High-Strength Refractory Fibrous Materials

Abstract

The disclosed materials, methods, and apparatus, provide novel ultra-high temperature materials (UHTM) in fibrous forms/structures; such “fibrous materials” can take various forms, such as individual filaments, short-shaped fiber, tows, ropes, wools, textiles, lattices, nano/microstructures, mesostructured materials, and sponge-like materials. At least four important classes of UHTM materials are disclosed in this invention: (1) carbon, doped-carbon and carbon alloy materials, (2) materials within the boron-carbon-nitride-X system, (3) materials within the silicon-carbon-nitride-X system, and (4) highly-refractory materials within the tantalum-hafnium-carbon-nitride-X and tantalum-hafnium-carbon-boron-nitride-X system. All of these material classes offer compounds/mixtures that melt or sublime at temperatures above 1800° C.—and in some cases are among the highest melting point materials known (exceeding 3000° C.). In many embodiments, the synthesis/fabrication is from gaseous, solid, semi-solid, liquid, critical, and supercritical precursor mixtures using one or more low molar mass precursor(s), in combination with one or more high molar mass precursor(s). Methods for controlling the growth, composition, and structures of UHTM materials through control of the thermal diffusion region are disclosed.

What is claimed is: 
     
         1 . A fibrous material comprising carbon and at least one additive element, wherein the concentration of carbon is at least 55 atomic percent, and wherein said fibrous material is grown in at least one localized reaction zone from gaseous, liquid, semi-solid, critical, or supercritical precursor fluid mixtures using at least one primary heating means. 
     
     
         2 . The fibrous material of  claim 1 , wherein said fibrous material is comprised of one or more fibers, wherein said fibers each have a length to diameter aspect ratio of at least 3:1. 
     
     
         3 . The fibrous material of  claim 1 , wherein said fibrous material is at least one of single fiber strand, many fiber strands, short-shaped fibers, an array of fibers, tows, ropes, fabrics, textiles, wools, lattices, nano/microstructures, mesostructured materials, and sponge-like materials. 
     
     
         4 . The fibrous material of  claim 1 , wherein said at least one additive elements is at least one of lithium, beryllium, boron, nitrogen, oxygen, fluorine, magnesium, aluminum, silicon, phosphorous, sulphur, chlorine, scandium, titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, zinc, gallium, germanium, selenium, bromine, yttrium, zirconium, niobium, molybdenum, technetium, ruthenium, rhodium, palladium, silver, cadmium, indium, tin, antimony, tellurium, iodine, lanthanum, cerium, praseodymium, neodymium, promethium, samarium, gadolinium, terbium, dysprosium, holmium, erbium, thullium, Ytterbium, hafnium, tantalum, tungsten, rhenium, osmium, iridium, platinum, gold, mercury, lead, bismuth, actinium, thorium, uranium, neptunium, plutonium, americium, curium, and californium. 
     
     
         5 . The fibrous material of  claim 1 , wherein said fibrous material has an internal crystalline structure that is one of
 a. amorphous, glassy, vitreous, random non-crystalline, or quasi-crystalline morphologies, wherein no apparent long-range order exists at length scales of 35 nm or above;   b. nanocrystalline morphologies, with grain sizes smaller than 100 nm;   c. crystalline ultra fine-grained morphologies, with grain sizes between 100-500 nm;   d. crystalline, fine-grained morphologies with grain sizes smaller than 5 microns; and   e. single crystals.   
     
     
         6 . The fibrous material of  claim 1 , wherein said fibrous material is at least one of glassy carbon, vitreous carbon, amorphous carbon, quasi-crystalline carbon, nanocrystalline carbon, diamond-like carbon, tetrahedrally-bonded amorphous carbon, turbostratically-disordered carbon, pyrolytic graphite, graphite, graphite aligned parallel to the fiber axis, graphene, graphene aligned parallel to the fiber axis, carbon nanotubes, carbon nanotubes aligned parallel to the fiber axis, fullerenes, carbon onions, diamond, lonsdaleite, and carbyne. 
     
     
         7 . The fibrous material of  claim 1 , wherein at least one thermal diffusion region is present at or near said localized reaction zone, wherein said thermal diffusion region is at least partially controlled by a secondary heating means. 
     
     
         8 . The fibrous material of  claim 7 , wherein said precursor fluid mixtures comprise a mixture of low molar mass and high molar mass precursors. 
     
     
         9 . A fibrous material comprising at least a first element and a second element,
 a. wherein said first element is at least one of silicon, carbon, and boron, and   b. wherein said second element is different from the first element and at least one of silicon, carbon, boron, nitrogen, and an additive element, and   c. wherein the concentration of nitrogen, if present, is no greater than 67 atomic percent, and the concentration of the additive element, if present, is no greater than 35 atomic percent, and   d. wherein said fibrous material is grown in at least one localized reaction zone from gaseous, liquid, semi-solid, critical, or supercritical precursor fluid mixtures using at least one primary heating means.   
     
     
         10 . The fibrous material of  claim 9 , wherein said first element is boron and said second element is carbon, and further comprising nitrogen and at least one additive element, wherein the concentration of boron is no greater than 95 atomic percent, the concentration of carbon is no greater than 95 atomic percent, the concentration of nitrogen is no greater than 67 atomic percent, and the concentration of the at least one additive element is no greater than 35 atomic percent. 
     
     
         11 . The fibrous material of  claim 9 , wherein said first element is boron and said second element is carbon, and further comprising nitrogen, wherein the concentration of boron is no greater than 95 atomic percent, the concentration of carbon is no greater than 95 atomic percent, and the concentration of nitrogen is no greater than 67 atomic percent. 
     
     
         12 . The fibrous material of  claim 10 , wherein said fibrous material has a cubic internal crystalline structure. 
     
     
         13 . The fibrous material of  claim 10 , wherein said fibrous material has the internal crystalline structure of heterodiamond. 
     
     
         14 . The fibrous material of  claim 10 , wherein said fibrous material has the rhombohedral-like internal crystalline structure of B 4 C. 
     
     
         15 . The fibrous material of  claim 10 , wherein the concentration of boron is between 20-30 atomic percent, the concentration of carbon is between 45-55 atomic percent, the concentration of nitrogen is between 20-30 atomic percent, and the concentration of the at least one additive element is no greater than 15 atomic percent. 
     
     
         16 . The fibrous material of  claim 9 , wherein said first element is silicon and said second element is carbon, and further comprising nitrogen and at least one additive element, wherein the concentration of silicon is no greater than 95 atomic percent, the concentration of carbon is no greater than 95 atomic percent, the concentration of nitrogen is no greater than 67 atomic percent, and the concentration of the at least one additive element is no greater than 35 atomic percent. 
     
     
         17 . The fibrous material of  claim 9 , wherein said first element is silicon and said second element is carbon, and further comprising nitrogen, wherein the concentration of silicon is no greater than 95 atomic percent, the concentration of carbon is no greater than 95 atomic percent, and the concentration of nitrogen is no greater than 67 atomic percent. 
     
     
         18 . The fibrous material of  claim 9 , wherein said first element is silicon and said second element is carbon, and further comprising at least one additive element, wherein the concentration of silicon is between 45-55 atomic percent, the concentration of carbon is between 45-55 atomic percent, and the concentration of the at least one additive element is no greater than 10 atomic percent. 
     
     
         19 . The fibrous material of  claim 9 , wherein said first element is silicon and said second element is carbon, wherein the concentration of silicon is between 45-55 atomic percent, and the concentration of carbon is between 45-55 atomic percent. 
     
     
         20 . The fibrous material of  claim 9 , wherein said first element is silicon and said second element is carbon, and further comprising at least one additive element, wherein the concentration of silicon is between 22-43 atomic percent, the concentration of carbon is between 57-77 atomic percent, and the concentration of the at least one additive element is no greater than 21 atomic percent. 
     
     
         21 . The fibrous material of  claim 9 , wherein said first element is silicon and said second element is carbon, wherein the concentration of silicon is between 22-43 atomic percent, and the concentration of carbon is between 57-77 atomic percent. 
     
     
         22 . The fibrous material of  claim 9 , wherein said first element is silicon and said second element is nitrogen, and further comprising at least one additive element, wherein the concentration of silicon is between 32-52 atomic percent, the concentration of nitrogen is between 47-67 atomic percent, and the concentration of the at least one additive element is no greater than 21 atomic percent. 
     
     
         23 . The fibrous material of  claim 9 , wherein said first element is silicon and said second element is nitrogen, wherein the concentration of silicon is between 32-52 atomic percent, and the concentration of nitrogen is between 47-67 atomic percent. 
     
     
         24 . The fibrous material of  claim 9 , wherein said first element is silicon and said second element is boron, and further comprising at least one additive element, wherein the concentration of silicon is between 7-33 atomic percent, the concentration of boron is between 33-94 atomic percent, and the concentration of the at least one additive element is no greater than 15 atomic percent. 
     
     
         25 . The fibrous material of  claim 9 , wherein said first element is silicon and said second element is boron, wherein the concentration of silicon is between 7-33 atomic percent, and the concentration of boron is between 33-94 atomic percent. 
     
     
         26 . The fibrous material of  claim 9 , wherein said fibrous material is comprised of one or more fibers, wherein said fibers each have a length to diameter aspect ratio of at least 3:1. 
     
     
         27 . The fibrous material of  claim 9 , wherein said fibrous material is at least one of single fiber strand, many fiber strands, short-shaped fibers, an array of fibers, tows, ropes, fabrics, textiles, wools, lattices, nano/microstructures, mesostructured materials, and sponge-like materials. 
     
     
         28 . The fibrous material of  claim 9 , wherein said at least one additive element is at least one of lithium, beryllium, boron, nitrogen, oxygen, fluorine, magnesium, aluminum, silicon, phosphorous, sulphur, chlorine, scandium, titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, zinc, gallium, germanium, selenium, bromine, yttrium, zirconium, niobium, molybdenum, technetium, ruthenium, rhodium, palladium, silver, cadmium, indium, tin, antimony, tellurium, iodine, lanthanum, cerium, praseodymium, neodymium, promethium, samarium, gadolinium, terbium, dysprosium, holmium, erbium, thullium, Ytterbium, hafnium, tantalum, tungsten, rhenium, osmium, iridium, platinum, gold, mercury, lead, bismuth, actinium, thorium, uranium, neptunium, plutonium, americium, curium, and californium. 
     
     
         29 . The fibrous material of  claim 9 , wherein said fibrous material has an internal crystalline structure that is one of
 a. amorphous, glassy, vitreous, random non-crystalline, or quasi-crystalline morphologies, wherein no apparent long-range order exists at length scales of 35 nm or above;   b. nanocrystalline morphologies, with grain sizes smaller than 100 nm;   c. crystalline ultra fine-grained morphologies, with grain sizes between 100-500 nm;   d. crystalline, fine-grained morphologies with grain sizes smaller than 5 microns; and   e. single crystals.   
     
     
         30 . The fibrous material  claim 9 , wherein at least one thermal diffusion region is present at or near said localized reaction zones, wherein said thermal diffusion region is at least partially controlled by a secondary heating means. 
     
     
         31 . The fibrous material of  claim 28 , wherein said precursor fluid mixtures comprise a mixture of low molar mass and high molar mass precursors. 
     
     
         32 . A fibrous material comprising at least a first element and a second element,
 a. wherein said first and second elements are at least two of tantalum, hafnium, carbon, boron, nitrogen and an additive element, and   b. wherein the concentration of nitrogen, if present, is no greater than 67 atomic percent, and the concentration of the additive element, if present, is no greater than 67 atomic percent, and   c. wherein said fibrous material is grown in at least one localized reaction zone from gaseous, liquid, semi-solid, critical, or supercritical precursor fluid mixtures using at least one primary heating means.   
     
     
         33 . The fibrous material of  claim 32 , wherein said first element is tantalum and said second element is hafnium, and further comprising carbon and at least one additive element, wherein the concentration of tantalum is no greater than 95 atomic percent, the concentration of hafnium is no greater than 95 atomic percent, and the concentration of carbon is between 5-67 atomic percent, and the concentration of the at least one additive element is no greater than 35 atomic percent. 
     
     
         34 . The fibrous material of  claim 32 , wherein said first element is tantalum and said second element is hafnium, and further comprising carbon, wherein the concentration of tantalum is no greater than 95 atomic percent, the concentration of hafnium is no greater than 95 atomic percent, and the concentration of carbon is between 5-67 atomic percent. 
     
     
         35 . The fibrous material of  claim 32 , wherein the first element is tantalum and said second element is hafnium, and further comprising carbon, wherein the concentration of tantalum is between 35-45 atomic percent, the concentration of hafnium is between 5-15 atomic percent, and the concentration of carbon is between 45-55 atomic percent. 
     
     
         36 . The fibrous material of  claim 32 , wherein said first element is hafnium and second element is carbon, further comprising nitrogen and at least one additive element, wherein the concentration of hafnium is no greater than 95 atomic percent, the concentration of carbon is no greater than 95 atomic percent, the concentration of nitrogen is between 5-67 atomic percent, and the concentration of the at least one additive element is no greater than 35 atomic percent. 
     
     
         37 . The fibrous material of  claim 32 , wherein said first element is hafnium and second element is carbon, further comprising nitrogen, wherein the concentration of hafnium is no greater than 95 atomic percent, the concentration of carbon is no greater than 95 atomic percent, and the concentration of nitrogen is between 5-67 atomic percent. 
     
     
         38 . The fibrous material of  claim 32 , wherein said fibrous material is comprised of one or more fibers, wherein said fibers each have a length to diameter aspect ratio of at least 3:1. 
     
     
         39 . The fibrous material of  claim 32 , wherein said fibrous material is at least one of single fiber strand, many fiber strands, short-shaped fibers, an array of fibers, tows, ropes, fabrics, textiles, wools, lattices, nano/microstructures, mesostructured materials, and sponge-like materials. 
     
     
         40 . The fibrous material of  claim 32 , wherein said additive element is at least one of lithium, beryllium, boron, nitrogen, oxygen, fluorine, magnesium, aluminum, silicon, phosphorous, sulphur, chlorine, scandium, titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, zinc, gallium, germanium, selenium, bromine, yttrium, zirconium, niobium, molybdenum, technetium, ruthenium, rhodium, palladium, silver, cadmium, indium, tin, antimony, tellurium, iodine, lanthanum, cerium, praseodymium, neodymium, promethium, samarium, gadolinium, terbium, dysprosium, holmium, erbium, thullium, Ytterbium, hafnium, tantalum, tungsten, rhenium, osmium, iridium, platinum, gold, mercury, lead, bismuth, actinium, thorium, uranium, neptunium, plutonium, americium, curium, and californium. 
     
     
         41 . The fibrous material of  claim 32 , wherein said fibrous material has an internal crystalline structure that is one of
 a. amorphous, glassy, vitreous, random non-crystalline, or quasi-crystalline morphologies, wherein no apparent long-range order exists at length scales of 35 nm or above;   b. nanocrystalline morphologies, with grain sizes smaller than 100 nm;   c. crystalline ultra fine-grained morphologies, with grain sizes between 100-500 nm;   d. crystalline, fine-grained morphologies with grain sizes smaller than 5 microns; and   e. single crystals.   
     
     
         42 . The fibrous material of  claim 32 , wherein at least one thermal diffusion region is present at or near said localized reaction zones, wherein said thermal diffusion region is at least partially controlled by a secondary heating means. 
     
     
         43 . The fibrous material of  claim 42 , wherein said precursor fluid mixtures comprise a mixture of low molar mass and high molar mass precursors. 
     
     
         44 . A method of fabricating ultra high temperature fibrous materials, comprising:
 a. introducing a low molar mass precursor species and a high molar mass precursor species into a reaction vessel, said high molar mass precursor having a molar mass substantively greater than the low molar mass precursor species, and   b. creating at least one localized reaction zone by a primary heating means, wherein at least partial decomposition of at least one said precursor species occurs in said reaction zone, and   c. establishing at least one thermal diffusion region at or near said reaction zone, said thermal diffusion region controlled at least in-part by a secondary heating means, and wherein said thermal diffusion region creates a concentration gradient of said low molar mass precursor species and said high molar mass precursor species, and   d. growing an ultra high temperature fibrous material at or near the reaction zone.   
     
     
         45 . The method of  claim 44 , wherein said precursor species contain at least one ultra-high-temperature element or compound. 
     
     
         46 . The method of  claim 44 , wherein said precursor species are in a gaseous, liquid, semi-solid, critical, or supercritical precursor state at or near said reaction zone. 
     
     
         47 . The method of  claim 44 , wherein said fibrous material is comprised of one or more fibers, wherein said fibers each have a length to diameter aspect ratio of at least 3:1, wherein said fibers each have a first end and a second end, said first ends being in or at said reaction zones during their growth. 
     
     
         48 . The method of  claim 47 , wherein said fibers are translated or spooled backwards as they are grown to maintain said first ends within said reaction zone during their growth. 
     
     
         49 . The method of  claim 47 , wherein said reaction zone is translated as said first end of said fiber grows to maintain said first end within said reaction zone during their growth. 
     
     
         50 . The method of  claim 44 , wherein said fibrous material is at least one of a single fiber strand, many fiber strands, short-shaped fibers, an array of fibers, tows, ropes, fabrics, textiles, wools, lattices, nano/microstructures, mesostructured materials, and sponge-like materials.