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Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.
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High temperature research in vacuum - magnesium oxide and zirconium dioxide interaction with refractory metal carbides, nitrates, and borides
Corrosion testing of nickel, cobalt, nickel cobalt alloy, borides, and other fuel cell catalyst samples for activity in oxidation of hydrazine
Improved ablative materials - design of chemical vapor plating reactor for preparing titanium boride and titanium carbide continuous filaments
Refractory oxides, carbides and borides in combination with metals investigated for stability in high temperature cermet applications
Heat treatment of carbide and boride strengthened chromium alloys to improve tensile and creep rupture strength
The behavior and properties of the refractory carbides, nitrides, and borides are being investigated by NASA as part of its research aimed at developing superior heat resistant materials for aerospace applications. Fundamental studies on the electronic and defect structures of the carbides indicate that there is promise for improving the strength and ductility of these materials. Studies of the zirconium-carbon-oxygen system show that zirconium oxycarbides of different compositions and lattice parameters can be formed between 1500 and 1900 C and are stable below 1500 C. More applied studies show that hot working generally improves the microstructure and therefore the strength of TiC and NbC. Sintering studies on UN indicate that very high densities can be achieved. Hot pressing of cermets of HfN and HfC produces good mechanical properties for high temperature bearing applications.
Attempts made to develop processes capable of producing metal composites in structural shapes and sizes suitable for space applications are described. The processes must be continuous and promise to lower fabrication costs. Special attention was given to the aluminum boride (Al/b) composite system. Results show that despite adequate temperature control, the consolidation characteristics did not improve as expected. Inadequate binder removal was identified as the cause responsible. An Al/c (aluminum-graphite) composite was also examined.
The feasibility of producing directionally solidified eutectic alloy composites by edge-defined, film-fed growth (EFG) was carried out. The three eutectic alloys which were investigated were gamma + delta, gamma/gamma prime + delta, and a Co-base TaC alloy containing Cr and Ni. Investigations into the compatibility and wettability of these metals with various carbides, borides, nitrides, and oxides disclosed that compounds with the largest (negative) heats of formation were most stable but poorest wetting. Nitrides and carbides had suitable stability and low contact angles but capillary rise was observed only with carbides. Oxides would not give capillary rise but would probably fulfill the other wetting requirements of EFG. Tantalum carbide was selected for most of the experimental portion of the program based on its exhibiting spontaneous capillary rise and satisfactory slow rate of degradation in the liquid metals. Samples of all three alloys were grown by EFG with the major experimental effort restricted to gamma + delta and gamma/gamma prime + delta alloys. In the standard, uncooled EFG apparatus, the thermal gradient was inferred from the growth speed and was 150 to 200 C/cm. This value may be compared to typical gradients of less than 100 C/cm normally achieved in a standard Bridgman-type apparatus. When a stream of helium was directed against the side of the bar during growth, the gradient was found to improve to about 250 C/cm. In comparison, a theoretical gradient of 700 C/cm should be possible under ideal conditions, without the use of chills. Methods for optimizing the gradient in EFG are discussed, and should allow attainment of close to the theoretical for a particular configuration.
A method of measuring the longitudinal residual stress distribution in boron fibers is presented. The residual stresses in commercial CVD boron on tungsten fibers of 102, 142, and 203 microns (4, 5.6, and 8 mil) diameters were determined. Results for the three sizes show a compressive stress at the surface 800 to -1400 MN/sq m 120 to -200 ksi), changing monotonically to a region of tensile stress within the boron. At approximately 25 percent of the original radius, the stress reaches a maximum tensile 600 to 1000 MN/sq m(90 to 150 ksi) and then decreases to compressive near the tungsten boride core. The core itself is under a compressive stress of approximately -1300 MN/sq m (-190 ksi). The effects of surface removal on core residual stress and core-initiated fracture are discussed.
By measuring the change in fracture stress of 203 micrometer diameter fibers of boron on tungsten (B/W) as a function of fiber diameter as reduced by chemical etching, it is shown that the flaws which limit B/W fiber strength are located at the surface and in the tungsten boride core. After etching to a diameter of 188 micrometers m virtually all fiber fractures were caused by core flaws, the average strength being 4.50 GN/sq m. If both the surface and core flaws are removed, the fracture strength, limited by flaws in the boron itself, is approximately 6.89 GN/sq m. This was measured on B/W fibers which were split longitudinally and had their cores removed by chemical etching. The longitudinal residual stress distribution was determined for 102 micrometer diameter B/W and B/C fibers.
Improvement in the strain-to-failure of CVD boron fibers is shown possible by contracting the tungsten boride core region and its inherent flaws. The results of three methods are presented in which etching and thermal processing techniques were employed to achieve core flaw contraction by internal stresses available in the boron sheath. After commercially and treatment induced surface flaws were removed from 203 micrometers (8 mil) fibers, the core flaw was observed to be essentially the only source of fiber fracture. Thus, fiber strain-to-failure was found to improve by an amount equal to the treatment induced contraction on the core flaw. Commercial feasibility considerations suggest as the most cost effective technique that method in which as-produced fibers are given a rapid heat treatment above 700 C. Preliminary results concerning the contraction kinetics and fracture behavior observed are presented and discussed both for high vacuum and argon gas heat treatment environments.
Improvement in the strain-to-failure of chemical-vapor-deposition boron fibers is shown possible by contracting the tungsten boride core region and its inherent flaws. Results of three methods are presented in which etching and thermal-processing techniques were employed to achieve core flaw contraction by internal stresses available in the boron sheath. After commercially and treatment-induced surface flaws were removed from 203-micron (8-mil) fibers, the core flaw was observed to be essentially the only source of fiber fracture. Thus, fiber strain-to-failure was found to improve by an amount equal to the treatment-induced contraction on the core flaw. To date, average fracture strains and stresses greater than 1.4% and 5.5 GN/sq m (800 ksi), respectively, have been achieved. Commercial feasibility considerations suggest as the most cost-effective technique that method in which as-produced fibers are given a rapid heat treatment above 700 C. Preliminary results concerning the contraction kinetics and fracture behavior observed with this technique are presented and discussed for both high-vacuum and argon-gas heat-treatment environments.
The axial residual stress distribution as a function of radius was determined from the fiber surface to the core including the average residual stress in the core. Such measurements on boron on tungsten (B/W) fibers show that the residual stresses for 102, 142, 203, and 366 micron diameter fibers were similar, being compressive at the surface and changing monotonically to a region of tensile within the boron. At approximately 25 percent of the original radius, the stress reaches a maximum tensile stress of about 860 mn/sq.m and then decreases to a compressive stress near the tungsten boride core. Data were presented for 203 micron diameter B/W fibers that show annealing above 900 C reduces the residual stresses. A comparison between 102 micron diameter B/W and boron on carbon (b/C) shows that the residual stresses were similar in the outer regions of the fibers, but that large differences near and in the core were observed. The effects of these residual stresses on the fracture of boron fibers were discussed.
Silicon sessile drop experiments were performed on a variety of commercially available refractory carbides, nitrides, oxides, and borides to examine the potential of these materials for applications involving either direct contact with molten silicon or as substrates for CVD coatings in the fabrication of dies and crucibles for containing molten silicon. Simultaneous experiments were also conducted with CVD layers of SiC, Si3N4, and SiOxNy. Silicon nitride layers, deposited with NH3:SiH4 ratios ranging from 100:1 down to 5:1, were examined in sessile drop experiments to determine if the layers are degraded as a result of using lower reagent ratios. Preliminary experiments were undertaken on the stability of CVD Si3N4 near the melting point of silicon. Silicon ribbon segments were grown from vitreous carbon dies which had been coated with CVD Si3N4. Depending upon the purity of the die materials, ribbon resistivity values up to 40 Omega cm were obtained.
Several refractory silicide, boride, and carbide coatings were examined. The coatings were applied to type 440C steel surfaces by radio-frequency sputtering. The friction and wear properties of the coatings were found to be related to stoichiometry and impurity content of the bulk coating as well as the degree of interfacial adherence between coating and substrate. Bulk coating stoichiometry could to a large extent be controlled by the application of a negative bias voltage during deposition. Adherence was promoted by the formation of an oxidized layer at the interface. Deliberate preoxidizing of the 440C produced enhanced adherence for many compounds which are related to the formation of a mixed oxide transition region.
A method of measuring axial residual stresses in boron fibers is presented. With this method, the axial residual stress distribution as a function of radius is determined from the fiber surface to the core including the average residual stress in the core. Such measurements on boron on tungsten (B/W) fibers show that the residual stresses for 102, 142, 203, and 366 micron diam fibers are similar, being compressive at the surface and changing monotonically to a region of tensile stress within the boron. At approximately 25% of the original radius, the stress reaches a maximum tensile stress of about 860 MN sq m and then decreases to a compressive stress near the tungsten boride core. Data are presented for 203-micron diam B/W fibers that show annealing above 900 C reduces the residual stresses. A comparison between 102-micron diam B/W and boron on carbon (B/C) show that the residual stresses are similar in the outer regions of the fibers, but that large differences near and in the core are observed. Fracture of boron fibers is discussed.
An advanced coreless boron fiber exhibits tensile strengths which are more than twice that of the normal CVD B/W fibers. The coreless fiber is made by the chemical removal of the tungsten boride core exposed by splitting the as-grown fiber. The easily splittable fiber is made by the chemical vapor deposition of boron on a larger than usual tungsten substrate. It is expected that the ease of splitting is related to residual stresses in these fibers. Measurements of the axial residual stresses in both the normal and the splittable fibers are presented and the results compared. Differences in these stresses are discussed in connection with the ease of splitting in the splittable fibers.
Metal direlectric surface interactions and dielectric films on metal substrates were investigated. Since interfacial interaction depends so heavily on the nature of the surfaces, analytical surface tools such as Auger emission spectroscopy, X-ray photoelectron spectroscopy and field ion microscopy were used to assist in surface and interfacial characterization. The results indicate that with metals contacting certain glasses in the clean state interfacial, bonding produces fractures in the glasses while when a film such as water is present, fractures occur in the metal near the interface. Friction forces were used to measure the interfacial bond strengths. Studies with metals contacting polymers using field ion microscopy revealed that strong bonding forces could develop being between a metal and polymer surface with polymer transferring to the metal surface in various ways depending upon the forces applied to the surface in contact. With the deposition of refractory carbides, silicides and borides onto metal and alloy substrates the presence of oxides at the interface or active gases in the deposition plasma were shown to alter interfacial properties and chemistry. Auger ion depth profile analysis indicated the chemical composition at the interface and this could be related to the mechanical, friction, and wear behavior of the coating.