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Series of coatings provides hard, impermeable, waterproof layer. Inclusion of color oxides imparts high emittance to surface. Refractory fillers investigated include TiO2, BaO.ZrO2, SrO.TiO2 ziron, spodumene, petalite, and kryptonite. Colorants include Cr2O3, NiO, and CoO.
A FORTRAN computer program (COREST) was developed to analyze the high-temperature paralinear oxidation behavior of metals. It is based on a mass-balance approach and uses typical gravimetric input data. COREST was applied to predominantly Cr2O3-forming alloys tested isothermally for long times. These alloys behaved paralinearly above 1100 C as a result of simultaneous scale formation and scale vaporization. Output includes the pertinent formation and vaporization constants and kinetic values of interest. COREST also estimates specific sample weight and specific scale weight as a function of time. Most importantly, from a corrosion standpoint, it estimates specific metal loss.
An hypothesis for mare basalt petrogenesis is presented. In the proposed model, both high- and low-Ti mare basalts are produced by partial melting and hybridization at depth accompanied by equilibrium between the hybrid liquids and the local olivine-pyroxenite residuum. The energy source for mare basalt formation is ultimately provided by radiogenic heating in the primordial lunar interior. The proposed dynamic model explains similarities in the Mg/(Mg+Fe) ratios and Cr2O3 contents of high-Ti and low-Ti basalts and avoids thermal problems inherent in previous models.
Target collection techniques and high pressure mass spectrometric sampling have been used to study the formation of volatile chromium-containing species in the reaction of Cr2O3 with O2 and NaCl gases. Experiments were performed at atmospheric pressure as a function of chromium temperature, oxygen pressure, and NaCl gas concentration. The major chromium-containing vapor species were found to be (NaCl)x CrO3 gas, with x = 1,2, and 3, which are products of heterogeneous reactions on the surface. The kinetics indicate first order dependence on oxygen and sodium chloride pressures.
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.
Experiments were performed determining the distribution of chromium between olivine, pyroxenes, and melt at oxygen fugacity values near those of lunar rocks for a wide range of bulk compositions. The range of values of D-Cr (wt% of Cr2O3 in crystals/Cr2O3 in melt) is 0.6-1.3 for olivine and 1.6-3.5 for pyroxene; this ratio shows no obvious dependence on any experimental parameter.
Target collection techniques and high pressure mass spectrometric sampling have been used to study the formation of volatile chromium-containing species in the reaction of Cr2O3 in the condensed state with gaseous O2 and NaCl. Experiments were performed at atmospheric pressure as a function of chromium temperature, oxygen pressure, and NaCl concentration. The major chromium-containing vapor species were found to be (NaCl)xCrO3, with x = 1,2, and 3, which are products of heterogeneous reactions on the surface. The kinetics indicate first order dependence on oxygen and sodium chloride pressures.
The reactions between partially stabilized zirconia, containing 8 weight-percent yttria, and oxides and sulfates of various elements were studied at 1200, 1300, and 1400 C for times to 800, 400, and 200 hours, respectively. These oxides and sulfates represent impurities and additives potentially present in gas turbine fuels or impurities in the turbine combustion air as well as the elements of the substrate alloys in contact with zirconia. Based on the results, these compounds can be classified in four groups: (1) compounds which did not react with zirconia (Na2SO4, K2SO4, Cr2O3, Al2O3 and NiO); (2) compounds that reached completely with both zirconia phases (CaO, BaO, and BaSO4); (3) compounds that reacted preferentially with monoclinic zirconia (Na2O, K2O, CoO, Fe2O3, MgO, SiO2, and ZnO); and (4) compounds that reacted preferentially with cubic zirconia (V2O5, P2O5).
Equilibrium and controlled cooling rate experiments on a synthetic analog of Apollo 15 quartz normative basalt 15597 are reported. While the partitioning of the major elements Ca, Mg, and Fe between pyroxene and liquid is rate independent, the K sub D parameter for Fe/Mg, which is calculated for low-Ca pyroxene, is temperature dependent. It is suggested that chemical trends observed in lunar pyroxenes are a consequence of three rate processes. The processes are (1) rate-dependent suppression of crystallization of other phases until lower temperature alters liquid composition and, therefore, the composition of the pyroxene that crystallizes; (2) the efficiency of fractional crystallization and the extent of crystal zoning are rate dependent; and (3) the partitioning of Al2O3, TiO2, and Cr2O3 between pyroxene and liquid depends on cooling rate.
Accurate electron microprobe analyses (approximately 50 ppm) were made for Al, Ca, Ti, Cr, Mn, and Ni in Mg-rich olivines which may derive from early lunar crust or deeper environments. Low-Ca contents consistently occur only in olivines from dunitic and troctolitic breccia: spinel troctolite and other rock types have high-Ca olivines suggesting derivation by near-surface processes. Rock 15445 has olivine with distinctly low CaO (approximately 0.01 wt.%). Chromium ranges to higher values (max.0.2 oxide wt.%) than for terrestrial harzburgites and lherzolites but is similar to the range in terrestrial komatiites. Divalent chromium may be indicated over trivalent Cr because olivines lack sufficient other elements for charge balance of the latter. NiO values in lunar specimens range from 0.00 to 0.07 wt.% and a weak anticorrelation with Cr2O3 suggests an oxidation state effect. Al2O3 values are mostly below 0.04-wt.% and show no obvious correlation with fragment type. TiO2 values lie below 0.13-wt.% and seem to correlate best with crystallization rate and plagioclase content of the host rock. High values of Al2O3 and TiO2 reported by other workers have not been confirmed, and are probably wrong.
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.
Results are reported on a combined INAA-petrologic study of 17 small (0.2-1.5 mg) Luna 24 lithic and mineral fragments and INAA study of 5 bulk soils and mineral separates from gabbro 24170. Lithic and mineral fragments are classified into VLT mare basalts (ferrobasalt and metabasalts), low-Ti, variolitic mare basalt, gabbros, melt rock and soil breccia. Data indicate 5 possible magma types, represented by: (1) VLT ferrobasalt and gabbro fragments, with low-TiO2 (about 1%), slightly bow-shaped REE pattern, and low REE concentrations (5-10X chondritic); (2) a ferrobasalt (Laul et al., 1978) and metabasalt fragments with major and trace element contents similar to (1), but positive Eu anomalies; (3) one gabbro fragment with distinctive pyroxene compositional trend (increasing Ti with nearly constant Fe/Fe + Mg) and highest REE contents of any Luna 24 mare basaltic sample, (4) a gabbro fragment with considerably less V and Cr2O3 than ferrobasalt and metabasalt fragments; and (5) variolitic basalt fragment with higher Ti2(2.3%) than other Luna 24 basalts and pyroxene that has increasing then decreasing Ti with increasing Fe/Fe + Mg. Trace element data place constraints on the nature of the source region and possible parent magmas for the Luna 24 VLT ferrobasalt.
Regression and pattern recognition techniques were applied to 16 chemical species in 34 Apollo 17 basalts. The classification scheme of Pratt et al., (1977) was used. Data were absent for 8 MnO, 3 Hf, 3 Tb, and 8 Cr2O3 analyses. Linear regression studies were utilized to predict these and values obtained were added to the original data base. Pattern recognition techniques were then applied to predict classifications for 30 different Apollo 17 rake basalts analyzed by Murali et al., (1977).
Polarized absorption spectra of lunar pyroxenes with a range of iron, calcium, magnesium, titanium and chromium contents were measured on polished, oriented single crystals; spectral data on pure synthetic FeSiO3 were also recorded. The bands at 1 and 2 microns were found to vary significantly in position with composition within the pyroxene quadrilateral; wavelengths increased with increasing calcium and iron. In the visible region, a weak band at 640 nm correlates in intensity with Cr2O3, but not with titanium as had been previously suggested. The 505-nm ferrous iron peak is a sharp doublet in most low-calcium pyroxenes but a singlet in augites. A peak at 475 nm and an intense absorption edge below 700 nm correlated with titanium content.
Calcium orthosilicate and barium zirconate were evaluated as the insulation layer of thermal barrier coatings for air cooled gas turbine components. Their reactions with various oxides and sulfates were studied at 1100 C and 1300 C for times ranging up to 400 and 200 hours, respectively. These oxides and sulfates represent potential impurities or additives in gas turbine fuels and in turbine combustion air, as well as elements of potential bond coat alloys. The phase compositions of the reaction products were determined by X-ray diffraction analysis. BaZrO3 and 2CaO-SiO2 both reacted with P2O5, V2O5, Cr2O3, Al2O3, and SiO2. In addition, 2CaO-SiO2 reacted with Na2O, BaO, MgO, and CoO and BaZrO3 reacted with Fe2O3.
Thermal fatigue and oxidation data were obtained for 11 plasma spray coated and 13 uncoated directionally solidified and single crystal MAR-M 246 blades. Blade coatings on the airfoil included several metal-oxide thermal barrier layers based on Al2O3, Cr2O3, or ZrO2. The 24 turbine blades were tested simultaneously for 3000 cycles in fluidized beds maintained at 950 and 25 C using a symmetrical 360 set thermal cycle. In 3000 cycles, only uncoated turbine blades exhibited cracking on the trailing edge near the platform; 3 of the 13 uncoated blades did not crack. Cracking occurred over the range 400 to 2750 cycles, with single crystal blades indicating the poorest thermal fatigue resistance. Oxidation of the uncoated blades was limited in 3000 cycles. All coatings indicated microscopically visible spalling at the trailing edge radius after 3000 cycles. Severe general spalling on the airfoil was observed for two multilayered coatings.
The effect of SO3 pressure in the gas phase on the Na2SO4 induced hot corrosion of Co-Cr, Ni-Cr, and Co-Cr-Al alloys was studied in the temperature range 700 to 750 C. The degradation of the Co-Cr and Ni-Cr alloys was found to be associated with the formation of liquid mixed sulfates (CoSO4-Na2SO4 or NiSO4-Na2SO4) which provided a selective dissolution of the Co or Ni and a subsequent sulfidation oxidation mode of attack which prevented the maintenance of a protective Cr2O3 film. A clear mechanism was not developed for the degradation of Co-Cr-Al alloys. A pitting corrosion morphology was induced by a number of different mechanisms.
The paper discusses element bulk compositions of 373 chondrules from 18 H3 to H6 chondrites determined by broad-beam electron probe analysis. Bulk chondrule FeO and Al2O3 amounts increase and TiO2 and Cr2O3 decrease with increasing petrologic type; normative faylite, albite, and plagioclase amounts increase through the petrologic sequence. Chondrule diameters correlate with phenocryst sizes in porphyritic chondrules of type 3 chondrites, but this correlation is diminished in the higher petrologic types. The compositional trends in chondrules through the petrologic sequence are attributed to diffusion and equilibration among chondrules, and between chondrules and matrix in response to increasing degrees of thermal metamorphism. It is suggested that H-group chondrites are formed by accretion of high-temperature (chondrules) and low-temperature (matrix) materials. Internal reheating of the parent materials to different temperatures caused compositional equilibration, grain coarsening, and reduction of FeO to Fe(0) by carbon.