Cr binary alloys without Mo, and the temperature effects on the weight gain of the Ni-Cr-Mo ternary alloys were different for each Cr content. However, the effect of the amounts of Mo was small. NiO, NiCr2O4, Cr2O3 and MoO2 were identified by X-ray diffraction on the surface of the Ni-Cr-Mo ternary alloys. According to the SEM observation, it seems that NiO was formed at the outermost layer, both NiCr2O4 and Cr2O3 at the inside layer, and MoO2 at the innermost layer. The formation of both NiO and Cr2O3 on the Ni-Cr-Mo ternary alloys was restrained compared with that of the Ni-Cr binary alloys. However, the adhesion of oxides to the Ni-Cr-Mo ternary alloys was lower than that of the Ni-Cr binary alloys.

Evaluation of Ni-Cr-base alloys for SOFC interconnect applications

NASA Astrophysics Data System (ADS)

Yang, Zhenguo; Xia, Guan-Guang; Stevenson, Jeffry W.

To further understand the suitability of Ni-Cr-base alloys for solid oxide fuel cell (SOFC) interconnect applications, three commercial Ni-Cr-base alloys, Haynes 230, Hastelloy S and Haynes 242 were selected and evaluated for oxidation behavior under different exposure conditions, scale conductivity and thermal expansion. Haynes 230 and Hastelloy S, which have a relatively high Cr content, formed a thin scale mainly comprised of Cr 2O 3 and (Mn,Cr,Ni) 3O 4 spinels under SOFC operating conditions, demonstrating excellent oxidation resistance and a high scale electrical conductivity. In contrast, a thick double-layer scale with a NiO outer layer above a chromia-rich substrate was grown on Haynes 242 in moist air or at the air side of dual exposure samples, indicating limited oxidation resistance for the interconnect application. With a face-centered-cubic (FCC) substrate, all three alloys possess a coefficient of thermal expansion (CTE) that is higher than that of candidate ferritic stainless steels, e.g. Crofer22 APU. Among the three alloys, Haynes 242, which is heavily alloyed with W and Mo and contains a low Cr content, demonstrated the lowest average CTE at 13.1 × 10 -6 K -1 from room temperature to 800 °C, but it was also observed that the CTE behavior of Haynes 242 was very non-linear.

Sol-gel derived (La 0.8M 0.2)CrO 3 (M dbnd Ca, Sr) coating layer on stainless-steel substrate for use as a separator in intermediate-temperature solid oxide fuel cell

NASA Astrophysics Data System (ADS)

A Lee, E.; Lee, S.; Hwang, H. J.; Moon, J.-W.

A ceramic coating technique is applied to reduce the voltage drop caused by oxidation of the metallic separator (SUS444) in intermediate-temperature (IT) solid oxide fuel cell (SOFCs) systems. Precursor solutions for (La, Ca)CrO 3 (LCC) and (La, Sr)CrO 3 (LSC) coatings are prepared by adding nitric acid and ethylene glycol into an aqueous solution of lanthanum, strontium (or calcium) and chromium nitrates. Dried LCC and LSC gel films are heat-treated at 400-800 °C after dip-coating on the SUS444 substrate. XRD and Fourier-transform infrared (FT-IR) analysis is used to examine the crystallization behaviour and chemical structure of the precursor solution. The oxidation behaviour of the coated SUS444 substrate is compared with an uncoated SUS444 substrate. The oxidation of the SUS444 is inhibited by the LCC and LSC thin film layers.

Comparison of the Isothermal Oxidation Behavior of As-Cast Cu-17 Percent Cr and Cu-17 Percent Cr-5 Percent Al. Part 2; Scale Microstructures

NASA Technical Reports Server (NTRS)

Raj, S. V.

2008-01-01

The isothermal oxidation kinetics of as-cast Cu-17%Cr and Cu-17%Cr-5%Al in air were studied between 773 and 1173 K under atmospheric pressure. Details of the oxidation kinetics of these alloys were discussed in Part I. This paper analyzes the microstructures of the scale and its composition in an attempt to elucidate the oxidation mechanisms in these alloys. The scales formed on Cu-17%Cr specimens oxidized between 773 and 973 K consisted of external CuO and subsurface Cu2O layers. The total thickness of these scales varied from about 10 m at 773 K to about 450 m at 973 K. In contrast, thin scales formed on Cu-17%Cr-5%Al alloys oxidized between 773 and 1173 K. The exact nature of these scales could not be determined by x-ray diffraction but energy dispersive spectroscopy analyses were used to construct a scale composition map. Phenomenological oxidation mechanisms are proposed for the two alloys.

Comparison of the Isothermal Oxidation Behavior of As-Cast Cu-17 Percent Cr and Cu-17 Percent Cr-5 Percent Al Part II: Scale Microstructures

NASA Technical Reports Server (NTRS)

Raj, Sai V.

2008-01-01

The isothermal oxidation kinetics of as-cast Cu-17%Cr and Cu-17%Cr-5%Al in air were studied between 773 and 1173 K under atmospheric pressure. Details of the oxidation kinetics of these alloys were discussed in Part I. This paper analyzes the microstructures of the scale and its composition in an attempt to elucidate the oxidation mechanisms in these alloys. The scales formed on Cu-17%Cr specimens oxidized between 773 and 973 K consisted of external CuO and subsurface Cu2O layers. The total thickness of these scales varied from about 10 m at 773 K to about 450 m at 973 K. In contrast, thin scales formed on Cu-17%Cr-5%Al alloys oxidized between 773 and 1173 K. The exact nature of these scales could not be determined by x-ray diffraction but energy dispersive spectroscopy analyses were used to construct a scale composition map. Phenomenological oxidation mechanisms are proposed for the two alloys.

Fate of chromium in soil

DOE Office of Scientific and Technical Information (OSTI.GOV)

Prokisch, J.; Gyori, Z.; Kovacs, B.

The chromium cycle in soil was studied with speciation of chromium. The aim was to look for the possibilities the mobilization of chromium(III) and to measure the rate of chromate reduction in nature and pot and field experiments in Hungarian soils. The authors developed a sensitive and simple method for chromium speciation with a microcolumn connected an inductively coupled plasma atomic emission spectrometer. Detection limits are convenient to measure chromium forms in a 0.01 M CaCl{sub 2} extract of a contaminated soil, but it is not enough to measure that of the uncontaminated soils. CR(VI) as chromate anion is notmore » adsorbed on pH dependent temporary charges of clays but in strongly acidic soil. Therefore CR(VI) can be leached out easily from the top layer of soil and can be transported into the ground water. Chromate ion can be reduced to CR(III) by organic matter of soil in acidic medium. CR(VI) is more stable at higher pH and lower humus content. Thus the reduction much quicker in the upper, weakly acidic top layer. CR(VI) oxidizes the organic matter of soil. The rate of this reaction depends on pH values, the humus content of the soil and temperature. CR(III) leaching in different uncontaminated soils was studied too. There are 3 pathways of mobilization of Cr(III). When pH decreases in soil the CR(III) becomes more soluble, similarly to the aluminium(III) ion. When the soil contains large quantity of water soluble organic ligands, Cr makes complexes with them and complexes formed can be leached out from the top layer. The third possibility is the oxidation of CR(III) to Cr(VI). It could happen on surface of manganese dioxide in the well-aired top layer.« less

Effects of the accumulated annealing parameter on the corrosion characteristics of a Zr-0.5Nb-1.0Sn-0.5Fe-0.25Cr alloy

NASA Astrophysics Data System (ADS)

Baek, Jong Hyuk; Jeong, Yong Hwan; Kim, In Sup

2000-07-01

Corrosion behavior, hydrogen pickup, oxide microstructure, and precipitate characterization have been studied in order to investigate the effect of the accumulated annealing parameter on the corrosion characteristics in a Zr-Nb-Sn-Fe-Cr alloy. An autoclave corrosion test was carried out in 400°C steam for 300 days on the Zr-0.5Nb-1.0Sn-0.5Fe-0.25Cr alloy, which had been given 18 different accumulated annealing parameters. The corrosion rate increased with increasing the accumulated annealing parameter. To investigate the crystal structure of oxide layer, the corroded specimens were prepared to have an equal oxide thickness (˜1.6 μm) by controlling exposure time. The relative fraction of tetragonal ZrO 2 also decreased gradually with increasing accumulated annealing parameter. From the hydrogen analysis of the corroded samples for 300 days, it was observed that, with increasing the size of precipitates, the hydrogen pickup was enhanced. It was revealed from transmission electron microscope (TEM) observation of the oxide that the larger precipitates still remained to be oxidized in the oxide layer and had undergone a reduction of Fe/Cr ratio from 2.1 to 1.5. The oxidation of the precipitates in the oxide gave rise to a volume expansion at the precipitate-oxide interface. This volume change could lead to the transformation in the oxide phase from tetragonal ZrO 2 to monoclinic ZrO 2 and in oxide structure from columnar grain to equiaxed grain. The precipitate in a Zr-0.5Nb-1.0Sn-0.5Fe-0.25Cr alloy is composed of Nb, Fe, and Cr and the Nb content in the precipitate increase with increasing accumulated annealing parameter. Thus, it can be thought that Nb within precipitates plays a key role in the microstructural change of oxide.

Factors Affecting the Development of Oxide Scales on Austenitic Stainless Steels during Hot Rolling in Steckel Mills

NASA Astrophysics Data System (ADS)

Cobo, S. J.; Rainforth, W. M.

2008-10-01

The hot rolling of austenitic stainless steels in Steckel Mills introduces particular characteristics to the development of oxides scales and surface structures. In this work, the formation of oxide structures during multipass hot rolling of 302 steel was studied under different sets of processing parameters in a laboratory system designed for the simulation of the Steckel process. The resulting surface structures were characterized by a set of complementary techniques involving scanning electron microscopy, energy-dispersive spectroscopy (EDS), X-ray diffraction (XRD), and glow discharge optical spectroscopy (GDOS). The surface analysis revealed two alternative surface structures: one consisting in a thin protective oxide layer rich in Cr2O3 and the other consisting in thick complex structures containing several successive nonprotective oxide scale and metal layers resulting from a cyclic oxidation pattern involving stages of protective oxidation, chemical breakaway, and duplex oxidation. The critical condition that determined the activation of one mechanism or the other was identified associated with the parabolic rate constant for Cr2O3 growth and the diffusivity of Cr in the alloy. The effects of changes in temperature, deformation, and furnace atmosphere are discussed. Alternatives for controlling scale development are presented.

A study of deformation and strain induced in bulk by the oxide layers formation on a Fe-Cr-Al alloy in high-temperature liquid Pb-Bi eutectic

DOE PAGES

Popovic, M. P.; Chen, K.; Shen, H.; ...

2018-03-29

At elevated temperatures, heavy liquid metals and their alloys are known to create a highly corrosive environment that causes irreversible degradation of most iron-based materials. In this paper, it has been found that an appropriate concentration of oxygen in the liquid alloy can significantly reduce this issue by creating a passivating oxide scale that controls diffusion, especially if Al is present in Fe-based materials (by Al-oxide formation). However, the increase of the temperature and of oxygen content in liquid phase leads to the increase of oxygen diffusion into bulk, and to promotion of the internal Al oxidation. This can causemore » a strain in bulk near the oxide layer, due either to mismatch between the thermal expansion coefficients of the oxides and bulk material, or to misfit of the crystal lattices (bulk vs. oxides). This work investigates the strain induced into proximal bulk of a Fe-Cr-Al alloy by oxide layers formation in liquid lead-bismuth eutectic utilizing synchrotron X-ray Laue microdiffraction. Finally, it is found that internal oxidation is the most likely cause for the strain in the metal rather than thermal expansion mismatch as a two-layer problem.« less

A study of deformation and strain induced in bulk by the oxide layers formation on a Fe-Cr-Al alloy in high-temperature liquid Pb-Bi eutectic

DOE Office of Scientific and Technical Information (OSTI.GOV)

Popovic, M. P.; Chen, K.; Shen, H.

At elevated temperatures, heavy liquid metals and their alloys are known to create a highly corrosive environment that causes irreversible degradation of most iron-based materials. In this paper, it has been found that an appropriate concentration of oxygen in the liquid alloy can significantly reduce this issue by creating a passivating oxide scale that controls diffusion, especially if Al is present in Fe-based materials (by Al-oxide formation). However, the increase of the temperature and of oxygen content in liquid phase leads to the increase of oxygen diffusion into bulk, and to promotion of the internal Al oxidation. This can causemore » a strain in bulk near the oxide layer, due either to mismatch between the thermal expansion coefficients of the oxides and bulk material, or to misfit of the crystal lattices (bulk vs. oxides). This work investigates the strain induced into proximal bulk of a Fe-Cr-Al alloy by oxide layers formation in liquid lead-bismuth eutectic utilizing synchrotron X-ray Laue microdiffraction. Finally, it is found that internal oxidation is the most likely cause for the strain in the metal rather than thermal expansion mismatch as a two-layer problem.« less

Environmental resistance of oxide tags fabricated on 304L stainless steel via nanosecond pulsed laser irradiation

DOE PAGES

Lawrence, Samantha Kay; Adams, David P.; Bahr, David F.; ...

2015-11-14

Nanosecond pulsed laser irradiation was used to fabricate colored, mechanically robust oxide “tags” on 304L stainless steel. Immersion in simulated seawater solution, salt fog exposure, and anodic polarization in a 3.5% NaCl solution were employed to evaluate the environmental resistance of these oxide tags. Single layer oxides outside a narrow thickness range (~ 100–150 nm) are susceptible to dissolution in chloride containing environments. The 304L substrates immediately beneath the oxides corrode severely—attributed to Cr-depletion in the melt zone during laser processing. For the first time, multilayered oxides were fabricated with pulsed laser irradiation in an effort to expand the protectivemore » thickness range while also increasing the variety of film colors attainable in this range. Layered films grown using a laser scan rate of 475 mm/s are more resistant to both localized and general corrosion than oxides fabricated at 550 mm/s. Furthermore, in the absence of pre-processing to mitigate Cr-depletion, layered films can enhance environmental stability of the system.« less

Effect of Pressures on the Corrosion Behaviours of Materials at 625°C

NASA Astrophysics Data System (ADS)

Li, W.; Huang, X.; Li, J.; Woo, O. T.; Sanchez, R.; Bibby, C. D.

2017-02-01

The corrosion behaviors of austenitic stainless steels (SS) 310, 304 and Ni- and Fe-based A-286 exposed to 0.1 MPa, 8 MPa and 29 MPa at 625°C for 1000 h were investigated. These represent exposure to superheated steam, subcritical and supercritical water (SCW) at 625°C, respectively. As SS 310 showed the smallest weight change, the oxide cross-sections made from 310 samples were examined by transmission electron microscopy. The results revealed a single-layer oxide at 0.1 MPa and dual-layer oxides at 8 MPa and 29 MPa, followed by a Cr-depleted region into the austenite substrate. The compositions of the inner oxides at 8 MPa and 29 MPa are Cr-rich and largely similar to those of the single-layer oxides at 0.1 MPa exposure. These results suggest that corrosion testing in superheated steam may be a suitable surrogate for scoping tests of materials under SCW conditions at >650°C.

Oxidation of Alloy 600 and Alloy 690: Experimentally Accelerated Study in Hydrogenated Supercritical Water

NASA Astrophysics Data System (ADS)

Moss, Tyler; Cao, Guoping; Was, Gary S.

2017-04-01

The objective of this study is to determine whether the oxidation of Alloys 600 and 690 in supercritical water occurs by the same mechanism in subcritical water. Coupons of Alloys 690 and 600 were exposed to hydrogenated subcritical and supercritical water from 633 K to 673 K (360 °C to 400 °C) and the oxidation behavior was observed. By all measures of oxide character and behavior, the oxidation process is the same above and below the supercritical line. Similar oxide morphologies, structures, and chemistries were observed for each alloy across the critical point, indicating that the oxidation mechanism is the same in both subcritical and supercritical water. Oxidation results in a multi-layer oxide structure composed of particles of NiO and NiFe2O4 formed by precipitation on the outer surface and a chromium-rich inner oxide layer formed by diffusion of oxygen to the metal-oxide interface. The inner oxide on Alloy 600 is less chromium rich than that observed on Alloy 690 and is accompanied by preferential oxidation of grain boundaries. The inner oxide on Alloy 690 initially forms by internal oxidation before a protective layer of chromium-rich MO is formed with Cr2O3 at the metal-oxide interface. Grain boundaries in Alloy 690 act as fast diffusion paths for chromium that forms a protective Cr2O3 layer at the surface, preventing grain boundary oxidation from occurring.

Mach 1 oxidation of thoriated nickel chromium at 1204 C /2200 F/.

NASA Technical Reports Server (NTRS)

Lowell, C. E.; Sanders, W. A.

1972-01-01

Electropolished and ground samples of TD-NiCr were exposed to a 1-atm, Mach 1 gas stream at 1204 C for times up to 50 hr. The samples were subjected to both cyclic and isothermal exposure. Weight change, metal loss, X-ray diffraction, metallographic, and electron microprobe analyses were performed. Neither surface preparation nor cyclic-against-isothermal-exposure conditions had a strong effect on the oxidation behavior of the alloy. Initially, a Cr2O3 layer was formed whose volatilization resulted in a very rapid loss of metal - more than 40 microns in the first hour. At about 1 hr, the Cr2O3 layer broke down and NiO began to cover the surface. By 5 hr, the NiO had covered the surface and the rate of loss slowed. The rate-controlling step was diffusion of Cr through NiO.

Effect of nanograin-boundary networks generation on corrosion of carburized martensitic stainless steel.

PubMed

Boonruang, Chatdanai; Thong-On, Atcharawadi; Kidkhunthod, Pinit

2018-02-02

Martensitic stainless steel parts used in carbonaceous atmosphere at high temperature are subject to corrosion which results in a large amount of lost energy and high repair and maintenance costs. This work therefore proposes a model for surface development and corrosion mechanism as a solution to reduce corrosion costs. The morphology, phase, and corrosion behavior of steel are investigated using GIXRD, XANES, and EIS. The results show formation of nanograin-boundary networks in the protective layer of martensitic stainless steel. This Cr 2 O 3 -Cr 7 C 3 nanograin mixture on the FeCr 2 O 4 layer causes ion transport which is the main reason for the corrosion reaction during carburizing of the steel. The results reveal the rate determining steps in the corrosion mechanism during carburizing of steel. These steps are the diffusion of uncharged active gases in the stagnant-gas layer over the steel surface followed by the conversion of C into C 4- and O into O 2- at the gas-oxide interface simultaneously with the migration of Cr 3+ from the metal-oxide interface to the gas-oxide interface. It is proposed that previous research on Al 2 O 3 coatings may be the solution to producing effective coatings that overcome the corrosion challenges discussed in this work.

Microstructure and Oxidation of a MAX Phase/Superalloy Hybrid Interface

NASA Technical Reports Server (NTRS)

Smialek, James L.; Garg, Anita

2014-01-01

Corrosion resistant, strain tolerant MAX phase coatings are of interest for turbine applications. Thin Cr2AlC MAX phase wafers were vacuum diffusion bonded to an advanced turbine disk alloy, LSHR, at 1100 C. The interface, examined by optical and scanning electron microscopy, revealed a primary diffusion zone consisting of 10 micrometers of beta-Ni(Co)Al, decorated with various NiCoCrAl, MC and M3B2 precipitates. On the Cr2AlC side, an additional 40 micrometers Al-depletion zone of Cr7C3 formed in an interconnected network with the beta-Ni(Co)Al. Oxidation of an exposed edge at 800 C for 100 h produced a fine-grained lenticular alumina scale over Cr2AlC and beta-Ni(Co)Al, with coarser chromia granules over the Cr7C3 regions. Subsequent growth of the diffusion layers was only 5 micrometers in total. A residual stress of 500 MPa was estimated for the MAX phase layer, but no interfacial damage was observed. Subsequent tests for 1000 h reveal similar results.

He + and Ar + bombardment induced chemical changes in CrOSi layers

NASA Astrophysics Data System (ADS)

Bertóti, I.; Tóth, A.; Mohai, M.; Kelly, R.; Marletta, G.

1996-08-01

The effects of 2 keV He + and Ar + bombardment on the surface composition and on the short range chemical structure of sputter deposited amorphous CrOSi layers (with approx. 1 : 1 : 1 atomic ratio) have been studied by XPS. It was found that Ar + bombardment causes an essentially complete reduction of chromium to metallic state (Cr 0) whereas it was partly oxidized in the as-received sample. At the same time about 30% of the oxidized silicon is converted to Si 0 which is stabilized by forming SiCr bonds. He + bombardment, on the contrary, leads to the disruption of SiCr bonds formed by the preceding Ar + bombardment, converting Cr 0 and Si 0 essentially to Cr 3+O, Cr 4+O and Si 4+O, and, at the same time raises the surface oxygen concentration up to three times of the nominal bulk value. The observed transformations are discussed, in connection with the great differences in energy deposition, in terms of direct energy transfer and of ion induced diffusion, together with a significant contribution from thermodynamic driving forces.

Evaluation of Cyclic Oxidation and Hot Corrosion Behavior of HVOF-Sprayed WC-Co/NiCrAlY Coating

NASA Astrophysics Data System (ADS)

Somasundaram, B.; Kadoli, Ravikiran; Ramesh, M. R.

2014-08-01

Corrosion of metallic structural materials at an elevated temperature in complex multicomponent gas environments are potential problems in many fossil energy systems, especially those using coal as a feedstock. Combating these problems involves a number of approaches, one of which is the use of protective coatings. The high velocity oxy fuel (HVOF) process has been used to deposit WC-Co/NiCrAlY composite powder on two types of Fe-based alloys. Thermocyclic oxidation behavior of coated alloys was investigated in the static air as well as in molten salt (Na2SO4-60%V2O5) environment at 700 °C for 50 cycles. The thermogravimetric technique was used to approximate the kinetics of oxidation. WC-Co/NiCrAlY coatings showed a lower oxidation rate in comparison to uncoated alloys. The oxidation resistance of WC-Co/NiCrAlY coatings can be ascribed to the oxide layer of Al2O3 and Cr2O3 formed on the outermost surface. Coated alloys extend a protective oxide scale composed of oxides of Ni and Cr that are known to impart resistance to the hot corrosion in the molten salt environment.

Enhanced spin-valve giant magneto-resistance in non-exchange biased sandwich films

DOE Office of Scientific and Technical Information (OSTI.GOV)

Mao, M; Cerjan, C; Law, B

2000-02-17

A large giant magnetoresistance (GMR) value of 7.5% has been measured in simple NiFeCo(1)/Cu/NiFeCo(2) sandwich films grown on a 30 {angstrom} Cr seed layer. This spin-valve GMR effect is consistent with the differential switching of the two NiFeCo layers due to an enhanced coercivity of the NiFeCo(1) layer grown on the Cr seed layer. A change in growth texture of the NiFeCo(1) layer from fcc (111) to bcc (110) crystallographic orientation leads to an increase in magnetic anisotropy and an enhancement in coercivity. The GMR value increases to 8.7% when a thin CoFe interfacial enhancing layer is incorporated. Further enhancementmore » in GMR values up to 14% is seen in the sandwich films by nano-oxide layer formation. The specular reflection at oxide/magnetic layer interface further extends the mean free path of spin-polarized electrons.« less

Formation of Cr-modified silicide coatings on a Ti-Nb-Si based ultrahigh-temperature alloy by pack cementation process

NASA Astrophysics Data System (ADS)

Qiao, Yanqiang; Guo, Xiping

2010-10-01

Cr-modified silicide coatings were prepared on a Ti-Nb-Si based ultrahigh temperature alloy by Si-Cr co-deposition at 1250 °C, 1350 °C and 1400 °C for 5-20 h respectively. It was found that both coating structure and phase constituents changed significantly with increase in the co-deposition temperature and holding time. The outer layers in all coatings prepared at 1250 °C for 5-20 h consisted of (Ti,X) 5Si 3 (X represents Nb, Cr and Hf elements). (Ti,X) 5Si 4 was found as the only phase constituent in the intermediate layers in both coatings prepared at 1250 °C for 5 and 10 h, but the intermediate layers in the coatings prepared at 1250 °C for 15 and 20 h were mainly composed of (Ti,X) 5Si 3 phase that was derived from the decomposition of (Ti,X) 5Si 4 phase. In the coating prepared at 1350 °C for 5 h, single (Ti,X) 5Si 3 phase was found in its outmost layer, the same as that in the outer layers in the coatings prepared at 1250 °C; but in the coatings prepared at 1350 °C for 10-20 h, (Nb 1.95Cr 1.05)Cr 2Si 3 ternary phase was found in the outmost layers besides (Ti,X) 5Si 3 phase. In the coatings prepared at 1400 °C for 5-20 h, (Nb 1.95Cr 1.05)Cr 2Si 3 ternary phase was the single phase constituent in their outmost layers. The phase transformation (Ti,X) 5Si 4 → (Ti,X) 5Si 3 + Si occurred in the intermediate layers of the coatings prepared at 1350 and 1400 °C with prolonging co-deposition time, similar to the situation in the coatings prepared at 1250 °C for 15 and 20 h, but this transformation has been speeded up by increase in the co-deposition temperature. The transitional layers were mainly composed of (Ti,X) 5Si 3 phase in all coatings. The influence of co-deposition temperature on the diffusion ability of Cr atoms was greater than that of Si atoms in the Si-Cr co-deposition processes investigated. The growth of coatings obeyed inverse logarithmic laws at all three co-deposition temperatures. The Si-Cr co-deposition coating prepared at 1350 °C for 10 h showed a good oxidation resistance due to the formation of SiO 2 and Nb, Cr-doped TiO 2 scale after oxidation at 1250 °C for 10 h.

Thermal and Photochemical Reactions of NO2 on a Chromium (III) Oxide Surface

NASA Astrophysics Data System (ADS)

Nishino, N.; Finlayson-Pitts, B. J.

2011-12-01

Chromium oxide (Cr2O3) is a major component of the oxide layer on stainless steel surfaces. It is also widely used as pigment in paints and roofs and as a protective coating on various surfaces. While many studies have focused on the catalytic activity of Cr2O3 surfaces for selective catalytic reduction (SCR), less attention has been paid to its surface chemistry involving atmospherically important species such as NO2 under atmospheric conditions. In this study, we have investigated thermal and photochemical reactions of NO2 in the presence and the absence of water vapor, using a thin layer of Cr2O3 as a model for the surface of stainless steel as well as other similarly coated surfaces in the boundary layer. A 30 nm thick Cr2O3 film was deposited on a germanium attenuated total reflectance (ATR) crystal, and the changes in the surface species were monitored by Fourier Transform Infrared (FTIR) spectroscopy. Upon NO2 adsorption, nitrate (NO3-) ions appeared likely coordinated to Cr3+ ion(s). The NO3- peaks reversibly shifted when water vapor was added, suggesting that NO3- become solvated. Irradiation at 311 nm led to a decrease in NO3- ions under both dry and humid conditions. The major gas-phase species formed by the irradiation was NO under dry conditions, while NO2 was mainly formed in the presence of H2O. Possible mechanisms and the implications for heterogeneous NO2 chemistry in the boundary layer will be discussed. The results will also be compared to similar chemistry on other surfaces.

Synthesis of Lithium Metal Oxide Nanoparticles by Induction Thermal Plasmas.

PubMed

Tanaka, Manabu; Kageyama, Takuya; Sone, Hirotaka; Yoshida, Shuhei; Okamoto, Daisuke; Watanabe, Takayuki

2016-04-06

Lithium metal oxide nanoparticles were synthesized by induction thermal plasma. Four different systems-Li-Mn, Li-Cr, Li-Co, and Li-Ni-were compared to understand formation mechanism of Li-Me oxide nanoparticles in thermal plasma process. Analyses of X-ray diffractometry and electron microscopy showed that Li-Me oxide nanoparticles were successfully synthesized in Li-Mn, Li-Cr, and Li-Co systems. Spinel structured LiMn₂O₄ with truncated octahedral shape was formed. Layer structured LiCrO₂ or LiCoO₂ nanoparticles with polyhedral shapes were also synthesized in Li-Cr or Li-Co systems. By contrast, Li-Ni oxide nanoparticles were not synthesized in the Li-Ni system. Nucleation temperatures of each metal in the considered system were evaluated. The relationship between the nucleation temperature and melting and boiling points suggests that the melting points of metal oxides have a strong influence on the formation of lithium metal oxide nanoparticles. A lower melting temperature leads to a longer reaction time, resulting in a higher fraction of the lithium metal oxide nanoparticles in the prepared nanoparticles.

Mechanistic insights into the oxidation behavior of Ni alloys in high-temperature CO 2

DOE PAGES

Oleksak, Richard P.; Baltrus, John P.; Nakano, Jinichiro; ...

2017-06-01

We present results of a Ni superalloy oxidized for short times in high purity CO 2 and similarly in Ar containing ≤ 1 ppb O 2. A detailed analysis of the oxidized surfaces reveals striking similarities for the two exposure environments, suggesting O 2 impurities control the oxidation process in high-temperature CO 2. Selective oxidation results in Cr-rich oxide layers grown by 2 outward diffusion, while Cr vacancies left in the metal contribute to significant void formation at the oxide/metal interface. Unlike for most of the alloy surface, the oxidation behavior of secondary phase metal carbides is considerably different inmore » the two environments.« less

Corrosion Behavior of Alloy 625 in PbSO4-Pb3O4-PbCl2-ZnO-10 Wt Pct CdO Molten Salt Medium

NASA Astrophysics Data System (ADS)

Mohammadi Zahrani, E.; Alfantazi, A. M.

2012-08-01

Corrosion behavior and degradation mechanisms of alloy 625 under a 47.288 PbSO4-12.776 Pb3O4-6.844PbCl2-23.108ZnO-10CdO (wt pct) molten salt mixture under air atmosphere were studied at 873 K, 973 K, and 1073 K (600 °C, 700 °C, and 800 °C). Electrochemical impedance spectroscopy (EIS), open circuit potential (OCP) measurements, and potentiodynamic polarization techniques were used to evaluate the degradation mechanisms and characterize the corrosion behavior of the alloy. Morphology, chemical composition, and phase structure of the corrosion products and surface layers of the corroded specimens were studied by scanning electron microscopy/energy-dispersive X-ray (SEM/EDX) and X-ray map analyses. Results confirmed that during the exposure of alloy 625 to the molten salt, chromium was mainly dissolved through an active oxidation process as CrO3, Cr2O3, and CrNbO4, while nickel dissolved only as NiO in the system. Formation of a porous and nonprotective oxide layer with low resistance is responsible for the weak protective properties of the barrier layer at high temperatures of 973 K and 1073 K (700 °C and 800 °C). There were two kinds of attack for INCONEL 625, including general surface corrosion and pitting. Pitting corrosion occurred due to the breakdown of the initial oxide layer by molten salt dissolution of the oxide or oxide cracking.

Erosion behavior of composite Al-Cr cathodes in cathodic arc plasmas in inert and reactive atmospheres

DOE Office of Scientific and Technical Information (OSTI.GOV)

Franz, Robert, E-mail: robert.franz@unileoben.ac.at; Mendez Martin, Francisca; Hawranek, Gerhard

2016-03-15

Al{sub x}Cr{sub 1−x} composite cathodes with Al contents of x = 0.75, 0.5, and 0.25 were exposed to cathodic arc plasmas in Ar, N{sub 2}, and O{sub 2} atmospheres and their erosion behavior was studied. Cross-sectional analysis of the elemental distribution of the near-surface zone in the cathodes by scanning electron microscopy revealed the formation of a modified layer for all cathodes and atmospheres. Due to intermixing of Al and Cr in the heat-affected zone, intermetallic Al-Cr phases formed as evidenced by x-ray diffraction analysis. Cathode poisoning effects in the reactive N{sub 2} and O{sub 2} atmospheres were nonuniform as a resultmore » of the applied magnetic field configuration. With the exception of oxide islands on Al-rich cathodes, reactive layers were absent in the circular erosion zone, while nitrides and oxides formed in the less eroded center region of the cathodes.« less

Improving the oxidation resistance of 316L stainless steel in simulated pressurized water reactor primary water by electropolishing treatment

NASA Astrophysics Data System (ADS)

Han, Guangdong; Lu, Zhanpeng; Ru, Xiangkun; Chen, Junjie; Xiao, Qian; Tian, Yongwu

2015-12-01

The oxidation behavior of 316L stainless steel specimens after emery paper grounding, mechanical polishing, and electropolishing were investigated in simulated pressurized water reactor primary water at 310 °C for 120 and 500 h. Electropolishing afforded improved oxidation resistance especially during the early immersion stages. Duplex oxide films comprising a coarse Fe-rich outer layer and a fine Cr-rich inner layer formed on all specimens after 500 h of immersion. Only a compact layer was observed on the electropolished specimen after 120 h of immersion. The enrichment of chromium in the electropolished layer contributed to the passivity and protectiveness of the specimen.

Formation of Cr2O3 Diffusion Barrier Between Cr-Contained Stainless Steel and Cold-Sprayed Ni Coatings at High Temperature

NASA Astrophysics Data System (ADS)

Xu, Ya-Xin; Luo, Xiao-Tao; Li, Cheng-Xin; Yang, Guan-Jun; Li, Chang-Jiu

2016-02-01

A novel approach to prepare a coating system containing an in situ grown Cr2O3 diffusion barrier between a nickel top layer and 310SS was reported. Cold spraying was employed to deposit Ni(O) interlayer and top nickel coating on the Cr-contained stainless steel substrate. Ni(O) feedstock was prepared by mechanical alloying of pure nickel powders in ambient atmosphere, acting as an oxygen provider. The post-spray annealing was adopted to grow in situ Cr2O3 layer between the substrate and nickel coating. The results revealed that the diffusible oxygen can be introduced into nickel powders by mechanical alloying. The oxygen content increases to 3.25 wt.% with the increase of the ball milling duration to 8 h, while Ni(O) powders maintain a single phase of Ni. By annealing the sample in Ar atmosphere at 900 °C, a continuous Cr2O3 layer of 1-2 μm thick at the interface between 310SS and cold-sprayed Ni coating is formed. The diffusion barrier effect evaluation by thermal exposure at 750 °C shows that the Cr2O3 oxide layer effectively suppresses the outward diffusion of Fe and Cr in the substrate effectively.

A Microstructural and Kinetic Investigation of the KCl-Induced Corrosion of an FeCrAl Alloy at 600 °C

DOE PAGES

Israelsson, Niklas; Unocic, Kinga A.; Hellström, K.; ...

2015-03-18

In this paper, the corrosion behaviour of a FeCrAl alloy was investigated at 600 °C in O 2 + H 2O with solid KCl applied. A kinetics and microstructural investigation showed that KCl accelerates corrosion and that potassium chromate formation depletes the protective scale in Cr, thus triggering the formation of a fast-growing iron-rich scale. Iron oxide was found to grow both inward and outward, on either side of the initial oxide. A chromia layer is formed with time underneath the iron oxide. Finally, it was found that although the alloy does not form a continuous pure alumina scale atmore » the investigated temperature, aluminium is, however, always enriched at the oxide/alloy interface.« less

Effect of Al and Cr Content on Air and Steam Oxidation of FeCrAl Alloys and Commercial APMT Alloy

DOE PAGES

Unocic, Kinga A.; Yamamoto, Yukinori; Pint, Bruce A.

2017-03-09

To develop the next generation of accident-tolerant fuel cladding for light-water nuclear reactors, wrought FeCrAlY alloys with varying amounts of Cr and Al and commercial Kanthal APMT alloy were evaluated for short-term (4 h) oxidation resistance in steam and air at 1200–1475 °C. Model alloys with lower Cr contents and higher Al contents were evaluated in this paper as lower Cr contents are desirable for radiation damage resistance during operation. As expected, a synergistic effect was found between the Cr and Al contents to enable protective Al 2O 3 formation under these conditions. Characterization of the alumina scales formed inmore » steam found that the scale morphology was affected by the alloy Y content and detailed scanning transmission electron microscopy (STEM) detected Y segregation along scale grain boundaries at 1200 °C. However, after 4 h at 1475 °C, Y and Hf were not segregated to the oxide grain boundaries formed on APMT and the scale had a single layer structure. Finally, compared to oxidation in air, STEM characterization of the outer scale showed differences in the Fe and Cr distributions in steam.« less

Method of bonding a conductive layer on an electrode of an electrochemical cell

DOEpatents

Bowker, J.C.; Singh, P.

1989-08-29

A dense, electronically conductive interconnection layer is bonded onto a porous, tubular, electronically conductive air electrode structure, optionally supported by a ceramic support, by (A) providing an air electrode surface, (B) forming on a selected portion of the electrode surface, without the use of pressure, particles of LaCrO[sub 3] doped with an element selected from the group consisting of Sr, Mg, Ca, Ba, Co, and mixtures thereof, where the particles have a deposit on their surface comprising calcium oxide and chromium oxide; (C) heating the particles with the oxide surface deposit in an oxidizing atmosphere at from 1,300 C to 1,550 C, without the application of pressure, to provide a dense, sintered, interconnection material bonded to the air electrode, where calcium and chromium from the surface deposit are incorporated into the structure of the LaCrO[sub 3]. A solid electrolyte layer can be applied to the uncovered portion of the air electrode, and a fuel electrode can be applied to the solid electrolyte, to provide an electrochemical cell. 4 figs.

Method of bonding a conductive layer on an electrode of an electrochemical cell

DOEpatents

Bowker, Jeffrey C.; Singh, Prabhakar

1989-01-01

A dense, electronically conductive interconnection layer 26 is bonded onto a porous, tubular, electronically conductive air electrode structure 16, optionally supported by a ceramic support 22, by (A) providing an air electrode surface, (B) forming on a selected portion of the electrode surface 24, without the use of pressure, particles of LaCrO.sub.3 doped with an element selected from the group consisting of Sr, Mg, Ca, Ba, Co, and mixtures thereof, where the particles have a deposit on their surface comprising calcium oxide and chromium oxide; (C) heating the particles with the oxide surface deposit in an oxidizing atmosphere at from 1,300.degree. C. to 1,550.degree. C., without the application of pressure, to provide a dense, sintered, interconnection material 26 bonded to the air electrode 16, where calcium and chromium from the surface deposit are incorporated into the structure of the LaCrO.sub.3. A solid electrolyte layer 18 can be applied to the uncovered portion of the air electrode, and a fuel electrode 20 can be applied to the solid electrolyte, to provide an electrochemical cell 10.

[The bonding mechanisms of base metals for metal-ceramic crown microstructure analysis of bonding agent and gold bond between porcelain and base metals].

PubMed

Wang, C C; Hsu, C S

1996-06-01

The use of base metal alloys for porcelain fused to a metal crown and bridges has increased recently because of lower price, high hardness, high tensile strength and high elastic modulus. The addition of beryllium to base metal alloys increased fluidity and improved casting fitness. Beryllium also controlled surface oxidation and bonding strength. The bonding agent and gold bonding agent also affected the bonding strength between porcelain and metal alloys. Four commercially available ceramic base alloys were studied (two alloys contained beryllium element, another two did not). The purpose of this investigation was to study the microstructure between porcelain matrix, bonding agent and alloy matrix interfaces. A scanning electron micro-probe analyzer and energy dispersive X-ray spectroscopy (EDXS) were used to study the distribution of elements (Ni, Cr, Mo, Cu, O, Si, Sn, Al) in four base alloys. The following results were obtained: 1. The thickness of the oxidized layer of Rexillium III alloy and Unitbond alloy (contained beryllium) was thinner than Unibond alloy and Wiron 88 alloy (no beryllium). 2. The thickness of the oxidized layer of alloys in air (10 minutes and 30 minutes) was thinner in Unitbond (2.45 microns and 3.80 microns) and thicker in Wiron 88 (4.39 microns and 5.96 microns). 3. The thickness of the oxidized layer occurring for a duration of ten minutes (in vaccum) showed that the Rexillium III alloy was the thinnest (1.93 microns), and Wiron 88 alloy was the thickest (2.30 microns). But in thirty minutes (vacuum), Unitbond alloy was the thinnest (3.37 microns), and Wiron 88 alloy was the thickest (5.51 microns). 4. The intensity of Cr elements was increased obviously near the interface between Unitbond alloy, Wiron 88 alloy (no beryllium) and oxidized layer, but the intensity of Ni and Mo elements was slightly increased. The intensity of Cr element was not increased markedly between Rexillium III alloy, Unitbond alloy (beryllium) and oxidized layer. 5. A white-grayish oxidized layer appeared at the metal-ceramic interfaces but the thickness of oxidized layer was not obviously different. 6. The use of bonding agent at metal-ceramic interface leads to the deposition of many Sn elements at about 40 microns range within the porcelain surface. 7. Second interaction phases at the porcelain layer appeared when gold bonding agent was used, and a 50-100 microns microleakage occurred at the metal-ceramic interface.

Mechanical properties of Cr-Cu coatings produced by electroplating

NASA Astrophysics Data System (ADS)

Riyadi, Tri Widodo Besar; Sarjito, Masyrukan, Riswan, Ricky Ary

2017-06-01

Hard chromium coatings has long been considered as the most used electrodeposited coating in several industrial applications such as in petrochemistry, oil and gas industries. When hard coatings used in fastener components, the sliding contact during fastening operation produces high tensile stresses on the surface which can generate microcracks. For component used in high oxidation and corrosion environment, deep cracks cannot be tolerated. In this work, a laminated structure of Cr-Cu coating was prepared using electroplating on carbon steel substrates. Two baths of chrome and copper electrolyte solutions were prepared to deposit Cr as the first layer and Cu as the second layer. The effect of current voltages on the thickness, hardness and specific wear rate of the Cu layer was investigated. The results show that an increase of the current voltages increased the thickness and hardness of the Cu layer, but reduced the specific wear rate. This study showed that the use of Cu can be a potential candidate as a laminated structure Cr-Cu for chromium plating.

Layered-to-Rock-Salt Transformation in Desodiated Na xCrO 2 ( x 0.4)

DOE PAGES

Bo, Shou-Hang; Li, Xin; Toumar, Alexandra J.; ...

2016-02-01

O3 layered sodium transition metal oxides (i.e., NaMO 2, M = Ti, V, Cr, Mn, Fe, Co, Ni) are a promising class of cathode materials for Na-ion battery applications. These materials, however, all suffer from severe capacity decay when the extraction of Na exceeds certain capacity limits. Understanding the causes of this capacity decay is critical to unlocking the potential of these materials for battery applications. In this work, we investigate the structural origins of capacity decay for one of the compounds in this class, NaCrO 2. The (de)sodiation processes of NaCrO 2 were studied both in situ and exmore » situ through X-ray and electron diffraction measurements. We demonstrate that Na xCrO 2 (0 < x < 1) remains in the layered structural framework without Cr migration up to a composition of Na 0.4CrO 2. Further removal of Na beyond this composition triggers a layered-to-rock-salt transformation, which converts P'3-Na 0.4CrO 2 into the rock-salt CrO 2 phase. This structural transformation proceeds via the formation of an intermediate O3 Na δCrO 2 phase that contains Cr in both Na and Cr slabs and shares very similar lattice dimensions with those of rock-salt CrO 2. It is intriguing to note that intercalation of alkaline ions (i.e., Na + and Li + ) into the rock-salt CrO 2 and O3 Na δCrO 2 structures is actually possible, albeit in a limited amount (~0.2 per formula unit). When these results were analyzed under the context of electrochemistry data, it was apparent that preventing the layered-to-rock-salt transformation is crucial to improve the cyclability of NaCrO 2. Possible strategies for mitigating this detrimental phase transition are proposed.« less

Passivation Characteristics of Alloy Corrosion-Resistant Steel Cr10Mo1 in Simulating Concrete Pore Solutions: Combination Effects of pH and Chloride

PubMed Central

Ai, Zhiyong; Sun, Wei; Jiang, Jinyang; Song, Dan; Ma, Han; Zhang, Jianchun; Wang, Danqian

2016-01-01

The electrochemical behaviour for passivation of new alloy corrosion-resistant steel Cr10Mo1 immersed in alkaline solutions with different pH values (13.3, 12.0, 10.5, and 9.0) and chloride contents (0.2 M and 1.0 M), was investigated by various electrochemical techniques: linear polarization resistance, electrochemical impedance spectroscopy and capacitance measurements. The chemical composition and structure of passive films were determined by XPS. The morphological features and surface composition of the immersed steel were evaluated by SEM together with EDS chemical analysis. The results evidence that pH plays an important role in the passivation of the corrosion-resistant steel and the effect is highly dependent upon the chloride contents. In solutions with low chloride (0.2 M), the corrosion-resistant steel has notably enhanced passivity with pH falling from 13.3 to 9.0, but does conversely when in presence of high chloride (1.0 M). The passive film on the corrosion-resistant steel presents a bilayer structure: an outer layer enriched in Fe oxides and hydroxides, and an inner layer, rich in Cr species. The film composition varies with pH values and chloride contents. As the pH drops, more Cr oxides are enriched in the film while Fe oxides gradually decompose. Increasing chloride promotes Cr oxides and Fe oxides to transform into their hydroxides with little protection, and this is more significant at lower pH (10.5 and 9.0). These changes annotate passivation characteristics of the corrosion-resistant steel in the solutions of different electrolyte. PMID:28773867

Passivation Characteristics of Alloy Corrosion-Resistant Steel Cr10Mo1 in Simulating Concrete Pore Solutions: Combination Effects of pH and Chloride.

PubMed

Ai, Zhiyong; Sun, Wei; Jiang, Jinyang; Song, Dan; Ma, Han; Zhang, Jianchun; Wang, Danqian

2016-09-01

The electrochemical behaviour for passivation of new alloy corrosion-resistant steel Cr10Mo1 immersed in alkaline solutions with different pH values (13.3, 12.0, 10.5, and 9.0) and chloride contents (0.2 M and 1.0 M), was investigated by various electrochemical techniques: linear polarization resistance, electrochemical impedance spectroscopy and capacitance measurements. The chemical composition and structure of passive films were determined by XPS. The morphological features and surface composition of the immersed steel were evaluated by SEM together with EDS chemical analysis. The results evidence that pH plays an important role in the passivation of the corrosion-resistant steel and the effect is highly dependent upon the chloride contents. In solutions with low chloride (0.2 M), the corrosion-resistant steel has notably enhanced passivity with pH falling from 13.3 to 9.0, but does conversely when in presence of high chloride (1.0 M). The passive film on the corrosion-resistant steel presents a bilayer structure: an outer layer enriched in Fe oxides and hydroxides, and an inner layer, rich in Cr species. The film composition varies with pH values and chloride contents. As the pH drops, more Cr oxides are enriched in the film while Fe oxides gradually decompose. Increasing chloride promotes Cr oxides and Fe oxides to transform into their hydroxides with little protection, and this is more significant at lower pH (10.5 and 9.0). These changes annotate passivation characteristics of the corrosion-resistant steel in the solutions of different electrolyte.

Hot Corrosion Behavior of Stainless Steel with Al-Si/Al-Si-Cr Coating

NASA Astrophysics Data System (ADS)

Fu, Guangyan; Wu, Yongzhao; Liu, Qun; Li, Rongguang; Su, Yong

2017-03-01

The 1Cr18Ni9Ti stainless steel with Al-Si/Al-Si-Cr coatings is prepared by slurry process and vacuum diffusion, and the hot corrosion behavior of the stainless steel with/without the coatings is studied under the condition of Na2SO4 film at 950 °C in air. Results show that the corrosion kinetics of stainless steel, the stainless steel with Al-Si coating and the stainless steel with Al-Si-Cr coating follow parabolic laws in several segments. After 24 h corrosion, the sequence of the mass gain for the three alloys is the stainless steel with Al-Si-Cr coating < the stainless steel with Al-Si coating < the stainless steel without any coating. The corrosion products of the three alloys are layered. Thereinto, the corrosion products of stainless steel without coating are divided into two layers, where the outside layer contains a composite of Fe2O3 and FeO, and the inner layer is Cr2O3. The corrosion products of the stainless steel with Al-Si coating are also divided into two layers, of which the outside layer mainly consists of Cr2O3, and the inner layer is mainly SiO2. The corrosion film of the stainless steel with Al-Si-Cr coating is thin and dense, which combines well with substrate. Thereinto, the outside layer is mainly Cr2O3, and the inside layer is Al2O3. In the matrix of all of the three alloys, there exist small amount of sulfides. Continuous and protective films of Cr2O3, SiO2 and Al2O3 form on the surface of the stainless steel with Al-Si and Al-Si-Cr coatings, which prevent further oxidation or sulfide corrosion of matrix metals, and this is the main reason for the much smaller mass gain of the two alloys than that of the stainless steel without any coatings in the 24 h hot corrosion process.

Influence of Magnesium Ions in the Seawater Environment on the Improvement of the Corrosion Resistance of Low-Chromium-Alloy Steel

PubMed Central

Song, Sol-Ji; Kim, Jung-Gu

2018-01-01

This study examined the synergic effect of alloying the element Cr and the environmental element Mg2+ ions on the corrosion property of a low-alloy steel in seawater at 60 °C, by means of electrochemical impedance spectroscopy (EIS), linear polarization resistance (LPR) tests and weight-loss tests. The Mg2+ ions in seawater played an important role in lowering the electron transfer of the rust layer in the Cr-containing steel. The corrosion resistance of the Cr-containing steel is superior to that of blank steel in Mg2+ ions containing seawater. XPS and XRD results indicated that the formation of MgFe2O4 and a mixed layer (Cr oxide + FeCr2O4 + MgCr2O4) improved the corrosion resistance of the low-alloy steel in the seawater. PMID:29361710

CuMn1.8O4 protective coatings on metallic interconnects for prevention of Cr-poisoning in solid oxide fuel cells

NASA Astrophysics Data System (ADS)

Sun, Zhihao; Wang, Ruofan; Nikiforov, Alexey Y.; Gopalan, Srikanth; Pal, Uday B.; Basu, Soumendra N.

2018-02-01

Cr-poisoning of the cathodes due to the presence of metallic interconnects is detrimental to the performance of intermediate temperature solid oxide fuel cell stacks. Applying a protective coating on the interconnect is an effective solution to preventing Cr-poisoning. In this study, the application of a protective CuMn1.8O4 spinel coating is explored. Dense coatings are deposited on both metallic flat plates and meshes by electrophoretic deposition followed by thermal densification steps. The coating is found to be a mixture of Mn3O4 and cubic spinel phases at room temperature but is a pure cubic spinel phase between 750 °C and 850 °C. A reaction layer between the Cr2O3 scale at the coating/interconnect interface and CuMn1.8O4 coating is found to be a mixture of (Cu,Mn,Cr)3-xO4 cubic spinel phases with Cr-rich precipitates believed to be Cr2O3, indicating that the coating layer acts as a Cr getter. Solubility experiments show that 1 mol of the CuMn1.8O4 phase can getter at least 1.83 mol of Cr2O3 at 800 °C. Electrochemical testing of cells in the presence of coated interconnects show that the CuMn1.8O4 coating getters Cr effectively for 12 days at 800 °C, leading to no performance loss of the cell due to Cr-poisoning.

Effect of reactive element oxide coating on the high temperature oxidation behaviour of FeCrAl alloys

NASA Astrophysics Data System (ADS)

Cueff, R.; Buscail, H.; Caudron, E.; Riffard, F.; Issartel, C.; El Messki, S.

2004-05-01

The influence of yttrium oxide coating (processed by the sol-gel method) on the oxidation behaviour of a commercial FeCrAl alloy (Kanthal A1) has been investigated during isothermal exposures in air at 1373 K. The scale growth kinetics of the uncoated alloy obey a parabolic rate law during the whole oxidation test, whereas the kinetic curves of the Y-coated specimen exhibit an initial transient stage for the first few hours, followed by a parabolic regime. The yttrium sol-gel coating deposited on the bare alloy does not provide the beneficial effect usually ascribed to reactive elements. No oxidation rate improvement of the coated alloy is observed, the parabolic rate constant values are strictly identical for both specimens. In situ X-ray diffraction reveals a marked influence of the reactive element on the composition of the oxide scale. The oxide layer formed on the yttrium-coated specimen comprised, in addition to α-alumina which is the main oxide also identified on the bare specimen, the presence of yttrium aluminates (YAlO 3, Y 3Al 5O 12) located in the outermost part of the layer.

Microstructure of rapidly solidified Nb-based pre-alloyed powders for additive manufacturing

NASA Astrophysics Data System (ADS)

Guo, Yueling; Jia, Lina; Kong, Bin; Zhang, Shengnan; Zhang, Fengxiang; Zhang, Hu

2017-07-01

For powder-based additive manufacturing, sphere-shaped Nb-37Ti-13Cr-2Al-1Si pre-alloyed powders were prepared by plasma rotating electrode processing (PREP). The microstructure, surface oxidation and microhardness of the pre-alloyed powders were systematically investigated. Results showed that the main phases were Nb solid solution (Nbss) and Cr2Nb. The Cr2Nb phases were further determined using transmission electron microscopy (TEM). Fine dendrite structures were observed in the as-fabricated pre-alloyed powders, which transformed to large grains after heat treatment (HT) at 1450 °C for 3 h. With the increase of powder size, the secondary dendrite arm spacing (SDAS) increased and the microhardness (HV) decreased. A clean powder surface free of oxide particles was obtained by PREP and an oxide layer with 9.39 nm in thickness was generated on the powder surface. Compared with Cr- and Nb-oxides, more Ti-oxides were formed on outmost powder surface with a higher content of Ti (up to 47.86 at.%). The differences upon the microstructure and microhardness of the pre-alloyed powders with different sizes were discussed.

CoxFe1-x oxide coatings on metallic interconnects for solid oxide fuel cells

NASA Astrophysics Data System (ADS)

Shen, Fengyu; Lu, Kathy

2016-10-01

In order to improve the performance of Cr-containing steel as an interconnect material for solid oxide fuel cells, CoFe alloy coatings with Co:Fe ratios of 9:1, 8:2, 7:3, 6:4, and 5:5 are deposited by electrodeposition and then oxidized to CoxFe1-x oxide coatings with a thickness of ∼6 μm as protective layers on the interconnect. The area specific resistance of the coated interconnect increases with the Fe content. Higher Co content oxide coatings are more effective in limiting the growth of the chromia scale while all coatings are effective in inhibiting Cr diffusion and evaporation. With the Co0.8Fe0.2 oxide coated interconnect, the electrochemical performance of the Sm0.5Sr0.5Co0.2Fe0.8O3 cathode is improved. Only 1.54 atomic percentage of Cr is detected on the surface of the Sm0.5Sr0.5Co0.2Fe0.8O3 cathode while no Cr is detected 0.66 μm or more into the cathode. CoxFe1-x oxide coatings are promising candidates for solid oxide fuel cell interconnects with the advantage of using existing cathode species for compatibility and performance enhancement.

Oxidative vaporization kinetics of Cr2O3 in oxygen from 1000 to 1300 C

NASA Technical Reports Server (NTRS)

Stearns, C. A.; Kohl, F. J.; Fryburg, G. C.

1974-01-01

Rates of oxidative vaporization of Cr2O3 on preoxidized resistively heated chromium were determined in flowing oxygen at a pressure of 0.115 Torr for temperatures from 1000 to 1300 C. Reaction controlled rates were obtained from experimental rates by a gold calibration technique, and these rates were shown to agree with those predicted by thermochemical analysis. The activation energy obtained for the oxidative vaporization reaction corresponded numerically with the thermochemical enthalpy of the reaction. A theoretical equation is given for calculating the rate from thermodynamic data using boundary-layer theory.

ESCA study of oxidation and hot corrosion of nickel-base superalloys. [Electron Spectroscopy for Chemical Analysis

NASA Technical Reports Server (NTRS)

Smith, S. R.; Carter, W. J., III; Mateescu, G. D.; Kohl, F. J.; Fryburg, G. C.; Stearns, C. A.

1980-01-01

A study of the high-temperature oxidation and Na2SO4-induced hot corrosion of nickel-base superalloys has been accomplished by using ESCA to determine the surface composition of the oxidized or corroded samples. Oxidation was carried out at 900 or 1000 C in slowly flowing O2 for samples of B-1900, NASA-TRW VIA, 713C, and IN-738. Hot corrosion of B-1900 was induced by applying a coating of Na2SO4 to preoxidized samples, then heating to 900 C in slowly flowing O2. For oxidized samples, the predominant type of scale formed by each superalloy showed a marked surface enrichment of Ti. For corroded samples, the transfer of significant amounts of material from the oxide layer to the surface of the salt layer was observed before the onset of rapidly accelerating weight gain. Marked changes in surface composition coincided with the beginning of accelerating corrosion, the most striking of which were a tenfold decrease in the sulfur to sodium ratio and an increase in the Cr(VI) to Cr(III) ratio.

Oxidation study of coated Crofer 22 APU steel in dry oxygen

NASA Astrophysics Data System (ADS)

Molin, Sebastian; Chen, Ming; Hendriksen, Peter Vang

2014-04-01

The effect of a dual layer coating composed of a layer of a Co3O4 and a layer of a La0.85Sr0.15MnO3/Co3O4 mixture on the high temperature corrosion of the Crofer 22 APU alloy is reported. Oxidation experiments were performed in dry oxygen at three temperatures: 800 °C, 850 °C and 900 °C for periods up to 1000 h. Additionally at 850 °C a 5000 h long oxidation test was performed to evaluate longer term suitability of the proposed coating. Corrosion kinetics were evaluated by measuring mass gain during oxidation. The corrosion kinetics for the coated samples are analyzed in terms of a parabolic rate law. Microstructural features were investigated by scanning electron microscopy, energy dispersive X-ray analysis and X-ray diffractometry. The coating is effective in reducing the corrosion rate and in ensuring long lifetime of coated alloys. The calculated activation energy for the corrosion process is around 1.8 eV. A complex Co-Mn-Cr spinel is formed caused by diffusion of Cr and Mn from the alloy into the Co3O4 coating and by additional diffusion of Mn from the LSM layer. Adding a layer of LSM/Co3O4, acting as an additional Mn source, on top of the cobalt spinel is beneficial for the improved corrosion resistance.

Impedance spectroscopy and microstructural characterization of the corrosion behavior of FeCrAl alloy in lead-bismuth eutectic

NASA Astrophysics Data System (ADS)

Chen, Xiang; Haasch, Rick; Stubbins, James F.

2012-12-01

The corrosion behavior of FeCrAl alloy in Lead-Bismuth Eutectic (LBE) saturated with oxygen at 550 °C was investigated. Impedance Spectroscopy (IS) measurement was made continuously on one specimen during the entire LBE exposure test to characterize the corrosion kinetics. Various microanalysis techniques, including SEM, EDS, XRD, AES, and XPS were used to analyze the corrosion products of post-exposure specimens. It was found that a very thin, adherent alumina oxide layer formed on the specimen surface and was able to protect the alloy from the corrosion attack in LBE. The thickness of the alumina surface layer increased very slowly with time reaching about 837 nm in average thickness after exposure for 3600-h in LBE. The IS measurements match the microanalysis results in three respects: first, a non-zero impedance measurement agrees with the existence of a continuous surface oxide layer; second, a general increase of the impedance was observed during the real-time IS measurement which means that the IS measurements reflect the growth rate of the oxide layer; and third, the oxide film thickness derived from the IS data compares favorably with the SEM film thickness measurements which establishes the validity of using IS to monitor the real-time corrosion kinetics of alloys in LBE.

Formation of thick stratiform Fe-Ti oxide layers in layered intrusion and frequent replenishment of fractionated mafic magma: Evidence from the Panzhihua intrusion, SW China

NASA Astrophysics Data System (ADS)

Song, Xie-Yan; Qi, Hua-Wen; Hu, Rui-Zhong; Chen, Lie-Meng; Yu, Song-Yue; Zhang, Jia-Fei

2013-03-01

Panzhihua intrusion is one of the largest layered intrusions that hosts huge stratiform Fe-Ti oxide layers in the central part of the Emeishan large igneous province, SW China. Up to 60 m thick stratiform massive Fe-Ti oxide layers containing 85 modal% of magnetite and ilmenite and overlying magnetite gabbro compose cyclic units of the Lower Zone of the intrusion. The cyclic units of the Middle Zone consist of magnetite gabbro and overlying gabbro. In these cyclic units, contents of Fe2O3(t), TiO2 and Cr and Fe3+/Ti4+ ratio of the rocks decrease upward, Cr content of magnetite and forsterite percentage of olivine decrease as well. The Upper Zone consists of apatite gabbro characterized by enrichment of incompatible elements (e.g., 12-18 ppm La, 20-28 ppm Y) and increasing of Fe3+/Ti4+ ratio (from 1.3 to 2.3) upward. These features indicate that the Panzhihua intrusion was repeatedly recharged by more primitive magma and evolved magmas had been extracted. Calculations using MELTS indicate that extensive fractionation of olivine and clinopyroxene in deep level resulted in increasing Fe and Ti contents in the magma. When these Fe-Ti-enriched magmas were emplaced along the base of the Panzhihua intrusion, Fe-Ti oxides became an early crystallization phase, leading to a residual magma of lower density. We propose that the unusually thick stratiform Fe-Ti oxide layers resulted from coupling of gravity settling and sorting of the crystallized Fe-Ti oxides from Fe-Ti-enriched magmas and frequent magma replenishment along the floor of the magma chamber.

TEM and AES investigations of the natural surface nano-oxide layer of an AISI 316L stainless steel microfibre.

PubMed

Ramachandran, Dhanya; Egoavil, Ricardo; Crabbe, Amandine; Hauffman, Tom; Abakumov, Artem; Verbeeck, Johan; Vandendael, Isabelle; Terryn, Herman; Schryvers, Dominique

2016-11-01

The chemical composition, nanostructure and electronic structure of nanosized oxide scales naturally formed on the surface of AISI 316L stainless steel microfibres used for strengthening of composite materials have been characterised using a combination of scanning and transmission electron microscopy with energy-dispersive X-ray, electron energy loss and Auger spectroscopy. The analysis reveals the presence of three sublayers within the total surface oxide scale of 5.0-6.7 nm thick: an outer oxide layer rich in a mixture of FeO.Fe 2 O 3 , an intermediate layer rich in Cr 2 O 3 with a mixture of FeO.Fe 2 O 3 and an inner oxide layer rich in nickel. © 2016 The Authors Journal of Microscopy © 2016 Royal Microscopical Society.

Resistance switching mode transformation in SrRuO3/Cr-doped SrZrO3/Pt frameworks via a thermally activated Ti out-diffusion process

PubMed Central

Jo, Yongcheol; Jung, Kyooho; Kim, Jongmin; Woo, Hyeonseok; Han, Jaeseok; Kim, Hyungsang; Hong, Jinpyo; Lee, Jeon-Kook; Im, Hyunsik

2014-01-01

This work reports on a mechanism for irreversible resistive switching (RS) transformation from bipolar to unipolar RS behavior in SrRuO3 (SRO)/Cr-doped SrZrO3 (SZO:Cr)/Pt capacitor structures prepared on a Ti/SiO2/Si substrate. Counter-clockwise bipolar RS memory current-voltage (I–V) characteristics are observed within the RS voltage window of −2.5 to +1.9 V, with good endurance and retention properties. As the bias voltage increases further beyond 4 V under a forward bias, a forming process occurs resulting in irreversible RS mode transformation from bipolar to unipolar mode. This switching mode transformation is a direct consequence of thermally activated Ti out-diffusion from a Ti adhesion layer. Transition metal Ti effectively out-diffuses through the loose Pt electrode layer at high substrate temperatures, leading to the unintended formation of a thin titanium oxide (TiOx where x < 2) layer between the Pt electrode and the SZO:Cr layer as well as additional Ti atoms in the SZO:Cr layer. Cross-sectional scanning electron microscopy, transmission electron microscopy and Auger electron spectroscopy depth-profile measurements provided apparent evidence of the Ti out-diffusion phenomenon. We propose that the out-diffusion-induced additional Ti atoms in the SZO:Cr layer contributes to the creation of the metallic filamentary channels. PMID:25483325

Influence of alloying elements on the oxidation behavior of NbAl3

NASA Technical Reports Server (NTRS)

Hebsur, M. G.; Stephens, J. R.; Smialek, J. L.; Barrett, C. A.; Fox, D. S.

1988-01-01

NbAL3 is one candidate material for advanced aeropropulsion systems because of its high melting point, low density, and good oxidation resistance. Although NbAl3 has the lowest oxidation rate among the binary Nb-Al alloys, it does not form exclusive layers of protective Al2O3 scales. Recently Perkin et al., have shown the feasibility of forming alumina scales on Nb-Al alloys at greatly reduced Al contents. However, the objective was to maintain the high Al content, and hence low density, while achieving the capability of growing protective alumina scales. Alloy development followed approaches similar to those used successfully for superalloys and oxidation resistant MCrAlY coatings. Among the three elements examined (Ti, Si, and Cr) as ternary additions to Nb-Al3, Cr was the most effective in favoring the selective oxidation of Al. Nb-41Al-8Cr formed exclusive layers of alumina and had a k sub p value of 0.22 mg squared/cm (sup 4)/hr at 1200 C. The addition of 1 wt percent Y to this alloy was also beneficial, resulting in nearly an order of magnitude decrease in K sub p at 1200 C. Further improvements were achieved by adding about 1 wt percent Si to the quaternary alloy. The k sub p value of 0.012 mg squared/cm (sup 4)/hr for Nb-40Al-8Cr-1Y-1Si at 1200 C was identical to the best NiAl + Zr alloys. These NbAl3 alloys also exhibited excellent cyclic oxidation resistance for 100 hr at 1200 C, being nearly equivalent to NiAl + Zr.

Influence of alloying elements on the oxidation behavior of NbAl3

NASA Technical Reports Server (NTRS)

Hebsur, M. G.; Stephens, J. R.; Smialek, J. L.; Barrett, C. A.; Fox, D. S.

1989-01-01

NbAl3 is one candidate material for advanced aeropropulsion systems because of its high melting point, low density, and good oxidation resistance. Although NbAl3 has the lowest oxidation rate among the binary Nb-Al alloys, it does not form exclusive layers of protective Al203 scales. Recently Perkin et al., have shown the feasibility of forming alumina scales on Nb-Al alloys at greatly reduced Al contents. However, the objective was to maintain the high Al content, and hence low density, while achieving the capability of growing protective alumina scales. Alloy development followed approaches similar to those used successfully for superalloys and oxidation resistant MCrAly coatings. Among the three elements examined (Ti, Si, and Cr) as ternary additions to Nb-Al3, Cr was the most effective in favoring the selective oxidation of Al. Nb-41Al-8Cr formed exclusive layers of alumina and had a k sub p value of 0.22 mg squared/cm (sup 4)/hr at 1200 C. The addition of 1 wt percent Y to this alloy was also beneficial, resulting in nearly an order of magnitude decrease in K sub p at 1200 C. Further improvements were achieved by adding about 1 wt percent Si to the quaternary alloy. The k sub p value of 0.012 mg squared/cm (sup 4)/hr for Nb-40Al-8Cr-1Y-1Si at 1200 C was identical to the best NiAl + Zr alloys. These NbAl3 alloys also exhibited excellent cyclic oxidation resistance for 100 hr at 1200 C, being nearly equivalent to NiAl + Zr.

The effect of doping (Mn,B)3O4 materials as protective layers in different metallic interconnects for Solid Oxide Fuel Cells

NASA Astrophysics Data System (ADS)

Miguel-Pérez, Verónica; Martínez-Amesti, Ana; Nó, María Luisa; Larrañaga, Aitor; Arriortua, María Isabel

2013-12-01

Spinel oxides with the general formula of (Mn,B)3O4 (B = Co, Fe) were used as barrier materials between the cathode and the metallic interconnect to reduce the rate of cathode degradation by Cr poisoning. The effect of doping at the B position was investigated terms of microstructure and electrical conductivity to determine its behaviour and effectiveness as a protective layer in contact with three metallic materials (Crofer 22 APU, SS430 and Conicro 4023 W 188). The analysis showed that the use of these materials considerably decreased the reactivity and diffusion of Cr between the cathode and the metallic interconnects. The protective layer doped with Fe at the B position exhibited the least amount of reactivity with the interconnector and cathode materials. The worst results were observed for SS430 cells coated with a protective layer perhaps due to their low Cr content. The Crofer 22 APU and Conicro 4023 W 188 samples exhibited very similar conductivity results in the presence of the MnCo1.9Fe0.1O4 protective coating. As a result, these two material combinations are a promising option for use as bipolar plates in SOFC.

Electrical and structural properties of epitaxially deposited chromium thin films

NASA Astrophysics Data System (ADS)

Ohashi, M.; Sawabu, M.; Nakanishi, H.; Ohashi, K.; Maeta, K.

2018-05-01

We studied the electrical resistance and crystal structure of epitaxial chromium (Cr) films. The lattice constant of the Cr films was larger than that of the bulk Cr because of MgO substrate on which Cr was epitaxially deposited. A chromium oxide layer having a thickness of 1 nm was found on all films from the result of X-ray reflectivity measurements. The electrical resistivity ρ(T) shows metallic behavior for all epitaxial Cr films in contrast with polycrystalline one. However, the magnitude of ρ tends to increase and the antiferromagnetic interaction is suppressed as decreasing thickness of film.

Corrosion behavior of pre-oxidized HR-224 superalloy in supercritical water environment at 700 °C

NASA Astrophysics Data System (ADS)

Liu, Yu-Chen; Chen, Shih-Ming; Ouyang, Fan-Yi; Kai, Ji-Jung

2018-07-01

Corrosion of cladding materials in supercritical water (SCW) environment is a key reliability issue for the safety of nuclear power plant. In this study, we propose to use the pre-oxidized treatment to provide better corrosion resistance of cladding materials in the SCW environment. The nickel-based superalloy HR-224 was first pre-oxidized in flowing air at 982 °C for 100 h to establish a continuous and dense scales and then exposed in the SCW environment with high oxygen content (8.3 ppm) at 700 °C and 24.8 MPa for cyclic oxidation testing up to 1300 h. The pre-oxidized samples exhibit better corrosion resistance than as-received samples in the SCW environment. After pre-oxidizing process, triple scales, Ni(Cr, Fe)2O4 spinel/Cr2O3/α-Al2O3 were observed, and the growth of inner α-Al2O3 layer is predominant in the SCW environment. The α-Al2O3 layer in pre-oxidized samples was found to effectively decrease outward migration of metal ions in Alloy HR-224 and thus provides better corrosion resistance than as-received samples in SCW environment.

The oxidation of Inconel-690 alloy at 600 K in air

NASA Astrophysics Data System (ADS)

Allen, G. C.; Dyke, J. M.; Harris, S. J.; Morris, A.

1988-03-01

The alloy Inconel-690 has been oxidised at 600 K in air for periods varying between 30 s and 120 h and the composition of the oxide layer formed examined by scanning Auger microscopy (SAM), scanning electron microscopy with energy dispersive analysis of X-rays (SEM/EDAX), secondary ion mass spectrometry (SIMS) and X-ray photoelectron spectroscopy (XPS). Analysis of the spectra revealed the formation of a layer of essentially α-Cr 2O 3 at room temperature. Oxidation at 600 K resulted in the formation of a duplex oxide film with a thin outer layer of iron(III) oxide. Beneath this was a mixed chromium, iron, nickel oxide. Following 8 h of oxidation at 600 K the oxide was approximately 10 nm thick but this was found to vary with the physical surface of the underlying alloy which also appeared to affect the relative rates of diffusion of the ionic species during film growth.

Residual stress determination in oxide layers at different length scales combining Raman spectroscopy and X-ray diffraction: Application to chromia-forming metallic alloys

DOE PAGES

Guerain, Mathieu; Grosseau-Poussard, Jean-Luc; Geandier, Guillaume; ...

2017-11-21

In oxidizing environments, the protection of metals and alloys against further oxidation at high temperature is provided by the oxide film itself. This protection is efficient only if the formed film adheres well to the metal (substrate), i.e., without microcracks and spalls induced by thermomechanical stresses. In this study, the residual stresses at both macroscopic and microscopic scales in the oxide film adhering to the substrate and over the damaged areas have been rigorously determined on the same samples for both techniques. Ni-30Cr and Fe-47Cr alloys have been oxidized together at 900 and 1000 °C, respectively, to create films withmore » a thickness of a few microns. A multi-scale approach was adopted: macroscopic stress was determined by conventional X-ray diffraction and Raman spectroscopy, while microscopic residual stress mappings were performed over different types of bucklings using Raman micro-spectroscopy and synchrotron micro-diffraction. A very good agreement is found at macro- and microscales between the residual stress values obtained with both techniques, giving confidence on the reliability of the measurements. In addition, relevant structural information at the interface between the metallic substrate and the oxide layer was collected by micro-diffraction, a non-destructive technique that allows mapping through the oxide layer, and both the grain size and the crystallographic orientation of the supporting polycrystalline metal located either under a buckling or not were measured.« less

Residual stress determination in oxide layers at different length scales combining Raman spectroscopy and X-ray diffraction: Application to chromia-forming metallic alloys

DOE Office of Scientific and Technical Information (OSTI.GOV)

Guerain, Mathieu; Grosseau-Poussard, Jean-Luc; Geandier, Guillaume

In oxidizing environments, the protection of metals and alloys against further oxidation at high temperature is provided by the oxide film itself. This protection is efficient only if the formed film adheres well to the metal (substrate), i.e., without microcracks and spalls induced by thermomechanical stresses. In this study, the residual stresses at both macroscopic and microscopic scales in the oxide film adhering to the substrate and over the damaged areas have been rigorously determined on the same samples for both techniques. Ni-30Cr and Fe-47Cr alloys have been oxidized together at 900 and 1000 °C, respectively, to create films withmore » a thickness of a few microns. A multi-scale approach was adopted: macroscopic stress was determined by conventional X-ray diffraction and Raman spectroscopy, while microscopic residual stress mappings were performed over different types of bucklings using Raman micro-spectroscopy and synchrotron micro-diffraction. A very good agreement is found at macro- and microscales between the residual stress values obtained with both techniques, giving confidence on the reliability of the measurements. In addition, relevant structural information at the interface between the metallic substrate and the oxide layer was collected by micro-diffraction, a non-destructive technique that allows mapping through the oxide layer, and both the grain size and the crystallographic orientation of the supporting polycrystalline metal located either under a buckling or not were measured.« less

Residual stress determination in oxide layers at different length scales combining Raman spectroscopy and X-ray diffraction: Application to chromia-forming metallic alloys

NASA Astrophysics Data System (ADS)

Guerain, Mathieu; Grosseau-Poussard, Jean-Luc; Geandier, Guillaume; Panicaud, Benoit; Tamura, Nobumichi; Kunz, Martin; Dejoie, Catherine; Micha, Jean-Sebastien; Thiaudière, Dominique; Goudeau, Philippe

2017-11-01

In oxidizing environments, the protection of metals and alloys against further oxidation at high temperature is provided by the oxide film itself. This protection is efficient only if the formed film adheres well to the metal (substrate), i.e., without microcracks and spalls induced by thermomechanical stresses. In this study, the residual stresses at both macroscopic and microscopic scales in the oxide film adhering to the substrate and over the damaged areas have been rigorously determined on the same samples for both techniques. Ni-30Cr and Fe-47Cr alloys have been oxidized together at 900 and 1000 °C, respectively, to create films with a thickness of a few microns. A multi-scale approach was adopted: macroscopic stress was determined by conventional X-ray diffraction and Raman spectroscopy, while microscopic residual stress mappings were performed over different types of bucklings using Raman micro-spectroscopy and synchrotron micro-diffraction. A very good agreement is found at macro- and microscales between the residual stress values obtained with both techniques, giving confidence on the reliability of the measurements. In addition, relevant structural information at the interface between the metallic substrate and the oxide layer was collected by micro-diffraction, a non-destructive technique that allows mapping through the oxide layer, and both the grain size and the crystallographic orientation of the supporting polycrystalline metal located either under a buckling or not were measured.

Interdiffusion behavior of U3Si2 with FeCrAl via diffusion couple studies

NASA Astrophysics Data System (ADS)

Hoggan, Rita E.; He, Lingfeng; Harp, Jason M.

2018-04-01

Uranium silicide (U3Si2) is a candidate to replace uranium oxide (UO2) as light water reactor (LWR) fuel because of its higher thermal conductivity and higher fissile density relative to the current standard, UO2. A class of Fe, Cr, Al alloys collectively known as FeCrAl alloys that have superior mechanical and oxidation resistance are being considered as an alternative to the standard Zirconium based LWR cladding. The interdiffusion behavior between FeCrAl and U3Si2 is investigated in this study. Commercially available FeCrAl, along with U3Si2 pellets were placed in diffusion couples. Individual tests were ran at temperatures ranging from 500 °C to 1000 °C for 30 h and 100 h. The interdiffusion was analyzed with an optical microscope, scanning electron microscope, and transmission electron microscope. Uniform and planar interdiffusion layers along the material interface were illustrated with backscatter electron micrographs and energy-dispersive X-ray spectroscopy. Electron diffraction was used to validate phases present in the system, including distinct U2Fe3Si/UFe2 and UFeSi layers at the material interface. U and Fe diffused far into the FeCrAl and U3Si2 matrix, respectively, in the higher temperature tests. No interaction was observed at 500 °C for 30 h.

In situ X-ray diffraction contribution to the study of reactive element oxide coating effect on the high temperature oxidation behaviour of FeCrAl alloys

NASA Astrophysics Data System (ADS)

Cueff, R.; Buscail, H.; Caudron, E.; Riffard, F.; Issartel, C.; Perrier, S.; El Messki, S.

2004-11-01

The influence of yttrium oxide coating (processed by sol-gel method) on the oxidation behaviour of a commercial FeCrAl alloy (Kanthal A1) has been investigated during isothermal exposures in air at 1373K. The scale growth kinetic of the uncoated alloy obeys a parabolic rate law during the whole oxidation test whereas the kinetic curve of the Y-coated specimen exhibits an initial transient stage during the first hours, followed by a parabolic regime. The yttrium sol-gel coating deposited on the bare alloy does not conduct to the beneficial effect usually ascribed to the reactive elements. No oxidation rate improvement of the coated alloy is observed, the parabolic rate constants values are strictly identical for the both specimens. In situ X-ray diffraction reveals a marked influence of the reactive element on the composition of the oxide scale. The oxide layer formed on the yttrium-coated specimen revealed, in addition to α-alumina which is the main oxide also identified on the bare specimen, the presence of yttrium aluminates (YAlO{3}, Y{3}Al{5}O{12}) located in the outermost part of the layer.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Bo, Shou-Hang; Li, Xin; Toumar, Alexandra J.

O3 layered sodium transition metal oxides (i.e., NaMO 2, M = Ti, V, Cr, Mn, Fe, Co, Ni) are a promising class of cathode materials for Na-ion battery applications. These materials, however, all suffer from severe capacity decay when the extraction of Na exceeds certain capacity limits. Understanding the causes of this capacity decay is critical to unlocking the potential of these materials for battery applications. In this work, we investigate the structural origins of capacity decay for one of the compounds in this class, NaCrO 2. The (de)sodiation processes of NaCrO 2 were studied both in situ and exmore » situ through X-ray and electron diffraction measurements. We demonstrate that Na xCrO 2 (0 < x < 1) remains in the layered structural framework without Cr migration up to a composition of Na 0.4CrO 2. Further removal of Na beyond this composition triggers a layered-to-rock-salt transformation, which converts P'3-Na 0.4CrO 2 into the rock-salt CrO 2 phase. This structural transformation proceeds via the formation of an intermediate O3 Na δCrO 2 phase that contains Cr in both Na and Cr slabs and shares very similar lattice dimensions with those of rock-salt CrO 2. It is intriguing to note that intercalation of alkaline ions (i.e., Na + and Li + ) into the rock-salt CrO 2 and O3 Na δCrO 2 structures is actually possible, albeit in a limited amount (~0.2 per formula unit). When these results were analyzed under the context of electrochemistry data, it was apparent that preventing the layered-to-rock-salt transformation is crucial to improve the cyclability of NaCrO 2. Possible strategies for mitigating this detrimental phase transition are proposed.« less

Evaluation of Ti-48Al-2Nb Under Fretting Conditions

NASA Technical Reports Server (NTRS)

Miyoshi, Kazuhisa; Lerch, Bradley A.; Draper, Susan L.; Raj, Sai V.

2001-01-01

An investigation was conducted to examine the fretting behavior of lambda-TiAl (Ti-48Al-2Cr-2Nb) in contact with a nickel-base superalloy (Inconel 718) in air at temperatures from 23 to 550 C. Fretting wear experiments were conducted with 9.4-mm-diameter hemispherical Inconel (IN) 718 pins in contact with Ti-48Al-2Cr-2Nb flats (and the reverse) at loads from 1 to 40 N and fretting frequencies from 50 to 160 Hz with slip amplitudes from 50 to 200 microns for 1 to 20 million fretting cycles. The results were similar for both combinations of pin and flat. Reference fretting wear experiments were also conducted with 9.4-mm-diameter hemispherical Ti-6Al-4V pins in contact with IN718 flats. The interfacial adhesive bonds between Ti-48Al-2Cr-2Nb and IN718 in contact were generally stronger than the cohesive bonds in the cohesively weaker Ti-48Al-2Cr-2Nb. The failed Ti-48Al-2Cr-2Nb subsequently transferred to the IN718 surface at any fretting condition. The wear scars produced on Ti-48Al-2Cr-2Nb contained metallic and oxide wear debris, scratches, plastically deformed asperities, cracks, and fracture pits. Oxide layers readily formed on the Ti-48Al-2Cr-2Nb surface at 550 C, but cracks easily occurred in the oxide layers. Factors including fretting frequency, temperature, slip amplitude, and load influenced the fretting behavior of Ti-48Al-2Cr-2Nb in contact with IN718. The wear volume loss of Ti-48Al-2Cr-2Nb generally decreased with increasing fretting frequency. The increasing rate of oxidation at elevated temperatures up to 200 C led to a drop in wear volume loss at 200 C. However, the fretting wear increased as the temperature was increased from 200 to 550 C. The highest temperatures of 450 and 550 C resulted in oxide film disruption with generation of cracks, loose wear debris, and pits on the Ti-48Al-2Cr-2Nb wear surface. The wear volume loss generally increased as the slip amplitude increased. The wear volume loss also generally increased as the load increased. Increasing slip amplitude and increasing load both tended to produce more metallic wear debris, causing severe abrasive wear in the contacting metals.

Comparison of iron and copper doped manganese cobalt spinel oxides as protective coatings for solid oxide fuel cell interconnects

NASA Astrophysics Data System (ADS)

Talic, Belma; Molin, Sebastian; Wiik, Kjell; Hendriksen, Peter Vang; Lein, Hilde Lea

2017-12-01

MnCo2O4, MnCo1.7Cu0.3O4 and MnCo1.7Fe0.3O4 are investigated as coatings for corrosion protection of metallic interconnects in solid oxide fuel cell stacks. Electrophoretic deposition is used to deposit the coatings on Crofer 22 APU alloy. All three coating materials reduce the parabolic oxidation rate in air at 900 °C and 800 °C. At 700 °C there is no significant difference in oxidation rate between coated samples and uncoated pre-oxidized Crofer 22 APU. The cross-scale area specific resistance (ASR) is measured in air at 800 °C using La0.85Sr0.1Mn1.1O3 (LSM) contact plates to simulate the interaction with the cathode in a SOFC stack. All coated samples have three times lower ASR than uncoated Crofer 22 APU after 4370 h aging. The ASR increase with time is lowest with the MnCo2O4 coating, followed by the MnCo1.7Fe0.3O4 and MnCo1.7Cu0.3O4 coatings. LSM plates contacted to uncoated Crofer 22 APU contain significant amounts of Cr after aging, while all three coatings effectively prevent Cr diffusion into the LSM. A complex Cr-rich reaction layer develops at the coating-alloy interface during oxidation. Cu and Fe doping reduce the extent of this reaction layer at 900 °C, while at 800 °C the effect of doping is insignificant.

Influence of Magnesium Ions in the Seawater Environment on the Improvement of the Corrosion Resistance of Low-Chromium-Alloy Steel.

PubMed

Song, Sol-Ji; Kim, Jung-Gu

2018-01-20

This study examined the synergic effect of alloying the element Cr and the environmental element Mg 2+ ions on the corrosion property of a low-alloy steel in seawater at 60 °C, by means of electrochemical impedance spectroscopy (EIS), linear polarization resistance (LPR) tests and weight-loss tests. The Mg 2+ ions in seawater played an important role in lowering the electron transfer of the rust layer in the Cr-containing steel. The corrosion resistance of the Cr-containing steel is superior to that of blank steel in Mg 2+ ions containing seawater. XPS and XRD results indicated that the formation of MgFe₂O₄ and a mixed layer (Cr oxide + FeCr₂O₄ + MgCr₂O₄) improved the corrosion resistance of the low-alloy steel in the seawater.

A sulfur segregation study of PWA 1480, NiCrAl, and NiAl alloys

NASA Technical Reports Server (NTRS)

Jayne, D. T.; Smialek, J. L.

1993-01-01

Some nickel based superalloys show reduced oxidation resistance from the lack of an adherent oxide layer during high temperature cyclic oxidation. The segregation of sulfur to the oxide-metal interface is believed to effect oxide adhesion, since low sulfur alloys exhibit enhanced adhesion. X ray Photoelectron Spectroscopy (XPS) was combined with an in situ sample heater to measure sulfur segregation in NiCrAl, PWA 1480, and NiAl alloys. The polished samples with a 1.5 to 2.5 nm (native) oxide were heated from 650 to 1100 C with hold times up to 6 hr. The sulfur concentration was plotted as a function of temperature versus time at temperature. One NiCrAl sulfur study was performed on the same casting used by Browning to establish a base line between previous Auger Electron Spectroscopy (AES) results and the XPS results of this study. Sulfur surface segregation was similar for PWA 1480 and NiCrAl and reached a maximum of 30 at% at 800 to 850 C. Above 900 C the sulfur surface concentration decreased to about 3 at% at 1100 C. These results are contrasted to the minimal segregation observed for low sulfur hydrogen annealed materials which exhibit improved scale adhesion.

Oxidation of SUS-316 stainless steel for fast breeder reactor fuel cladding under oxygen pressure controlled by Ni/NiO oxygen buffer

NASA Astrophysics Data System (ADS)

Saito, Minoru; Furuya, Hirotaka; Sugisaki, Masayasu

1985-09-01

Oxidation of SUS-316 stainless steel for a fast breeder reactor fuel cladding was examined in the temperature range of 843-1010 K under the oxygen pressure of 1017 t - 10 t-13 Pa hy use of an experimental technique of a Ni/NiO oxygen buffer. The formation of the duplex oxide layer, i.e. an outer Fe 3O 4 layer and an inner (Fe, Cr, Ni)-spinel layer, was observed and the oxidation kinetics was found to obey the parabolic rate law. The oxygen pressure and temperature dependence of the parabolic rate constant kp( PO2, T) was determined as follows: kp( PO2, T)/ kg2 · m-1 · s-1 = 0.170( PO2/ Pa) 0.141exp[-114 × 10 3/( RT/ J)]. On the basis of the oxidation kinetics and the metallographic information, the outward diffusion of Fe in the outer oxide layer was assigned to be the rate-determining process.

Oxidation and the Effects of High Temperature Exposures on Notched Fatigue Life of an Advanced Powder Metallurgy Disk Superalloy

NASA Technical Reports Server (NTRS)

Sudbrack, Chantal K.; Draper, Susan L.; Gorman, Timothy T.; Telesman, Jack; Gab, Timothy P.; Hull, David R.

2012-01-01

Oxidation and the effects of high temperature exposures on notched fatigue life were considered for a powder metallurgy processed supersolvus heat-treated ME3 disk superalloy. The isothermal static oxidation response at 704 C, 760 C, and 815 C was consistent with other chromia forming nickel-based superalloys: a TiO2-Cr2O3 external oxide formed with a branched Al2O3 internal subscale that extended into a recrystallized - dissolution layer. These surface changes can potentially impact disk durability, making layer growth rates important. Growth of the external scales and dissolution layers followed a cubic rate law, while Al2O3 subscales followed a parabolic rate law. Cr- rich M23C6 carbides at the grain boundaries dissolved to help sustain Cr2O3 growth to depths about 12 times thicker than the scale. The effect of prior exposures was examined through notched low cycle fatigue tests performed to failure in air at 704 C. Prior exposures led to pronounced debits of up to 99 % in fatigue life, where fatigue life decreased inversely with exposure time. Exposures that produced roughly equivalent 1 m thick external scales at the various isotherms showed statistically equivalent fatigue lives, establishing that surface damage drives fatigue debit, not exposure temperature. Fractographic evaluation indicated the failure mode for the pre-exposed specimens involved surface crack initiations that shifted with exposure from predominately single intergranular initiations with transgranular propagation to multi-initiations from the cracked external oxide with intergranular propagation. Weakened grain boundaries at the surface resulting from the M23C6 carbide dissolution are partially responsible for the intergranular cracking. Removing the scale and subscale while leaving a layer where M23C6 carbides were dissolved did not lead to a significant fatigue life improvement, however, also removing the M23C6 carbide dissolution layer led to nearly full recovery of life, with a transgranular initiation typical to that observed in unexposed specimens.

Effects of lead on oxidation behavior of Alloy 690TT within a high temperature aqueous environment

NASA Astrophysics Data System (ADS)

Hou, Qiang; Liu, Zhiyong; Li, Chengtao; Li, Xiaogang

2017-12-01

The chemical compositions, phases and structures of two oxide films on Alloy 690TT following exposure for 4400 h in pure water with and without lead at 320 °C were studied by surface analysis techniques. The analysis of a lead-doped oxide film prepared by a focused ion beam (FIB) demonstrated that both Cr-rich and Ni-rich oxides were alternatively distributed within the outer layer, whereas the inner layer was porous and poorly protected, causing severe corrosion of the alloy and a thicker film was formed. A duplex film model was proposed for the effects discussion of lead on the oxidation mechanism.

Thermal Stability of NaxCrO2 for Rechargeable Sodium Batteries; Studies by High-Temperature Synchrotron X-ray Diffraction.

PubMed

Yabuuchi, Naoaki; Ikeuchi, Issei; Kubota, Kei; Komaba, Shinichi

2016-11-30

Thermal stability and phase transition processes of NaCrO 2 and Na 0.5 CrO 2 are carefully examined by high-temperature synchrotron X-ray diffraction method. O3-type NaCrO 2 shows anisotropic thermal expansion on heating, which is a common character as layered materials, without phase transition in the temperature range of 27-527 °C. In contrast, for the desodiated phase, in-plane distorted P3-type layered oxide (P'3 Na 0.5 CrO 2 ), phase transition occurs in the following order. Monoclinic distortion associated with Na/vacancy ordering is gradually lost on heating, and its symmetry increases and changes to a rhombohedral lattice at 207 °C. On further heating, phase segregation to two P3 layered metastable phases, which have different interlayer distances (17.0 and 13.5 Å, presumably sodium-rich and sodium-free P3 phases, respectively) are observed on heating to 287-477 °C, but oxygen loss is not observed. Oxygen loss is observed at temperatures only above 500 °C, resulting in the formation of corundum-type Cr 2 O 3 and O3 NaCrO 2 as thermodynamically stable phases. From these results, possibility of Na x CrO 2 as a positive electrode material for safe rechargeable sodium batteries is also discussed.

Degradation of nonmodified and rhodium modified aluminide coating deposited on CMSX 4 superalloy.

PubMed

Zagula-Yavorska, Maryana; Wierzbińska, Małgorzata; Gancarczyk, Kamil; Sieniawski, Jan

2016-07-01

The Ni-base superalloy CMSX 4 used in the turbine blades of aircraft engines was coated with rhodium layer (0.5-μm thick). Next coated CMSX 4 superalloy was aluminized by the CVD method. The rhodium modified aluminide coating and nonmodified aluminide coating were oxidized at 1100°C at the air atmosphere. The rhodium modified aluminide coating showed about twice better oxidation resistance than the nonmodified one. The spallation equal 62% of the total area was observed on the surface of the nonmodified coating whereas only 36% spallation area was observed on the surface of the rhodium modified aluminide coating after the oxidation test. The oxide layer formed on the surface of the nonmodified coating was composed of nonprotective (Ni,Cr)Al2 O4 and (Ni,Cr)O phases. Aluminium in the coating reacts with oxygen, forming a protective α-Al2 O3 oxide on the surface of the rhodium modified aluminide coating. When the oxide cracks and spalls due to oxidation, additional aluminium from the coating diffuses to the surface to form the oxide. The presence of protective Al2 O3 oxide on the surface of the rhodium modified aluminide coating slows coating degradation. Therefore, rhodium modified aluminide coating has better oxidation resistance than the nonmodified one. © 2016 The Authors Journal of Microscopy © 2016 Royal Microscopical Society.

Investigation of the surface composition of electrodeposited black chromium by X-ray photoelectron spectroscopy

NASA Astrophysics Data System (ADS)

Survilienė, S.; Češūnienė, A.; Jasulaitienė, V.; Jurevičiūtė, I.

2015-01-01

The paper reviews black chromium electrodeposited from a trivalent chromium bath containing ZnO as a second main component. The chemical compositions of the top layers of the black chromium coatings were studied by the X-ray photoelectron spectroscopy method. The surface of black chromium was found to be almost entirely covered with organic substances. To gain information on the state of each element in the deposit bulk, the layer-by-layer etching of the black chromium surface with argon gas was used. Analysis of XPS spectra has shown that the top layers of black chromium without zinc are composed of various Cr(III) components, organic substances and metallic Cr, whereas metallic Cr is almost absent in black chromium containing some amount of Zn(II) compounds. The ratios of metal/oxide phases were found to be 10/27 and 2/28 for black chromium without and with zinc, respectively. It has been determined that owing to the presence of ZnO in the Cr(III) bath, the percentage of metallic chromium is substantially reduced in black chromium which is quite important for good solar selective characteristics of the coating. The results confirm some of earlier observations and provide new information on the composition of the near-surface layers.

The geochemical cycling of trace elements in a biogenic meromictic lake

NASA Astrophysics Data System (ADS)

Balistrieri, Laurie S.; Murray, James W.; Paul, Barbara

1994-10-01

The geochemical processes affecting the behavior and speciation of As, Co, Cr, Cu, Fe, Mn, Mo, Ni, Pb, V, and Zn in Hall Lake, Washington, USA, are assessed by examining dissolved and acid soluble particulate profiles of the elements and utilizing results from thermodynamic calculations. The water column of this meromictic lake is highly stratified and contains distinctive oxic, suboxic, and anoxic layers. Changes in the redox state of the water column with depth affect the distribution of all the elements studied. Most noticeable are increases in dissolved Co, Cr, Fe, Mn, Ni, Pb, and Zn concentrations across the oxic-suboxic boundary, increases in dissolved As, Co, Cr, Fe, Mn, and V concentrations with depth in the anoxic layer, significant decreases in dissolved Cu, Ni, Pb, and Zn concentrations in the anoxic region below the sulfide maximum, and large increases in acid soluble particulate concentrations of As, Cr, Cu, Fe, Mo, Ni, Pb, V, and Zn in the anoxic zone below the sulfide maximum. Thermodynamic calculations for the anoxic region indicate that all redox sensitive elements exist in their reduced forms, the primary dissolved forms of Cu, Ni, Pb, and Zn are metal sulfide solution complexes, and solid sulfide phases of Cu, Fe, Mo, and Pb are supersaturated. Calculations using a vertical diffusion and reaction model indicate that the oxidation rate constant for Mn(II) in Hall Lake is estimated to be 0.006 d -1 and is at the lower end of the range of microbial oxidation rates observed in other natural systems. The main geochemical processes influencing the distribution and speciation of trace elements in Hall Lake appear to be transformations of dissolved elements between their oxidation states (As, Cr, Cu, Fe, Mn, V), cocycling of trace elements with Mn and Fe (As, Co, Cr, Cu, Mo, Ni, Pb, V, Zn), formation of soluble metal sulfide complexes (Co, Cu, Ni, Pb, Zn), sorption (As, Co, Cr, Ni, V), and precipitation (Cu, Fe, Mn, Mo, Pb, Zn).

The geochemical cycling of trace elements in a biogenic meromictic lake

USGS Publications Warehouse

Balistrieri, L.S.; Murray, J.W.; Paul, B.

1994-01-01

The geochemical processes affecting the behavior and speciation of As, Co, Cr, Cu, Fe, Mn, Mo, Ni, Pb, V, and Zn in Hall Lake, Washington, USA, are assessed by examining dissolved and acid soluble particulate profiles of the elements and utilizing results from thermodynamic calculations. The water column of this meromictic lake is highly stratified and contains distinctive oxic, suboxic, and anoxic layers. Changes in the redox state of the water column with depth affect the distribution of all the elements studied. Most noticeable are increases in dissolved Co, Cr, Fe, Mn, Ni, Pb, and Zn concentrations across the oxic-suboxic boundary, increases in dissolved As, Co, Cr, Fe, Mn, and V concentrations with depth in the anoxic layer, significant decreases in dissolved Cu, Ni, Pb, and Zn concentrations in the anoxic region below the sulfide maximum, and large increases in acid soluble particulate concentrations of As, Cr, Cu, Fe, Mo, Ni, Pb, V, and Zn in the anoxic zone below the sulfide maximum. Thermodynamic calculations for the anoxic region indicate that all redox sensitive elements exist in their reduced forms, the primary dissolved forms of Cu, Ni, Pb, and Zn are metal sulfide solution complexes, and solid sulfide phases of Cu, Fe, Mo, and Pb are supersaturated. Calculations using a vertical diffusion and reaction model indicate that the oxidation rate constant for Mn(II) in Hall Lake is estimated to be 0.006 d-1 and is at the lower end of the range of microbial oxidation rates observed in other natural systems. The main geochemical processes influencing the distribution and speciation of trace elements in Hall Lake appear to be transformations of dissolved elements between their oxidation states (As, Cr, Cu, Fe, Mn, V), cocycling of trace elements with Mn and Fe (As, Co, Cr, Cu, Mo, Ni, Pb, V, Zn), formation of soluble metal sulfide complexes (Co, Cu, Ni, Pb, Zn), sorption (As, Co, Cr, Ni, V), and precipitation (Cu, Fe, Mn, Mo, Pb, Zn). ?? 1994.

The entrapment of corrosion products from CoCr implant alloys in the deposits of calcium phosphate: a comparison of serum, synovial fluid, albumin, EDTA, and water.

PubMed

Lewis, A C; Kilburn, M R; Heard, P J; Scott, T B; Hallam, K R; Allen, G C; Learmonth, I D

2006-08-01

Physical wear of orthopedic implants is inevitable. CoCr alloy samples, typically used in joint reconstruction, corrode rapidly after removal of the protective oxide layer. The behavior of CoCr pellets immersed in human serum, foetal bovine serum (FBS), synovial fluid, albumin in phosphate-buffered saline (PBS), EDTA in PBS, and water were studied using X-ray Photoelectron Spectroscopy (XPS) and Time-of-Flight Secondary Ion Mass Spectroscopy (ToF-SIMS). The difference in the corrosive nature of human serum, water, albumin in PBS and synovial fluid after 5 days of immersion was highlighted by the oxide layer, which was respectively 15, 3.5, 1.5, and 1.5 nm thick. The thickness of an additional calcium phosphate deposit from human serum and synovial fluid was 40 and 2 nm, respectively. Co and Cr ions migrated from the bulk metal surface and were trapped in this deposit by the phosphate anion. This may account for the composition of wear debris from CoCr orthopedic implants, which is known to consist predominantly of hydroxy-phosphate compounds. Known components of synovial fluid including proteoglycans, pyrophosphates, phospholipids, lubricin, and superficial zone protein (SZP), have been identified as possible causes for the lack of significant calcium phosphate deposition in this environment. Circulation of these compounds around the whole implant may inhibit calcium phosphate deposition.

Solute redistribution and phase stability at FeCr/TiO 2–x interfaces under ion irradiation

DOE PAGES

Xu, Y.; Aguiar, J. A.; Yadav, S. K.; ...

2015-02-26

Cr diffusion in trilayer thin films of 100 nm Fe–18Cr/125 nm TiO 2–x/100 nm Fe–18Cr deposited on MgO substrates at 500 °C was studied by either annealing at 500 °C or Ni 3+ ion irradiation at 500 °C. Microchemistry and microstructure evolution at the metal/oxide interfaces were investigated using (high-resolution) transmission electron microscopy, energy-dispersive X-ray spectroscopy and electron energy loss spectroscopy. Diffusion of Cr into the O-deficient TiO 2 layer, with negligible segregation to the FeCr/TiO 2–x interface itself, was observed under both annealing and irradiation. Cr diffusion into TiO 2–x was enhanced in ion-irradiated samples as compared to annealed.more » Irradiation-induced voids and amorphization of TiO 2–x was also observed. The experimental results are rationalized using first-principles calculations that suggest an energetic preference for substituting Ti with Cr in sub-stoichiometric TiO 2. Furthermore, the implications of these results on the irradiation stability of oxide-dispersed ferritic alloys are discussed.« less

Layered Li-Mn-M-oxides as cathodes for Li-ion batteries:. Recent trends

NASA Astrophysics Data System (ADS)

Shaju, K. M.; Subba Rao, G. V.; Chowdari, B. V. R.

2002-12-01

There is an increasing demand for manganese (Mn) based mixed oxides which can effectively replace the presently used LiCoO2 as cathode in Li-ion batteries (LIB). The well-studied spinel, LiMn2O4 and its doped derivatives give a capacity of 100-120 mAh/g, but show capacity-fading on cycling especially above 55°C. The layered LiMnO2, isostructural to LiCoO2 (so called O3-structure) can be a viable cathode. However, studies have shown that it undergoes conversion to spinel structure on cycling and thus gives capacity-fading. Other alternative systems recently studied are: O2-structured layered Li-M-Mn-oxides with the general formula Li(2/3)+x(MyMn1-y)O2, M = Li, Ni, Co; x ≤ 0.33 and y = 0.1-0.67, O3-Li(Ni1/2Mn1/2)O2, Li(NixCo1-2xMnx)O2, and M'-substituted Li2MnO3 (M' = Ni, Co, Cr). Some of them are shown to have stable cycling performance, good rate-capability and structural stability over charge-discharge cycling in the 2.5-4.6 V region. Further, the electrochemical processes in the above mixed oxides have been shown to involve Ni2+/4+ or Cr3+/6+ redox couple, thus invoking novel ideas to develop new cathode materials. A brief review of the work done on the above O2- and O3-layered Li-Mn-M-oxides (M = metal) as cathodes for LIB is presented.

Effects of compositional changes on the performance of a thermal barrier coating system. [for aircraft gas turbine engines

NASA Technical Reports Server (NTRS)

Stecura, S.

1979-01-01

Systems consisting of Ni-base bond coatings containing about 16Cr, 6Al, and from 0.15 to 1.08Y (all in wt %) and zirconium oxide layers containing from 4.0 to 24.4Y2O3 were evaluated for suitability as thermal barrier systems for advanced aircraft gas turbine engine components. The evaluations were performed in a cyclic furnace between 990 and 280 C as well as between 1095 and 280 C on solid specimens; in a natural gas-oxygen torch rig between about 1200 and 100 C on solid specimens and up to 1580 C surface temperatures on air-cooled blades; and in a Mach 1.0 burner rig up to 1570 C surface temperatures on air-cooled blades. The data indicate that the best systems consist of combinations involving the Ni-16.4Cr-5.1Al-0.15Y and Ni-17.0Cr-5.4Al-0.35Y bond coatings and the 6.2Y2O3- and 7.9Y2O3- (all in wt %) stabilized zirconium oxide layers.

Aqueous chemical growth of alpha-Fe2O3-alpha-Cr203 nanocompositethin films

DOE Office of Scientific and Technical Information (OSTI.GOV)

Vayssieres, Lionel; Guo, Jinghua; Nordgren, Joseph

2001-06-30

We are reporting here on the inexpensive fabrication and optical properties of an iron(III) oxide chromium(III) oxide nanocomposite thin film of corundum crystal structure. Its novel and unique-designed architecture consists of uniformed, well-defined and oriented nanorods of Hematite (alpha-Fe2O3) of 50 nm in diameter and 500nm in length and homogeneously distributed nonaggregated monodisperse spherical nanoparticles of Eskolaite (alpha-Cr2O3) of 250 nm in diameter. This alpha-Fe2O3 alpha-Cr2O3 nanocomposite thin film is obtained by growing, directly onto transparent polycrystalline conducting substrate, an oriented layer of hematite nanorods and growing subsequently, the eskolaite layer. The synthesis is carried out by a template-free, low-temperature,more » multilayer thin film coating process using aqueous solution of metal salts as precursors. Almost 100 percent of the light is absorbed by the composite film between 300 and 525 nm and 40 percent at 800 nm which yields great expectations as photoanode materials for photovoltaic cells and photocatalytic devices.« less

Corrosion of metals and alloys in sulfate melts at 750 C

NASA Technical Reports Server (NTRS)

Misra, A. K.

1986-01-01

The corrosion of Ni, Co, Ni-10Cr, Co-21Cr, and IN738 was studied at 750 C in the presence of molten sulfate mixtures (Na2SO4-Li2SO4 and Na2SO4-CoSO4) and in an atmosphere consisting of O2 + 0.12 percent SO2-SO3. The corrosion was observed to be similar for both Na2SO4-Li2SO4 and Na2SO4-CoSO4 melts. The corrosion of Ni and Co took place by the formation of a mixed oxide plus sulfide scale, very similar to the corrosion in SO2 or SO3 alone. The initial stage for the corrosion of Ni-10Cr involved the formation of a thick NiO + Ni3S2 duplex scale, and Cr sulfide was formed during the later stages. A pitting type of morphology was observed for both Co-21Cr and IN738. The pit was Cr sulfide at the beginning, and subsequently the sulfides oxidized to Cr2O3. A base-metal oxide layer was present above the pit, and this was observed to be formed very early in the corrosion process. A mechanism is proposed to explain this. In general, the formation of sulfides appears to be the primary mode of degradation in mixed sulfide melts.

Magnetic interaction reversal in watermelon nanostructured Cr-doped Fe nanoclusters

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kaur, Maninder; Dai, Qilin; Bowden, Mark

2013-01-01

Cr-doped core-shell Fe/Fe-oxide nanoclusters (NCs) were synthesized at varied atomic percentages of Cr from 0 at. % to 8 at. %. The low concentrations of Cr (<10 at. %) were selected in order to inhibit the complete conversion of the Fe-oxide shell to Cr2O3 and the Fe core to FeCr alloy. The magnetic interaction in Fe/Fe-oxide NCs (rv25 nm) can be controlled by antiferromagnetic Cr-dopant. We report the origin of r-FeCr phase at very low Cr concentration (2 at. %) unlike in previous studies, and the interaction reversal from dipolar to exchange interaction in watermelon-like Cr-doped core-shell NCs. The giantmore » magnetoresistance (GMR) effect,1,2 where an antiferromagnetic (AFM) exchange coupling exists between two ferromagnetic (FM) layers separated by a certain type of magnetic or non-magnetic spacer,3 has significant potential for application in the magnetic recording industry. Soon after the discovery of the GMR, the magnetic properties of multilayer systems (FeCr) became a subject of intensive study. The application of bulk iron-chromium (Fe-Cr) alloys has been of great interest, as these alloys exhibit favorable prop- erties including corrosion resistance, high strength, hardness, low oxidation rate, and strength retention at elevated temper- ature. However, the structural and magnetic properties of Cr-doped Fe nanoclusters (NCs) have not been investigated in-depth. Of all NCs, Fe-based clusters have unique magnetic properties as well as favorable catalytic characteristics in reactivity, selectivity, and durability.4 The incorporation of dopant of varied type and concentration in Fe can modify its chemical ordering, thereby optimizing its electrical, optical, and magnetic properties and opening up many new applications. The substitution of an Fe atom (1.24 A°) by a Cr atom (1.25 A° ) can easily modify the magnetic properties, since (i) the curie temperature (Tc ) of Fe is 1043 K, while Cr is an itinerant AFM with a bulk Neel temperature TN =311 K, and (ii) Fe and Cr share the same crystal structure (bcc) with only 0.5% difference between their lattice constants.« less

Corrosion of inconel in high-temperature borosilicate glass melts containing simulant nuclear waste

NASA Astrophysics Data System (ADS)

Mao, Xianhe; Yuan, Xiaoning; Brigden, Clive T.; Tao, Jun; Hyatt, Neil C.; Miekina, Michal

2017-10-01

The corrosion behaviors of Inconel 601 in the borosilicate glass (MW glass) containing 25 wt.% of simulant Magnox waste, and in ZnO, Mn2O3 and Fe2O3 modified Mg/Ca borosilicate glasses (MZMF and CZMF glasses) containing 15 wt.% of simulant POCO waste, were evaluated by dimensional changes, the formation of internal defects and changes in alloy composition near corrosion surfaces. In all three kinds of glass melts, Cr at the inconel surface forms a protective Cr2O3 scale between the metal surface and the glass, and alumina precipitates penetrate from the metal surface or formed in-situ. The corrosion depths of inconel 601 in MW waste glass melt are greater than those in the other two glass melts. In MW glass, the Cr2O3 layer between inconel and glass is fragmented because of the reaction between MgO and Cr2O3, which forms the crystal phase MgCr2O4. In MZMF and CZMF waste glasses the layers are continuous and a thin (Zn, Fe, Ni, B)-containing layer forms on the surface of the chromium oxide layer and prevents Cr2O3 from reacting with MgO or other constituents. MgCr2O4 was observed in the XRD analysis of the bulk MW waste glass after the corrosion test, and ZrSiO4 in the MZMF waste glass, and ZrSiO4 and CaMoO4 in the CZMF waste glass.

Irradiation-induced formation of a spinel phase at the FeCr/MgO interface

DOE PAGES

Xu, Yun; Yadav, Satyesh Kumar; Aguiar, Jeffery A.; ...

2015-04-27

Oxide dispersion strengthened ferritic/martensitic alloys have attracted significant attention for their potential uses in future nuclear reactors and storage vessels, as the metal/oxide interfaces act as stable high-strength sinks for point defects while also dispersing helium. Here, in order to unravel the evolution and interplay of interface structure and chemistry upon irradiation in these types of materials, an atomically sharp FeCr/MgO interface was synthesized at 500 °C and separately annealed and irradiated with Ni 3+ ions at 500 °C. After annealing, a slight enrichment of Cr atoms was observed at the interface, but no other structural changes were found. However,more » under irradiation, sufficient Cr diffuses across the interface into the MgO to form a Cr-enriched transition layer that contains spinel precipitates. First-principles calculations indicate that it is energetically favorable to incorporate Cr, but not Fe, substitutionally into MgO. Furthermore, our results indicate that irradiation can be used to form new phases and complexions at interfaces, which may have different radiation tolerance than the pristine structures.« less

Influence of deposition temperature and amorphous carbon on microstructure and oxidation resistance of magnetron sputtered nanocomposite Crsbnd C films

NASA Astrophysics Data System (ADS)

Nygren, Kristian; Andersson, Matilda; Högström, Jonas; Fredriksson, Wendy; Edström, Kristina; Nyholm, Leif; Jansson, Ulf

2014-06-01

It is known that mechanical and tribological properties of transition metal carbide films can be tailored by adding an amorphous carbon (a-C) phase, thus making them nanocomposites. This paper addresses deposition, microstructure, and for the first time oxidation resistance of magnetron sputtered nanocomposite Crsbnd C/a-C films with emphasis on studies of both phases. By varying the deposition temperature between 20 and 700 °C and alternating the film composition, it was possible to deposit amorphous, nanocomposite, and crystalline Crsbnd C films containing about 70% C and 30% Cr, or 40% C and 60% Cr. The films deposited at temperatures below 300 °C were X-ray amorphous and 500 °C was required to grow crystalline phases. Chronoamperometric polarization at +0.6 V vs. Ag/AgCl (sat. KCl) in hot 1 mM H2SO4 resulted in oxidation of Crsbnd C, yielding Cr2O3 and C, as well as oxidation of C. The oxidation resistance is shown to depend on the deposition temperature and the presence of the a-C phase. Physical characterization of film surfaces show that very thin C/Cr2O3/Crsbnd C layers develop on the present material, which can be used to improve the oxidation resistance of, e.g. stainless steel electrodes.

H2S adsorption on chromium, chromia, and gold/chromia surfaces: Photoemission studies

NASA Astrophysics Data System (ADS)

Rodriguez, J. A.; Chaturvedi, S.; Kuhn, M.; van Ek, J.; Diebold, U.; Robbert, P. S.; Geisler, H.; Ventrice, C. A., Jr.

1997-12-01

The reaction of H2S with chromium, chromia, and Au/chromia films grown on a Pt(111) crystal has been investigated using synchrotron-based high-resolution photoemission spectroscopy. At 300 K, H2S completely decomposes on polycrystalline chromium producing a chemisorbed layer of S that attenuates the Cr 3d valence features. No evidence was found for the formation of CrSx species. The dissociation of H2S on Cr3O4 and Cr2O3 films at room temperature produces a decrease of 0.3-0.8 eV in the work function of the surface and significant binding-energy shifts (0.2-0.6 eV) in the Cr 3p core levels and Cr 3d features in the valence region. The rate of dissociation of H2S increases following the sequence: Cr2O3

Design for Oxidation Resistance

NASA Technical Reports Server (NTRS)

Smialek, James L.; Schaeffer, Jon C.; Barrett, Charles A.

1997-01-01

Alloys intended for use in high-temperature environment rely on the formation of a continuous, compact, slow-growing oxide layer for oxidation and hot corrosion resistance. To be protective, this oxide layer must be chemically, thermodynamically stable. Successful alloy design for oxidative environment is best achieved by developing alloys that are capable of forming adherent scales of either alumina (Al2O3), chromia (Cr2O3), or silica (SiO2). In this article, emphasis has been placed on the issue related to high-temperature oxidation of superalloys used in gas turbine engine application. Despite the complexity of these alloys, optimal performance has been associated with protective alumina scale formation. As will be described below, both compositional makeup and protective coatings play key role in providing oxidation protection. Other high-temperature materials described include nickel and titanium aluminide intermetallics, refractory metal, and ceramics.

Tensile properties of V-5Cr-5Ti alloy after exposure in air environment

DOE Office of Scientific and Technical Information (OSTI.GOV)

Natesan, K.; Soppet, W.K.

1997-04-01

Oxidation studies were conducted on V-5Cr-5Ti alloy specimens in an air environment to evaluate the oxygen uptake behavior of the alloy as a function of temperature and exposure time. The oxidation rates, calculated from parabolic kinetic measurements of thermogravimetric testing and confirmed by microscopic analysis of cross sections of exposed specimens, were 5, 17, and 27 {mu}m per year after exposure at 300, 400, and 500{degrees}C, respectively. Uniaxial tensile tests were conducted at room temperature and at 500{degrees}C on preoxidized specimens of the alloy to examine the effects of oxidation and oxygen migration on tensile strength and ductility. Correlations weremore » developed between tensile strength and ductility of the oxidized alloy and microstructural characteristics such as oxide thickness, depth of hardened layer, depth of intergranular fracture zone, and transverse crack length.« less

Laser shock processing effects on isothermal oxidation resistance of GH586 superalloy

NASA Astrophysics Data System (ADS)

Hua, Yinqun; Rong, Zhen; Ye, Yunxia; Chen, Kangmin; Chen, Ruifang; Xue, Qing; Liu, Haixia

2015-03-01

The oxidation is one of the main failure mode of Ni-based alloy at high temperature, laser shock processing not only can improve the mechanical properties but also the oxidation resistance. So the study on laser shock processing effects on oxidation resistance of this alloy is necessary. The aim of this paper is to investigate the effects of laser shock processing on microstructure, micro-hardness and isothermal oxidation resistance of GH586 superalloy. Scanning electron microscopy, energy-dispersive spectrum, transmission electron microscope, and X-ray diffraction technique were used to analyze the microstructure changes and the surface morphologies of the oxide scales. In addition, micro-hardness of LSP-treated samples was measured. The results show that the average grains size on the surfaces of LSP specimen was found to be significantly finer compared to the untreated one (33.3 μm vs. 18.5 μm). Highly tangled and dense dislocation arrangements and a high amount of twins have been observed. After the oxidation, the defects density (dislocations and twins) in the specimen decreased. The oxidation kinetics approximately followed a parabolic oxidation law at 800 °C and 900 °C. The oxidation layer was composed of Cr2O3, NiCr2O4, TiO2, and Al2O3, which generated more quickly on the surface treated by LSP during initial oxidation. The average oxidation rate was lower after LSP due to the dense, tiny and homogeneous oxidation layer. The results show that the specimens treated by LSP have a better high temperature oxidation resistance.

Enhanced room-temperature magnetoresistance in self-assembled Ag-coated multiphasic chromium oxide nanocomposites.

PubMed

Dwivedi, S; Biswas, S

2016-09-14

Self-assembled Ag-coated multiphasic diluted magnetic chromium oxide nanocomposites were developed by a facile chemical synthesis route involving a reaction of CrO3 in the presence of Ag(+) ions in an aqueous solution of poly-vinyl alcohol (PVA) and sucrose. The tiny ferromagnetic single domains of tetragonal and orthorhombic CrO2 (t-CrO2 and o-CrO2) embedded in a dominantly insulating matrix of antiferromagnetic Cr2O3 and Cr3O8, and paramagnetic CrO3 and Cr2O, with a correlated diamagnetic thin and discontinuous shell layer of Ag efficiently tailor useful magnetic and room-temperature magnetoresistance (RTMR) properties. The t-CrO2, o-CrO2, possible canted ferromagnetism due to spin disorder in the matrix components, and the associated exchange interactions are the elements responsible for the observed ferromagnetism in the composite structure. The chain of ferromagnetic centers embedded in the composite matrix constitutes a type of magnetic tunnel junction through which spin-polarized electrons can effectively move without significant local interruptions. Electrical transport measurements showed that the spin-dependent tunneling (SDT) mechanism in the engineered microstructure of the nanocomposites exists even at room temperature (RT). A typical sample unveils a markedly enhanced RTMR-value, e.g., -80% at an applied field (H) of 3 kOe, compared to the reported values for compacted CrO2 powders or composites. The enhanced RTMR-value observed in the Coulomb blockade regime appears not only due to the considerably suppressed spin flipping at RT but primarily due to a highly effective SDT mechanism through an interlinked structure of Ag-coated multiphasic chromium oxide nanocomposites.

Interaction of coal-derived synthesis gas impurities with solid oxide fuel cell metallic components

NASA Astrophysics Data System (ADS)

Marina, Olga A.; Pederson, Larry R.; Coyle, Christopher A.; Edwards, Danny J.; Chou, Yeong-Shyung; Cramer, Carolyn N.

Oxidation-resistant alloys find use as interconnect materials, heat exchangers, and gas supply tubing in solid oxide fuel cell (SOFC) systems, especially when operated at temperatures below ∼800 °C. If fueled with synthesis gas derived from coal or biomass, such metallic components could be exposed to impurities contained in those fuel sources. In this study, coupons of ferritic stainless steels Crofer 22 APU and SS 441, austenitic nickel-chromium superalloy Inconel 600, and an alumina-forming high nickel alloy alumel were exposed to synthesis gas containing ≤2 ppm phosphorus, arsenic and antimony, and reaction products were tested. Crofer 22 APU coupons coated with a (Mn,Co) 3O 4 protective layer were also evaluated. Phosphorus was found to be the most reactive. On Crofer 22 APU, the (Mn,Cr) 3O 4 passivation layer reacted to form an Mn-P-O product, predicted to be manganese phosphate from thermochemical calculations, and Cr 2O 3. On SS 441, reaction of phosphorus with (Mn,Cr) 3O 4 led to the formation of manganese phosphate as well as an Fe-P product, predicted from thermochemical calculations to be Fe 3P. Minimal interactions with antimony or arsenic in synthesis gas were limited to Fe-Sb and Fe-As solid solution formation. Though not intended for use on the anode side, a (Mn,Co) 3O 4 spinel coating on Crofer 22 APU reacted with phosphorus in synthesis gas to produce products consistent with Mn 3(PO 4) 2 and Co 2P. A thin Cr 2O 3 passivation layer on Inconel 600 did not prevent the formation of nickel phosphides and arsenides and of iron phosphides and arsenides, though no reaction with Cr 2O 3 was apparent. On alumel, an Al 2O 3 passivation layer rich in Ni did not prevent the formation of nickel phosphides, arsenides, and antimonides, though no reaction with Al 2O 3 occurred. This work shows that unprotected metallic components of an SOFC stack and system can provide a sink for P, As and Sb impurities that may be present in fuel gases, and thus complicate experimental studies of impurity interactions with the anode.

Degradation of a two-layer thermal barrier coating under thermal cycling. [for superalloys of aircraft turbine engine blades

NASA Technical Reports Server (NTRS)

Maier, R. D.; Scheuermann, C. M.; Andrews, C. W.

1981-01-01

A two-layer plasma-sprayed thermal barrier coating on a directionally solidified nickel-base eutectic alloy substrate was characterized prior to and after thermal cycling to 1095 C in an accelerated furnace test. The coating was comprised of an inner layer of Ni-16.4Cr-5.1Al-0.15Y (wt%) bond coat and an outer layer of ZrO2-7.9Y2O3 (wt%) thermal barrier. Characterization of the bond coat revealed that substantial amounts of yttrium and aluminum were oxidized during plasma-spraying in air. The oxidation of these elements reduced the protective capacity of the bond coat so that, on thermal exposure, severe degradation of the bond coat resulted and large amounts of nickel oxide formed. This nickel oxide was demonstrated to grow outward into the thermal barrier, which appears to have increased the stresses in the thermal barrier and contributed to its failure near the thermal barrier-bond coat interface.

Interaction of Fe-Al-Cr-C with the melt of an alkali metal carbonate

NASA Astrophysics Data System (ADS)

Nikitina, E. V.

2015-08-01

The interaction of an Fe-Al-Cr-C (29.5 wt % Fe, 29.35 wt % Cr, 2.56 wt % C, 38.59 wt % Al) alloy with the melt of a lithium, sodium, or potassium carbonate containing 1-5 wt % addition to a salt phase is studied by gravimetry and measuring the corrosion potential and anode polarization curves in the temperature range 500-600°C. As passivators, the substances that decrease the corrosion losses due to hardening and thickening of an oxide film (lithium, sodium, potassium hydroxides) are used. As corrosion stimulators (activators), sodium chloride, fluoride, and sulfate are used. The coalloying of iron with chromium and aluminum results in high corrosion resistance against both frontal (continuous) and local (pitting, intercrystalline) corrosion as a result of formation of chemically resistant and high-adhesion oxide layers with their participation. X-ray diffraction analysis reveals gamma aluminum oxide, spinel (alumochromite) traces, and lithium aluminate at the surface.

Does the conductivity of interconnect coatings matter for solid oxide fuel cell applications?

NASA Astrophysics Data System (ADS)

Goebel, Claudia; Fefekos, Alexander G.; Svensson, Jan-Erik; Froitzheim, Jan

2018-04-01

The present work aims to quantify the influence of typical interconnect coatings used for solid oxide fuel cells (SOFC) on area specific resistance (ASR). To quantify the effect of the coating, the dependency of coating thickness on the ASR is examined on Crofer 22 APU at 600 °C. Three different Co coating thicknesses are investigated, 600 nm, 1500 nm, and 3000 nm. Except for the reference samples, the material is pre-oxidized prior to coating to mitigate the outward diffusion of iron and consequent formation of poorly conducting (Co,Fe)3O4 spinel. Exposures are carried out at 600 °C in stagnant laboratory air for 500 h and subsequent ASR measurements are performed. Additionally the microstructure is investigated with scanning electron microscopy (SEM). On all pre-oxidized samples, a homogenous dense Co3O4 top layer is observed beneath which a thin layer of Cr2O3 is present. As the ASR values range between 7 and 12 mΩcm2 for all pre-oxidized samples, even though different Co3O4 thicknesses are observed, the results strongly suggest that for most applicable cases the impact of the coating on ASR is negligible and the main contributor is Cr2O3.

Compact chromium oxide thin film resistors for use in nanoscale quantum circuits

DOE Office of Scientific and Technical Information (OSTI.GOV)

Nash, C. R.; Fenton, J. C.; Constantino, N. G. N.

We report on the electrical characterisation of a series of thin amorphous chromium oxide (CrO{sub x}) films, grown by dc sputtering, to evaluate their suitability for use as on-chip resistors in nanoelectronics. By increasing the level of oxygen doping, the room-temperature sheet resistance of the CrO{sub x} films was varied from 28 Ω/◻ to 32.6 kΩ/◻. The variation in resistance with cooling to 4.2 K in liquid helium was investigated; the sheet resistance at 4.2 K varied with composition from 65 Ω/◻ to above 20 GΩ/◻. All of the films measured displayed linear current–voltage characteristics at all measured temperatures. For on-chip devices for quantummore » phase-slip measurements using niobium–silicon nanowires, interfaces between niobium–silicon and chromium oxide are required. We also characterised the contact resistance for one CrO{sub x} composition at an interface with niobium–silicon. We found that a gold intermediate layer is favourable: the specific contact resistivity of chromium-oxide-to-gold interfaces was 0.14 mΩcm{sup 2}, much lower than the value for direct CrO{sub x} to niobium–silicon contact. We conclude that these chromium oxide films are suitable for use in nanoscale circuits as high-value resistors, with resistivity tunable by oxygen content.« less

A new diffusion-inhibited oxidation-resistant coating for superalloys

NASA Technical Reports Server (NTRS)

Gedwill, M. A.; Glasgow, T. K.; Levine, S. R.

1981-01-01

A concept for enhanced protection of superalloys consists of adding an oxidation- and diffusion-resistant cermet layer between the superalloy and the outer oxidation-resistant metallic alloy coating. Such a duplex coating was compared with a physical-vapor-deposited (PVD) NiCrAlY coating in cyclic oxidation at 1150 C. The substrate alloy was MA 754 - an oxide-dispersion-strengthened superalloy that is difficult to coat. The duplex coating, applied by plasma spraying, outperformed the PVD coating on the basis of weight change and both macroscopic and metallographic observations.

Electrochemical corrosion and surface analyses of a ni-cr alloy in bleaching agents.

PubMed

Tamam, Evşen; Aydın, A Kevser; Bilgiç, Semra

2014-10-01

The aim of this study was to evaluate the corrosion behavior of a Ni-Cr dental casting alloy subjected to 10% hydrogen peroxide (HP) and 10% carbamide peroxide (CP) bleaching solutions and to determine the composition of the surface oxide layer formed on the alloy specimens. Ten cylindrical specimens (4 mm in diameter × 25 mm in height) were cast from a Ni-Cr alloy (Wiron 99) and divided into two groups (n = 5). A potentiodynamic polarization test was used to compare the corrosion rates of specimens in HP and CP (pH = 6.5). Before cyclic polarization tests, all alloy specimens were allowed to reach a steady open circuit potential (Ecorr ) for a period of 1 hour. Then tests were initiated at 100 mV versus standard calomel electrode (SCE) below Ecorr and scanned at a rate of 1 mV/s in the anodic direction until reaching 1000 mV over the Ecorr value. The scan then was reversed back to the Ecorr of the specimens. The open circuit potentials (Ecorr ) and the current densities (Icorr ) were determined using the anodic Tafel regions extrapolating from the curves. Differences in Ecorr and Icorr were determined using one-way ANOVA (α = 0.05). In addition, corrosion rates were calculated from these curves. Before and after polarization tests, a scanning electron microscope (SEM) examination accompanied by energy dispersive X-ray spectroscopy (EDS) was used to analyze the surface morphology. The surface characterization of the passive film formed on alloy specimens was also performed by using X-ray photoelectron spectroscopy (XPS). In this study, bleaching agents had an effect on the anodic process for two groups. Although no statistical difference was identified between the groups for both corrosion parameters, results indicated that the effect of CP on the corrosion behavior was less than that of HP. These results agreed with the SEM observations. XPS data showed that oxide layers formed on all groups contained mainly Cr2 O3 , NiO, and MoO3 , and the amounts of oxides formed on CP-treated specimens were higher than HP treated ones. Also, molybdenum rates were increased with CP application compared to HP. The comparison of the effects of the two bleaching agents at 10% showed that the alloy suffered less corrosion with CP than HP. This result was also confirmed by the SEM and XPS data. The presence of Mo on the oxide layer affected the oxide layer, leading to lower corrosion rates. © 2014 by the American College of Prosthodontists.

At last! The single-crystal X-ray structure of a naturally occurring sample of the ilmenite-type oxide FeCrO3.

PubMed

Pérez-Cruz, María Ana; Elizalde-González, María de la Paz; Escudero, Roberto; Bernès, Sylvain; Silva-González, Rutilo; Reyes-Ortega, Yasmi

2015-10-01

A natural single crystal of the ferrimagnetic oxide FeCrO3, which was found in an opencast mine situated in the San Luis Potosí State in Mexico, has been characterized in order to elucidate some outstanding issues about the actual structure of this material. The single-crystal X-ray analysis unambiguously shows that transition metal cations are segregated in alternating layers normal to the threefold crystallographic axis, affording a structure isomorphous to that of ilmenite (FeTiO3), in the space group R3̅. The possible occurrence of cation antisite and vacancy defects is below the limit of detection available from X-ray data. Structural and magnetic results are in agreement with the coherent slow intergrowth of magnetic phases provided by the two antiferromagnetic corundum-type parent oxides Fe2O3 (hematite) and Cr2O3 (eskolaite). Our results are consistent with the most recent density functional theory (DFT) studies carried out on digital FeCrO3 [Sadat Nabi & Pentcheva (2011). Phys. Rev. B, 83, 214424], and suggest that synthetic samples of FeCrO3 might present a cation distribution different to that of the ilmenite structural type.

Electrode and method of interconnection sintering on an electrode of an electrochemical cell

DOEpatents

Ruka, R.J.; Kuo, L.J.H.

1994-01-11

An electrode structure is made by applying a base layer of doped LaCrO[sub 3] particles on a portion of an electrode and then coating the particles with a top layer composition such as CaO+Al[sub 2]O[sub 3], SrO+Al[sub 2]O[sub 3], or BaO+Al[sub 2]O[sub 3], and then heating the composition for a time effective to melt the composition and allow it to fill any open porosity in the base layer of doped LaCrO[sub 3] to form an interconnection, after which solid oxide electrolyte can be applied to the remaining portion of the electrode and the electrolyte can be covered with a cermet exterior electrode. 2 figures.

Electrode and method of interconnection sintering on an electrode of an electrochemical cell

DOEpatents

Ruka, Roswell J.; Kuo, Lewis J. H.

1994-01-01

An electrode structure (10) is made by applying a base layer of doped LaCrO.sub.3 particles on a portion of an electrode (16) and then coating the particles with a top layer composition such as CaO+Al.sub.2 O.sub.3, SrO+Al.sub.2 O.sub.3, or BaO+Al.sub.2 O.sub.3, and then heating the composition for a time effective to melt the composition and allow it to fill any open porosity in the base layer of doped LaCrO.sub.3 to form an interconnection (26), after which solid oxide electrolyte (18) can be applied to the remaining portion of the electrode (16) and the electrolyte (18) can be covered with a cermet exterior electrode (20).

Chromium speciation in oxide-type compounds: application to minerals, gems, aqueous solutions and silicate glasses

NASA Astrophysics Data System (ADS)

Farges, François

2009-09-01

Cr K-edge XANES spectra were obtained for a variety of Cr-bearing model compounds containing Cr(II), Cr(III), Cr(IV), Cr(V) and Cr(VI), in which the Cr-site symmetry is D4h, Oh and Td. The centroid position of the pre-edge feature is a better indicator of the Cr valence than the edge position. In Cr-rich oxides, higher-energy transitions must be excluded in order to refine a robust valence for Cr. The pre-edge for chromates is not unique and varies as a function of the CrO4 2- moiety distortion, which is often related to Cr-polymerization (monochromate vs. dichromate). Both the analogy with the Mn K-pre-edge information and ab initio FEFF calculations of the pre-edge feature for Cr(III) and Cr(VI) confirm the experimental trends. This methodology is applied to the Cr K-edge pre-edge feature collected in gems (emerald, spinel and ruby), the layered minerals fuchsite and kämmererite, two Cr-bearing aqueous solutions and a set of sodo-calcic silicate glasses used for bottling sparkling white wine. In emerald and fuchsite, the Cr-site is differently distorted than its ruby or spinel counterpart. In a Cr(III)-bearing aqueous solution and sodo-calcic glass, no evidence for Cr(III) with Td and C3v symmetry is detected. However, minor amounts of chromate moieties (most likely monomeric) are detected in a glass synthesized in air. Preliminary spectra for the wine bottle glass suggest that only trace amounts of chromates might possibly be present in these glasses.

Preparation of Layered-Spinel Microsphere/Reduced Graphene Oxide Cathode Materials for Ultrafast Charge-Discharge Lithium-Ion Batteries.

PubMed

Luo, Dong; Fang, Shaohua; Yang, Li; Hirano, Shin-Ichi

2017-12-22

Although Li-rich layered oxides (LLOs) have the highest capacity of any cathodes used, the rate capability of LLOs falls short of meeting the requirements of electric vehicles and smart grids. Herein, a layered-spinel microsphere/reduced graphene oxide heterostructured cathode (LS@rGO) is prepared in situ. This cathode is composed of a spinel phase, two layered structures, and a small amount of reduced graphene oxide (1.08 wt % of carbon). The assembly delivers a considerable charge capacity (145 mA h g -1 ) at an ultrahigh charge- discharge rate of 60 C (12 A g -1 ). The rate capability of LS@rGO is influenced by the introduced spinel phase and rGO. X-ray absorption and X-ray photoelectron spectroscopy data indicate that Cr ions move from octahedral lattice sites to tetrahedral lattice sites, and that Mn ions do not participate in the oxidation reaction during the initial charge process. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Development of Protective Coatings for Chromium-Base Alloys

NASA Technical Reports Server (NTRS)

English, J. J.; MacMillan, C. A.; Williams, D. N.; Bartlett, E. S.

1966-01-01

Chromium alloy sheet was clad with 5 to 10-mil-thick oxidation-resistant nickel-base alloy foils. Specimens also contained 1/2 to 1-mil-thick intermediate layers of platinum, tungsten, and/or W-25Re. Cladding was done by the isostatic hot gas-pressure bonding,.process. The clad chromium-alloy specimens were cyclic oxidation tested at 2100 F and 2300 F for up to 200 hours to determine the effectiveness of these metal claddings in protecting the chromium alloy Cr-5W from oxidation and contamination. Cladding systems consisting of 5-mil-thick Ni-20Cr-20W modified with 3 to 5 weight percent aluminum and containing a 1 /2-mil tungsten diffusion barrier demonstrated potential for long-time service at temperatures as high as 2300 F.

CoFe 2O 4 spinel protection coating thermally converted from the electroplated Co-Fe alloy for solid oxide fuel cell interconnect application

NASA Astrophysics Data System (ADS)

Bi, Z. H.; Zhu, J. H.; Batey, J. L.

CoFe 2O 4 has been demonstrated as a potential spinel coating for protecting the Cr-containing ferritic interconnects. This spinel had an electrical conductivity of 0.85 S cm -1 at 800 °C in air and an average coefficient of thermal expansion (CTE) of 11.80 × 10 -6 K -1 from room temperature to 800 °C. A series of Co-Fe alloys were co-deposited onto the Crofer 22 APU ferritic steel via electroplating with an acidic chloride solution. After thermal oxidation in air at 800 °C, a CoFe 2O 4 spinel layer was attained from the plated Co 0.40Fe 0.60 film. Furthermore, a channeled Crofer 22 APU interconnect electrodeposited with a 40-μm Co 0.40Fe 0.60 alloy film as a protective coating was evaluated in a single-cell configuration. The presence of the dense, Cr-free CoFe 2O 4 spinel layer was effective in blocking the Cr migration/transport and thus contributed to the improvement in cell performance stability.

Influence of Oxidation Treatments and Surface Finishing on the Electrochemical Behavior of Ni-20Cr HVOF Coatings

NASA Astrophysics Data System (ADS)

Ruiz-Luna, H.; Porcayo-Calderon, J.; Alvarado-Orozco, J. M.; Mora-García, A. G.; Martinez-Gomez, L.; Trápaga-Martínez, L. G.; Muñoz-Saldaña, J.

2017-12-01

The low-temperature electrochemical behavior of HVOF Ni-20Cr coatings was assessed. The coatings were evaluated in different conditions including as-sprayed, as-ground, and heat-treated in air and argon atmospheres. A detailed analysis of the coatings was carried out by means of XRD, SEM, and EPMA, prior and after the corrosion test. The corrosion rate was analyzed in a NaCl solution saturated with CO2. Results demonstrate that the use of a low-oxygen partial pressure favors the formation of a Cr2O3 layer on the surface of the coatings. According to the electrochemical results, the lower corrosion rates were obtained for the heat-treated coatings irrespective of the surface finishing, being the ground and argon heat-treated condition that shows the best corrosion performance. This behavior is due to the synergistic effect of the low-pressure heat treatment and the grinding processes. The grinding promotes a more homogeneous reaction area without surface heterogeneities such as voids, and the pre-oxidation treatment decreases the porosity content of the coating and also allows the growing of a Cr-rich oxide scale which acts as a barrier against the ions of the aqueous solution.

Surface structure of MgO underlayer with Ti diffusion for (002) oriented L10 FePt-based heat assisted magnetic recording media

NASA Astrophysics Data System (ADS)

Hinata, Sintaro; Jo, Shin; Saito, Shin

2018-05-01

Surface morphology of the MgO layer and magnetic properties of FePt-C layer deposited on the MgO were investigated for the FePt-based heat assisted magnetic recording media. Stacking structure of the underlayer for the FePt-C layer was MgO (0-5 nm)/Cr80Mn20 (0-30 nm)/Cr50Ti50 (0-50 nm)/glass sub.. Surface observation result for the MgO film by using an atomic force microscope revealed the existence of nodules with a height of about 2 nm and a network-like convex structure with a height difference of about sub nm (boundary wall, BW) on the MgO crystal grain boundary. Density of the nodules largely depends on the surface roughness of the CrTi layer, RaCrTi and it is suppressed from 10 to 2/0.5 μm2 by reducing RaCrTi from 420 to 260 pm. Height of the BW depends on thickness of the MgO layer, tMgO and it can be suppressed by reducing tMgO to less than 4 nm. From the cross-sectional energy dispersive x-ray mapping, it is clarified that the BW is formed by atomic diffusion of Ti atoms from CrTi layer due to the substrate heating process, and a compound consists of Mg, Ti and O atoms. This BW can be used as a template to magnetically isolate the FePt column in the FePt-based granular film, such as FePt-SiO2, if the size of the BW is reduced to less than 10 nm. M-H loop of the FePt-C granular film deposited on the underlayer showed that the nodule and BW induce oxidation of the FePt grains, and reduction of intergranular exchange coupling.

Effects of laser polishing on surface microstructure and corrosion resistance of additive manufactured CoCr alloys

NASA Astrophysics Data System (ADS)

Wang, W. J.; Yung, K. C.; Choy, H. S.; Xiao, T. Y.; Cai, Z. X.

2018-06-01

Laser polishing of 3D printed metal components has drawn great interest in view of its potential applications in the dental implant industries. In this study, corrosion resistance, surface composition and crystalline structure of CoCr alloys were investigated. The corrosion resistance, micromorphology, composition, phase transformations and crystalline structures of samples were characterized using an electrochemical analyzer, scanning electron microscope (SEM), energy dispersive X-ray spectroscopy (EDX), X-ray diffraction (XRD) and transmission electron microscope (TEM), respectively. The results indicate that high laser powers and low object distances within a certain range can facilitate the formation of complex oxide films, which exhibits high corrosion resistance. Further, object distances have a significant influence on cooling rates during the solidification of the melt pool in laser polishing, and fast cooling generates vast amounts of vacancies and defects, which result in the crystalline phase transformation from γ to ε. Consequently, the formed oxides play an important role in corrosion resistance on the outer layer, and inner layer with γ phase also helps keep the CoCr alloys in a stable structure with high resistant to corrosion. The two process parameters in laser polishing, laser power and object distances, are demonstrated as being important for controlling the surface microstructures and corrosion resistance of the additive manufactured CoCr alloy components.

[Calculation of environmental dredging depth of heavy sediments in Zhushan Bay of Taihu Lake metal polluted].

PubMed

Jiang, Xia; Wang, Wen-Wen; Wang, Shu-Hang; Jin, Xiang-Can

2012-04-01

Horizontal distribution of heavy metals in surface sediments of Zhushan Bay was investigated, and core sediment samples were collected in the representative area. Core sediments were divided into oxide layer (A), polluted layer (B), upper polluted transition layer(C1), lower polluted transition layer(C2) and normal mud layer(D) from top to bottom. The change of total contents of Cr, Ni, Cu, Zn, As, Cd, Hg, Pb and contents of biological available Cr, Ni, Cu, Zn, As, Cd, Pb with depths were analyzed. Ecological risk assessment of heavy metals in sediments was done by potential ecological risk index method. At last, environmental dredging depth was calculated. The results shows that the contents of Cr, Ni, Cu, Zn, As, Cd, Hg, Pb are 30.56-216.58, 24.07-59.95, 16.71-140.30, 84.31-193.43, 3.39-22.30, 0.37-1.59, 0.00-0.80 and 9.67-99.35 mg x kg(-1), respectively. The average concentrations of Cr, Ni, Cu, Zn, As, Cd, Hg, Pb are 79.74, 37.74, 44.83, 122.39, 10.39, 0.77, 0.14 and 40.08 mg x kg(-1), respectively. Heavy metals in the surface sediments of Zhushan Bay mainly distribute in the west bank and the estuaries of Taige canal, Yincun Port, and Huanshan River,and Cd pollution is relatively serious. There is an accumulative effect of heavy metals in Zhushan Bay, and the contents of biological available metals decrease with depths. Ecological risk grades of Cd in layer A and B are high, and the comprehensive potential ecological risk grades of each layer are in middle or low. The environmental dredging layers are A and B, and the average dredging depth is 0.39 m.

Resistance to High-Temperature Oxidation and Wear of Various Ferrous Alloys Used in Rolling Mills

NASA Astrophysics Data System (ADS)

Delaunois, Fabienne; Stanciu, Victor Ioan; Sinnaeve, Mario

2018-03-01

Various materials are commonly used to manufacture work rolls for hot rolling mills, such as ICDP (Indefinite Chill Double Pour) cast irons, high-chromium white cast irons, and high speed steels (HSS). Various chemical compositions and microstructures are studied in order to optimize the in-use behavior of those grades of rolls. In this paper, six grades of ferrous alloys (an ICDP cast iron; an ICDP cast iron enriched in vanadium, niobium, and molybdenum; a HSS; a graphitic HSS; a high-chromium white cast iron (Hi-Cr); and a niobium-molybdenum-doped high-chromium white cast iron) were investigated. High-temperature oxidation tests with gravimetric means at 575 °C in water vapor atmosphere and sliding wear tests were carried out. The oxidation kinetics was followed during oxidation test. The microstructure was observed by optical and scanning electron microscopies. The oxides formed on the surface of the samples were analyzed by XRD and EDS. The thickness of the oxide scales and the mass gain were measured after oxidation test. The results showed that the behavior of all the grades differed. The oxide scale of HSS and HSS-G grades was fine and their friction coefficient was low. The weight gain after oxidation test of HSS was high. Hi-Cr and M-Hi-Cr grades presented highly porous oxide layer and an important increase of the friction coefficient during wear test. ICDP and M-ICDP had intermediate behavior.

Characterization of Cr poisoning in a solid oxide fuel cell cathode using a high-energy x-ray microbeam.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Liu, D. J.; Almer, J.; Cruse, T.

2010-01-01

A key feature of planar solid oxide fuel cells (SOFCs) is the feasibility of using metallic interconnects made of high temperature ferritic stainless steels, which reduce system cost while providing excellent electric conductivity. Such interconnects, however, contain high levels of chromium, which has been found to be associated with SOFC cathode performance degradation at SOFC operating temperatures; a phenomenon known as Cr poisoning. Here, we demonstrate an accurate measurement of the phase and concentration distributions of Cr species in a degraded SOFC, as well as related properties including deviatoric strain, integrated porosity, and lattice parameter variation, using high energy microbeammore » X-ray diffraction and radiography. We unambiguously identify (MnCr){sub 3}O{sub 4} and Cr{sub 2}O{sub 3} as the two main contaminant phases and find that their concentrations correlate strongly with the cathode layer composition. Cr{sub 2}O{sub 3} deposition within the active cathode region reduces porosity and produces compressive residual strains, which hinders the reactant gas percolation and can cause structural breakdown of the SOFC cathode. The information obtained through this study can be used to better understand the Cr-poisoning mechanism and improve SOFC design.« less

Development of Simultaneous Corrosion Barrier and Optimized Microstructure in FeCrAl Heat-Resistant Alloy for Energy Applications. Part II: The Optimized Creep-Resistant Microstructure

NASA Astrophysics Data System (ADS)

Pimentel, G.; Aranda, M. M.; Chao, J.; González-Carrasco, J. L.; Capdevila, C.

2015-09-01

The first part of this two-part study reported the possibility of simultaneously generating a dense, self-healing α-alumina layer by thermal oxidation and a coarse-grained microstructure with a potential goodness for high-temperature creep resistance in a FeCrAl oxide dispersion-strengthened ferritic alloy that was cold deformed after hot rolling and extrusion. In this second part, the factors affecting the formation of the coarse-grained microstructure such as strain gradients induced during the rolling process are analyzed. It is concluded that larger strain gradients lead to more refined and more isotropic grain structures.

High-temperature oxidation/corrosion of iron-based superalloys

NASA Technical Reports Server (NTRS)

Lemkey, F. D.; Smeggil, J. G.; Bailey, R. S.; Schuster, J. C.; Nowotny, H.

1987-01-01

The oxidation and sulfidation of several novel iron-base superalloys were evaluated in high-temperature cyclic tests. The experimental austenitic alloys examined were modifications of NASAUT-4GA which were developed for Stirling-engine application. The weight gains and resulting surface scales were measured and analyzed. Mixed oxide scales were found to form on all specimens exposed above 871 C. The build-up of these scales led to a depletion of Mn and Cr in a zone adjacent to the oxides. In addition, the initial oxidation of the Fe-rich alloy was inhibited by a thin but tenacious Si layer which formed at the interface between oxides and the parent layer. Sulfidation tests using Na2SO4 coatings resulted in the formation of a protective spinel and alpha-Fe2O3 phases. Preferential attack of the carbide phase by hydrogen was not observed after 350 h at 871 C.

Effect of La0.1Sr0.9Co0.5Mn0.5O3-δ protective coating layer on the performance of La0.6Sr0.4Co0.8Fe0.2O3-δ solid oxide fuel cell cathode

NASA Astrophysics Data System (ADS)

Chou, Ping-Yi; Ciou, Chun-Jing; Lee, Yu-Chen; Hung, I.-Ming

2012-01-01

This study investigates the interface reactivity between La0.1Sr0.9Co0.5Mn0.5O3-δ (LSCM) protective coating layer and Crofer22H interconnects. Additionally, we report the mechanism of Cr poisoning of the La0.6Sr0.4Co0.8Fe0.2O3-δ (LSCF) cathode's electrochemical properties. The phase, chemical composition, and element distribution of compounds formed at the LSCM-Crofer22H interface are analyzed by X-ray diffraction (XRD) and electron dispersive microscopy (EDS). After heat treatment at 800 °C for 100 h, the LSCM/Crofer22H sample contains SrCrO3, a compound with good conductivity; the area specific resistance (ASR) for the LSCM/Crofer22H interconnect is approximately 17-40 mΩ cm2. We found that the amount of (Mn0.98Fe0.02)(Mn0.02Fe0.48Cr1.5)O4, Cr3O4, and (Fe,Cr)2O3 oxides form in LSCF/LSCM/Crofer22H is significantly less than that in LSCF/Crofer22H. LSCF conductivity after heating at 800 °C for 100 h, is notably higher when in contact with LSCM/Crofer22H than it is when in contact with Crofer22H. These results demonstrate that the LSCM protective coating prevents LSCF cathode poisoning by Cr evaporated from the Corfer22H interconnects.

Tape method of forming a thin layer of doped lanthanum chromite particles and of bonding such on an electrode

DOEpatents

Richards, Von L.; Singhal, Subhash C.; Pal, Uday B.

1992-01-01

A combustible polymer film, useful for application of an interconnection on an electrode is made by: (1) providing doped LaCro.sub.3 particles; (2) dispersing doped LaCrO.sub.3 particles in a solvent, to provide a dispersion; (3) screening the dispersion to provide particles in the range of from 30 micrometers to 80 micrometers; (4) admixing a fugitive polymer with the particles; (5) casting the dispersion to provide a film; (6) drying the film; and (7) stripping the film. The film can then be applied to a porous, preheated electrode top surface, and then electrochemical vapor depositing a dense skeletal LaCrO.sub.3 structure, between and around the doped LaCrO.sub.3 particles. Additional solid oxide electrolyte and fuel electrode layers can then be added to provide a fuel cell.

Tape method of forming a thin layer of doped lanthanum chromite particles and of bonding such on an electrode

DOEpatents

Richards, V.L.; Singhal, S.C.; Pal, U.B.

1992-07-21

A combustible polymer film, useful for application of an interconnection on an electrode is made by: (1) providing doped LaCro[sub 3] particles; (2) dispersing doped LaCrO[sub 3] particles in a solvent, to provide a dispersion; (3) screening the dispersion to provide particles in the range of from 30 micrometers to 80 micrometers; (4) admixing a fugitive polymer with the particles; (5) casting the dispersion to provide a film; (6) drying the film; and (7) stripping the film. The film can then be applied to a porous, preheated electrode top surface, and then a dense skeletal LaCrO[sub 3] structure is electrochemically vapor deposited between and around the doped LaCrO[sub 3] particles. Additional solid oxide electrolyte and fuel electrode layers can then be added to provide a fuel cell. 4 figs.

Characterization of interfacial reactions and oxide films on 316L stainless steel in various simulated PWR primary water environments

NASA Astrophysics Data System (ADS)

Chen, Junjie; Xiao, Qian; Lu, Zhanpeng; Ru, Xiangkun; Peng, Hao; Xiong, Qi; Li, Hongjuan

2017-06-01

The effect of water chemistry on the electrochemical and oxidizing behaviors of 316L SS was investigated in hydrogenated, deaerated and oxygenated PWR primary water at 310 °C. Water chemistry significantly influenced the electrochemical impedance spectroscopy parameters. The highest charge-transfer resistance and oxide-film resistance occurred in oxygenated water. The highest electric double-layer capacitance and constant phase element of the oxide film were in hydrogenated water. The oxide films formed in deaerated and hydrogenated environments were similar in composition but different in morphology. An oxide film with spinel outer particles and a compact and Cr-rich inner layer was formed in both hydrogenated and deaerated water. Larger and more loosely distributed outer oxide particles were formed in deaerated water. In oxygenated water, an oxide film with hematite outer particles and a porous and Ni-rich inner layer was formed. The reaction kinetics parameters obtained by electrochemical impedance spectroscopy measurements and oxidation film properties relating to the steady or quasi-steady state conditions in the time-period of measurements could provide fundamental information for understanding stress corrosion cracking processes and controlling parameters.

Method of forming a dense, high temperature electronically conductive composite layer on a porous ceramic substrate

DOEpatents

Isenberg, A.O.

1992-04-21

An electrochemical device, containing a solid oxide electrolyte material and an electrically conductive composite layer, has the composite layer attached by: (A) applying a layer of LaCrO[sub 3], YCrO[sub 3] or LaMnO[sub 3] particles, on a portion of a porous ceramic substrate, (B) heating to sinter bond the particles to the substrate, (C) depositing a dense filler structure between the doped particles, (D) shaving off the top of the particles, and (E) applying an electronically conductive layer over the particles as a contact. 7 figs.

Development of Ultra-high Purity (UHP) Fe-Based Alloys with High Creep and Oxidation Resistance for A-USC Technology

NASA Astrophysics Data System (ADS)

Hamdani, Fethi; Das, Nishith K.; Shoji, Tetsuo

2018-06-01

The design of ultra-high purity (UHP) Fe-based model alloys for advanced ultra-supercritical (A-USC) technology is attempted in this work. Creep testing has been performed in air at 700 °C and a stress level of 150 MPa. Analysis of the fracture surface and cross section of the crept specimen was performed. To evaluate the oxidation resistance in A-USC conditions, oxidation testing was performed in supercritical water (SCW) at 700 °C and 25 MPa. Weight gain (WG) measurements and meticulous characterization of the oxide scale were carried out. Based on thermodynamics and density functional theory calculations, some reactive elements in the Fe-Cr-Ni system were designated to promote precipitation strengthening and to improve the hydrogen-accelerated oxidation resistance. The addition of a 2 wt pct Mo into Fe-22Cr-22Ni-0.6Nb wt pct-based matrix did not significantly improve the creep resistance. The addition of 0.26 wt pct Zr coupled with cold working was effective for improving creep properties. The Mo-modified model alloy showed almost the same WG value as SUS310, while the Zr-modified alloy showed a higher WG value. Meanwhile, a Cr-enriched continuous oxide layer was formed at the oxidation front of the Zr-modified alloy and SUS310S after exposure to SCW conditions.

Development of Ultra-high Purity (UHP) Fe-Based Alloys with High Creep and Oxidation Resistance for A-USC Technology

NASA Astrophysics Data System (ADS)

Hamdani, Fethi; Das, Nishith K.; Shoji, Tetsuo

2018-03-01

The design of ultra-high purity (UHP) Fe-based model alloys for advanced ultra-supercritical (A-USC) technology is attempted in this work. Creep testing has been performed in air at 700 °C and a stress level of 150 MPa. Analysis of the fracture surface and cross section of the crept specimen was performed. To evaluate the oxidation resistance in A-USC conditions, oxidation testing was performed in supercritical water (SCW) at 700 °C and 25 MPa. Weight gain (WG) measurements and meticulous characterization of the oxide scale were carried out. Based on thermodynamics and density functional theory calculations, some reactive elements in the Fe-Cr-Ni system were designated to promote precipitation strengthening and to improve the hydrogen-accelerated oxidation resistance. The addition of a 2 wt pct Mo into Fe-22Cr-22Ni-0.6Nb wt pct-based matrix did not significantly improve the creep resistance. The addition of 0.26 wt pct Zr coupled with cold working was effective for improving creep properties. The Mo-modified model alloy showed almost the same WG value as SUS310, while the Zr-modified alloy showed a higher WG value. Meanwhile, a Cr-enriched continuous oxide layer was formed at the oxidation front of the Zr-modified alloy and SUS310S after exposure to SCW conditions.

High temperature corrosion of a nickel base alloy by helium impurities

NASA Astrophysics Data System (ADS)

Rouillard, F.; Cabet, C.; Wolski, K.; Terlain, A.; Tabarant, M.; Pijolat, M.; Valdivieso, F.

2007-05-01

High temperature corrosion properties of Haynes 230 were investigated in a purposely-designed facility under a typical very high temperature reactor (VHTR) impure helium medium. The study was focused on the surface oxide scale formation and its stability at about 1223 K. The alloy developed a Mn/Cr rich oxide layer on its surface under impure helium at 1173 K. Nevertheless, a deleterious reaction destructing the chromium oxide was evidenced above a critical temperature, TA. Reagents and products of this last reaction were investigated.

Development of Simultaneous Corrosion Barrier and Optimized Microstructure in FeCrAl Heat-Resistant Alloy for Energy Applications. Part 1: The Protective Scale

NASA Astrophysics Data System (ADS)

Pimentel, G.; Aranda, M. M.; Chao, J.; González-Carrasco, J. L.; Capdevila, C.

2015-09-01

Coarse-grained Fe-based oxide dispersion-strengthened (ODS) steels are a class of advanced materials for combined cycle gas turbine systems to deal with operating temperatures and pressures of around 1100°C and 15-30 bar in aggressive environments, which would increase biomass energy conversion efficiencies up to 45% and above. This two-part paper reports the possibility of the development of simultaneous corrosion barrier and optimized microstructure in a FeCrAl heat-resistant alloy for energy applications. The first part reports the mechanism of generating a dense, self-healing α-alumina layer by thermal oxidation, during a heat treatment that leads to a coarse-grained microstructure with a potential value for high-temperature creep resistance in a FeCrAl ODS ferritic alloy, which will be described in more detail in the second part.

Novel Chemical Process for Producing Chrome Coated Metal

PubMed Central

Pelar, Christopher; Greenaway, Karima; Zea, Hugo; Wu, Chun-Hsien

2018-01-01

This work demonstrates that a version of the Reduction Expansion Synthesis (RES) process, Cr-RES, can create a micron scale Cr coating on an iron wire. The process involves three steps. I. A paste consisting of a physical mix of urea, chrome nitrate or chrome oxide, and water is prepared. II. An iron wire is coated by dipping. III. The coated, and dried, wire is heated to ~800 °C for 10 min in a tube furnace under a slow flow of nitrogen gas. The processed wires were then polished and characterized, primarily with scanning electron microscopy (SEM). SEM indicates the chrome layer is uneven, but only on the scale of a fraction of a micron. The evidence of porosity is ambiguous. Elemental mapping using SEM electron microprobe that confirmed the process led to the formation of a chrome metal layer, with no evidence of alloy formation. Additionally, it was found that thickness of the final Cr layer correlated with the thickness of the precursor layer that was applied prior to the heating step. Potentially, this technique could replace electrolytic processing, a process that generates carcinogenic hexavalent chrome, but further study and development is needed. PMID:29303977

Novel Chemical Process for Producing Chrome Coated Metal.

PubMed

Pelar, Christopher; Greenaway, Karima; Zea, Hugo; Wu, Chun-Hsien; Luhrs, Claudia C; Phillips, Jonathan

2018-01-05

This work demonstrates that a version of the Reduction Expansion Synthesis (RES) process, Cr-RES, can create a micron scale Cr coating on an iron wire. The process involves three steps. I. A paste consisting of a physical mix of urea, chrome nitrate or chrome oxide, and water is prepared. II. An iron wire is coated by dipping. III. The coated, and dried, wire is heated to ~800 °C for 10 min in a tube furnace under a slow flow of nitrogen gas. The processed wires were then polished and characterized, primarily with scanning electron microscopy (SEM). SEM indicates the chrome layer is uneven, but only on the scale of a fraction of a micron. The evidence of porosity is ambiguous. Elemental mapping using SEM electron microprobe that confirmed the process led to the formation of a chrome metal layer, with no evidence of alloy formation. Additionally, it was found that thickness of the final Cr layer correlated with the thickness of the precursor layer that was applied prior to the heating step. Potentially, this technique could replace electrolytic processing, a process that generates carcinogenic hexavalent chrome, but further study and development is needed.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Lutzer, B.; Simsek, S.; Zimmermann, C.

In order to improve the electrical behaviour of metal-insulator-metal capacitors with ZrO{sub 2} insulator grown by Atomic Layer Deposition, the influence of the insertion of interfacial Cr layers between Pt electrodes and the zirconia is investigated. An improvement of the α-voltage coefficient of capacitance as low as 567 ppm/V{sup 2} is achieved for a single layer of Cr while maintaining a high capacitance density of 10.7 fF/μm{sup 2} and a leakage current of less than 1.2 × 10{sup −8} A/cm{sup 2} at +1 V. The role of the interface is discussed by means of X-ray photoelectron spectroscopy and high-resolution transmission electron microscopy showing themore » formation of Zr stabilized chromia oxide phase with a dielectric constant of 16.« less

Methanol-tolerant cathode catalyst composite for direct methanol fuel cells

DOEpatents

Zhu, Yimin; Zelenay, Piotr

2006-09-05

A direct methanol fuel cell (DMFC) having a methanol fuel supply, oxidant supply, and its membrane electrode assembly (MEA) formed of an anode electrode and a cathode electrode with a membrane therebetween, a methanol oxidation catalyst adjacent the anode electrode and the membrane, an oxidant reduction catalyst adjacent the cathode electrode and the membrane, comprises an oxidant reduction catalyst layer of Pt.sub.3Cr/C so that oxidation at the cathode of methanol that crosses from the anode through the membrane to the cathode is reduced with a concomitant increase of net electrical potential at the cathode electrode.

Corrosion resistant PEM fuel cell

DOEpatents

Li, Yang; Meng, Wen-Jin; Swathirajan, Swathy; Harris, Stephen Joel; Doll, Gary Lynn

2001-07-17

The present invention contemplates a PEM fuel cell having electrical contact elements (including bipolar plates/septums) comprising a titanium nitride coated light weight metal (e.g., Al or Ti) core, having a passivating, protective metal layer intermediate the core and the titanium nitride. The protective layer forms a barrier to further oxidation/corrosion when exposed to the fuel cell's operating environment. Stainless steels rich in CR, Ni, and Mo are particularly effective protective interlayers.

Corrosion resistant PEM fuel cell

DOEpatents

Li, Yang; Meng, Wen-Jin; Swathirajan, Swathy; Harris, Stephen Joel; Doll, Gary Lynn

2002-01-01

The present invention contemplates a PEM fuel cell having electrical contact elements (including bipolar plates/septums) comprising a titanium nitride coated light weight metal (e.g., Al or Ti) core, having a passivating, protective metal layer intermediate the core and the titanium nitride. The protective layer forms a barrier to further oxidation/corrosion when exposed to the fuel cell's operating environment. Stainless steels rich in CR, Ni, and Mo are particularly effective protective interlayers.

Corrosion resistant PEM fuel cell

DOEpatents

Li, Yang; Meng, Wen-Jin; Swathirajan, Swathy; Harris, Stephen J.; Doll, Gary L.

1997-01-01

The present invention contemplates a PEM fuel cell having electrical contact elements (including bipolar plates/septums) comprising a titanium nitride coated light weight metal (e.g., Al or Ti) core, having a passivating, protective metal layer intermediate the core and the titanium nitride. The protective layer forms a barrier to further oxidation/corrosion when exposed to the fuel cell's operating environment. Stainless steels rich in CR, Ni, and Mo are particularly effective protective interlayers.

Coatings for directional eutectics

NASA Technical Reports Server (NTRS)

Rairden, J. R.; Jackson, M. R.

1976-01-01

Significant advances have been made in the development of an environmentally stable coating for a very high strength, directionally solidified eutectic alloy designated NiTaC-13. Three duplex (two-layer) coatings survived 3,000 hours on a cyclic oxidation test (1,100 C to 90 C). These coatings were fabricated by first depositing a layer of NiCrAl(Y) by vacuum evaporation from an electron beam heated source, followed by depositing an aluminizing overlayer. The alloy after exposure with these coatings was denuded of carbide fibers at the substrate/coating interface. It was demonstrated that TaC fiber denudation can be greatly retarded by applying a carbon-bearing coating. The coating was applied by thermal spraying followed by aluminization. Specimens coated with NiCrAlCY+Al survived over 2,000 hours in the cyclic oxidation test with essentially no TaC denudation. Coating ductility was studied for coated and heat-treated bars, and stress rupture life at 871 C and 1,100 C was determined for coated and cycled bars.

Electrochromic material and electro-optical device using same

DOEpatents

Cogan, Stuart F.; Rauh, R. David

1992-01-01

An oxidatively coloring electrochromic layer of composition M.sub.y CrO.sub.2+x (0.33.ltoreq.y.ltoreq.2.0 and x.ltoreq.2) where M=Li, Na or K with improved transmittance modulation, improved thermal and environmental stability, and improved resistance to degradation in organic liquid and polymeric electrolytes. The M.sub.y CrO.sub.2+x provides complementary optical modulation to cathodically coloring materials in thin-film electrochromic glazings and electrochromic devices employing polymeric Li.sup.+ ion conductors.

Electrochromic material and electro-optical device using same

DOEpatents

Cogan, S.F.; Rauh, R.D.

1992-01-14

An oxidatively coloring electrochromic layer of composition M[sub y]CrO[sub 2+x] (0.33[le]y[le]2.0 and x[le]2) where M=Li, Na or K with improved transmittance modulation, improved thermal and environmental stability, and improved resistance to degradation in organic liquid and polymeric electrolytes. The M[sub y]CrO[sub 2+x] provides complementary optical modulation to cathodically coloring materials in thin-film electrochromic glazings and electrochromic devices employing polymeric Li[sup +] ion conductors. 12 figs.

Thermal barrier coating life prediction model development

NASA Technical Reports Server (NTRS)

Strangman, T. E.; Neumann, J. F.; Tasooji, A.

1985-01-01

This program focuses on predicting the lives of two types of strain-tolerant and oxidation-resistant thermal barrier coating (TBC) systems that are produced by commercial coating suppliers to the gas turbine industry. The plasma-sprayed TBC system is composed of a low pressure, plasma sprayed applied, oxidation resistant NiCrAlY bond coating. The other system is an air plasma sprayed yttria (8 percent) partially stabilized zirconia insulative layer.

Thermal and photochemical reactions of NO2 on chromium(III) oxide surfaces at atmospheric pressure.

PubMed

Nishino, Noriko; Finlayson-Pitts, Barbara J

2012-12-05

While many studies of heterogeneous chemistry on Cr(2)O(3) surfaces have focused on its catalytic activity, less is known about chemistry on this surface under atmospheric conditions. We report here studies of the thermal and photochemical reactions of NO(2) on Cr(2)O(3) at one atm in air. In order to follow surface species, the interaction of 16-120 ppm NO(2) with a 15 nm Cr(2)O(3) thin film deposited on a germanium crystal was monitored in a flow system using attenuated total reflectance (ATR) coupled to a Fourier transform infrared (FTIR) spectrometer. Gas phase products were monitored in the effluent of an ~285 ppm NO(2)-air mixture that had passed over Cr(2)O(3) powder in a flow system. A chemiluminescence NO(y) analyzer, a photometric O(3) analyzer and a long-path FTIR spectrometer were used to probe the gaseous products. In the absence of added water vapor, NO(2) formed nitrate (NO(3)(-)) ions coordinated to Cr(3+). These surface coordinated NO(3)(-) were reversibly solvated by water under humid conditions. In both dry and humid cases, nitrate ions decreased during irradiation of the surface at 302 nm, and NO and NO(2) were generated in the gas phase. Under dry conditions, NO was the major gaseous product while NO(2) was the dominant species in the presence of water vapor. Heating of the surface after exposure to NO(2) led to the generation of both NO(2) and NO under dry conditions, but only NO(2) in the presence of water vapor. Elemental chromium incorporated into metal alloys such as stainless steel is readily oxidized in contact with ambient air, forming a chromium-rich metal oxide surface layer. The results of these studies suggest that active photo- and thermal chemistry will occur when boundary layer materials containing chromium(III) or chromium oxide such as stainless steel, roofs, automobile bumpers etc. are exposed to NO(2) under tropospheric conditions.

(S)TEM analysis of functional transition metal oxides

NASA Astrophysics Data System (ADS)

Chi, Miaofang

Perovskite vanadates (AVO3) form an ideal family to study the structure-property relationships in transition metal oxides because their physical properties can easily be tailored by varying the A-site cations. (S)TEM is an ideal tool for this type of study due to its capacity for simultaneous imaging and chemical analysis. Determination of the oxidation state of vanadium in complex oxides have been carried out by electron energy loss spectroscopy. SrVO3/LaAlO3 is then studied both experimentally and theoretically as a prototype system. Extra electrons have been detected on the interface layer, and further proven to originate mainly from a change in the local bonding configuration of V at the La-O terminated substrate surface. Cr-containing stainless steel deposited with a LaCrO3 thin-film layer is a promising interconnect material of Solid Oxide Fuel Cells (SOFC). Our investigation on its microstructural evolution reveals that the LaCrO 3 thin film plays a role in inhibiting the growth of an oxide layer on the metal surface and thus protects the surface of the stainless steel. Ca-doped LaCoO3 is a promising SOFC cathode material. The domain structures and the oxidation state of Co in Ca-doped LaCoO3, which are directly related to its mechanical properties and electronic conductivity, are investigated by in-situ TEM and EELS. The formation of microcracks is observed during thermal cycles. Ca-doping in LaCoO3 is shown to not only improve the electronic conductivity of the material, but is also likely to strengthen the grain boundaries. The realization of its application in SOFCs depends on depressing the ferroelastisity to reduce strain formation during thermal cycles. The application of the (S)TEM techniques used for studying the perovskite systems are further extended to other compounds containing transition metal elements. The refractory minerals from Comet 81 P/Wild-2 are studied to investigate the formation of the early solar system. A relatively high Ti3+/Ti 4+ ratio in fassaite and the presence of osbornite indicate that the Comet refractory minerals formed in the inner solar nebula and were later transported to the outer solar system where the comet formed. This implies a much more dynamic and perhaps more violent solar nebula than was previously suspected.

Temperature dependence of corrosion of ferritic stainless steel in dual atmosphere at 600-800 °C

NASA Astrophysics Data System (ADS)

Alnegren, Patrik; Sattari, Mohammad; Svensson, Jan-Erik; Froitzheim, Jan

2018-07-01

The ferritic stainless steel AISI 441 (EN 1.4509) is exposed for 1000 h to air - 3% H2O on one side and to Ar - 5% H2 - 3% H2O on the other at temperatures 600, 700, and 800 °C. Conditions are chosen to mimic the environment of metallic interconnects in an operating solid oxide fuel cell (SOFC). At 600 °C, ∼25 μm thick Fe2O3/(Fe,Cr)3O4 forms on large parts of the air side of the samples. Reference samples exposed to air - 3% H2O on both sides form thin protective layers of (Cr,Mn)3O4/Cr2O3 at the same temperature. At higher temperatures, 700 and 800 °C, all samples form protective layers of (Cr,Mn)3O4/Cr2O3 regardless of exposure to single or dual atmosphere. It is concluded that corrosion resistance in a dual atmosphere has an inverse dependence on temperature. Different hypotheses for the underlying cause for the dual atmosphere effect are discussed and compared to the experimental data.

Effects of compositional changes on the performance of a thermal barrier coating system. [yttria-stabilized zirconia coatings on gas turbine engine blades

NASA Technical Reports Server (NTRS)

Stecura, S.

1978-01-01

Currently proposed thermal barrier systems for aircraft gas turbine engines consist of NiCrAlY bond coating covered with an insulating oxide layer of yttria-stabilized zirconia. The effect of yttrium concentration (from 0.15 to 1.08 w/o) in the bond coating and the yttria concentration (4 to 24.4 w/o) in the oxide layer were evaluated. Furnace, natural gas-oxygen torch, and Mach 1.0 burner rig cyclic tests on solid specimens and air-cooled blades were used to identify trends in coating behavior. Results indicate that the combinations of yttrium levels between 0.15 - 0.35 w/o in the bond coating and the yttria concentration between 6 - 8 w/o in the zirconium oxide layer were the most adherent and resistant to high temperature cyclic exposure.

Cr-substituted LiCoPO4 core with a conductive carbon layer towards high-voltage lithium-ion batteries

NASA Astrophysics Data System (ADS)

Wang, Yue; Chen, Junhong; Qiu, Jingyi; Yu, Zhongbao; Ming, Hai; Li, Meng; Zhang, Songtong; Yang, Yusheng

2018-02-01

Electrical and ionic conductivity are two major limiting factors for LiCoPO4 cathode material. To overcome these shortcomings, a Cr-substituted LiCoPO4 core with a conductive carbon layer cathode material is synthesized using the sol-gel method. The physical chemistry properties of these materials are systematically investigated by using various characterization methods. For instance, the XRD and Rietveld refinement results reveal that Cr successfully substitutes the Co within the LiCoPO4 core to form LiCo1-1.5xCrxPO4/C (x = 0, 0.02, 0.04, 0.06) without changing the olivine structure but exhibits a decrease in the unit cell volume with increasing Cr substitution. SEM and TEM images indicate that Cr substitution does not lead to changes in the basic morphology of LiCo1-1.5xCrxPO4/C (x = 0, 0.02, 0.04, 0.06) material, which is composed of agglomerated nanoparticles with an 8 nm carbon layer on the surface. The EDS and XPS results confirm that Cr is uniformly distributed on the surface and that the oxidation state of Cr is +3. FTIR spectra indicate that the antisite defect concentration decreases with increasing Cr substitution. Furthermore, Cr substitution significantly improves the electrochemical performances of LiCo1-1.5xCrxPO4/C (x = 0.02, 0.04, 0.06) cathode. Notably, the LiCo0.94Cr0.04PO4/C delivers an initial discharge capacity of 144 mA h g-1 at 0.1 C and shows a capacity retention of 71% after 100 cycles between 3.0 and 5.0 V. The CV and EIS results indicate that the polarization is reduced and that the electronic and ionic conductivities are improved by Cr substitution. The good electrochemical performances for Cr-substituted LiCoPO4/C electrodes are attributed to the lower antisite defect concentration, as the reduction of polarization, the improvement of electronic and ion conductivity and the uniform carbon layer. These features will accelerate the commercial application of LiCoPO4 towards the start-art of the high voltage lithium-ion batteries.

High-Temperature Erosive Behavior of Plasma Sprayed Cr3C2-NiCr/Cenosphere Coating

NASA Astrophysics Data System (ADS)

Mathapati, Mahantayya; Doddamani, Mrityunjay; Ramesh, M. R.

2018-02-01

This research examines the deposition of Cr3C2-NiCr/cenosphere and Cr3C2-NiCr coatings on MDN 321 steel through the process of plasma spray. In this process, the solid particle erosion test is established at 200, 400, 600 °C with 30° and 90° impact angles. Alumina erodent is adopted to investigate the erosive behavior of the coating at higher temperatures. The properties of the Cr3C2-NiCr/cenosphere coating are established based on the microhardness, the adhesive strength, the fracture toughness, and the ductility. To quantify volume loss as a result of erosion, an optical profilometer is used. At higher temperature, decrease in the erosion volume loss of Cr3C2-NiCr/cenosphere and Cr3C2-NiCr coatings is observed. The erosion-resistive property of Cr3C2-NiCr/cenosphere coating is higher than that of MDN 321 steel by 76%. This property is influenced by high-temperature stability of mullite, alumina, and protective oxide layer that is formed at elevated temperatures. The morphology of eroded coating discloses a brittle mode of material removal.

The effect of yttrium and thorium on the oxidation behavior of Ni-Cr-Al alloys

NASA Technical Reports Server (NTRS)

Kumar, A.; Nasrallah, M.; Douglass, D. L.

1974-01-01

The effect of quaternary additions of 0.5% Y, 0.5 and 1.0% Th to a base alloy of Ni-10CR-5Al on the oxidation behavior and mechanism was studied during oxidation in air over the range of 1000 to 1200 C. The presence of yttrium decreased the oxidation kinetics slightly, whereas, the addition of thorium caused a slight increase. Oxide scale adherence was markedly improved by the addition of the quaternary elements. Although a number of oxides formed on yttrium containing alloys, quantitative X-ray diffraction clearly showed that the rate-controlling step was the diffusion of aluminum through short circuit paths in a thin layer of alumina that formed parabolically with time. Although the scale adherence of the yttrium containing alloy was considerably better than the base alloys, spalling did occur that was attributed to the formation of the voluminous YAG particles which grew in a mushroom-like manner, lifting the protective scale off the subrate locally. The YAG particles formed primarily at grain boundaries in the substrate in which the yttrium originally existed as YNi9.

Enhanced photoelectrochemical and optical performance of ZnO films tuned by Cr doping

NASA Astrophysics Data System (ADS)

Salem, M.; Akir, S.; Massoudi, I.; Litaiem, Y.; Gaidi, M.; Khirouni, K.

2017-04-01

In this paper, pure and Cr-doped nanostructured Zinc oxide thin films were synthesized by simple and low cost co-precipitation and spin-coating method with Cr concentration varying between 0.5 and 5 at.%. Crystalline structure of the prepared films was investigated by X-ray diffraction (XRD) and Raman spectroscopy techniques. XRD analysis indicated that the films were indexed as the hexagonal phase of wurtzite-type structure and demonstrated a decrease in the crystallite size with increasing Cr doping content. Cr doping revealed a significant effect on the optical measurements such as transmission and photoluminescence properties. The optical measurements indicated that Cr doping decreases the optical band gap and it has been shifted from 3.41 eV for pure ZnO film to 3.31 eV for 5 at.% Cr-doped one. The photoelectrochemical (PEC) sensing characteristics of Cr-doped ZnO layers were investigated. Amongst all photo-anodes with different Cr dopant concentration, the 2 at.% Cr incorporated ZnO films exhibited fast response and higher photoconduction sensitivity.

Corrosion resistant PEM fuel cell

DOEpatents

Li, Y.; Meng, W.J.; Swathirajan, S.; Harris, S.J.; Doll, G.L.

1997-04-29

The present invention contemplates a PEM fuel cell having electrical contact elements (including bipolar plates/septums) comprising a titanium nitride coated light weight metal (e.g., Al or Ti) core, having a passivating, protective metal layer intermediate the core and the titanium nitride. The protective layer forms a barrier to further oxidation/corrosion when exposed to the fuel cell`s operating environment. Stainless steels rich in Cr, Ni, and Mo are particularly effective protective interlayers. 6 figs.

Development of analytical procedures for the determination of hexavalent chromium in corrosion prevention coatings used in the automotive industry.

PubMed

Séby, F; Castetbon, A; Ortega, R; Guimon, C; Niveau, F; Barrois-Oudin, N; Garraud, H; Donard, O F X

2008-05-01

The European directive 2000/53/EC limits the use of Cr(VI) in vehicle manufacturing. Although a maximum of 2 g of Cr(VI) was authorised per vehicle for corrosion prevention coatings of key components, since July 2007 its use has been prohibited except for some particular applications. Therefore, the objective of this work was to develop direct analytical procedures for Cr(VI) determination in the different steel coatings used for screws. Instead of working directly with screws, the optimisation of the procedures was carried out with metallic plates homogeneously coated to improve the data comparability. Extraction of Cr(VI) from the metallic parts was performed by sonication. Two extraction solutions were tested: a direct water extraction solution used in standard protocols and an ammonium/ammonia buffer solution at pH 8.9. The extracts were further analysed for Cr speciation by high-performance liquid chromatography (HPLC) inductively coupled plasma (ICP) atomic emission spectrometry or HPLC ICP mass spectrometry depending on the concentration level. When possible, the coatings were also directly analysed by solid speciation techniques (X-ray photoelectron spectroscopy, XPS, and X-ray absorption near-edge structure, XANES) for validation of the results. Very good results between the different analytical approaches were obtained for the sample of coating made up of a heated paint containing Zn, Al and Cr when using the extracting buffer solution at pH 8.9. After a repeated four-step extraction procedure on the same portion test, taking into account the depth of the surface layer reached, good agreement with XPS and XANES results was obtained. In contrast, for the coatings composed of an alkaline Zn layer where Cr(VI) and Cr(III) are deposited, only the extraction procedure using water allowed the detection of Cr(VI). To elucidate the Cr(VI) reduction during extraction at pH 8.9, the reactivity of Cr(VI) towards different species of Zn generally present in the coatings (metallic Zn and zinc oxide) was studied. The results showed that metallic Zn rapidly reduces Cr(VI), whereas this reaction is less evident in the presence of zinc oxide. Water was then retained for coatings containing metallic Zn.

High-Temperature Oxidation of Fe3Al Intermetallic Alloy Prepared by Additive Manufacturing LENS

PubMed Central

Łyszkowski, Radosław

2015-01-01

The isothermal oxidation of Fe-28Al-5Cr (at%) intermetallic alloy microalloyed with Zr and B (<0.08 at%) in air atmosphere, in the temperature range of 1000 to 1200 °C, was studied. The investigation was carried out on the thin-walled (<1 mm) elements prepared by Laser Engineered Net Shaping (LENS) from alloy powder of a given composition. Characterization of the specimens, after the oxidation, was conducted using X-ray diffraction (XRD) and scanning electron microscopy (SEM, with back-scatter detector (BSE) and energy-dispersive X-ray spectroscopy (EDS) attachments). The investigation has shown, that the oxidized samples were covered with a thin, homogeneous α-Al2O3 oxide layers. The intensity of their growth indicates that the material lost its resistance to oxidation at 1200 °C. Structural analysis of the thin-walled components’ has not shown intensification of the oxidation process at the joints of additive layers. PMID:28788014

Comparative study of the native oxide on 316L stainless steel by XPS and ToF-SIMS

DOE Office of Scientific and Technical Information (OSTI.GOV)

Tardio, Sabrina, E-mail: s.tardio@surrey.ac.uk; Abel, Marie-Laure; Castle, James E.

2015-09-15

The very thin native oxide film on stainless steel, of the order of 2 nm, is known to be readily modified by immersion in aqueous media. In this paper, X-ray photoelectron spectroscopy (XPS) and time of flight secondary ions mass spectrometry are employed to investigate the nature of the air-formed film and modification after water emersion. The film is described in terms of oxide, hydroxide, and water content. The preferential dissolution of iron is shown to occur on immersion. It is shown that a water absorbed layer and a hydroxide layer are present above the oxide-like passive film. The concentrations ofmore » water and hydroxide appear to be higher in the case of exposure to water. A secure method for the peak fitting of Fe2p and Cr2p XPS spectra of such films on their metallic substrates is described. The importance of XPS survey spectra is underlined and the feasibility of C{sub 60}{sup +} SIMS depth profiling of a thin oxide layer is shown.« less

Method of forming a dense, high temperature electronically conductive composite layer on a porous ceramic substrate

DOEpatents

Isenberg, Arnold O.

1992-01-01

An electrochemical device, containing a solid oxide electrolyte material and an electrically conductive composite layer, has the composite layer attached by: (A) applying a layer of LaCrO.sub.3, YCrO.sub.3 or LaMnO.sub.3 particles (32), on a portion of a porous ceramic substrate (30), (B) heating to sinter bond the particles to the substrate, (C) depositing a dense filler structure (34) between the doped particles (32), (D) shaving off the top of the particles, and (E) applying an electronically conductive layer over the particles (32) as a contact.

Oxidative vaporization kinetics of chromium (III) oxide in oxygen from 1270 to 1570 K

NASA Technical Reports Server (NTRS)

Stearns, C. A.; Kohl, F. J.; Fryburg, G. C.

1974-01-01

Rates of oxidative vaporization of Cr2O3 on preoxidized resistively heated chromium were determined in flowing oxygen at 0.115 torr for temperatures from 1270 to 1570 K. Reaction controlled rates were obtained from experimental rates by a gold calibration technique. These rates were shown to agree with those predicted by thermochemical analysis. The activation energy obtained for the oxidative vaporation reaction corresponded numerically with the thermochemical enthalpy of the reaction. A theoretical equation is given for calculating the rate from thermodynamic data by using boundary layer theory.

Chromium(iii) oxidation by biogenic manganese oxides with varying structural ripening.

PubMed

Tang, Yuanzhi; Webb, Samuel M; Estes, Emily R; Hansel, Colleen M

2014-09-20

Manganese (Mn) oxides, which are generally considered biogenic in origin within natural systems, are the only oxidants of Cr(iii) under typical environmental conditions. Yet the influence of Mn biooxide mineral structural evolution on Cr(iii) oxidation under varying geochemical conditions is unknown. In this study we examined the role of light, organic carbon, pH, and the structure of biogenic Mn oxides on Cr(iii) oxidation. Aging of Mn oxides produced by a marine bacterium within the widespread Roseobacter clade resulted in structural ripening from a colloidal hexagonal to a particulate triclinic birnessite phase. The structurally diverse Mn oxides were then reacted with aqueous Cr(iii) within artificial seawater in the presence or absence of carbon and light. Here we found that Cr(iii) oxidation capacity was highest at near neutral pH and in the combined presence of carbon and light. Mn oxide ripening from a hexagonal to a triclinic birnessite phase led to decreased Cr(iii) oxidation in the presence of carbon and light, whereas no change in reactivity was observed in the absence of carbon and/or in the dark. As only minimal Cr(iii) oxidation was observed in the absence of Mn oxides, these results strongly point to coupled Mn oxide- and photo-induced generation of organic and/or oxygen radicals involved in Cr(iii) oxidation. Based on Mn oxide concentration and structural trends, we postulate that Mn(ii) produced from the oxidation of Cr(iii) by the primary Mn oxide is recycled in the presence of organics and light conditions, (re)generating secondary hexagonal birnessite and thereby allowing for continuous oxidation of Cr(iii). In the absence of this Mn oxide regeneration, Cr(iii) induced structural ripening of the hexagonal birnessite precludes further Cr(iii) oxidation. These results highlight the complexity of reactions involved in Mn oxide mediated Cr(iii) oxidation and suggest that photochemical carbon reactions are requisite for sustained Cr(iii) oxidation and persistence of reactive Mn oxides.

The role of yttrium and titanium during the development of ODS ferritic steels obtained through the STARS route: TEM and XAS study

NASA Astrophysics Data System (ADS)

Ordás, Nerea; Gil, Emma; Cintins, Arturs; de Castro, Vanessa; Leguey, Teresa; Iturriza, Iñigo; Purans, Juris; Anspoks, Andris; Kuzmin, Alexei; Kalinko, Alexandr

2018-06-01

Oxide Dispersion Strengthened Ferritic Steels (ODS FS) are candidate materials for structural components in future fusion reactors. Their high strength and creep resistance at elevated temperatures and their good resistance to neutron radiation damage is obtained through extremely fine microstructures containing a high density of nanometric precipitates, generally yttrium and titanium oxides. This work shows transmission electron microscopy (TEM) and extended X-ray absorption fine structure (EXAFS) characterization of Fe-14Cr-2W-0.3Ti-0.24Y ODS FS obtained by the STARS route (Surface Treatment of gas Atomized powder followed by Reactive Synthesis), an alternative method to obtain ODS alloys that avoids the mechanical alloying to introduce Y2O3 powder particles. In this route, FS powders already containing Ti and Y, precursors of the nanometric oxides, are obtained by gas atomization. Then, a metastable Cr- and Fe-rich oxide layer is formed on the surface of the powder particles. During consolidation by HIP at elevated temperatures, and post-HIP heat treatments above the HIP temperature, this oxide layer at Prior Particle Boundaries (PPBs) dissociates, the oxygen diffuses, and Y-Ti-O nano-oxides precipitate in the ferritic matrix. TEM characterization combined with XAFS and XANES analyses have proven to be suitable tools to follow the evolution of the nature of the different oxides present in the material during the whole processing route and select appropriate HIP and post-HIP parameters to promote profuse and fine Y-Ti-O nanometric precipitates.

Development of Cold Spray Coatings for Accident-Tolerant Fuel Cladding in Light Water Reactors

NASA Astrophysics Data System (ADS)

Maier, Benjamin; Yeom, Hwasung; Johnson, Greg; Dabney, Tyler; Walters, Jorie; Romero, Javier; Shah, Hemant; Xu, Peng; Sridharan, Kumar

2018-02-01

The cold spray coating process has been developed at the University of Wisconsin-Madison for the deposition of oxidation-resistant coatings on zirconium alloy light water reactor fuel cladding with the goal of improving accident tolerance during loss of coolant scenarios. Coatings of metallic (Cr), alloy (FeCrAl), and ceramic (Ti2AlC) materials were successfully deposited on zirconium alloy flats and cladding tube sections by optimizing the powder size, gas preheat temperature, pressure and composition, and other process parameters. The coatings were dense and exhibited excellent adhesion to the substrate. Evaluation of the samples after high-temperature oxidation tests at temperatures up to 1300°C showed that the cold spray coatings significantly mitigate oxidation kinetics because of the formation of thin passive oxide layers on the surface. The results of the study indicate that the cold spray coating process is a viable near-term option for developing accident-tolerant zirconium alloy fuel cladding.

Characterization and corrosion behavior of F6NM stainless steel treated in high temperature water

NASA Astrophysics Data System (ADS)

Li, Zheng-yang; Cai, Zhen-bing; Yang, Wen-jin; Shen, Xiao-yao; Xue, Guo-hong; Zhu, Min-hao

2018-03-01

F6NM martensitic stainless steel was exposed to 350 °C water condition for 500, 1500, and 2500 h to simulate pressurized water reactor (PWR) condition. The characterization and corrosion behavior of the oxide film were investigated. Results indicate that the exposed steel surface formed a double-layer oxide film. The outer oxide film is Fe-rich and contains two type oxide particles. However, the inner oxide film is Cr-rich, and two oxide films, whose thicknesses increase with increasing exposure time. The oxide film reduces the corrosion behavior because the outer oxide film has many crack and pores. Finally, the mechanism and factors affecting the formation of the oxide film were investigated.

Thermomechanical Performance of C and SiC Multilayer, Fiber-Reinforced, CVI SiC Matrix Composites

NASA Technical Reports Server (NTRS)

Morscher, Gregory N.; Singh, Mrityunjay

2004-01-01

Hybrid fiber approaches have been attempted in the past to alloy desirable properties of different fiber-types for mechanical properties, thermal stress management, and oxidation resistance. Such an approach has potential for the CrSiC and SiCrSiC composite systems. SiC matrix composites with different stacking sequences of woven C fiber (T300) layers and woven Sic fiber (Hi-NicalonTM) layers were fabricated using the standard CVI process. Delamination occurred to some extent due to thermal mismatch for all of the composites. However, for the composites with a more uniform stacking sequence, minimal delamination occurred, enabling tensile properties to be determined at room temperature and elevated temperatures (stress-rupture in air). Composites were seal-coated with a CVI SiC layer as well as a proprietary C-B-Si (CBS) layer. Definite improvement in rupture behavior was observed in air for composites with increasing SiC fiber content and a CBS layer. The results will be compared to standard C fiber reinforced CVI SiC matrix and Hi-Nicalon reinforced CVI SiC matrix composites.

In-situ observation of equilibrium transitions in Ni films; agglomeration and impurity effects.

PubMed

Thron, Andrew M; Greene, Peter; Liu, Kai; van Benthem, Klaus

2014-02-01

Dewetting of ultra-thin Ni films deposited on SiO2 layers was observed, in cross-section, by in situ scanning transmission electron microscopy. Holes were observed to nucleate by voids which formed at the Ni/SiO2 interface rather than at triple junctions at the free surface of the Ni film. Ni islands were observed to retract, in attempt to reach equilibrium on the SiO2 layer. SiO2 layers with 120 nm thickness were found to limit in situ heating experiments due to poor thermal conductivity of SiO2. The formation of graphite was observed during the agglomeration of ultra-thin Ni films. Graphite was observed to wet both the free surface and the Ni/SiO2 interface of the Ni islands. Cr forms surface oxide layers on the free surface of the SiO2 layer and the Ni islands. Cr does not prevent the dewetting of Ni, however it will likely alter the equilibrium shape of the Ni islands. © 2013 Published by Elsevier B.V.

Long-term evaluation of solid oxide fuel cell candidate materials in a 3-cell generic stack test fixture, part III: Stability and microstructure of Ce-(Mn,Co)-spinel coating, AISI441 interconnect, alumina coating, cathode and anode

NASA Astrophysics Data System (ADS)

Chou, Yeong-Shyung; Stevenson, Jeffry W.; Choi, Jung-Pyung

2014-07-01

A generic solid oxide fuel cell stack test fixture was developed to evaluate candidate materials and processing under realistic conditions. Part III of the work investigated the stability of Ce-(Mn,Co) spinel coating, AISI441 metallic interconnect, alumina coating, and cell's degradation. After 6000 h test, the spinel coating showed densification with some diffusion of Cr. At the metal interface, segregation of Si and Ti was observed, however, no continuous layer formed. The alumina coating for perimeter sealing areas appeared more dense and thick at the air side than the fuel side. Both the spinel and alumina coatings remained bonded. EDS analysis of Cr within the metal showed small decrease in concentration near the coating interface and would expect to cause no issue of Cr depletion. Inter-diffusion of Ni, Fe, and Cr between spot-welded Ni wire and AISI441 interconnect was observed and Cr-oxide scale formed along the circumference of the weld. The microstructure of the anode and cathode was discussed relating to degradation of the top and middle cells. Overall, the Ce-(Mn,Co) spinel coating, alumina coating, and AISI441 steel showed the desired long-term stability and the developed generic stack fixture proved to be a useful tool to validate candidate materials for SOFC.

Process for producing Ti-Cr-Al-O thin film resistors

DOEpatents

Jankowski, Alan F.; Schmid, Anthony P.

2001-01-01

Thin films of Ti-Cr-Al-O are used as a resistor material. The films are rf sputter deposited from ceramic targets using a reactive working gas mixture of Ar and O.sub.2. Resistivity values from 10.sup.4 to 10.sup.10 Ohm-cm have been measured for Ti-Cr-Al-O film <1 .mu.m thick. The film resistivity can be discretely selected through control of the target composition and the deposition parameters. The application of Ti-Cr-Al-O as a thin film resistor has been found to be thermodynamically stable, unlike other metal-oxide films. The Ti-Cr-Al-O film can be used as a vertical or lateral resistor, for example, as a layer beneath a field emission cathode in a flat panel display; or used to control surface emissivity, for example, as a coating on an insulating material such as vertical wall supports in flat panel displays.

Flat panel display using Ti-Cr-Al-O thin film

DOEpatents

Jankowski, Alan F.; Schmid, Anthony P.

2002-01-01

Thin films of Ti--Cr--Al--O are used as a resistor material. The films are rf sputter deposited from ceramic targets using a reactive working gas mixture of Ar and O.sub.2. Resistivity values from 10.sup.4 to 10.sup.10 Ohm-cm have been measured for Ti--Cr--Al--O film <1 .mu.m thick. The film resistivity can be discretely selected through control of the target composition and the deposition parameters. The application of Ti--Cr--Al--O as a thin film resistor has been found to be thermodynamically stable, unlike other metal-oxide films. The Ti--Cr--Al--O film can be used as a vertical or lateral resistor, for example, as a layer beneath a field emission cathode in a flat panel display; or used to control surface emissivity, for example, as a coating on an insulating material such as vertical wall supports in flat panel displays.

TI--CR--AL--O thin film resistors

DOEpatents

Jankowski, Alan F.; Schmid, Anthony P.

2000-01-01

Thin films of Ti--Cr--Al--O are used as a resistor material. The films are rf sputter deposited from ceramic targets using a reactive working gas mixture of Ar and O.sub.2. Resistivity values from 10.sup.4 to 10.sup.10 Ohm-cm have been measured for Ti--Cr--Al--O film <1 .mu.m thick. The film resistivity can be discretely selected through control of the target composition and the deposition parameters. The application of Ti--Cr--Al--O as a thin film resistor has been found to be thermodynamically stable, unlike other metal-oxide films. The Ti--Cr--Al--O film can be used as a vertical or lateral resistor, for example, as a layer beneath a field emission cathode in a flat panel display; or used to control surface emissivity, for example, as a coating on an insulating material such as vertical wall supports in flat panel displays.

High-temperature frictional wear behavior of MCrAlY-based coatings deposited by atmosphere plasma spraying

NASA Astrophysics Data System (ADS)

Tao, Chong; Wang, Lei; Song, Xiu

2017-02-01

Al2O3-Cr2O3/NiCoCrAlYTa coatings were prepared via atmosphere plasma spraying (APS). The microstructure and phase composition of the coatings were analyzed by X-ray diffraction (XRD), scanning electron microscopy (SEM), laser confocal scanning microscopy (LSCM), and transmission electron microscopy (TEM). The dry frictional wear behavior of the coatings at 500°C in static air was investigated and compared with that of 0Cr25Ni20 steel. The results show that the coatings comprise the slatted layers of oxide phases, unmelted particles, and pores. The hot abrasive resistance of the coatings is enhanced compared to that of 0Cr25Ni20, and their mass loss is approximately one-fifteenth that of 0Cr25Ni20 steel. The main wear failure mechanisms of the coatings are abrasive wear, fatigue wear, and adhesive wear.

Oxidation behavior of thermal barrier coating systems with Al interlayer under isothermal loading

NASA Astrophysics Data System (ADS)

Ali, I.; Sokołowski, P.; Grund, T.; Pawłowski, L.; Lampke, T.

2018-06-01

In the present study, the phenomena related to the Thermally Grown Oxides (TGO) in atmospheric plasma sprayed Thermal Barrier Coatings (TBCs) are discussed. CoNiCrAlY bond coatings were sprayed on Inconel 600 substrates. Subsequently, thin Al layers were deposited by DC-Magnetron sputtering. Finally, yttria-stabilized zirconia (YSZ) top coatings were deposited to form a three-layered TBC system. The thus produced aluminum interlayer containing thermal barrier coatings (Al-TBC) were subjected to isothermal exposure with different holding times at 1150 °C and compared with reference TBCs of the same kind, but without Al interlayers (R-TBC). The oxide film formation in the interface between bond coating (BC) and top coating (TC) was investigated by scanning electron microscope (SEM) after 100 and 300 h of high temperature isothermal exposure. The growth of this oxide film as a function of the isothermal exposure time was studied. As a result, the designed Al-TBC system exhibited better oxidation resistance in the BC/TC interface than the two-layered R-TBC system. This was lead back to the Al enrichment, which slows down the formation rate of transition metal oxides during thermal loading.

Effect of low current density and low frequency on oxidation resistant and coating activity of coated FeCrAl substrate by γ-Al2O3 powder

NASA Astrophysics Data System (ADS)

Leman, A. M.; Feriyanto, Dafit; Zakaria, Supaat; Sebayang, D.; Rahman, Fakhrurrazi; Jajuli, Afiqah

2017-09-01

High oxidation resistant is the needed material properties for material that operates in high temperature such as catalytic converter material. FeCrAl alloy acts as metallic material and is used as substrate material that is coated by ceramic material i.e. γ-Al2O3. The main purpose of this research is to increase oxidation resistant of metallic material as it will help improve the life time of metallic catalytic converter. Ultrasonic technique (UB) and Nickel electroplating technique (EL) were used to achieve the objective. UB was carried out using various time of 1, 1.5, 2, 2.5 and 3 h, in low frequency of 35 kHz and ethanol as the electrolyte. Meanwhile, EL was conducted using various times of 15, 30, 45, 60 and 75 minutes, DC power supply was 1.28A and sulphamate type as the solution. The characterization and analysis were carried out using Scanning Electron Microscopy (SEM) and box furnace at various temperature of 1000, 1100 and 1200 °C. SEM analysis shows the surface morphology of treated and untreated samples. Untreated samples shows finer surface structure as compared to UB and EL samples. It was caused by γ-Al2O3 which was embedded during UB and EL process on the surface of FeCrAl substrate to develop protective oxide layer. The layer was used to protect the substrate from extreme environment condition and temperature operation. Oxidation resistant analysis shows that treated samples had lower mass change as compared to untreated samples. Lowest mass change of treated samples were located at UB 1.5 h and EL at 30 minute with 0.00475 g and 0.00243 g for temperature of 1000 °C, 0.00495 g and 000284 g for temperature of 1100 °C and 0.00519 g and 0.00304 g for temperature 1200 °C, Based on the overall results, it can be concluded that EL 30 minute samples was the appropriate parameter to coat FeCrAl by γ-Al2O3 to develop metallic catalytic converter that is high oxidation resistant in high temperature operation.

Study of the effects of gaseous environments on sulfidation attack of superalloys

NASA Technical Reports Server (NTRS)

Smeggil, J. G.; Bornstein, N. S.

1977-01-01

Studies were conducted to examine the effect of the gaseous corrodents NaCl, HCl, and NaOH on the high temperature oxidation and Na2SO4-induced corrosion behavior of the alumina former NiAl, the chromia former Ni-25 wt.% Cr, elemental Cr, and the superalloy B-1900. Experiments were conducted at 900 and 1050 C in air in the presence and absence of the gaseous corrodents. Effects involving both reaction rates and microstructural changes in oxide morphology were observed due to the presence of these corrodents at levels anticipated to be present in operating industrial and marine gas turbines. The effect of gaseous NaCl, HCl, and possibly NaOH on NiAl in simple oxidation was to remove aluminum from below the protective alumina layer and to simultaneously weaken the adherence of the protective alumina oxide scale to the substrate. The aluminum removed from below the oxide scale was redeposited on its surface as alpha-Al2O3 whiskers. With respect to the chromia formers, gaseous NaCl and HCl promoted breakaway oxidation kinetics and changes in the microstructures of the oxide scales.

Iron-based alloy and nitridation treatment for PEM fuel cell bipolar plates

DOEpatents

Brady, Michael P [Oak Ridge, TN; Yang, Bing [Oak Ridge, TN; Maziasz, Philip J [Oak Ridge, TN

2010-11-09

A corrosion resistant electrically conductive component that can be used as a bipolar plate in a PEM fuel cell application is composed of an alloy substrate which has 10-30 wt. % Cr, 0.5 to 7 wt. % V, and base metal being Fe, and a continuous surface layer of chromium nitride and vanadium nitride essentially free of base metal. A oxide layer of chromium vanadium oxide can be disposed between the alloy substrate and the continuous surface nitride layer. A method to prepare the corrosion resistant electrically conductive component involves a two-step nitridization sequence by exposing the alloy to a oxygen containing gas at an elevated temperature, and subsequently exposing the alloy to an oxygen free nitrogen containing gas at an elevated temperature to yield a component where a continuous chromium nitride layer free of iron has formed at the surface.

Effect of sulfur removal on Al2O3 scale adhesion

NASA Astrophysics Data System (ADS)

Smialek, James L.

1991-03-01

If the role of reactive element dopants in producing A12O3 scale adhesion on NiCrAl alloys is to getter sulfur and prevent interfacial segregation, then eliminating sulfur from undoped alloys should also produce adherence. Four experiments successfully produced scale adhesion by sulfur removal alone. (1) Repeated oxidation and polishing of a pure NiCrAl alloy lowered the sulfur content from 10 to 2 parts per million by weight (ppmw), presumably by removing the segregated interfacial layer after each cycle. Total scale spallation changed to total retention after 13 such cycles, with no changes in the scale or interfacial morphology. (2) Thinner samples became adherent after fewer oxidation polishing cycles because of a more limited supply of sulfur. (3) Spalling in subsequent cyclic oxidation tests of samples from experiment (1) was a direct function of the initial sulfur content. (4) Desulfurization to 0.1 ppmw levels was accomplished by annealing melt-spun foil in 1 arm H2. These foils produced oxidation weight change curves for 500 1-hour cycles at 1100 °C similar to those for Y- or Zr-doped NiCrAl. The transition between adherent and nonadherent behavior was modeled in terms of sulfur flux, sulfur content, and sulfur segregation.

Chromium and yttrium-doped magnesium aluminum oxides prepared from layered double hydroxides

NASA Astrophysics Data System (ADS)

García-García, J. M.; Pérez-Bernal, M. E.; Ruano-Casero, R. J.; Rives, V.

2007-12-01

Layered double hydroxides with the hydrotalcite-like structures, containing Mg 2+ and Al 3+, doped with Cr 3+ and Y 3+, have been prepared by precipitation at constant pH. The weight percentages of Cr 3+ and Y 3+ were 1, 2, or 3%, and 0.5 or 1%, respectively. Single phases were obtained in all cases, whose crystallinity decreased as the content in Cr and Y was increased. The solids have been characterised by element chemical analysis, powder X-ray diffraction, thermal analyses (differential, thermogravimetric and programmed reduction), FT-IR and UV-vis spectroscopies; the specific surface areas have been determined from nitrogen adsorption isotherms at -196 °C. Upon calcination at 1200 °C for 5 h in air all solids display a mixed structure (spinel and rock salt for MgO); these solids have also been characterised by these techniques and their chromatic coordinates (CIE - L∗a∗b∗) have been determined. Their pink colour makes these solids suitable for being used as ceramic pigments.

Corrosion, ion release and Mott-Schottky probe of chromium oxide coatings in saline solution with potential for orthopaedic implant applications

NASA Astrophysics Data System (ADS)

Ogwu, A. A.; Oje, A. M.; Kavanagh, J.

2016-04-01

We report our investigation on chromium oxide thin film coatings that show a negligible ion release during electrochemical corrosion testing in saline solution. The chemical constituents of the films prepared by reactive magnetron sputtering were identified to be predominantly Cr2O3 based on Raman spectroscopy anti-symmetric stretching vibration modes for CrIII-O and other peaks and an FTIR spectroscopy E u vibrational mode at 409 cm-1. X-ray photoelectron spectroscopy, multiplet fitting for 2P 3/2 and 2P 1/2 states also confirmed the predominantly Cr2O3 stoichiometry in the films. The prepared chromium oxide coatings showed superior pitting corrosion resistance compared to the native chromium oxide films on bare uncoated stainless steel when tested under open circuit potential, potentiodynamic polarisation and cyclic voltammetry in saline solution. The chromium ion released into solution during the corrosion testing of stainless steel substrates coated with chromium oxide coatings was found to be negligibly small based on atomic absorption spectroscopy measurements. Our Mott-Schottky analysis investigation showed that the negligibly small ion release from the chromium oxide coated steel substrates is most likely due to a much lower defect density on the surface of the deposited coatings compared to the native oxide layer on the uncoated steel substrates. This opens up the opportunity for using chromium oxide surface coatings in hip, knee and other orthopaedic implants where possible metal ion release in vivo still poses a great challenge.

Coatings for directional eutectics

NASA Technical Reports Server (NTRS)

Rairden, J. R.; Jackson, M. R.

1976-01-01

Coatings developed to provide oxidation protection for the directionally-solidified eutectic alloy NiTaC-B (4.4 weight percent Cr) were evaluated. Of seven Co-, Fe- and Ni-base coatings that were initially investigated, best resistance to cyclic oxidation was demonstrated by duplex coatings fabricated by depositing a layer of NiCrAl(Y) by vacuum evaporation from an electron beam source followed by deposition of an Al overlayer using the pack cementation process. It was found that addition of carbon to the coating alloy substantially eliminated the problem of fiber denudation in TaC-type eutectic alloys. Burner rig cycled NiTaC-B samples coated with Ni-20Cr-5Al-0.1C-0.1Y+Al and rupture-tested at 1100 deg C performed as well as or better than uncoated, vacuum cycled and air-tested NiTaC-13; however, a slight degradation with respect to uncoated material was noted in air-stress rupture tests at 870 deg C for both cycled and uncycled samples.

Structure and magnetic properties of Co2FeSi film deposited on Si/SiO2 substrate with Cr buffer layer

NASA Astrophysics Data System (ADS)

Chatterjee, Payel; Basumatary, Himalay; Raja, M. Manivel

2018-05-01

Co2FeSi thin films of 25 nm thickness with 50 nm thick Cr buffer layer was deposited on thermally oxidized Si substrates. Structural and magnetic properties of the films were studied as a function of annealing temperature and substrate temperatures. While the coercivity increases with increase in annealing temperature, it is found to decrease with increase in substrate temperature. A minimum coercivity of 18 Oe has been obtained for the film deposited at 550°C substrate temperature. This was attributed to the formation of L12 phase as observed from the GIXRD studies. The films with a good combination of soft magnetic properties and L21 crystal structure are suitable for spintronic applications.

Structural and crystal orientation analysis of Al-Si coating on Ni-based superalloy by means of EBSD technique

NASA Astrophysics Data System (ADS)

Muslimin, A. N.; Sugiarti, E.; Aritonang, T.; Purawiardi, R. I.; Desiati, R. D.

2018-03-01

Ni-based superalloy is widely used for high performance components in power generation turbine due to its excellent mechanical properties. However, Ni-based superalloy has low oxidation resistantance. Therefore, surface coating is required to improve oxidation resistance at high temperatures. Al-Si as a coting material was successfully co-deposited on Ni-based substrate by pack cementation method at 900 °C for about 4 hours. The oxidation test was carried out at high temperature of 1000 °C for 100 hours. Micro structural characterization and analysis on crystal orientation were perfomed by using Field Emission Scanning Electron Microscope (FE-SEM) and Electron Back Scatter Diffraction (EBSD) technique, respectively. The results showed that the coating layer with a homogenous layer and had a thickness of 53 μm consisting of β-NiAl with cubic structure and Ni2Al3 with hexagonal structure. TGO layer was developed after oxidation and had a thickness of about 5 μm consisting of α-Al2O3 and spinel NiCr2O4. The phase composition map and crystal orientation acquired by EBSD technique was also discussed both in TGO and coating layers.

Elevated temperature tribology of cobalt and tantalum-based alloys

DOE PAGES

Scharf, T. W.; Prasad, S. V.; Kotula, P. G.; ...

2014-12-31

This paper describes the friction and wear behavior of a Co–Cr alloy sliding on a Ta–W alloy. Measurements were performed in a pin-on-flat configuration with a hemispherically tipped Co-base alloy pin sliding on a Ta–W alloy flat from ambient to 430°C. Focused ion beam-scanning electron microscopy (FIB-SEM) and cross-sectional transmission electron microscopy (TEM) were used to identify the friction-induced changes to the chemistry and crystal structure in the subsurface regions of wear tracks. During sliding contact, transfer of material varied as a function of the test temperature, either from pin-to-flat, flat-to-pin, or both, resulting in either wear loss and/or volumemore » gain. Friction coefficients (μ) and wear rates also varied as a function of test temperature. The lowest friction coefficient (μ=0.25) and wear rate (1×10 –4 mm 3/N•m) were observed at 430°C in argon atmosphere. This was attributed to the formation of a Co-base metal oxide layer (glaze), predominantly (Co, Cr)O with Rocksalt crystal structure, on the pin surface. Part of this oxide film transferred to the wear track on Ta–W, providing a self-mated oxide-on-oxide contact. Once the oxide glaze is formed, it is able to provide friction reduction for the entire temperature range of this study, ambient to 430°C. Furthermore, the results of this study indicate that glazing the surfaces of Haynes alloys with continuous layers of cobalt chrome oxide prior to wear could protect the cladded surfaces from damage.« less

Elevated temperature tribology of cobalt and tantalum-based alloys

DOE Office of Scientific and Technical Information (OSTI.GOV)

Scharf, T. W.; Prasad, S. V.; Kotula, P. G.

This paper describes the friction and wear behavior of a Co–Cr alloy sliding on a Ta–W alloy. Measurements were performed in a pin-on-flat configuration with a hemispherically tipped Co-base alloy pin sliding on a Ta–W alloy flat from ambient to 430°C. Focused ion beam-scanning electron microscopy (FIB-SEM) and cross-sectional transmission electron microscopy (TEM) were used to identify the friction-induced changes to the chemistry and crystal structure in the subsurface regions of wear tracks. During sliding contact, transfer of material varied as a function of the test temperature, either from pin-to-flat, flat-to-pin, or both, resulting in either wear loss and/or volumemore » gain. Friction coefficients (μ) and wear rates also varied as a function of test temperature. The lowest friction coefficient (μ=0.25) and wear rate (1×10 –4 mm 3/N•m) were observed at 430°C in argon atmosphere. This was attributed to the formation of a Co-base metal oxide layer (glaze), predominantly (Co, Cr)O with Rocksalt crystal structure, on the pin surface. Part of this oxide film transferred to the wear track on Ta–W, providing a self-mated oxide-on-oxide contact. Once the oxide glaze is formed, it is able to provide friction reduction for the entire temperature range of this study, ambient to 430°C. Furthermore, the results of this study indicate that glazing the surfaces of Haynes alloys with continuous layers of cobalt chrome oxide prior to wear could protect the cladded surfaces from damage.« less

Design of alumina forming FeCrAl steels for lead or lead-bismuth cooled fast reactors

NASA Astrophysics Data System (ADS)

Lim, Jun; Hwang, Il Soon; Kim, Ji Hyun

2013-10-01

Iron-chromium-aluminum alloys containing 15-20 wt.% Cr and 4-6 wt.% Al have shown excellent corrosion resistance in the temperature range up to 600 °C or higher in liquid lead and lead-bismuth eutectic environments by the formation of protective Al2O3 layers. However, the higher Cr and Al concentrations in ferritic alloys could be problematic because of severe embrittlement in the manufacturing process as well as in service, caused by the formation of brittle phases. For this reason, efforts worldwide have so far mainly focused on the development of aluminizing surface treatments. However, aluminizing surface treatments have major disadvantages of cost, processing difficulties and reliability issues. In this study, a new FeCrAl alloy is proposed for structural materials in lead and lead-bismuth cooled nuclear applications. The alloy design relied on corrosion experiments in high temperature lead and lead-bismuth eutectic environments and computational thermodynamic calculations using the commercial software, JMatPro. The design of new alloys has focused on the optimization of Cr and Al levels for the formation of an external Al2O3 layer which can provide excellent oxidation and corrosion resistance in liquid lead alloys in the temperature range 300-600 °C while still retaining workable mechanical properties.

Origin and significance of high nickel and chromium concentrations in pliocene lignite of the Kosovo Basin, Serbia

USGS Publications Warehouse

Ruppert, L.; Finkelman, R.; Boti, E.; Milosavljevic, M.; Tewalt, S.; Simon, N.; Dulong, F.

1996-01-01

Trace element data from 59 Pliocene lignite cores from the lignite field in the Kosovo Basin, southern Serbia, show localized enrichment of Ni and Cr (33-304 ppm and 8-176 ppm, respectively, whole-coal basis). Concentrations of both elements decrease from the western and southern boundaries of the lignite field. Low-temperature ash and polished coal pellets of selected bench and whole-coal samples were analyzed by X-ray diffraction and scanning electron microscopy with energy-dispersive X-ray analyses. These analyses show that most of the Ni and Cr are incorporated in detrital and, to a lesser degree, in authigenic minerals. The Ni- and Cr-bearing detrital minerals include oxides, chromites, serpentine-group minerals and rare mixed-layer clays. Possible authigenic minerals include Ni-Fe sulfates and sulfides. Analyses of three lignite samples by a supercritical fluid extraction technique indicate that some (1-11%) of the Ni is organically bound. Ni- and Cr-bearing oxides, mixed-layer clays, chromites and serpentine-group minerals were also identified in weathered and fresh samples of laterite developed on serpentinized Paleozoic peridotite at the nearby Glavica and C??ikatovo Ni mines. These mines are located along the western and northwestern rim, respectively, of the Kosovo Basin, where Ni contents are highest. The detrital Ni- and Cr-bearing minerals identified in lignite samples from the western part of the Kosovo Basin may have been transported into the paleoswamp by rivers that drained the two Paleocene laterites. Some Ni may have been transported directly into the paleoswamp in solution or, alternatively, Ni may have been leached from detrital minerals by acidic peat water and adsorbed onto organic matter and included into authigenic mineral phases. No minable source of Ni and Cr is known in the southern part of the lignite field; however, the mineral and chemical data from the lignite and associated rocks suggest that such a source area may exist.

Effects of Cr-N-ZrO 2 seed layer formed on glass substrates for longitudinal recording media

NASA Astrophysics Data System (ADS)

Suzuki, Hiroyuki; Djayaprawira, David D.; Takahashi, Yoshio; Ishikawa, Akira; Ono, Toshinori; Yahisa, Yotsuo

1999-03-01

Effects of Cr-N-ZrO 2 seed layer deposited on glass substrates before the deposition of C/Co-Cr-Pt/Cr-Ti layers for longitudinal recording media have been investigated. The product of v and Is, the activation volume and the saturation magnetization per unit volume, media noise Nd and S0/ Nd, which is the half value of peak-to-peak output voltage of an isolated pulse over Nd at 11.8 kFC/mm, are evaluated. We find that vIs is decreased by adding N and ZrO 2 to Cr seed layer. Nd is reduced as vIs decreases by adding nitrogen to the Cr seed layer. This is mainly due to the decreased grain sizes of both Cr-Ti underlayer and Co-Cr-Pt magnetic layer. The Nd is further reduced by the addition of ZrO 2 to the Cr-N seed layer. Highest S0/ Nd is achieved for the media with Cr-N-ZrO 2 seed layer. On the other hand, the media with Cr-ZrO 2 seed layer deposited without nitrogen show the higher Nd. Therefore the decrease of the grain size by addition of nitrogen into Ar is essential to reduce Nd, and the ZrO 2 addition to the Cr-N seed layer seems to enhance the effect of grain size reduction by nitrogen addition.

Microstructure and elevated-temperature erosion-oxidation behaviour of aluminized 9Cr-1Mo Steel

NASA Astrophysics Data System (ADS)

Huttunen-Saarivirta, E.; Honkanen, M.; Tsipas, S. A.; Omar, H.; Tsipas, D.

2012-10-01

Degradation of materials by a combination of erosive wear and atmospheric oxidation at elevated temperatures constitutes a problem in some power generation processes, such as fluidized-bed combustion. In this work, 9Cr-1Mo steel, a common tube material in combustion chambers, is coated by a pack cementation method from an Al-containing pack in order to improve the resistance to erosion-oxidation at elevated temperatures. The resulting coating is studied in terms of microstructure and microhardness and tested for its resistance against impacts by sand particles in air at temperatures of 550-700 °C under several conditions, with thickness changes and appearance of the exposed surfaces being studied. The coating was found to contain several phases and layers, the outermost of which was essentially Al-rich and contained e.g., small AlN precipitates. The microhardness values for such coating ranged from 950 to 1100 HV20g. The coating provided the substrate with increased protection particularly against normal particle impacts, as manifested by smaller thickness losses for coated specimens as compared to uncoated counterparts. However, much of the coating was lost under all test conditions, despite the fact that particle debris formed a homogeneous layer on the surface. These results are described and discussed in this paper.

Thermophysical Properties of Matter - The TPRC Data Series. Volume 6. Specific Heat - Nonmetallic Liquids and Gases

DTIC Science & Technology

1970-01-01

dlcarbide (Cr5C2) Heptachromium tricarbide (CrTCj) Chromium chlorides: CrCl2 CrClj Chromium dichloride (CrC^) Chromium trichloride (CrC...methane (see Propane) Dysprosia (see Dysprosium oxide) Dysprosium Dysprosium trichloride hexahydrate (DyClj-6HjO) Dysprosium oxide (DyjOj...Dysprosium sesquioxide (see Dysprosium oxide) Didysprosium trioxide (see Dysprosium oxide) Erbia (see Erbium oxide) Erbium Erbium trichloride

Corrosion behavior and oxide properties of Zr 1.1 wt%Nb 0.05 wt%Cu alloy

NASA Astrophysics Data System (ADS)

Park, Jeong-Yong; Choi, Byung-Kwon; Yoo, Seung Jo; Jeong, Yong Hwan

2006-12-01

The corrosion behavior and oxide properties of Zr-1.1 wt%Nb-0.05 wt%Cu (ZrNbCu) and Zircaloy-4 have been investigated. The corrosion rate of the ZrNbCu alloy was much lower than that of the Zirclaoy-4 in the 360 °C water and 360 °C PWR-simulating loop condition without a neutron flux and it was increased with an increase of the final annealing temperature from 470 °C to 570 °C. TEM observations revealed that the precipitates in the ZrNbCu were β-Nb and ZrNbFe-precipitate with β-Nb being more frequently observed and that the precipitates were more finely distributed in the ZrNbCu alloy. It was also observed that the oxides of the ZrNbCu and Zircaloy-4 consisted of two and seven layers, respectively, after 1000 days in the PWR-simulating loop condition and that the thickness of a fully-developed layer was higher in the ZrNbCu than in the Zircaloy-4. It was also found that the β-Nb in ZrNbCu was oxidized more slowly when compared to the Zr(Fe, Cr) 2 in Zirclaoy-4 when the precipitates in the oxide were observed by TEM. Cracks were observed in the vicinity of the oxidized Zr(Fe, Cr) 2, while no cracks were formed near β-Nb which had retained a metallic state. From the results obtained, it is suggested that the oxide formed on the ZrNbCu has a more protective nature against a corrosion when compared to that of the Zircaloy-4.

High temperature Oxidation of ODS alloy with zirconia dispersions synthesized using Arc Plasma Sintering

NASA Astrophysics Data System (ADS)

Bandriyana; Sujatno, A.; Salam, R.; Sugeng, B.; Dimyati, A.

2017-02-01

Microstructure formation and oxidation behaviour of the Oxide Dispersion Strengthened (ODS) steels for application as structure material in Nuclear Power Plant was investigated. A mixture composed of Fe and 12 wt. % Cr powder with addition of 0.5 and 1 wt.% ZrO2 particles was milled and isostatic pressed to form a sample coin. The coin was then consolidated in the Arc Plasma Sintering (APS) for 4 minutes. The samples were subjected to the high temperature oxidation test in the Magnetic Suspension Balance (MSB). The oxidation test was carried out at 700°C for 6 hours to evaluate the oxide growth in the early stage of it formation by extraction the mass gain curve. The Scanning Electron Microscope (SEM) imaging and X-ray Diffraction Spectroscopy (EDX) elemental mapping were performed to study the microstructure change and compositional distribution. SEM and EDX observation revealed the time dependent development of the Fe-Cr-phases during consolidation. The oxidation rate behaviour of the samples followed the parabolic rate characteristic for inward oxidation process driven by oxygen inward diffusion through the oxide scale with the maximum weight gain around of 60 g/m2. The oxidation resistance was strongly affected by the formation of the oxide protective layer on the surface. In so far, addition of zirconia particles has played no significant role to the oxidation behaviour.

Failure Mechanisms of the Protective Coatings for the Hot Stamping Applications

NASA Astrophysics Data System (ADS)

Zhao, Chen

In the present study, four different nitriding techniques were carried on the ductile irons NAAMS-D6510 and cast steels NAAMS-S0050A, which are widely used stamping die materials; duplex treatments (PVD CrN coating+nitriding) were carried on H13 steels, which are common inserts for the hot stamping dies. Inclined impact-sliding wear tests were performed on the nitriding cases under simulated stamping conditions. Surface profilometer, scanning electron microscopy (SEM), energy-dispersive X-ray spectroscopy (EDS) and X-ray photoelectron spectroscopy (XPS) were used to investigate the wear and failure mechanisms of the protective coatings. It was found that the nitrided ductile iron samples performed better than the nitrided cast steel specimens. High temperature inclined impact-sliding wear tests were carried out on the CrN coatings. It was found that the coating performed better at elevated temperature. XPS analysis indicated the top surface layer (about 3-4nm) of the coating was oxidized at 400 °C and formed a Cr2O3 protective film. The in-situ formation of the thin Cr2O3 protective layer likely led to the change of wear mechanisms from severe adhesive failure to mild abrasive wear.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ballinger, Ronald G

A material that resists lead-bismuth eutectic (LBE) attack and retains its strength at 700°C would be an enabling technology for LBE-cooled reactors. No single alloy currently exists that can economically meet the required performance criteria of high strength and corrosion resistance. A Functionally Graded Composite (FGC) was developed with layers engineered to perform these functions. F91 was chosen as the structural layer of the composite for its strength and radiation resistance. Fe-12Cr-2Si, an alloy developed from previous work in the Fe-Cr-Si system, was chosen as the corrosion-resistant cladding layer because of its chemical similarity to F91 and its superior corrosionmore » resistance in both oxidizing and reducing environments. Fe-12Cr-2Si experienced minimal corrosion due to its self-passivation in oxidizing and reducing environments. Extrapolated corrosion rates are below one micron per year at 700ï°C. Corrosion of F91 was faster, but predictable and manageable. Diffusion studies showed that 17 microns of the cladding layer will be diffusionally diluted during the three year life of fuel cladding. 33 microns must be accounted for during the sixty year life of coolant piping. 5 cm coolant piping and 6.35 mm fuel cladding preforms were produced on a commercial scale by weld-overlaying Fe-12Cr-2Si onto F91 billets and co-extruding them. An ASME certified weld was performed followed by the prescribed quench-and-tempering heat treatment for F91. A minimal heat affected zone was observed, demonstrating field weldability. Finally, corrosion tests were performed on the fabricated FGC at 700ï°C after completely breaching the cladding in a small area to induce galvanic corrosion at the interface. None was observed. This FGC has significant impacts on LBE reactor design. The increases in outlet temperature and coolant velocity allow a large increase in power density, leading to either a smaller core for the same power rating or more power output for the same size core. This FGC represents an enabling technology for LBE cooled fast reactors.« less

Thermal barrier coating life prediction model development

NASA Technical Reports Server (NTRS)

Demasi, J. T.; Sheffler, K. D.

1986-01-01

The objective of this program is to establish a methodology to predict Thermal Barrier Coating (TBC) life on gas turbine engine components. The approach involves experimental life measurement coupled with analytical modeling of relevant degradation modes. The coating being studied is a flight qualified two layer system, designated PWA 264, consisting of a nominal ten mil layer of seven percent yttria partially stabilized zirconia plasma deposited over a nominal five mil layer of low pressure plasma deposited NiCoCrAlY. Thermal barrier coating degradation modes being investigated include: thermomechanical fatigue, oxidation, erosion, hot corrosion, and foreign object damage.

Manganese containing layer for magnetic recording media

DOEpatents

Lambeth, David N.; Lee, Li-Lien; Laughlin, David E.

1999-01-01

The present invention provides for a magnetic recording media incorporating Mn-containing layers between a substrate and a magnetic layer to provide media having increased coercivity and lower noise. The Mn-containing layer can be incorporated in a rotating, translating or stationary recording media to operate in conjunction with magnetic transducing heads for recording and reading of magnetic data, as well as other applications. The magnetic recording medium of the invention preferably includes a Co or Co alloy film magnetic layer, and Mn-containing layer, preferably comprised of VMn, TiMn, MnZn, CrMnMo, CrMnW, CrMnV, and CrMnTi, and most preferably a CrMn alloy, disposed between the substrate and the magnetic layer to promote an epitaxial crystalline structure in the magnetic layer. The medium can further include seed layers, preferably polycrystalline MgO for longitudinal media, underlayers, and intermediate layers. Underlayers and intermediate layers are comprised of materials having either an A2 structure or a B2-ordered crystalline structure disposed between the seed layer and the magnetic layer. Materials having an A2 structure are preferably Cr or Cr alloys, such as CrV, CrMo, CrW and CrTi. Materials having a B2-ordered structure having a lattice constant that is substantially comparable to that of Cr, such as those preferably selected from the group consisting of NiAl, AILCo, FeAl, FeTi, CoFe, CoTi, CoHf, CoZr, NiTi, CuBe, CuZn, A-LMn, AlRe, AgMg, and Al.sub.2 FeMn.sub.2, and is most preferably FeAl or NiAl.

Processing of catalysts by atomic layer epitaxy: modification of supports

NASA Astrophysics Data System (ADS)

Lindblad, Marina; Haukka, Suvi; Kytökivi, Arla; Lakomaa, Eeva-Liisa; Rautiainen, Aimo; Suntola, Tuomo

1997-11-01

Different supports were modified with titania, zirconia and chromia by the atomic layer epitaxy technique (ALE). In ALE, a metal precursor is bound to the support in saturating gas-solid reactions. Surface oxides are grown by alternating reactions of the metal precursor and an oxidizing agent. Growth mechanisms differ depending on the precursor-support pair and the processing conditions. In this work, the influences of the support, precursor and reaction temperature were investigated by comparing the growth of titania from Ti(OCH(CH 3) 2) 4 on silica and alumina, titania from TiCl 4 and Ti(OCH(CH 3) 2) 4 on silica, and zirconia from ZrCl 4 on silica and alumina. The modification of porous oxides supported on metal substrates (monoliths) was demonstrated for the growth of chromia from Cr(acac) 3.

Short-term static corrosion tests in lead-bismuth

NASA Astrophysics Data System (ADS)

Soler Crespo, L.; Martín Muñoz, F. J.; Gómez Briceño, D.

2001-07-01

Martensitic steels have been proposed to be used as structural materials and as spallation target window in hybrid systems devoted to the transmutation of radioactive waste of long life and high activity. However, their compatibility with lead-bismuth in the operating conditions of these systems depends on the existence of a protective layer such as an oxide film. The feasibility of forming and maintaining an oxide layer or maintaining a pre-oxidised one has been studied. Martensitic steel F82Hmod. (8% Cr) has been tested in lead-bismuth under static and isothermal conditions at 400°C and 600°C. In order to study the first stages of the interaction between the steel and the eutectic, short-term tests (100 and 665 h) have been carried out. Pre-oxidised and as-received samples have been tested in atmospheres with different oxidant potential. For low oxygen concentration in lead-bismuth due to unexpected oxygen consumption in the experimental device, dissolution of as-received F82Hmod. occurs and pre-oxidation does not prevent the material dissolution. For high oxygen concentration, the pre-oxidation layer seems to improve the feasibility of protecting stainless steels controlling the oxygen potential of lead-bismuth with a gas phase.

Hydride Microstructure at the Metal-Oxide Interface of Zircaloy-4 from H.B. Robinson Nuclear Reactor

DOE Office of Scientific and Technical Information (OSTI.GOV)

Cinbiz, Mahmut N; Edmondson, Philip D; Terrani, Kurt A

2017-01-01

This study investigates the hydride rim microstructure at the metal-oxide interface of Zircaloy-4 cladding segment removed from H.B. Robinson Nuclear Reactor by utilizing high resolution electron microscopy techniques with energy dispersive x-ray spectroscopy at Oak Ridge National Laboratory under the NSUF Rapid Turnout Experiment program. A complex stacking and orientation of hydride platelets has been observed below the sub-oxide layer. Furthermore, radial hydride platelets have been observed. EDS signals of both Fe and Cr has been reduced within hydrides whereas EDS signal of Sn is unaffected.

Comparison of the Isothermal Oxidation Behavior of As-Cast Cu-17%Cr and Cu-17%Cr-5%Al. Part 1; Oxidation Kinetics

NASA Technical Reports Server (NTRS)

Raj. Sai V.

2008-01-01

The isothermal oxidation kinetics of as-cast Cu-17%Cr and Cu-17%Cr-5%Al in air were studied between 773 and 1173 K under atmospheric pressure. These observations reveal that Cu- 17%Cr-5%Al oxidizes at significantly slower rates than Cu-17%Cr. The rate constants for the alloys were determined from generalized analyses of the data without an a priori assumption of the nature of the oxidation kinetics. Detailed analyses of the isothermal thermogravimetric weight change data revealed that Cu-17%Cr exhibited parabolic oxidation kinetics with an activation energy of 165.9 +/- 9.5 kJ/mol. In contrast, the oxidation kinetics for the Cu-17%Cr- 5%Al alloy exhibited a parabolic oxidation kinetics during the initial stages followed by a quartic relationship in the later stages of oxidation. Alternatively, the oxidation behavior of Cu-17%CR- 5%Al could be better represented by a logarithmic relationship. The parabolic rate constants and activation energy data for the two alloys are compared with literature data to gain insights on the nature of the oxidation mechanisms dominant in these alloys.

Comparison of the Isothermal Oxidation Behavior of As-Cast Cu-17%Cr and Cu-17%Cr-5%Al. Part 1; Oxidation Kinetics

NASA Technical Reports Server (NTRS)

Raj. Sai V.

2008-01-01

The isothermal oxidation kinetics of as-cast Cu-17%Cr and Cu-17%Cr-5%Al in air were studied between 773 and 1173 K under atmospheric pressure. These observations reveal that Cu- 17%Cr-5%Al oxidizes at significantly slower rates than Cu-17%Cr. The rate constants for the alloys were determined from generalized analyses of the data without an a priori assumption of the nature of the oxidation kinetics. Detailed analyses of the isothermal thermogravimetric weight change data revealed that Cu-17%Cr exhibited parabolic oxidation kinetics with an activation energy of 165.9 9.5 kJ mol-1. In contrast, the oxidation kinetics for the Cu-17%Cr- 5%Al alloy exhibited a parabolic oxidation kinetics during the initial stages followed by a quartic relationship in the later stages of oxidation. Alternatively, the oxidation behavior of Cu-17%CR- 5%Al could be better represented by a logarithmic relationship. The parabolic rate constants and activation energy data for the two alloys are compared with literature data to gain insights on the nature of the oxidation mechanisms dominant in these alloys.

Comparison of the Isothermal Oxidation Behavior of As-Cast Cu-17 Percent Cr and Cu-17 Percent Cr-5 Percent Al. Part 1; Oxidation Kinetics

NASA Technical Reports Server (NTRS)

Raj, S. V.

2008-01-01

The isothermal oxidation kinetics of as-cast Cu-17%Cr and Cu-17%Cr-5%Al in air were studied between 773 and 1173 K under atmospheric pressure. These observations reveal that Cu-17%Cr-5%Al oxidizes at significantly slower rates than Cu-17%Cr. The rate constants for the alloys were determined from generalized analyses of the data without an a priori assumption of the nature of the oxidation kinetics. Detailed analyses of the isothermal thermogravimetric weight change data revealed that Cu-17%Cr exhibited parabolic oxidation kinetics with an activation energy of 165.9+/-9.5 kJ/mol. In contrast, the oxidation kinetics for the Cu-17%Cr-5%Al alloy exhibited a parabolic oxidation kinetics during the initial stages followed by a quartic relationship in the later stages of oxidation. Alternatively, the oxidation behavior of Cu-17%CR-5%Al could be better represented by a logarithmic relationship. The parabolic rate constants and activation energy data for the two alloys are compared with literature data to gain insights on the nature of the oxidation mechanisms dominant in these alloys.

Oxidation behaviour of ferritic stainless steel grade Crofer 22 APU at 700 °C in flowing Ar-75%CO2-12%H2O

NASA Astrophysics Data System (ADS)

Shariff, Nurul Atikah; Othman, Norinsan Kamil; Jalar, Azman

2013-11-01

The oxidation of Ferritic Stainless Steel (FSS) grade Crofer 22 APU has been investigated. FSS alloys were exposed to isothermal conditions in a horizontal tube furnace at a 700 °C in flowing Ar-75%CO2-12%H2O at a pressure of approximately 1 atm. The results showed that the growth of non protective Fe2O3 and spinel was observed after 50 h exposure in the presence of 12% H2O. The weight was increased significantly with time of exposure. The formation of different oxides is presented on the interface of the specimen such as MnCr2O4, Fe3O4 and Fe2O3 were revealed by X-ray diffraction and supported by EDAX analysis. FSS did not form a protective Cr2O3 layer due to water vapour accelerates the kinetics oxidation. Data of microstructure observation is presented and discussed in this paper in term of water vapour effects.

Developments of the Physical and Electrical Properties of NiCr and NiCrSi Single-Layer and Bi-Layer Nano-Scale Thin-Film Resistors.

PubMed

Cheng, Huan-Yi; Chen, Ying-Chung; Li, Chi-Lun; Li, Pei-Jou; Houng, Mau-Phon; Yang, Cheng-Fu

2016-02-25

In this study, commercial-grade NiCr (80 wt % Ni, 20 wt % Cr) and NiCrSi (55 wt % Ni, 40 wt % Cr, 5 wt % Si) were used as targets and the sputtering method was used to deposit NiCr and NiCrSi thin films on Al₂O₃ and Si substrates at room temperature under different deposition time. X-ray diffraction patterns showed that the NiCr and NiCrSi thin films were amorphous phase, and the field-effect scanning electronic microscope observations showed that only nano-crystalline grains were revealed on the surfaces of the NiCr and NiCrSi thin films. The log (resistivity) values of the NiCr and NiCrSi thin-film resistors decreased approximately linearly as their thicknesses increased. We found that the value of temperature coefficient of resistance (TCR value) of the NiCr thin-film resistors was positive and that of the NiCrSi thin-film resistors was negative. To investigate these thin-film resistors with a low TCR value, we designed a novel bi-layer structure to fabricate the thin-film resistors via two different stacking methods. The bi-layer structures were created by depositing NiCr for 10 min as the upper (or lower) layer and depositing NiCrSi for 10, 30, or 60 min as the lower (or upper) layer. We aim to show that the stacking method had no apparent effect on the resistivity of the NiCr-NiCrSi bi-layer thin-film resistors but had large effect on the TCR value.

Developments of the Physical and Electrical Properties of NiCr and NiCrSi Single-Layer and Bi-Layer Nano-Scale Thin-Film Resistors

PubMed Central

Cheng, Huan-Yi; Chen, Ying-Chung; Li, Chi-Lun; Li, Pei-Jou; Houng, Mau-Phon; Yang, Cheng-Fu

2016-01-01

In this study, commercial-grade NiCr (80 wt % Ni, 20 wt % Cr) and NiCrSi (55 wt % Ni, 40 wt % Cr, 5 wt % Si) were used as targets and the sputtering method was used to deposit NiCr and NiCrSi thin films on Al2O3 and Si substrates at room temperature under different deposition time. X-ray diffraction patterns showed that the NiCr and NiCrSi thin films were amorphous phase, and the field-effect scanning electronic microscope observations showed that only nano-crystalline grains were revealed on the surfaces of the NiCr and NiCrSi thin films. The log (resistivity) values of the NiCr and NiCrSi thin-film resistors decreased approximately linearly as their thicknesses increased. We found that the value of temperature coefficient of resistance (TCR value) of the NiCr thin-film resistors was positive and that of the NiCrSi thin-film resistors was negative. To investigate these thin-film resistors with a low TCR value, we designed a novel bi-layer structure to fabricate the thin-film resistors via two different stacking methods. The bi-layer structures were created by depositing NiCr for 10 min as the upper (or lower) layer and depositing NiCrSi for 10, 30, or 60 min as the lower (or upper) layer. We aim to show that the stacking method had no apparent effect on the resistivity of the NiCr-NiCrSi bi-layer thin-film resistors but had large effect on the TCR value. PMID:28344296

Probing the Origin of Interfacial Carriers in SrTiO 3$-$LaCrO 3 Superlattices

DOE PAGES

Comes, Ryan B.; Spurgeon, Steven R.; Kepaptsoglou, Despoina M.; ...

2017-01-13

Emergent phenomena at complex oxide interfaces could provide the basis for a wide variety of next-generation devices, including photovoltaics and spintronics. To date, detailed characterization and computational modeling of interfacial defects, cation intermixing, and film stoichiometry have helped to explain many of the novel behaviors observed at a single heterojunction. Unfortunately, many of the techniques employed to characterize a single heterojunction are less effective for a superlattice made up of a repeating series of interfaces that induce collective interfacial phenomena throughout a film. These repeating interfaces present an untapped opportunity to introduce an additional degree of complexity, such as confinedmore » electric fields, that cannot be realized in a single heterojunction. In this work, we explore the properties of SrTiO 3–LaCrO 3 superlattices to understand the role of defects, including variations in cation stoichiometry of individual layers of the superlattice, intermixing across interfaces, and interfacial oxygen vacancies. Using X-ray photoelectron spectroscopy (XPS) and scanning transmission electron microscopy electron energy-loss spectroscopy (STEM-EELS), we quantify the stoichiometry of individual layers of the superlattice and determine the degree of intermixing in these materials. By comparing these results to both density functional theory (DFT) models and STEM-EELS measurements of the Ti and Cr valence in each layer of the superlattice, we correlate different types of defects with the associated materials properties of the superlattice. In conclusion, we show that a combination of ab initio modeling and complementary structural characterization methods can offer unique insight into structure–property relationships in many oxide superlattice systems.« less

Etching of Cr tips for scanning tunneling microscopy of cleavable oxides

DOE Office of Scientific and Technical Information (OSTI.GOV)

Huang, Dennis; Liu, Stephen; Zeljkovic, Ilija

Here, we report a detailed three-step roadmap for the fabrication and characterization of bulk Cr tips for spin-polarized scanning tunneling microscopy. Our strategy uniquely circumvents the need for ultra-high vacuum preparation of clean surfaces or films. First, we demonstrate the role of ex situ electrochemical etch parameters on Cr tip apex geometry, using scanning electron micrographs of over 70 etched tips. Second, we describe the suitability of the in situ cleaved surface of the layered antiferromagnet La 1.4Sr 1.6Mn 2O 7 to evaluate the spin characteristics of the Cr tip, replacing the ultra-high vacuum-prepared test samples that have been usedmore » in prior studies. Third, we outline a statistical algorithm that can effectively delineate closely spaced or irregular cleaved step edges, to maximize the accuracy of step height and spin-polarization measurements.« less

Etching of Cr tips for scanning tunneling microscopy of cleavable oxides

DOE PAGES

Huang, Dennis; Liu, Stephen; Zeljkovic, Ilija; ...

2017-02-21

Here, we report a detailed three-step roadmap for the fabrication and characterization of bulk Cr tips for spin-polarized scanning tunneling microscopy. Our strategy uniquely circumvents the need for ultra-high vacuum preparation of clean surfaces or films. First, we demonstrate the role of ex situ electrochemical etch parameters on Cr tip apex geometry, using scanning electron micrographs of over 70 etched tips. Second, we describe the suitability of the in situ cleaved surface of the layered antiferromagnet La 1.4Sr 1.6Mn 2O 7 to evaluate the spin characteristics of the Cr tip, replacing the ultra-high vacuum-prepared test samples that have been usedmore » in prior studies. Third, we outline a statistical algorithm that can effectively delineate closely spaced or irregular cleaved step edges, to maximize the accuracy of step height and spin-polarization measurements.« less

Oxidation Behavior of Ferritic Stainless Steels under SOFC Interconnect Exposure Conditions

DOE Office of Scientific and Technical Information (OSTI.GOV)

Yang, Zhenguo; Walker, Matthew S.; Singh, Prabhakar

The oxidation of ferritic stainless steels has been studied under solid oxide fuel cell (SOFC) interconnect “dual” exposure conditions, i.e. simultaneous exposure to air on one side of the sample, and moist hydrogen on the other side. This paper focuses on the oxidation behavior of ferritic stainless steels during the isothermal oxidation in the dual environments. It was found that scales grown on the air side under these dual exposure conditions can be significantly different from scales grown on samples exposed to air on both sides. In contrast, no substantial difference was observed between the scales grown on the fuelmore » side of the dual atmosphere samples and scales grown on samples exposed to moist hydrogen on both sides. AISI430, with 17% Cr, suffered localized attack via formation of Fe2O3 hematite-rich nodules on the air side of dual exposure samples, while the spinel top layer of the air side scale of Crofer22 APU (23% Cr) was enriched in iron. For E-brite, with the highest Cr content (27%), no unusual phases were found in the scale on the air side, but it was noticed the air side scale was less dense and appeared to be more prone to defects than the scale grown in air only. The anomalous oxidation behavior of ferritic stainless steels on the air side of dual exposure specimens is related to the transport of hydrogen through the steel and its subsequent presence in the air side scale.« less

Thermal Shock and Oxidation Behavior of HiPIMS TiAlN Coatings Grown on Ti-48Al-2Cr-2Nb Intermetallic Alloy

PubMed Central

Badini, Claudio; Deambrosis, Silvia M.; Padovano, Elisa; Fabrizio, Monica; Ostrovskaya, Oxana; Miorin, Enrico; D’Amico, Giuseppe C.; Montagner, Francesco; Biamino, Sara; Zin, Valentina

2016-01-01

A High Power Impulse Magnetron Sputtering (HiPIMS) method for depositing TiAlN environmental barrier coatings on the surface of Ti-48Al-2Cr-2Nb alloy was developed in view of their exploitation in turbine engines. Three differently engineered TiAlN films were processed and their performance compared. Bare intermetallic alloy coupons and coated specimens were submitted to thermal cycling under oxidizing atmosphere up to 850 °C or 950 °C, at high heating and cooling rates. For this purpose, a burner rig able to simulate the operating conditions of the different stages of turbine engines was used. Microstructures of the samples were compared before and after each test using several techniques (microscopy, XRD, and XPS). Coating-intermetallic substrate adhesion and tribological properties were investigated too. All the TiAlN films provided a remarkable increase in oxidation resistance. Good adhesion properties were observed even after repeated thermal shocks. HiPIMS pretreatments of the substrate surfaces performed before the coating deposition significantly affected the oxidation rate, the oxide layer composition and the coating/substrate adhesion. PMID:28774082

X-Ray Photoelectron Study of the Oxides Formed on Nickel Metal and Nickel-Chromium 20% Alloy Surfaces Under Reducing and Oxidizing Potentials in Basic, Neutral and Acidic Solutions

NASA Astrophysics Data System (ADS)

Payne, Brad P.; Keech, Peter G.; McIntyre, N. Stewart

The corrosion products produced on polycrystalline Ni metal and Ni-Cr (20%) (NiCr) alloy surfaces exposed to aqueous environments chosen to emulate possible solution conditions in the steam generator (SG) tubing of pressurized water reactors (PWR) were studied using XPS. Additional measurements modelling the distribution of oxidized Ni and Cr species on select alloy specimens were carried out using ToF SIMS. Exposure of Ni metal and NiCr alloy samples to mildly oxidizing potentials in basic solutions resulted in the preferential growth of a β-Ni(OH)2 phase; driven by the dissolution of metallic Ni at both 25°C and 150°C. The presence of β-Ni(OH)2, Cr(OH)3 and small amounts of a Cr6+-containing oxide on NiCr specimens oxidized under mildly oxidizing conditions at 150°C in neutral solutions suggested that the dissolution of both metallic Ni and Cr followed by the back deposition of the corresponding corrosion products was responsible for oxide growth under these conditions. In acidic media oxide nucleation at 150°C under mildly oxidizing potentials was determined to occur via the dissolution of both Ni and Cr species on NiCr specimens as well. The increased stability of Ni2+ in acidic solution led to a limited precipitation of β-Ni(OH)2 resulting in the formation of very thin oxides containing higher levels of Cr(OH)3. Reactions on metallic Ni and NiCr surfaces under highly oxidizing potentials resulted in an increase in the NiO content of these films compared to similar exposures carried out at milder oxidation conditions attributed to accelerated dehydration of the β-Ni(OH)2 phase. In addition, an increase in the Cr(OH)3 contribution on the alloy surface oxidized at a more oxidative potential suggested a more rapid dissolution of Cr under these conditions; overall, uneven films were formed from these conditions. The composition of the corrosion product formed after an exposure to a highly oxidizing potential was found to be unchanged following a subsequent reaction of equivalent length at a much lower oxidizing potential in basic solution.

Adhesion layer for etching of tracks in nuclear trackable materials

DOEpatents

Morse, Jeffrey D.; Contolini, Robert J.

2001-01-01

A method for forming nuclear tracks having a width on the order of 100-200 nm in nuclear trackable materials, such as polycarbonate (LEXAN) without causing delamination of the LEXAN. The method utilizes an adhesion film having a inert oxide which allows the track to be sufficiently widened to >200 nm without delamination of the nuclear trackable materials. The adhesion film may be composed of a metal such as Cr, Ni, Au, Pt, or Ti, or composed of a dielectric having a stable surface, such as silicon dioxide (SiO.sub.2), silicon nitride (SiN.sub.x), and aluminum oxide (AlO). The adhesion film can either be deposited on top of the gate metal layer, or if the properties of the adhesion film are adequate, it can be used as the gate layer. Deposition of the adhesion film is achieved by standard techniques, such as sputtering or evaporation.

Ambient temperature NO oxidation over Cr-based amorphous mixed oxide catalysts: effects from the second oxide components

DOE Office of Scientific and Technical Information (OSTI.GOV)

Wang, Aiyong; Lin, Bo; Zhang, Hanlei

2017-01-01

Three series of Cr-based mixed oxides (Cr-Co, Cr-Fe, and Cr-Ni oxides) with high specific surface areas and amorphous textures were synthesized using a novel sol-gel method. These mixed oxides, in comparison to their pure metal oxide (CrOx, Co3O4, FeOx and NiO) counterparts, display enhanced performance for catalytic oxidation of low-concentration NO at room temperature. The best performing catalysts achieve 100% NO conversion for ~30 h of operation at a high space velocity of 45,000 ml g-1 h-1. The amorphous structure was found to be critical for these catalysts to maintain high activity and durability. Control of Cr/M (M=Co, Fe andmore » Ni) molar ratio, nitrate precursor decomposition temperature and catalyst calcination temperature was key to the synthesis of these highly active catalysts.« less

Synthesis, characterization, and thermal stability of SiO2/TiO2/CR-Ag multilayered nanostructures

NASA Astrophysics Data System (ADS)

Díaz, Gabriela; Chang, Yao-Jen; Philipossian, Ara

2018-06-01

The controllable synthesis and characterization of novel thermally stable silver-based particles are described. The experimental approach involves the design of thermally stable nanostructures by the deposition of an interfacial thick, active titania layer between the primary substrate (SiO2 particles) and the metal nanoparticles (Ag NPs), as well as the doping of Ag nanoparticles with an organic molecule (Congo Red, CR). The nanostructured particles were composed of a 330-nm silica core capped by a granular titania layer (10 to 13 nm in thickness), along with monodisperse 5 to 30 nm CR-Ag NPs deposited on top. The titania-coated support (SiO2/TiO2 particles) was shown to be chemically and thermally stable and promoted the nucleation and anchoring of CR-Ag NPs, which prevented the sintering of CR-Ag NPs when the structure was exposed to high temperatures. The thermal stability of the silver composites was examined by scanning electron microscopy (SEM) and high-resolution transmission electron microscopy (HRTEM). Larger than 10 nm CR-Ag NPs were thermally stable up to 300 °C. Such temperature was high enough to destabilize the CR-Ag NPs due to the melting point of the CR. On the other hand, smaller than 10 nm Ag NPs were stable at temperatures up to 500 °C because of the strong metal-metal oxide binding energy. Energy dispersion X-ray spectroscopy (EDS) was carried out to qualitatively analyze the chemical stability of the structure at different temperatures which confirmed the stability of the structure and the existence of silver NPs at temperatures up to 500 °C.

Surfaces and Interfaces of Magnetoelectric Oxide Systems

NASA Astrophysics Data System (ADS)

Cao, Shi

Magnetoelectric materials Cr2O3, hexagonal LuFeO 3 and YbFeO3 are studied in this thesis. The surface of chromia (Cr2O3) has a surface electronic structure distinct from the bulk. Our work shows that placing a Cr2O3 single crystal into a single domain state will result in net Cr2O 3 spin polarization at the boundary, even in the presence of a gold overlayer. From the Cr 2p3/2 X-ray magnetic circular dichroism signal, there is clear evidence of interface polarization with overlayers of both Pd and Pt on chromia. Cobalt thin films on Cr2O3(0001) show larger magnetic contrast in magnetic force microscopy indicating enhancement of perpendicular anisotropy induced by Cr2O3. The interfacial charge transfer between mechanically exfoliated few-layer graphene and Cr2O3(0001) surfaces has been investigated showing hole doping of few-layer graphene. Density functional theory calculations furthermore confirm the p-type nature of the graphene on top of chromia, and suggest that the chromia is able to induce a significant carrier spin polarization in the graphene layer. The surface termination and the nominal valence states for hexagonal LuFeO3 thin films were characterized. The stable surface terminates in a Fe-O layer. This is consistent wit the results of density functional calculations. The structural transition at about 1000 °C, from the hexagonal to the orthorhombic phase of LuFeO3, has been investigated in thin films of LuFeO3. The electronic structure for the conduction bands of both hexagonal and orthorhombic LuFeO3 thin films have been measured. Dramatic differences in both the spectral features and the linear dichroism are observed. We have also studied the ferrimagnetism in h-YbFeO3 by measuring the magnetization of Fe and Yb separately. The results directly show antialignment of magnetization of Yb and Fe ions in h-YbFeO3 at low temperature, with an exchange field on Yb of about 17 kOe. All ferrimagnets, by default, are magnetoelectrics. These findings directly demonstrate that ferrimagnetic order exists in h-YbFeO3.

Experimental Determination of Isotopic Fractionation of Chromium(III) During Oxidation by Manganese Oxides

NASA Astrophysics Data System (ADS)

Bain, D. J.; Bullen, T. D.

2004-12-01

In environmental conditions, chromium (Cr) exists in either the immobile, micronutrient trivalent form (Cr(III)) or the mobile, toxic hexavalent (Cr(VI)) form. Cr(VI) quickly reduces upon encountering Fe(II) or soil organic material (SOM). Therefore, it is often assumed that human Cr additions to terrestrial systems will impact localized areas and natural sources pose minimal threat to human or ecosystem health. However, oxidation and mobilization of Cr(III) by common manganese (Mn) oxides is less understood, especially in field settings. Moreover, Cr(VI)'s anionic form should enhance mobility through Fe- and SOM-poor soil and saprolite matrices. The variety of redox environments along a flowpath makes Cr source identification difficult with only concentration and speciation data. However, Cr has four stable isotopes (50, 52, 53, and 54), and characteristic fractionations during redox transformations might allow clarification of sources and flowpaths. For example, Cr(VI) reduction by a variety of reductants discriminates against heavy Cr, resulting in an increasingly heavy Cr(VI) fraction as reduction proceeds (α Cr(III)-Cr(VI) ˜ 0.996). Measurement of isotopic fractionation in other environmental Cr transformations, including oxidation, is necessary to understand Cr fate and transport. Recent estimates of isotopic fractionation between Cr aqueous species based on theoretical considerations indicate that at equilibrium α Cr(III)-Cr(VI) ˜ 0.994. To test this theoretical prediction, we are assessing the isotopic variability of aqueous Cr during oxidation of Cr(III) on MnO2 materials such as birnessite in laboratory experiments. Initial results indicate that the isotopic composition of the product Cr(VI) ranges from -2.50 to +0.71 ‰ δ 53Cr, suggesting an important role for kinetic isotope effects during the initial oxidation process. Large fluctuations in isotopic composition continue after dissolved Cr(VI) and Cr(III) ratios stabilize and net Cr(VI) production rates are very slow. Moreover, the Cr(VI) isotopic composition fluctuates between heavy and light compositions several times over the course of reaction. Overall, however, the long term trend appears to be toward the equilibrium fractionation predicted by theory. This adds further credence to hypothesized multiple oxidation pathways existing in the system and suggests that multiple processes with off-setting fractionations are driving the system. If these results are representative of natural systems, environmental Cr samples that have been oxidized or been oxidized/reduced multiple times along a flowpath, will have isotopic compositions that vary widely, depending predominantly on sample collection time. In turn, this suggests that Cr isotopic compositions alone will not clarify Cr fate and transport, especially at larger scales (e.g., catchments), and other geochemical and hydrologic constraints will be required.

A study of early corrosion behaviors of FeCrAl alloys in liquid lead-bismuth eutectic environments

NASA Astrophysics Data System (ADS)

Lim, Jun; Nam, Hyo On; Hwang, Il Soon; Kim, Ji Hyun

2010-12-01

Lead and lead-bismuth eutectic (LBE) alloy have been increasingly receiving attention as heavy liquid metal coolants (HLMC) for future nuclear energy systems. The compatibility of structural materials and components with lead-bismuth eutectic liquid at high temperature is one of key issues for the commercialization of lead fast reactors. In the present study, the corrosion behaviors of iron-based alumina-forming alloys (Kanthal-AF®, PM2000, MA956) were investigated by exposing to stagnant LBE environments at 500 °C and 550 °C for up to 500 h. After exposures, the thickness and chemistry of the oxide layer on the specimens were analyzed by scanning electron microscopy, scanning transmission electron microscopy and energy dispersive X-ray spectroscopy. As a result, the oxide characteristics and the corrosion resistance were compared. In this study, it was shown that the corrosion resistance of FeCrAl ODS steels (PM2000, MA956) are superior to that of FeCrAl ferritic steel (Kanthal-AF®) in higher temperature LBE.

Thermal barrier coating life-prediction model development

NASA Technical Reports Server (NTRS)

Strangman, T. E.; Neumann, J.; Liu, A.

1986-01-01

The program focuses on predicting the lives of two types of strain-tolerant and oxidation-resistant thermal barrier coating (TBC) systems that are produced by commercial coating suppliers to the gas turbine industry. The plasma-sprayed TBC system, composed of a low-pressure plasma-spray (LPPS) or an argon shrouded plasma-spray (ASPS) applied oxidation resistant NiCrAlY or (CoNiCrAlY) bond coating and an air-plasma-sprayed yttria partially stabilized zirconia insulative layer, is applied by both Chromalloy, Klock, and Union Carbide. The second type of TBS is applied by the electron beam-physical vapor deposition (EB-PVD) process by Temescal. The second year of the program was focused on specimen procurement, TMC system characterization, nondestructive evaluation methods, life prediction model development, and TFE731 engine testing of thermal barrier coated blades. Materials testing is approaching completion. Thermomechanical characterization of the TBC systems, with toughness, and spalling strain tests, was completed. Thermochemical testing is approximately two-thirds complete. Preliminary materials life models for the bond coating oxidation and zirconia sintering failure modes were developed. Integration of these life models with airfoil component analysis methods is in progress. Testing of high pressure turbine blades coated with the program TBS systems is in progress in a TFE731 turbofan engine. Eddy current technology feasibility was established with respect to nondestructively measuring zirconia layer thickness of a TBC system.

Amorphous iron–chromium oxide nanoparticles with long-term stability

DOE Office of Scientific and Technical Information (OSTI.GOV)

Iacob, Mihail; Institute of Chemistry of ASM, Academiei str. 3, Chisinau 2028, Republic of Moldova; Cazacu, Maria, E-mail: mcazacu@icmpp.ro

2015-05-15

Highlights: • Fe–Cr oxide nanoparticles with pre-established metals ratio were obtained. • The amorphous state and its long-term stability were highlighted by X-ray diffraction. • The average diameter of dried nanoparticles was 3.5 nm, as was estimated by TEM, AFM. • In hexane dispersion, nanoparticles with diameter in the range 2.33–4.85 nm were found. • Superparamagnetic state of NPs co-exists with diamagnetism of the organic layer. - Abstract: Iron–chromium nanoparticles (NPs) were obtained through the thermal decomposition of μ{sub 3}-oxo heterotrinuclear (FeCr{sub 2}O) acetate in the presence of sunflower oil and dodecylamine (DA) as surfactants. The average diameter of themore » NPs was 3.5 nm, as estimated on the basis of transmission electron microscopy and atomic force microscopy images. Both techniques revealed the formation of roughly approximated spheres with some irregularities and agglomerations in larger spherical assemblies of 50–100 nm. In hexane, NPs with diameters in the 2.33–4.85 nm range are individually dispersed, as emphasized by dynamic light scattering measurements. The amorphous nature of the product was emphasized by X-ray powder diffraction. The study of the magnetic properties shows the presence of superparamagnetic state of iron–chromium oxide NPs and the diamagnetic contribution from DA layer forming a shell of NPs.« less

Exploration and engineering of physical properties in high-quality Sr2CrReO6 epitaxial films

NASA Astrophysics Data System (ADS)

Lucy, Jeremy Matthew

Double perovskites have proven to be highly interesting materials, particularly in the past two decades, with many materials in this family exhibiting strong correlations. These materials are some of many novel complex oxides with potential spintronics application. Sr2CrReO6, in particular, is a double perovskite with one of the highest Curie temperatures of its class (> 620 K in bulk and ~510-600 K in thin films), as well as high spin polarization, ferrimagnetic behavior, and semiconducting properties. This dissertation covers recent work in exploring and tuning physical properties in epitaxial films of Sr2CrReO6. It starts by providing a background for the field of spintronics and double perovskites, bulk and thin film synthesis of Sr2CrReO6, and standard and specialized characterization techniques utilized in both university and national laboratories, and then provides reports of work on Sr2CrReO6 epitaxial films. Examples of exploration and engineering of properties of Sr2CrReO 6 include: (1) tuning of electrical resistivity, such as at T= 7 K by a factor of 18,000%, via control of oxygen partial pressure during film growth; (2) enhancement of interfacial double perovskite ordering, demonstrated with high-angle annular dark-field scanning transmission electron microscopy, via the use of double perovskite buffer layer substrates; (3) measurement of magnetization suppression near film/substrate interfaces via polarized neutron reflectometry, which reveals a reduction of thickness (from 5.6 nm to 3.6 nm) of the magnetically suppressed interface region due to buffer layer enhancement; (4) strain tunability of atomic spin and orbital moments of Cr, Re, and O atoms probed with x-ray magnetic circular dichroism, which demonstrates ferrimagnetic behavior and reveals important magnetic contributions of the oxygen sites (~0.02 muB/site); (5) strain tunability of large magnetocrystalline anisotropy via applied epitaxial strain, revealing anisotropy fields of up to 10s of tesla; and (6) depth-resolved synchrotron x-ray studies of correlated magnetic and structural relaxation in a thick relaxing film. The utilized techniques and demonstrated results for Sr2CrReO6 will hopefully benefit researchers of complex oxide materials and perhaps stimulate further work on this and other related materials.

Magnetic effect on oxide-scale growth of Fe-5Cr alloy

NASA Astrophysics Data System (ADS)

Zhou, C. H.; Li, X. W.; Wang, S. H.; Ma, H. T.

2018-01-01

The oxidation behaviour of Fe-5Cr alloy was investigated at 650°C in the presence of magnetic field. Results indicated that the oxide scales were both consisted of an outer Fe-oxide scale and an inner mixed-oxide scale in the presence or absence of magnetic field. The oxide-scale growth of Fe-5Cr alloy, gained by measuring the oxide-scale thickness, was verified to follow parabolic lawyer. And the oxidation kinetics showed that the applied magnetic field retarded the oxide-scale growth of Fe-5Cr alloy.

Extraction of hexavalent chromium from chromated copper arsenate treated wood under alkaline conditions.

PubMed

Radivojevic, Suzana; Cooper, Paul A

2008-05-15

Information on chromium (Cr) oxidation states is essential for the assessment of environmental and health risks associated with the overall life-cycle of chromated copper arsenate (CCA) treated wood products because of differences in toxicity between trivalent [Cr(III)] and hexavalent [Cr(VI)] chromium compounds. Hypothetical Cr(VI) fixation products were investigated in CCA type C treated sawdust of aspen and red pine during or following preservative fixation by extraction with Cr(VI)-specific extractants. Cr(VI) was found only in alkaline extracts of treated wood. A major source of Cr(VI) was method-induced oxidation of fixed Cr(III) during alkaline extraction, as confirmed by demonstrated oxidation of Cr(III) from CrCl3 treated wood. Oxidation of nontoxic and immobile Cr(III) to toxic and mobile Cr(VI) was facilitated by the presence of wood at pH > 8.5. Thermodynamic equilibrium between Cr(III) and Cr(VI) is affected by pH, temperature, rates of dissolution of CrIII) compounds, and oxygen availability. Results of this study recommend against alkaline extraction protocols for determination of Cr(VI) in treated wood. This Cr oxidation mechanism can act as a previously unrecognized route for generation of hazardous Cr(VI) if CCA treated wood is exposed to alkaline conditions during its production, use, or waste management.

Dimensionally Controlled Lithiation of Chromium Oxide

DOE Office of Scientific and Technical Information (OSTI.GOV)

Fister, Tim T.; Hu, Xianyi; Esbenshade, Jennifer

Oxide conversion reactions are an alternative approach for high capacity lithium ion batteries but are known to suffer from structural irreversibility associated with the phase separation and reconstitution of reduced metal species and Li2O. In particular, the morphology of the reduced metal species is thought to play a critical role in the electrochemical properties of a conversion material. Here we use a model electrode with alternating layers of chromium and chromium oxide to better understand and control these phase changes in real-time and at molecular length scales. Despite lacking crystallinity at the atomic scale, this superstructure is observed (with X-raymore » reflectivity, XR) to lithiate and delithiate in a purely one-dimensional manner, preserving the layered structure. The XR data show that the metal layers act as nucleation sites for the reduction of chromium in the conversion reaction. Irreversibility during delithiation is due to the formation of a ternary phase, LiCrO2, which can be further delithiated at higher potentials. The results reveal that the combination of confining lithiation to nanoscale sheets of Li2O and the availability of reaction sites in the metal layers in the layered structure is a strategy for improving the reversibility and mass transport properties that can be used in a wide range of conversion materials.« less

Density functional theory study of bulk and single-layer magnetic semiconductor CrPS4

NASA Astrophysics Data System (ADS)

Zhuang, Houlong L.; Zhou, Jia

2016-11-01

Searching for two-dimensional (2D) materials with multifunctionality is one of the main goals of current research in 2D materials. Magnetism and semiconducting are certainly two desirable functional properties for a single 2D material. In line with this goal, here we report a density functional theory (DFT) study of bulk and single-layer magnetic semiconductor CrPS4. We find that the ground-state magnetic structure of bulk CrPS4 exhibits the A-type antiferromagnetic ordering, which transforms to ferromagnetic (FM) ordering in single-layer CrPS4. The calculated formation energy and phonon spectrum confirm the stability of single-layer CrPS4. The band gaps of FM single-layer CrPS4 calculated with a hybrid density functional are within the visible-light range. We also study the effects of FM ordering on the optical absorption spectra and band alignments for water splitting, indicating that single-layer CrPS4 could be a potential photocatalyst. Our work opens up ample opportunities of energy-related applications of single-layer CrPS4.

Effect of Er,Cr:YSGG laser, air abrasion, and silane application on repaired shear bond strength of composites.

PubMed

Cho, S D; Rajitrangson, P; Matis, B A; Platt, J A

2013-01-01

Aged resin composites have a limited number of carbon-carbon double bonds to adhere to a new layer of resin. Study objectives were to 1) evaluate various surface treatments on repaired shear bond strength between aged and new resin composites and 2) to assess the influence of a silane coupling agent after surface treatments. Eighty disk-shape resin composite specimens were fabricated and thermocycled 5000 times prior to surface treatment. Specimens were randomly assigned to one of the three surface treatment groups (n=20): 1) air abrasion with 50-μm aluminum oxide, 2) tribochemical silica coating (CoJet), or 3) Er,Cr:YSGG (erbium, chromium: yttrium-scandium-gallium-garnet) laser or to a no-treatment control group (n=20). Specimens were etched with 35% phosphoric acid, rinsed, and dried. Each group was divided into two subgroups (n=10): A) no silanization and B) with silanization. The adhesive agent was applied and new resin composite was bonded to each conditioned surface. Shear bond strength was evaluated and data analyzed using two-way analysis of variance (ANOVA). Air abrasion with 50-μm aluminum oxide showed significantly higher repair bond strength than the Er,Cr:YSGG laser and control groups. Air abrasion with 50-μm aluminum oxide was not significantly different from tribochemical silica coating. Tribochemical silica coating had significantly higher repair bond strength than Er,Cr:YSGG laser and the control. Er,Cr:YSGG laser and the control did not have significantly different repair bond strengths. Silanization had no influence on repair bond strength for any of the surface treatment methods. Air abrasion with 50-μm aluminum oxide and tribochemical silica followed by the application of bonding agent provided the highest repair shear bond strength values, suggesting that they might be adequate methods to improve the quality of repairs of resin composites.

Continued development of abradable gas path seals. [for gas turbine engines

NASA Technical Reports Server (NTRS)

Shiembob, L. T.

1975-01-01

Major program objectives were the continued development of NiCrAlY feltmetal and honeycomb systems for knife edge seal applications in the 1144 to 1366 K temperature range, and to initiate abradable seal material evaluation for blade tip seal applications in the 1366 to 1589 K temperature range. Larger fiber size, higher density feltmetal showed greatly improved erosion resistance with a slight reduction in abradability compared to the baseline feltmetal. Pack aluminide coating of the honeycomb extended the oxidation resistance and slightly improved the abradability of this material. Evaluation through selected abradability, erosion and oxidation testing, and pertinent metallography led to selection of a plasma sprayed yttria stabilized zirconia (ZrO2)/CoCrAlY layered system as the system with the most potential to meet the 1589 K requirement for blade tip seals. This system demonstrated structural integrity, erosion resistance, and some degree of abradability.

Electrically Conductive and Protective Coating for Planar SOFC Stacks

DOE Office of Scientific and Technical Information (OSTI.GOV)

Choi, Jung-Pyung; Stevenson, Jeffry W.

Ferritic stainless steels are preferred interconnect materials for intermediate temperature SOFCs because of their resistance to oxidation, high formability and low cost. However, their protective oxide layer produces Cr-containing volatile species at SOFC operating temperatures and conditions, which can cause cathode poisoning. Electrically conducting spinel coatings have been developed to prevent cathode poisoning and to maintain an electrically conductive pathway through SOFC stacks. However, this coating is not compatible with the formation of stable, hermetic seals between the interconnect frame component and the ceramic cell. Thus, a new aluminizing process has been developed by PNNL to enable durable sealing, preventmore » Cr evaporation, and maintain electrical insulation between stack repeat units. Hence, two different types of coating need to have stable operation of SOFC stacks. This paper will focus on the electrically conductive coating process. Moreover, an advanced coating process, compatible with a non-electrically conductive coating will be« less

Water Vapor Effects on the Oxidation Behavior of Fe-Cr and Ni-Cr Alloys in Atmospheres Relevant to Oxy-fuel Combustion

DOE Office of Scientific and Technical Information (OSTI.GOV)

Mu, N.; Jung, K. Y.; Yanar, N. M.

2011-10-01

The oxidation behavior of a number of Fe–Cr- and Ni–Cr-based alloys was studied in atmospheres relevant to oxyfuel combustion at 650 °C. Oxidation was greatly enhanced in ferritic model alloys exposed in low p(O{sub 2}) CO{sub 2} + 30%H{sub 2}O and Ar + 30%H{sub 2}O gases. Rapidly growing iron oxides appear to be porous and gas permeable. Transition from non-protective to protective oxidation occurs on alloys with higher Cr contents between 13.5 and 22 wt% in H{sub 2}O. Excess oxygen, usually found in the actual oxyfuel combustion environments, disrupts the selective oxidation of Fe–Cr alloys by accelerating vaporization of early-formedmore » Cr{sub 2}O{sub 3} in combination with accelerated chromia growth induced by the H{sub 2}O. Rapid Cr consumption leads to the nucleation and rapid growth of iron oxides. On the contrary, Ni–Cr alloys are less affected by the presence of H{sub 2}O and excess O{sub 2}. The difference between Fe–Cr and Ni–Cr alloys is not clear but is postulated to involve less acceleration of chromia growth by water vapor for the latter group of alloys.« less

Oxidation behavior of Cr(III) during thermal treatment of chromium hydroxide in the presence of alkali and alkaline earth metal chlorides.

PubMed

Mao, Linqiang; Gao, Bingying; Deng, Ning; Liu, Lu; Cui, Hao

2016-02-01

The oxidation behavior of Cr(III) during the thermal treatment of chromium hydroxide in the presence of alkali and alkaline earth metal chlorides (NaCl, KCl, MgCl2, and CaCl2) was investigated. The amounts of Cr(III) oxidized at various temperatures and heating times were determined, and the Cr-containing species in the residues were characterized. During the transformation of chromium hydroxide to Cr2O3 at 300 °C approximately 5% of the Cr(III) was oxidized to form intermediate compounds containing Cr(VI) (i.e., CrO3), but these intermediates were reduced to Cr2O3 when the temperature was above 400 °C. Alkali and alkaline earth metals significantly promoted the oxidation of Cr(III) during the thermal drying process. Two pathways were involved in the influences the alkali and alkaline earth metals had on the formation of Cr(VI). In pathway I, the alkali and alkaline earth metals were found to act as electron transfer agents and to interfere with the dehydration process, causing more intermediate Cr(VI)-containing compounds (which were identified as being CrO3 and Cr5O12) to be formed. The reduction of intermediate compounds to Cr2O3 was also found to be hindered in pathway I. In pathway II, the alkali and alkaline earth metals were found to contribute to the oxidation of Cr(III) to form chromates. The results showed that the presence of alkali and alkaline earth metals significantly increases the degree to which Cr(III) is oxidized during the thermal drying of chromium-containing sludge. Copyright © 2015 Elsevier Ltd. All rights reserved.

Effect of NiFeCr seed and capping layers on exchange bias and planar Hall voltage response of NiFe/Au/IrMn trilayer structures

NASA Astrophysics Data System (ADS)

Talantsev, Artem; Elzwawy, Amir; Kim, CheolGi

2018-05-01

Thin films and cross junctions, based on NiFe/Au/IrMn structures, were grown on Ta and NiFeCr seed layers by magnetron sputtering. The effects of substitution of Ta with NiFeCr in seed and capping layers on an exchange bias field are studied. A threefold improvement of the exchange bias value in the structures, grown with NiFeCr seed and capping layers, is demonstrated. The reasons for this effect are discussed. Formation of clusters in the NiFeCr capping layer is proved by atomic force microscopy technique. Ta replacement on NiFeCr in the capping layer results in the enhancement of magnetoresistive response and a reduction of noise.

Hydrogen permeation in FeCrAl alloys for LWR cladding application

NASA Astrophysics Data System (ADS)

Hu, Xunxiang; Terrani, Kurt A.; Wirth, Brian D.; Snead, Lance L.

2015-06-01

FeCrAl, an advanced oxidation-resistant iron-based alloy class, is a highly prevalent candidate as an accident-tolerant fuel cladding material. Compared with traditional zirconium alloy fuel cladding, increased tritium permeation through FeCrAl fuel cladding to the primary coolant is expected, raising potential safety concerns. In this study, the hydrogen permeability of several FeCrAl alloys was obtained using a static permeation test station, which was calibrated and validated using 304 stainless steel. The high hydrogen permeability of FeCrAl alloys leads to concerns with respect to potentially significant tritium release when used for fuel cladding in LWRs. The total tritium inventory inside the primary coolant of a light water reactor was quantified by applying a 1-dimensional steady state tritium diffusion model to demonstrate the dependence of tritium inventory on fuel cladding type. Furthermore, potential mitigation strategies for tritium release from FeCrAl fuel cladding were discussed and indicate the potential for application of an alumina layer on the inner clad surface to serve as a tritium barrier. More effort is required to develop a robust, economical mitigation strategy for tritium permeation in reactors using FeCrAl clad fuel assemblies.

Modifications to EPA Method 3060A to Improve Extraction of Cr(VI) from Chromium Ore Processing Residue-Contaminated Soils

USGS Publications Warehouse

Mills, Christopher T.; Bern, Carleton R.; Wolf, Ruth E.; Foster, Andrea L.; Morrison, Jean M.; Benzel, William M.

2017-01-01

It has been shown that EPA Method 3060A does not adequately extract Cr(VI) from chromium ore processing residue (COPR). We modified various parameters of EPA 3060A toward understanding the transformation of COPR minerals in the alkaline extraction and improving extraction of Cr(VI) from NIST SRM 2701, a standard COPR-contaminated soil. Aluminum and Si were the major elements dissolved from NIST 2701, and their concentrations in solution were correlated with Cr(VI). The extraction fluid leached additional Al and Si from the method-prescribed borosilicate glass vessels which appeared to suppress the release of Cr(VI). Use of polytetrafluoroethylene vessels and intensive grinding of NIST 2701 increased the amount of Cr(VI) extracted. These modifications, combined with an increased extraction fluid to sample ratio of ≥900 mL g–1 and 48-h extraction time resulted in a maximum release of 1274 ± 7 mg kg–1 Cr(VI). This is greater than the NIST 2701 certified value of 551 ± 35 mg kg–1 but less than 3050 mg kg–1 Cr(VI) previously estimated by X-ray absorption near edge structure spectroscopy. Some of the increased Cr(VI) may have resulted from oxidation of Cr(III) released from brownmillerite which rapidly transformed during the extractions. Layered-double hydroxides remained stable during extractions and represent a potential residence for unextracted Cr(VI).

Magnetic properties and crystal texture of Co alloy thin films prepared on double bias Cr

NASA Astrophysics Data System (ADS)

Deng, Y.; Lambeth, D. N.; Lee, L.-L.; Laughlin, D. E.

1993-05-01

A double layer Cr film structure has been prepared by sputter depositing Cr on single crystal Si substrates first without substrate bias and then with various substrate bias voltages. Without substrate bias, Cr{200} texture grows on Si at room temperature; thus the first Cr layer acts like a seed Cr layer with the {200} texture, and the second Cr layer, prepared with substrate bias, tends to replicate the {200} texture epitaxially. CoCrTa and CoNiCr films prepared on these double Cr underlayers, therefore, tend to have a {112¯0} texture with their c-axes oriented in the plane of the film. At the same time, the bias sputtering of the second Cr layer increases the coercivity of the subsequently deposited magnetic films significantly. Comparison studies of δM curves show that the use of the double Cr underlayers reduces the intergranular exchange interactions. The films prepared on the Si substrates have been compared with the films prepared on canasite and glass substrates. It has also been found that the magnetic properties are similar for films on canasite and on glass.

An investigation of passivity and breakdown of amorphous chromium-bromine thin films for surface modification of metallic biomaterials

NASA Astrophysics Data System (ADS)

Cormier, Lyne Mercedes

1998-12-01

The objectives of this investigation of amorphous Cr-B thin films as prospective coatings for biomaterials applications were to (i) produce and characterize an amorphous Cr-B thin film coating by magnetron sputtering, (ii) evaluate its corrosion resistance in physiologically relevant electrolytes, and (iii) propose a mechanism for the formation/dissolution of the passive film formed on amorphous Cr-B in chloride-containing near-neutral salt electrolytes. Dense (zone T) amorphous Cr75B25 thin films produced by DC magnetron sputtering were found to be better corrosion barriers than nanoczystalline or porous (zone 1) amorphous Cr75B25 thin films. The growth morphology and microstructure were a function of the sputtering pressure and substrate temperature, in agreement with the structure zone model of Thornton. The passivity/loss of passivity of amorphous Cr 75B25 in near-neutral salt solutions was explained using a modified bipolar layer model. The chromate ions identified by X-Ray Photoelectron Spectroscopy (XPS) in the outer layer of the passive film were found to play a determinant role in the passive behaviour of amorphous Cr75B 25 thin films in salt solutions. In near-neutral salt solutions of pH = 5 to 7, a decrease in pH combined with an increase in chloride concentration resulted in less dissolution of the Cr75B25 thin films. The apparent breakdown potential at 240 mV (SCE) obtained by Cyclic Potentiodynamic Anodic Polarization (CPAP) was associated with oxidation of species within the passive film, but not to dissolution leading to immediate loss of passivity. Pit Propagation Rate (PPR) testing evaluated the stable pitting potential to be between 600 and 650 mV. Amorphous Cr75B25 thin films ranked the best among other Cr-based materials such as 316L stainless steel, CrB2 and Cr investigated in this study for general corrosion behaviour in NaCl and Hanks solutions by CPAP testing. In terms of corrosion resistance, amorphous Cr75B25 thin films were recognized as a promising material for surface modification of biomaterials.

Hexavalent Chromium Causes the Oxidation of Thioredoxin in Human Bronchial Epithelial Cells

PubMed Central

Myers, Judith M.; Antholine, William E.; Myers, Charles R.

2008-01-01

Hexavalent chromium [Cr(VI)] species such as chromates are cytotoxic. Inhalational exposure is a primary concern in many Cr-related industries and their immediate environments, and bronchial epithelial cells are directly exposed to inhaled Cr(VI). Chromates are readily taken up by cells and are reduced to reactive Cr species which may also result in the generation of reactive oxygen species (ROS). The thioredoxin (Trx) system has a key role in the maintenance of cellular thiol redox balance and is essential for cell survival. Cells normally maintain the cytosolic (Trx1) and mitochondrial (Trx2) thioredoxins largely in the reduced state. Redox western blots were used to assess the redox status of the thioredoxins in normal human bronchial epithelial cells (BEAS-2B) incubated with soluble Na2CrO4 or insoluble ZnCrO4 for different periods of time. Both chromates caused a dose- and time-dependent oxidation of Trx2 and Trx1. Trx2 was more susceptible in that it could all be converted to the oxidized form, whereas a small amount of reduced Trx1 remained even after prolonged treatment with higher Cr concentrations. Only one of the dithiols, presumably the active site, of Trx1 was oxidized by Cr(VI). Cr(VI) did not cause significant GSH depletion or oxidation indicating that Trx oxidation does not result from a general oxidation of cellular thiols. With purified Trx and thioredoxin reductase (TrxR) in vitro, Cr(VI) also resulted in Trx oxidation. It was determined that purified TrxR has pronounced Cr(VI) reducing activity, so competition for electron flow from TrxR might impair its ability to reduce Trx. The in vitro data also suggested some direct redox interaction between Cr(VI) and Trx. The ability of Cr(VI) to cause Trx oxidation in cells could contribute to its cytotoxic effects, and could have important implications for cell survival, redox-sensitive cell signaling, and the cells' tolerance of other oxidant insults. PMID:18328613

Oxidation behavior of nickel-chromium-aluminum-yttrium - Magnesium oxide and nickel-chromium-aluminum-yttrium - zirconate type of cermets

NASA Technical Reports Server (NTRS)

Zaplatynsky, I.

1976-01-01

The 1100 and 1200 C cyclic oxidation resistance of dense Ni-Cr-Al-Y - MgO, Ni-Cr-Al-Y - CaZrO3, Ni-Cr-Al-Y - SrZrO3, Ni-Cr-Al-Y - MgZro3 cermets and a 70 percent dense Ni-Cr-Al-Y developmental material was determined. The cermets contained 60 and 50 volume percent of Ni-Cr-Al-Y which formed a matrix with the oxide particles imbedded in it. The cermets containing MgO were superior to cermets based on zirconates and to the porous Ni-Cr-Al-Y material.

Composite Ni/NiO-Cr2O3 Catalyst for Alkaline Hydrogen Evolution Reaction

PubMed Central

Bates, Michael K.; Jia, Qingying; Ramaswamy, Nagappan; Allen, Robert J.; Mukerjee, Sanjeev

2015-01-01

We report a Ni–Cr/C electrocatalyst with unprecedented mass-activity for the hydrogen evolution reaction (HER) in alkaline electrolyte. The HER kinetics of numerous binary and ternary Ni-alloys and composite Ni/metal-oxide/C samples were evaluated in aqueous 0.1 M KOH electrolyte. The highest HER mass-activity was observed for Ni–Cr materials which exhibit metallic Ni as well as NiOx and Cr2O3 phases as determined by X-ray diffraction (XRD) and X-ray absorption spectroscopy (XAS) analysis. The onset of the HER is significantly improved compared to numerous binary and ternary Ni-alloys, including Ni–Mo materials. It is likely that at adjacent Ni/NiOx sites, the oxide acts as a sink for OHads, while the metallic Ni acts as a sink for the Hads intermediate of the HER, thus minimizing the high activation energy of hydrogen evolution via water reduction. This is confirmed by in situ XAS studies that show that the synergistic HER enhancement is due to NiOx content and that the Cr2O3 appears to stabilize the composite NiOx component under HER conditions (where NiOx would typically be reduced to metallic Ni0). Furthermore, in contrast to Pt, the Ni(Ox)/Cr2O3 catalyst appears resistant to poisoning by the anion exchange ionomer (AEI), a serious consideration when applied to an anionic polymer electrolyte interface. Furthermore, we report a detailed model of the double layer interface which helps explain the observed ensemble effect in the presence of AEI. PMID:26191118

Removal of hexavalent chromium in carbonic acid solution by oxidizing slag discharged from steelmaking process in electric arc furnace

NASA Astrophysics Data System (ADS)

Yokoyama, Seiji; Okazaki, Kohei; Sasano, Junji; Izaki, Masanobu

2014-02-01

Hexavalent chromium (Cr(VI)) is well-known to be a strong oxidizer, and is recognized as a carcinogen. Therefore, it is regulated for drinking water, soil, groundwater and sea by the environmental quality standards all over the world. In this study, it was attempted to remove Cr(VI) ion in a carbonic acid solution by the oxidizing slag that was discharged from the normal steelmaking process in an electric arc furnace. After the addition of the slag into the aqueous solution contained Cr(VI) ion, concentrations of Cr(VI) ion and total chromium (Cr(VI) + trivalent chromium (Cr(III)) ions decreased to lower detection limit of them. Therefore, the used slag could reduce Cr(VI) and fix Cr(III) ion on the slag. While Cr(VI) ion existed in the solution, iron did not dissolve from the slag. From the relation between predicted dissolution amount of iron(II) ion and amount of decrease in Cr(VI) ion, the Cr(VI) ion did not react with iron(II) ion dissolved from the slag. Therefore, Cr(VI) ion was removed by the reductive reaction between Cr(VI) ion and the iron(II) oxide (FeO) in the slag. This reaction progressed on the newly appeared surface of iron(II) oxide due to the dissolution of phase composed of calcium etc., which existed around iron(II) oxide grain in the slag.

Oxidation behaviour of ferritic stainless steel grade Crofer 22 APU at 700 °C in flowing Ar−75%CO{sub 2}−12%H{sub 2}O

DOE Office of Scientific and Technical Information (OSTI.GOV)

Shariff, Nurul Atikah; Othman, Norinsan Kamil; Jalar, Azman

2013-11-27

The oxidation of Ferritic Stainless Steel (FSS) grade Crofer 22 APU has been investigated. FSS alloys were exposed to isothermal conditions in a horizontal tube furnace at a 700 °C in flowing Ar−75%CO{sub 2}−12%H{sub 2}O at a pressure of approximately 1 atm. The results showed that the growth of non protective Fe{sub 2}O{sub 3} and spinel was observed after 50 h exposure in the presence of 12% H{sub 2}O. The weight was increased significantly with time of exposure. The formation of different oxides is presented on the interface of the specimen such as MnCr{sub 2}O{sub 4}, Fe{sub 3}O{sub 4} andmore » Fe{sub 2}O{sub 3} were revealed by X-ray diffraction and supported by EDAX analysis. FSS did not form a protective Cr{sub 2}O{sub 3} layer due to water vapour accelerates the kinetics oxidation. Data of microstructure observation is presented and discussed in this paper in term of water vapour effects.« less

Impact of Sr-Incorporation on Cr Oxidation and Water Dissociation in La(1-x)SrxCrO3

DOE Office of Scientific and Technical Information (OSTI.GOV)

Stoerzinger, Kelsey A.; Du, Yingge; Ihm, Kyuwook

2018-01-17

The oxidation and reduction of metal oxides and their interaction with the environment play a critical role in material stability and the ability to catalyze reactions. The local change in valence and formation of surface adsorbates affect the oxide electronic structure and chemical reactivity, yet are challenging to probe experimentally. Here we present a detailed study of the oxidation and reduction of Cr in the perovskite oxide family of La(1-x)SrxCrO3 using ambient pressure X-ray photoelectron spectroscopy. The incorporation of Sr increases the propensity to oxidize the surface, leading to the presence of Cr4+ and Cr6+ principally confined to the topmore » unit cell when in equilibrium with O2 gas. These acidic sites are readily reduced to Cr3+ in equilibrium with H2O vapor, and the resultant amount of hydroxyls formed from the dissociation of H2O is directly proportional to the density of surface sites which had been oxidized. Our quantification of the redox stability of La(1-x)SrxCrO3 and the relationship between the extent of oxidation, reduction, and hydroxylation with Sr yields important insight into the surface functionality during electrochemical applications.« less

Impact of Sr-Incorporation on Cr Oxidation and Water Dissociation in La (1- x ) Sr x CrO 3

DOE Office of Scientific and Technical Information (OSTI.GOV)

Stoerzinger, Kelsey A.; Du, Yingge; Ihm, Kyuwook

The oxidation and reduction of metal oxides and their interaction with the environment play a critical role in material stability and the ability to catalyze reactions. The local change in valence and formation of surface adsorbates affect the oxide electronic structure and chemical reactivity, yet are challenging to probe experimentally. Here we present a detailed study of the oxidation and reduction of Cr in the perovskite oxide family of La(1-x)SrxCrO3 using ambient pressure X-ray photoelectron spectroscopy. The incorporation of Sr increases the propensity to oxidize the surface, leading to the presence of Cr4+ and Cr6+ principally confined to the topmore » unit cell when in equilibrium with O2 gas. These acidic sites are readily reduced to Cr3+ in equilibrium with H2O vapor, and the resultant amount of hydroxyls formed from the dissociation of H2O is directly proportional to the density of surface sites which had been oxidized. Our quantification of the redox stability of La(1-x)SrxCrO3 and the relationship between the extent of oxidation, reduction, and hydroxylation with Sr yields important insight into the surface functionality during electrochemical applications.« less

Cyclic and isothermal oxidation behavior at 1100 and 1200 C of Ni-20Cr, Ni-20Cr-3Mn, Ni-20Cr-3Si, and Ni-40Cr alloys

NASA Technical Reports Server (NTRS)

Lowell, C. E.

1973-01-01

Alloys of Ni-20Cr, Ni-20Cr-3Mn, Ni-20Cr-3Si, and Ni-40Cr were cyclically oxidized at 1100 and 1200 C for up to 100 hours. Oxidation behavior was judged by sample thickness and weight change, metallography, diffraction, and microprobe analysis. The least attacked were Ni-40Cr and Ni-20Cr-3Si. The alloy Ni-20Cr-3Mn was much less attacked than Ni-20Cr, but more than the other alloys. The formation of Cr2O3 accounted for the increased resistance of Ni-Cr and Ni-20Cr-3Si, and the formation of MnCr2O4 accounts for the improvement in Ni-20Cr-3mn over Ni-20Cr.

Preparation of Copper and Chromium Alloyed Layers on Pure Titanium by Plasma Surface Alloying Technology

NASA Astrophysics Data System (ADS)

He, Xiaojing; Li, Meng; Wang, Huizhen; Zhang, Xiangyu; Tang, Bin

2015-05-01

Cu-Cr alloyed layers with different Cu and Cr contents on pure titanium were obtained by means of plasma surface alloying technology. The microstructure, chemical composition and phase composition of Cu-Cr alloyed layers were analyzed by scanning electron microscopy (SEM), energy dispersive spectrometer (EDS) and X-ray diffraction (XRD), respectively. The experimental results demonstrate that the alloyed layers are bonded strongly to pure titanium substrate and consist of unbound Ti, CuTi, Cu3Ti, CuTi3 and Cr2Ti. The thickness of Cu5Cr5 and Cu7Cr3 alloyed layer are about 18 μm and 28 μm, respectively. The antibacterial properties against gram-negative Escherichia coli (E.coli, ATCC10536) and gram-positive Staphylococcus aureus (S. aureus, ATCC6538) of untreated pure titanium and Cu-Cr alloyed specimen were investigated by live/dead fluorescence staining method. The study shows that Cu-Cr alloyed layers exhibit excellent antibacterial activities against both E.coli and S.aureus within 24 h, which may be attributed to the formation of Cu-containing phases.

High temperature oxidation behavior of ODS steels

NASA Astrophysics Data System (ADS)

Kaito, T.; Narita, T.; Ukai, S.; Matsuda, Y.

2004-08-01

Oxide dispersion strengthened (ODS) steels are being developing for application as advanced fast reactor cladding and fusion blanket materials, in order to allow increased operation temperature. Oxidation testing of ODS steel was conducted under a controlled dry air atmosphere to evaluate the high temperature oxidation behavior. This showed that 9Cr-ODS martensitic steels and 12Cr-ODS ferritic steels have superior high temperature oxidation resistance compared to 11 mass% Cr PNC-FMS and 17 mass% Cr ferritic stainless steel. This high temperature resistance is attributed to earlier formation of the protective α-Cr 2O 3 on the outer surface of ODS steels.

Synthesis and characterization of Cr-MSU-1 and its catalytic application for oxidation of styrene

NASA Astrophysics Data System (ADS)

Liu, Hong; Wang, Zhigang; Hu, Hongjiu; Liang, Yuguang; Wang, Mengyang

2009-07-01

Chromium-containing mesoporous silica material Cr-MSU-1 was synthesized using lauryl alcohol-polyoxyethylene (23) ether as templating agent under the neutral pH condition by two-step method. The sample was characterized by XRD, TEM, FT-IR, UV-Vis, ESR, ICP-AES and N 2 adsorption. Its catalytic performance for oxidation of styrene was studied. Effects of the solvent used, the styrene/H 2O 2 mole ratio and the reaction temperature and time on the oxidation of styrene over the Cr-MSU-1 catalyst were examined. The results indicate that Cr ions have been successfully incorporated into the framework of MSU-1 and the Cr-MSU-1 material has a uniform worm-like holes mesoporous structure. After Cr-MSU-1 is calcined, most of Cr 3+ is oxidized to Cr 5+ and Cr 6+ in tetrahedral coordination and no extra-framework Cr 2O 3 is formed. The Cr-MSU-1 catalyst is highly active for the selective oxidation of styrene and the main reaction products over Cr-MSU-1 are benzaldehyde and phenylacetaldehyde. Its catalytic performance remains stable within five repeated runs and no leaching is noticed for this chromium-based catalyst.

Piston and Ring Assembly Friction Studies in Cummins 903 Engine

DTIC Science & Technology

1989-06-01

5.0 um/div, horiz = 1.0 mm/div, Sample Interval of 7.0 um 121 Cr Oxide plasma ring on Cummins kaman-Cr Oxide, non lubricated 1.88I .9B 1I .8e8 I T 48...Chromium Oxide Liner, No Lubricant 122 Cr Oxide Plasma ring on Cummins-Naman Cr Oxide, Synthetic A oil 1.88- .908 I .788 T 1 .680 N .48 f C 38" " : " • Oo

Electron energy loss spectroscopy analysis of lithium deintercalated Li5/3-xTi7/3CrO7

NASA Astrophysics Data System (ADS)

Díaz-Carrasco, P.; Moreau, P.; Guyomard, D.; Kuhn, A.; García-Alvarado, F.

2006-05-01

Electron energy loss spectroscopy has been used to investigate the average oxidation state of Cr in both electrochemically and chemically delithiathed Li5/3-xTi7/3CrO7. The O K edge, Ti L2,3 and Cr L2,3 edge were monitored. Upon removal of Li ions, the oxygen K edge shows a continuous change while the Cr L edges remain almost unchanged. The Cr 2p multiplet was compared with reference samples (Cr2O3, CrO2 and K2Cr2O7) in order to assess on the sensitivity of the Cr L-edge to the oxidation state of chromium ion. The similarity between the Cr L spectra of Cr2O3 and CrO2 makes the valence analysis difficult in Li5/3-xTi7/3CrO7 but the presence of CrVI is excluded in oxidized samples. However, evolution of the low energy loss spectra observed in the 10 15 eV region confirms the modification of the electronic structure and partial oxidation of CrIII to CrIV.

Effect of aluminizing of Cr-containing ferritic alloys on the seal strength of a novel high-temperature solid oxide fuel cell sealing glass

NASA Astrophysics Data System (ADS)

Chou, Yeong-Shyung; Stevenson, Jeffry W.; Singh, Prabhakar

A novel high-temperature alkaline earth silicate sealing glass was developed for solid oxide fuel cell (SOFC) applications. The glass was used to join two metallic coupons of Cr-containing ferritic stainless steel for seal strength evaluation. In previous work, SrCrO 4 was found to form along the glass/steel interface, which led to severe strength degradation. In the present study, aluminization of the steel surface was investigated as a remedy to minimize or prevent the strontium chromate formation. Three different processes for aluminization were evaluated with Crofer22APU stainless steel: pack cementation, vapor-phase deposition, and aerosol spraying. It was found that pack cementation resulted in a rough surface with occasional cracks in the Al-diffused region. Vapor-phase deposition yielded a smoother surface, but the resulting high Al content increased the coefficient of thermal expansion (CTE), resulting in the failure of joined coupons. Aerosol spraying of an Al-containing salt resulted in the formation of a thin aluminum oxide layer without any surface damage. The room temperature seal strength was evaluated in the as-fired state and in environmentally aged conditions. In contrast to earlier results with uncoated Crofer22APU, the aluminized samples showed no strength degradation even for samples aged in air. Interfacial and chemical compatibility was also investigated. The results showed aluminization to be a viable candidate approach to minimize undesirable chromate formation between alkaline earth silicate sealing glass and Cr-containing interconnect alloys for SOFC applications.

Organic vapor discrimination with chemiresistor arrays of temperature modulated tin-oxide nanowires and thiolate-monolayer-protected gold nanoparticles.

PubMed

Scholten, K; Bohrer, F I; Dattoli, E; Lu, W; Zellers, E T

2011-03-25

This paper explores the discrimination of organic vapors with arrays of chemiresistors (CRs) employing interface layers of tin-oxide nanowires (NWs) and thiolate-monolayer-protected gold nanoparticles (MPNs). The former devices use contact-printed mats of NWs on micro-hotplate membranes to bridge a pair of metal electrodes. Oxidation at the NW surface causes changes in charge transport, the temperature dependence of which differs among different vapors, permitting vapor discrimination. The latter devices use solvent cast films of MPNs on interdigital electrodes operated at room temperature. Sorption into the organic monolayers causes changes in film tunneling resistance that differ among different vapors and MPN structures, permitting vapor discrimination. Here, we compare the performance and assess the 'complementarity' of these two types of sensors. Calibrated responses from an NW CR operated at two different temperatures and from a set of four different MPN CRs were generated for three test vapors: n-hexane, toluene, and nitromethane. This pooled data set was then analyzed using principal components regression classification models with varying degrees of random error superimposed on the responses via Monte Carlo simulation in order to estimate the rates of recognition/discrimination for arrays comprising different combinations of sensors. Results indicate that the diversity of most of the dual MPN-CR arrays exceeds that of the dual NW-CR array. Additionally, in assessing all possible arrays of 4-6 CR sensors, the recognition rates of the hybrid arrays (i.e. MPN + NW) were no better than that of the 4-sensor array containing only MPN CRs.

Frictional and structural characterization of ion-nitrided low and high chromium steels

NASA Technical Reports Server (NTRS)

Spalvins, T.

1985-01-01

Low Cr steels AISI 41410, AISI 4340, and high Cr austenitic stainless steels AISI 304, AISI 316 were ion nitrided in a dc glow discharge plasma consisting of a 75 percent H2 - 25 percent N2 mixture. Surface compound layer phases were identified, and compound layer microhardness and diffusion zone microhardness profiles were established. Distinct differences in surface compound layer hardness and diffusion zone profiles were determined between the low and high Cr alloy steels. The high Cr stainless steels after ion nitriding displayed a hard compound layer and an abrupt diffusion zone. The compound layers of the high Cr stainless steels had a columnar structure which accounts for brittleness when layers are exposed to contact stresses. The ion nitrided surfaces of high and low Cr steels displayed a low coefficient of friction with respect to the untreated surfaces when examined in a pin and disk tribotester.

Recent progress in the study of protective rust-layer formation on weathering steel

DOE Office of Scientific and Technical Information (OSTI.GOV)

Yamashita, M.; Misawa, T.

Latest understanding of protective rust layer on weathering steel and its application for structural steels is discussed. Phase transformation of the weathering steel rust layer during long-time exposure brings {alpha}-(Fe{sub 1{minus}x},Cr{sub x})OOH, Cr-substituted goethite, as the final protective rust layer. It is said that the Cr content in the Cr-substituted goethite layer increases gradiently with reaching the rust-steel interface. This increase in the Cr content gives densely packed fine crystal structure end cation selective ability, which impedes the penetration of aggressive corrosives including anions such as Cl{sup {minus}} and SO{sub 4}{sup 2{minus}}. Quite recently, new surface-treatment technique employing Cr{sub 2}(SO{submore » 4}){sub 3}, was proposed, which provides a possibility for obtaining the protective rust layer in a relatively short period even in the severe environment such as coastal region.« less

Corrosion of Alloy 690 process pot by sulfate containing high level radioactive waste at feed stage

NASA Astrophysics Data System (ADS)

Sengupta, P.; Soudamini, N.; Kaushik, C. P.; Jagannath; Mishra, R. K.; Kale, G. B.; Raj, K.; Das, D.; Sharma, B. P.

2008-02-01

Prolonged exposure of Alloy 690 process pot to sulfate containing high level radioactive waste leads to (a) depletion of Cr from the alloy, (b) intergranular attack and (c) building up of Cr 2O 3-Ni 2O 3-Fe 2O 3 mixed oxide surface layer containing Na and Cs sulfate precipitates. Time dependence of material loss from Alloy 690 is found to follow a linear relationship of the type Δ w (material loss) = -7.05 + 0.05 t. Corrosion rate calculated for 2400 h exposure is 3.66 mpy. Cr and Ni leach rates obtained for the same sample are 1.61 g m -2 d -1 and 2.52 g m -2 d -1, respectively. Ni leach rates followed a linear time dependence relationship of the type dNL Ni/d t (leach rate) = -0.09 + 0.027 t, whereas Cr leach rates obeyed a non-linear relationship of the type dNL Cr/d t (leach rate) = 0.241 + 0.027 t - 1.33 × 10 -4t1/2.

Cr6+-containing phases in the system CaO-Al2O3-CrO42--H2O at 23 °C

NASA Astrophysics Data System (ADS)

Pöllmann, Herbert; Auer, Stephan

2012-01-01

Synthesis and investigation of lamellar calcium aluminium hydroxy salts was performed to study the incorporation of chromate ions in the interlayer of lamellar calcium aluminium hydroxy salts. Different AFm-phases (calcium aluminate hydrate with alumina, ferric oxide, mono-anion phase) containing chromate were synthesized. These AFm-phases belong to the group of layered double hydroxides (LDHs). 3CaO·Al2O3·CaCrO4·nH2O and C3A·1/2Ca(OH)2·1/2CaCrO4·12H2O were obtained as pure phases and their different distinct interlayer water contents and properties determined. Solid solution of chromate-containing phases and tetracalcium-aluminate-hydrate (TCAH) were studied. The uptake of chromate into TCAH from solutions was proven. Chromate contents in solution decrease to <0.2 mg/l.

Oxidation studies of Fe10CrAl-RE alloys exposed to Pb at 550 °C for 10,000 h

NASA Astrophysics Data System (ADS)

Ejenstam, Jesper; Halvarsson, Mats; Weidow, Jonathan; Jönsson, Bo; Szakalos, Peter

2013-11-01

Five experimental FeCrAl-RE alloys have been exposed up to 10,000 h in stagnant liquid Pb at 550 °C. The test matrix consisted of three 10 wt.% Cr alloys, with an Al content ranging from 4 to 8 wt.% (10Cr-4Al, 10Cr-6Al and 10Cr-8Al), one alloy without additions of reactive elements (RE) (10Cr-6Al), and one reference alloy with 21 wt.% Cr and 5 wt.% Al (21Cr-5Al). The evaluation showed a clear difference in oxidation properties, and it was possible to divide the alloys into two distinct groups. A critical Al concentration in the interval of 4-6 wt.% at the given RE content was required to form a thin protective oxide. However, the absence of RE addition in one of the two 10Cr-6Al alloys resulted in a significant reduction in oxidation resistance, comparable with 10Cr-4Al. None of the alloys were severely corroded, however Pb penetrated to a relatively large extent into the porous oxide of the low performing alloys. A 100 nm thick oxide scale, partly consisting of alumina (Al2O3), was observed for the high performing 10Cr-6Al alloy. The Fe10CrAl-RE alloys showed overall very good corrosion resistance and are hence a promising new alloy category for liquid Pb applications.

In Situ Atomic Scale Visualization Of Surface Kinetics Driven Dynamics Of Oxide Growth On A Ni–Cr Surface

DOE Office of Scientific and Technical Information (OSTI.GOV)

Luo, Langli; Zou, Lianfeng; Schreiber, Daniel K.

2016-01-20

We report in situ atomic-scale visualization of the dynamical three-dimensional (3D) growth of NiO during initial oxidation of Ni-10at%Cr using environmental transmission electron microscopy (ETEM). Despite the thermodynamic preference for Cr2O3 formation, cubic NiO oxides nucleated and grew epitaxially as the dominating oxide phase on the Ni-Cr (100) surface during initial oxidation. The growth of NiO islands proceeds through step-by-step adatom mechanism in 3D, which is sustained by surface diffusion of Ni and O atoms. Although the shapes of oxide islands are controlled by strain energy between oxide and alloy substrate, local surface kinetic variations can lead to the changemore » of surface planes of oxide islands. These results demonstrate that surface diffusion dominates initial oxidation of Ni-Cr in these test conditions.« less

Formation of microstructural features in hot-dip aluminized AISI 321 stainless steel

NASA Astrophysics Data System (ADS)

Huilgol, Prashant; Rajendra Udupa, K.; Udaya Bhat, K.

2018-02-01

Hot-dip aluminizing (HDA) is a proven surface coating technique for improving the oxidation and corrosion resistance of ferrous substrates. Although extensive studies on the HDA of plain carbon steels have been reported, studies on the HDA of stainless steels are limited. Because of the technological importance of stainless steels in high-temperature applications, studies of their microstructural development during HDA are needed. In the present investigation, the HDA of AISI 321 stainless steel was carried out in a pure Al bath. The microstructural features of the coating were studied using scanning electron microscopy and transmission electron microscopy. These studies revealed that the coating consists of two regions: an Al top coat and an aluminide layer at the interface between the steel and Al. The Al top coat was found to consist of intermetallic phases such as Al7Cr and Al3Fe dispersed in an Al matrix. Twinning was observed in both the Al7Cr and the Al3Fe phases. Furthermore, the aluminide layer comprised a mixture of nanocrystalline Fe2Al5, Al7Cr, and Al. Details of the microstructural features are presented, and their formation mechanisms are discussed.

Comparison of reproduce signal and noise of conventional and keepered CoCrTa/Cr thin film media

NASA Astrophysics Data System (ADS)

Sin, Kyusik; Ding, Juren; Glijer, Pawel; Sivertsen, John M.; Judy, Jack H.; Zhu, Jian-Gang

1994-05-01

We studied keepered high coercivity CoCrTa/Cr thin film media with a Cr isolation layer between the CoCrTa storage and an overcoating of an isotropic NiFe soft magnetic layer. The influence of the thickness of the NiFe and Cr layers, and the effects of head bias current on the signal output and noise, were studied using a thin film head. The reproduced signal increased by 7.3 dB, but the signal-to-noise ratio decreased by 4 dB at a linear density of 2100 fr/mm (53.3 kfr/in.) with a 1000 Å thick NiFe keeper layer. The medium noise increased with increasing NiFe thickness and the signal output decreased with decreasing Cr thickness. A low output signal obtained with very thin Cr may be due to magnetic interactions between the keeper layer and magnetic media layer. It is observed that signal distortion and timing asymmetry of the output signals depend on the thickness of the keeper layer and the head bias current. The signal distortion increased and the timing asymmetry decreased as the head bias current was increased. These results may be associated with different permeability of the keeper under the poles of the thin film head due to the superposition of head bias and bit fields.

Thermal barrier coating life-prediction model development. Annual report no. 2

DOE Office of Scientific and Technical Information (OSTI.GOV)

Strangman, T. E.; Neumann, J.; Liu, A.

1986-10-01

The program focuses on predicting the lives of two types of strain-tolerant and oxidation-resistant thermal barrier coating (TBC) systems that are produced by commercial coating suppliers to the gas turbine industry. The plasma-sprayed TBC system, composed of a low-pressure plasma-spray (LPPS) or an argon shrouded plasma-spray (ASPS) applied oxidation resistant NiCrAlY or (CoNiCrAlY) bond coating and an air-plasma-sprayed yttria partially stabilized zirconia insulative layer, is applied by both Chromalloy, Klock, and Union Carbide. The second type of TBS is applied by the electron beam-physical vapor deposition (EB-PVD) process by Temescal. The second year of the program was focused on specimenmore » procurement, TMC system characterization, nondestructive evaluation methods, life prediction model development, and TFE731 engine testing of thermal barrier coated blades. Materials testing is approaching completion. Thermomechanical characterization of the TBC systems, with toughness, and spalling strain tests, was completed. Thermochemical testing is approximately two-thirds complete. Preliminary materials life models for the bond coating oxidation and zirconia sintering failure modes were developed. Integration of these life models with airfoil component analysis methods is in progress. Testing of high pressure turbine blades coated with the program TBS systems is in progress in a TFE731 turbofan engine. Eddy current technology feasibility was established with respect to nondestructively measuring zirconia layer thickness of a TBC system.« less

The Passive Film Growth Mechanism of New Corrosion-Resistant Steel Rebar in Simulated Concrete Pore Solution: Nanometer Structure and Electrochemical Study

PubMed Central

Jiang, Jin-yang; Wang, Danqian; Chu, Hong-yan; Ma, Han; Liu, Yao; Gao, Yun; Shi, Jinjie; Sun, Wei

2017-01-01

An elaborative study was carried out on the growth mechanism and properties of the passive film for a new kind of alloyed corrosion-resistant steel (CR steel). The passive film naturally formed in simulated concrete pore solutions (pH = 13.3). The corrosion resistance was evaluated by various methods including open circuit potential (OCP), linear polarization resistance (LPR) measurements, and electrochemical impedance spectroscopy (EIS). Meanwhile, the 2205 duplex stainless steel (SS steel) was evaluated for comparison. Moreover, the passive film with CR steel was studied by means of X-ray photoelectron spectroscopy (XPS), transmission electron microscopy (TEM), Atomic Force Microscope (AFM), and the Mott‑Schottky approach. The results showed that the excellent passivity of CR steel could be detected in a high alkaline environment. The grain boundaries between the fine passive film particles lead to increasing Cr oxide content in the later passivation stage. The filling of cation vacancies in the later passivation stage as well as the orderly crystalized inner layer contributed to the excellent corrosion resistance of CR steel. A passive film growth model for CR steel was proposed. PMID:28772772

Ring head recording on perpendicular media: Output spectra for CoCr and CoCr/NiFe media

NASA Astrophysics Data System (ADS)

Stubbs, D. P.; Whisler, J. W.; Moe, C. D.; Skorjanec, J.

1985-04-01

The recording density response for sputtered CoCr (thickness=0.5 μm) and CoCr/NiFe (t=0.25 μm/0.5 μm) as well as evaporated CoNi (t=0.12 μm) and Co surface-doped iron oxide particulate media has been measured by reading and writing with Mn-Zn ferrite heads (gap length=0.375 μm, track width=37 μm) in contact with the media. Measurements to 200 kfc/i (thousand flux changes per inch) show a gap null around 115 kfc/i. The data have been normalized by dividing out the head sensitivity to obtain the value of spacing plus transition width (d+a) for the various media. For the CoCr media this value varied from 0.075-0.088 μm; for CoNi, 0.100 μm, and for the particulate medium, 0.163 μm. In addition, testing with a larger gapped Mn-Zn ferrite head (g=2.43 μm) shows that the head fields are distorted by the soft magnetic underlayer in dual layer CoCr/NiFe samples when the gap length is large compared to the distance to the underlayer.

The Passive Film Growth Mechanism of New Corrosion-Resistant Steel Rebar in Simulated Concrete Pore Solution: Nanometer Structure and Electrochemical Study.

PubMed

Jiang, Jin-Yang; Wang, Danqian; Chu, Hong-Yan; Ma, Han; Liu, Yao; Gao, Yun; Shi, Jinjie; Sun, Wei

2017-04-14

An elaborative study was carried out on the growth mechanism and properties of the passive film for a new kind of alloyed corrosion-resistant steel (CR steel). The passive film naturally formed in simulated concrete pore solutions (pH = 13.3). The corrosion resistance was evaluated by various methods including open circuit potential (OCP), linear polarization resistance (LPR) measurements, and electrochemical impedance spectroscopy (EIS). Meanwhile, the 2205 duplex stainless steel (SS steel) was evaluated for comparison. Moreover, the passive film with CR steel was studied by means of X-ray photoelectron spectroscopy (XPS), transmission electron microscopy (TEM), Atomic Force Microscope (AFM), and the Mott‑Schottky approach. The results showed that the excellent passivity of CR steel could be detected in a high alkaline environment. The grain boundaries between the fine passive film particles lead to increasing Cr oxide content in the later passivation stage. The filling of cation vacancies in the later passivation stage as well as the orderly crystalized inner layer contributed to the excellent corrosion resistance of CR steel. A passive film growth model for CR steel was proposed.

Photocatalytic decomposition of Congo red under visible light irradiation using MgZnCr-TiO2 layered double hydroxide.

PubMed

Ma, Chi; Wang, Fenghua; Zhang, Chang; Yu, Zhigang; Wei, Jingjing; Yang, Zhongzhu; Li, Yongqiu; Li, Zihao; Zhu, Mengying; Shen, Liuqing; Zeng, Guangming

2017-02-01

The new nanophotocatalyst MgZnCr-TiO 2 was prepared by co-precipitation under different molar ratio of metals (Zn:Cr) and the loaded amount of TiO 2 . And it was characterized by X-ray diffraction, Raman spectroscopy, X-ray photoelectron spectroscopy et al. Langmuir model fitted well the adsorption isotherm with the value of R 2 0.9765, the maximum adsorption capacity was 526.32 mg g -1 , the adsorption followed pseudo second order kinetic by MgZnCr-TiO 2 (1:1:2-0.05). The photocatalytic oxidation of Congo red was used to determine the photocatalytic performance of MgZnCr-TiO 2 (1:1:2-0.05) under visible light irradiation, and the removal rate reached 98% after reaction for 40 min. The degradation mechanism of Congo red also was proposed, and the MgZnCr-TiO 2 (1:1:2-0.05) was stable after five cycles. Compared to the adsorption, Congo red was removed fundamentally by photocatalysis and it is expected to be an effective way to eliminate Congo red. Copyright © 2016 Elsevier Ltd. All rights reserved.

Mercury- and silver-rich ferromanganese oxides, southern California Borderland: Deposit model and environmental implications

USGS Publications Warehouse

Hein, J.R.; Koschinsky, A.; McIntyre, B.R.

2005-01-01

Mercury- and silver-enriched ferromanganese oxide crusts were recovered at water depths of 1,750 tol,300 m from La Victoria knoll, located about 72 km off the coast of northern Baja California. No other ferromanganese precipitate found so far in the modern ocean basins is similarly enriched in Hg and Ag. The precipitates consist of submetallic gray, brecciated, Mn oxide layers overlain by brown earthy, laminated Fe-Mn oxide crusts. Both oxide types are rich in Hg (to 10 ppm) and Ag (to 5.5 ppm). The Mn-rich layers are composed of ??MnO2, with lesser amounts of 10A?? and 7A?? manganates, whereas the Mn phase in the Fe-Mn crusts is solely ??MnO2. The Fe phase in both layers is X-ray amorphous. Established criteria for distinguishing hydrothermal versus hydrogenetic crusts indicate that the Mn-rich layers are predominantly of low-temperature hydrothermal origin, whereas the Fe-Mn crusts are hydrogenetic, although there is some overlap in the source of chemical components in both types. La Victoria knoll is uplifted continental basement rock with basalt, andesite, and schist cropping out at the surface; the knoll may have an intrusive core. The Hg and Ag were derived from leaching by hydrothermal fluids of organic matter-rich sediments in basins adjacent to La Victoria knoll and, to a lesser extent, from continental basement rocks underlying the knoll and adjacent basins. Both rock types are notably enriched in Ag and Hg. Faults were the main fluid transport pathway, and hydrothermal circulation was driven by high heat flow associated with thinned crust. Other elements derived from the hydrothermal fluids include Tl, Cd, Cr, and Li. The main host for Hg and Ag is FeOOH, although MnO2 likely hosts some of the Ag. Minor sulfide and barite also may contain small amounts of these metals. Possible analogs in the geologic record for this deposit type are found in the Basin and Range province of the western United States and Mexico. The discovery highlights the fact that fluids circulating along faults in the offshore California borderland are transporting potentially toxic metals (Hg, Ag, Tl, As, Cd, Cr, Pb, and Ni) and depositing them on and just below the ocean floor. ?? 2005 Society of Economic Geologists, Inc.

The Cross-Sectional Investigation of Oxide Scale FeCr Alloys and Commercial Ferritic Steel Implanted with Lanthanum and Titanium Dopants after Oxidation Test at 900°C

NASA Astrophysics Data System (ADS)

Saryanto, Hendi; Sebayang, Darwin; Untoro, Pudji; Sujitno, Tjipto

2018-03-01

The cross-sectional examinations of oxide scales formed by oxidation on the surface of FeCr alloys and Ferritic Steel that implanted with lanthanum and titanium dopants were observed and investigated. Scanning electron microscopy (SEM) coupled with energy dispersive X-ray spectroscopy (EDS) has been used to study the cross-sectional oxides produced by specimens after oxidation process. X-ray diffraction (XRD) analysis was used to strengthen the analysis of the oxide scale morphology, oxide phases and oxidation products. Cross-sectional observations show the effectiveness of La implantation for improving thinner and stronger scale/substrate interface during oxidation process. The result shows that the thickness of oxide scales formed on the surface of La implanted FeCr alloy and ferritic steel was found less than 3 μm and 300 μm, respectively. The oxide scale formed on the surface of La implanted specimens consisted roughly of Cr2O3 with a small amount of FeO mixture, which indicates that lanthanum implantation can improve the adherence, reduce the growth of the oxide scale as well as reduce the Cr evaporation. On the other side, the oxide scale formed on the surface of FeCr alloys and ferritic steel that implanted with titanium dopant was thicker, indicating that significant increase in oxidation mass gain. It can be noticed that titanium implantation ineffectively promotes Cr rich oxide. At the same time, the amount of Fe increased and diffused outwards, which caused the formation and rapid growth of FeO.

Nanoscale assembly of high-temperature oxidation-resistant nanocomposites.

PubMed

Peng, Xiao

2010-02-01

Structural considerations for designing a high-temperature oxidation-resistant metallic material are proposed, based on the dependence of the material structure on a promotion of the development of a protective scale of chromia or alumina. The material should have numerous sites on its surface for nucleating the protective oxides at the onset of oxidation and abundant grain boundaries in deeper areas for simultaneously supplying sufficient flux of the protective-oxide-forming elements toward the surface for a rapid linkage of the oxide nuclei through their lateral growth. Based on these considerations, we fabricated, using an electrochemical deposition method, novel nanocomposites which have a nanocrystalline metal matrix containing Cr and/or Al nanoparticles dispersed at the nano length scale. The validity of the design considerations is verified by comparing the high-temperature oxidation of a typical Ni-Cr nanocomposite system with two types of conventional Ni-Cr materials having similar or higher Cr content but different structure: one is a composite having a nanocrystalline Ni matrix containing Cr microparticles dispersed at the microscale and the other are micron-grained Ni-Cr alloys with the Cr distribution at the atomic length scale.

Nanoscale assembly of high-temperature oxidation-resistant nanocomposites

NASA Astrophysics Data System (ADS)

Peng, Xiao

2010-02-01

Structural considerations for designing a high-temperature oxidation-resistant metallic material are proposed, based on the dependence of the material structure on a promotion of the development of a protective scale of chromia or alumina. The material should have numerous sites on its surface for nucleating the protective oxides at the onset of oxidation and abundant grain boundaries in deeper areas for simultaneously supplying sufficient flux of the protective-oxide-forming elements toward the surface for a rapid linkage of the oxide nuclei through their lateral growth. Based on these considerations, we fabricated, using an electrochemical deposition method, novel nanocomposites which have a nanocrystalline metal matrix containing Cr and/or Al nanoparticles dispersed at the nano length scale. The validity of the design considerations is verified by comparing the high-temperature oxidation of a typical Ni-Cr nanocomposite system with two types of conventional Ni-Cr materials having similar or higher Cr content but different structure: one is a composite having a nanocrystalline Ni matrix containing Cr microparticles dispersed at the microscale and the other are micron-grained Ni-Cr alloys with the Cr distribution at the atomic length scale.

High Temperature Oxidation Studies on Alloys Containing Dispersed Phase Particles and Clarification of the Mechanism of Growth of SiO2.

DTIC Science & Technology

1986-08-28

beneath the Cr 0 layer. ’ 2~ 2 3 Nickel and cobalt based alloys were also tested with additions of Si N. . IN 3 4 particles and were found to behave in a...additions of Si ION, a high temperature compound found in the P*~~ 4 f°.-0 Si"Ali-O-N system, to cobalt - chromium alloys4 The particular SiAlON used in...a chromium spinel appeared as a product aLong with CrO0 Fe0. and Fe0 . At higher chromium concentrations Fe 0 was eliminat das a- detectable product

Nested potassium hydroxide etching and protective coatings for silicon-based microreactors

NASA Astrophysics Data System (ADS)

de Mas, Nuria; Schmidt, Martin A.; Jensen, Klavs F.

2014-03-01

We have developed a multilayer, multichannel silicon-based microreactor that uses elemental fluorine as a reagent and generates hydrogen fluoride as a byproduct. Nested potassium hydroxide etching (using silicon nitride and silicon oxide as masking materials) was developed to create a large number of channels (60 reaction channels connected to individual gas and liquid distributors) of significantly different depths (50-650 µm) with sloped walls (54.7° with respect to the (1 0 0) wafer surface) and precise control over their geometry. The wetted areas were coated with thermally grown silicon oxide and electron-beam evaporated nickel films to protect them from the corrosive fluorination environment. Up to four Pyrex layers were anodically bonded to three silicon layers in a total of six bonding steps to cap the microchannels and stack the reaction layers. The average pinhole density in as-evaporated films was 3 holes cm-2. Heating during anodic bonding (up to 350 °C for 4 min) did not significantly alter the film composition. Upon fluorine exposure, nickel films (160 nm thick) deposited on an adhesion layer of Cr (10 nm) over an oxidized silicon substrate (up to 500 nm thick SiO2) led to the formation of a nickel fluoride passivation layer. This microreactor was used to investigate direct fluorinations at room temperature over several hours without visible signs of film erosion.

Oxidation-chlorination of binary Ni-Cr alloys in flowing Ar-O2-Cl2 gas mixtures at 1200 K

NASA Technical Reports Server (NTRS)

Mcnallan, M. J.; Lee, Y. Y.; Chang, Y. W.; Jacobson, N. S.; Doychak, J.

1991-01-01

Nickel-chromium alloys are resistant to oxidation because of the selective oxidation of chromium to form a protective Cr2O3 scale. In chlorine-containing environments, volatile corrosion products can also be formed. The mixed oxidation-chlorination of Ni-4.5Cr, Ni-13.8Cr, and Ni-26.5Cr (by weight) alloys in Ar-O2-Cl2 gas mixtures is investigated using thermogravimetric analysis and atmospheric-pressure-sampling mass spectrometry, followed by examination of the corrosion products using scanning electron microscopy and X-ray diffraction analysis. The overall kinetics of the corrosion are affected by the relative amounts of oxides and chlorides formed and the composition of the oxide corrosion products.

A study of the oxide dispersion and recrystallization in NiCrAl prepared from preoxidized powder

NASA Technical Reports Server (NTRS)

Glasgow, T. K.

1975-01-01

The SAP technique of dispersion strengthening (formation of an oxide dispersion by preoxidation of metal powders) was applied to atomized powder of the alloy Ni-17Cr-5Al-0.2 Y. SAP-NiCrAl was worked by extrusion and rod rolling at 1205 C and by swaging at 760 C. A variety of annealing treatments were applied after working to determine the recrystallization response. NiCrAlY, similarly prepared from atomized powder, but without a preoxidation treatment, was examined for comparison. The SAP-NiCrAl of this study exhibited oxide particle size and spacing much larger than that usually observed in oxide dispersion strengthened alloys; nonetheless, it was possible to achieve abnormal (secondary) recrystallization in the SAP-NiCrAl as has been reported for other oxide dispersion strengthened alloys. In contrast, unoxidized NiCrAlY exhibited only primary recrystallization.

Microstructure/Oxidation/Microhardness Correlations in Gamma-Based and Tau-Based Al-Ti-Cr Alloys

NASA Technical Reports Server (NTRS)

Brady, Michael P.; Smialek, J. L.; Humphrey, D. L.

1994-01-01

The relationships between alloy microstructure and air oxidation kinetics and alloy microstructure and microhardness in the Al-Ti-Cr system for exposures at 800 C and 1000 C were investigated. The relevant phases were identified as tau (Ll2), gamma (LIO), r-Al2Ti, TiCrAl (laves), and Cr2AI. Protective alumina formation was associated with tau, Al-rich TiCrAl, and gamma/TiCrAl mixtures. Brittleness was associated with the TiCrAl phase and tau decomposition to A12Ti + Cr2AI. It was concluded that two-phase gamma + TiCrAl alloys offer the greatest potential for oxidation resistance and room temperature ductility in the Al-Ti-Cr system.

Magnetic interaction reversal in watermelon nanostructured Cr-doped Fe nanoclusters

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kaur, Maninder; Qiang, You, E-mail: youqiang@uidaho.edu; Dai, Qilin

2013-11-11

Cr-doped core-shell Fe/Fe-oxide nanoclusters (NCs) were synthesized at varied atomic percentages of Cr from 0 at. % to 8 at. %. The low concentrations of Cr (<10 at. %) were selected in order to inhibit the complete conversion of the Fe-oxide shell to Cr{sub 2}O{sub 3} and the Fe core to FeCr alloy. The magnetic interaction in Fe/Fe-oxide NCs (∼25 nm) can be controlled by antiferromagnetic Cr-dopant. We report the origin of σ-FeCr phase at very low Cr concentration (2 at. %) unlike in previous studies, and the interaction reversal from dipolar to exchange interaction in watermelon-like Cr-doped core-shell NCs.

Hexavalent Chromium Generation within Naturally Structured Soils and Sediments

DOE PAGES

Hausladen, Debra M.; Fendorf, Scott

2017-01-13

Chromium(VI) produced from the oxidation of indigenous Cr(III) minerals is increasingly being recognized as a threat to groundwater quality. A critical determinant of Cr(VI) generation within soils and sediments is the necessary interaction of two low-solubility phases$-$Cr(III) silicates or (hydr)oxides and Mn(III/IV) oxides—that lead to its production. Here in this paper, we investigate the potential for Cr(III) oxidation by Mn oxides within fixed solid matrices common to soils and sediments. Artificial aggregates were constructed from Cr(OH) 3- and Cr 0.25Fe 0.75(OH) 3-coated quartz grains and either mixed with synthetic birnessite or inoculated with the Mn(II)-oxidizing bacterium Leptothrix cholodnii. In aggregatesmore » simulating low organic carbon environments, we observe Cr(VI) concentrations within advecting solutes at levels more than twenty-times the California drinking water standard. Chromium(VI) production is highly dependent on Cr-mineral solubility; increasing Fe-substitution (x = 0 to x = 0.75) decreases the solubility of the solid and concomitantly decreases total Cr(VI) generation by 37%. In environments with high organic carbon, reducing conditions within aggregate cores (microbially) generate sufficient Fe(II) to suppress Cr(VI) efflux. Our results illustrate Cr(VI) generation from reaction with Mn oxides within structured media simulating soils and sediments and provide insight into how fluctuating hydrologic and redox conditions impact coupled processes controlling Cr and Mn cycling.« less

Hexavalent Chromium Generation within Naturally Structured Soils and Sediments

DOE Office of Scientific and Technical Information (OSTI.GOV)

Hausladen, Debra M.; Fendorf, Scott

Chromium(VI) produced from the oxidation of indigenous Cr(III) minerals is increasingly being recognized as a threat to groundwater quality. A critical determinant of Cr(VI) generation within soils and sediments is the necessary interaction of two low-solubility phases$-$Cr(III) silicates or (hydr)oxides and Mn(III/IV) oxides—that lead to its production. Here in this paper, we investigate the potential for Cr(III) oxidation by Mn oxides within fixed solid matrices common to soils and sediments. Artificial aggregates were constructed from Cr(OH) 3- and Cr 0.25Fe 0.75(OH) 3-coated quartz grains and either mixed with synthetic birnessite or inoculated with the Mn(II)-oxidizing bacterium Leptothrix cholodnii. In aggregatesmore » simulating low organic carbon environments, we observe Cr(VI) concentrations within advecting solutes at levels more than twenty-times the California drinking water standard. Chromium(VI) production is highly dependent on Cr-mineral solubility; increasing Fe-substitution (x = 0 to x = 0.75) decreases the solubility of the solid and concomitantly decreases total Cr(VI) generation by 37%. In environments with high organic carbon, reducing conditions within aggregate cores (microbially) generate sufficient Fe(II) to suppress Cr(VI) efflux. Our results illustrate Cr(VI) generation from reaction with Mn oxides within structured media simulating soils and sediments and provide insight into how fluctuating hydrologic and redox conditions impact coupled processes controlling Cr and Mn cycling.« less

Structural Evolution of a Ni Alloy Surface During High-Temperature Oxidation

DOE PAGES

Oleksak, Richard P.; Carney, Casey S.; Holcomb, Gordon R.; ...

2017-11-20

We show that considerable structural transformations occur at a Ni alloy surface during the transient stages of high-temperature oxidation. This was demonstrated by exposing the alloy to high-temperature CO 2 for short times at both atmospheric and supercritical pressures. A protective Cr-rich oxide layer formed after only 5 min at 700 °C and persisted for longer exposures up to 500 h. Voids formed and grew over time by the condensation of metal vacancies generated during oxidation, while the alloy surface recrystallized after sufficient oxidation had occurred. The oxygen potential established at the oxide/alloy interface led to oxidation along the newlymore » formed grain boundaries as well as adjacent to and inside of the voids. Al, the most stable oxide-former and present at low concentration in the alloy, was preferentially oxidized in these regions. Furthermore, the results provide an improved understanding of the internal oxidation of Al and its role in enhancing scale adhesion for this class of Ni alloys.« less

Effects of MAR-M247 substrate (modified) composition on coating oxidation coating/substrate interdiffusion. M.S. Thesis. Final Report; [protective coatings for hot section components of gas turbine engines

NASA Technical Reports Server (NTRS)

Pilsner, B. H.

1985-01-01

The effects of gamma+gamma' Mar-M247 substrate composition on gamma+beta Ni-Cr-Al-Zr coating oxidation and coating/substrate interdiffusion were evaluated. These results were also compared to a prior study for a Ni-Cr-Al-Zr coated gamma Ni-Cr-Al substrate with equivalent Al and Cr atomic percentages. Cyclic oxidation behavior at 1130 C was investigated using change in weight curves. Concentration/distance profiles were measured for Al, Cr, Co, W, and Ta. The surface oxides were examined by X-ray diffraction and scanning electron microscopy. The results indicate that variations of Ta and C concentrations in the substrate do not affect oxidation resistance, while additions of grain boundary strengthening elements (Zr, Hf, B) increase oxidation resistance. In addition, the results indicate that oxidation phenomena in gamma+beta/gamma+gamma' Mar-M247 systems have similar characteristics to the l gamma+beta/gamma Ni-Cr-Al system.

Hydrogen permeation in FeCrAl alloys for LWR cladding application

DOE PAGES

Hu, Xunxiang; Terrani, Kurt A.; Wirth, Brian D.; ...

2015-03-19

FeCrAl is an advanced oxidation-resistant iron-based alloy class, is a highly prevalent candidate as an accident-tolerant fuel cladding material. Compared with traditional zirconium alloy fuel cladding, increased tritium permeation through FeCrAl fuel cladding to the primary coolant is expected, raising potential safety concerns. In our study, the hydrogen permeability of several FeCrAl alloys was obtained using a static permeation test station, which was calibrated and validated using 304 stainless steel. The high hydrogen permeability of FeCrAl alloys leads to concerns with respect to potentially significant tritium release when used for fuel cladding in LWRs. Also, the total tritium inventory insidemore » the primary coolant of a light water reactor was quantified by applying a 1-dimensional steady state tritium diffusion model to demonstrate the dependence of tritium inventory on fuel cladding type. Furthermore, potential mitigation strategies for tritium release from FeCrAl fuel cladding were discussed and indicate the potential for application of an alumina layer on the inner clad surface to serve as a tritium barrier. More effort is required to develop a robust, economical mitigation strategy for tritium permeation in reactors using FeCrAl clad fuel assemblies.« less

Anti-oxidative and anti-inflammatory vasoprotective effects of caloric restriction in aging: role of circulating factors and SIRT1

PubMed Central

Csiszar, Anna; Labinskyy, Nazar; Jimenez, Rosario; Pinto, John T.; Ballabh, Praveen; Losonczy, Gyorgy; Pearson, Kevin J.; de Cabo, Rafael; Ungvari, Zoltan

2009-01-01

Endothelial-dysfunction, oxidative stress and inflammation are associated with vascular aging and promote the development of cardiovascular-disease. Caloric restriction (CR) mitigates conditions associated with aging, but its effects on vascular dysfunction during aging remain poorly defined. To determine whether CR exerts vasoprotective effects in aging, aortas of ad libitum (AL) fed young and aged and CR-aged F344 rats were compared. Aging in AL-rats was associated with impaired acetylcholine-induced relaxation, vascular oxidative stress and increased NF-κB-activity. Lifelong CR significantly improved endothelial function, attenuated vascular ROS production, inhibited NF-κB activity and down-regulated inflammatory genes. To elucidate the role of circulating factors in mediation of the vasoprotective effects of CR, we determined whether sera obtained from CR-animals can confer anti-oxidant and anti-inflammatory effects in cultured coronary-arterial endothelial cells (CAECs), mimicking the effects of CR. In CAECs cultured in the presence of AL-serum TNFα elicited oxidative-stress, NF-κB-activation and inflammatory gene expression. By contrast, treatment of CAECs with CR-serum attenuated TNFα-induced ROS generation and prevented NF-κB-activation and induction of inflammatory genes. siRNA-knockdown of SIRT1 mitigated the anti-oxidant and anti-inflammatory effects of CR-serum. CR exerts anti-oxidant and anti-inflammatory vascular effects, which are likely mediated by circulating factors, in part, via a SIRT1-dependent pathway. PMID:19549533

First-principles study of the effect of Cr and Al on the oxidation resistance of WSi2

NASA Astrophysics Data System (ADS)

Wang, Shuanglun; Pan, Yong; Lin, Yuanhua

2018-04-01

By means of first-principles approach, we systematically investigate the effect of Cr and Al on the oxidation resistance of WSi2. The interstice sites oxygen prefers to occupy are considered. Moreover, Cr and Al tend to occupy the Si sites of WSi2, and they are thermodynamically stable. The oxygen diffusion in various interstitial sites of undoped and doped WSi2 are studied, respectively. Importantly, Cr and Al can improve oxidation resistance of WSi2 obviously, and Cr, Al co-doped system has the best oxidation resistance. The improvement of oxidation resistance is attributed to the formation of Alsbnd O and Crsbnd O bonds.

The Effect of the Concentration of Oxidant, Cr(VI), on the Iron Oxidation in Saline Water

NASA Astrophysics Data System (ADS)

Ahn, H.; Jo, H. Y.; Ryu, J. H.; Koh, Y. K.

2014-12-01

Deep geological disposal is currently considered as the most appropriate method to isolate high level radioactive wastes (HLRWs) from the ecosystem. If groundwater seeps into underground disposal facilities, water molecules can be dissociated to radicals or peroxides, which can oxidize metal canisters and HLRWs. The oxidized radionuclides with a high solubility can be dissolved in the groundwater. Some dissolved radionuclides can act as oxidants. The continuous radiolysis of water molecules, which results from continuous seepage of groundwater, can enable the continuous production of the radioactive oxidants, resulting in an increase in concentration of oxidants. In this study, the effect of oxidant concentration on iron oxidation in the presence of salt was evaluated. Zero valent iron (ZVI) particles were reacted with Cr(VI) solutions with initial Cr(VI) concentrations ranged from 50 to 300 mg/L in reactors. The initial pH and NaCl concentration were fixed at 3 and 0.5 M, respectively. An increase in the initial Cr(VI) concentration caused an increase in the rate and extend of H2 gas production. The decrement of Cr(VI) was increased as the initial Cr(VI) concentration was increased. The penetration of H+ ions in the presence Cl- ions through the passive film on the ZVI particles caused the reaction between H+ ions and ZVI particles, producing H2 gas and Fe2+ ions. The passive film was damaged during the reaction due to the eruption of H2 gas or peptization by Cl- ions. The Fe2+ ions were reacted with Cr(VI) ions in the solution, producing Fe(III)-Cr(III) (oxy)hydroxides on the passive film of ZVI particles or in the solution as colloidal particles. The Fe(III)-Cr(III) (oxy)hydroxides tends to be precipitated as colloidal particles at a high Cr(VI) concentration and precipitated on the passive film at a low Cr(VI) concentration. The passive film was repaired or thickened by additional formation of Fe(III)-Cr(III) (oxy)hydroxides at a lower Cr(VI) concentration.

Oxidation and corrosion behavior of modified-composition, low-chromium 304 stainless steel alloys

NASA Technical Reports Server (NTRS)

Stephens, J. R.; Barrett, C. A.

1977-01-01

The effects of substituting less strategic elements than Cr on the oxidation and corrosion resistance of AISI 304 stainless steel were investigated. Cyclic oxidation resistance was evaluated at 870 C. Corrosion resistance was determined by exposure of specimens to a boiling copper-rich solution of copper sulfate and sulfuric acid. Alloy substitutes for Cr included Al, Mn, Mo, Si, Ti, V, Y, and misch metal. A level of about 12% Cr was the minimum amount of Cr required for adequate oxidation and corrosion resistance in the modified composition 304 stainless steels. This represents a Cr saving of at least 33%. Two alloys containing 12% Cr and 2% Al plus 2% Mo and 12% Cr plus 2.65% Si were identified as most promising for more detailed evaluation.

Microstructure and High Temperature Oxidation Property of Fe-Cr-B Based Metal/Ceramic Composite Manufactured by Powder Injection Molding Process

NASA Astrophysics Data System (ADS)

Joo, Yeun-Ah; Kim, Young-Kyun; Yoon, Tae-Sik; Lee, Kee-Ahn

2018-03-01

This study investigated the microstructure and high temperature oxidation property of Fe-Cr-B metal/ceramic composite manufactured using powder injection molding process. Observations of initial microstructure showed a unique structure where α-Fe and (Cr, Fe)2B form a continuous three-dimensional network. High temperature oxidation tests were performed at 900, 1000 and 1100 °C, for 24 h, and the oxidation weight gain according to each temperature condition was 0.13, 0.84 and 6.4 mg/cm2, respectively. The oxidation results according to time at 900 and 1000 °C conditions represented parabolic curves, and at 1100 °C condition formed a rectilinear curve. Observation and phase analysis results of the oxides identified Cr2O3 and SiO2 at 900 and 1000 °C. In addition to Cr2O3 and SiO2, CrBO3 and FeCr2O4 formed due to phase decomposition of boride were identified at 1100 °C. Based on the findings above, this study suggested the high temperature oxidation mechanism of Fe-Cr-B metal/ceramic composite manufactured using powder injection molding, and the possibility of its application as a high temperature component material was also discussed.

Diffusional creep and creep degradation in the dispersion-strengthened alloy TD-NiCr

NASA Technical Reports Server (NTRS)

Whittenberger, J. D.

1972-01-01

Dispersoid-free regions were observed in TD-NiCr (Ni-20Cr-2ThO2) after slow strain rate testing in air from 1145 to 1590 K. Formation of the dispersoid-free regions appears to be the result of diffusional creep. The net effect of this creep is the degradation of TD-NiCr to a duplex microstructure. Degradation is further enhanced by the formation of voids and integranular oxidation in the thoria-free regions. These regions apparently provided sites for void formation and oxide growth since the strength and oxidation resistance of Ni-20Cr is much less than Ni-20Cr-2ThO2. This localized oxidation does not appear to reduce the static load bearing capacity of TD-NiCr since long stress rupture lives were observed even with heavily oxidized microstructures. But this oxidation does significantly reduce the ductility and impact resistance of the material. Dispersoid-free bands and voids were also observed for two other dispersion strengthened alloys, TD-NiCrAl and IN-853. Thus, it appears that diffusional creep is charactertistic of dispersion-strengthened alloys and can play a major role in the creep degradation of these materials.

Diminution of Oxidative Damage to Human Erythrocytes and Lymphocytes by Creatine: Possible Role of Creatine in Blood.

PubMed

Qasim, Neha; Mahmood, Riaz

2015-01-01

Creatine (Cr) is naturally produced in the body and stored in muscles where it is involved in energy generation. It is widely used, especially by athletes, as a staple supplement for improving physical performance. Recent reports have shown that Cr displays antioxidant activity which could explain its beneficial cellular effects. We have evaluated the ability of Cr to protect human erythrocytes and lymphocytes against oxidative damage. Erythrocytes were challenged with model oxidants, 2, 2'-azobis(2-amidinopropane) dihydrochloride (AAPH) and hydrogen peroxide (H2O2) in the presence and absence of Cr. Incubation of erythrocytes with oxidant alone increased hemolysis, methemoglobin levels, lipid peroxidation and protein carbonyl content. This was accompanied by decrease in glutathione levels. Antioxidant enzymes and antioxidant power of the cell were compromised while the activity of membrane bound enzyme was lowered. This suggests induction of oxidative stress in erythrocytes by AAPH and H2O2. However, Cr protected the erythrocytes by ameliorating the AAPH and H2O2 induced changes in these parameters. This protective effect was confirmed by electron microscopic analysis which showed that oxidant-induced cell damage was attenuated by Cr. No cellular alterations were induced by Cr alone even at 20 mM, the highest concentration used. Creatinine, a by-product of Cr metabolism, was also shown to exert protective effects, although it was slightly less effective than Cr. Human lymphocytes were similarly treated with H2O2 in absence and presence of different concentrations of Cr. Lymphocytes incubated with oxidant alone had alterations in various biochemical and antioxidant parameters including decrease in cell viability and induction of DNA damage. The presence of Cr attenuated all these H2O2-induced changes in lymphocytes. Thus, Cr can function as a blood antioxidant, protecting cells from oxidative damage, genotoxicity and can potentially increase their lifespan.

Diminution of Oxidative Damage to Human Erythrocytes and Lymphocytes by Creatine: Possible Role of Creatine in Blood

PubMed Central

Qasim, Neha; Mahmood, Riaz

2015-01-01

Creatine (Cr) is naturally produced in the body and stored in muscles where it is involved in energy generation. It is widely used, especially by athletes, as a staple supplement for improving physical performance. Recent reports have shown that Cr displays antioxidant activity which could explain its beneficial cellular effects. We have evaluated the ability of Cr to protect human erythrocytes and lymphocytes against oxidative damage. Erythrocytes were challenged with model oxidants, 2, 2'-azobis(2-amidinopropane) dihydrochloride (AAPH) and hydrogen peroxide (H2O2) in the presence and absence of Cr. Incubation of erythrocytes with oxidant alone increased hemolysis, methemoglobin levels, lipid peroxidation and protein carbonyl content. This was accompanied by decrease in glutathione levels. Antioxidant enzymes and antioxidant power of the cell were compromised while the activity of membrane bound enzyme was lowered. This suggests induction of oxidative stress in erythrocytes by AAPH and H2O2. However, Cr protected the erythrocytes by ameliorating the AAPH and H2O2 induced changes in these parameters. This protective effect was confirmed by electron microscopic analysis which showed that oxidant-induced cell damage was attenuated by Cr. No cellular alterations were induced by Cr alone even at 20 mM, the highest concentration used. Creatinine, a by-product of Cr metabolism, was also shown to exert protective effects, although it was slightly less effective than Cr. Human lymphocytes were similarly treated with H2O2 in absence and presence of different concentrations of Cr. Lymphocytes incubated with oxidant alone had alterations in various biochemical and antioxidant parameters including decrease in cell viability and induction of DNA damage. The presence of Cr attenuated all these H2O2-induced changes in lymphocytes. Thus, Cr can function as a blood antioxidant, protecting cells from oxidative damage, genotoxicity and can potentially increase their lifespan. PMID:26555819

Effect of Si Content on Oxide Formation on Surface of Molten Fe-Cr-C Alloy Bath During Oxygen Top Blowing

NASA Astrophysics Data System (ADS)

Mihara, Ryosuke; Gao, Xu; Kim, Sun-joong; Ueda, Shigeru; Shibata, Hiroyuki; Seok, Min Oh; Kitamura, Shin-ya

2018-02-01

Using a direct observation experimental method, the oxide formation behavior on the surface of Fe-Cr-5 mass pct C-Si alloy baths during decarburization by a top-blown Ar-O2 mixture was studied. The effects of the initial Si and Cr content of the alloy, temperature, and oxygen feed ratio on oxide formation were investigated. The results showed that, for alloys without Si, oxide particles, unstable oxide films, and stable oxide films formed sequentially. The presence of Si in the alloy changed the formation behavior of stable oxide film, and increased the crucial C content when stable oxide film started to form. Increasing the temperature, decreasing the initial Cr content, and increasing the ratio of the diluting gas decreased the critical C content at which a stable oxide film started to form. In addition, the P CO and a_{{{Cr}2 {O}3 }} values at which oxides started to form were estimated using Hilty's equation and the equilibrium relation to understand the formation conditions and the role of each parameter in oxide formation.

Preparation and characterization of α-Al2O3 film by low temperature thermal oxidation of Al8Cr5 coating

NASA Astrophysics Data System (ADS)

Zhang, Min; Xu, Bajin; Ling, Guoping

2015-03-01

In this paper, α-Al2O3 film was prepared by low temperature thermal oxidation of Al8Cr5 coating. The Al8Cr5 alloy coating was prepared on SUS430 stainless steel through a two-step approach including electrodepositing Cr/Al composite coating and subsequent heat treatment at 740 °C for 16 h. After mechanical polishing removal of voids on the surface, the Al8Cr5 coating was thermal oxidized at 720 °C in argon for 100 h. The samples were characterized by SEM, EDX, XRD, XPS and TEM. XPS detection on the surface of oxidized Al8Cr5 coating showed that the oxide film mainly consisted of Al2O3. TEM characterization of the oxide film showed that it was α-Al2O3 films ca. 110 nm. The formation of α-Al2O3 films at low temperature can be attributed to the formation of Cr2O3 nuclei at the initial stage of oxidation which lowers the nucleation energy barrier of α-Al2O3.

Wear Characteristic of Stellite 6 Alloy Hardfacing Layer by Plasma Arc Surfacing Processes

PubMed Central

Zhou, Xiaowei

2017-01-01

The microstructure and wear resistance of Stellite 6 alloy hardfacing layer at two different temperatures (room temperature and 300°C) were investigated by plasma arc surfacing processes on Q235 Steel. Tribological test was conducted to characterize the wear property. The microstructure of Stellite 6 alloy coating mainly consists of α-Co and (Cr, Fe)7C3 phases. The friction coefficient of Stellite 6 alloys fluctuates slightly under different loads at 300°C. The oxide layer is formed on the coating surface and serves as a special lubricant during the wear test. Abrasive wear is the dominant mechanism at room temperature, and microploughing and plasticity are the key wear mechanisms at 300°C. PMID:29359005

Experimental investigation and micromagnetic simulations of hybrid CoCr2O4/Ni coaxial nanostructures.

PubMed

Li, W J; Wang, C J; Zhang, X M; Irfan, M; Khan, U; Liu, Y W; Han, X F

2018-06-15

Multiphase CoCr 2 O 4 /Ni core-shell nanowires (NWs) have been synthesized within anodic aluminum oxide membranes by the combination of the sol-gel method with electrodeposition techniques. X-ray diffraction and x-ray photoemission spectroscopy results confirmed the formation of a cubic spinel structure of CoCr 2 O 4 shell with space group Fd-3m (227). The morphology and composition of the as-grown NWs were studied by field emission scanning electron microscopy, as well as transmission electron microscopy. The magnetic properties of the CoCr 2 O 4 NT shell and hybrid CoCr 2 O 4 /Ni NWs were measured at low temperature using a physical property measurement system. The temperature dependence of the magnetization curves showed that CoCr 2 O 4 NTs undergo a transition from a paramagnetic state to a ferrimagnetic state at about 90 K and a spiral ordering transition temperature near 22 K. An enhanced coercivity and saturation field were observed for the CoCr 2 O 4 /Ni core-shell NWs compared to the single-phase Ni NWs. Micromagnetic simulation results indicated that there is a strong coupling between the shell and core layers during the magnetization reversal process. The combination of hard CoCr 2 O 4 and soft Ni in a single NW structure may have potential applications in future multifunctional devices.

Experimental investigation and micromagnetic simulations of hybrid CoCr2O4/Ni coaxial nanostructures

NASA Astrophysics Data System (ADS)

Li, W. J.; Wang, C. J.; Zhang, X. M.; Irfan, M.; Khan, U.; Liu, Y. W.; Han, X. F.

2018-06-01

Multiphase CoCr2O4/Ni core–shell nanowires (NWs) have been synthesized within anodic aluminum oxide membranes by the combination of the sol–gel method with electrodeposition techniques. X-ray diffraction and x-ray photoemission spectroscopy results confirmed the formation of a cubic spinel structure of CoCr2O4 shell with space group Fd-3m (227). The morphology and composition of the as-grown NWs were studied by field emission scanning electron microscopy, as well as transmission electron microscopy. The magnetic properties of the CoCr2O4 NT shell and hybrid CoCr2O4/Ni NWs were measured at low temperature using a physical property measurement system. The temperature dependence of the magnetization curves showed that CoCr2O4 NTs undergo a transition from a paramagnetic state to a ferrimagnetic state at about 90 K and a spiral ordering transition temperature near 22 K. An enhanced coercivity and saturation field were observed for the CoCr2O4/Ni core–shell NWs compared to the single-phase Ni NWs. Micromagnetic simulation results indicated that there is a strong coupling between the shell and core layers during the magnetization reversal process. The combination of hard CoCr2O4 and soft Ni in a single NW structure may have potential applications in future multifunctional devices.

Use of valence band Auger electron spectroscopy to study thin film growth: oxide and diamond-like carbon films

NASA Astrophysics Data System (ADS)

Steffen, H. J.

1994-12-01

It is demonstrated how Auger line shape analysis with factor analysis (FA), least-squares fitting and even simple peak height measurements may provide detailed information about the composition, different chemical states and also defect concentration or crystal order. Advantage is taken of the capability of Auger electron spectroscopy to give valence band structure information with high surface sensitivity and the special aspect of FA to identify and discriminate quantitatively unknown chemical species. Valence band spectra obtained from Ni, Fe, Cr and NiFe40Cr20 during oxygen exposure at room temperature reveal the oxidation process in the initial stage of the thin layer formation. Furthermore, the carbon chemical states that were formed during low energy C(+) and Ne(+) ion irradiation of graphite are delineated and the evolution of an amorphous network with sp3 bonds is disclosed. The analysis represents a unique method to quantify the fraction of sp3-hybridized carbon in diamond-like materials.

Effect of Sulfur and Chlorine on Fireside Corrosion Behavior of Inconel 740 H Superalloy

NASA Astrophysics Data System (ADS)

Jin-tao, Lu; Yan, Li; Zhen, Yang; Jin-yang, Huang; Ming, Zhu; Gu, Y.

2018-03-01

Fireside corrosion behavior of Inconel 740H superalloy was studied at 750 °C in simulated coal ash/flue gas environments by means of XRD, SEM and EDS. The results indicated that the corrosion behavior was strongly related to the SO2 levels and was significantly affected by NaCl additions. In presence of the atmospheres with 0.1 % SO2, the alloy exhibited the highest corrosion resistance due to formation of a stable and dense Cr2O3 film. In presence of the atmosphere with 1.5 % SO2, however, a non-coherent and porous Cr2O3 film was formed. The thickness of film and internal sulfides were substantially increased. The NaCl additions significantly accelerated the corrosion process. A non-protective outer oxide film was formed, composed by multiple layers with serious inner sulfide and spallation. The depths of internal oxidizing and sulfuration zones were significantly increased. The mechanism of ash corrosion formation was also discussed.

Effect of synovial fluid, phosphate-buffered saline solution, and water on the dissolution and corrosion properties of CoCrMo alloys as used in orthopedic implants.

PubMed

Lewis, A C; Kilburn, M R; Papageorgiou, I; Allen, G C; Case, C P

2005-06-15

The corrosion and dissolution of high- and low-carbon CoCrMo alloys, as used in orthopedic joint replacements, were studied by immersing samples in phosphate-buffered saline (PBS), water, and synovial fluid at 37 degrees C for up to 35 days. Bulk properties were analyzed with a fine ion beam microscope. Surface analyses by X-ray photoelectron spectroscopy and Auger electron spectroscopy showed surprisingly that synovial fluid produced a thin oxide/hydroxide layer. Release of ions into solution from the alloy also followed an unexpected pattern where synovial fluid, of all the samples, had the highest Cr concentration but the lowest Co concentration. The presence of carbide inclusions in the alloy did not affect the corrosion or the dissolution mechanisms, although the carbides were a significant feature on the metal surface. Only one mechanism was recognized as controlling the thickness of the oxide/hydroxide interface. The analysis of the dissolved metal showed two mechanisms at work: (1) a protein film caused ligand-induced dissolution, increasing the Cr concentration in synovial fluid, and was explained by the equilibrium constants; (2) corrosion at the interface increased the Co in PBS. The effect of prepassivating the samples (ASTM F-86-01) did not always have the desired effect of reducing dissolution. The release of Cr into PBS increased after prepassivation. The metal-synovial fluid interface did not contain calcium phosphate as a deposit, typically found where samples are exposed to calcium rich bodily fluids. (c) 2005 Wiley Periodicals, Inc.

A study of the oxide dispersion and recrystallization in NiCrAl prepared from preoxidized powder

NASA Technical Reports Server (NTRS)

Glasgow, T. K.

1975-01-01

The sintered aluminum powder (SAP) technique of dispersion strengthening (formation of an oxide dispersion by preoxidation of metal powders) was applied to atomized powder of a nickel alloy containing, by weight, 17% Cr, 5% Al, and 0.2% Y. The SAP-NiCrAl alloy (without the ytterbium removed by oxdation) was worked by extrusion and rod rolling at 1205 C and by swaging at 760 C. Annealing treatments were applied after working to determine the recrystallization response. The NiCrAlY alloy, similarly prepared from atomized powder, but without a preoxidation treatment, was examined for comparison. The SAP-NiCrAl alloy exhibited oxide particle size and spacing much larger than that usually observed in oxide dispersion strengthened alloys; nonetheless, it was possible to achieve abnormal (secondary) recrystallization in the SAP-NiCrAl alloy as has been reported for other oxide dispersion strengthened alloys. In contrast, the unoxidized NiCrAlY alloy exhibited only primary recrystallization.

RedOx-controlled sorption of iodine anions by hydrotalcite composites

DOE Office of Scientific and Technical Information (OSTI.GOV)

Levitskaia, Tatiana G.; Chatterjee, Sayandev; Arey, Bruce W.

2016-01-01

The radioactive contaminant iodine-129 (I-129) is one of the top risk drivers at radiological waste disposal and contaminated groundwater sites where nuclear material fabrication or reprocessing has occurred. Currently there are very few options available to treat I-129 in the groundwater, which is partially related to its complex biogeochemical behavior in the subsurface and occurrence in the multiple chemical forms. We hypothesize that layered hydrotalcite materials containing redox active transition metal ions offer a potential solution, benefiting from the simultaneous adsorption of iodate (IO3-) and iodide (I-) anions, which exhibit different electronic and structural properties and therefore may require dissimilarmore » hosts. To test this hypothesis, Cr3+- based materials were selected based on the rationale that Cr3+ readily reduces IO3- in solution. It was combined with either redox-active Co2+ or redox-inactive Ni2+ so that two model materials were prepared by hydrothermal synthesis including Co2+-Cr3+ and Ni2+-Cr3+(M-Cr). Obtained M-Cr materials comprised of Co2+-Cr3+ or Ni2+-Cr3+ layered hydrotalcite and small fractions of Co3O4 spinel or Ni(OH)2 theophrastite phases were structurally characterized before and after uptake of periodate (IO4-), IO3-, and I- anions. It was found that the IO3- uptake is driven by its chemical reduction to I2 and I-. Interestingly, in the Co2+-Cr3+ hydrotalcite, Co2+ and not Cr3+ serves as a reductant while in the Ni2+-Cr3+ hydrotalcite Cr3+ is responsible for the reduction of IO3-. A different uptake mechanism was identified for the IO4- anion. The Co2+-Cr3+ hydrotalcite phase efficiently uptakes IO4- by a diffusion-limited ion exchange mechanism and is not accompanied by the redox process, while Cr3+ in the Ni2+-Cr3+ hydrotalcite reduces IO4- to IO3-, I2 and I-. Iodide exhibited high affinity only to the Co-Cr material. The Co-Cr material performed remarkably well for the removal of IO3-, I- and total iodine from the groundwater collected from the US DOE Hanford site, WA, USA outperforming non-redox active hydrotalcites (e.g., Mg2+-Al3+) reported previously. This work demonstrates that redox-controlled sorption can be a highly effective method for the treatment of anions based on elements with mobile oxidation states. Further, multiple anions of interest could be simultaneously removed through combination of approaches.« less

High-Temperature Oxidation Behavior of Al-Co-Cr-Ni-(Fe or Si) Multicomponent High-Entropy Alloys

NASA Astrophysics Data System (ADS)

Butler, T. M.; Alfano, J. P.; Martens, R. L.; Weaver, M. L.

2015-01-01

High-entropy alloys (HEAs) are a class of alloys that are being considered for a number of applications. In the present study, the microstructures and 1050°C oxidation behaviors of two HEAs, Al10Cr22.5Co22.5Ni22.5Fe22.5 (at.%) and Al20Cr25Co25Ni25Si5 have been investigated along with Al15Cr10Co35Ni35Si5, which is a high-temperature shape-memory alloy. Oxide formation occurred via selective oxidation in a manner that was consistent with the oxide formation model devised by Giggins and Pettit for model Ni-Cr-Al alloys. The lower Al content alloy formed an external Cr2O3 scale and an internal subscale consisting of Al2O3 and AlN precipitates. The higher Al content alloys exhibited smaller mass gains and formed external Al2O3 scales without any internal oxidation of the alloys.

X-ray photoelectron spectroscopy study of nickel and nickel-base alloy surface alterations in simulated hot corrosion conditions with emphasis on eventual application to turbine blade corrosion

NASA Technical Reports Server (NTRS)

Mateescu, G. D.; Smith, S. R.

1979-01-01

Research on the high temperature oxidation and Na2SO4 induced hot corrosion of some nickel base superalloys was accomplished by using ESCA to determine the surface composition of the oxidized or corroded samples. Oxidation was carried out at 900 or 1000 C in slowly flowing O2 for samples of B-1900, NASA-TRW VIA, 713C, and IN-738. Oxidation times ranged from 0.5 to 100 hr. Hot corrosion of B-1900 was induced applying a coating of Na2SO4 to peroxidized samples, the heating to 900 C in slowly flowing O2. For oxidized samples, the predominant type of scale formed by each superalloy was determined, and a marked surface enrichment of Ti was found in each case. For corroded samples, the transfer of significant amounts of material from the oxide layer to the surface of the salt layer was observed to occur long before the onset of accelerating weight-gain. Changes in surface composition were observed to coincide with the beginning of accelerating corrosion, the most striking of which was a tenfold decrease in the sulfur to sodium ration and an increase in the Cr(VI) ratio.

Al-Mn CVD-FBR coating on P92 steel as protection against steam oxidation at 650 °C: TGA-MS study

NASA Astrophysics Data System (ADS)

Castañeda, S. I.; Pérez, F. J.

2018-02-01

The initial stages oxidation of the P92 ferritic/martensitic steel with and without Al-Mn coating at 650 °C in Ar+40%H2O for 240 h were investigated by mass spectrometry (MS) and thermogravimetric analysis (TGA). TGA-MS measurements were conducted in a closed steam loop. An Al-Mn coating was deposited on P92 steel at 580 °C for 2 h by chemical vapour deposition in a fluidized bed reactor (CVD-FBR). The coating as-deposited was treated in the same reactor at 700 °C in Ar for 2h, in order to produce aluminide phases that form the protective alumina layer (Al2O3) during oxidation. MS measurements at 650 °C of the Al-Mn/P92 sample for 200 h indicated the presence of (Al-Mn-Cr-Fe-O) volatile species of small intensity. Uncoated P92 steel oxidized under the same steam oxidation conditions emitted greater intensities of volatile species of Cr, Fe and Mo in comparison with intensities from coated steel. TGA measurements verified that the mass gained by the coated sample was up to 300 times lower than for uncoated P92 steel. The morphology, composition and structure of samples by Scanning Electron Microscopy SEM, Backscattered Electron (BSE) detection, X-ray Energy Dispersive Spectrometry (EDAX) and X-ray Diffraction (XRD) are described.

Study of microstructure and magnetotransport properties of CrO2 prepared under HTHP

NASA Astrophysics Data System (ADS)

Fan, Y. B.; Zheng, R. K.; Wen, G. H.

2018-05-01

The microstructure of the CrO2 particles prepared by high temperature and high pressure (HTHP) method was studied by HRTEM. It is found that the CrO2 particles synthesized at 500 and 550 °C are covered by Cr2O3 surface layers of about 6 nm thick. However, the CrO2 particles synthesized at 400 and 450 °C do not have Cr2O3 surface layers. The saturation magnetization of the CrO2 particles synthesized at different temperatures is all very close to the theoretical value. The magnetoresistance (MR) of the CrO2 particles synthesized at 500 and 550 °C is much larger than that of the CrO2 particles synthesized at 400 and 450 °C, which should be due to the enhancement of tunneling magnetoresistance by insulating Cr2O3 surface layers. The tunneling MR of the CrO2 particles can be fitted well by expression of C1(M/Ms)2 + C2(M/Ms)4 + C3(M/Ms)6. The proportion of the higher-order terms of (M/Ms)2 in the expression is tightly related to the existence of the Cr2O3 surface layer.

Selective Internal Oxidation as a Mechanism for Intergranular Stress Corrosion Cracking of Ni-Cr-Fe Alloys

NASA Astrophysics Data System (ADS)

Capell, Brent M.; Was, Gary S.

2007-06-01

The mechanism of selective internal oxidation (SIO) for intergranular stress corrosion cracking (IGSCC) of nickel-base alloys has been investigated through a series of experiments using high-purity alloys and a steam environment to control the formation of NiO on the surface. Five alloys (Ni-9Fe, Ni-5Cr, Ni-5Cr-9Fe, Ni-16Cr-9Fe, and Ni-30Cr-9Fe) were used to investigate oxidation and intergranular cracking behavior for hydrogen-to-water vapor partial pressure ratios (PPRs) between 0.001 and 0.9. The Ni-9Fe, Ni-5Cr, and Ni-5Cr-9Fe alloys formed a uniform Ni(OH)2 film at PPRs less than 0.09, and the higher chromium alloys formed chromium-rich oxide films over the entire PPR range studied. Corrosion coupon results show that grain boundary oxides extended for significant depths (>150 nm) below the sample surface for all but the highest Cr containing alloy. Constant extension rate tensile (CERT) test results showed that intergranular cracking varied with PPR and cracking was more pronounced at a PPR value where nonprotective Ni(OH)2 was able to form and a link between the nonprotective Ni(OH)2 film and the formation of grain boundary oxides is suggested. The observation of grain boundary oxides in stressed and unstressed samples as well as the influence of alloy content on IG cracking and oxidation support SIO as a mechanism for IGSCC.

Temperature-dependent selective oxidation processes for Ni-5Cr and Ni-4Al

DOE PAGES

Kruska, Karen; Schreiber, Daniel K.; Olszta, Matthew J.; ...

2018-05-09

The selective oxidation of Ni-5Cr and Ni-4 Al alloys is evaluated during high (800 °C) and low (420 °C) temperature exposures with the oxygen partial pressure moderated by a Ni/NiO powder buffer. Internal oxidation of Cr and Al is observed throughout the matrix and at grain boundaries at 800 °C accompanied by the ejection of Ni onto the surface for both. At 420 °C, matrix internal oxidation was eliminated and only Ni-4 Al exhibited intergranular (IG) oxidation. Surprisingly, a protective surface oxide rapidly formed for Ni-5Cr blocking IG oxidation. Finally, this is contradictory to results in 330–360 °C hydrogenated watermore » environments where both alloys show IG oxidation.« less

Temperature-dependent selective oxidation processes for Ni-5Cr and Ni-4Al

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kruska, Karen; Schreiber, Daniel K.; Olszta, Matthew J.

The selective oxidation of Ni-5Cr and Ni-4 Al alloys is evaluated during high (800 °C) and low (420 °C) temperature exposures with the oxygen partial pressure moderated by a Ni/NiO powder buffer. Internal oxidation of Cr and Al is observed throughout the matrix and at grain boundaries at 800 °C accompanied by the ejection of Ni onto the surface for both. At 420 °C, matrix internal oxidation was eliminated and only Ni-4 Al exhibited intergranular (IG) oxidation. Surprisingly, a protective surface oxide rapidly formed for Ni-5Cr blocking IG oxidation. Finally, this is contradictory to results in 330–360 °C hydrogenated watermore » environments where both alloys show IG oxidation.« less

Non-classical behaviour of higher valence dopants in chromium (III) oxide by a Cr vacancy compensation mechanism

NASA Astrophysics Data System (ADS)

Carey, John J.; Nolan, Michael

2017-10-01

Modification of metal oxides with dopants that have a stable oxidation in their parent oxides which is higher than the host system is expected to introduce extra electrons into the material to improve carrier mobility. This is essential for applications in catalysis, SOFCs and solar energy materials. Density functional theory calculations are used to investigate the change in electronic and geometric structure of chromium (III) oxide by higher valence dopants, namely; Ce, Ti, V and Zr. For single metal doping, we find that the dopants with variable oxidation states, Ce, Ti and V, adopt a valence state of  +3, while Zr dopant has a  +4 oxidation state and reduces a neighbouring Cr cation. Chromium vacancy formation is greatly enhanced for all dopants, and favoured over oxygen vacancy formation. The Cr vacancies generate holes which oxidise Ce, Ti and V from  +3 to  +4, while also oxidising lattice oxygen sites. For Zr doping, the generated holes oxidise the reduced Cr2+ cation back to Cr3+ and also two lattice oxygen atoms. Three metal atoms in the bulk lattice facilitate spontaneous Cr vacancy from charge compensation. A non-classical compensation mechanism is observed for Ce, Ti and V; all three metals are oxidised from  +3 to  +4, which explains experimental observations that these metals have a  +4 oxidation state in Cr2O3. Charge compensation of the three Zr metals proceeds by a classical higher valence doping mechanism; the three dopants reduce three Cr cations, which are subsequently charge compensated by a Cr vacancy oxidising three Cr2+ to Cr3+. The compensated structures are the correct ground state electronic structure for these doped systems, and used as a platform to investigate cation/anion vacancy formation. Unlike the single metal doped bulks, preference is now given for oxygen vacancy formation over Cr vacancy formation, indicating that the dopants increase the reducibility of Cr2O3 with Ce doping showing the strongest enhancement. The importance of the correct ground state in determining the formation of defects is emphasised.

Biomarkers of oxidative stress in electroplating workers exposed to hexavalent chromium.

PubMed

Pan, Chih-Hong; Jeng, Hueiwang Anna; Lai, Ching-Huang

2018-01-01

This study evaluates levels of biomarkers of oxidative DNA damage and lipid peroxidation in 105 male workers at 16 electroplating companies who had been exposed to hexavalent chromium (Cr(VI)). The study participants were 230 non-smoking male workers, comprising 105 electroplating workers who had been exposed to chromium and 125 control subjects who performed office tasks. Personal air samples, spot urine samples, hair samples, fingernail samples and questionnaires were used to quantify exposure to Cr(VI), oxidative DNA damage, lipid peroxidation, and environmental pollutants. Both the geometric mean personal concentrations of Cr(VI) of the Cr-exposed workers and the total Cr concentrations in the air to which they were exposed significantly exceeded those for the control subjects. The geometric mean concentrations of Cr in urine, hair and fingernails, and the urinary 8-hydroxy-2'-deoxyguanosine (8-OHdG), and malondialdehyde (MDA) levels in the Cr(VI) exposed workers exceeded those in the control subjects. Daily cumulative Cr(VI) exposure and urinary Cr were significantly correlated with urinary 8-OHdG levels following adjustments for covariates. A ten-fold increase in urinary Cr level was associated with a 1.73-fold increase in urinary 8-OHdG level. Daily cumulative Cr(VI) exposure and urinary Cr level were significantly correlated with urinary MDA level following adjustments for covariates. A ten-fold increase in urinary Cr was associated with a 1.45-fold increase in urinary MDA. Exposure to Cr(VI) increased oxidative DNA injury and the oxidative deterioration of lipids in electroplating workers.

Role of oxygen diffusion at Ni/Cr2O3 interface in intergranular oxidation of Ni-Cr alloy

NASA Astrophysics Data System (ADS)

Medasani, Bharat; Sushko, Maria; Schreiber, Daniel; Rosso, Kevin; Bruemmer, Stephen

Certain Ni-Cr alloys used in nuclear systems experience intergranular oxidation and stress corrosion cracking when exposed to high-temperature water leading to their degradation and unexpected failure. To develop a mechanistic understanding of grain boundary oxidation processes, we proposed a mesoscale metal alloy oxidation model that combines quantum Density Functional Theory (DFT) with mesoscopic Poisson-Nernst-Planck/classical DFT. This framework encompasses the chemical specificity of elementary diffusion processes and mesoscale reactive dynamics, and allows modeling oxidation processes on experimentally relevant length scales from first principles. As a proof of concept, a preliminary model was previously employed that limited oxygen diffusion pathways to those through the oxide phase and did not allow oxygen diffusion in the alloy or across oxide/alloy interfaces. In this work, we expand the model to include oxygen diffusion pathways along Ni/Cr2O3 interfaces and demonstrate the increasing importance of such pathways for intergranular oxidation of Ni-Cr alloys with high Cr content. This work is supported by the U.S. Dept. of Energy, Office of Science, Basic Energy Sciences, Materials Sciences and Engineering Division. Simulations are performed using PNNL Institutional Computing facility.

Hybrid Organic/Inorganic Materials Depth Profiling Using Low Energy Cesium Ions

NASA Astrophysics Data System (ADS)

Noël, Céline; Houssiau, Laurent

2016-05-01

The structures developed in organic electronics, such as organic light emitting diodes (OLEDs) or organic photovoltaics (OPVs) devices always involve hybrid interfaces, joining metal or oxide layers with organic layers. No satisfactory method to probe these hybrid interfaces physical chemistry currently exists. One promising way to analyze such interfaces is to use in situ ion beam etching, but this requires ion beams able to depth profile both inorganic and organic layers. Mono- or diatomic ion beams commonly used to depth profile inorganic materials usually perform badly on organics, while cluster ion beams perform excellently on organics but yield poor results when organics and inorganics are mixed. Conversely, low energy Cs+ beams (<500 eV) allow organic and inorganic materials depth profiling with comparable erosion rates. This paper shows a successful depth profiling of a model hybrid system made of metallic (Au, Cr) and organic (tyrosine) layers, sputtered with 500 eV Cs+ ions. Tyrosine layers capped with metallic overlayers are depth profiled easily, with high intensities for the characteristic molecular ions and other specific fragments. Metallic Au or Cr atoms are recoiled into the organic layer where they cause some damage near the hybrid interface as well as changes in the erosion rate. However, these recoil implanted metallic atoms do not appear to severely degrade the depth profile overall quality. This first successful hybrid depth profiling report opens new possibilities for the study of OLEDs, organic solar cells, or other hybrid devices.

No effect of creatine supplementation on oxidative stress and cardiovascular parameters in spontaneously hypertensive rats

PubMed Central

2012-01-01

Background Exacerbated oxidative stress is thought to be a mediator of arterial hypertension. It has been postulated that creatine (Cr) could act as an antioxidant agent preventing increased oxidative stress. The aim of this study was to investigate the effects of nine weeks of Cr or placebo supplementation on oxidative stress and cardiovascular parameters in spontaneously hypertensive rats (SHR). Findings Lipid hydroperoxidation, one important oxidative stress marker, remained unchanged in the coronary artery (Cr: 12.6 ± 1.5 vs. Pl: 12.2 ± 1.7 nmol·mg-1; p = 0.87), heart (Cr: 11.5 ± 1.8 vs. Pl: 14.6 ± 1.1 nmol·mg-1; p = 0.15), plasma (Cr: 67.7 ± 9.1 vs. Pl: 56.0 ± 3.2 nmol·mg-1; p = 0.19), plantaris (Cr: 10.0 ± 0.8 vs. Pl: 9.0 ± 0.8 nmol·mg-1; p = 0.40), and EDL muscle (Cr: 14.9 ± 1.4 vs. Pl: 17.2 ± 1.5 nmol·mg-1; p = 0.30). Additionally, Cr supplementation affected neither arterial blood pressure nor heart structure in SHR (p > 0.05). Conclusions Using a well-known experimental model of systemic arterial hypertension, this study did not confirm the possible therapeutic effects of Cr supplementation on oxidative stress and cardiovascular dysfunction associated with arterial hypertension. PMID:22480293

No effect of creatine supplementation on oxidative stress and cardiovascular parameters in spontaneously hypertensive rats.

PubMed

Alves, Christiano Rr; Murai, Igor H; Ramona, Pamella; Nicastro, Humberto; Bechara, Luiz Rg; Lancha, Antonio H; Brum, Patrícia C; Irigoyen, Maria C; Gualano, Bruno

2012-04-05

Exacerbated oxidative stress is thought to be a mediator of arterial hypertension. It has been postulated that creatine (Cr) could act as an antioxidant agent preventing increased oxidative stress. The aim of this study was to investigate the effects of nine weeks of Cr or placebo supplementation on oxidative stress and cardiovascular parameters in spontaneously hypertensive rats (SHR). Lipid hydroperoxidation, one important oxidative stress marker, remained unchanged in the coronary artery (Cr: 12.6 ± 1.5 vs. Pl: 12.2 ± 1.7 nmol·mg-1; p = 0.87), heart (Cr: 11.5 ± 1.8 vs. Pl: 14.6 ± 1.1 nmol·mg-1; p = 0.15), plasma (Cr: 67.7 ± 9.1 vs. Pl: 56.0 ± 3.2 nmol·mg-1; p = 0.19), plantaris (Cr: 10.0 ± 0.8 vs. Pl: 9.0 ± 0.8 nmol·mg-1; p = 0.40), and EDL muscle (Cr: 14.9 ± 1.4 vs. Pl: 17.2 ± 1.5 nmol·mg-1; p = 0.30). Additionally, Cr supplementation affected neither arterial blood pressure nor heart structure in SHR (p > 0.05). Using a well-known experimental model of systemic arterial hypertension, this study did not confirm the possible therapeutic effects of Cr supplementation on oxidative stress and cardiovascular dysfunction associated with arterial hypertension.

Dependence of magnetic properties on different buffer layers of Mn3.5Ga thin films

NASA Astrophysics Data System (ADS)

Takahashi, Y.; Sato, K.; Shima, T.; Doi, M.

2018-05-01

D022-Mn3.5Ga thin films were prepared on MgO (100) single crystalline substrates with different buffer layer (Cr, Fe, Cr/Pt and Cr/Au) using an ultra-high-vacuum electron beam vapor deposition system. From XRD patterns, a fundamental (004) peak has clearly observed for all samples. The relatively low saturation magnetization (Ms) of 178 emu/cm3, high magnetic anisotropy (Ku) of 9.1 Merg/cm3 and low surface roughness (Ra) of 0.30 nm were obtained by D022-Mn3.5Ga film (20 nm) on Cr/Pt buffer layer at Ts = 300 °C, Ta = 400 °C (3h). These findings suggest that MnGa film on Cr/Pt buffer layer is a promising PMA layer for future spin electronics devices.

Chromium cycling in soils and water: links, gaps, and methods.

PubMed

Bartlett, R J

1991-05-01

The major links in the cycling of chromium in soils and in natural waters are between chromium(III) and chromium (VI). Between the larger links are lesser links involving processes of mobilization and oxidation of CrIII and reduction of CrVI. The gaps are mainly in our understanding of the factors that control these processes. If soluble CrIII is added to an "average" soil, a portion of it will become immediately oxidized by manganese oxides to CrVI. The rest of the CrIII may remain reduced for long periods of time, even in the presence of electron-accepting manganese oxides. However, this less available CrIII can be mobilized by low molecular weight organic complexers and then oxidized where redox conditions are optimal. Usually part of any CrVI added to a soil or sediment will be reduced instantly, especially under acid conditions. On the other hand, high concentrations of polluting CrVI may quickly exhaust the readily available reducing power of the matrix material and excess CrVI, the thermodynamically stable form in air, may persist for years in soils or lagoons without reduction. Cleanup of chromium pollution must involve the surrounding of both CrIII and CrVI with excesses of slowly available reducing substances and sealing them permanently from inputs of atmospheric oxygen. Monitoring the effectiveness of the measures is mandatory, but fortunately the chemical testing for CrVI in soil and water is simple and problem free compared with most colorimetric determinations.

Modification of tribology and high-temperature behavior of Ti 48Al 2Cr 2Nb intermetallic alloy by laser cladding

NASA Astrophysics Data System (ADS)

Liu, Xiu-Bo; Wang, Hua-Ming

2006-06-01

In order to improve the tribology and high-temperature oxidation properties of the Ti-48Al-2Cr-2Nb intermetallic alloy simultaneously, mixed NiCr-Cr 3C 2 precursor powders had been investigated for laser cladding treatment to modify wear and high-temperature oxidation resistance of the material. The alloy samples were pre-placed with NiCr-80, 50 and 20%Cr 3C 2 (wt.%), respectively, and laser treated at the same parameters, i.e., laser output power 2.8 kW, beam scanning speed 2.0 mm/s, beam dimension 1 mm × 18 mm. The treated samples underwent tests of microhardness, wear and high-temperature oxidation. The results showed that laser cladding with different constitution of mixed precursor NiCr-Cr 3C 2 powders improved surface hardness in all cases. Laser cladding with NiCr-50%Cr 3C 2 resulted in the best modification of tribology and high-temperature oxidation behavior. X-ray diffraction (XRD), optical microscope (OM), scanning electron microscopy (SEM) and energy-dispersive spectrometer (EDS) analyses indicated that the formation of reinforced Cr 7C 3, TiC and both continuous and dense Al 2O 3, Cr 2O 3 oxide scales were supposed to be responsible for the modification of the relevant properties. As a result, the present work had laid beneficial surface engineering foundation for TiAl alloy applied as future light weight and high-temperature structural candidate materials.

Survey of Thermal-Fluids Evaluation and Confirmatory Experimental Validation Requirements of Accident Tolerant Cladding Concepts with Focus on Boiling Heat Transfer Characteristics

DOE Office of Scientific and Technical Information (OSTI.GOV)

Brown, Nicholas R.; Wysocki, Aaron J.; Terrani, Kurt A.

The U.S. Department of Energy Office of Nuclear Energy (DOE-NE) Advanced Fuels Campaign (AFC) is working closely with the nuclear industry to develop fuel and cladding candidates with potentially enhanced accident tolerance, also known as accident tolerant fuel (ATF). Thermal-fluids characteristics are a vital element of a holistic engineering evaluation of ATF concepts. One vital characteristic related to boiling heat transfer is the critical heat flux (CHF). CHF plays a vital role in determining safety margins during normal operation and also in the progression of potential transient or accident scenarios. This deliverable is a scoping survey of thermal-fluids evaluation andmore » confirmatory experimental validation requirements of accident tolerant cladding concepts with a focus on boiling heat transfer characteristics. The key takeaway messages of this report are: 1. CHF prediction accuracy is important and the correlations may have significant uncertainty. 2. Surface conditions are important factors for CHF, primarily the wettability that is characterized by contact angle. Smaller contact angle indicates greater wettability, which increases the CHF. Surface roughness also impacts wettability. Results in the literature for pool boiling experiments indicate changes in CHF by up to 60% for several ATF cladding candidates. 3. The measured wettability of FeCrAl (i.e., contact angle and roughness) indicates that CHF should be investigated further through pool boiling and flow boiling experiments. 4. Initial measurements of static advancing contact angle and surface roughness indicate that FeCrAl is expected to have a higher CHF than Zircaloy. The measured contact angle of different FeCrAl alloy samples depends on oxide layer thickness and composition. The static advancing contact angle tends to decrease as the oxide layer thickness increases.« less

The role of NaCl in flame chemistry, in the deposition process, and in its reactions with protective oxides as related to hot corrosion

NASA Technical Reports Server (NTRS)

Kohl, F. J.; Stearns, C. A.

1979-01-01

Sodium chloride is believed to be the primary source of turbine engine contamination that contributes to hot corrosion. The behavior of NaCl-containing aerosols ingested with turbine intake air is very complex; some of the NaCl may vaporize during combustion while some may remain as particulates. The NaCl can lead to Na2SO4 formation by several possible routes or it can contribute to corrosion directly. Hydrogen or oxygen atom reaction with NaCl(c) was shown to result in the release of Na(g). Gaseous NaCl in flames can be partially converted to gaseous Na2SO4 by homogeneous reactions. The remaining gaseous NaCl and other Na-containing molecules can act as sodium carriers for condensate deposition of Na2SO4 on cool surfaces. A frozen boundary layer theory was developed to predict the rates of deposition. The condensed phase NaCl can be converted directly to condensed Na2SO4 by reaction with sulfur oxides and O2. Reaction of gaseous NaCl with Cr2O3 results in the vapor phase transport of chromium by the formation of complex Cr-containing gaseous molecules. Similar gaseous complexes are formed with molybdenum. The presence of gaseous NaCl was shown to affect the oxidation kinetics of Ni-Cr alloys. It also causes changes in the surface morphology of Al2O3 scales formed on Al-containing alloys.

Barrier Properties of Layered-Silicate Reinforced Ethylenepropylenediene Monomer/Chloroprene Rubber Nanorubbers.

PubMed

Wu, Chang Mou; Hsieh, Wen Yen; Cheng, Kuo Bin; Lai, Chiu-Chun; Lee, Kuei Chi

2018-05-09

The triacetin and nitroglycerin barrier properties of layered-silicate reinforced ethylenepropylenediene monomer/chloroprene rubber (EPDM/CR) nanorubbers were investigated as rocket-propellant inhibitors. EPDM/CR nanorubbers with intercalated structures were formulated and prepared by the melt-compounding method. The triacetin permeability and nitroglycerin absorption were observed to decrease with increasing layered-silicate content. The layered silicates also improved the flame retardancies of the nanorubbers by forming silicate reinforced carbonaceous chars. Layered-silicate reinforced EPDM/CR nanorubbers are potentially effective rocket propellant-inhibiting materials.

A Comparative Study of Raw and Metal Oxide Impregnated Carbon Nanotubes for the Adsorption of Hexavalent Chromium from Aqueous Solution

PubMed Central

Qureshi, Muhammad I.; Al-Baghli, Nadhir

2017-01-01

The present study reports the use of raw, iron oxide, and aluminum oxide impregnated carbon nanotubes (CNTs) for the adsorption of hexavalent chromium (Cr(VI)) ions from aqueous solution. The raw CNTs were impregnated with 1% and 10% loadings (weight %) of iron oxide and aluminum oxide nanoparticles using wet impregnation technique. The synthesized materials were characterized using scanning electron microscopy (SEM) and thermogravimetric analysis (TGA). Batch adsorption experiments were performed to assess the removal efficiency of Cr(VI) ions from water and the effects of pH, contact time, adsorbent dosage, and initial concentration of the Cr(VI) ions were investigated. Results of the study revealed that impregnated CNTs achieved significant increase in the removal efficiency of Cr(VI) ions compared to raw CNTs. In fact, both CNTs impregnated with 10% loading of iron and aluminum oxides were able to remove up to 100% of Cr(VI) ions from aqueous solution. Isotherm studies were carried out using Langmuir and Freundlich isotherm models. Adsorption kinetics of Cr(VI) ions from water was found to be well described by the pseudo-second-order model. The results suggest that metallic oxide impregnated CNTs have very good potential application in the removal of Cr(VI) ions from water resulting in better environmental protection. PMID:28487625

Effect of Element Substitution at V site on Thermoelectric Properties of Aurivillius Phase Bi2VO5.5

NASA Astrophysics Data System (ADS)

Kohri, Hitoshi; Yagasaki, Takayoshi

2016-10-01

Thermoelectric oxides are suitable at the high temperature range because of chemical stability. Aurivillius compounds are bismuth layered oxides, and known as oxygen ion conductors. The Aurivillius compounds consist of Perovskite layers and Bi-O layers. It is expected that nano-layered structure shows high Seebeck coefficients due to the quantum confinement of carriers in Perovskite layers. It was reported that the Seebeck coefficient of hot pressed specimens for Aurivillius phase Bi2VO5.5 was a high value of -28.3 mVK-1 at 1010 K, and the electrical resistivity of one was also a high value of 0.033 Ωm at 1010 K. In this paper, the effect of element substitution at the V site on thermoelectric properties of Aurivillius phase Bi2VO5.5 was investigated. Bi2V1- x M x O5.5 (M = Cr, Mo, W x = 0, 0.05, 0.1, 0.2) were prepared by solid-state reaction. The electrical resistivity of Cr-substituted specimens were indicated at larger values than the ones for unsubstituted specimens over the measurement temperature range. The resistivity above 800 K was reduced by substitution of W or Mo. W as a substituted element was effective for reducing the thermal conductivity of Bi2VO5.5. The maximum value of the dimensionless figure of merit ZT was 0.05 at 799 K for Bi2V0.8Mo0.2O5.5 and at 902 K for Bi2V0.8W0.1O5.5. The maximum ZT of an unsubstituted sample was 0.02 at 993 K. From these results, it was found that tungsten or molybdenum substitution was effective to improve ZT for Aurivillius phase Bi2VO5.5.

Characterization of oxide nanoparticles in Al-free and Al-containing oxide dispersion strengthened ferritic steels.

PubMed

Lee, Jae Hoon; Kim, Jeoung Han

2013-09-01

Oxide nanoparticles in oxide dispersion strengthened (ODS) ferritic steels with and without Al have been characterized by transmission electron microscopy. It is confirmed that most of the complex oxide particles consist of Y2TiO5 for 18Cr-ODS steel and YAlO3 or YAl5O12 for 18Cr5Al-ODS steel, respectivley. The addition of 5% Al in 18Cr-ODS steel leads to the formation of larger oxide particles and the reduction in their number density. For 18Cr-ODS steel, 87% of the oxide particles are coherent. The misfit strain of the coherent particles and a few semi-coherent particles is about 0.034 and 0.056, respectively. For 18Cr5Al-ODS steel, 75% of the oxide particles are semi-coherent, of which the misfit strain is 0.091 and 0.125, respectively. These results suggest that for the Al-containing ODS steel the Al addition accelerates the formation of semi-coherent oxide particles and its larger coherent and semi-coherent particles result in the larger misfit strain between the oxide particle and alloy matrix, indicating that the coherence of oxide nanoparticles in ODS steels is size-dependent.

Study of fracture toughness and bend test morphologies of HVOF sprayed Cr3C2-25% NiCr coating after heat treatment

NASA Astrophysics Data System (ADS)

Shrivastava, Sharad; Upadhyaya, Rohit

2018-04-01

Majority of the industrial components are subjected to high temperature exposure, where crack propagation occurs due to shear failure. The paper involves the study of the fracture toughness of heat treated Cr3C2-NiCr coating at three different service temperatures (750°C, 850°C, and 950°C for 1-hour aging) using indentation techniques to measure the crack resistance of the coating. At 750°C and 850°C, the coating cracked at the bend area, but not spalled. At 950°C, the coating spalled and delaminated from the substrate indicating poor adhesion after prolonged exposure. The influence of heat treatment on the fracture toughness and adhesion properties of the Cr3C2-25%NiCr coating were also investigated. The high temperature exposure at 950°C, resulted in a shear failure of the coating due to the presence of splat contraction. The increase in temperature increases the fracture toughness KIC of the coating, with the decrease in hardness. It was observed that the oxidation levels enhanced on the top layer of the coating, which acted like a core region for crack initiation at 950°C resulting in shear failure during bend test.

Studies of electrochemical oxidation of Zircaloy nuclear reactor fuel cladding using time-of-flight-energy elastic recoil detection analysis

NASA Astrophysics Data System (ADS)

Whitlow, H. J.; Zhang, Y.; Wang, Y.; Winzell, T.; Simic, N.; Ahlberg, E.; Limbäck, M.; Wikmark, G.

2000-03-01

The trend towards increased fuel burn-up and higher operating temperatures in order to achieve more economic operation of nuclear power plants places demands on a better understanding of oxidative corrosion of Zircaloy (Zry) fuel rod cladding. As part of a programme to study these processes we have applied time-of-flight-energy elastic recoil detection (ToF-E ERD), electrochemical impedance measurements and scanning electron microscopy to quantitatively characterise thin-oxide films corresponding to the pre-transition oxidation regime. Oxide films of different nominal thickness in the 9-300 nm range were grown on a series of rolled Zr and Zry-2 plates by anodisation in dilute H 2SO 4 with applied voltages. The dielectric thickness of the oxide layer was determined from the electrochemical impedance measurements and the surface topography characterised by scanning electron microscopy. ToF-E ERD with a 60 MeV 127I 11+ ion beam was used to determine the oxygen content and chemical composition of the oxide layer. In the Zr samples, the oxygen content (O atom cm -2) that was determined by ERD was closely similar to the O content derived from impedance measurements from the dielectric film. The absolute agreement was well within the uncertainty associated with the stopping powers. Moreover, the measured composition of the thick oxide layers corresponded to ZrO 2 for the films thicker than 65 nm where the oxide layer was resolved in the ERD depth profile. Zry-2 samples exhibited a similar behaviour for small thickness ( ⩽130 nm) but had an enhanced O content at larger thicknesses that could be associated either with enhanced rough surface topography or porous oxide formation that was correlated with the presence of Second Phase Particles (SPP) in Zry-2. The concentration of SPP elements (Fe, Cr, Ni) in relation to Zr was the same in the outer 9×10 17 atom cm -2 of oxide as in the same thickness of metal. The results also revealed the presence of about 1 at.% 32S in the oxides on the Zr and Zry-2 samples which presumably originates from the electrolyte.

Multiscale model of metal alloy oxidation at grain boundaries

DOE Office of Scientific and Technical Information (OSTI.GOV)

Sushko, Maria L.; Alexandrov, Vitali Y.; Schreiber, Daniel K.

2015-06-07

High temperature intergranular oxidation and corrosion of metal alloys is one of the primary causes of materials degradation in nuclear systems. In order to gain insights into grain boundary oxidation processes, a mesoscale metal alloy oxidation model at experimentally relevant length scales is established by combining quantum Density Functional Theory (DFT) and mesoscopic Poisson-Nernst-Planck/classical DFT with predictions focused on Ni alloyed with either Cr or Al. Analysis of species and fluxes at steady-state conditions indicates that the oxidation process involves vacancy-mediated transport of Ni and the minor alloying element to the oxidation front and the formation of stable metal oxides.more » The simulations further demonstrate that the mechanism of oxidation for Ni-5Cr and Ni-4Al is qualitatively different. Intergranular oxidation of Ni-5Cr involves the selective oxidation of the minor element and not matrix Ni, due to slower diffusion of Ni relative to Cr in the alloy and due to the significantly smaller energy gain upon the formation of nickel oxide compared to that of Cr2O3. This essentially one-component oxidation process results in continuous oxide formation and a monotonic Cr vacancy distribution ahead of the oxidation front, peaking at alloy/oxide interface. In contrast, Ni and Al are both oxidized in Ni-4Al forming a mixed spinel NiAl2O4. Different diffusivities of Ni and Al give rise to a complex elemental distribution in the vicinity of the oxidation front. Slower diffusing Ni accumulates in the oxide and metal within 3 nm of the interface, while Al penetrates deeper into the oxide phase. Ni and Al are both depleted from the region 3–10 nm ahead of the oxidation front creating voids. The oxide microstructure is also different. Cr2O3 has a plate-like structure with 1.2 - 1.7 nm wide pores running along the grain boundary, while NiAl2O4 has 1.5 nm wide pores in the direction parallel to the grain boundary and 0.6 nm pores in the perpendicular direction providing an additional pathway for oxygen diffusion through the oxide.« less

Influence of extractable soil manganese on oxidation capacity of different soils in Korea

NASA Astrophysics Data System (ADS)

Chon, Chul-Min; Kim, Jae Gon; Lee, Gyoo Ho; Kim, Tack Hyun

2008-08-01

We examined the relationship between soil oxidation capacity and extractable soil manganese, iron oxides, and other soil properties. The Korean soils examined in this study exhibited low to medium Cr oxidation capacities, oxidizing 0.00-0.47 mmol/kg, except for TG-4 soils, which had the highest capacity for oxidizing added Cr(III) [>1.01 mmol/kg of oxidized Cr(VI)]. TG and US soils, with high Mn contents, had relatively high oxidation capacities. The Mn amounts extracted by dithionite-citrate-bicarbonate (DCB) (Mnd), NH2OH·HCl (Mnh), and hydroquinone (Mnr) were generally very similar, except for the YS1 soils, and were well correlated. Only small proportions of either total Mn or DCB-extractable Mn were extracted by NH2OH·HCl and hydroquinone in the YS1 soils, suggesting inclusion of NH2OH·HCl and hydroquinone-resistant Mn oxides, because these extractants are weaker reductants than DCB. No Cr oxidation test results were closely related to total Mn concentrations, but Mnd, Mnh, and Mnr showed a relatively high correlation with the Cr tests ( r = 0.655-0.851; P < 0.01). The concentrations of Mnd and Mnh were better correlated with the Cr oxidation tests than was the Mnr concentration, suggesting that the oxidation capacity of our soil samples can be better explained by Mnd and Mnh than by Mnr. The first component in principal components analysis indicated that extractable soil Mn was a main factor controlling net Cr oxidation in the soils. Total soil Mn, Fe oxides, and the clay fraction are crucial for predicting the mobility of pollutants and heavy metals in soils. The second principal component indicated that the presence of Fe oxides in soils had a significant relationship with the clay fraction and total Mn oxide, and was also related to heavy-metal concentrations (Zn, Cd, and Cu, but not Pb).

Degradation of TCE, Cr(VI), sulfate, and nitrate mixtures by granular iron in flow-through columns under different microbial conditions.

PubMed

Gandhi, Sumeet; Oh, Byung-Taek; Schnoor, Jerald L; Alvarez, Pedro J J

2002-04-01

Flow-through aquifer columns packed with a middle layer of granular iron (Fe0) were used to study the applicability and limitations of bio-enhanced Fe0 barriers for the treatment of contaminant mixtures in groundwater. Concentration profiles along the columns showed extensive degradation of hexavalent chromium Cr(VI), nitrate, sulfate, and trichloroethene (TCE), mainly in the Fe0 layer. One column was bioaugmented with Shevanella algae BRY, an iron-reducing bacterium that could enhance Fe0 reactivity by reductive dissolution of passivating iron oxides. This strain did not enhance Cr(VI), which was rapidly reduced by iron, leaving little room for improvement by microbial participation. Nevertheless, BRY-enhanced nitrate removal (from 15% to 80%), partly because this strain has a wide range of electron acceptors, including nitrate. Sulfate was removed (55%) only in a column that was bioaugmented with a mixed culture containing sulfate-reducing bacteria. Apparently, these bacteria used H2 (produced by Fe0 corrosion) as electron donor to respire sulfate. Most of the TCE was degraded in the zone containing Fe0 (50-70%), and bioaugmentation with BRY slightly increased the removal efficiency to about 80%. Microbial colonization of the Fe0 surface was confirmed by scanning electron microscopy.

Vacuum Plasma Spray of CuCrNb Alloy for Advanced Liquid - Fuel Combustion Chambers

NASA Technical Reports Server (NTRS)

Zimmerman, Frank

2000-01-01

The copper-8 atomic percent chromium-4 atomic percent niobium (CuCrNb) alloy was developed by Glenn Research Center (formally Lewis Research Center) as an improved alloy for combustion chamber liners. In comparison to NARloy-Z, the baseline (as in Space Shuttle Main Engine) alloy for such liners, CuCrNb demonstrates mechanical and thermophysical properties equivalent to NARloy-Z, but at temperatures 100 C to 150 C (180 F to 270 F) higher. Anticipated materials related benefits include decreasing the thrust cell liner weight 5% to 20%, increasing the service life at least two fold over current combustion chamber design, and increasing the safety margins available to designers. By adding an oxidation and thermal barrier coating to the liner, the combustion chamber can operate at even higher temperatures. For all these benefits, however, this alloy cannot be formed using conventional casting and forging methods because of the levels of chromium and niobium, which exceed their solubility limit in copper. Until recently, the only forming process that maintains the required microstructure of CrNb intermetallics is powder metallurgy formation of a billet from powder stock, followed by extrusion. This severely limits its usefulness in structural applications, particularly the complex shapes required for combustion chamber liners. Vacuum plasma spray (VPS) has been demonstrated as a method to form structural articles including small combustion chambers from the CuCrNb alloy. In addition, an oxidation and thermal barrier layer can be formed integrally on the hot wall of the liner that improve performance and extend service life. This paper discusses the metallurgy and thermomechanical properties of VPS formed CuCrNb versus the baseline powder metallurgy process, and the manufacturing of small combustion chamber liners at Marshall Space Flight Center using the VPS process. The benefits to advanced propulsion initiatives of using VPS to fabricate combustion chamber liners while maintaining the superior CuCrNb properties are also presented.

Blending Cr 2O 3 into a NiO-Ni electrocatalyst for sustained water splitting

DOE PAGES

Gong, Ming; Zhou, Wu; Kenney, Michael James; ...

2015-08-24

The rising H 2 economy demands active and durable electrocatalysts based on low-cost, earth-abundant materials for water electrolysis/photolysis. Here we report nanoscale Ni metal cores over-coated by a Cr 2O 3-blended NiO layer synthesized on metallic foam substrates. The Ni@NiO/Cr 2O 3 triphase material exhibits superior activity and stability similar to Pt for the hydrogen-evolution reaction in basic solutions. The chemically stable Cr 2O 3 is crucial for preventing oxidation of the Ni core, maintaining abundant NiO/Ni interfaces as catalytically active sites in the heterostructure and thus imparting high stability to the hydrogen-evolution catalyst. The highly active and stable electrocatalystmore » enables an alkaline electrolyzer operating at 20 mA cm –2 at a voltage lower than 1.5 V, lasting longer than 3 weeks without decay. Thus, the non-precious metal catalysts afford a high efficiency of about 15 % for light-driven water splitting using GaAs solar cells.« less

Neutral complexes as oxidants for the reduced form of parsley (Petroselinum crispum) [2Fe--2S] ferredoxin. Evidence for partial blocking by redox-inactive Cr(III) complexes.

PubMed Central

Adzamli, I K; Kim, H O; Sykes, A G

1982-01-01

The 1 : 1 reactions of three neutral Co(III) oxidants, Co(acac)3, Co(NH3)3(NO2)3 and Co(acac)2(NH3)(NO2), with reduced parsley (Petroselinum crispum) [2Fe--2S] ferredoxin (which carries a substantial negative charge), have been studied at 25 degrees C, pH 8.0 (Tris/HCl), I0.10 (NaCl). Whereas it has previously been demonstrated that with Co(NH3)6+ as oxidant the reaction if completely blocked by redox-inactive Cr(NH3)63+, the neutral oxidants are only partially blocked by this same complex. The effects of three Cr(III) complexes, Cr(NH3)63+%, Cr(en)33+ and (en)2Cr . mu(OH,O2CCH3) . CR(en)24+ have been investigated. Kinetic data for the response of 3+, neutral, as well as 1--oxidants to the presence of 3+ (and 4+) Cr(III) complexes can now be rationalized in terms of a single functional site on the protein for electron transfer. Electrostatics have a significant influence on association at this site. PMID:7115307

Role of Oxides and Porosity on High-Temperature Oxidation of Liquid-Fueled HVOF Thermal-Sprayed Ni50Cr Coatings

NASA Astrophysics Data System (ADS)

Song, B.; Bai, M.; Voisey, K. T.; Hussain, T.

2017-02-01

High chromium content in Ni50Cr thermally sprayed coatings can generate a dense and protective scale at the surface of coating. Thus, the Ni50Cr coating is widely used in high-temperature oxidation and corrosion applications. A commercially available gas atomized Ni50Cr powder was sprayed onto a power plant steel (ASME P92) using a liquid-fueled high velocity oxy-fuel thermal spray with three processing parameters in this study. Microstructure of as-sprayed coatings was examined using oxygen content analysis, mercury intrusion porosimetry, scanning electron microscope (SEM), energy-dispersive x-ray spectroscopy (EDX) and x-ray diffraction (XRD). Short-term air oxidation tests (4 h) of freestanding coatings (without boiler steel substrate) in a thermogravimetric analyzer at 700 °C were performed to obtain the kinetics of oxidation of the as-sprayed coating. Long-term air oxidation tests (100 h) of the coated substrates were performed at same temperature to obtain the oxidation products for further characterization in detail using SEM/EDX and XRD. In all samples, oxides of various morphologies developed on top of the Ni50Cr coatings. Cr2O3 was the main oxidation product on the surface of all three coatings. The coating with medium porosity and medium oxygen content has the best high-temperature oxidation performance in this study.

Interdiffusion-driven synthesis of tetragonal chromium (III) oxide on BaTi O3

NASA Astrophysics Data System (ADS)

Asa, M.; Vinai, G.; Hart, J. L.; Autieri, C.; Rinaldi, C.; Torelli, P.; Panaccione, G.; Taheri, M. L.; Picozzi, S.; Cantoni, M.

2018-03-01

Interfaces play a crucial role in the study of novel phenomena emerging at heterostructures comprising metals and functional oxides. For this reason, attention should be paid to the interface chemistry, which can favor the interdiffusion of atomic species and, under certain conditions, lead to the formation of radically different compounds with respect to the original constituents. In this work, we consider Cr/BaTi O3 heterostructures grown on SrTi O3 (100) substrates. Chromium thin films (1-2 nm thickness) are deposited by molecular beam epitaxy on the BaTi O3 layer, and subsequently annealed in vacuum at temperatures ranging from 473 to 773 K. A disordered metallic layer is detected for annealing temperatures up to 573 K, whereas, at higher temperatures, we observe a progressive oxidation of chromium, which we relate to the thermally activated migration of oxygen from the substrate. The chromium oxidation state is +3 and the film shows a defective rocksalt structure, which grows lattice matched on the underlying BaTi O3 layer. One out of every three atoms of chromium is missing, producing an uncommon tetragonal phase with C r2O3 stoichiometry. Despite the structural difference with respect to the ordinary corundum α-C r2O3 phase, we demonstrate both experimentally and theoretically that the electronic properties of the two phases are, to a large extent, equivalent.

Microstructure and properties of FeSiCr/PA6 composites by injection molding using FeSiCr powders by phosphating and coupling treatment

NASA Astrophysics Data System (ADS)

Wang, Lulu; Qiao, Liang; Zheng, Jingwu; Cai, Wei; Ying, Yao; Li, Wangchang; Che, Shenglei; Yu, Jing

2018-04-01

FeSiCr/PA6 composites were prepared by injection molding using the FeSiCr powders modified by different phosphating agents and KH550 coupling agent. The resistivity, impact strength, magnetic permeability and magnetic loss of the FeSiCr/PA6 composites were measured. The morphologies of different FeSiCr powders and the FeSiCr/PA6 composites were also observed by scanning electron microscope (SEM). The results showed that 1-Hydroxyethylidene-1,1-diphosphonic acid, phytic acid and H3PO4 could improve the electrical resistivity of FeSiCr powders by forming the dense phosphating layer except diphenylphosphinic acid. However, the resistivity of FeSiCr/PA6 composites using the FeSiCr powders treated by all the four phosphating agents had no obvious increase though the phosphating layer on the surface of FeSiCr powder came into being. The nylon insulation layer had much stronger influence than the phosphating layer on electrical resistivity of the composites. After adding appropriate KH550 coupling agent, the impact strengths of FeSiCr/PA6 composites were significantly improved, which may be associated with the tiny gap between FeSiCr powder and PA6 matrix. The effects of the phosphating agents on the magnetic permeability and loss of the FeSiCr/PA6 were small and the mechanism were also discussed.

The oxidation of Cr(III) to Cr(VI) in the environment by atmospheric oxygen during the bush fires.

PubMed

Panichev, N; Mabasa, W; Ngobeni, P; Mandiwana, K; Panicheva, S

2008-05-30

The presence of Cr(VI) in soils and plants of remote unpolluted areas can be explained by partial oxidation of Cr(III) with atmospheric oxygen during seasonable bush fires, which are rather frequent event in South Africa. Experiments with thermal treatment of a veld grass, Hyperthelia dissoluta, in muffle furnace at high temperature, followed by electrothermal atomic absorption spectrometry (ETAAS) determination of chromium, show a remarkable increase in Cr(VI) concentration from initial 2.5 to 23.2% after the treatment of grass ash at 500 degrees C and to 58.1% at 900 degrees C. Before ETAAS determination, the two chromium species of interest were separated by the treatment of samples with 0.1M Na2CO3. Thermodynamic calculations confirm the possibility of Cr(III) to Cr(VI) oxidation with atmospheric oxygen at high temperature in alkaline media, which is typical for vegetation ash. Analysis of field samples show that percent of Cr(VI), in respect to the total amount of chromium increased from initial 2.5% in grass to 9.3% in ash of grass. Without oxidation the percent of Cr(VI) in grass and ash of grass should be a constant value. After the fire Cr(VI) concentration in top soil (0-3 cm) increased from 0.3+/-0.05 to 1.8+/-0.5 microg g(-1) and the total Cr from 26+/-9 to 69+/-14 microg g(-1). The reason for the appearance of additional amount of Cr on top soil can be explained by condensation of chromium species from flame and shouldering ash on a soil surface. The results of studies demonstrate that Cr(VI) is formed by Cr(III) oxidation with atmospheric oxygen at high temperature during bush fires.

Computational discovery of ferromagnetic semiconducting single-layer CrSnTe 3

DOE PAGES

Zhuang, Houlong L.; Xie, Yu; Kent, P. R. C.; ...

2015-07-06

Despite many single-layer materials being reported in the past decade, few of them exhibit magnetism. Here we perform first-principles calculations using accurate hybrid density functional methods (HSE06) to predict that single-layer CrSnTe 3 (CST) is a ferromagnetic semiconductor, with band gaps of 0.9 and 1.2 eV for the majority and minority spin channels, respectively. We determine the Curie temperature as 170 K, significantly higher than that of single-layer CrSiTe 3 (90K) and CrGeTe 3 (130 K). This is due to the enhanced ionicity of the Sn-Te bond, which in turn increases the superexchange coupling between the magnetic Cr atoms. Wemore » further explore the mechanical and dynamical stability and strain response of this single-layer material for possible epitaxial growth. Lastly, our study provides an intuitive approach to understand and design novel single-layer magnetic semiconductors for a wide range of spintronics and energy applications.« less

Study of the Au-Cr bilayer system using X-ray reflectivity, GDOES, and ToF-SIMS

DOE PAGES

Jonnard, Philippe; Modi, Mohammed H.; Le Guen, Karine; ...

2018-04-17

Here, we study a Au (25 nm)/Cr (10 nm) bilayer system as a model of mirror for the soft X–ray energy range. The Au and Cr thin films are a few nanometer thick and are deposited on a float glass substrate. The sample is characterized by using 3 complementary techniques: soft X–ray reflectivity, glow discharge optical emission spectrometry (GDOES), and time–of–flight secondary ion mass spectroscopy (ToF–SIMS). Soft X–ray reflectivity provides information about the thickness and roughness of the different layers, while GDOES is used to obtain the elemental depth profile of the stack and ToF–SIMS to obtain the elemental andmore » chemical depth profiles. GDOES and ToF–SIMS have both a nanometer depth resolution. A coherent description of the bilayer stack is obtained through the combination of these techniques. It consists in 5 layers namely a surface contamination layer, a principal gold layer, a Au–Cr mixed layer, a Cr layer, and another contamination layer at the top of the substrate.« less

Study of the Au-Cr bilayer system using X-ray reflectivity, GDOES, and ToF-SIMS

DOE Office of Scientific and Technical Information (OSTI.GOV)

Jonnard, Philippe; Modi, Mohammed H.; Le Guen, Karine

Here, we study a Au (25 nm)/Cr (10 nm) bilayer system as a model of mirror for the soft X–ray energy range. The Au and Cr thin films are a few nanometer thick and are deposited on a float glass substrate. The sample is characterized by using 3 complementary techniques: soft X–ray reflectivity, glow discharge optical emission spectrometry (GDOES), and time–of–flight secondary ion mass spectroscopy (ToF–SIMS). Soft X–ray reflectivity provides information about the thickness and roughness of the different layers, while GDOES is used to obtain the elemental depth profile of the stack and ToF–SIMS to obtain the elemental andmore » chemical depth profiles. GDOES and ToF–SIMS have both a nanometer depth resolution. A coherent description of the bilayer stack is obtained through the combination of these techniques. It consists in 5 layers namely a surface contamination layer, a principal gold layer, a Au–Cr mixed layer, a Cr layer, and another contamination layer at the top of the substrate.« less

Influence of oxygenation on chromium redox reactions with manganese sulfide (MnS(s)).

PubMed

Wadhawan, Amar R; Livi, Kenneth J; Stone, Alan T; Bouwer, Edward J

2015-03-17

Manganese sulfide (MnS(s)) minerals exist in sulfidic environments and can have unique reactive abilities because of sulfide, which is a known reductant, and Mn, the oxyhydroxides of which are known oxidants. This study elucidated the role of MnS(s) in controlling Cr speciation with implications on its fate and toxicity in the natural environment, specifically sulfidic sediments that undergo biogeochemical changes due to sediment resuspension during dredging, bioturbation, and flood events. In continuously mixed batch reaction experiments, aqueous CrVI reduction under anaerobic conditions occurred primarily on the surface of MnS(s) displaying a biphasic behavior- the initial rapid removal of CrVI from solution was followed by a slow decline due to surface passivation by reaction products, mainly sorbed or precipitated CrIII. The reaction progress increased with MnS(s) surface area loading but decreased on increasing CrVI concentration and pH, suggesting that surface site regeneration through product desorption was the rate-controlling mechanism. Below circum-neutral pH, higher solubility of MnS(s) resulted in additional CrVI reduction by reduced sulfur species in solution, whereas increased CrIII solubility lowered surface passivation allowing for more reactive sites to participate in the reaction. Aeration of MnS(s) at pH≥7 caused the formation of a heterogeneous MnIII(hydr)oxide that was composed of hausmanite and manganite. CrVI reoccurrence was observed on aeration of CrVI-spiked MnS(s) from the oxidation of product CrIII. The reoccurrence at pH≥7 was attributed to the oxidation of product CrIII by MnIII(hydr)oxide, whereas the reoccurrence at pH<7 was hypothesized from the oxidation of product CrIII by intermediate aqueous MnIII and/or sulfur species. Just as with Cr, MnS(s) may play an important role in speciation, fate, and transport of other environmental contaminants.

Simultaneous determination of Cr(III) and Cr(VI) in tannery wastewater using low pressure ion chromatography combined with flow injection spectrophotometry

NASA Astrophysics Data System (ADS)

Chen, Shujuan; Zhang, Xinshen; Yu, Lingyun; Wang, Li; Li, Hui

2012-03-01

Trivalent and hexavalent chromium have been successfully separated and determined using low pressure ion chromatography combined with flow injection spectrophotometric analysis (LPIC-FIA). A column packed with crosslinking starch microspheres was used for on-line separation of Cr(III) from Cr(VI) in a flow-injection system because of its absorptive effect on Cr(III). To determine the concentration of Cr(III) and Cr(VI) in samples, we used 3.0 mmol/L nitric acid to elute adsorbed Cr(III) from the column and then used ceric sulfate-sulfuric acid as oxidant to convert all Cr(III) into Cr(VI). Then, Cr(VI) directly came from the samples and Cr(VI) came from Cr(III) successively formed a amaranthine complex with diphenycarbazide and the complex shows a maximum absorption at 530 nm. Analytical parameters including the concentration of eluent and oxidant solution, oxidizing temperature, length of oxidizing reaction coil, reaction coil and injection coil, interfering effects, etc., were optimized. The limit of detection was 1.25 μg/L for Cr(VI) and 3.76 μg/L for Cr(III). The linear relationship between absorption with the concentration of Cr(VI) and Cr(III) was 0.001-1.000 mg/L and 0.030-1.000 mg/L with correlation coefficients of 0.9995 and 0.9994, respectively. The relative standard deviation of Cr(VI) and Cr(III) was 1.21% and 1.66%, respectively (n = 10). Major cations and anions did not show any interference. We validated this method through certified reference materials and through measuring the recovery in tannery wastewater.

Method and closing pores in a thermally sprayed doped lanthanum chromite interconnection layer

DOEpatents

Singh, Prabhakar; Ruka, Roswell J.

1995-01-01

A dense, substantially gas-tight electrically conductive interconnection layer is formed on an air electrode structure of an electrochemical cell by (A) providing an air electrode surface; (B) forming on a selected portion of the electrode surface, a layer of doped LaCrO.sub.3 particles doped with an element or elements selected from Ca, Sr, Ba, Mg, Co, Ni, Al and mixtures thereof by thermal spraying doped LaCrO.sub.3 particles, either by plasma arc spraying or flame spraying; (C) depositing a mixture of CaO and Cr.sub.2 O.sub.3 on the surface of the thermally sprayed layer; and (D) heating the doped LaCrO.sub.3 layer coated with CaO and Cr.sub.2 O.sub.3 surface deposit at from about 1000.degree. C. to 1200.degree. C. to substantially close the pores, at least at a surface, of the thermally sprayed doped LaCrO.sub.3 layer. The result is a dense, substantially gas-tight, highly doped, electrically conductive interconnection material bonded to the electrode surface. A solid electrolyte layer can be applied to the nonselected portion of the air electrode. A fuel electrode can be applied to the solid electrolyte, to form an electrochemical cell, for example for generation of electrical power.

Method and closing pores in a thermally sprayed doped lanthanum chromite interconnection layer

DOEpatents

Singh, P.; Ruka, R.J.

1995-02-14

A dense, substantially gas-tight electrically conductive interconnection layer is formed on an air electrode structure of an electrochemical cell by (A) providing an air electrode surface; (B) forming on a selected portion of the electrode surface, a layer of doped LaCrO{sub 3} particles doped with an element or elements selected from Ca, Sr, Ba, Mg, Co, Ni, Al and mixtures thereof by thermal spraying doped LaCrO{sub 3} particles, either by plasma arc spraying or flame spraying; (C) depositing a mixture of CaO and Cr{sub 2}O{sub 3} on the surface of the thermally sprayed layer; and (D) heating the doped LaCrO{sub 3} layer coated with CaO and Cr{sub 2}O{sub 3} surface deposit at from about 1,000 C to 1,200 C to substantially close the pores, at least at a surface, of the thermally sprayed doped LaCrO{sub 3} layer. The result is a dense, substantially gas-tight, highly doped, electrically conductive interconnection material bonded to the electrode surface. A solid electrolyte layer can be applied to the nonselected portion of the air electrode. A fuel electrode can be applied to the solid electrolyte, to form an electrochemical cell, for example for generation of electrical power. 5 figs.

Development and High Temperature Property Evaluation of Ni-Co-Cr-Al Composite Electroforms

NASA Astrophysics Data System (ADS)

Srivastava, Meenu; Siju; Balaraju, J. N.; Ravisankar, B.

2015-05-01

Ni-Co-Cr-Al composite electroforms were developed with cobalt content of 10 and 40 wt.%. Cr and Al nano-particles were suspended in sulphamate electrolyte and co-deposited in the Ni-Co matrices. The surface morphology was investigated using field emission scanning electron microscope and the composition analyzed by energy-dispersive x-ray analysis. The oxidation resistance of the electroforms was studied from 600 to 1000 °C. The weight gain of Ni-10 wt.%Co-Cr-Al was less (better oxidation resistance) compared to Ni-Cr-Al and Ni-40 wt.%Co-Cr-Al. The x-ray diffraction studies revealed that the oxidation product formed on the surface of Ni-Cr-Al and Ni-10 wt.%Co-Cr-Al consisted of NiO and Al2O3, while Ni-40 wt.%Co-Cr-Al comprised oxides such as NiCo2O4, CrO3, CoO, NiO, and Al2O3. The hot corrosion behavior was investigated in 75%Na2SO4 + 25%NaCl environment at 800 °C. It was found that the hot corrosion resistance of the composite coating improved with increase in cobalt content. The probable composition suitable for high-temperature applications was found to be Ni-10 wt.%Co-Cr-Al.

Barrier Properties of Layered-Silicate Reinforced Ethylenepropylenediene Monomer/Chloroprene Rubber Nanorubbers

PubMed Central

Hsieh, Wen Yen; Cheng, Kuo Bin; Lai, Chiu-Chun; Lee, Kuei Chi

2018-01-01

The triacetin and nitroglycerin barrier properties of layered-silicate reinforced ethylenepropylenediene monomer/chloroprene rubber (EPDM/CR) nanorubbers were investigated as rocket-propellant inhibitors. EPDM/CR nanorubbers with intercalated structures were formulated and prepared by the melt-compounding method. The triacetin permeability and nitroglycerin absorption were observed to decrease with increasing layered-silicate content. The layered silicates also improved the flame retardancies of the nanorubbers by forming silicate reinforced carbonaceous chars. Layered-silicate reinforced EPDM/CR nanorubbers are potentially effective rocket propellant-inhibiting materials. PMID:29747427

Perpendicular recording media for hard disk drives

NASA Astrophysics Data System (ADS)

Piramanayagam, S. N.

2007-07-01

Perpendicular recording technology has recently been introduced in hard disk drives for computer and consumer electronics applications. Although conceptualized in the late 1970s, making a product with perpendicular recording that has competing performance, reliability, and price advantage over the prevalent longitudinal recording technology has taken about three decades. One reason for the late entry of perpendicular recording is that the longitudinal recording technology was quite successful in overcoming many of its problems and in staying competitive. Other reasons are the risks, problems, and investment needed in making a successful transition to perpendicular recording technology. Iwasaki and co-workers came up with many inventions in the late 1970s, such as single-pole head, CoCr alloy media with a perpendicular anisotropy, and recording media with soft magnetic underlayers [S. Iwasaki and K. Takemura, IEEE Trans. Magn. 11, 1173 (1975); S. Iwasaki and Y. Nakamura, IEEE Trans. Magn. 14, 436 (1978); S. Iwasaki, Y. Nakamura, and K. Ouchi, IEEE Trans. Magn. 15, 1456 (1979)]. Nevertheless, the research on perpendicular recording media has been intense only in the past five years or so. The main reason for the current interest comes from the need to find an alternative technology to get away from the superparamagnetic limit faced by the longitudinal recording. Out of the several recording media materials investigated in the past, oxide based CoCrPt media have been considered a blessing. The media developed with CoCrPt-oxide or CoCrPt -SiO2 have shown much smaller grain sizes, lower noise, and larger thermal stability than the perpendicular recording media of the past, which is one of the reasons for the success of perpendicular recording. Moreover, oxide-based perpendicular media have also overtaken the current longitudinal recording media in terms of better recording performance. Several issues that were faced with the soft underlayers have also been solved by the use of antiferromagnetically coupled soft underlayers and soft underlayers that are exchange coupled with an antiferromagnetic layer. Significant improvements have also been made in the head design. All these factors now make perpendicular recording more competitive. It is expected that the current materials could theoretically support areal densities of up to 500-600Gbits/in.2. In this paper, the technologies associated with perpendicular recording media are reviewed. A brief background of magnetic recording and the challenges faced by longitudinal recording technology are presented first, followed by the discussions on perpendicular recording media. Detailed discussions on various layers in the perpendicular recording media and the recent advances in these layers have been made. Some of the future technologies that might help the industry beyond the conventional perpendicular recording technology are discussed at the end of the paper.

Speciation of hexavalent chromium in welding fumes interference by air oxidation of chromium.

PubMed

Zatka, V J

1985-06-01

The determination of various chromium species in welding fume normally involves digestion in a hot alkaline solution. This work confirms that Cr(III) can be oxidized to Cr(VI) during this digestion. However, only dissolved forms of Cr(III), such as the hydroxochromate(III) ion, [Cr(OH)4], are susceptible to oxidation under these conditions. The air oxidation of Cr(III) can be prevented by hydrolytic destabilization of the hydroxochromate(III) complex by the presence of magnesium hydroxide precipitate. The procedure has been used successfully in the determination of insoluble chromium(VI) in welding fumes. Excellent reproducibility is documented for soluble and insoluble chromium(VI) fractions in the analysis of a bulk sample of welding fume.

Zinc-aluminum oxide solid solution nanosheets obtained by pyrolysis of layered double hydroxide as the photoanodes for dye-sensitized solar cells.

PubMed

Xu, Zhiyuan; Shi, Jingjing; Haroone, Muhammad Sohail; Chen, Wenpeng; Zheng, Shufang; Lu, Jun

2018-04-01

Due to the superiority of metal-doped ZnO compared to TiO 2 , the Zn-M (M = Al 3+ , Ga 3+ , Cr 3+ , Ti 4+ , Ce 4+ ) mixed metal oxide solid solutions have been extensively studied for photocatalytic and photovoltaic applications. In this work, a systematic research has proceeded for the preparation of a zinc-aluminum oxide semiconductor as a photoanode for the dye-sensitized solar cells (DSSCs) by a simple pyrolysis route with the Zn-Al layered double hydroxide (LDH) as a precursor. The Zn-Al oxide solid solution has been applied for DSSCs as an electron acceptor, which is used to study the influence of different Al content and sintering temperature on the device efficiency. Finally, the Zn-Al oxide solid solution with calcination temperature 600 °C and Al 27 at.% content exhibits the best performance. The photoelectric efficiency improved 100 times when the Al 3+ content decreased from 44 to 27 at.%. The Zn x Al y O solid solution show a reasonable efficiency as photoanode materials in DSSCs, with the best preliminary performance reported so far, and shows its potential application for the photovoltaic devices. Copyright © 2018 Elsevier Inc. All rights reserved.

Development of RF sputtered chromium oxide coating for wear application

NASA Technical Reports Server (NTRS)

Bhushan, B.

1979-01-01

The radio frequency sputtering technique was used to deposite a hard refractory, chromium oxide coating on an Inconel X-750 foil 0.1 mm thick. Optimized sputtering parameters for a smooth and adherent coating were found to be as follows: target-to-substrate spacing, 41.3 mm; argon pressure, 5-10 mTorr; total power to the sputtering module, 400 W (voltage at the target, 1600 V), and a water-cooled substrate. The coating on the annealed foil was more adherent than that on the heat-treated foil. Substrate biasing during the sputter deposition of Cr2O3 adversely affected adherence by removing naturally occurring interfacial oxide layers. The deposited coatings were amorphous and oxygen deficient. Since amorphous materials are extremely hard, the structure was considered to be desirable.

Distinct GABAergic targets of feedforward and feedback connections between lower and higher areas of rat visual cortex.

PubMed

Gonchar, Yuri; Burkhalter, Andreas

2003-11-26

Processing of visual information is performed in different cortical areas that are interconnected by feedforward (FF) and feedback (FB) pathways. Although FF and FB inputs are excitatory, their influences on pyramidal neurons also depend on the outputs of GABAergic neurons, which receive FF and FB inputs. Rat visual cortex contains at least three different families of GABAergic neurons that express parvalbumin (PV), calretinin (CR), and somatostatin (SOM) (Gonchar and Burkhalter, 1997). To examine whether pathway-specific inhibition (Shao and Burkhalter, 1996) is attributable to distinct connections with GABAergic neurons, we traced FF and FB inputs to PV, CR, and SOM neurons in layers 1-2/3 of area 17 and the secondary lateromedial area in rat visual cortex. We found that in layer 2/3 maximally 2% of FF and FB inputs go to CR and SOM neurons. This contrasts with 12-13% of FF and FB inputs onto layer 2/3 PV neurons. Unlike inputs to layer 2/3, connections to layer 1, which contains CR but lacks SOM and PV somata, are pathway-specific: 21% of FB inputs go to CR neurons, whereas FF inputs to layer 1 and its CR neurons are absent. These findings suggest that FF and FB influences on layer 2/3 pyramidal neurons mainly involve disynaptic connections via PV neurons that control the spike outputs to axons and proximal dendrites. Unlike FF input, FB input in addition makes a disynaptic link via CR neurons, which may influence the excitability of distal pyramidal cell dendrites in layer 1.

Crack Free Tungsten Carbide Reinforced Ni(Cr) Layers obtained by Laser Cladding

NASA Astrophysics Data System (ADS)

Amado, J. M.; Tobar, M. J.; Yáñez, A.; Amigó, V.; Candel, J. J.

The development of hardfacing coatings has become technologically significant in many industries A common approach is the production of metal matrix composites (MMC) layers. In this work NiCr-WC MMC hardfacing layers are deposited on C25 steel by means of laser cladding. Spheroidal fused tungsten carbides is used as reinforcement phase. Three different NiCr alloys with different Cr content were tested. Optimum conditions to obtain dense, uniform carbide distribution and hardness close to nominal values were defined. The effect of Cr content respect to the microstructure, susceptibility for cracking and the wear rate of the resulting coating will also be discussed.

LaNi0.6Co0 4O3-δ dip-coated on Fe-Cr mesh as a composite cathode contact material on intermediate solid oxide fuel cells

NASA Astrophysics Data System (ADS)

Morán-Ruiz, Aroa; Vidal, Karmele; Larrañaga, Aitor; Laguna-Bercero, Miguel Angel; Porras-Vázquez, Jose Manuel; Slater, Peter Raymond; Arriortua, María Isabel

2014-12-01

The feasibility of using Crofer22APU mesh dip coated with LaNi0.6Co0.4O3-δ (LNC) ceramic paste as a uniform contact layer on a Crofer22APU channeled interconnect was studied. The control of LNC dip coating thickness on Fe-Cr mesh was carried out by rheological measurements of the suspension. SEM cross-section of formed composite contact material showed good adherence between ceramic and metallic components. The measured area specific resistance (ASR) value at 800 °C was 0.46 ± 0.01 mΩ cm2, indicating low contact resistance itself. The long term stability of metallic/ceramic composite was also studied. The contact resistance, when composite contact material was adhered to channeled Crofer22APU interconnect, was 5.40 ± 0.01 mΩ cm2, which is a suitable value for the performance of IT-SOFC stack. The stability of the system after treating at 800 °C for 1000 h was characterized using X-ray Micro-Diffraction (XRMD), Scanning Electron Microscope equipped with an Energy Dispersive X-ray analyzer (SEM-EDX) and X-ray Photoelectron Spectroscopy (XPS) techniques. The oxidation rate of the alloy and Fe3O4 phase formation were enhanced on the channels of the interconnect. Thus, the formation of CrO3 (g) and CrO2(OH)2 (g) species was accelerated on the composite surface under the channel. Through XRMD and XPS analysis the coexistence of two perovskite phases (initial LNC and Cr-perovskite) was observed.

Synthesis and characterization of Cd Cr and Zn Cd Cr layered double hydroxides intercalated with dodecyl sulfate

NASA Astrophysics Data System (ADS)

Guo, Ying; Zhang, He; Zhao, Lan; Li, Guo-Dong; Chen, Jie-Sheng; Xu, Lin

2005-06-01

Cd-Cr and Zn-Cd-Cr layered double hydroxides (CdCr-LDH and ZnCdCr-LDH) containing alkyl sulfate as the interlamellar anion have been prepared through a coprecipitation technique. The resulting compounds were characterized using X-ray diffraction, infrared spectroscopy, thermogravimetric analysis, and scanning electron microscopy. Magnetic property measurements indicate that antiferromagnetic interactions occur between the chromium ions in the two compounds at low temperatures. The introduction of zinc influences the ligand field of Cr III and the Cr III-Cr III interactions in the LDH compound. It is found that both CdCr-LDH and ZnCdCr-LDH can be delaminated by dispersion in formamide, leading to translucent and stable colloidal solutions.

Multiscale model of metal alloy oxidation at grain boundaries

NASA Astrophysics Data System (ADS)

Sushko, Maria L.; Alexandrov, Vitaly; Schreiber, Daniel K.; Rosso, Kevin M.; Bruemmer, Stephen M.

2015-06-01

High temperature intergranular oxidation and corrosion of metal alloys is one of the primary causes of materials degradation in nuclear systems. In order to gain insights into grain boundary oxidation processes, a mesoscale metal alloy oxidation model is established by combining quantum Density Functional Theory (DFT) and mesoscopic Poisson-Nernst-Planck/classical DFT with predictions focused on Ni alloyed with either Cr or Al. Analysis of species and fluxes at steady-state conditions indicates that the oxidation process involves vacancy-mediated transport of Ni and the minor alloying element to the oxidation front and the formation of stable metal oxides. The simulations further demonstrate that the mechanism of oxidation for Ni-5Cr and Ni-4Al is qualitatively different. Intergranular oxidation of Ni-5Cr involves the selective oxidation of the minor element and not matrix Ni, due to slower diffusion of Ni relative to Cr in the alloy and due to the significantly smaller energy gain upon the formation of nickel oxide compared to that of Cr2O3. This essentially one-component oxidation process results in continuous oxide formation and a monotonic Cr vacancy distribution ahead of the oxidation front, peaking at alloy/oxide interface. In contrast, Ni and Al are both oxidized in Ni-4Al forming a mixed spinel NiAl2O4. Different diffusivities of Ni and Al give rise to a complex elemental distribution in the vicinity of the oxidation front. Slower diffusing Ni accumulates in the oxide and metal within 3 nm of the interface, while Al penetrates deeper into the oxide phase. Ni and Al are both depleted from the region 3-10 nm ahead of the oxidation front creating voids. The oxide microstructure is also different. Cr2O3 has a plate-like structure with 1.2-1.7 nm wide pores running along the grain boundary, while NiAl2O4 has 1.5 nm wide pores in the direction parallel to the grain boundary and 0.6 nm pores in the perpendicular direction providing an additional pathway for oxygen diffusion through the oxide. The proposed theoretical methodology provides a framework for modeling metal alloy oxidation processes from first principles and on the experimentally relevant length scales.

Multiscale model of metal alloy oxidation at grain boundaries

DOE Office of Scientific and Technical Information (OSTI.GOV)

Sushko, Maria L., E-mail: maria.sushko@pnnl.gov; Alexandrov, Vitaly; Schreiber, Daniel K.

2015-06-07

High temperature intergranular oxidation and corrosion of metal alloys is one of the primary causes of materials degradation in nuclear systems. In order to gain insights into grain boundary oxidation processes, a mesoscale metal alloy oxidation model is established by combining quantum Density Functional Theory (DFT) and mesoscopic Poisson-Nernst-Planck/classical DFT with predictions focused on Ni alloyed with either Cr or Al. Analysis of species and fluxes at steady-state conditions indicates that the oxidation process involves vacancy-mediated transport of Ni and the minor alloying element to the oxidation front and the formation of stable metal oxides. The simulations further demonstrate thatmore » the mechanism of oxidation for Ni-5Cr and Ni-4Al is qualitatively different. Intergranular oxidation of Ni-5Cr involves the selective oxidation of the minor element and not matrix Ni, due to slower diffusion of Ni relative to Cr in the alloy and due to the significantly smaller energy gain upon the formation of nickel oxide compared to that of Cr{sub 2}O{sub 3}. This essentially one-component oxidation process results in continuous oxide formation and a monotonic Cr vacancy distribution ahead of the oxidation front, peaking at alloy/oxide interface. In contrast, Ni and Al are both oxidized in Ni-4Al forming a mixed spinel NiAl{sub 2}O{sub 4}. Different diffusivities of Ni and Al give rise to a complex elemental distribution in the vicinity of the oxidation front. Slower diffusing Ni accumulates in the oxide and metal within 3 nm of the interface, while Al penetrates deeper into the oxide phase. Ni and Al are both depleted from the region 3–10 nm ahead of the oxidation front creating voids. The oxide microstructure is also different. Cr{sub 2}O{sub 3} has a plate-like structure with 1.2–1.7 nm wide pores running along the grain boundary, while NiAl{sub 2}O{sub 4} has 1.5 nm wide pores in the direction parallel to the grain boundary and 0.6 nm pores in the perpendicular direction providing an additional pathway for oxygen diffusion through the oxide. The proposed theoretical methodology provides a framework for modeling metal alloy oxidation processes from first principles and on the experimentally relevant length scales.« less

Biological versus mineralogical chromium reduction: potential for reoxidation by manganese oxide.

PubMed

Butler, Elizabeth C; Chen, Lixia; Hansel, Colleen M; Krumholz, Lee R; Elwood Madden, Andrew S; Lan, Ying

2015-11-01

Hexavalent chromium (Cr(vi), present predominantly as CrO4(2-) in water at neutral pH) is a common ground water pollutant, and reductive immobilization is a frequent remediation alternative. The Cr(iii) that forms upon microbial or abiotic reduction often co-precipitates with naturally present or added iron (Fe), and the stability of the resulting Fe-Cr precipitate is a function of its mineral properties. In this study, Fe-Cr solids were formed by microbial Cr(vi) reduction using Desulfovibrio vulgaris strain RCH1 in the presence of the Fe-bearing minerals hematite, aluminum substituted goethite (Al-goethite), and nontronite (NAu-2, Clay Minerals Society), or by abiotic Cr(vi) reduction by dithionite reduced NAu-2 or iron sulfide (FeS). The properties of the resulting Fe-Cr solids and their behavior upon exposure to the oxidant manganese (Mn) oxide (birnessite) differed significantly. In microcosms containing strain RCH1 and hematite or Al-goethite, there was significant initial loss of Cr(vi) in a pattern consistent with adsorption, and significant Cr(vi) was found in the resulting solids. The solid formed when Cr(vi) was reduced by FeS contained a high proportion of Cr(iii) and was poorly crystalline. In microcosms with strain RCH1 and hematite, Cr precipitates appeared to be concentrated in organic biofilms. Reaction between birnessite and the abiotically formed Cr(iii) solids led to production of significant dissolved Cr(vi) compared to the no-birnessite controls. This pattern was not observed in the solids generated by microbial Cr(vi) reduction, possibly due to re-reduction of any Cr(vi) generated upon oxidation by birnessite by active bacteria or microbial enzymes. The results of this study suggest that Fe-Cr precipitates formed in groundwater remediation may remain stable only in the presence of active anaerobic microbial reduction. If exposed to environmentally common Mn oxides such as birnessite in the absence of microbial activity, there is the potential for rapid (re)formation of dissolved Cr(vi) above regulatory levels.

Two-Dimensional Superconductivity Emerged at Monatomic Bi(2-) Square Net in Layered Y2O2Bi via Oxygen Incorporation.

PubMed

Sei, Ryosuke; Kitani, Suguru; Fukumura, Tomoteru; Kawaji, Hitoshi; Hasegawa, Tetsuya

2016-09-07

Discovery of layered superconductors such as cuprates and iron-based compounds has unveiled new science and compounds. In these superconductors, quasi-two-dimensional layers including transition metal cations play principal role in the superconductivity via carrier doping by means of aliovalent-ion substitution. Here, we report on a two-dimensional superconductivity at 2 K in ThCr2Si2-type layered oxide Y2O2Bi possessing conducting monatomic Bi(2-) square net, possibly associated with an exotic superconductivity. The superconductivity emerges only in excessively oxygen-incorporated Y2O2Bi with expanded inter-net distance, in stark contrast to nonsuperconducting pristine Y2O2Bi reported previously. This result suggests that the element incorporation into hidden interstitial site could be an alternative approach to conventional substitution and intercalation methods for search of novel superconductors.

Alloy composition effects on oxidation products of VIA, B-1900, 713C, and 738X: A high temperature diffractometer study

NASA Technical Reports Server (NTRS)

Garlick, R. G.; Lowell, C.

1973-01-01

High temperature X-ray diffraction studies were performed to investigate isothermal and cyclic oxidation at 1000 and 1100 C of the nickel-base superalloys VIA, B-1900, 713C, and 738X. Oxidation was complex. The major oxides, Al2O3, Cr2O3, and the spinels, formed in amounts consistent with alloy chemistry. The alloys VIA and B-1900 (high Al, low Cr alloys) tended to form Al2O3 and NiAl2O4; 738X (high Cr, low Al) formed Cr2O3 and NiCr2O4. A NiTa2O6 type of oxide formed in amounts approximately proportional to the refractory metal content of the alloy. One of the effects of cycling was to increase the amount of spinels formed.

The High-Temperature Wear and Oxidation Behavior of CrC-Based HVOF Coatings

NASA Astrophysics Data System (ADS)

Houdková, Šárka; Česánek, Zdeněk; Smazalová, Eva; Lukáč, František

2018-01-01

Three commercially available chromium carbide-based powders with different kinds of matrix (Cr3C2-25%NiCr; Cr3C2-25%CoNiCrAlY and Cr3C2-50%NiCrMoNb) were deposited by an HVOF JP-5000 spraying gun, evaluated and compared. The influence of heat treatment on the microstructure and properties, as well as the oxidation resistance in a hot steam environment ( p = 24 MPa; T = 609 °C), was evaluated by SEM and XRD with respect to their potential application in the steam power industry. The sliding wear resistance measured at room and elevated ( T = 600 °C) temperatures according to ASTM G-133. For all three kinds of chromium carbide-based coatings, the precipitation of secondary carbides from the supersaturated matrix was observed during the heat treatment. For Cr3C2-25%NiCr coating annealed in hot steam environment as well as for Cr3C2-25%CoNiCrAlY coating in both environments, the inner carbide oxidation was recorded. The sliding wear resistance was found equal at room temperature, regardless of the matrix composition and content, while at elevated temperatures, the higher wear was measured, varying in dependence on the matrix composition and content. The chromium carbide-based coating with modified matrix composition Cr3C2-50%NiCrMoNb is suitable to replace the Cr3C2-25%NiCr coating in a hot steam environment to eliminate the risk of failure caused by inner carbide oxidation.

Oxidation of Cr(III)-Fe(III) Mixed-phase Hydroxides by Chlorine: Implications on the Control of Hexavalent Chromium in Drinking Water.

PubMed

Chebeir, Michelle; Liu, Haizhou

2018-05-17

The occurrence of chromium (Cr) as an inorganic contaminant in drinking water is widely reported. One source of Cr is its accumulation in iron-containing corrosion scales of drinking water distribution systems as Cr(III)-Fe(III) hydroxide, i.e., FexCr(1-x)(OH)3(s), where x represents the Fe(III) molar content and typically varies between 0.25 and 0.75. This study investigated the kinetics of inadvertent hexavalent chromium Cr(VI) formation via the oxidation of FexCr(1-x)(OH)3(s) by chlorine as a residual disinfectant in drinking water, and examined the impacts of Fe(III) content and drinking water chemical parameters including pH, bromide and bicarbonate on the rate of Cr(VI) formation. Data showed that an increase in Fe(III) molar content resulted in a significant decrease in the stoichiometric Cr(VI) yield and the rate of Cr(VI) formation, mainly due to chlorine decay induced by Fe(III) surface sites. An increase in bicarbonate enhanced the rate of Cr(VI) formation, likely due to the formation of Fe(III)-carbonato surface complexes that slowed down the scavenging reaction with chlorine. The presence of bromide significantly accelerated the oxidation of FexCr(1-x)(OH)3(s) by chlorine, resulting from the catalytic effect of bromide acting as an electron shuttle. A higher solution pH between 6 and 8.5 slowed down the oxidation of Cr(III) by chlorine. These findings suggested that the oxidative conversion of chromium-containing iron corrosion products in drinking water distribution systems can lead to the occurrence of Cr(VI) at the tap, and the abundance of iron, and a careful control of pH, bicarbonate and bromide levels can assist the control of Cr(VI) formation.

Oxidative Weathering of Earth's Surface 3.7 Billion Years ago? - A Chromium Isotope Perspective

NASA Astrophysics Data System (ADS)

Frei, R.; Crowe, S.; Bau, M.; Polat, A.; Fowle, D. A.; Døssing, L. N.

2015-12-01

The Great Oxidation Event signals the first large-scale oxygenation of the atmosphere roughly 2.4 Gyr ago. Geochemical signals diagnostic of oxidative weathering, however, extend as far back as 3.3-2.9 Gyr ago. 3.8-3.7 Gyr old rocks from Isua, Greenland stand as a deep time outpost, recording information on Earth's earliest surface chemistry and the low oxygen primordial biosphere. We find positive Cr isotope values (average δ53Cr = +0.05 +/- 0.10 permil; δ53Cr = (53Cr/52Cr)sample/(53Cr/52Cr)SRM 979 - 1) x 1000, where SRM 979 denotes Standard Reference Material 979 in both the Fe and Si-rich mesobands of 7 compositionally distinct quartz-magnetite and magnesian banded iron formation (BIF) samples collected from the eastern portion of the Isua BIF (Western Greenland). These postively fractioned Cr isotopes, relative to the igneous silicate Earth reservoir, in metamorphosed BIFs from Isua indicate oxidative Cr cycling 3.8-3.7 Gyr ago. We also examined the distribution of U, which is immobile in its reduced state but mobile when it is oxidized. Elevated U/Th ratios (mean U/Th ratio of 0.70 ± 0.29) in these BIFs relative to the contemporary crust, also signal oxidative mobilization of U. We suggest that reactive oxygen species (ROS) accumulated in Earth's surface environment inducing the oxidative weathering of rocks during the deposition of the Isua BIFs. The precise threshold atmospheric O2 concentrations for the induction of Cr isotope fractionation remain uncertain, but we argue that our data are consistent with the very low levels of oxygen or other ROS indicated by other proxies. Importantly, any trace of Cr that cycled through redox reactions on land would tend both to be heavy, and to mobilize into the contemporaneous run-off more readily than Cr weathered directly as Cr(III). Once having reached the oceans, this fractionated Cr would have been stripped from seawater by Fe (oxy)hydroxides formed during the deposition of BIFs from low oxygen oceans. The reactive oxygen species recorded in Isua sediments may also have been sufficient to support aerobic metabolisms, which are known to occur in extant bacteria at oxygen concentrations as low as 10-8 atm.

Oxide compounds on Ni-Cr alloys.

PubMed

Baran, G R

1984-11-01

Five Ni-Cr alloys were studied in order to identify the compounds formed on the alloy surface during oxidation under conditions similar to those encountered during dental laboratory procedures prior to application of porcelain. After the alloys were oxidized, the films covering the surfaces were removed with the aid of a Br-methanol solution. X-ray diffraction was used to analyze the compounds formed. Oxides of nearly all elements contained by the alloys were found after low-temperature (650 degrees C) oxidation, while NiO and particularly Cr2O3 were predominant after oxidation at high temperatures (1000 degrees C).

Effect of Alloying Additions on Oxidation Behaviors of Ni-Fe Based Superalloy for Ultra-Supercritical Boiler Applications

NASA Astrophysics Data System (ADS)

Lu, Jintao; Yang, Zhen; Zhao, Xinbao; Yan, Jingbo; Gu, Y.

A new kind of Ni-Fe-based superalloy is designed recently for 750 °C-class A-USC boiler tube. The oxidation behavior of the designed alloys with various combinations of anti-oxidation additions, Cr, Al and Si, was investigated at 750 °C and 850 °C, respectively. The results indicated that the oxidation rate of tested alloys decreased with the increase of the sum of additions. Cr addition may drop the relative constant of parabolic rate greatly when temperature is raised. But the oxide scale, mainly consisted of NiCr spinel at 750 °C and NiCrMn spinel at 850 °C, was similar while the Cr content is in a range of 20-25 wt.% at tested temperatures. Al addition, however, showed the best effective to reduce the oxidation rates. Internal Al-rich oxide was observed at the scale/metal interface for alloys added with high content of Al and was increased with Al content increase. Very tiny difference between the oxide scales of the Si-added alloys was identified when Si content varies among 0.02-0.05 wt.%. Basing on these results, this presentation discussed the optimum combination of anti-oxidation additions as well as oxidation mechanisms in the designed Ni-Fe-base superalloy.

Cyclic oxidation behavior of plasma sprayed NiCrAlY/WC-Co/cenosphere coating

NASA Astrophysics Data System (ADS)

Mathapati, Mahantayya; Ramesh M., R.; Doddamani, Mrityunjay

2018-04-01

Components working at elevated temperature like boiler tubes of coal and gas fired power generation plants, blades of gas and steam turbines etc. experience degradation owing to oxidation. Oxidation resistance of such components can be increased by developing protective coatings. In the present investigation NiCrAlY-WC-Co/Cenosphere coating is deposited on MDN 321 steel substrate using plasma spray coating. Thermo cyclic oxidation behavior of coating and substrate is studied in static air at 600 °C for 20 cycles. The thermo gravimetric technique is used to approximate the kinetics of oxidation. X-Ray Diffraction (XRD), Scanning Electron Microscope (SEM), Energy Dispersive Spectroscopy (EDS) and X-ray mapping techniques are used to characterize the oxidized samples. NiCrAlY-WC-Co/Cenosphere coating exhibited lower oxidation rate in comparison to MDN 321 steel substrate. The lower oxidation rate of coating is attributed to formation of Al2O3, Cr2O3, NiO and CoWO4 oxides on the outermost surface.

Chromium uptake and consequences for metabolism and oxidative stress in chamomile plants.

PubMed

Kováčik, Jozef; Babula, Petr; Klejdus, Bořivoj; Hedbavny, Josef

2013-08-21

Chromium Cr(III) toxicity toward chamomile metabolism and oxidative stress-related parameters after 7 days of exposure was studied. Cr preferentially accumulated in the roots and evoked extensive both dose-dependent and dose-independent increase in fluorescence signals of ROS, NO and thiols. Superoxide increased mainly at the highest Cr dose, whereas H2O2 accumulation revealed a discontinuous trend in relation to external Cr supply, and this could be owing to variation in activities of peroxidases. Glutathione and ascorbate quantification, using LC-MS/MS equipment, revealed strong stimulation despite low shoot Cr amounts. Phenolic enzyme activities, except for PAL, were depressed by Cr presence, whereas phenolic metabolites were stimulated, indicating various time dynamics. Among free amino acids, their sum and even proline decreased in the roots, whereas soluble proteins increased. Mineral nutrients showed negligible responses with only Zn and Cu being depleted in both shoots and roots. Cr staining using Cr(III)-specific (naphthalimide-rhodamine) and metal nonspecific (Phen Green) dyes indicated that the former correlated well with AAS quantification of Cr amount. Use of Phen Green is also discussed. These data indicate that Cr-induced oxidative stress is not simply a function of exposure time and applied concentration. Microscopic observations in terms of oxidative stress and chromium uptake are presented here for the first time.

Oxidation in oxygen at 900 deg and 1000 deg C of four nickel-base cast superalloys: NASA-TRW VIA, B-1900, alloy 713C, and IN-738

NASA Technical Reports Server (NTRS)

Fryburg, G. C.; Kohl, F. J.; Stearns, C. A.

1977-01-01

The oxidation at 900 and 1,000 C of four nickel-base superalloys in 1 atmosphere of slowly flowing oxygen was investigated. Thermogravimetric rate data were obtained for periods to 100 hours. The morphology and composition of the oxide scales formed after 100 hours were studied by optical microscopy, X-ray diffraction, electron microprobe, scanning electron microscopy, and X-ray photoelectron spectroscopy (ESCA). Alloys B-1900 and VIA were found to be primarily alumina formers, though probably 25 percent of their surface was covered by CR2O3-containing oxides at 900 C. Alloys 713C and IN-738 were primarily chromia formers, though the surface of 713C at 1,000 C was covered with NiO, and the surface of IN-738 at both temperatures was covered with a thin layer of TiO2.

Reduction-oxidation Enabled Glass-ceramics to Stainless Steel Bonding Part II interfacial bonding analysis

DOE Office of Scientific and Technical Information (OSTI.GOV)

Dai, Steve Xunhu

2015-09-01

Among glass-ceramic compositions modified with a variety of oxidants (AgO, FeO, NiO, PbO, SnO, CuO, CoO, MoO 3 and WO 3) only CuO and CoO doped glass-ceramics showed existence of bonding oxides through reduction-oxidation (redox) at the GC-SS interface. The CuO-modified glass-ceramics demonstrate the formation of a continuous layer of strong bonding Cr 2O 3 at the interface in low partial oxygen (PO 2) atmosphere. However, in a local reducing atmosphere, the CuO is preferentially reduced at the surface of glass-ceramic rather than the GC-SS interface for redox. The CoO-modified glass-ceramics demonstrate improved GC-SS bonding. But the low mobility ofmore » Co ++ ions in the GC limited the amount of CoO that can diffuse to and participate in redox at the interface.« less

Capabilities to improve corrosion resistance of fuel claddings by using powerful laser and plasma sources

NASA Astrophysics Data System (ADS)

Borisov, V. M.; Trofimov, V. N.; Sapozhkov, A. Yu.; Kuzmenko, V. A.; Mikhaylov, V. B.; Cherkovets, V. Ye.; Yakushkin, A. A.; Yakushin, V. L.; Dzhumayev, P. S.

2016-12-01

The treatment conditions of fuel claddings of the E110 alloy by using powerful UV or IR laser radiation, which lead to the increase in the corrosion resistance at the high-temperature ( T = 1100°C) oxidation simulating a loss-of-coolant accident, are determined. The possibility of the complete suppression of corrosion under these conditions by using pulsed laser deposition of a Cr layer is demonstrated. The behavior of protective coatings of Al, Al2O3, and Cr planted on steel EP823 by pulsed laser deposition, which is planned to be used in the BREST-OD-300, is studied. The methods of the almost complete suppression of corrosion in liquid lead to the temperature of 720°C are shown.

Thermal barrier coating life and isothermal oxidation of low-pressure plasma-sprayed bond coat alloys

NASA Technical Reports Server (NTRS)

Brindley, W. J.; Miller, R. A.

1990-01-01

The paper investigates the isothermal oxidation kinetics of Ni-35Cr-6Al-0.95Y, Ni-18Cr-12Al-0.3Y, and Ni-16Cr-6Al-0.3Y low-pressure plasma-sprayed bond coat alloys and examines the effect of these alloys on the thermal barrier coating (TBC) cyclic life. TBC life was examined by cycling substrates coated with the different bond coats and a ZrO2-7 wt pct Y2O3 TBC in an air-rich burner rig flame between 1150 C and room temperature. The oxidation kinetics of the three bond coat alloys was examined by isothermal oxidation of monolithic NJiCrAlY coupons at 1083 C. The Ni-35Cr-6Al-0.95Y alloy exhibits comparatively high isothermal oxidation weight gains and provides the longest TBC life, whereas the Ni-16Cr-6Al-0.3Y alloy had the lowest weight gains and provided the shortest TBC life. The results show that, although bond coat oxidation is known to have a strong detrimental effect on TBC life, it is not the only bond coat factor that determines TBC life.

Investigation of high temperature corrosion behavior on 304L austenite stainless steel in corrosive environments

DOE Office of Scientific and Technical Information (OSTI.GOV)

Sahri, M. I.; Othman, N. K.; Samsu, Z.

2014-09-03

In this work, 304L stainless steel samples were exposed at 700 °C for 10hrs in different corrosive environments; dry oxygen, molten salt, and molten salt + dry oxygen. The corrosion behavior of samples was analyzed using weight change measurement technique, optical microscope (OM) and Scanning Electron Microscope (SEM) equipped with Energy Dispersive X-ray (EDX). The existence phases of corroded sample were determined using X-ray Diffraction (XRD). The lowest corrosion rate was recorded in dry oxygen while the highest was in molten salt + dry oxygen environments with the value of 0.0062 mg/cm{sup 2} and −13.5225 mg/cm{sup 2} respectively. The surfacemore » morphology of sample in presence of salt mixture showed scale spallation. Oxide scales of Fe{sub 3}O{sub 4}, Fe{sub 2}O{sub 3} were the main phases developed and detected by XRD technique. Cr{sub 2}O{sub 3} was not developed in every sample as protective layers but chromate-rich oxide was developed. The cross-section analysis found the oxide scales were in porous, thick and non-adherent that would not an effective barrier to prevent from further degradation of alloy. EDX analysis also showed the Cr-element was low compared to Fe-element at the oxide scale region.« less

Chromium in urban sediment particulates: an integrated micro-chemical and XANES study

NASA Astrophysics Data System (ADS)

Taylor, Kevin; Byrne, Patrick; Hudson-Edwards, Karen

2015-04-01

Chromium is generally common within the urban sediment cascade as a result of abundant industrial and transport-related sources. The risks that Cr-bearing particles pose to ecosystems and humans depend on the solid phase chemical speciation of Cr in the particles. In this study, we use bulk chemical digests, sequential chemical extraction analysis, electron microscopy, electron microprobe and microfocus XANES analysis to describe the solid-phase speciation of Cr in urban particulate matter from both aquatic sediment and road dust sediment (RDS) in Manchester, UK. Cr-bearing grains within RDS are predominantly iron oxide grains, commonly of goethite or haematite mineralogy, but Cr-bearing silicate glass grains are also present. Iron oxide glass grains most likely have sorbed Cr, and derive from the rusting of Cr-steel particles from vehicles. Electron microprobe analysis indicates concentrations of Cr up to 3200 μg/g in these grains, and XANES analysis indicates that Cr(III) is the dominant oxidation state, with some trace amounts of Cr(VI). Cr-bearing grains within aquatic sediments are dominated by alumino-silicate glass grains derived from industrial waste. These grains contain Cr-rich areas with up to 19% Cr2O3 and XANES analysis indicates that Cr is present as Cr(III). The dominance of Cr(III) in these urban particulate grains suggests limited bioavailability or toxicity. However, the presence within two markedly different grain types (iron oxides and silicate glasses) indicates that the long-term geochemical behaviour and environmental risk of RDS and the aquatic sediments studied are likely to be quite different. These findings highlight the importance of understanding sources of metal contaminants in urban environments and the geochemical processes that affect their transfer through the urban sediment cascade and the wider river basin.

Formation of freestanding ZrO{sub 2} nanotubes for Cr(VI) removal

DOE Office of Scientific and Technical Information (OSTI.GOV)

Bashirom, Nurulhuda, E-mail: nurulhuda.usm2014@gmail.com; Ye, Beh Chin, E-mail: cyebeh@gmail.com; Razak, Khairunisak Abdul, E-mail: khairunisak@usm.my

2016-07-06

Freestanding ZrO{sub 2} nanotubes (ZNTs) were produced using a simple anodization method in fluorinated ethylene glycol electrolyte containing 1 ml 1 M K{sub 2}CO{sub 3}. The pH of the bath was kept constant at 8. The potassium carbonate (K{sub 2}CO{sub 3}) was added into electrolyte to promote the detachment of anodic ZrO{sub 2} film from the underlying zirconium (Zr) substrate. The poor adherence of ZNTs layer was due to generation of CO{sub 2} gas that was thought to occur between metal|oxide interfaces. The effect of anodization voltages towards the detachment of ZNTs layer was systematically studied at 20 V, 40more » V, 50 V and 60 V for 1 hour. The formation of CO{sub 2} gas is a function of anodization voltage, in which at 60 V, a good anodic film separation seen due to higher formation of CO{sub 2} gas. A preliminary study shown the capability of ZNTs in removing 5 ppm of Cr(VI) aqueous solution under illumination of UV light.« less

Electric field control of ferromagnetism at room temperature in GaCrN (p-i-n) device structures

NASA Astrophysics Data System (ADS)

El-Masry, N. A.; Zavada, J. M.; Reynolds, J. G.; Reynolds, C. L.; Liu, Z.; Bedair, S. M.

2017-08-01

We have demonstrated a room temperature dilute magnetic semiconductor based on GaCrN epitaxial layers grown by metalorganic chemical vapor deposition. Saturation magnetization Ms increased when the GaCrN film is incorporated into a (p-GaN/i-GaCrN/n-GaN) device structure, due to the proximity of mediated holes present in the p-GaN layer. Zero field cooling and field cooling were measured to ascertain the absence of superparamagnetic behavior in the films. A (p-GaN/i-GaCrN/n-GaN) device structure with room temperature ferromagnetic (FM) properties that can be controlled by an external applied voltage has been fabricated. In this work, we show that the applied voltage controls the ferromagnetic properties, by biasing the (p-i-n) structure. With forward bias, ferromagnetism in the GaCrN layer was increased nearly 4 fold of the original value. Such an enhancement is due to carrier injection of holes into the Cr deep level present in the i-GaCrN layer. A "memory effect" for the FM behavior of the (p-i-n) GaCrN device structure persisted for 42 h after the voltage bias was turned off. These measurements also support that the observed ferromagnetism in the GaCrN film is not due to superparamagnetic clusters but instead is a hole-mediated phenomenon.

Ambient-temperature NO oxidation over amorphous CrOx-ZrO 2 mixed oxide catalysts: Significant promoting effect of ZrO 2

DOE Office of Scientific and Technical Information (OSTI.GOV)

Wang, Aiyong; Guo, Yanglong; Gao, Feng

2017-03-01

Three series of Cr-based mixed oxides (Cr-Co, Cr-Fe, and Cr-Ni oxides) with high specific surface areas and amorphous textures are synthesized using a novel sol-gel method. These mixed oxides, in comparison to their pure metal oxide (CrOx, Co3O4, FeOx and NiO) counterparts, display enhanced performance for catalytic oxidation of low-concentration NO at room temperature. Over best performing catalysts, 100% NO conversion can be maintained up to 30 h of operation at a high space velocity of 45,000 ml g-1 h-1. The amorphous structure is found to be critical for these catalysts to maintain high activity and durability. Cr/M (M=Co, Femore » and Ni) molar ratio, nitrate precursor decomposition temperature and catalyst calcination temperature are important criteria for the synthesis of the highly active catalysts. This work was supported by National Basic Research Program of China (2013CB933200), National Natural Science Foundation of China (21577035, 21577034), Commission of Science and Technology of Shanghai Municipality (15DZ1205305) and 111 Project (B08021). Aiyong Wang gratefully acknowledges the China Scholarship Council for the Joint-Training Scholarship Program with the Pacific Northwest National Laboratory (PNNL). PNNL is operated for the U.S. Department of Energy (DOE) by Battelle. FG and CHFP are supported by the U.S. DOE/Office of Energy Efficiency and Renewable Energy, Vehicle Technologies Office.« less

Inner-sphere oxidation of ternary iminodiacetatochromium(III) complexes involving DL-valine and L-arginine as secondary ligands. Isokinetic relationship for the oxidation of ternary iminodiacetato-chromium(III) complexes by periodate.

PubMed

Ewais, Hassan A; Dahman, Faris D; Abdel-Khalek, Ahmed A

2009-02-04

In this paper, the kinetics of oxidation of [CrIII(HIDA)(Val)(H2O)2]+ and [CrIII(HIDA)(Arg)(H2O)2]+ (HIDA = iminodiacetic acid, Val = DL-valine and Arg = L-arginine) were studied. The choice of ternary complexes was attributed to two considerations. Firstly, in order to study the effect of the secondary ligands DL-valine and L-arginine on the stability of binary complex [CrIII(HIDA)(IDA)(H2O)] towards oxidation. Secondly, transition metal ternary complexes have received particular focus and have been employed in mapping protein surfaces as probes for biological redox centers and in protein capture for both purification and study. The results have shown that the reaction is first order with respect to both [IO4(-)] and the complex concentration, and the rate increases over the pH range 2.62 - 3.68 in both cases. The experimental rate law is consistent with a mechanism in which both the deprotonated forms of the complexes [CrIII(IDA)(Val)(H2O)2] and [CrIII(IDA)(Arg)(H2O)2] are significantly more reactive than the conjugate acids. The value of the intramolecular electron transfer rate constant for the oxidation of [CrIII(HIDA)(Arg)(H2O)2]+, k3 (1.82 x 10(-3) s(-1)), is greater than the value of k1 (1.22 x 10(-3) s(-1)) for the oxidation of [CrIII(HIDA)(Val)(H2O)2]+ at 45.0 degrees C and I = 0.20 mol dm(-3). It is proposed that electron transfer proceeds through an inner-sphere mechanism via coordination of IO4(-) to chromium(III). The oxidation of [CrIII(HIDA)(Val)(H2O)2]+ and [CrIII(HIDA)(Arg)(H2O)2]+ by periodate may proceed through an inner-sphere mechanism via two electron transfer giving chromium(VI). The value of the intramolecular electron transfer rate constant for the oxidation of [CrIII(HIDA)(Arg)(H2O)2]+, k3, is greater than the value of k1 for the oxidation of [CrIII(HIDA)(Val)(H2O)2]+. A common mechanism for the oxidation of ternary iminodiacetatochromium(III) complexes by periodate is proposed, and this is supported by an excellent isokinetic relationship between DeltaH* and DeltaS* values for these reactions.

Inner-sphere oxidation of ternary iminodiacetatochromium(III) complexes involving DL-valine and L-arginine as secondary ligands. Isokinetic relationship for the oxidation of ternary iminodiacetato-chromium(III) complexes by periodate

PubMed Central

Ewais, Hassan A; Dahman, Faris D; Abdel-Khalek, Ahmed A

2009-01-01

Background In this paper, the kinetics of oxidation of [CrIII(HIDA)(Val)(H2O)2]+ and [CrIII(HIDA)(Arg)(H2O)2]+ (HIDA = iminodiacetic acid, Val = DL-valine and Arg = L-arginine) were studied. The choice of ternary complexes was attributed to two considerations. Firstly, in order to study the effect of the secondary ligands DL-valine and L-arginine on the stability of binary complex [CrIII(HIDA)(IDA)(H2O)] towards oxidation. Secondly, transition metal ternary complexes have received particular focus and have been employed in mapping protein surfaces as probes for biological redox centers and in protein capture for both purification and study. Results The results have shown that the reaction is first order with respect to both [IO4-] and the complex concentration, and the rate increases over the pH range 2.62 – 3.68 in both cases. The experimental rate law is consistent with a mechanism in which both the deprotonated forms of the complexes [CrIII(IDA)(Val)(H2O)2] and [CrIII(IDA)(Arg)(H2O)2] are significantly more reactive than the conjugate acids. The value of the intramolecular electron transfer rate constant for the oxidation of [CrIII(HIDA)(Arg)(H2O)2]+, k3 (1.82 × 10-3 s-1), is greater than the value of k1 (1.22 × 10-3 s-1) for the oxidation of [CrIII(HIDA)(Val)(H2O)2]+ at 45.0°C and I = 0.20 mol dm-3. It is proposed that electron transfer proceeds through an inner-sphere mechanism via coordination of IO4- to chromium(III). Conclusion The oxidation of [CrIII(HIDA)(Val)(H2O)2]+ and [CrIII(HIDA)(Arg)(H2O)2]+ by periodate may proceed through an inner-sphere mechanism via two electron transfer giving chromium(VI). The value of the intramolecular electron transfer rate constant for the oxidation of [CrIII(HIDA)(Arg)(H2O)2]+, k3, is greater than the value of k1 for the oxidation of [CrIII(HIDA)(Val)(H2O)2]+. A common mechanism for the oxidation of ternary iminodiacetatochromium(III) complexes by periodate is proposed, and this is supported by an excellent isokinetic relationship between ΔH* and ΔS* values for these reactions. PMID:19193241

Development of ODS FeCrAl alloys for accident-tolerant fuel cladding

DOE Office of Scientific and Technical Information (OSTI.GOV)

Dryepondt, Sebastien N.; Hoelzer, David T.; Pint, Bruce A.

2015-09-18

FeCrAl alloys are prime candidates for accident-tolerant fuel cladding due to their excellent oxidation resistance up to 1400 C and good mechanical properties at intermediate temperature. Former commercial oxide dispersion strengthened (ODS) FeCrAl alloys such as PM2000 exhibit significantly better tensile strength than wrought FeCrAl alloys, which would alloy for the fabrication of a very thin (~250 m) ODS FeCrAl cladding and limit the neutronic penalty from the replacement of Zr-based alloys by Fe-based alloys. Several Fe-12-Cr-5Al ODS alloys where therefore fabricated by ball milling FeCrAl powders with Y2O3 and additional oxides such as TiO 2 or ZrO 2. Themore » new Fe-12Cr-5Al ODS alloys showed excellent tensile strength up to 800 C but limited ductility. Good oxidation resistance in steam at 1200 and 1400 C was observed except for one ODS FeCrAl alloy containing Ti. Rolling trials were conducted at 300, 600 C and 800 C to simulate the fabrication of thin tube cladding and a plate thickness of ~0.6mm was reached before the formation of multiple edge cracks. Hardness measurements at different stages of the rolling process, before and after annealing for 1h at 1000 C, showed that a thinner plate thickness could likely be achieved by using a multi-step approach combining warm rolling and high temperature annealing. Finally, new Fe-10-12Cr-5.5-6Al-Z gas atomized powders have been purchased to fabricate the second generation of low-Cr ODS FeCrAl alloys. The main goals are to assess the effect of O, C, N and Zr contents on the ODS FeCrAl microstructure and mechanical properties, and to optimize the fabrication process to improve the ductility of the 2nd gen ODS FeCrAl while maintaining good mechanical strength and oxidation resistance.« less

The effect of molten salt on high temperature behavior of stainless steel and titanium alloy with the presence of water vapor

NASA Astrophysics Data System (ADS)

Baharum, Azila; Othman, Norinsan Kamil; Salleh, Emee Marina

2018-04-01

The high temperature oxidation experiment was conducted to study the behavior of titanium alloy Ti6A14V and stainless steel 316 in Na2SO4-50%NaCl + Ar-20%O2 (molten salt) and Na2SO4-50%NaCl + Ar-20%O2 + 12% H2O (molten salt + water vapor) environment at 900°C for 30 hours using horizontal tube furnace. The sample then was investigated using weight change measurement analysis and X-ray diffraction (XRD) analysis to study the weight gained and the phase oxidation that occurred. The weight gained of the titanium alloy was higher in molten salt environment compared to stainless steel due to the rapid growth in the oxide scale but showed almost no change of weight gained upon addition of water vapor. This is due to the alloy was fully oxidized. Stainless steel showed more protection and better effect in molten salt environment compared to mixed environment showed by slower weight gain and lower oxidation rate. Meanwhile, the phase oxidation test of the samples showed that the titanium alloy consist of multi oxide layer of rutile (TiO2) and Al2O3 on the surface of the exposed sample. While stainless steel show the formation of both protective Cr-rich oxide and non-protective Fe-rich oxide layer. This can be concluded that stainless steel is better compared to Ti alloy due to slow growing of chromia oxide. Therefore it is proven that stainless steel has better self-protection upon high temperature exposure.

Ionic Segregation on Grain Boundaries in Thermally Grown Alumina Scales

DOE Office of Scientific and Technical Information (OSTI.GOV)

Pint, Bruce A; Unocic, Kinga A

2012-01-01

This study first examined segregation behaviour in the alumina scale formed after 100 h at 1100 C on bare and MCrAlYHfSi-coated single-crystal superalloys with {approx}10 ppma La and Y. For the bare superalloy, Hf and Ti were detected on the grain boundaries of the inner columnar alumina layer. Increasing the oxidation temperature to 1200 C for 2 h did not change the segregation behavior. With the bond coating, both Y and Hf were segregated to the grain boundaries as expected. However, there was evidence of Ti-rich oxide particles near the gas interface suggesting that Ti diffused from the superalloy throughmore » the coating. To further understand these segregation observations with multiple dopants, other alumina-forming systems were examined. Alumina scale grain boundary co-segregation of Ti with Y is common for FeCrAl alloys. Co-segregation of Hf and Ti was observed in the scale formed on co-doped NiAl. No La segregation was detected in the scale formed on NiCrAl with only a 19 ppma La addition, however, the scale was adherent.« less

The effect of organic compounds in the oxidation kinetics of Cr(III) by H 2O 2

NASA Astrophysics Data System (ADS)

Pettine, Maurizio; Gennari, Francesca; Campanella, Luigi; Millero, Frank J.

2008-12-01

The oxidation of Cr(III) has been studied in NaCl solutions in the presence of two siderophore models, acetohydroxamic acid (Aha) and benzohydroxamic acid (Bha), the natural siderophore Desferal (DFOB) and the synthetic aminocarboxilate (ethylenedinitrilo)-tetra-acetic acid (EDTA) as a function of pH (8-9), ionic strength (0.01-2 M) and temperature (10-50 °C), at different Cr(III)-organic compound ratios. The addition of Aha and Bha caused the rates to increase at low ligand/Cr(III) ratios and decrease at high ratios. The variation of the pseudo first order rate constant ( k1) as a function of the ligand concentration has been attributed to the formation of three Cr(III)-organo species (1:1, 1:2, 1:3), which can form in the presence of monohydroxamic acids. A kinetic model has been developed that gives a value of 600 (min -1) for the pseudo first order rate constant k and values approaching zero for k and k. These kinetic results demonstrate that these monohydroxamic acids are able to bind with Cr(III) under experimental conditions that may occur in natural waters and can increase the oxidation rates of Cr(III) with H 2O 2 by a factor of 3.5 at an Aha/Cr(III) ratio of about 50-100. The monohydroxamic acids also affect the rates on aged products of Cr(III), suggesting that these ligands are able to affect the oxidation rates by releasing reactive Cr(III). DFOB and EDTA do not have a great effect on the oxidation of Cr(III) with H 2O 2. This is thought to be due to the much longer times they need to form complexes with Cr(III) compared to Aha and Bha. The rates for the formation of DFOB and EDTA complexes with Cr(III) are not competitive with the rates of the formation of aged Cr(III). After allowing Cr(III) and DFOB to react for 5 days to form the complex, reaction rates of Cr(III) with H 2O 2 appear to be lowered probably because of steric hindrance of the chelated Cr(III).

Parametric and experimentally informed BWR Severe Accident Analysis Utilizing FeCrAl - M3FT-17OR020205041

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ott, Larry J.; Howell, Michael; Robb, Kevin R.

Iron-chromium-aluminum (FeCrAl) alloys are being considered as advanced fuel cladding concepts with enhanced accident tolerance. At high temperatures, FeCrAl alloys have slower oxidation kinetics and higher strength compared with zirconium-based alloys. FeCrAl could be used for fuel cladding and spacer or mixing vane grids in light water reactors and/or as channel box material in boiling water reactors (BWRs). There is a need to assess the potential gains afforded by the FeCrAl accident-tolerant-fuel (ATF) concept over the existing zirconium-based materials employed today. To accurately assess the response of FeCrAl alloys under severe accident conditions, a number of FeCrAl properties and characteristicsmore » are required. These include thermophysical properties as well as burst characteristics, oxidation kinetics, possible eutectic interactions, and failure temperatures. These properties can vary among different FeCrAl alloys. Oak Ridge National Laboratory has pursued refined values for the oxidation kinetics of the B136Y FeCrAl alloy (Fe-13Cr-6Al wt %). This investigation included oxidation tests with varying heating rates and end-point temperatures in a steam environment. The rate constant for the low-temperature oxidation kinetics was found to be higher than that for the commercial APMT FeCrAl alloy (Fe-21Cr-5Al-3Mo wt %). Compared with APMT, a 5 times higher rate constant best predicted the entire dataset (root mean square deviation). Based on tests following heating rates comparable with those the cladding would experience during a station blackout, the transition to higher oxidation kinetics occurs at approximately 1,500°C. A parametric study varying the low-temperature FeCrAl oxidation kinetics was conducted for a BWR plant using FeCrAl fuel cladding and channel boxes using the MELCOR code. A range of station blackout severe accident scenarios were simulated for a BWR/4 reactor with Mark I containment. Increasing the FeCrAl low-temperature oxidation rate constant (3 times and 10 times that of the rate constant for APMT) had a negligible impact on the early stages of the accident and minor impacts on the accident progression after the first relocation of the fuel. At temperatures below 1,500°C, increasing the rate constant for APMT by a factor of 10 still resulted in only minor FeCrAl oxidation. In general, the gains afforded by the FeCrAl enhanced ATF concept with respect to accident sequence timing and combustible gas generation are consistent with previous efforts. Compared with the traditional Zircaloy-based cladding and channel box system, the FeCrAl concept could provide a few extra hours of time for operators to take mitigating actions and/or for evacuations to take place. A coolable core geometry is retained longer, enhancing the ability to stabilize an accident. For example, a station blackout was simulated in which cooling water injection was lost 36 hours after shutdown. The timing to first fuel relocation was delayed by approximately 5 h for the FeCrAl ATF concept compared with that of the traditional Zircaloy-based cladding and channel box system.« less

Synthesis and study of electronic state of Sr2CrO2Co2As2 with CoAs conduction layers

NASA Astrophysics Data System (ADS)

Suzuki, Atsushi; Ohta, Hiroto; Aruga Katori, Hiroko

2017-06-01

We successfully synthesized a new member of compounds with the CoAs layer, Sr2CrO2Co2As2, and its partially substituted systems Sr2CrO2(Tmx Co1- x )2As2 (Tm = Fe, Ni), and measured magnetization and electric resistivity of these polycrystalline compounds. As a result of magnetic measurement for Sr2CrO2Co2As2, magnetic moments of Co do not construct an itinerant electronic ferromagnetism unlike other compounds with the CoPn (Pn=P and As) layers. Both Sr2CrO2(Tmx Co1- x )2As2 with Tm = Fe and Ni also do not show an itinerant electronic ferromagnetism down to 2 K. For each solid solution of Sr2CrO2(Fe x Co1- x )2As2 with x > 0.0, ρ weakly increases with the decrease of T at low temperature region, indicating that the mixed occupancy of Cr and Fe within the conducting layers occurs in Sr2CrO2(Fe x Co1- x )2As2. We conclude that the absence of ferromagnetism in Sr2CrO2Co2As2 is due to the self-electron-doping from Cr to the conduction bands and the attempt to recover the ferromagnetism by the hole-doping effect is prevented by the mixed occupancy of Cr and Fe in Sr2CrO2 (Fe x Co1- x )2As2 with x > 0.0. The result of our structural analysis supports that the disappearance of itinerant electronic ferromagnetism in Sr2CrO2Co2As2 is due to the self-electron-doping from Cr.

Oxidation products of INCONEL alloys 600 and 690 in pressurized water reactor environments and their role in intergranular stress corrosion cracking

NASA Astrophysics Data System (ADS)

Ferguson, J. B.; Lopez, Hugo F.

2006-08-01

In this work, thermodynamic arguments for the stability of Ni and Cr compounds developed under pressurized water reactor environments ( P_{H_2 O} and P_{H_2 } ) were experimentally tested. A mechanism is proposed to explain crack initiation and propagation alloy 600 along the grain boundaries, where Cr2O3 has formed from the leaching of Cr from the matrix, leaving behind a porous Ni-rich region. The mechanism is based on the thermodynamic potential for the transformation of a protective NiO surface layer into an amorphous nonprotective Ni(OH)2 gel. This gel would also form along the grain boundaries and when hydrogenated steam reaches the porous Ni-rich regions. Crack initiation is then favored by tensile stressing of the grain boundary regions, which can easily rupture the gelatinous film. The leaching of matrix Cr to form nonprotective CrOOH gel at the crack tip followed by the exposure of fresh porous Ni to the environment could explain crack propagation in INCONEL alloy 600. The proposed crack initiation mechanism is not expected to occur in alloy 690 where a protective Cr2O3 film covers the entire metal surface. However, crack propagation along the grain boundaries in alloy 600 and precracked alloy 690 is expected to be active as hydroxide-forming reactions weaken the boundaries.

Preparation of multilayered nanocrystalline thin films with composition-modulated interfaces

NASA Astrophysics Data System (ADS)

Biro, D.; Barna, P. B.; Székely, L.; Geszti, O.; Hattori, T.; Devenyi, A.

2008-06-01

The properties of multilayer thin film structures depend on the morphology and structure of interfaces. A broad interface, in which the composition is varying, can enhance, e.g., the hardness of multilayer thin films. In the present experiments multilayers of TiAlN and CrN as well as TiAlN, CrN and MoS 2 were studied by using unbalanced magnetron sputter sources. The sputter sources were arranged side by side on an arc. This arrangement permits development of a transition zone between the layers, where the composition changes continuously. The multilayer system was deposited by one-fold oscillating movement of substrates in front of sputter sources. Thicknesses of layers could be changed both by oscillation frequency and by the power applied to sputter sources. Ti/Al: 50/50 at%, pure chromium and MoS 2 targets were used in the sputter sources. The depositions were performed in an Ar-N 2 mixture at 0.22 Pa working pressure. The sputtering power of the TiAl source was feed-back adjusted in fuzzy-logic mode in order to avoid fluctuation of the TiAl target sputter rate due to poisoning of the target surface. Structure characterization of films deposited on <1 0 0> Si wafers covered by thermally grown SiO 2 was performed by cross-sectional transmission electron microscopy. At first a 100 nm thick Cr base layer was deposited on the substrate to improve adhesion, which was followed by a CrN transition layer. The CrN transition layer was followed by a 100 nm thick TiAlN/CrN multilayer system. The TiAlN/CrN/MoS 2 multilayer system was deposited on the surface of this underlayer system. The underlayer systems Cr, CrN and TiAlN/CrN were crystalline with columnar structure according to the morphology of zone T of the structure zone models. The column boundaries contained segregated phases showing up in the under-focused TEM images. The surface of the underlayer system was wavy due to dome-shaped columns. The nanometer-scaled TiAlN/CrN/MoS 2 multilayer system followed this waviness. Crystallinity of the TiAlN and CrN layers in the multilayer system decreases with increasing thickness of the MoS 2 layer.

[Research of the surface oxide film on anodizing Ni-Cr porcelain alloy].

PubMed

Zhu, Song; Sun, Hong-Chen; Zhang, Jing-Wei; Li, Zong-Hui

2006-08-01

To study the shape, thickness and oxide percentage of major metal element of oxide film on Ni-Cr porcelain alloy after anodizing pretreatment. 10 samples were made and divided into 2 groups at random. Then after surface pretreatment, the oxide films of two samples of each group were analyzed using electronic scanning microscope. The rest 3 samples were measured by X-ray photoelectron spectroscopy (XPS) and Auger electron spectroscopy (AES). Lightly selective solution appeared because the different component parts of the alloy have dissimilar electrode, whose dissolve velocity were quite unlike. The sample's metal surface expanded, so the mechanical interlocking of porcelain and metal increased bond strength. The thickness of oxide film was 1.72 times of the control samples. The oxide percentage of major metal elements such as Cr, Ni and Mo were higher, especially Cr. It initially involved the formation of a thin oxide bound to the alloy and second, the ability of the formed oxide to saturate the porcelain, completing the chemical bond of porcelain to metal. The method of anodizing Ni-Cr porcelain alloy can easily control the forming of oxide film which was thin and its surface pattern was uniform. It is repeated and a good method of surface pretreatment before firing cycle.

Small angle neutron scattering study of nano sized microstructure in Fe-Cr ODS steels for gen IV in-core applications.

PubMed

Han, Young-Soo; Mao, Xiadong; Jang, Jinsung

2013-11-01

The nano-sized microstructures in Fe-Cr oxide dispersion strengthened steel for Gen IV in-core applications were studied using small angle neutron scattering. The oxide dispersion strengthened steel was manufactured through hot isostatic pressing with various chemical compositions and fabrication conditions. Small angle neutron scattering experiments were performed using a 40 m small angle neutron scattering instrument at HANARO. Nano sized microstructures, namely, yttrium oxides and Cr-oxides were quantitatively analyzed by small angle neutron scattering. The yttrium oxides and Cr-oxides were also observed by transmission electron microscopy. The microstructural analysis results from small angle neutron scattering were compared with those obtained by transmission electron microscopy. The effects of the chemical compositions and fabrication conditions on the microstructure were investigated in relation to the quantitative microstructural analysis results obtained by small angle neutron scattering. The volume fraction of Y-oxide increases after fabrication, and this result is considered to be due to the formation of non-stochiometric Y-Ti-oxides.

Influence of nanovoids on α-α' phase separation in FeCrAl oxide dispersion strengthened alloy

DOE Office of Scientific and Technical Information (OSTI.GOV)

Capdevila, Carlos; Aranda, M. M.; Rememnteria, R.

2015-08-10

The presence of nanovoids in the vicinity of oxide particles in FeCrAl oxide dispersion strengthened (ODS) alloy has been identified. These nanovoids are inherent to the manufacturing route and remain quite resistant during heat treatments. Positron annihilation spectroscopy (PAS) experiments demonstrate that these nanovoids trap Cr inside thereby reducing the Cr-content in the matrix. In conclusion, this might lead to a delay in the α–α' phase separation process as observed by atom probe tomography (APT).

Effect of Specimen Thickness on Microstructural Changes During Oxidation of the NiCrW Alloy 230 at 950–1050°C

DOE PAGES

Jalowicka, A.; Duan, R.; Huczkowski, P.; ...

2015-09-25

An accurate procedure for predicting oxidation-induced damage and lifetime limits is crucial for the reliable operation of high-temperature metallic components in practical applications. In order to develop a predictive oxidation lifetime model for Ni–Cr alloys, specimens of wrought NiCrW alloy 230 with different thicknesses were cyclically oxidized in air at 950–1050°C for up to 3000 h. After prolonged exposure, two types of carbides as well as a Cr-rich nitride (π-phase) precipitated in the γ-Ni matrix. In the case of oxidation-induced loss of Cr from the alloy resulted in the formation of subscale zones, which were free of the Cr-rich carbidemore » and nitride but also of the Ni-W rich M 6C. The width of the M 6C-free zone was smaller than that free of the Cr-rich precipitates. Thermodynamic and diffusion calculations of the observed time- and temperature-dependent Cr depletion processes identified that back diffusion of C occurred which resulted in an increased volume fraction of M 23C 6 in the specimen core. Moreover, with increasing time and temperature, the amount of π-phase in the specimen core increased. The subscale depletion of the initially present Cr-nitrides and the formation of Cr-nitrides in the specimen center is believed to be related to a mechanism which is qualitatively similar to that described for the Cr carbide enrichment. However, with increasing time and decreasing specimen thickness, N uptake from the atmosphere becomes apparent. As a result, the precipitates present in the specimen center eventually consisted almost exclusively of nitrides.« less

Effect of Specimen Thickness on Microstructural Changes During Oxidation of the NiCrW Alloy 230 at 950-1050°C

NASA Astrophysics Data System (ADS)

Jalowicka, A.; Duan, R.; Huczkowski, P.; Chyrkin, A.; Grüner, D.; Pint, B. A.; Unocic, K. A.; Quadakkers, W. J.

2015-11-01

An accurate procedure for predicting oxidation-induced damage and lifetime limits is crucial for the reliable operation of high-temperature metallic components in practical applications. In order to develop a predictive oxidation lifetime model for Ni-Cr alloys, specimens of wrought NiCrW alloy 230 with different thicknesses were cyclically oxidized in air at 950-1050°C for up to 3000 h. After prolonged exposure, two types of carbides as well as a Cr-rich nitride (π-phase) precipitated in the γ-Ni matrix. The oxidation-induced loss of Cr from the alloy resulted in the formation of subscale zones, which were free of the Cr-rich carbide and nitride but also of the Ni-W rich M6C. The width of the M6C-free zone was smaller than that free of the Cr-rich precipitates. Thermodynamic and diffusion calculations of the observed time- and temperature-dependent Cr depletion processes identified that back diffusion of C occurred which resulted in an increased volume fraction of M23C6 in the specimen core. With increasing time and temperature, the amount of π-phase in the specimen core increased. The subscale depletion of the initially present Cr-nitrides and the formation of Cr-nitrides in the specimen center is believed to be related to a mechanism which is qualitatively similar to that described for the Cr carbide enrichment. However, with increasing time and decreasing specimen thickness, N uptake from the atmosphere becomes apparent. As a result, the precipitates present in the specimen center eventually consisted almost exclusively of nitrides.

Reduction of Cr(VI) to Cr(III) by green rust - sulphate

NASA Astrophysics Data System (ADS)

Skovbjerg, L.; Stipp, S.

2003-04-01

Chromium is widely used in industrial processes such as leather tanning, electro-plating and as colour pigments. Unfortunately, hexavalent chromium is both toxic and very soluble so it can be a problem for groundwater resources. Given the right redox conditions, however, Cr(VI) can be reduced to trivalent chromium, which is much less soluble and is an essential trace nutrient. Fe(II), an element common in soil and sediments under anaerobic conditions, can serve as a reducing agent for Cr(VI). Green Rust (GR) is a layered Fe(II),Fe(III)-hydroxide with various anions compensating charge in the interlayers. It is very effective in reducing Cr(VI) to Cr(III). GR exists in nature and is thought to be precursor for the formation of Fe(III)-oxides and oxyhydroxides at the redox boundary. It may be that the formation of GR is a key process in the effectiveness of reactive barriers for groundwater remediation that are based on Fe(0). The purpose of this work is to investigate the mechanisms controlling Cr(VI) reduction by Green Rust, to examine the effect of Cr adsorption and incorporation on GR morphology and composition, and to define the role of parameters such as interlayer anion, initial Cr(VI) concentration and time. We are using freshly synthesised material that has not been dried to avoid structural changes that may accompany dehydration and rehydration. X-Ray Diffraction (XRD) is used to characterise mineral structural changes and Atomic Force Microscopy (AFM), to examine changes in morphology as reactions take place. By adjusting the concentration of Cr(VI), we can control the rate of surface change and we can observe the nanoscale particles directly.

Unusual Oxidative Limitations for Al-MAX Phases

NASA Technical Reports Server (NTRS)

Smialek, James L.

2017-01-01

Alumina-forming MAX phases are well-known for their excellent oxidation resistance, rivaling many metallic NiAl, NiCrAl, and FeCrAl counterparts and with upper temperature capability possible to approximately1400C. However a number of limitations have been emerging that need to be acknowledged to permit robust performance in demanding applications. Ti2AlC and Ti3AlC2 possess excellent scale adhesion, cyclic oxidation/moisture/volatility resistance, and TBC compatibility. However they are very sensitive to Al content and flux in order to maintain an exclusive Al2O3 scale without runaway oxidation of ubiquitous TiO2 transient scales. Accelerated oxidation has been shown to occur for Al-depleted, damaged, or roughened surfaces at temperatures less than 1200C. Conversely, Cr2AlC is less sensitive to transients, but exhibits volatile losses at 1200C or above if common Cr7C3 impurity phases are present. Poor scale adhesion is exhibited after oxidation at 1150C or above, where spallation occurs at the Cr7C3 (depletion zone) interface. Delayed spallation is significant and suggests a moisture-induced phenomenon similar to non-adherent metallic systems. Re-oxidation of this surface does not reproduce the initial pure Al2O3 behavior, but initiates a less-protective scale. Cr2AlC has also been shown to have good long term bonding with superalloys at 800C, but exhibits significant Beta-NiAl + Cr7C3 diffusion zones at 1100C and above. This may set limits on Cr2AlC as a high temperature TBC bond coat on Ni-based superalloys, while improving corrosion resistance in lower temperature applications.

Maintenance of cellular ATP level by caloric restriction correlates chronological survival of budding yeast

DOE Office of Scientific and Technical Information (OSTI.GOV)

Choi, Joon-Seok; Lee, Cheol-Koo, E-mail: cklee2005@korea.ac.kr

Highlights: •CR decreases total ROS and mitochondrial superoxide during the chronological aging. •CR does not affect the levels of oxidative damage on protein and DNA. •CR contributes extension of chronological lifespan by maintenance of ATP level -- Abstract: The free radical theory of aging emphasizes cumulative oxidative damage in the genome and intracellular proteins due to reactive oxygen species (ROS), which is a major cause for aging. Caloric restriction (CR) has been known as a representative treatment that prevents aging; however, its mechanism of action remains elusive. Here, we show that CR extends the chronological lifespan (CLS) of budding yeastmore » by maintaining cellular energy levels. CR reduced the generation of total ROS and mitochondrial superoxide; however, CR did not reduce the oxidative damage in proteins and DNA. Subsequently, calorie-restricted yeast had higher mitochondrial membrane potential (MMP), and it sustained consistent ATP levels during the process of chronological aging. Our results suggest that CR extends the survival of the chronologically aged cells by improving the efficiency of energy metabolism for the maintenance of the ATP level rather than reducing the global oxidative damage of proteins and DNA.« less

Behaviour of F82H mod. stainless steel in lead-bismuth under temperature gradient

NASA Astrophysics Data System (ADS)

Gómez Briceño, D.; Martín Muñoz, F. J.; Soler Crespo, L.; Esteban, F.; Torres, C.

2001-07-01

Austenitic steels can be used in a hybrid system in contact with liquid lead-bismuth eutectic if the region of operating temperatures is not beyond 400°C. For higher temperatures, martensitic steels are recommended. However, at long times, the interaction between the structural material and the eutectic leads to the dissolution of some elements of the steel (Ni, Cr and Fe, mainly) in the liquid metal. In a non-isothermal lead-bismuth loop, the material dissolution takes place at the hot leg of the circuit and, due to the mass transfer, deposition occurs at the cold leg. One of the possible ways to improve the performance of structural materials in lead-bismuth is the creation of an oxide layer. Tests have been performed in a small natural convection loop built of austenitic steel (316L) that has been operating for 3000 h. This loop contains a test area in which several samples of F82Hmod. martensitic steel have been tested at different times. A gas with an oxygen content of 10 ppm was bubbled in the hot area of the circuit during the operation time. The obtained results show that an oxide layer is formed on the samples introduced in the loop at the beginning of the operation and this layer increases with time. However, the samples introduced at different times during the loop operation, are not protected by oxide layers and present material dissolution in some cases.

Quantifying Cr(VI) Production and Export from Serpentine Soil of the California Coast Range

DOE PAGES

McClain, Cynthia N.; Fendorf, Scott; Webb, Samuel M.; ...

2016-11-22

Here, hexavalent chromium (Cr(VI)) is generated in serpentine soils and exported to surface and groundwaters at levels above health-based drinking water standards. Although Cr(VI) concentrations are elevated in serpentine soil pore water, few studies have reported field evidence documenting Cr(VI) production rates and fluxes that govern Cr(VI) transport from soil to water sources. We report Cr speciation (i) in four serpentine soil depth profiles derived from the California Coast Range serpentinite belt and (ii) in local surface waters. Within soils, we detected Cr(VI) in the same horizons where Cr(III)-minerals are colocated with biogenic Mn(III/IV)-oxides, suggesting Cr(VI) generation through oxidation bymore » Mn-oxides. Water-extractable Cr(VI) concentrations increase with depth constituting a 7.8 to 12 kg/km 2 reservoir of Cr(VI) in soil. Here, Cr(VI) is produced at a rate of 0.3 to 4.8 kg Cr(VI)/km 2/yr and subsequently flushed from soil during water infiltration, exporting 0.01 to 3.9 kg Cr(VI)/km 2/yr at concentrations ranging from 25 to 172 μg/L. Although soil-derived Cr(VI) is leached from soil at concentrations exceeding 10 μg/L, due to reduction and dilution during transport to streams, Cr(VI) levels measured in local surface waters largely remain below California’s drinking water limit.« less

Quantifying Cr(VI) Production and Export from Serpentine Soil of the California Coast Range.

PubMed

McClain, Cynthia N; Fendorf, Scott; Webb, Samuel M; Maher, Kate

2017-01-03

Hexavalent chromium (Cr(VI)) is generated in serpentine soils and exported to surface and groundwaters at levels above health-based drinking water standards. Although Cr(VI) concentrations are elevated in serpentine soil pore water, few studies have reported field evidence documenting Cr(VI) production rates and fluxes that govern Cr(VI) transport from soil to water sources. We report Cr speciation (i) in four serpentine soil depth profiles derived from the California Coast Range serpentinite belt and (ii) in local surface waters. Within soils, we detected Cr(VI) in the same horizons where Cr(III)-minerals are colocated with biogenic Mn(III/IV)-oxides, suggesting Cr(VI) generation through oxidation by Mn-oxides. Water-extractable Cr(VI) concentrations increase with depth constituting a 7.8 to 12 kg/km 2 reservoir of Cr(VI) in soil. Here, Cr(VI) is produced at a rate of 0.3 to 4.8 kg Cr(VI)/km 2 /yr and subsequently flushed from soil during water infiltration, exporting 0.01 to 3.9 kg Cr(VI)/km 2 /yr at concentrations ranging from 25 to 172 μg/L. Although soil-derived Cr(VI) is leached from soil at concentrations exceeding 10 μg/L, due to reduction and dilution during transport to streams, Cr(VI) levels measured in local surface waters largely remain below California's drinking water limit.

Steam Oxidation Behavior of Alloy 617 at 900 °C to 1100 °C

NASA Astrophysics Data System (ADS)

Liang, Zhiyuan; Wang, Yungang; Zhao, Qinxin

2018-07-01

The steam oxidation behavior of solid solution strengthened alloy 617 at 900 °C-1100 °C was investigated. The oxidation products were characterized by scanning electron microscopy, X-ray diffraction, and energy-dispersive spectroscopy. The results show that the oxidation kinetics of alloy 617 in steam followed the parabolic oxidation law. The calculated activity energy of alloy 617 was 223.47 kJ/mol. The oxidation products were mainly composed of external and internal scales and prior oxides at grain boundaries. External oxide scales were MnCr2O4, TiO2, and Cr2O3. Internal oxidation scales and prior oxides were Al2O3 and some Cr2O3 dissolved into Al2O3. The growth mechanism of oxide scales on alloy 617 is proposed.

Steam Oxidation Behavior of Alloy 617 at 900 °C to 1100 °C

NASA Astrophysics Data System (ADS)

Liang, Zhiyuan; Wang, Yungang; Zhao, Qinxin

2018-05-01

The steam oxidation behavior of solid solution strengthened alloy 617 at 900 °C-1100 °C was investigated. The oxidation products were characterized by scanning electron microscopy, X-ray diffraction, and energy-dispersive spectroscopy. The results show that the oxidation kinetics of alloy 617 in steam followed the parabolic oxidation law. The calculated activity energy of alloy 617 was 223.47 kJ/mol. The oxidation products were mainly composed of external and internal scales and prior oxides at grain boundaries. External oxide scales were MnCr2O4, TiO2, and Cr2O3. Internal oxidation scales and prior oxides were Al2O3 and some Cr2O3 dissolved into Al2O3. The growth mechanism of oxide scales on alloy 617 is proposed.

Cyclic furnace oxidation of clad WI-52 systems at 1040 C and 1090 C

NASA Technical Reports Server (NTRS)

Gedwill, M. A.

1972-01-01

Cyclic furnace oxidation studies were conducted on the cobalt alloy WI-52 clad with Ni-30Cr, Fe-25Cr-4A1, and Ni-20Cr-4A1 foils (0.051 to 0.254 mm thick). Tests as long as 400 hours using 1- and 20-hour cycles showed that the Ni-Cr- and Fe-Cr-A1 claddings were about equally protective at both temperatures. The protective ability of these alloys was influenced by exposure temperature and cladding thickness. At both temperatures, they protected WI-52 about as well as, or better than, a widely used commercial aluminide coating. The Ni-Cr-Al claddings did not protect WI-52 nearly as well. Interdiffusion generally influenced the oxidation behavior of all clad WI-52 systems.

Elevated Temperature Corrosion Studies of AlCrN and TiAlN Coatings by PAPVD on T91 Boiler Steel

NASA Astrophysics Data System (ADS)

Goyal, Lucky; Chawla, Vikas; Hundal, Jasbir Singh

2017-11-01

The present investigation discusses the hot corrosion behavior of AlCrN and TiAlN nano-coatings on T91 boiler steel by PAPVD process subjected to molten salt of Na2SO4-60%V2O5 at 900 °C for 50 cycles. Surface and cross-sectional studies were performed by AFM, SEM/EDS and XRD techniques to understand the corrosion kinetics and mechanism. T91 bare boiler steel as well as TiAlN-coated specimen has shown higher internal oxidation as well as weight gain. The better corrosion resistance of AlCrN-coated specimen has been observed by virtue of higher availability of Cr and Al in the oxide scale as well as adherent and dense coating. The betterment of AlCrN coating can be attributed to low internal oxidation as well as movement of Cr and Al toward oxide scale to form protective corrosion barriers.

Monitoring the in-situ oxide growth on uranium by ultraviolet-visible reflectance spectroscopy

NASA Astrophysics Data System (ADS)

Schweke, Danielle; Maimon, Chen; Chernia, Zelig; Livneh, Tsachi

2012-11-01

We demonstrate the in-situ monitoring of oxide growth on U-0.1 wt. % Cr by means of UV-visible reflectance spectroscopy in the thickness range of ˜20-150 nm. Two different approaches are presented: In the "modeling approach," we employ a model for a metallic substrate covered by a dielectric layer, while taking into account the buildup of oxygen gradient and surface roughness. Then, we fit the simulated spectra to the experimental one. In the "extrema analysis," we derive an approximated analytical expression, which relates the oxide thickness to the position of the extrema in the reflectance spectra based on the condition for optical interference of the reflected light. Good agreement is found between the values extracted by the two procedures. Activation energy of ˜21 kcal/mole was obtained by monitoring the oxide growth in the temperature range of 22-90 °C. The upper bound for the thickness determination is argued to be mostly dictated by cracking and detachment processes in the formed oxide.

Gas-to-particle conversion in the particle precipitation-aided chemical vapor deposition process II. Synthesis of the perovskite oxide yttrium chromite

DOE Office of Scientific and Technical Information (OSTI.GOV)

Dieten, V.E.J. van; Dekker, J.P.; Hurkmans, E.J.

1993-11-01

In the particle precipitation-aided chemical vapor deposition process, an aerosol is formed in the gas phase at elevated temperatures. The particles are deposited on a cooled substrate. Coherent layers with a controlled porosity can be obtained by a simultaneous heterogeneous reaction, which interconnects the deposited particles. The synthesis of submicrometer powder of the perovskite oxide yttrium chromite (YCrO[sub 3]) by gas to particle conversion, which is the first step of the PP-CVD process, has been investigated, and preliminary results are shown. The powders have been synthesized using yttrium trichloride vapor (YCl[sub 3]), chromium trichloride vapor (CrCl[sub 3]), and steam andmore » oxygen as reactants. The influence of the input molar ratio of the elements on the composition and characteristics of the powders has been investigated. Phase composition has been determined by X-ray diffraction (XRD). The powders have been characterized by transmission electron microscopy (TEM) and sedimentation field flow fractionation (SF[sup 3]). At a reaction temperature of 1283 K the powders consist of the chromium sesquioxide (Cr[sub 2]O[sub 3]), or a mixture of Cr[sub 2]O[sub 3] and YCrO[sub 3]. At stoichiometeric input amounts of metal chlorides and steam the formation of YCrO[sub 3] seems to be favored. 19 refs., 6 figs., 3 tabs.« less

The Corrosion Behavior of Stainless Steel 316L in Novel Quaternary Eutectic Molten Salt System

NASA Astrophysics Data System (ADS)

Wang, Tao; Mantha, Divakar; Reddy, Ramana G.

2017-03-01

In this article, the corrosion behavior of stainless steel 316L in a low melting point novel LiNO3-NaNO3-KNO3-NaNO2 eutectic salt mixture was investigated at 695 K which is considered as thermally stable temperature using electrochemical and isothermal dipping methods. The passive region in the anodic polarization curve indicates the formation of protective oxides layer on the sample surface. After isothermal dipping corrosion experiments, samples were analyzed using SEM and XRD to determine the topography, corrosion products, and scale growth mechanisms. It was found that after long-term immersion in the LiNO3-NaNO3-KNO3-NaNO2 molten salt, LiFeO2, LiFe5O8, Fe3O4, (Fe, Cr)3O4 and (Fe, Ni)3O4 oxides were formed. Among these corrosion products, LiFeO2 formed a dense and protective layer which prevents the SS 316L from severe corrosion.

TEM in situ micropillar compression tests of ion irradiated oxide dispersion strengthened alloy

NASA Astrophysics Data System (ADS)

Yano, K. H.; Swenson, M. J.; Wu, Y.; Wharry, J. P.

2017-01-01

The growing role of charged particle irradiation in the evaluation of nuclear reactor candidate materials requires the development of novel methods to assess mechanical properties in near-surface irradiation damage layers just a few micrometers thick. In situ transmission electron microscopic (TEM) mechanical testing is one such promising method. In this work, microcompression pillars are fabricated from a Fe2+ ion irradiated bulk specimen of a model Fe-9%Cr oxide dispersion strengthened (ODS) alloy. Yield strengths measured directly from TEM in situ compression tests are within expected values, and are consistent with predictions based on the irradiated microstructure. Measured elastic modulus values, once adjusted for the amount of deformation and deflection in the base material, are also within the expected range. A pillar size effect is only observed in samples with minimum dimension ≤100 nm due to the low inter-obstacle spacing in the as received and irradiated material. TEM in situ micropillar compression tests hold great promise for quantitatively determining mechanical properties of shallow ion-irradiated layers.

Selenium alleviates chromium toxicity by preventing oxidative stress in cabbage (Brassica campestris L. ssp. Pekinensis) leaves.

PubMed

Qing, Xuejiao; Zhao, Xiaohu; Hu, Chengxiao; Wang, Peng; Zhang, Ying; Zhang, Xuan; Wang, Pengcheng; Shi, Hanzhi; Jia, Fen; Qu, Chanjuan

2015-04-01

The beneficial role of selenium (Se) in alleviation of chromium (Cr)-induced oxidative stress is well established. However, little is known about the underlying mechanism. The impacts of exogenous Se (0.1mg/L) on Cr(1mg/L)-induced oxidative stress and antioxidant systems in leaves of cabbage (Brassica campestris L. ssp. Pekinensis) were investigated by using cellular and biochemical approaches. The results showed that supplementation of the medium with Se was effective in reducing Cr-induced increased levels of lipid peroxides and superoxide free radicals (O(-)2(·)), as well as increasing activities of superoxide dismutase (SOD) and peroxidase (POD). Meanwhile, 1mg/L Cr induced loss of plasma membrane integrity, growth inhibition, as well as ultrastructural changes of leaves were significantly reversed due to Se supplementation in the medium. In addition, Se application significantly altered the subcellular distribution of Cr which transported from mitochondria, nucleus and the cell-wall material to the soluble fraction and chloroplasts. However, Se application did no significant alteration of Cr effects on osmotic adjustment accumulating products. The study suggested that Se is able to protect leaves of cabbage against Cr toxicity by alleviation of Cr induced oxidative stress, and re-distribution of Cr in the subcellular of the leaf. Furthermore, free radicals, lipid peroxides, activity of SOD and POD, and subcellular distribution of Cr can be considered the efficient biomarkers to indicate the efficiency of Se to detoxification Cr. Copyright © 2015 Elsevier Inc. All rights reserved.

Structural characterization of ultrathin Cr-doped ITO layers deposited by double-target pulsed laser ablation

NASA Astrophysics Data System (ADS)

Cesaria, Maura; Caricato, Anna Paola; Leggieri, Gilberto; Luches, Armando; Martino, Maurizio; Maruccio, Giuseppe; Catalano, Massimo; Grazia Manera, Maria; Rella, Roberto; Taurino, Antonietta

2011-09-01

In this paper we report on the growth and structural characterization of very thin (20 nm) Cr-doped ITO films, deposited at room temperature by double-target pulsed laser ablation on amorphous silica substrates. The role of Cr atoms in the ITO matrix is carefully investigated with increasing doping content by transmission electron microscopy (TEM). Selected-area electron diffraction, conventional bright field and dark field as well as high-resolution TEM analyses, and energy dispersive x-ray spectroscopy demonstrate that (i) crystallization features occur despite the low growth temperature and small thickness, (ii) no chromium or chromium oxide secondary phases are detectable, regardless of the film doping levels, (iii) the films crystallize as crystalline flakes forming large-angle grain boundaries; (iv) the observed flakes consist of crystalline planes with local bending of the crystal lattice. Thickness and compositional information about the films are obtained by Rutherford back-scattering spectrometry. Results are discussed by considering the combined effects of growth temperature, smaller ionic radius of the Cr cation compared with the trivalent In ion, doping level, film thickness, the double-target doping technique and peculiarities of the pulsed laser deposition method.

Spectral ellipsometry as a method for characterization of nanosized films with ferromagnetic layers

NASA Astrophysics Data System (ADS)

Hashim, H.; Singkh, S. P.; Panina, L. V.; Pudonin, F. A.; Sherstnev, I. A.; Podgornaya, S. V.; Shpetnyi, I. A.; Beklemisheva, A. V.

2017-11-01

Nanosized films with ferromagnetic layers are widely used in nanoelectronics, sensor systems and telecommunications. Their properties may strongly differ from those of bulk materials that is on account of interfaces, intermediate layers and diffusion. In the present work, spectral ellipsometry and magnetooptical methods are adapted for characterization of the optical parameters and magnetization processes in two- and three-layer Cr/NiFe, Al/NiFe and Cr(Al)/Ge/NiFe films onto a sitall substrate for various thicknesses of Cr and Al layers. At a layer thickness below 20 nm, the complex refractive coefficients depend pronouncedly on the thickness. In two-layer films, remagnetization changes weakly over a thickness of the top layer, but the coercive force in three-layer films increases by more than twice upon remagnetization, while increasing the top layer thickness from 4 to 20 nm.

Oxidation kinetics of some Ni-Cr alloys.

PubMed

Baran, G

1983-01-01

Oxidation kinetics of four Ni-Cr alloys and a high-purity nickel standard was determined under isothermal conditions in an air atmosphere. In addition, weight gains of the alloys were measured during a simulated pre-oxidation treatment. The alloys' behavior suggests that mechanisms of oxidation vary with temperature and alloy composition.

Solute transport and the prediction of breakaway oxidation in gamma + beta Ni-Cr-Al alloys

NASA Technical Reports Server (NTRS)

Nesbitt, J. A.; Heckel, R. W.

1984-01-01

The Al transport and the condition leading to breakaway oxidation during the cyclic oxidation of gamma + beta NiCrAl alloys have been studied. The Al concentration/distance profiles were measured after various cyclic oxidation exposures at 1200 C. It was observed that cyclic oxidation results in a decreasing Al concentration at the oxide/metal interface, maintaining a constant flux of Al to the Al2O3 scale. It was also observed that breakaway oxidation occurs when the Al concentration at the oxide/metal interface approaches zero. A numerical model was developed to simulate the diffusional transport of Al and to predict breakaway oxidation in gamma + beta NiCrAl alloys undergoing cyclic oxidation. In a comparison of two alloys with similar oxide spalling characteristics, the numerical model was shown to predict correctly the onset of breakaway oxidation in the higher Al-content alloy.

Wetted foam liquid fuel ICF target experiments

DOE PAGES

Olson, R. E.; Leeper, R. J.; Yi, S. A.; ...

2016-05-26

We are developing a new NIF experimental platform that employs wetted foam liquid fuel layer ICF capsules. We will use the liquid fuel layer capsules in a NIF sub-scale experimental campaign to explore the relationship between hot spot convergence ratio (CR) and the predictability of hot spot formation. DT liquid layer ICF capsules allow for flexibility in hot spot CR via the adjustment of the initial cryogenic capsule temperature and, hence, DT vapor density. Our hypothesis is that the predictive capability of hot spot formation is robust and 1D-like for a relatively low CR hot spot (CR~15), but will becomemore » less reliable as hot spot CR is increased to CR>20. Simulations indicate that backing off on hot spot CR is an excellent way to reduce capsule instability growth and to improve robustness to low-mode x-ray flux asymmetries. In the initial experiments, we will test our hypothesis by measuring hot spot size, neutron yield, ion temperature, and burn width to infer hot spot pressure and compare to predictions for implosions with hot spot CR's in the range of 12 to 25. Larger scale experiments are also being designed, and we will advance from sub-scale to full-scale NIF experiments to determine if 1D-like behavior at low CR is retained as the scale-size is increased. The long-term objective is to develop a liquid fuel layer ICF capsule platform with robust thermonuclear burn, modest CR, and significant α-heating with burn propagation.« less

The oxidation and corrosion of ODS alloys

NASA Technical Reports Server (NTRS)

Lowell, Carl E.; Barrett, Charles A.

1990-01-01

The oxidation and hot corrosion of high temperature oxide dispersion strengthened (ODS) alloys are reviewed. The environmental resistance of such alloys are classified by oxide growth rate, oxide volatility, oxide spalling, and hot corrosion limitations. Also discussed are environmentally resistant coatings for ODS materials. It is concluded that ODS NiCrAl and FeCrAl alloys are highly oxidation and corrosion resistant and can probably be used uncoated.

Genesis of hexavalent chromium from natural sources in soil and groundwater.

PubMed

Oze, Christopher; Bird, Dennis K; Fendorf, Scott

2007-04-17

Naturally occurring Cr(VI) has recently been reported in ground and surface waters. Rock strata rich in Cr(III)-bearing minerals, in particular chromite, are universally found in these areas that occur near convergent plate margins. Here we report experiments demonstrating accelerated dissolution of chromite and subsequent oxidation of Cr(III) to aqueous Cr(VI) in the presence of birnessite, a common manganese mineral, explaining the generation of Cr(VI) by a Cr(III)-bearing mineral considered geochemically inert. Our results demonstrate that Cr(III) within ultramafic- and serpentinite-derived soils/sediments can be oxidized and dissolved through natural processes, leading to hazardous levels of aqueous Cr(VI) in surface and groundwater.

Genesis of hexavalent chromium from natural sources in soil and groundwater

PubMed Central

Oze, Christopher; Bird, Dennis K.; Fendorf, Scott

2007-01-01

Naturally occurring Cr(VI) has recently been reported in ground and surface waters. Rock strata rich in Cr(III)-bearing minerals, in particular chromite, are universally found in these areas that occur near convergent plate margins. Here we report experiments demonstrating accelerated dissolution of chromite and subsequent oxidation of Cr(III) to aqueous Cr(VI) in the presence of birnessite, a common manganese mineral, explaining the generation of Cr(VI) by a Cr(III)-bearing mineral considered geochemically inert. Our results demonstrate that Cr(III) within ultramafic- and serpentinite-derived soils/sediments can be oxidized and dissolved through natural processes, leading to hazardous levels of aqueous Cr(VI) in surface and groundwater. PMID:17420454

Multitechnique characterisation of 304L surface states oxidised at high temperature in steam and air atmospheres

NASA Astrophysics Data System (ADS)

Mamede, Anne-Sophie; Nuns, Nicolas; Cristol, Anne-Lise; Cantrel, Laurent; Souvi, Sidi; Cristol, Sylvain; Paul, Jean-François

2016-04-01

In case of a severe accident occurring in a nuclear reactor, surfaces of the reactor coolant system (RCS), made of stainless steel (304L) rich in Cr (>10%) and Ni (8-12%), are oxidised. Fission products (FPs) are released from melt fuel and flow through the RCS. A part of them is deposited onto surfaces either by vapour condensation or by aerosol deposition mechanisms. To be able to understand the nature of interactions between these FPs and the RCS surfaces, a preliminary step is to characterize the RSC surface states in steam and air atmosphere at high temperatures. Pieces of 304L stainless steel have been treated in a flow reactor at two different temperatures (750 °C and 950 °C) for two different exposition times (24 h and 72 h). After surfaces analysing by a unique combination of surface analysis techniques (XPS, ToF-SIMS and LEIS), for 304L, the results show a deep oxide scale with multi layers and the outer layer is composed of chromium and manganese oxides. Oxide profiles differ in air or steam atmosphere. Fe2O3 oxide is observed but in minor proportion and in all cases no nickel is detected near the surface. Results obtained are discussed and compared with the literature data.

Corrosion evaluation of heat recovery steam generator superheater tube in two methods of testing: Tafel polarization and electrochemical impedance spectroscopy (EIS)

NASA Astrophysics Data System (ADS)

Santoso, Rio Pudjidarma; Riastuti, Rini

2018-05-01

The purpose of this research is to evaluate the corrosion process which occurs on the water side of Heat Recovery Steam Generator (HRSG) superheater tube. The tube was 13CrMo44 and divided into 3 types of specimen: new tube, used tube (with oxide layer on surface), cleaned-used tube (without oxide layer on surface). The evaluation of corrosion parameters wasperformed using deaerated ultra-high purity water (boiler feed water) in two methods of testing: Tafel polarization and Electrochemical Impedance Spectroscopy (EIS). Tafel polarization was excellent as its capability to show the value of corrosion current and the corrosion rate explicitly, on the other hand, EIS was excellent as its capability to explain for corrosion mechanism on metal interface in detail. Both methods showed that the increase of electrolyte temperature from 25°C to 55°C would increase the corrosion rate with the mechanism of decreasing polarization resistance due to thinning out the passive film thickness and enlarge the area of reduction reaction of cathode. Magnetite oxide scale which is laid on the surface of used tube specimen shows protective nature to reduce the corrosion rate, and clear up this oxide would increase the corrosion rate back as new tube.

Steam Oxidation Behavior of Advanced Steels and Ni-Based Alloys at 800 °C

NASA Astrophysics Data System (ADS)

Dudziak, T.; Boroń, L.; Deodeshmukh, V.; Sobczak, J.; Sobczak, N.; Witkowska, M.; Ratuszek, W.; Chruściel, K.

2017-03-01

This publication studies the steam oxidation behavior of advanced steels (309S, 310S and HR3C) and Ni-based alloys (Haynes® 230®, alloy 263, alloy 617 and Haynes® 282®) exposed at 800 °C for 2000 h under 1 bar pressure, in a pure water steam system. The results revealed that all exposed materials showed relatively low weight gain, with no spallation of the oxide scale within the 2000 h of exposure. XRD analysis showed that Ni-based alloys developed an oxide scale consisting of four main phases: Cr2O3 (alloy 617, Haynes® 282®, alloy 263 and Haynes® 230®), MnCr2O4 (alloy 617, Haynes® 282® and Haynes® 230®), NiCr2O4 (alloy 617) and TiO2 (alloy 263, Haynes® 282®). In contrast, advanced steels showed the development of Cr2O3, MnCr2O4, Mn7SiO12, FeMn(SiO4) and SiO2 phases. The steel with the highest Cr content showed the formation of Fe3O4 and the thickest oxide scale.

Volatile products from the interaction of KCl(g) with Cr2O3 and LaCrO3 in oxidizing environments

NASA Technical Reports Server (NTRS)

Kohl, F. J.; Miller, R. A.; Stearns, C. A.; Fryburg, G. C.; Dillard, J. G.

1977-01-01

Cooled target collection techniques and high pressure mass spectrometric sampling were used to measure the relative rates of oxidative vaporization and to identify the volatile products emanating from samples of chromia and Mg-doped lanthanum chromite. The materials were exposed to partial pressures of KCl with and without H2O in one atmosphere of slowly flowing oxygen at elevated temperatures. Chromia and fresh samples of lanthanum chromite exhibited enhanced rates of oxidative vaporization upon exposure to these reactants. Mass spectrometric identification showed that the enhancements resulted from the heterogeneous formation of complex molecules of the type KCl sub 1,2,3 CrO3 and KOH sub l,2 CrO3. Lanthanum chromite that had undergone prolonged oxidative vaporization exhibited no enhanced oxidation upon exposure to the reactants.

Fullerene/layered antiferromagnetic reconstructed spinterface: Subsurface layer dominates molecular orbitals' spin-split and large induced magnetic moment

NASA Astrophysics Data System (ADS)

Shao, Yangfan; Pang, Rui; Pan, Hui; Shi, Xingqiang

2018-03-01

The interfaces between organic molecules and magnetic metals have gained increasing interest for both fundamental reasons and applications. Among them, the C60/layered antiferromagnetic (AFM) interfaces have been studied only for C60 bonded to the outermost ferromagnetic layer [S. L. Kawahara et al., Nano Lett. 12, 4558 (2012) and D. Li et al., Phys. Rev. B 93, 085425 (2016)]. Here, via density functional theory calculations combined with evidence from the literature, we demonstrate that C60 adsorption can reconstruct the layered-AFM Cr(001) surface at elevated annealing temperatures so that C60 bonds to both the outermost and the subsurface Cr layers in opposite spin directions. Surface reconstruction drastically changes the adsorbed molecule spintronic properties: (1) the spin-split p-d hybridization involves multi-orbitals of C60 and top two layers of Cr with opposite spin-polarization, (2) the subsurface Cr atom dominates the C60 electronic properties, and (3) the reconstruction induces a large magnetic moment of 0.58 μB in C60 as a synergistic effect of the top two Cr layers. The induced magnetic moment in C60 can be explained by the magnetic direct-exchange mechanism, which can be generalized to other C60/magnetic metal systems. Understanding these complex hybridization behaviors is a crucial step for molecular spintronic applications.

Enhancement of oxidative vaporization of chromium (III) oxide and chromium by oxygen atoms

NASA Technical Reports Server (NTRS)

Fryburg, G. C.; Kohl, F. J.; Stearns, C. A.

1974-01-01

Rates of oxidative vaporization of Cr2O3 were found to be markedly enhanced in the presence of O atoms. Investigations were conducted over the temperature range 470 to 1520 K. For Cr2O3 the enhancement was about 10 to the 9th power at 820 K in oxygen containing 2.5 percent atoms. Rapid oxidative vaporization of bare chromium was observed below 1070 K, the rate being about one-half that of Cr2O3. Results are interpreted in terms of thermochemical analysis.

Enhanced Corrosion Resistance of PVD-CrN Coatings by ALD Sealing Layers

NASA Astrophysics Data System (ADS)

Wan; Zhang, Teng Fei; Ding, Ji Cheng; Kim, Chang-Min; Park, So-Won; Yang, Yang; Kim, Kwang-Ho; Kwon, Se-Hun

2017-04-01

Multilayered hard coatings with a CrN matrix and an Al2O3, TiO2, or nanolaminate-Al2O3/TiO2 sealing layer were designed by a hybrid deposition process combined with physical vapor deposition (PVD) and atomic layer deposition (ALD). The strategy was to utilize ALD thin films as pinhole-free barriers to seal the intrinsic defects to protect the CrN matrix. The influences of the different sealing layers added in the coatings on the microstructure, surface roughness, and corrosion behaviors were investigated. The results indicated that the sealing layer added by ALD significantly decreased the average grain size and improved the corrosion resistance of the CrN coatings. The insertion of the nanolaminate-Al2O3/TiO2 sealing layers resulted in a further increase in corrosion resistance, which was attributed to the synergistic effect of Al2O3 and TiO2, both acting as excellent passivation barriers to the diffusion of corrosive substances.

HRTEM/AEM and SEM study of fluid-rock interactions: Interaction of copper, silver, selenium, chromium, and cadmium-bearing solutions with geological materials at near surface conditions, with an emphasis on phyllosilicates. Progress report, September 1, 1992--September 1, 1993

DOE Office of Scientific and Technical Information (OSTI.GOV)

Veblen, D.R.; Ilton, E.S.

1993-05-01

TEM of naturally occurring Cu-rich biotites and feldspars from weathered portions of porphyry copper deposits has shown that copper is not in the structure of these minerals, is present in their weathering products such as copper-rich vermiculite layers, submicroscopic iron oxyhydroxides and native copper inclusions, and chrysocoua. Reaction of acidic solutions bearing-Cu{sup 2+}, Ag{sup +}, Cr{sup 6+}, and Se{sup 4+}, at 25C, with biotite indicates that ferrous iron in biotite can reduce Cu{sup 2+}, Ag+, and Cr{sup 6+} to Cu{degrees}, Ag{degrees}, and Cr(III), respectively. However, Se{sup 4+} does not appear to be reduced. Copper is reduced in the interlayer region,more » silver is reduced in the interlayer and on the biotite surfaces, and chromium is reduced at the biotite surface. TEM shows that the reduction of copper and silver by biotite can produce native metal inclusions, whereas reduction of Cr(VI) to CR(III) did not produce any Cr-bearing precipitates. The copper and silver experiments show that iron in biotite can be a much stronger reducing agent than iron in solution. TEM and XPS of biotites reacted with CR(VI) clearly show that edges or (hkO) faces are much more reactive than the basal planes, where the edges are strongly enriched in CR(III) relative to the basal planes. In contrast, biotites reacted with Cr(IH)-bearing solutions show little fractionation between the edges and basal planes. Another important result of our XPS studies is that we demonstrated that the oxidation state of near surface iron in biotite can be quantified.« less

Chromium Oxidation State in Planetary Basalts: Oxygen Fugacity Indicator and Critical Variable for Cr-Spinel Stability

NASA Technical Reports Server (NTRS)

Bell, A. S.; Burger, P. V.; Le, Loan; Papike, J. J.; Jone, J.; Shearer, C. K.

2014-01-01

Cr is a ubiquitous and relatively abundant minor element in basaltic, planetary magmas. At the reduced oxidation states (

Capabilities to improve corrosion resistance of fuel claddings by using powerful laser and plasma sources

DOE Office of Scientific and Technical Information (OSTI.GOV)

Borisov, V. M., E-mail: borisov@triniti.ru; Trofimov, V. N.; Sapozhkov, A. Yu.

2016-12-15

The treatment conditions of fuel claddings of the E110 alloy by using powerful UV or IR laser radiation, which lead to the increase in the corrosion resistance at the high-temperature (T = 1100°C) oxidation simulating a loss-of-coolant accident, are determined. The possibility of the complete suppression of corrosion under these conditions by using pulsed laser deposition of a Cr layer is demonstrated. The behavior of protective coatings of Al, Al{sub 2}O{sub 3}, and Cr planted on steel EP823 by pulsed laser deposition, which is planned to be used in the BREST-OD-300, is studied. The methods of the almost complete suppressionmore » of corrosion in liquid lead to the temperature of 720°C are shown.« less

DOE Office of Scientific and Technical Information (OSTI.GOV)

Zohar, S.; Choi, Y.; Love, D. M.

We use X-ray Excited Luminescence Microscopy to investigate the elemental and layer resolved magnetic reversal in an interlayer exchange coupled (IEC) epitaxial Fe/Cr wedge/Co heterostructure. The transition from strongly coupled parallel Co-Fe reversal for Cr thickness t(Cr) < 0.34 nm to weakly coupled layer independent reversal for t(Cr) > 1.5 nm is punctuated at 0.34 < t(Cr) < 1.5 nm by a combination of IEC guided domain wall motion and stationary zig zag domain walls. Domain walls nucleated at switching field minima are guided by IEC spatial gradients and collapse at switching field maxima.

Microstructure and property of diamond-like carbon films with Al and Cr co-doping deposited using a hybrid beams system

NASA Astrophysics Data System (ADS)

Dai, Wei; Liu, Jingmao; Geng, Dongsen; Guo, Peng; Zheng, Jun; Wang, Qimin

2016-12-01

DLC films with weak carbide former Al and carbide former Cr co-doping (Al:Cr-DLC) were deposited by a hybrid beams system comprising an anode-layer linear ion beam source (LIS) and high power impulse magnetron sputtering using a gas mixture of C2H2 and Ar as the precursor. The doped Al and Cr contents were controlled via adjusting the C2H2 fraction in the gas mixture. The composition, microstructure, compressive stress, mechanical properties and tribological behaviors of the Al:Cr-DLC films were researched carefully using X-ray photoelectron spectroscopy, transmission electron microscopy, Raman spectroscopy, stress-tester, nanoindentation and ball-on-plate tribometer as function of the C2H2 fraction. The results show that the Al and Cr contents in the films increased continuously as the C2H2 fraction decreased. The doped Cr atoms preferred to bond with the carbon while the Al atoms mainly existed in metallic state. Structure modulation with alternate multilayer consisted of Al-poor DLC layer and Al-rich DLC layer was found in the films. Those periodic Al-rich DLC layers can effectively release the residual stress of the films. On the other hand, the formation of the carbide component due to Cr incorporation can help to increase the film hardness. Accordingly, the residual stress of the DLC films can be reduced without sacrificing the film hardness though co-doping Al and Cr atoms. Furthermore, it was found that the periodic Al-rich layer can greatly improve the elastic resilience of the DLC films and thus decreases the film friction coefficient and wear rate significantly. However, the existence of the carbide component would cause abrasive wear and thus deteriorate the wear performance of the films.

Overlay coating degradation by simultaneous oxidation and coating/substrate interdiffusion. Ph.D. Thesis

NASA Technical Reports Server (NTRS)

Nesbitt, J. A.

1983-01-01

Degradation of NiCrAlZr overlay coatings on various NiCrAl substrates was examined after cyclic oxidation. Concentration/distance profiles were measured in the coating and substrate after various oxidation exposures at 1150 C. For each stubstrate, the Al content in the coating decreased rapidly. The concentration/distance profiles, and particularly that for Al, reflected the oxide spalling resistance of each coated substrate. A numerical model was developed to simulate diffusion associated with overlay-coating degradation by oxidation and coating/substrate interdiffusion. Input to the numerical model consisted of the Cr and Al content of the coating and substrate, ternary diffusivities, and various oxide spalling parameters. The model predicts the Cr and Al concentrations in the coating and substrate after any number of oxidation/thermal cycles. The numerical model also predicts coating failure based on the ability of the coating to supply sufficient Al to the oxide scale. The validity of the model was confirmed by comparison of the predicted and measured concentration/distance profiles. The model was subsequently used to identify the most critical system parameters affecting coating life.

Coatings for directional eutectics. [cyclic furnace oxidation tests

NASA Technical Reports Server (NTRS)

Jackson, M. R.; Rairden, J. R.; Hampton, L. V.

1974-01-01

Coating compositions were evaluated for oxidation protection of directionally solidified composite alloy NiTaC-13. These coatings included three NiCrAlY compositions (30-5-1, 25-10-1 and 20-15-1), two FeCrAlY compositions (30-5-1 and 25-10-1), a CoCrAlY composition (25-10-1), and one duplex coating, Ni-35Cr + Al. Duplicate pin samples of each composition were evaluated using two cyclic furnace oxidation tests of 100 hours at 871 C and 500 hours at 1093 C. The two best coatings were Ni-20Cr-15Al-lY and Ni-35Cr + Al. The two preferred coatings were deposited on pins and were evaluated in detail in .05 Mach cyclic burner rig oxidation to 1093 C. The NiCrAlY coating was protective after 830 hours of cycling, while the duplex coating withstood 630 hours. Test bars were coated and cycled for up to 500 hours. Tensile tests indicated no effect of coatings on strength. In 871 C air stress rupture, a degradation was observed for coated relative to bare material. The cycled NiCrAlY coating offered excellent protection with properties superior to the bare cycled NiTaC-13 in 1093 C air stress rupture.

Influence of Cr doping on the stability and structure of small cobalt oxide clusters.

PubMed

Tung, Nguyen Thanh; Tam, Nguyen Minh; Nguyen, Minh Tho; Lievens, Peter; Janssens, Ewald

2014-07-28

The stability of mass-selected pure cobalt oxide and chromium doped cobalt oxide cluster cations, ConO+m and Con-1CrO+m (n = 2, 3; m = 2-6 and n = 4; m = 3-8), has been investigated using photodissociation mass spectrometry. Oxygen-rich ConO+m clusters (m ≥ n + 1 for n = 2, 4 and m ≥ n + 2 for n = 3) prefer to photodissociate via the loss of an oxygen molecule, whereas oxygen poorer clusters favor the evaporation of oxygen atoms. Substituting a single Co atom by a single Cr atom alters the dissociation behavior. All investigated Con-1 CrO+m clusters, except CoCrO+2 and CoCrO+3, prefer to decay by eliminating a neutral oxygen molecule. Co2O+2, Co4O+3, Co4O+4, and CoCrO+2 are found to be relatively difficult to dissociate and appear as fragmentation product of several larger clusters, suggesting that they are particularly stable. The geometric structures of pure and Cr doped cobalt oxide species are studied using density functional theory calculations. Dissociation energies for different evaporation channels are calculated and compared with the experimental observations. The influence of the dopant atom on the structure and the stability of the clusters is discussed.

Effect of Cr2O3 addition on the oxidation induration mechanism of Hongge vanadium titanomagnetite pellets

NASA Astrophysics Data System (ADS)

Li, Wei; Wang, Nan; Fu, Gui-qin; Chu, Man-sheng; Zhu, Miao-yong

2018-04-01

As part of a research project to develop a novel clean smelting process for the comprehensive utilization of Hongge vanadium titanomagnetite (HVTM), in this study, the effect of Cr2O3 addition on the oxidation induration mechanism of HVTM pellets (HVTMPs) was investigated in detail. The results showed that the compressive strength of the HVTMPs was greatly weakened by the Cr2O3 addition, mainly because of a substantial increase in the porosity of the HVTMPs. The Cr2O3 addition marginally affected the phase composition but greatly affected the microstructural changes of the HVTMPs. Increased amounts of Cr2O3 resulted in a decrease in the uniform distribution of the hematite grains and in an increase in the Fe-Cr solid solutions (Fe1.2Cr0.8O3 and Fe0.7Cr1.3O3) embedded in the hematite grains. Moreover, the compact hematite was destroyed by forming a dispersed structure and the hematite recrystallization was hindered during the oxidation induration, which adversely affected the compressive strength. On the basis of these results, a schematic was formulated to describe the oxidation induration mechanism with different amounts of added Cr2O3. This study provides theoretical and technical foundations for the effective production of HVTMPs and a reference for chromium-bearing minerals.

Structural and optical studies of Mg doped nanoparticles of chromium oxide (Cr2O3) synthesized by co-precipitation method

NASA Astrophysics Data System (ADS)

Singh, Jarnail; Verma, Vikram; Kumar, Ravi

2018-04-01

We present here the synthesization, structural and optical studies of Mg doped nanoparticles of Chromium oxide (Cr2O3) prepared using co-precipitation method. These samples were characterized using powder X-ray diffraction (XRD), Field emission scanning electron microscopy (FESEM), Raman spectroscopy and UV-Vis spectroscopy techniques. We have demonstrated that there is negligible change in optical band gap with the Mg doping. The prepared Cr2O3 nanoparticles are spherical in shape, but they are transformed into platelets when doped with Mg. The XRD studies reveal that the Mg doping in Cr2O3 doesn't affect the structure of Chromium oxide (Cr2O3).

Mechanical properties and oxidation and corrosion resistance of reduced-chromium 304 stainless steel alloys

NASA Technical Reports Server (NTRS)

Stephens, J. R.; Barrett, C. A.; Gyorgak, C. A.

1979-01-01

An experimental program was undertaken to identify effective substitutes for part of the Cr in 304 stainless steel as a method of conserving the strategic element Cr. Although special emphasis was placed on tensile properties, oxidation and corrosion resistance were also examined. Results indicate that over the temperature range of -196 C to 540 C the yield stress of experimental austenitic alloys with only 12 percent Cr compare favorably with the 18 percent Cr in 304 stainless steel. Oxidation resistance and in most cases corrosion resistance for the experimental alloys were comparable to the commercial alloy. Effective substitutes for Cr included Al, Mo, Si, Ti, and V, while Ni and Mn contents were increased to maintain an austenitic structure.

A novel process of electroless Ni-P plating with plasma electrolytic oxidation pretreatment

NASA Astrophysics Data System (ADS)

Liu, Zhenmin; Gao, Wei

2006-12-01

A novel Ni based coating - plasma electrolytic oxidation (PEO) pre-treatment followed by electroless nickel (EN) plating - has been developed to produce pore free Ni coatings on AZ91 magnesium alloy. The application of the PEO film between the nickel coating and the substrate acts as an effective barrier and catalytic layer for the subsequent nickel plating. The potentiodynamic tests indicated that the corrosion current density of the PEO + EN plating on AZ91 decreased by almost two orders of magnitudes compared to the traditional EN coating. Salt fog spray testing further proved this improvement. More importantly, the new technique does not use Cr +6 and HF in its pretreatment, therefore is a much environmentally friendlier process.

Thermal barrier coating life-prediction model development

NASA Technical Reports Server (NTRS)

Strangman, T. E.; Neumann, J.

1985-01-01

Life predictions are made for two types of strain-tolerant and oxidation-resistant Thermal Barrier Coating (TBC) systems produced by commercial coating suppliers to the gas turbine industry. The plasma-sprayed TBC system, composed of a low-pressure plasma spray (LPPS) applied oxidation-resistant NiCrAlY bond coating and an air-plasma-sprayed yttria (8 percent) partially stabilized zirconia insulative layer, is applied by both Chromalloy and Klock. The second type of TBC is applied by the electron-beam/physical vapor deposition process by Temescal. Thermomechanical and thermochemical testing of the program TBCs is in progress. A number of the former tests has been completed. Fracture mechanics data for the Chromalloy plasma-sprayed TBC system indicate that the cohesive toughness of the zirconia layer is increased by thermal cycling and reduced by high temperature exposure at 1150 C. Eddy current technology feasibility has been established with respect to nondestructively measuring zirconia layer thickness of a TBC system. High pressure turbine blades have been coated with program TBC systems for a piggyback test in a TFE731-5 turbofan factory engine test. Data from this test will be used to validate the TBC life models.

The effect of Be and Cr electrode deposition rate on the performance of MIS solar cells

NASA Astrophysics Data System (ADS)

Moharram, A. H.; Panayotatos, P.; Yeh, J. L.; Lalevic, B.

1985-07-01

An experimental study has been performed on MIS solar cells with Be, Cr and layered Cr-Be electrodes on single crystal Si, Wacker and Monsanto poly-Si substrates. Electrical characterization in the dark and under illumination was correlated to X-ray and Auger spectroscopy results. It was found that the electrode deposition rate directly affects the oxygen content of the electrodes for all metal-substrate configurations. This oxygen is believed to originate from the deposition ambient as well as from the SiO2 layer. In the case of cells with Cr and layered Cr-Be electrodes oxygen acts to reduce the electrode work function (thus increasing the open-circuit voltage) in direct proportion to the relative content of oxygen to chromium.

Cr/B 4C multilayer mirrors: Study of interfaces and X-ray reflectance

DOE PAGES

Burcklen, C.; Soufli, R.; Gullikson, E.; ...

2016-03-24

Here, we present an experimental study of the effect of layer interfaces on the x-ray reflectance in Cr/B 4C multilayer interference coatings with layer thicknesses ranging from 0.7 nm to 5.4 nm. The multilayers were deposited by magnetron sputtering and by ion beam sputtering. Grazing incidence x-ray reflectometry, soft x-ray reflectometry, and transmission electron microscopy reveal asymmetric multilayer structures with a larger B 4C-on-Cr interface, which we modeled with a 1–1.5 nm thick interfacial layer. Reflectance measurements in the vicinity of the Cr L 2,3 absorption edge demonstrate fine structure that is not predicted by simulations using the currently tabulatedmore » refractive index (optical constants) values for Cr.« less

Fretting Wear of Ti-48Al-2Cr-2Nb

NASA Technical Reports Server (NTRS)

Miyoshi, Kazuhisa; Lerch, Bradley A.; Draper, Susan L.

2001-01-01

An investigation was conducted to examine the wear behavior of gamma titanium aluminide (Ti-48Al-2Cr-2Nb in atomic percent) in contact with a typical nickel-base superalloy under repeated microscopic vibratory motion in air at temperatures from 296-823 K. The surface damage observed on the interacting surfaces of both Ti-48Al-2Cr-2Nb and superalloy consisted of fracture pits, oxides, metallic debris, scratches, craters, plastic deformation, and cracks. The Ti-48Al-2Cr-2Nb transferred to the superalloy at all fretting conditions and caused scuffing or galling. The increasing rate of oxidation at elevated temperatures led to a drop in Ti-48Al-2Cr-2Nb wear at 473 K. Mild oxidative wear was observed at 473 K. However, fretting wear increased as the temperature was increased from 473-823 K. At 723 and 823 K, oxide disruption generated cracks, loose wear debris, and pits on the Ti-48Al-2Cr-2Nb wear surface. Ti-48Al-2Cr-2Nb wear generally decreased with increasing fretting frequency. Both increasing slip amplitude and increasing load tended to produce more metallic wear debris, causing severe abrasive wear in the contacting metals. Keywords

Development of low-Cr ODS FeCrAl alloys for accident-tolerant fuel cladding

NASA Astrophysics Data System (ADS)

Dryepondt, Sebastien; Unocic, Kinga A.; Hoelzer, David T.; Massey, Caleb P.; Pint, Bruce A.

2018-04-01

Low-Cr oxide dispersion strengthened (ODS) FeCrAl alloys were developed as accident tolerant fuel cladding because of their excellent oxidation resistance at very high temperature, high strength and improved radiation tolerance. Fe-12Cr-5Al wt.% gas atomized powder was ball milled with Y2O3+FeO, Y2O3+ZrO2 or Y2O3+TiO2, and the resulting powders were extruded at 950 °C. The resulting fine grain structure, particularly for the Ti and Zr containing alloys, led to very high strength but limited ductility. Comparison with variants of commercial PM2000 (Fe-20Cr-5Al) highlighted the significant impact of the powder consolidation step on the alloy grain size and, therefore, on the alloy mechanical properties at T < 500 °C. These low-Cr compositions exhibited good oxidation resistance at 1400 °C in air and steam for 4 h but could not form a protective alumina scale at 1450 °C, similar to observations for fine grained PM2000 alloys. The effect of alloy grain size, Zr and Ti additions, and impurities on the alloy mechanical and oxidation behaviors are discussed.

Microstructure of Al2O3 scales formed on NiCrAl alloys. Ph.D. Thesis - Case Western Reserve Univ.

NASA Technical Reports Server (NTRS)

Smialek, J. L.

1981-01-01

The structure of transient scales formed on pure and Y or Zr-doped Ni-15Cr-13Al alloys oxidized for 0.1 hr at 1100 C was studied by the use of transmission electron microscopy. Crystallographically oriented scales were found on all three alloys, but especially for the Zr-doped NiCrAl. The oriented scales consisted of alpha-(Al,Cr)2O3, Ni(Al,Cr)2O4 and gamma-Al2O3. They were often found in intimate contact with each other such that the close-packed planes and directions of one oxide phase were aligned with those of another. The prominent structural features of the oriented scales were approximately equal to micrometer subgrains; voids, antiphase domain boundaries and aligned precipitates were also prevalent. Randomly oriented alpha-Al2O3 was also found and was the only oxide ever observed at the immediate oxide metal interface. These approximately 0.15 micrometer grains were populated by intragranular voids which decreased in size and number towards the oxide metal interface. A sequence of oxidation was proposed in which the composition of the growing scale changed from oriented oxides rich in Ni and Cr to oriented oxides rich in Al. At the same time the structure changed from cubic spinels to hexagonal corundums with apparent precipitates of one phase in the matrix of the other. Eventually randomly oriented pure alpha-Al2O3 formed as the stable oxide with an abrupt transition: there was no gradual loss of orientation, no gradual compositional change or no gradual decrease in precipitate density.