Investigation of N2O4 environmental effects on specially heat-treated Ti-6A1-4V alloy Final report
Mechanical properties and nitrogen tetroxide stress corrosion resistance of Ti-6Al-4V alloy with different heat treatments
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Mechanical properties and nitrogen tetroxide stress corrosion resistance of Ti-6Al-4V alloy with different heat treatments
Titanium (Ti) containing materials are of high interest to the aerospace industry due to its high temperature capability, strength, and light weight. As with most metals an exterior oxide layer naturally exists in environments that contain oxygen (i.e. air). At high temperatures, water vapor plays a key role in the volatility of materials including oxide surfaces. This study will evaluate cold pressed titanium dioxide (TiO2) powder pellets at a temperature range of 1400 C - 1200 C in water containing environments to determine the volatile hydroxyl species using the transpiration method. The water content ranged from 0-76 mole% and the oxygen content range was 0-100 mole % during the 20-250 hour exposure times. Preliminary results indicate that oxygen is not a key contributor at these temperatures and the following reaction is the primary volatile equation for all three temperatures: TiO2 (s) + H2O (g) = TiO(OH)2 (g).
Both the NASA Glenn Research Center and the U.S. Army Research Laboratory, Development and Engineering Center (ARDEC) have worked to develop oxide ceramic films grown on 60 nitinol (60-wt% nickel and 40-wt% titanium) to decrease friction and increase wear resistance under unlubricated conditions. In general, oxide and nonoxide ceramic films have unique capabilities as mechanical-, chemical-, and thermal-barrier materials in diverse applications, including high-temperature bearings and gas bearings requiring low friction, wear resistance, and chemical stability. All oxide ceramic films grown on 60 nitinol were furnished by ARDEC, and materials and surface characterization and tribological experiments were conducted at Glenn.
The paper describes the procedures which led to selection of a diffusion-coated siliconized oxidation-resistant reinforced carbon-carbon composite as a candidate for use in the leading edge structure of the Space Shuttle for the purpose of providing thermal protection. Materials were evaluated on the basis of oxidation-inhibitor performance, strength properties, and fabricability. Compounds of titanium, tantalum, zirconium, silicon, hafnium, aluminum, and boron were compounded with the reinforced carbon-carbon material in two different processing techniques to discover an oxidation-inhibited system which provided multicycle protection at temperatures up to 4000 F. Details of the manufacture and testing of the reinforced carbon-carbon composites are provided.
Static oxidation kinetics of the super-alpha 2 titanium-aluminide alloy Ti-25Al-10Nb-3V-1Mo (at. percent) were investigated in air over the temperature range of 650 to 1000 C using thermogravimetric analysis. The oxidation kinetics were complex at all exposure temperatures and displayed up to three distinct oxidation rates. Breakaway oxidation occurred after long exposure times at high temperatures. Oxidation products were determined using x ray diffraction techniques, electron microprobe analysis, and energy dispersive x ray analysis. Oxide scale morphology was examined by scanning electron microscopy of the surfaces and cross sections of oxidized specimens. The oxides during the parabolic stages were compact and multilayered, consisting primarily of TiO2 doped with Nb, a top layer of Al2O3, and a thin bottom layer of TiN. The transition between the second and third parabolic stage was found to be linked to the formation of a TiAl layer at the oxide-metal interface. Porosity was formed during the third stage, causing degradation of the oxide and the beginning of breakaway oxidation.
Static oxidation kinetics of the super-alpha 2 titanium-aluminide alloy Ti-25Al-10Nb-3V-1Mo (at. percent) were investigated in air over the temperature range of 650 to 1000 C using thermogravimetric analysis. The oxidation kinetics were complex at all exposure temperatures and displayed up to three distinct oxidation rates. Breakaway oxidation occurred after long exposure times at high temperatures. Oxidation products were determined using X-ray diffraction techniques, electron microprobe analysis, and energy dispersive X-ray analysis. Oxide scale morphology was examined by scanning electron microscopy of the surfaces and cross sections of oxidized specimens. The oxides during the parabolic stages were compact and multilayered, consisting primarily of TiO2 doped with Nb, a top layer of Al2O3, and a thin bottom layer of TiN. The transition between the second and third parabolic stage was found to be linked to the formation of a TiAl layer at the oxide-metal interface. Porosity was formed during the third stage, causing degradation of the oxide and the beginning of breakaway oxidation.
Fretting experiments were conducted on titanium, a series of Ni-Cr-Al alloys and on some high temperature turbine alloys at room temperature and at elevated temperatures in air and in various inert environments. It was found that, depending on temperature and environment, the fretting behavior of the materials examined could be classified according to four general types of behavior. Briefly, these types of behavior were: (1) the complete absence of oxidation, as in inert environments, generally leading to low rates of fretting wear but high fretting friction; (2) gradual attrition of surface oxide with each fretting stroke, found in these experiments to operate in concert with other dominating mechanisms; (3) rapid oxidation at surface fatigue damage sites, resulting in undermining and rapid disintegration of the load bearing surface; and (4) the formation of coherent, protective oxide film, resulting in low rates of fretting wear. An analytical model predicting conditions favorable to the fourth type of behavior was outlined.
Sputtered coatings of the refractory metal carbides are of great interest for applications where hard wear-resistant materials are desired. The usefulness of sputtered refractory carbides is often limited, in practice, by spalling or interfacial separation. In this work improvements in the adherence of refractory carbides on iron, nickel and titanium based alloys were obtained by using oxidation, reactive sputtering or sputtered interlayers to alter the coating-substrate interfacial region. X-ray photoelectron spectroscopy and argon ion etching were used to characterize the interfacial regions, and an attempt was made to correlate adherence as measured in wear tests with the chemical nature of the interface.
Sputtered coatings of the refractory metal carbides are of great interest for applications where hard wear-resistant materials are desired. The usefulness of sputtered refractory carbides is often limited in practice by spalling or interfacial separation. In this work improvements in the adherence of refractory carbides on iron, nickel and titanium base alloys were obtained by using oxidation, reactive sputtering or sputtered interlayers to alter the coating-substrate interfacial region. X-ray photoelectron spectroscopy and argon ion etching were used to characterize the interfacial regions, and an attempt was made to correlate adherence as measured in wear tests with the chemical nature of the interface.
Commercially pure titanium and heats of Armco ingot iron and steels containing from 0.008-1.23 w/oC were annealed or normalized and machined into hollow cylinders. Coefficients of diffusion for alpha-Ti and alpha-Fe were determined by the lag-time technique. Steady state permeation experiments yield first power pressure dependence for alpha-Ti and Sievert's law square root dependence for Armco iron and carbon steels. As in the case of diffusion, permeation data confirm that alpha-titanium is subject to at least partial phase boundary reaction control while the steels are purely diffusion controlled. The permeation rate in steels also decreases as the carbon content increases. As a consequence of Sievert's law, the computed hydrogen solubility decreases as the carbon content increases. This decreases in explained in terms of hydrogen trapping at carbide interfaces. Oxidizing and nitriding the surfaces of alpha-titanium membranes result in a decrease in the permeation rate for such treatment on the gas inlet surfaces but resulted in a slight increase in the rate for such treatment on the gas outlet surfaces. This is explained in terms of a discontinuous TiH2 layer.
Gamma titanium aluminides have received considerable attention over the last decade. These alloys are known to have low density, good high temperature strength retention, and good oxidation and corrosion resistance. However, poor ductility and low fracture toughness have been the key limiting factors in the full utilization of these alloys. More recently, Gamma-met PX has been developed by GKSS, Germany. These alloys have been observed to have superior strengths at elevated temperatures and quasi-static deformation rates and good oxidation resistance at elevated temperatures when compared with other gamma titanium aluminides. The present paper discusses results of a study to understand dynamic response of gamma-met PX in uniaxial compression. The experiments were conducted by using a modified split Hopkinson pressure bar between room temperature and 900 C and strain rates of up to 3500 per second. The Gamma met PX alloy showed superior strength when compared to nickel based superalloys and other gamma titanium aluminides at all test temperatures. It also showed strain and strain-rate hardening at all levels of strain rates and temperatures and without yield anomaly up to 900 C. After approximately 600 C, thermal softening is observed at all strain rates with the rate of thermal softening increasing dramatically between 800 and 900 C. However, these flow stress levels are comparatively higher in Gamma met PX than those observed for other TiAl alloys.
Oxidation and embrittlement are concerns in use of titanium foils for shielding advanced space transportation system vehicles during Earth reentry. Ti-6Al-4V in 0.003 in. and 0.035 in. thicknesses were exposed to multiple cycles of simulated space transportation system ascent/reentry conditions at temperatures ranging from 1000 F to 1200 F. Residual mechanical tests and metallurgical analyses were made on the specimens after exposure. Results show that tensile elongation is the mechanical property most affected by the reentry environment. Results are presented to show a comparison of residual properties of foil specimens from static oxidation exposure and cyclic oxidation exposure.
Oxidation and embrittlement are concerns in use of titanium foils for shielding advanced space transportation system vehicles during earth reentry. Ti-6Al-4V in 0.003 in. and 0.035 in. thicknesses were exposed to multiple cycles of simulated space transportation system ascent/reentry conditions at temperatures ranging from 1000 F to 1200 F. Residual mechanical tests and metallurgical analyses were made on the specimens after exposure. Results show that tensile elongation is the mechanical property most affected by the reentry environment. Results are presented to show a comparison of residual properties of foil specimens from static oxidation exposure and cyclic oxidation exposure.
This article recounts briefly some of the more critical stress-corrosion failures that have been experienced at Marshall Space Flight Center and the corrective action taken. Some of the recent stress corrosion studies are described and preliminary results tabulated. Specific problems described are the H-1 Engine LOX dome, the pneumatic line fitting sleeve problems and the more recent problem with wave springs used on MF-flared tube fittings. The use of nitric oxide in preventing stress-corrosion failures in titanium tanks is also discussed.
Auto-vacuum cleaning technique was applied to titanium parts prior to welding. This provides oxide-free welding surfaces. Diffusion welding can be accomplished in as little as five minutes of hot pressing. Roll welding can be accomplished with only ten percent deformation.
Tungsten carbide, which is known to be active for hydrogen oxidation and CO tolerant has a hexagonal structure. Titanium carbide is inactive and has a cubic structure. Four different samples of the cubic alloys Wx-1TixC were prepared and found to be active and CO tolerant. These alloys are of interest as possible phosphoric acid fuel cell catalysts. They also are of interest as opportunities to study the activity of W in a different crystalline environment and to correlate the activities of the surface sites with surface composition.
Intermetallic composites based upon titanium aluminide matrices and silicon carbide of aluminum oxide fibers are emerging candidates for future hypersonic vehicle airframes and engines. To tailor the properties of these 'engineered' materials for specific application, to increase process yield, and to reduce costs, 'intelligent processing of materials' (IPM) control strategies are being explored for their processing. Recent progress is evaluated in the development of predictive process models, advanced sensors and control methodologies (the components of the IPM approach) for the critical near net-shape consolidation process step of continuous fiber reinforced intermetallic composite manufacture.
Three silver-base brazes containing either noble metal palladium (Palcusil-10 and Palcusil-15) or active metal titanium (Ticusil) were evaluated for high-temperature oxidation resistance, and their effectiveness in joining yttria stabilized zirconia (YSZ) to a corrosion-resistant ferritic stainless steel. Thermogravimetric analysis (TGA), and optical- and scanning electron microscopy (SEM) coupled with energy dispersive spectrometry (EDS) were used to evaluate the braze oxidation behavior and the structure and chemistry of the YSZ/braze/steel joints. The effect of the braze type and processing conditions on the interfacial microstructure and composition of the joint regions is discussed with reference to the chemical changes that occur at the interface. It was found that chemical interdiffusion of the constituents of YSZ, steel and the brazes led to compositional changes and/or interface reconstruction, and metallurgically sound joints.