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At least 37 records · Page 2

Oxidation resistant nanocrystalline MCrAl(Y) coatings and methods of forming such coatings

The present disclosure relates to an oxidation resistant nanocrystalline coating and a method of forming an oxidation resistant nanocrystalline coating. An oxidation resistant coating comprising an MCrAl(Y) alloy may be deposited on a substrate, wherein M, includes iron, nickel, cobalt, or combinations thereof present greater than 50 wt % of the MCrAl(Y) alloy, chromium is present in the range of 15 wt % to 30 wt % of the MCrAl(Y) alloy, aluminum is present in the range of 6 wt % to 12 wt % of the MCrAl(Y) alloy and yttrium, is optionally present in the range of 0.1 wt % to 0.5 wt % of the MCrAl(Y) alloy. In addition, the coating may exhibit a grain size of 200 nm or less as deposited.

36 MATERIALS SCIENCE↗

Flight Qualified Micro Sun Sensor

A prototype small, lightweight micro Sun sensor (MSS) has been flight qualified as part of the attitude-determination system of a spacecraft or for Mars surface operations. The MSS has previously been reported at a very early stage of development in NASA Tech Briefs, Vol. 28, No. 1 (January 2004). An MSS is essentially a miniature multiple-pinhole electronic camera combined with digital processing electronics that functions analogously to a sundial. A micromachined mask containing a number of microscopic pinholes is mounted in front of an active-pixel sensor (APS). Electronic circuits for controlling the operation of the APS, readout from the pixel photodetectors, and analog-to-digital conversion are all integrated onto the same chip along with the APS. The digital processing includes computation of the centroids of the pinhole Sun images on the APS. The spacecraft computer has the task of converting the Sun centroids into Sun angles utilizing a calibration polynomial. The micromachined mask comprises a 500-micron-thick silicon wafer, onto which is deposited a 57-nm-thick chromium adhesion- promotion layer followed by a 200-nm-thick gold light-absorption layer. The pinholes, 50 microns in diameter, are formed in the gold layer by photolithography. The chromium layer is thin enough to be penetrable by an amount of Sunlight adequate to form measurable pinhole images. A spacer frame between the mask and the APS maintains a gap of .1 mm between the pinhole plane and the photodetector plane of the APS. To minimize data volume, mass, and power consumption, the digital processing of the APS readouts takes place in a single field-programmable gate array (FPGA). The particular FPGA is a radiation- tolerant unit that contains .32,000 gates. No external memory is used so the FPGA calculates the centroids in real time as pixels are read off the APS with minimal internal memory. To enable the MSS to fit into a small package, the APS, the FPGA, and other components are mounted on a single two-sided board following chip-on-board design practices

Liebe, Carl Christian↗

Temperature and oxygen concentration effects on anisotropy in chromium hard mask etching for nanoscale fabrication

Chromium and its oxides are valuable as functional materials and plasma-etching hard masks in micro- and nanofabrication. While the continuous decrease in feature sizes opens new opportunities for applications of patterned chromium, the demands placed on the patterning process require a new level of mechanistic understanding. In this work, we investigate plasma etching with chlorine/oxygen chemistry using temperature and oxygen concentration as a means to controllably pattern chromium at the nanometer level. Building on our previous studies on blanket film chromium etching, we look here at patterned trenches 15–100 nm wide in 20 and 10 nm thick chromium films. We vary oxygen concentrations from 1.5% to 81% at substrate temperatures of +20 and −50 °C, respectively. Feature and trench profiles are evaluated from high-resolution cross-sectional SEM images. The ternary chromium etch product shows very different profiles as oxygen, temperature, and feature size are varied. We find the highest anisotropy at −50 °C and 50% oxygen concentration. Etch results suggest that the redeposition of nonvolatile intermediate reaction compounds enhances anisotropy at low temperature, whereas re-emission of reactive species causes undercut at the higher etching temperature.

Staaks, Daniel (ORCID:0000000204825507)↗

Aluminum and Other Coatings for the Passivation of Tritium Storage Vessels

Using a highly sensitive residual gas analyzer, the off-gassing of hydrogen, water, and hydrocarbons from surface-treated storage vessels containing deuterium was measured. The experimental storage vessels were compared to a low-off-gassing, electro-polished 304L canister. Alternative vessels were made out of aluminum, or were coatings on 304L steel. Coatings included powder pack aluminide, electro-plated aluminum, powder pack chromide, dense electro-plated chromium, copper plated, and copper plated with 25 and 50 percent nano-diamond. Vessels were loaded with low pressure deuterium to observe exchange with protium or hydrogen as observed with formation of HD and HDO. Off gas of D 2 O or possible CD 4 was observed at mass 20. The main off-gas in all of the studies was H 2 . The studies indicated that coatings required significant post-coating treatment to reduce off-gas and enhance the permeation barrier from gases likely added during the coating process. Dense packed aluminum coatings needed heating to drive off water. Electro-plated aluminum, chromium and copper coatings appeared to trap hydrogen from the plating process. Nano-diamond appeared to enhance the exchange rate with hydrogen off gas, and its coating process trapped significant amounts of hydrogen. Aluminum caused more protium exchange than chromium-treated surfaces. Aluminum coatings released more water, but pure aluminum vessels released small amounts of hydrogen, little water, and generally performed well. Chromium coating had residual hydrogen that was difficult to totally outgas but otherwise gave low residuals for water and hydrocarbons. Our studies indicated that simple coating of as received 304L metal will not adequately block hydrogen. The base vessel needs to be carefully out-gassed before applying a coating, and the coating process will likely add additional hydrogen that must be removed. Initial simple bake-out and leak checks up to 350° C for a few hours was found to be inadequate. All of the studies indicated that vessels needed several days of vacuum baking at 350-450° C to fully outgas the residual gases, which were mostly hydrogen. The current standard practice of out-gassing from ultra-clean, electro-polished 304L vessels with both vacuum bake-out and followed by an oxidative bake out to enhance the chromium surface performed the best in these studies.

08 HYDROGEN↗

Sputtering of cobalt and chromium by argon and xenon ions near the threshold energy region

Sputtering yields of cobalt and chromium by argon and xenon ions with energies below 50 eV are reported. The targets were electroplated on copper substrates. Measurable sputtering yields were obtained from cobalt with ion energies as low as 10 eV. The ion beams were produced by an ion gun. A radioactive tracer technique was used for the quantitative measurement of the sputtering yield. Co-57 and Cr-51 were used as tracers. The yield-energy curves are observed to be concave, which brings into question the practice of finding threshold energies by linear extrapolation.

Handoo, A. K.↗

Removal of Residual Chromium from Aluminum Oxide by Containerless Liquid-phase Processing

Berneuil sapphire was purified of Cr 3+ by containerless melting and processing at ca. 2550 K in high purity argon, dry air and pure oxygen. Recovered material was examined by laser induced fluorescence and Raman spectroscopy. The Cr 3+ fluorescence intensity decreased in processed specimens at rates proportional to the chromium concentration and p(O 2 ) 0.21 . The initial chromium concentration was ca. 5 ppm and decreased by factors of ca. 50, 3000, and 2x10 5 after processing for 300 seconds in argon, air and oxygen, respectively. Evidence is presented that the Cr 3+ was removed predominantly as CrO 2 (g) and not by conversion to other oxidation states of chromium in the condensed phase. A comparison of the Raman peak shifts for as-received and processed samples indicates that considerable stress was retained during containerless solidification of the highly undercooled melts.

sapphire↗

Resveratrol protects the ovary against chromium-toxicity by enhancing endogenous antioxidant enzymes and inhibiting metabolic clearance of estradiol

Resveratrol (RVT), a polyphenolic component in grapes and red wine, has been known for its cytoprotective actions against several diseases. However, beneficial effects of RVT against early exposure to endocrine disrupting chemicals (EDCs) have not been understood. EDCs are linked to several ovarian diseases such as premature ovarian failure, polycystic ovary syndrome, early menopause and infertility in women. Hexavalent chromium (CrVI) is a heavy metal EDC, and widely used in > 50 industries. Environmental contamination with CrVI in the US is rapidly increasing, predisposing the human to several illnesses including cancers and still birth. Our lab has been involved in determining the molecular mechanism of CrVI-induced female infertility and intervention strategies to mitigate CrVI effects. Lactating mother rats were exposed to CrVI (50 ppm potassium dichromate) from postpartum days 1–21 through drinking water with or without RVT (10 mg/kg body wt., through oral gavage daily). During this time, F1 females received respective treatments through mother's milk. On postnatal day (PND) 25, blood and the ovary, kidney and liver were collected from the F1 females for analyses. CrVI increased atresia of follicles by increasing cytochrome C and cleaved caspase-3; decreasing antiapoptotic proteins; decreasing estradiol (E{sub 2}) biosynthesis and enhancing metabolic clearance of E{sub 2}, increasing oxidative stress and decreasing endogenous antioxidants. RVT mitigated the effects of CrVI by upregulating cell survival proteins and AOXs; and restored E{sub 2} levels by inhibiting hydroxylation, glucuronidation and sulphation of E{sub 2}. This is the first study to report the protective effects of RVT against any toxicant in the ovary. - Highlights: • Resveratrol (RVT) protects the ovary against CrVI-toxicity. • RVT mitigated CrVI-induced apoptosis and follicle atresia. • RVT restored estradiol level against CrVI-toxicity. • RVT inhibited metabolic clearance of estradiol in the ovary, kidney and liver. • RVT mitigated CrVI toxicity by upregulating cell survival proteins and antioxidants.

60 APPLIED LIFE SCIENCES↗

Enhanced thermoelectric performance of Mg 2 Si 1-x Sn x codoped with Bi and Cr

Magnesium silicides are favorable thermoelectric materials considering resource abundance and cost. Chromium (Cr) doping in magnesium silicides has not yet been explored. Using first-principles calculations, we have studied the stability of Mg 2 Si with chromium (1.85, 3.7, 5.55, and 6.25% Cr) and tin (12.5 and 50% Sn). Three Mg 2 Si compounds doped with Sn, (Sn + Bi), and (Sn + Bi + Cr) are used to explain doping effects on thermoelectric performance. Notably, Cr behaves nonmagnetically for ≤2%Cr, after which ferromagnetic ordering is favored (≤12.96% Cr), despite its elemental antiferromagnetic state. With alloying of Sn (70.4%), Mg 2 Si remains an indirect-band-gap semiconductor, but adding small amounts of Bi (3.7%) increases the carrier concentration such that electrons occupy conduction bands, making it a degenerate semiconductor. Mg 2 Si 0.296 Sn 0.666 Bi 0.037 is found to give the highest thermoelectric figure of merit (ZT) and power factor (PF) at 700 K, i.e., 1.75 and 7.04 mWm –1 K –2 , respectively. Adding small %Cr decreases ZT and PF to 0.78 and 4.33 mWm –1 K –2 , respectively. Such a degradation in thermoelectric (TE) performance is attributed to two factors: (i) uniform doping acting as an electron acceptor, decreasing conduction, and (ii) the loss of low-lying conduction band degeneracy with doping, decreasing the Seebeck coefficients. In conclusion, a study of configurations of Cr doping suggests that Cr has a tendency to form clusters inside the lattice, which play a crucial role in tuning the magnetic and TE performance of doped Mg 2 Si compounds.

36 MATERIALS SCIENCE↗

Systematic Catalyst Variation for Improved Stereoselective Epoxide Polymerization: Subtle Modifications Resulting in Superior Efficiency

Isotactic poly(propylene oxide) (iPPO) is a semicrystalline polyether that has emerged as a high-strength, photodegradable material for marine applications. To improve the accessibility of i PPO, catalysts with higher activity and selectivity are required. Using rational catalyst design informed by computational insights, we developed a flexibly tethered, bimetallic chromium catalyst exhibiting high enantioselectivity ( k rel ∼ 100) and unprecedented activity (TOF ∼ 50,000 h −1 ) for propylene oxide (PO) polymerization. Mechanistic studies reveal that high enantioselectivity originates from increased steric bulk at the ortho position of the salicylimine moiety, which increases steric repulsion between the alkoxide chain end and the ligand in the disfavored transition state. Furthermore, introducing geminal dimethyl groups that rigidify the flexible tether between the two ligand moieties significantly enhances catalyst activity by destabilizing the resting state during polymerization. The catalyst remains active at loadings as low as 0.5 ppm, enabling the synthesis of colorless, tough i PPO.

Ren, Bai-Hao [Cornell Univ., Ithaca, NY (United St↗

Local Structure of Fe–Cr Powders Prepared by Mechanical Alloying

We have studied the structure of Fe–Cr alloys prepared by mechanical alloying. According to X-ray diffraction data, all of the alloys are single-phase and consist of a BCC solid solution. The local structure of the alloys has been studied by Mössbauer spectroscopy. Analysis of the local environment of the Fe atoms leads us to assume clustering processes in the alloy containing 20 at % Cr and suggests that the alloys containing 35 and 50 at % Cr experience phase separation into regions of a homogeneous disordered chromium- enriched solid solution and an iron-enriched imperfect structure containing a considerable amount of dissolved gases.

36 MATERIALS SCIENCE↗

High-performance corrosion-resistant high-entropy alloys

This disclosure provides alloy compositions comprising the main constituent elements iron, nickel, cobalt, molybdenum, and chromium. In one embodiment, the alloy comprises 10.0 to 30.0 wt % iron; 30.0 to 60.0 wt % nickel; 10.0 to 25.0 wt % cobalt; 1.0 to 15.0 wt % molybdenum; 15.0 to 25.0 wt % chromium by weight; where the sum of iron and nickel is at least 50 wt %; and, where the balance comprises minor elements, the total amount of minor elements being about 5% or less by weight. The alloy compositions have use as coatings to protect metals and alloys from corrosion in extreme environments where corrosion is a major concern such as with exposure to sea water or sea water with CO 2 .

Hawk, Jeffrey A.↗

Behavior under LOCA conditions on enhanced accident tolerant chromium coated zircaloy-4 claddings

For enhanced accident tolerant fuels for light water reactors application, chromium coatings on zirconium based nuclear fuel claddings are developed and studied at CEA in the framework of the French CEA-EDF-AREVA collaborative program. The results obtained so far, mainly on Zircaloy-4 substrate, show very good corrosion resistance in nominal conditions and significant enhancement of the resistance of the material to oxidation in steam at high temperature (HT), up to 1300 Celsius degrees, with a drastic decrease of hydrogen release and/or pick-up. The present paper reports some new results obtained on chromium coated Zircaloy-4 claddings tested in loss-of-coolant accident (LOCA) conditions. In order to investigate the potential effect of the coating on the cladding mechanical behavior at HT and the capacity of the coating to sustain significant substrate deformation (i.e., during ballooning until burst occurrence) without generalized cracking/peeling, a preliminary limited set of internal pressure creep and temperature ramp tests have been performed in steam environment thanks to the EDGAR facility. The thermal-mechanical tests were done for testing/burst temperatures ranging from 600 C. degrees (α{sub Zr} phase domain) up to 1000 C. degrees (β{sub Zr} phase domain) on 50 cm long low-tin Zircaloy-4 cladding samples with a 15 μm thick outer chromium coating. It is shown that: -) whatever the applied temperature/pressure values, the chromium coating is still fully adherent after having experienced ballooning and burst, including at the vicinity of the burst opening where the Zircaloy-4 clad substrate is highly deformed; -) a HT strengthening effect of the coating on the overall creep clad behavior is evidenced when compared to uncoated Zircaloy-4 cladding materials tested in the same conditions; -) as a consequence, it is observed that, in the 600-750 C. degrees temperature range (α{sub Zr} phase domain) and after burst occurrence, the balloon sizes (i.e., 'uniform' and maximum hoop strains) are generally reduced when compared to uncoated materials; -) regarding the burst mechanism in the β{sub Zr} phase temperature range (1000 C. degrees), it is interesting to observe that, even if some ballooning occurred prior to the cladding failure, the actual burst openings are generally very small (in the order of 1 mm{sub 2} or less), reducing the risk of fuel fragments dispersal in the coolant.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

NASA's activities in the conservation of strategic aerospace materials

The United States imports 50-100 percent of certain metals critical to the aerospace industry, namely, cobalt, columbium, chromium, and tantalum. In an effort to reduce this dependence on foreign sources, NASA is planning a program called Conservation of Strategic Aerospace Materials (COSAM), which will provide technology minimizing strategic metal content in the components of aerospace structures such as aircraft engines. With a proposed starting date of October 1981, the program will consist of strategic element substitution, process technology development, and alternate materials research. NASA's two-fold pre-COSAM studies center on, first, substitution research involving nickel-base and cobalt-base superalloys (Waspaloy, Udimet-700, MAE-M247, Rene 150, HA-188) used in turbine disks, low-pressure blades, turbine blades, and combustors; and, second, alternate materials research devoted initially to investigating possible structural applications of the intermetallic alloys nickel aluminide and iron aluminide.

Stephens, J. R.↗

Comparison of Four Strong Acids on the Precipitation Potential of Gypsum in Brines During Distillation of Pretreated, Augmented Urine

In this study, three different mineral acids were substituted for sulfuric acid (H2SO4) in the urine stabilizer solution to eliminate the excess of sulfate ions in pretreated urine and assess the impact on maximum water recovery to avoid precipitation of minerals during distillation. The study evaluated replacing 98% sulfuric acid with 85% phosphoric acid (H3PO4), 37% hydrochloric acid (HCl), or 70% nitric acid (HNO3). The effect of lowering the oxidizer concentration in the pretreatment formulation also was studied. This paper summarizes the test results, defines candidate formulations for further study, and specifies the injection masses required to stabilize urine and minimize the risk of mineral precipitation during distillation. In the first test with a brine ersatz acidified with different acids, the solubility of calcium in gypsum saturated solutions was measured. The solubility of gypsum was doubled in the brines acidified with the alternative acids compared to sulfuric acid. In a second series of tests, the alternative acid pretreatment concentrations were effective at preventing precipitation of gypsum and other minerals up to 85% water recovery from 95th-percentile pretreated, augmented urine. Based on test results, phosphoric acid is recommended as the safest alternative to sulfuric acid. It also is recommended that the injected mass concentration of chromium trioxide solution be reduced by 75% to minimize liquid resupply mass by about 50%, reduce toxicity of brines, and reduce the concentration of organic acids in distillate. The new stabilizer solution formulations and required doses to stabilize urine and prevent precipitation of minerals up to 85% water recovery are given. The formulations in this study were tested on a limited number of artificially augmented urine batches collected from employees at the Johnson Space Center (JSC). This study successfully demonstrated that the desired physical and chemical stability of pretreated urine and brines can be achieved using alternate pretreatment formulations under laboratory conditions. Additional testing and hazard assessments will be required to determine the feasibility of utilizing the proposed urine pretreatment formulations on ISS.

Muirhead, Dean↗

A fetal whole ovarian culture model for the evaluation of CrVI-induced developmental toxicity during germ cell nest breakdown

Prenatal exposure to endocrine disrupting chemicals (EDCs), including bisphenol A, dioxin, pesticides, and cigarette smoke, has been linked to several ovarian diseases such as premature ovarian failure (POF) and early menopause in women. Hexavalent chromium (CrVI), one of the more toxic heavy metals, is widely used in more than 50 industries. As one of the world's leading producers of Cr compounds, the U.S. is facing growing challenges in protecting human health against adverse effects of CrVI. Our recent findings demonstrated that in vivo CrVI exposure during gestational period caused POF in F1 offspring. Our current research focus is three-fold: (i) to identify the effect of CrVI on critical windows of great vulnerability of fetal ovarian development; (ii) to understand the molecular mechanism of CrVI-induced POF; (iii) to identify potential intervention strategies to mitigate or inhibit CrVI effects. In order to accomplish these goals we used a fetal whole ovarian culture system. Fetuses were removed from the normal pregnant rats on gestational day 13.5. Fetal ovaries were cultured in vitro for 12 days, and treated with or without 0.1 ppm potassium dichromate (CrVI) from culture day 2–8, which recapitulated embryonic day 14.5–20.5, in vivo. Results showed that CrVI increased germ cell/oocyte apoptosis by increasing caspase 3, BAX, p53 and PUMA; decreasing BCL2, BMP15, GDF9 and cKIT; and altering cell cycle regulatory genes and proteins. This model system may serve as a potential tool for high throughput testing of various drugs and/or EDCs in particular to assess developmental toxicity of the ovary. - Highlights: • CrVI (0.1 ppm, a regulatory dose) increased germ cell apoptosis of fetal ovaries. • CrVI (0.1 ppm) increased pro-apoptotic proteins. • CrVI (0.1 ppm) decreased cyclins and CDK1 and cell survival proteins. • CrVI (0.1 ppm) increased oxidative stress during fetal ovarian development. • We propose fetal ovarian culture model for high-throughput testing of heavy-metals.

60 APPLIED LIFE SCIENCES↗

Infrared absorptivities of transition metals at room and liquid-helium temperatures.

Evaluation of experimental data concerning the normal spectral absorptivities of the transition metals, nickel, iron, platinum, and chromium, at both room and liquid-helium temperatures in the wavelength range from 2.5 to 50 microns. The absorptivities were derived from reflectivity measurements made relative to a room-temperature vapor-deposited gold reference mirror. The absorptivity of the gold reference mirror was measured calorimetrically, by use of infrared laser sources. Investigation of various methods of sample-surface preparation resulted in the choice of a vacuum-annealing process as the final stage. The experimental results are discussed on the basis of the anomalous-skin-effect theory modified for multiple conduction bands. As predicted, the results approach a single-band model toward the longer wavelengths. Agreement between theory and experiment is considerably improved by taking into account the modification of the relaxation time due to the photon-electron-phonon interaction proposed by Holstein (1954) and Gurzhi (1958); but, particularly at helium temperatures, the calculated curve is consistently below the experimental results.

Jones, M. C.↗

Dislocation loop evolution during in-situ ion irradiation of model FeCrAl alloys

Model FeCrAl alloys of Fe-10%Cr-5%Al, Fe-12%Cr-4.5%Al, Fe-15%Cr-4%Al, and Fe-18%Cr-3%Al (in wt %) were irradiated with 1 MeV Kr++ ions in-situ with transmission electron microscopy to a dose of 2.5 displacements per atom (dpa) at 320 °C. In all cases, the microstructural damage consisted of dislocation loops with ½< 111 > and <100 > Burgers vectors. The proportion of ½< 111 > dislocation loops varied from ~50% in the Fe-10%Cr-5%Al model alloy and the Fe-18Cr%-3%Al model alloy to a peak of ~80% in the model Fe-15%Cr-4.5%Al alloy. The dislocation loop volume density increased with dose for all alloys and showed signs of approaching an upper limit. The total loop populations at 2.5 dpa had a slight (and possibly insignificant) decline as the chromium content was increased from 10 to 15 wt %, but the Fe-18%Cr-3%Al alloy had a dislocation loop population ~50% smaller than the other model alloys. As a result, the largest dislocation loops in each alloy had image sizes of close to 20 nm in the micrographs, and the median diameters for all alloys ranged from 6 to 8 nm. Nature analysis by the inside-outside method indicated most dislocation loops were interstitial type.

36 MATERIALS SCIENCE↗

Mach 1 oxidation of thoriated nickel chromium at 1204 C (2200 F)

TD NiCr was exposed to a Mach 1, 1-atmosphere gas stream at 1204 C for times up to 50 hours. Weight change, metal thickness loss, X-ray diffraction, metallographic, and electron microprobe analyses were made. Neither surface preparation nor thermal cycling had an appreciable effect on the results. Initially, Cr2O3 formed and volatilized, allowing a rapid metal loss rate of 40 microns per hour. After about 1 hour the Cr2O3 broke down, resulting in an NiO overgrowth. The metal loss rate then slowed to 2.5 microns per hour and remained constant to 50 hours.

Lowell, C. E.↗