The Printability of Ternary Metal Boride (MAB) Materials using Laser Powder Bed Fusion
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A two phase HfB2-SiB4 material which is useful as a high temperature oxidation resistant coating. This invention relates to ceramic coatings and more particularly to ceramic coatings containing metal borides. Boride materials are known to have good oxidation resistance, with HfB2 considered to be the best pure boride for oxidation applications. It has been shown that the addition of 10 to 20 percent SiC to HfB2 increases the oxidation resistance. The HfB2-SiC materials are prepared by hot pressing powder mixtures. Hot pressing powder mixtures has limited ability to produce fine grained multiphase materials due to particle coarsening during the sintering process. Additionally, the purity of the final monolithic structure is limited to the purity of the starting powders. Chemical vapor deposition (CVD) offers a method of producing highly pure multiphase ceramics, with better control of microstructure. Researchers have tried to produce HfB2-SiC coatings by CVD but without success.
A limited investigation of the deterioration characteristics of 22 refractory materials was conducted by exposing them to a stagnation temperature of 3,800 F in a Mach number 2 ceramic-heated jet at the Langley Research Center. The materials tested were six materials whose major constituent was silicon carbide, five cermets whose major constituent was titanium carbide, six materials whose major constituents were metal borides, four cermets containing alumina, and one silicon nitride model. Tests consisted of obtaining weight change and appearance changes for 1/2-inch-diameter hemispherical-nose cylindrical models exposed to the air jet for 30 seconds at a time for a total of four runs or 2 minutes exposure. Curves of weight changes plotted against the number of 30-second tests in the jet were obtained. Estimates of average surface temperature near the stagnation point of the model were obtained by use of a special temperature-measuring camera. The models were examined before and after the completion of the tests for possible changes in microstructure; no significant changes were found. The data obtained were analyzed with the view that the oxidation characteristics of the materials were the main factor in deterioration of the materials under the conditions of the tests. It was concluded that only those materials which changed in weight the least could be recommended for further extensive application-oriented evaluations. The following materials fell in this category: silicon carbide - silicon, chromium - 28-percent alumina cermet, titanium boride - 5-percent boron carbide. The remainder of the materials tested had oxidation characteristics which appeared to be too severely limiting of their general applications to flight vehicles.
Refractory materials such as metallic borides, often considered as ultra high temperature ceramics (UHTC), are characterized by high melting point, high hardness, and good chemical inertness. These materials have many applications which require high temperature materials that can operate with no or limited oxidation. Ab initio, first principles methods are the most accurate modeling approaches available and represent a parameter free description of the material based on the quantum mechanical equations. Using these methods, many of the intrinsic properties of these material can be obtained. We performed ab initio calculations based on density functional theory for the UHTC materials ZrB2 and HfB2. Computational results are presented for structural information (lattice constants, bond lengths, etc), electronic structure (bonding motifs, densities of states, band structure, etc), thermal quantities (phonon spectra, phonon densities of states, specific heat), as well as information about point defects such as vacancy and antisite formation energies.
A tough ultra-high temperature ceramic (UHTC) composite comprises grains of UHTC matrix material, such as HfB.sub.2, ZrB.sub.2 or other metal boride, carbide, nitride, etc., surrounded by a uniform distribution of acicular high aspect ratio reinforcement ceramic rods or whiskers, such as of SiC, is formed from uniformly mixing a powder of the UHTC material and a pre-ceramic polymer selected to form the desired reinforcement species, then thermally consolidating the mixture by hot pressing. The acicular reinforcement rods may make up from 5 to 30 vol % of the resulting microstructure.
Electrocatalysts and supports for the positive electrode of moderate temperature single-unit rechargeable alkaline fuel cells are being investigated and developed. Candidate support materials were drawn from transition metal carbides, borides, nitrides and oxides which have high conductivity (greater than 1 ohm/cm). Candidate catalyst materials were selected largely from metal oxides of the form ABO sub x (where A = Pb, Cd, Mn, Ti, Zr, La, Sr, Na, and B = Pt, Pd, Ir, Ru, Ni (Co) which were investigated and/or developed for one function only, O2 reduction or O2 evolution. The electrical conductivity requirement for catalysts may be lower, especially if integrated with a higher conductivity support. All candidate materials of acceptable conductivity are subjected to corrosion testing. Materials that survive chemical testing are examined for electrochemical corrosion activity. For more stringent corrosion testing, and for further evaluation of electrocatalysts (which generally show significant O2 evolution at at 1.4 V), samples are held at 1.6 V or 0.6 V for about 100 hours. The surviving materials are then physically and chemically analyzed for signs of degradation. To evaluate the bifunctional oxygen activity of candidate catalysts, Teflon-bonded electrodes are fabricated and tested in a floating electrode configuration. Many of the experimental materials being studied have required development of a customized electrode fabrication procedure. In advanced development, the goal is to reduce the polarization to about 300 to 350 mV. Approximately six support materials and five catalyst materials were identified to date for further development. The test results will be described.
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.
A near-net, complex shaped ceramic fiber reinforced silicon carbide based composite bodies with graded compositions and stress zones is disclosed. To provide the composite a fiber preform is first fabricated and an interphase is applied by chemical vapor infiltration, sol-gel or polymer processes. This first body is further infiltrated with a polymer mixture containing carbon, and/or silicon carbide, and additional oxide, carbide, or nitride phases forming a second body. One side of the second body is spray coated or infiltrated with slurries containing high thermal expansion and oxidation resistant. crack sealant phases and the other side of this second body is coated with low expansion phase materials to form a third body. This third body consisting of porous carbonaceous matrix surrounding the previously applied interphase materials, is then infiltrated with molten silicon or molten silicon-refractory metal alloys to form a fourth body. The resulting fourth body comprises dense composites consisting of fibers with the desired interphase which are surrounded by silicon carbide and other second phases materials at the outer and inner surfaces comprising material of silicon, germanium, refractory metal suicides, borides, carbides, oxides, and combinations thereof The resulting composite fourth body has different compositional patterns from one side to the other.
Continuing pressures for higher performance and efficiency in propulsion are driving ever more demanding needs for high-temperature materials. Some immediate applications in spaceflight include combustion chambers for advanced chemical rockets and turbomachinery for jet engines and power conversion in nuclear-electric propulsion. In the case of rockets, the combination of high stresses and high temperatures make the characterization of creep properties very important. Creep is even more important in the turbomachinery, where a long service life is an additional constraint. Some very high-temperature materials are being developed, including platinum group metals, carbides, borides, and silicides. But the measurement of creep properties at very high temperatures is itself problematic, because the testing instrument must operate at such high temperatures. Conventional techniques are limited to about 1700 C. A new, containerless technique for measuring creep deformation has been developed. This technique is based on electrostatic levitation (ESL) of a spherical sample, which is heated to the measurement temperature and rotated at a rate such that the centrifugal acceleration causes creep deformation. Creep of samples has been demonstrated at up to 2300 C in the ESL facility at NASA MSFC, while ESL itself has been applied at over 3000 C, and has no theoretical maximum temperature. The preliminary results and future directions of this NASA-funded research collaboration will be presented.
Borides of transition metals, hafnium, zirconium, niobium, lanthanum and holmium tested for hardness at high temperature
Numerous advanced space and missile technologies including propulsion systems require operations at high temperatures. Some very high-temperature materials are being developed to meet these needs, including refractory metal alloys, carbides, borides, and silicides. System design requires data for materials properties at operating temperatures. Materials property data are not available at the desired operating temperatures for many materials of interest. The objective of this work is to provide important physical property data at ultra-high temperatures. The MSFC Electrostatic Levitation (ESL) facility can provide measurements of thermophysical properties which include: creep strength, emissivity, density and thermal expansion. ESL uses electrostatic fields to position samples between electrodes during processing and characterization experiments. Samples float between the electrodes during studies and are free from any contact with a container or test apparatus. This provides a high purity environment for the study of high-temperature, reactive materials. ESL can be used to process a wide variety of materials including metals, alloys, ceramics, glasses and semiconductors. A system for the determination of total hemispherical emissivity is being developed for the MSFC ESL facility by AZ Technology Inc. The instrument has been designed to provide emissivity measurements for samples during ESL experiments over the temperature range 700-3400K. A novel non-contact technique for the determination of high-temperature creep strength has been developed. Data from selected ESL-based characterization studies will be presented. The ESL technique could advance space and missile technologies by advancing the knowledge base and the technology readiness level for ultra-high temperature materials. Applications include non-eroding nozzle materials and lightweight, high-temperature alloys for turbines and structures.
Propulsion system efficiency increases as operating temperatures are increased. Some very high-temperature materials are being developed, including refractory metal alloys, carbides, borides, and silicides. System design requires data for materials properties at operating temperatures. Materials property data are not available for many materials of interest at the desired operating temperatures (up to approx. 3000 K). The objective of this work is to provide important physical property data at ultra-high temperatures. The MSFC Electrostatic levitation (ESL) facility can provide measurements of thermophysical properties which include: creep strength, density and thermal expansion for materials being developed for propulsion applications. The ESL facility uses electrostatic fields to position samples between electrodes during processing and characterization studies. Because the samples float between the electrodes during studies, they are free from any contact with a container or test apparatus. This provides a high purity environment for the study of high-temperature, reactive materials. ESL can be used to process a wide variety of materials including metals, alloys, ceramics, glasses and semiconductors. The MSFC ESL has provided non-contact measurements of properties of materials up to 3400 C. Density and thermal expansion are measured by analyzing digital images of the sample at different temperatures. Our novel, non-contact method for measuring creep uses rapid rotation to deform the sample. Digital images of the deformed samples are analyzed to obtain the creep properties, which match those obtained using ASTM Standard E-139 for Nb at 1985 C. Data from selected ESL-based characterization studies will be presented. The ESL technique could support numerous propulsion technologies by advancing the knowledge base and the technology readiness level for ultra-high temperature materials. Applications include non-eroding nozzle materials and lightweight, high-temperature alloys for turbines and structures.
Processing studies designed to produce boride composites with metal additives to lower fabrication temperatures and increase the impact strength are reported. Hot pressing experiments were performed with ZrB2 and Fe, Ti, and Zr employed singly as additives. Data for the characterization, impact tests, slow bend tests, and fracture strength are presented.
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.
High temperature research in vacuum - magnesium oxide and zirconium dioxide interaction with refractory metal carbides, nitrates, and borides
Refractory oxides, carbides and borides in combination with metals investigated for stability in high temperature cermet applications
The absence of gravity allows containerless processing of materials which could not otherwise be processed. High melting point, hard materials such as borides, nitrides, and refractory metals are usually brittle in their crystalline form. The absence of dislocations in amorphous materials frequently endows them with flexibility and toughness. Systematic studies of the properties of many amorphous materials have not been carried out. The requirements for their production is that they can be processed in a controlled way without container interaction. Containerless processing in microgravity could permit the control necessary to produce amorphous forms of hard materials.