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At least 217 records · Page 12

Fabrication of Lanthanum Telluride 14-1-11 Zintl High-Temperature Thermoelectric Couple

The development of more efficient thermoelectric couple technology capable of operating with high-grade heat sources up to 1,275 K is key to improving the performance of radioisotope thermoelectric generators. Lanthanum telluride La3-xTe4 and 14-1-11 Zintls (Yb14MnSb11) have been identified as very promising materials. The fabrication of advanced high-temperature thermoelectric couples requires the joining of several dissimilar materials, typically including a number of diffusion bonding and brazing steps, to achieve a device capable of operating at elevated temperatures across a large temperature differential (up to 900 K). A thermoelectric couple typically comprises a heat collector/ exchanger, metallic interconnects on both hot and cold sides, n-type and ptype conductivity thermoelectric elements, and cold-side hardware to connect to the cold-side heat rejection and provide electrical connections. Differences in the physical, mechanical, and chemical properties of the materials that make up the thermoelectric couple, especially differences in the coefficients of thermal expansion (CTE), result in undesirable interfacial stresses that can lead to mechanical failure of the device. The problem is further complicated by the fact that the thermoelectric materials under consideration have large CTE values, are brittle, and cracks can propagate through them with minimal resistance. The inherent challenge of bonding brittle, high-thermal-expansion thermoelectric materials to a hot shoe material that is thick enough to carry the requisite electrical current was overcome. A critical advantage over prior art is that this device was constructed using all diffusion bonds and a minimum number of assembly steps. The fabrication process and the materials used are described in the following steps: (1) Applying a thin refractory metal foil to both sides of lanthanum telluride. To fabricate the n-type leg of the advanced thermoelectric couple, the pre-synthesized lanthanum telluride coupon was diffusion bonded to the metal foil using a thin adhesion layer. (2) Repeating a similar process for the 14-1-11 Zintl p-type leg of the advanced thermoelectric couple. (3) Bonding thick CTE-matched metal plates on the metallized lanthanum telluride and Yb14MnSb11 to form the hot and cold sides of the thermoelectric couple. The calculated conversion efficiency of such an advanced couple would be about 10.5 percent, about 35 percent better than heritage radioisotope thermoelectric technology that relies on Si-Ge alloys. In addition, unlike Si-Ge alloys, these materials can be combined with many other thermoelectric materials optimized for operation at lower temperatures to achieve conversion efficiency in excess of 15 percent (a factor of 2 increase over heritage technology).

Ravi, Vilupanur A.↗

Molecular-orbital model for metal-sapphire interfacial strength

Self-consistent-field X-Alpha scattered-wave cluster molecular-orbital models have been constructed for transition and noble metals (Fe, Ni, Cu, and Ag) in contact with a sapphire (Al2O3) surface. It is found that a chemical bond is established between the metal d-orbital electrons and the nonbonding 2p-orbital electrons of the oxygen anions on the Al2O3 surface. An increasing number of occupied metal-sapphire antibonding molecular orbitals explains qualitatively the observed decrease of contact shear strength through the series Fe, Ni, Cu, and Ag.

Johnson, K. H.↗

The Strength of the Metal. Aluminum Oxide Interface

The strength of the interface between metals and aluminum oxide is an important factor in the successful operation of devices found throughout modern technology. One finds the interface in machine tools, jet engines, and microelectronic integrated circuits. The strength of the interface, however, should be strong or weak depending on the application. The diverse technological demands have led to some general ideas concerning the origin of the interfacial strength, and have stimulated fundamental research on the problem. Present status of our understanding of the source of the strength of the metal - aluminum oxide interface in terms of interatomic bonds are reviewed. Some future directions for research are suggested.

Pepper, S. V.↗

Multiscale Modeling of Grain Boundaries in ZrB2: Structure, Energetics, and Thermal Resistance

A combination of ab initio, atomistic and finite element methods (FEM) were used to investigate the structures, energetics and lattice thermal conductance of grain boundaries for the ultra high temperature ceramic ZrB2. Atomic models of idealized boundaries were relaxed using density functional theory. Information about bonding across the interfaces was determined from the electron localization function. The Kapitza conductance of larger scale versions of the boundary models were computed using non-equilibrium molecular dynamics. The interfacial thermal parameters together with single crystal thermal conductivities were used as parameters in microstructural computations. FEM meshes were constructed on top of microstructural images. From these computations, the effective thermal conductivity of the polycrystalline structure was determined.

Lawson, John W.↗

NASA Facts: AERoBOND Project

Sustainability of the commercial air travel industry requires new aircraft with ultra-efficient structures and designs, which will depend largely on lightweight polymer composites and new assembly methods. Manufacturers of commercial transport aircraft are compelled to install thousands of redundant fasteners into bonded joints to prevent failures due to unpredictable weak bonds. The Adhesive-Free Bonding of Complex Composites (AERoBOND) process enables re-flow of matrix resin during assembly to eliminate the material discontinuity at the interface, thereby eliminating the dependence of mechanical performance on interfacial adhesion.

Frank Louis Palmieri↗

Improved adherence of sputtered titanium carbide coatings on nickel- and titanium-base alloys

Rene 41 and Ti-6Al-4V alloys were radio frequency sputter coated with titanium carbide by several techniques in order to determine the most effective. Coatings were evaluated in pin-on-disk tests. Surface analysis by X-ray photoelectron spectroscopy was used to relate adherence to interfacial chemistry. For Rene 41, good coating adherence was obtained when a small amount of acetylene was added to the sputtering plasma. The acetylene carburized the alloy surface and resulted in better bonding to the TiC coating. For Ti-6Al-4V, the best adherence and wear protection was obtained when a pure titanium interlayer was used between the coating and the alloy. The interlayer is thought to prevent the formation of a brittle, fracture-prone, aluminum oxide layer.

Wheeler, D. R.↗

Sulfur and Moisture Effects on Alumina Scale and TBC Spallation

It has been well established that a few ppmw sulfur impurity may segregate to the interface of thermally grown alumina scales and the underlying substrate, resulting in bond degradation and premature spallation. This has been shown for NiAl and NiCrAl-based alloys, bare single crystal superalloys, or coated superalloys. The role of reactive elements (especially Y) has been to getter the sulfur in the bulk and preclude interfacial segregation. Pt additions are also very beneficial, however a similar thermodynamic explanation does not apply. The purpose of the present discussion is to highlight some observations of these effects on Rene'142, Rene'N5, PWA1480, and PWA1484. For PWA1480, we have mapped cyclic oxidation and spallation in terms of potential sulfur interfacial layers and found that a cumulative amount of about one monolayer is sufficient to degrade long term adhesion. Depending on substrate thickness, optimum performance occurs if sulfur is reduced below about 0.2-0.5 ppmw. This is accomplished in the laboratory by hydrogen annealing or commercially by melt-fluxing. Excellent 1150 C cyclic oxidation is thus demonstrated for desulfurized Rene'142, Rene'N5, and PWA1484. Alternatively, a series of N5 alloys provided by GE-AE have shown that as little as 15 ppmw of Y dopant was effective in providing remarkable scale adhesion. In support of a Y-S gettering mechanism, hydrogen annealing was unable to desulfurize these alloys from their initial level of 5 ppmw S. This impurity and critical doping level corresponds closely to YS or Y2S3 stoichiometry. In many cases, Y-doped alloys or alloys with marginal sulfur levels exhibit an oxidative sensitivity to the ambient humidity called Moisture-Induced Delayed Spallation (MIDS). After substantial scale growth, coupled with damage from repeated cycling, cold samples may spall after a period of time, breathing on them, or immersing them in water. While stress corrosion arguments may apply, we propose that the underlying cause is related to a hydrogen embrittlement reaction: Al alloy + 3 H2O = Al(OH)3 + 3H(+) + 3e(-). This mechanism is derived from an analogous moisture-induced hydrogen embrittlement mechanism originally shown for Ni3Al and FeAl intermetallics. Consequently, a cathodic hydrogen charging technique was used to demonstrate that electrolytic de-scaling occurs for these otherwise adherent alumina scales formed on Y-doped Rene'N5, in support of hydrogen effects. Finally, some TBC observations are discussed in light of all of the above. Plasma sprayed 8YSZ coatings, produced on PWA1484 without a bond coat, were found to survive more than 1000 1-hr cycles at 1100 C when desulfurized to below 0.1 ppmw. At higher sulfur (1.2 ppmw) levels, moisture sensitivity and delayed TBC failure, referred to as Desk Top Spallation, occurred at just 200 hr. Despite a large degree of scatter, a factor of 5 in life improvement is indicated for desulfurized samples in cyclic furnace tests, confirming the beneficial effect of low sulfur alloys on model TBC systems. (DTS and moisture effects are also observed on commercially applied PVD 7YSZ coatings on Rene'N5+Y with Pt-aluminide bond coats). These types of catastrophic failure were subverted on the model system by segmenting the substrate into a network of 0.010 high ribs, spaced in. apart, prior to plasma spraying. No failures occurred after 1000 cycles at 1150 C or after 2000 cycles at 1100 C, even after water immersion. The benefit is described in terms of elasticity models and a critical buckling stress.

Smialek, James L.↗

Improved adhesion of Ni films on X-ray damaged polytetrafluoroethylene

The considered investigation shows that the adhesion of evaporated Ni on polytetrafluoroethylene (PTFE) is enhanced by irradiating the PTFE surface prior to evaporation. Evidence obtained with the aid of X-ray photoelectron spectroscopy is presented concerning the association of the enhanced adhesion with an interfacial chemical reaction. Evaporated Ni clearly adheres better to the X-ray damaged PTFE surface than to the undamaged surface. There is evidence that the improved adhesion is not related to the Ni-C bond, but rather to the NiF2. A possible mechanism which may be consistent with the data is the formation of a F-Ni-C complex, where C is a member of the polymer chain.

Wheeler, D. R.↗

An X-ray photoelectron spectroscopy study of the thermal nitridation of SiO2/Si

The dependence of the nitrogen distribution in thermally nitrided SiO2 films on the nitridation time and temperature has been studied by means of X-ray photoelectron spectroscopy (XPS). The photoelectron peak intensities were measured by fitting Voigt profiles to the XPS spectra and were used to calculate the film composition as a function of film depth, applying an analytical method described in detail. The times of appearance of the maxima in interfacial nitrogen concentration are shown for 800, 1000, and 1150 C, and the data are related to a kinetic model of Vasquez and Madhukar (1985), which considers the effect of interfacial strain on the nitridation kinetics. In addition, the intensity of a fluorine marker (from the HF used in the etching step) was found to correlate with the nitrogen concentration. It is postulated that the F bonds preferentially to defects. This hypothesis and the measured F intensities are consistent with the proposed strain-dependent energy of defect formation.

Vasquez, R. P.↗

Autohesive strength development in polysulfone resin and graphite-polysulfone composites

The effects of bonding temperature and contact time on autohesive strength development in thermoplastic polysulfone resin and graphite-polysulfone composites were investigated. Two test methods were examined to measure autohesion in the neat resin samples. These included an interfacial tension test and a compact tension fracture toughness test. Autohesive strength development in fiber-reinforced composites was measured using a double cantilever beam interlaminar fracture toughness test. The results of the tests were compared with current diffusion theories explaining crack healing and welding of glassy polymers. Discrepancies between the results of the present investigation and the diffusion theories are discussed.

Howes, Jeremy C.↗

Residual Stresses in Thermal Barrier Coatings for a Cu-8Cr-4Nb Substrate System

Analytical calculations were conducted to determine the thermal stresses developed in a coated copper-based alloy, Cu-8%(at.%)Cr-4%Nb (designated as GRCop-84), after plasma spraying and during heat-up in a simulated rocket engine environment. Finite element analyses were conducted for two coating systems consisting of a metallic top coat, a pure copper bond coat and the GRCop-84. The through thickness temperature variations were determined as a function of coating thickness for two metallic coatings, a Ni-17%(wt%)Cr-6%Al-0.5%Y alloy and a Ni-50%(at.%)Al alloy. The residual stresses after low-pressure plasma spraying of the NiCrAlY and NiAl coatings on GRCop-84 substrate were also evaluated. These analyses took into consideration a 50.8 mm copper bond coat and the effects of an interface coating roughness. The through the thickness thermal stresses developed in coated liners were also calculated after 15 minutes of exposure in a rocket environment with and without an interfacial roughness.

Ghosn, Louis J.↗

Intrinsic bond strength of metal films on polymer substrates

A semiquantitative method for the measurement of the intrinsic bond strength between elastic substrates and elastic films that fail by brittle fracture is described. Measurements on a polyethylene terephthalate (PET)-Ni couple were used to verify the essential features of the analysis. It was found that the interfacial shear strength of Ni on PET doubled after ion etching.

Wheeler, Donald R.↗

Zinc Oxide Nanowire Interphase for Enhanced Lightweight Polymer Fiber Composites

The objective of this work was to increase the interfacial strength between aramid fiber and epoxy matrix. This was achieved by functionalizing the aramid fiber followed by growth of a layer of ZnO nanowires on the fiber surface such that when embedded into the polymer, the load transfer and bonding area could be substantially enhanced. The functionalization procedure developed here created functional carboxylic acid surface groups that chemically interact with the ZnO and thus greatly enhance the strength of the interface between the fiber and the ZnO.

Sodano, Henry A.↗

Research and development of HgZnTe as an infrared material

Interfacial morphology and Fermi level pinning behavior at the interfaces of Al, Ag, and Pt with UHV-cleaved CdTe and ZnTe have been studied using X-ray and ultraviolet photoemission spectroscopies. Results are compared to metal/HgCdTe interface formation, where the weak HgTe bond and consequent ease of Hg loss strongly influence semiconductor disruption and metal-semiconductor intermising. For Al/CdTe, the strong Al-Te reaction yields a significantly more extensive Al-Te reacted region than has been observed for HgCdTe. The Al/ZnTe interface is observed to be more abrupt than Al/CdTe. The final Fermi level pinning positions, Ef-Evbm for Al, Ag, and Pt on p-type CdTe and p-ZnTe have been determined. Efi is found to be roughly the same for both CdTe and ZnTe, with the value for ZnTe lying approximately 0.2 eV closer to the VBM for all three metals. From these results, one would expect Schottky barriers of about the same height for these metals on p-CdTe and p-ZnTe; and also that, in principle, metal interfaces with the two alloys HgCdTe and HgZnTe would have the same properties. Comparisons and implications for electrical behavior of metal contacts to the alloys are discussed.

Wahi, A. K.↗

Toward Optimum Scale and TBC Adhesion on Single Crystal Superalloys

Single crystal superalloys exhibit excellent cyclic oxidation resistance if their sulfur content is reduced from typical impurity levels of approximately 5 ppmw to below 0.5 ppmw. Excellent alumina scale adhesion was documented for PWA 1480 and PWA 1484 without yttrium additions. Hydrogen annealing produced effective desulfurization of PWA 1480 to less than 0.2 ppmw and was also used to achieve controlled intermediate levels. The direct relationship between cyclic oxidation behavior and sulfur content was shown. An adhesion criterion was proposed based on the total amount of sulfur available for interfacial segregation, e.g., less than or equal to 0.2 ppmw S will maximize adhesion for a 1 mm thick sample. PWA 1484, melt desulfurized to 0.3 ppmw S, also exhibited excellent cyclic oxidation resistance and encouraging TBC lives (10 mils of 8YSZ, plasma sprayed without a bond coat) in 1100 C cyclic oxidation tests.

Smialek, James L.↗

Structural Analysis of Helios Filament-Wound Tanks Subjected to Internal Pressure and Cooling

A finite-element stress analysis is performed on Helios filament-wound hydrogen tanks to examine the stress field and effect of end dome geometry on the stress field. Each tank is composed of a central circular cylindrical section with either geodesic or hemispherical end domes, which have metallic polar bosses. The tanks are subjected to combined and separate internal pressure and temperature loading conditions, and the stress contributions of each loading component are examined. The tank-wall-polar-boss interfacial meridional tensile stress in the hemispherical dome is found to be approximately 27 percent lower than that in the geodesic dome. The effects of both material anisotropy and the aluminum lining on the intensities of tensile meridional stress at the tank-wall-polar-boss bonding interface are examined.

Ko, William L↗

Surface characterization and failure analysis of thermally aged, polyimide bonded titanium

This study of high temperature stable adhesive systems using 6Al-4V titanium adherends found that certain adhesive/adherends exhibit a change from cohesive to adhesive failure mode during long term 450 F thermal aging. Lap-shear specimens which exhibited adhesive failures were subjected to failure analysis using scanning transmission electron microscopy (STEM) and surface analysis techniques. Data is presented which supports the conclusion of interfacial failures for these samples.

Peters, P. D.↗

Interfacial Strength and Physical Properties of Functionalized Graphene - Epoxy Nanocomposites

The toughness and coefficient of thermal expansion of a series of functionalized graphene sheet - epoxy nanocomposites are investigated. Functionalized graphene sheets are produced by splitting graphite oxide into single graphene sheets through a rapid thermal expansion process. These graphene sheets contain approx. 10% oxygen due to the presence of hydroxide, epoxide, and carboxyl functional groups which assist in chemical bond formation with the epoxy matrix. Intrinsic surface functionality is used to graft alkyl amine chains on the graphene sheets, and the addition of excess hardener insures covalent bonding between the epoxide matrix and graphene sheets. Considerable improvement in the epoxy dimensional stability is obtained. An increase in nanocomposite toughness is observed in some cases.

Miller, Sandi G.↗