Research Into the Diffusion of Carbon Into Zirconium and Zirconium Carbide
Diffusion of carbon into zirconium and zirconium carbide
ZIRCONIUM CARBIDE↗
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Structure of zirconium-93 and zirconium-91 as shown by the reactions Zr-92(d,p)Zr-93 and Zr-92(d,t)Zr-91
Deuterons of 13-MeV incident energy were scattered from Zr-92(d,p)Zr-93. The Zr-92(d,p)Zr-93 data analysis resulted in the location of 47 levels up to an excitation energy of 4.84 MeV, and the spins of 43 of these levels were identified. Essentially all the strength of the 2d5/2, 3s1/2, 2d3/2, and 1g7/2 shells was observed; and the excitation energy of their centroids was computed to be 0.00, 1.21, 2.23, and 2.37 MeV, respectively. Also, 43 percent of the 1h11/2 strength, 21 percent of the 2f7/2 strength, and 3 percent of the 3p3/2 strength were observed. In addition, the Zr-92(d,t)Zr-91 data analysis resulted in the location of 26 levels up to an excitation energy of 4.01 MeV, and the spins of 21 of these levels were identified. Most of the expected strength of the 2d5/2 and 1g9/2 shells was obtained, and the excitation energy of their centroids was computed to be 0.31 and 3.19 MeV, respectively. In addition, six l=1 states are populated belonging to either the 2p1/2 or 2p3/2 shells.
Baron, N.↗
A simple spectrophotometric method for determination of zirconium or hafnium in selected molybdenum-base alloys
A simple analytical procedure is described for accurately and precisely determining the zirconium or hafnium content of molybdenum-base alloys. The procedure is based on the reaction of the reagent Arsenazo III with zirconium or hafnium in strong hydrochloric acid solution. The colored complexes of zirconium or hafnium are formed in the presence of molybdenum. Titanium or rhenium in the alloy have no adverse effect on the zirconium or hafnium complex at the following levels in the selected aliquot: Mo, 10 mg; Re, 10 mg; Ti, 1 mg. The spectrophotometric measurement of the zirconium or hafnium complex is accomplished without prior separation with a relative standard deviation of 1.3 to 2.7 percent.
Dupraw, W. A.↗
Zirconium fluoride glass - Surface crystals formed by reaction with water
The hydrated surfaces of a zirconium barium fluoride glass, which has potential for application in optical fibers and other optical elements, were observed by scanning electron microscopy. Crystalline zirconium fluoride was identified by analysis of X-ray diffraction patterns of the surface crystals and found to be the main constituent of the surface material. It was also found that hydrated zirconium fluorides form only in highly acidic fluoride solutions. It is possible that the zirconium fluoride crystals form directly on the glass surface as a result of its depletion of other ions. The solubility of zirconium fluoride is suggested to be probably much lower than that of barium fluoride (0.16 g/100 cu cm at 18 C). Dissolution was determined to be the predominant process in the initial stages of the reaction of the glass with water. Penetration of water into the glass has little effect.
Doremus, R. H.↗
The effect of sulfur and zirconium Co-doping on the oxidation of NiCrAl
The adhesion behavior of Al2O3 scales formed on NiCrAl+Zr alloys was examined as a function of both sulfur and zirconium doping levels. In general, very high levels of zirconium were required to counteract the detrimental effects of sulfur. A sulfur-zirconium adherence map was constructed, as determined from the oxidation and spalling behavior in 1100 C cyclic tests. For low sulfur alloys, the amount of zirconium required for adherence at any given sulfur level can be described by Zr greater than 600 S sup 0.2 (in ppma). These results underscore the importance of sulfur to adhesion mechanisms and suggests that sulfur gettering is a first order effect of reactive element additions to MCrAl alloys.
Smialek, James L.↗
The effect of sulfur and zirconium co-doping on the oxidation of NiCrAl
The adhesion behavior of Al2O3 scales formed on NiCrAl+Zr alloys was examined as a function of both sulfur and zirconium doping levels. In general, very high levels of zirconium were required to counteract the detrimental effects of sulfur. A sulfur-zirconium adherence map was constructed, as determined from the oxidation and spalling behavior in 1100 C cyclic tests. For low sulfur alloys (less than 500 ppma), the amount of zirconium required for adherence at any given sulfur level can be described by Zr greater than 600 S(0.2) (in ppma). These results underscore the importance of sulfur to adhesion mechanisms and suggest that sulfur gettering is a first order effect of reactive element additions to MCrAl alloys.
Smialek, James L.↗
Nanophase Nickel-Zirconium Alloys for Fuel Cells
Nanophase nickel-zirconium alloys have been investigated for use as electrically conductive coatings and catalyst supports in fuel cells. Heretofore, noble metals have been used because they resist corrosion in the harsh, acidic fuel cell interior environments. However, the high cost of noble metals has prompted a search for less-costly substitutes. Nickel-zirconium alloys belong to a class of base metal alloys formed from transition elements of widely different d-electron configurations. These alloys generally exhibit unique physical, chemical, and metallurgical properties that can include corrosion resistance. Inasmuch as corrosion is accelerated by free-energy differences between bulk material and grain boundaries, it was conjectured that amorphous (glassy) and nanophase forms of these alloys could offer the desired corrosion resistance. For experiments to test the conjecture, thin alloy films containing various proportions of nickel and zirconium were deposited by magnetron and radiofrequency co-sputtering of nickel and zirconium. The results of x-ray diffraction studies of the deposited films suggested that the films had a nanophase and nearly amorphous character.
Narayanan, Sekharipuram↗
Reduced-Gravity Measurements of the Effect of Oxygen on Properties of Zirconium
The influence of oxygen on the thermophysical properties of zirconium is being investigated using MSL-EML (Material Science Laboratory - Electromagnetic Levitator) on ISS (International Space Station) in collaboration with NASA, ESA (European Space Agency), and DLR (German Aerospace Center). Zirconium samples with different oxygen concentrations will be put into multiple melt cycles, during which the density, viscosity, surface tension, heat capacity, and electric conductivity will be measured at various undercooled temperatures. The facility check-up of MSL-EML and the first set of melting experiments have been successfully performed in 2015. The first zirconium sample will be tested near the end of 2015. As part of ground support activities, the thermophysical properties of zirconium and ZrO were measured using a ground-based electrostatic levitator located at the NASA Marshall Space Flight Center. The influence of oxygen on the measured surface tension was evaluated. The results of this research will serve as reference data for those measured in ISS.
Zhao, J.↗
Containerless Liquid to Solid Nucleation Pathways in Two Representative Grades of Commercially Available Zirconium
Experimental measurements were conducted to determine the solid metal nucleation pathways of radiatively cooling, molten zirconium spheres of two different commercially available purity grades in a high-vacuum, high-temperature electrostatic levitator. The ensemble distribution of maximum undercooling temperatures was interpreted using Poisson statistics to determine the temperature dependence of the solid metal nucleation rate. For a sample of nominally 99.95% pure zirconium, the results are consistent with heterogeneous solid metal nucleation either on static catalyst particles at least ~30 nm diameter or on a surface coating. For a sample of nominally 99% pure zirconium, however, it appears that heterogeneous solid metal nucleation occurred either on a polydispersion of ~10 nm (mean diameter) static catalyst particles or on dynamic catalyst particles which precipitated from a solution which became supersaturated as the melt cooled. A quantitative analysis of the compositions of both samples suggests that the catalysts probably consisted of one or more of the following elements: niobium, molybdenum, hafnium, and oxygen.
containerless, nucleation, zirconium↗
High temperature, low-cycle fatigue of copper-base alloys in argon. Part 2: Zirconium-copper at 482, 538 and 593 C
Zirconium-copper (1/2 hard) was tested in argon over the temperature range from 482 to 593 C in an evaluation of short-term tensile and low-cycle fatigue behavior. The effect of strain rate on the tensile properties was evaluated at 538 C and in general it was found that the yield and ultimate strengths increased as the strain rate was increased from 0.0004 to 0.01/sec. Ductility was essentially insensitive to strain rate in the case of the zirconium-copper alloy. Strain-rate and hold-time effects on the low cycle fatigue behavior of zirconium-copper were evaluated in argon at 538 C. These effects were as expected in that decreased fatigue life was noted as the strain rate decreased and when hold times were introduced into the tension portion of the strain-cycle. Hold times in compression were much less detrimental than hold times in tension.
Conway, J. B.↗
Zirconium and hafnium in meteorites
The abundances of zirconium and hafnium have been determined in nine stony meteorites by a new, precise neutron-activation technique. The Zr/Hf abundance ratios for the chondrites vary in a rather narrow range, consistent with previously published observations from our group. Replicate analyses of new, carefully selected clean interior samples of the Cl chondrite Orgueil yield mean zirconium and hafnium abundances of 5.2 and 0.10 ppm, respectively. These abundances are lower than we reported earlier for two Cl chondrite samples which we now suspect may have suffered contamination. The new Cl zirconium and hafnium abundances are in closer agreement with predictions based on theories of nucleosynthesis than the earlier data.
Ehmann, W. D.↗
The effect of zirconium on the isothermal oxidation of nominal Ni-14Cr-24Al alloys
The isothermal oxidation of Ni-14Cr-24Al-xZr-type alloys was performed in still air at 1100, 1150, and 1200 C for times up to 200 hr. The zirconium content of the alloys varied from 0-0.63 atom percent (a/o). The oxidized surfaces were studied by optical microscopy, X-ray diffraction, and scanning electron microscopy. The base alloy was an alumina former with the zirconium-containing alloys also developing some ZrO2. The addition of zirconium above 0.066 a/o increased the rate of weight gain relative to the base alloy. Due to oxide penetratio, the weight gain increased with Zr content; however, the scale thickness did not increase. The Zr did increase the adherence of the oxide, particularly at 1200 C. The delta W/A vs. time data fit the parabolic model of oxidation. The specific diffusion mechanism operative could not be identified by analysis of the calculated activation energies. Measurements of the Al2O3 scale lattice constants yielded the same values for all alloys.
Kahn, A. S.↗
The effect of zirconium on the cyclic oxidation of NiCrAl alloys
This paper examines results with cyclic oxidation tests of Ni(9-20) Cr(15-30) Al-(x)Zr alloys carried out at 1100 C and 1200 C in static air. The concentration of zirconium varies from 0 to 0.63 atomic percent. Significant aluminum penetration is found in metallographic and electron microscopic examination of oxidized surfaces. Small amounts of zirconium lead to minimal penetration, and with increased zirconium content pronounced oxide penetration is observed.
Barrett, C. A.↗
Containerless Liquid to Solid Nucleation Pathways in Two Representative Grades of Commercially Available Zirconium
Experimental measurements were conducted to determine the solid metal nucleation pathways of radiatively cooling, molten zirconium spheres of two different commercially available purity grades in a high-vacuum, high-temperature electrostatic levitator. The ensemble distribution of maximum undercooling temperatures was interpreted using Poisson statistics to determine the temperature dependence of the solid metal nucleation rate. For a sample of nominally 99.95% pure zirconium, the results are consistent with heterogeneous solid metal nucleation either on static catalyst particles at least approx. 30 nm diameter or on a surface coating. For a sample of nominally 99% pure zirconium, however, it appears that heterogeneous solid metal nucleation occurred either on a polydispersion of approx. 10 nm (mean diameter) static catalyst particles or on dynamic catalyst particles that precipitated from a solution that became supersaturated as the melt cooled.
Rulison, A. J.↗
Ablation Resistant Zirconium and Hafnium Ceramics
High temperature ablation resistant ceramic composites have been made. These ceramics are composites of zirconium diboride and zirconium carbide with silicon carbide, hafnium diboride and hafnium carbide with silicon carbide and ceramic composites which contain mixed diborides and/or carbides of zirconium and hafnium. along with silicon carbide.
Bull, Jeffrey↗
Studies in zirconium oxidation
Study provides insight into the oxidation mechanism of zirconium by combining electrical measurements with oxidation data. The measurement of electrical potential across growing scale on zirconium and the determination of conventional weight-change oxidation data were carried out at 550, 700, and 800 degrees C.
Draley, J. E.↗
High temperature mechanical properties of a zirconium-modified, precipitation- strengthened nickel, 30 percent copper alloy
A precipitation-strengthened Monel-type alloy has been developed through minor alloying additions of zirconium to a base Ni-30Cu alloy. The results of this exploratory study indicate that thermomechanical processing of a solution-treated Ni-30Cu-0.2Zr alloy produced a dispersion of precipitates. The precipitates have been tentatively identified as a Ni5Zr compound. A comparison of the mechanical properties, as determined by testing in air, of the zirconium-modified alloy to those of a Ni-30Cu alloy reveals that the precipitation-strengthened alloy has improved tensile properties to 1200 K and improved stress-rupture properties to 1100 K. The oxidation characteristics of the modified alloy appeared to be equivalent to those of the base Ni-30Cu alloy.
Whittenberger, J. D.↗
Critical role of nitrogen during high temperature scaling of zirconium
The mechanisms of scale cracking, scale color changes, and scale growth, and their interrelations, were studied in zirconium specimens at elevated temperatures in air, oxygen and nitrogen. Nitrogen was found to be responsible for monoclinic-to-cubic ZrO2 conversion, for scale cracking and breakaway on zirconium nitride, and for the formation of ZrN on the metal interface underneath an outer oxide layer.
Evans, E. B.↗