KR20150013173A - Refractory metal boride ceramics and methods of making thereof - Google Patents

Abstract

The present invention relates to a composition having nanoparticles of refractory-metal boride and elastomeric matrix. The composition is not in powder form. The composition comprises a metal component, boron and an organic component. The metal component is a refractory metal compound that can be decomposed into nanoparticles or particles of refractory metal or refractory metal nanoparticles. The organic component is an organic compound having a Karr yield of at least 60% by weight or a thermosetting substance prepared from the organic compound. The present invention relates to refractory metal particles or refractory-metal compounds capable of reacting with or decomposing into refractory-metal nanoparticles, boron and organic compounds having a Karr yield of at least 60% by weight to form a precursor mixture ≪ / RTI > The present invention relates to compositions that are not in powder form.

Description

TECHNICAL FIELD [0001] The present invention relates to refractory metal boride ceramics,

This application claims the benefit of US Provisional Patent Application No. 13/768/219 filed February 15, 2013, U.S. Provisional Application No. 61 / 590,852 filed January 26, 2012, May 1, 2012 U.S. Provisional Application No. 61 / 640,744, filed July 9, 2012, and U.S. Provisional Patent Application Serial No. 61 / 669,201, filed on August 28, 2012, and U.S. Provisional Application No. 61 / 693,930, filed August 28, . This application is a continuation-in-part of US Non-Patent Application No. 13 / 749,794 filed on January 25, 2013. These and all other publications and patent documents referred to throughout this non-provisional application are incorporated herein by reference.

The present application relates generally to the synthesis of refractory-metal borides such as titanium borides and zirconium borides.

The refractory transition metal boride (MB) has a known highest melting point (2600-3900 ° C) and also a pronounced hardness, chemical stability. Thermal conductivity, abrasion resistance, electrocatalytic activity, and neutron absorption capability. Films, fibers and powders of these ceramics have been prepared from polymerization precursors, but large monolithic forms make the polymerization process difficult. Refractory MBs are typically produced by powder metallurgical methods such as hot press sintering at temperatures above 2000 ° C. The metal boride ceramics typically produced by the above energy- and time-intensive techniques induce brittle materials, which are partly due to the large granular structure and non-uniformity in MB particle size.

Since the late 1960s, high temperature ceramic materials have been of interest for applications such as grinding / machining, ball bearings, weapons, fibers, brake linings and turbine blades, but structural applications have been poorly understood due to their brittleness and vulnerability in shear and tensile Respectively. More recently, interest in ultra-high temperature materials for hypersonic vehicles (Mach 5-20) with new propulsion and structural concepts has revived. These vehicles are ballistic missiles, hypersonic cruise missiles, re-entry vehicles. Space-proximity vehicles, interceptor missiles, and hypersonic cruise aircraft, which can be easily divided into single-use consumer and recycling systems. These consumable and recyclable space vehicles, next-generation rocket engines and hypersonic space aircraft require rigid materials and structural components that can operate at temperatures above 2200 ° C and exhibit high melting temperatures, high strength, environmental tolerance (oxidation resistance) And thermal conductivity. Hypersonic commercial aircraft can travel less than an hour from New York to Los Angeles. Therefore, the current growing interest in hypersonic vehicles and weapons points to the need for new extreme high temperature materials for wing cutting edge technology and noise tips, along with propulsion system components.

For these applications, it will be evolved if materials capable of being easily processed into molded components with the required thermo-physical and thermochemical properties and properties and capable of being carried out without some cooling form at temperatures above 2200 ° C . The material does not currently exist. Refractory interstitial transition metal borides are extremely hard, inert refractory materials. Unfortunately, they are also brittle and difficult to machine.

At present, attempts to form metal boride ceramics from metal compounds and boron sources such as boron oxide and boron carbide and metal compounds (oxides and halides) have resulted in powder or poorly formed films. When the mixture is heated. The result is a mixture of "hot atoms" of metal and boron with removal of hydrogen halide and formation of metal boride in conventional nucleation and growth planning. The solvent thermal reaction in benzene relies on the reaction between a boron source such as boron trichloride in the presence of a refractory metal compound (metal halide) and metal sodium, and forms sodium chloride as a by-product. The present process is extremely difficult and inherently very uneven to produce and control powdered metal boride, resulting in large micrometer sized particles due to rapid reaction kinetics. Another method involved the reaction of metal oxides with boron carbide at extremely high temperatures to produce powdered metal boride and carbon monoxide.

At present, there is interest in metal borides with small particle size and high surface area, such as titanium boride, zirconium boride and hafnium boride, which are used in ballistic inorganic, electronic and thermal conductive materials, advanced supersonic engines, Because it can be applied to gas state-of-the-art technologies and nuclear reactors on vehicles. We are interested in refractory metal borides for state-of-the-art technology and noise cap applications that require moderate high temperatures. The refractory metal boride is combined with other ceramics such as silicon carbide to improve the oxidation resistance of the material in a very high temperature range. Many of these metal borides also have metallic conductivity and / or unusual magnetic properties. These materials have typically been prepared by high temperature powder technology, which is limited in their ability to produce homogeneous materials with controlled composition and macroscopic properties.

The present disclosure describes compositions comprising nanoparticles of refractory-metal borides and elastomeric matrices. The composition is not in powder form.

Also disclosed herein are compositions comprising a metal component, boron and an organic component. The metal component is selected from refractory metal compounds that can be decomposed into nanoparticles or particles of refractory metals and refractory-metal nanoparticles. The organic component is selected from an organic compound having a char yield of at least 60% by weight and a thermosetting material made from the organic compound.

In addition, the present application is also directed to a process for forming a precursor mixture comprising combining refractory metal or particles of a refractory-metal compound that can be reacted or decomposed with refractory-metal nanoparticles, boron and an organic compound having a Karr yield of at least 60 wt% Method.

In addition,

Providing a precursor mixture of refractory-metal compounds, boron and organic compounds capable of decomposing into particles of refractory metal or refractory-metal nanoparticles; Heating said precursor mixture in an inert atmosphere at a temperature that causes decomposition of the refractory-metal compound to form said precursor mixture to form step-up and refractory-metal nanoparticles to form a metal nanoparticle composition; And heating the metal nanoparticle composition in an inert atmosphere, argon or nitrogen at a temperature which causes formation of a ceramic comprising nanoparticles of refractory-metal boride in the elastomeric matrix. The organic compound has a Tard yield of at least 60% by weight when heated at elevated pressure.

Also disclosed herein are compositions comprising nanoparticles of refractory-metal boride. The composition is not in powder form.

In addition, the present application describes a composition comprising the metal component and boron.

The present invention also relates to a process for the preparation of nanoparticles comprising refractory metal particles or refractory-metal nanoparticles or particles of refractory-metal compounds capable of reacting with boron to form a precursor mixture, And heating the precursor mixture under an inert atmosphere or at a temperature to cause formation of the precursor mixture.

BRIEF DESCRIPTION OF THE DRAWINGS A more complete description of the present invention will be provided by way of example embodiments and with reference to the accompanying drawings, in which: Fig.
Figure 1 illustrates schematically a method of forming the above compositions.
Figure 2 schematically illustrates the metal nanoparticles 10 embedded in the thermosetting matrix 20.
Figure 3 illustrates schematically the transition (40) of the boron atoms and carbon atoms from the carbon matrix (30) to the nanoparticles (50).
4 schematically illustrates metal boride nanoparticles 60 in the elastomeric matrix 70. FIG.
Figure 5 shows X-ray diffraction (XRD) of a sample containing TiB ₂ and TiC nanoparticles.
Figure 6 shows a photograph of a sample containing TiB ₂ and TiC nanoparticles.
Figure 7 shows an XRD of a sample containing ZrB ₂ and ZrC nanoparticles.
8 shows a photograph of a sample containing ZrB ₂ and ZrC nanoparticles.
Figure 9 shows the XRD of the samples containing HfB ₂ and HfC nanoparticles.
Figure 10 shows a photograph of a sample containing HfB ₂ and HfC nanoparticles.
Figure 11 shows the XRD of a sample containing WB ₂ and WC nanoparticles.
Figure 12 shows the XRD of a sample containing TaB ₂ and TaC nanoparticles.
13 shows a photograph of a sample containing TaB ₂ and TaC nanoparticles.
Figure 14 illustrates the XRD of a sample containing TiB _2, TiC, ZrB2, ZrC, and nanoparticles.
15 shows an XRD of a sample containing TaB _2, TaC, HfB _2, HfC, and nanoparticles.
16 shows an XRD of a sample containing only ZrB ₂ nanoparticles.
Figure 17 illustrates the XRD of a sample containing ZrB _2, ZrC, ZrN, and nanoparticles.

In the following, for purposes of explanation and not limitation, the details are set forth in order to provide a thorough understanding of the subject matter. It will be apparent, however, to one skilled in the art that the present subject matter may be practiced in other manners that depart from these specific details. In other instances, detailed descriptions of well-known methods and apparatus have been omitted to avoid obscuring the subject matter with unnecessary detail. Any numerical range disclosed herein includes numerical values within the range of the peripheral error of the range end points and all numerical values within the range.

(1) a method for in situ formation of a refractory metal diboride (MB) (IV-VI group) in the presence or absence of a carbon matrix in one step to provide a molded composition having structural integrity, (2) (3) conversion to molded thermosetting materials; (4) metal boride and metal boride-metal carbide carbon matrix compositions in multi-stages; (5) nanoparticle metal nanoparticles; Boron and nanoparticle metal boride-nanoparticle metal carbide carbon matrix compositions and (6) fiber-reinforced nanoparticle metal boride-nanoparticle metal carbide carbon matrix composites.

The synthetic methods described herein can lead to the formation of nanoparticle metal boride. To form a rigid molded refractory metal boride solid component / hybrid, the composition may be bound under pressure to remove air pockets and allow the reactants to intimately contact at least in a thermo-firing step. Therefore, due to its fundamental properties, the present invention enables the boride-metal carbide carbon hybrid to be readily formed by a liquid molding process (injection molding, injection molding, vacuum molding, spreading, etc.) It is a much less expensive process than processing sintered materials.

In the absence of a carbon precursor, a metal boride / nitride can be formed. Said material. Method The light conditions are the same as described elsewhere herein except for the absence of carbon compounds. The metal and boron precursor compositions can be molded under high pressure and then heated to the temperature necessary to separate (remove from the mold), or to form metal borides and metal nitrides in the mold. The metal boride can be formed by heating under an argon or helium atmosphere, while the metal boride-metal nitride is formed by heating in a nitrogen atmosphere and the metal nitride is formed mainly on the outer part of the solid component. The above-described method does not produce a thermosetting material since no carbon precursor is present.

The method may produce a solid refractory metal (Ti, W, Nb, Zr, Mo, Cr, V, Ta, and Hf) boride formed from metal nanoparticles. Mixed phases using multiple metals can also be generated. The ceramic is produced as nanoparticles. a) a metal compound capable of forming a stable boride or carbide and being decomposed into highly reactive metal nanoparticles, b) a boron element, and c) a carbon precursor which is melted and contains only carbon and hydrogen, The combination can be thermally converted into a solid form that contains both (d) a high yield of both pure metal boride and metal carbide, and possibly some of the amount is pure carbon. The amount of metal boride and metal carbide formed depends on the amount of boron element and carbon precursor present in the precursor composition (metal nanoparticles, boron and carbon precursor). The suitable metal nanoparticles are formed from the thermal decomposition of metal compounds (including, but not limited to, carbonyls and hydrides) in the precursor composition in situ. The carbon source may be processed into processible aromatics-containing acetylene or a low molecular weight polymer exhibiting an extremely high Kar yield. The carbon precursor may contain only C and H to ensure that hetero atoms (e.g., nitrogen) are not incorporated into the interstitial sites of the metal nanoparticles during the reaction to form the metal boride and metal carbide carbon matrix compositions. The metal boride and metal carbide are formed between 500 to 1600 ° C from the reaction of the highly reactive metal nanoparticles with the boron element and the carbon precursor (decomposed above 400 ° C) under inert conditions and the reaction occurs rapidly at higher temperatures . The temperature at which the synthesis process occurs may be much less than the temperatures typically associated with the formation of borides and carbide ceramics. The carbon precursors are used or are present for interlocking or bonding individually formed ceramic nanoparticles together as they are formed within the resulting nanostructured or amorphous elastic carbon. The formed carbon provides structural integrity and serves as a matrix for ensuring a molded composition for the high surface area ceramic nanoparticles formed. The pressure can be applied to the composition during conversion to a molded thermoset material to ensure heat treatment and intimate contact of the reactants and removal of any voids or air pockets to ensure high-density ceramics free from defects.

In the method described herein (Fig. 1), the metal compound is combined with the boron element and the carbon precursor to be melted. The carbon precursor is a compound such as the polymer or resin having functional unsaturation that interacts with metal nanoparticles formed from metal compounds. The unsaturation also allows the carbon precursor to proceed from the melt to form a thermosetting or crosslinked polymer. A typical precursor composition is boron. A carbon precursor and a metal compound or a plurality of metal compounds. Upon heating the composition, the carbon precursor may be thermally converted to a solid, thermoset material 20 that melts at its melting point and is formed through reaction of the unsaturated moiety. The carbon precursor may also be cured to the B stage to partially increase the viscosity, but may still be melted to improve processability and retention of uniformity within the precursor composition. The metal compound may be thermally decomposed into nanoparticles 10 or the metal powder may react with the organic components to form nanoparticles embedded in the solid thermosetting material during the above or subsequent steps (FIG. 2).

Alternatively, the formation of the metal nanoparticles may occur during the next step in the process, which is an extended thermal treatment at a higher temperature. Heat treatment of the thermosetting material above 500 캜 induces carbonization of the carbon precursor 30 and also reaction 40 between the metal nanoparticles 50 and both the boron source and the carbonized carbon precursor presently both form metal boride ceramics Main component) and metal carbide ceramics (minor component) nanoparticles 60 (Fig. 3-4). The solid formed ceramics obtained by using a large proportion of boron to carbon precursor can be adjusted to contain mainly metal borides. Also, the formation of reactive metal nanoparticles may occur during the thermal treatment step instead of the early thermosetting step. Additionally, if a sufficiently high proportion of carbon precursor is used, excess pure solid carbon will remain as a buried matrix of boride and carbide ceramics. The reaction can also be carried out so that only the metal boride is produced using only the refractory metal compound and boron without the thermoset-forming carbon precursor. Accordingly, the amount of metal boride, metal carbide, and carbon in the resulting composition may vary based on the amount of each individual component (metal compound, boron and molten processible carbon compound) mixed for use in the precursor composition . The reaction is carried out under non-reactive inert gas such as argon or helium or under vacuum.

The same reaction is carried out in a stream of nitrogen or when the organic compound contains nitrogen. Metal nitride nanoparticles can also be formed. Depending on the form and thickness of the composition, both the metal boride, and the metal nitride and the metal carbide can be formed together with the metal carbide and the metal boride on the interior of the composition, where nitrogen can not be in intimate contact.

Reaction of the metal salt and decomposition into metal nanoparticles can occur at low temperatures with the reaction with ceramics up to 1200 ° C, but higher temperatures can be required for micrometer-sized metal powders to at least 1600 ° C. Smaller sized particles react faster than large particle size powders and can be consumed collectively at lower temperatures. The particle size of the metal boride / carbide / nitride can be adjusted as a function of the upward temperature treatment by providing a ceramic with a higher particle size at all higher exposure temperatures.

Regardless of the total proportion of metal compound and boron element to carbon source, the refractory metal boride and metal carbide can be formed as nanoparticles. This is a very desirable result because it is generally accepted that uniform nanoparticle hybrids of ceramics have properties superior to their more conventional nanoparticle objects. Currently, the ceramics are assembled from micron-sized powdered particles by sintering techniques at extremely high temperatures. Excess carbon atoms can be carried out for reaction with the metal content and for carbon to be carried out so that the refractory metal boride and carbide are combined or the reaction is stoichiometrically capable of producing only metal borides and metal carbides together with a trace amount of carbon matrix It can be used to ensure the formation of a matrix. The amount of metal boride, metal carbide, and carbon in the resulting composition may vary based on the amount of each individual component (metal compound, boron, and melt processible carbon compound) mixed for use in the precursor composition. When the reaction is carried out in a nitrogen atmosphere, the metal nanoparticles may preferentially react with nitrogen relative to boron and carbon, which provide the corresponding metal nitrides.

The carbon, ceramic and metal fibers can be incorporated into various mixtures of precursor compositions composed of boron, metal compounds of group IV-VI and acetylene-containing aromatic compounds or polymers (carbon sources) and the resulting fiber- And then heated to a higher temperature. After the same heat treatment, the above defined steps lead to a composition of metal boride, metal carbide, carbon and any proportion of fibers intended to act as a reinforcing component. The precursor compositions (metal salt, boron, and carbon precursor) described above are mixed with continuous or cut fibers and heated until converted to a molded thermoset form. Further heating above 500 ° C under an inert atmosphere (argon) forms a fiber-reinforced refractory metal boride-metal carbide-carbon matrix hybrid. Depending on the ceramic being formed, rigid solid formed hybrids can be used for structural applications above 3000C. The hybrids may be exposed to an upward temperature to ensure that the physical properties remain intact and are used unchanged. The precursor composition may contain a combination of different refractory metal compounds that induce a mixture of ceramics in the hybrid water that may be beneficial for a particular application.

As described above, when the metal compound, boron and carbon precursor composition are heated in a nitrogen atmosphere, the metal nitride-containing ceramics can be formed with direct incorporation of nitrogen into the lattice of metal atoms / nanoparticles. Thus, the metal boride / metal carbide / metal-matrix composition or metal boride / metal nitride / metal carbide metal-matrix composition or combinations thereof can be selectively formed by changing the atmosphere to effect the reaction . When fiber experiments are performed in a nitrogen atmosphere, metal carbide carbon matrix hybrid with fiber reinforced refractory metal boride / metal nitride / metal nitride can be formed on the outer surface in particular. The hybrids may have significant oxidation stability and temperature performance at temperatures above 3000 < 0 > C.

The molded solid precursor composition is a precursor metal component under pressure. Boron and carbon sources or metal components and boron compositions. For example, if the metal component is a metal hydride, the various precursor compositions can be formulated and milled to a very small particle size, e.g., a size of up to 100 [mu] m to 10 [mu] m. The molded pellets or other molded components can be carried out under pressure which binds the small comminuted particles in intimate contact and can be performed with structural conversion for removal from the pressure system followed by thermal conversion to ceramic. Heating of the molded precursor is carried out at a very slow rate (e. G., 10 < / RTI > to 10 < RTI ID = 0.0 > , 5, 3 or 2 [deg.] C / min) under ambient conditions. The heating can be carried out under vacuum or under an inert atmosphere such as argon or nitrogen. By controlling the heating rate and the decomposition rate of the metal hydride, the metal boride or the metal boride / carbide is formed as nanoparticles, and as the processing proceeds, the exothermic reaction takes place at the temperature required to obtain the nanoparticle ceramic of high yield Can be easily adjusted during a slow heating rate of < / RTI > Since the metal hydrides and the boron or metal hydrides, boron and carbon source are in intimate contact, the atoms (metal and boron or metal, boron and carbon atoms) of each reactant are bound to the nanoparticle metal Strong bonds between the borides can be ensured. As formed, the ceramic nanoparticles (metal borides) exhibit strong interactions in solid ceramics and the solid formed ceramics formed exhibit stiffness, rigidity and structural integrity.

The method is shown in Fig. 1 and schematically in Figs. Any of the reactions described is not limited to the currently claimed methods and compositions. The nanoparticle morphology of the refractory metal is considered to be very reactive with the boron element and the carbon source, thereby lowering the formation temperature of the metal boride and the metal carbide. Furthermore, at least a stoichiometric amount of metal nanoparticles and boron and possibly a slight excess of boron and a minimal amount of carbon precursor may be included in the precursor composition. Any excess boron reacts with carbon to form boron carbide, thereby reducing the amount of metal carbide that can potentially be formed. This flowability provides the ability to vary and control the properties of the resulting ceramic carbon matrix hybrid. The metal boride and metal carbide carbon-matrix hybrids are expected to exhibit enhanced stiffness due to the presence of relatively elastic carbon present in amorphous or nanotubular to graphitic carbon form.

The inherent presence of the "elastic" carbon matrix can intensify the inherently brittle sintered ceramics. The carbon can enable operation of the enhanced ceramic at extremely high temperatures due to the high melting point of carbon (> 3000 ° C). The ceramic / carbon-matrix composition is currently being sought for the above reasons and the method of the present invention is firstly carried out in a first step, in contrast to the conventional means of forming a ceramic powder and then producing a metal boride shaped composition under sintering conditions The hybrid can be directly produced. Only minor or very small amounts of carbon may be required to achieve this effect. In addition, the ratio of ceramic to carbon is readily adjusted based on the ratio of metal-compound or metal powder to boron element to carbon-precursor.

The fiber-reinforced refractory metal boride carbon matrix hybrid can exhibit prominent mechanical properties for use under environmentally extremely high temperature conditions. The finely divided fiber-reinforced refractory nanoparticles metal boride carbonaceous composite enables the bonding of fully dense molded solid components, which can be interpreted as a huge economic advantage of increased operating temperature and mechanical integrity. , And high crack resistance for use in high stress and temperature applications such as advanced engine components for nuclear reactors and fuel cells. The fiber-reinforced ceramic blend may be advantageous in the construction of manufacturing facilities that require high temperature properties and structural integrity of the blend, such as in a steel mill and coal flame electrical installation. The rigid, easily formed ceramic blend is a next generation jet engine and an engine for hypersonic vehicles designed to operate at a higher internal temperature and stress than those currently in service, advanced automotive engine and support components, and advanced engine components And in the design of support structural components. Hot ship decks can be easily assembled for aircraft carriers that require better heat resistance of metal boride / metal carbide ceramic-carbon blends. In addition, lightweight, rigid and rigid ceramics that are easily manufactured in an adjustable form can be very important for the assembly of better military weapons that are reassembled in a reactor or mold in a molded structure. The ability to produce rigid molded refractory metal boride components in one step enhances their importance due to their economic advantages and elimination of the need for machining into molded components.

The method described above can produce nano-sized metal borides from well-formed metal nanoparticles within a relatively narrow size range. The process appears to be largely mediated by the high reactivity of the metal nanoparticles to the excess boron and carbon source, and the kinetics described above suggest that the boron and carbon incorporation rates into the metal lattice and the subsequent rate at the proper crystallographic location for the formation of the ceramic Can be determined by redemetification, which means that the rate of the process can be directly controlled by the temperature.

The formation of ceramic carbon matrix hybrids through the use of meltable carbon materials is known. However, in these schemes, the boride ceramic powder is first formed using different reaction chemistries and then added to the subsequently carbonized precursor carbon material. It is also possible to form metal boride powders from metal oxides and boron carbide by a high temperature reaction above 2000 ° C in a process similar to that described in the previous paragraph (ie, "atomically" formed) and carbon monoxide is formed as a byproduct. In either case, the boron carbide is not formed from the reaction of the metal nanoparticles and the boron element to produce ceramic nanoparticles whose concentration can be easily controlled.

In the first step of the process, the three components can be blended and mixed thoroughly. One is a refractory metal nanoparticle or a metal component that can be a refractory-metal compound that can be broken down into particles of a refractory metal. Any refractory metal, including, but not limited to, transition metals of Group IV-VI, including, but not limited to, titanium, zirconium, hafnium, tungsten, niobium, molybdenum, chromium, tantalum or vanadium may be used. When a pure metal is used, it may be in the form of nanoparticles or other particles such as powders. When the metal particles are used, the metal may be directly reactive with boron or an organic component. Suitable powders include, but are not limited to, tungsten and tantalum.

Instead of a pure metal, a compound containing a metal atom may be used. The compounds decompose at elevated temperatures to release metal atoms that can react with boron or organic components. Suitable such compounds include, but are not limited to, salts, hydrides, carbonyl compounds or halides of refractory metals. Examples include titanium hydrides, zirconium hydrides and hafnium hydrides. Other examples and embodiments of the types of compounds that can be used with the metals described herein are described in U.S. Patent 6,673,953; 6,770,583; 6,846,345; 6,884,861; 7,722,851; 7,819,938; 8,277, 534].

The second component is elemental boron. Suitable boron is readily available in powder form. 95-97% boron is suitable and higher pure boron powder (99%) is preferred. The boron powder may be pulverized to reduce its particle size.

The third component is an organic compound having a Karr yield of at least 60% by weight. The Tard yield may also be as high as at least 70 wt%, 80 wt%, 90 wt%, or 95 wt%. The Karr yield of potential compounds can be determined by comparing the sample weights before and after heating to at least 1000 ° C for at least 1 hour in an inert atmosphere such as nitrogen or argon. Any such compound with a high Karr yield can be used because the char performance can play a role in the reaction mechanism. The Karr yield can be measured at the pressure to be used when the heating step is also carried out at elevated pressure. Thus, compounds having a low Tard yield at atmospheric pressure but a high Tard yield under external pressure or conditions under which the described process is carried out may be suitable for producing metal borides, carbides and nitrides. The organic compound may be removed to form a pure metal boride and optionally a metal nitride.

Certain organic compounds may exhibit any of the following characteristics including combinations of mutually consistent characteristics: those containing only carbon and nitrogen; Those containing aromatic and acetylene groups; Carbon, nitrogen. And those containing only nitrogen or oxygen; Not containing oxygen; And containing nitrogen atoms other than oxygen. It can have a melting point of up to 400 ° C, 350 ° C, 300 ° C, 250 ° C, 200 ° C or 150 ° C and melting can take place prior to polymerization or bonsaiing of the compound. Examples of the organic compound include 1,2,4,5-tetrakis (phenylethynyl) benzene (TPEB), 4,4'-diethynylbiphenyl (DEBP), N, N ' N, N '- (1,4-phenylenedimethylidene) -bis (3,4-dicyanoaniline) (dianilphthalonitrile), And 1,3-bis (3,4-dicyanophenoxy) benzene (resorcinol phthalonitrile) or a precursor polymer thereof. A precursor polymer such as a precursor polymer of TPEB or other suitable organic compound may also be used. The different compounds may be mixed together and / or reacted with the precursor polymer prior to use as the organic compound of the precursor composition. The presence of nitrogen atoms in organic compounds can produce metal nitrides in ceramics without the use of a nitrogen atmosphere.

One or more metals, metal compounds and / or organic compounds may be used. Two or more different metals may be used to produce two different metal borides, carbides and / or nitrides in the ceramic. Also, in some cases, only one compound may be used if the metal component and the organic component are the same compound. The compounds are high in carbon and hydrogen content and can produce refractory metals bound to the compounds as well as produce high Karr yields.

Any component in the precursor material is a plurality of fibers or other fibers. Examples of fibers include, but are not limited to, carbon fibers, ceramic fibers, and metal fibers. The fibers can be any dimension that can be incorporated into the blend and can be cut or split into shorter dimensions.

The precursor mixture, which may be mixed in the melting step and / or bound under pressure, then undergoes a heating step to form the metal nanoparticle composition. This can be done while the mixture is in the mold. This ensures that the final product will have the same shape as the mold, because it will melt if the organic component of the mixture is not already liquid, and if the mixture is filled into the mold during heating and the ceramic is formed, The precursor mixture is heated under an inert atmosphere at a temperature which causes decomposition of the refractory-metal compound to form refractory-metal nanoparticles. If the organic compound is volatile, the heating may be carried out under pressure to avoid evaporation of the organic compound. As used herein, the heating step involves the formation of nanoparticles from a metal powder. As the reaction proceeds from the metal powder, the metal particles become smaller. There is no need to prove that nanoparticles are formed to continue with the process. However, any known technique for detecting nanoparticles such as SEM, TEM, or x-ray diffraction analysis (XRD) can be used to demonstrate that the metal components suitably produce nanoparticles in some cases. Suitable heating temperatures include, but are not limited to, 150-500 or 700 ° C.

Heating of the precursor may also cause polymerization of the organic compound into the thermosetting material. The metal nanoparticles 10 are then dispersed throughout the thermosetting material 20, as shown in FIG. The organic compound may also be polymerized before nanoparticles are formed. A thermoset material having refractory-metal compounds or particles of refractory metal (including nanoparticles) dispersed throughout can be used as the final product. The thermosetting material may also be processed to the desired shape and then heated to form the following ceramic. The thermosetting material is not formed when the organic compound is excluded.

The metal source can be uniformly dispersed or embedded in the thermosetting material as an intermediate solids solid. In this step, the composition may have a form to retain upon further heating and conversion of the metal source to the ceramic from the reaction of the product carbon matrix.

The precursor mixture may be bound to a molded solid component under pressure which promotes close contact of the reactants to provide a highly dense ceramic solid or to densify the final product. The precursor mixture may be converted to ceramics by squeezing under external pressure and releasing from pressure and then heating to a thermoset material. Alternatively, the precursor mixture may be squeezed under external pressure and maintained at the pressure during heating with the thermoset material and ceramic.

In the second heating step, the metal nanoparticle composition is heated to form a ceramic. The heating is performed at a temperature that causes the formation of refractory-metal boride 60 and refractory-metal carbide nanoparticles in the elastomeric matrix 70 (FIG. 4). The elastomeric matrix may comprise graphite carbon, carbon nanotubes and / or amorphous carbon. When organic compounds are excluded, there is no elastomeric matrix. When nitrogen is present, metal nitride nanoparticles can be formed. There may be higher concentrations of nitride on the surface than inside. Suitable heating temperatures include, but are not limited to, 500-1900 占 폚.

The nanoparticles that may be formed include but are not limited to titanium boride, titanium carbide, zirconium boride, zirconium carbide, hafnium boride, hafnium carbide, tungsten boride, tungsten carbide, tantalum carbide, and HfaC ₂ It does not. The presence and composition of the metal boride or carbide particles may be varied by any known technique for detecting nanoparticles, such as SEM, TEM, or XRD. The nanoparticles may have an average diameter of less than 100 nm, 50 nm, or 30 nm. These can generally be spherical in shape or non-spherical, for example, nanorods.

The ceramic comprises at least 5 wt%, 10 wt%, 20 wt%, 30 wt%, 40 wt%, 50 wt%, 60 wt%, 70 wt%, 80 wt%, 90 wt%, 95 wt% , Or 99% by weight of the nanoparticles of the present invention. The percentage of nanoparticles can be determined in part by the molar ratio of metal to boride and carbon atoms in the precursor mixture. At a ratio of 1: 1, nearly all boron and carbon can be incorporated into the nanoparticles and small amounts or trace amounts of the elastomeric matrix remain. Higher amounts of boron can lead to higher ratios of metal boride to metal carbide nanoparticles. With higher amounts of organic compounds, the fraction of metal carbide nanoparticles is lower and the fraction of elastomeric matrix is higher. By this method, changes in the ratio of metal to boron to organics can be used to provide a mixture of metal borides and metal carbides when carried out in an inert atmosphere, such as argon, and to provide metal borides, metal carbides And metal nitrides. When a metal nitride is produced, an increase in the amount of carbon in the precursor mixture may lower the amount of the metal nitride in the ceramic. When the organic compound is excluded, the product is almost all nanoparticles.

The ceramic may not be formed as a powder but may be in the form of a solid unbroken mass. It may contain less than 20% by volume of voids or a low void volume of 10%, 5%, or 1%. It may have the same form as the precursor mixture (if it is a solid) or may take the form of a mold located during heating. The ceramic can retain its shape in that it can not be deformed when it is handled and can not change its shape or brakes without the use of extreme forces. The ceramic composition may be rigid rigid and may have structural integrity. The degree of properties may depend on the amount of ceramic to carbon in the solid ceramic composition. Any form may be formed to produce a product useful for incorporation into an apparatus. The product may be sufficient to have a minimum size of at least 1 cm at all dimensions. That is, the entire surface of the article is at least 5 mm from the mass center of the article. Larger products can be manufactured, such as having a minimum size of at least 10 cm at all dimensions. In addition, the composition may have a smaller size such as 1 mm, 2 mm, or 5 mm.

A third heating step may also be performed if the ceramic is heated in an oxygen-containing atmosphere to form an oxide of refractory metal on the surface of the ceramic. For example, titanium oxide can be formed on the surface. The surface oxidation can protect the interior of the ceramic from further oxidation.

The following examples are given to illustrate specific applications. These specific embodiments are not intended to limit the scope of the disclosure herein. U.S. Provisional Application No. 61 / 590,852; 61 / 640,744; 61 / 669,201; Any other suitable methods and materials described in U.S. 61 / 693,930 may be used. Any carbon source, a boron element source. Metal compounds and / or other parameters described herein may be used in any combination with the presently described methods and combined with any of the materials and / or parameters described herein.

Example 1

1: 2.1: 0.01 in a proportion of TiH _2, boron, and the formulation of the precursor composition of TPEB - TPEB (0.129g; 0.270 mmol ), boron (0.455g, 42.1mmol), and TiH ₂ (1.00g; 20.0 mmol) Was used as a precursor composition for the formation of refractory nanoparticles (TiB ₂ ) bound or buried with excess carbon fully mixed and acting as a matrix material. The ratio of the three reactants can be easily varied by the described formulation methods.

Example 2

A preliminary TGA-DSC thermal analysis study to determine the conditions for the formation of refractory TiB ₂ ceramic solids in one step by heating to 1400 ° C at 1400 ° C under an argon atmosphere - a sample of the precursor composition prepared in Example 1 (16.8960 mg) was weighed with a TGA ceramic pan and cleaned in a TGA chamber at 10 ° C per minute to 1400 ° C using a Q600 TGA-DSC TA instrument, which was flushed with argon stream (110 cc / min) for 15 minutes followed by a solid ceramic material Respectively. The DSC thermogram showed a small melting endothermic reaction (TPEB) at about 194 ° C and an exothermic transition peak at about 282 ° C (reaction / cure of the ethynyl group of TPEB to form a molded thermoset polymer). As the heating continued, the DSC thermogram showed a combination of exothermic reaction peaks at about 590 ° C followed by a transition beginning at 480 ° C and an endothermic reaction at about 533 ° C. During this heat treatment to 1400 占 폚, the sample only lost a small amount of weight at 1400 占 폚 and retained 96.78% by weight. The ceramic carbon solid composition was formed in one step and exhibited structural integrity.

Example 3

Formation of nanoparticles in one step by a controlled heating refractory TiB ₂ ceramic solid under an argon atmosphere up to 1300 ℃ - a sample of the precursor composition prepared in Example 1 (88.8430 mg), together with the weighed out and a flat surface in a TGA ceramic pan Packed and bonded to a solid thermosetting polymer molded in a TGA chamber at 250C under argon atmosphere to 10O < 0 > C per minute at 250 < 0 > C for 2 hours. During the heat treatment to 250 캜, the sample showed an endothermic transition at about 195 캜 due to the melting point of TPEB. The isothermal heat treatment at 250 占 폚 caused the reaction of the vinyl units in the TPEB to be converted into the thermosetting polymer. The solid polymeric sample composed of TiH ₂ and boron embedded in the polymeric thermosetting material was then slowly heated to 1300 ° C at 3 ° C per minute and heated at 1300 ° C for 3 hours to obtain a solid ceramic material having 96.06% . Above 400 ° C, TiH ₂ is decomposed to Ti nanoparticles and H ₂ ; The H ₂ was evaporated from the sample. Further heating to above 500 ° C to 1300 ° C results in the formation of highly reactive Ti nanoparticles and a high yield of TiB ₂ nanoparticles and small amounts of TiC nanoparticles buried in excess carbon formed during the simple carbonization process Induced the reaction with carbon atoms formed from carbonization of TPEB during thermal treatment. More importantly, the nanoparticulate refractory ceramic matrix hybrid was formed in one step. XRD analysis of the solid samples (Figure 5) showed a clear response with formation of TiB ₂ (87%) and TiC (13%). The particle size for TiB ₂ was 21.5 nm and for TiC was 12.4 nm. Figure 6 shows a photograph of a typical sample.

Example 4

ZrH _2, boron, and TPEB formulated in a precursor composition of a (1:: 1 0.02) - TPEB (0.100 g; 0.209 mmol), boron (0.115 g, 10.6 mmol), and ZrH2; a (1.00 g 10.7 mmol) completely Was used as a precursor composition for the formation of refractory nanoparticles (ZrB ₂ ) which were mixed and bound to an excess of carbon to act as a matrix material. The ratio of the three reactants can be easily varied by the described formulation methods.

Example 5

Formation of refractory ZrB ₂ solid ceramic composition in one step by heating to 1400 ° C under argon atmosphere to 10 ° C per minute - Samples (12.1180 mg) of the precursor composition prepared in Example 4 were weighed in a TGA ceramic pan and placed on a flat surface Packed together and heated in a TGA chamber from 10 ° C to 1400 ° C under an argon stream (110 cc / min) to produce a solid material having 98.03% by weight. During the heat treatment, the sample exhibited an exothermic reaction transition peak at about 292 占 폚 due to curing into a molded solid thermosetting polymer at about 194 占 폚 (endothermic reaction transition: TPEB). After cooling to 1400 ° C at room temperature, the solid ceramic composition was removed from the TGA pan. The molded solid ceramic refractory ZrB ₂ ceramic carbonaceous material was formed in one stage and was hard and showed structural integrity.

Example 6

Formation of nanoparticulate refractory ZrB ₂ ceramic solids in one step by controlled heating at 3 ° C / min under 1300 ° C under an argon atmosphere - Samples (115.7420 mg) of the powdered composition prepared as in Example 4 were mixed with TGA ceramic Packed in a pan and packed into a flat surface and heated in a TGA chamber to 5O < 0 > C / minute to 250 < 0 > C under argon flow (110 cc / min) and heated at 250 [deg.] C for 1 hour to bond to the molded solid thermoset polymer. During the heat treatment, the sample showed an endothermic reaction transition at about 195 캜 due to the melting point of TPEB. Ethynyl units in TPEB were reacted at 250 < 0 > C by isothermal heat treatment and converted to molded solid thermosetting polymers. The resulting thermoset polymer contained homogeneously distributed ZrH ₂ and boron, embedded in the domain of the polymer. Further heated at the above 500 ℃ and evaporated to H ₂ from a sample, such as ZrH ₂ was formed by decomposition Zr nanoparticles and H _2. The solid thermosetting polymer sample is slowly heated to 1300 DEG C at 3 DEG C per minute and left at that temperature for 3 hours to obtain a solid ceramic material held at 93.27 wt%. Highly reactive Zr nanoparticles were reacted with boron and the resulting carbon atoms formed from the decomposition of TPEB during the simple carbonization process by heating from 500 ° C to 1300 ° C to form excess carbon-embedded ZrB ₂ and ZrC nanoparticles. More importantly, the novel refractory metal ceramic carbon matrix composition was formed in one step. XRD analysis showed pure high yield ZrB2 and ZrC nanoparticles embedded in amorphous carbon matrix as the product formed during the heat treatment. The XRD studies have shown each ZrB ₂ and ZrC an average particle size of 35nm and 32nm in ZrB2 and ZrC nanoparticles of about 50/50 both for the solid carbon in the ceramic composition.

Example 7

ZrH _2, boron and TPEB (1: 2.0: 0.02) formulation of the precursor composition of the - TPEB (0.100 g; 0.209 mmol ), boron (0.233 g, 21.5 mmol), and ZrH _2; a (1.00 g 10.7 mmol) completely Was used as a precursor composition for the formation of ZrB ₂ , a refractory nanoparticle buried or bonded with an excess of carbon mixed and acting as a matrix material. The ratio of the three reactants can easily be varied by the above-described formulation method.

Example 8

Stoichiometric with the amount of boron and relative to the solid ceramic within ZrC produced in one step by a controlled heating to the 3 ℃ / min under an argon atmosphere up to 1400 ℃ nanoparticles yield refractory ZrB ₂ formed of - Example 7 (115.7420 mg) were weighed with a TGA ceramic pan and packed onto a flat surface and heated in a TGA chamber to 5O < 0 > C / minute to 250 < 0 > C under argon flow (110 cc / min) Lt; / RTI > for 1 hour to bind to the molded solid thermosetting polymer. During the heat treatment, the sample showed an endothermic reaction transition at about 195 캜 due to the melting point of TPEB. Ethynyl units in TPEB were reacted at 250 < 0 > C by isothermal heat treatment and converted to molded solid thermosetting polymers. The obtained thermosetting polymer contained 1 mole of ZrH ₂ and 2 moles of boron uniformly distributed, embedded in the domain of the polymer. Further heated at the above 500 ℃ and evaporated to H ₂ equal to ZrH ₂ as digested with Zr nanoparticles and H ₂ was formed from the sample. The solid thermoset polymer sample is slowly heated to 3O < 0 > C / minute to 1400 < 0 > C and left at that temperature for 3 hours to obtain a ceramic solid having structural integrity retained at 97.27% by weight. By heating from 500 ° C to 1400 ° C, highly reactive Zr nanoparticles were reacted with boron and the resulting carbon atoms formed from the decomposition of TPEB during the simple carbonization process to form excess carbon-embedded ZrB ₂ and ZrC nanoparticles. The refractory metal ceramic carbon matrix composition was formed in one step. XRD analysis (FIG. 7) showed ZrB ₂ nanoparticles relatively pure and high yield relative to ZrC embedded in an amorphous carbon matrix as a product formed during the heat treatment. The XRD study showed a mean particle size of 46nm and 19.6nm of ZrC and ZrB2 nanoparticles of about 75/25 both for each of ZrC and ZrB _2. Figure 8 shows a photograph of a typical sample.

Example 9

ZrH _2, boron and TPEB formulated in a precursor composition of a (1: 2:: 0 0.006 ) - TPEB (0.033 g; 0.069 mmol), boron (0.233 g, 21.5 mmol), and _{ZrH 2 (1.00 g; 10.7 mmol} ) were fully mixed and used as the precursor composition for the formation of excess carbon and the embedded or bonded refractory nanoparticles ZrB ₂ which serves as a matrix material. The ratio of the three reactants can easily be varied by the above-described formulation method.

Example 10

High yield nanoparticles in ZrC nanoparticles in a solid phase produced in one step by heating at 3 ° C / min to 1300 ° C under argon atmospheres using stoichiometric amounts of boron and a smaller amount of TPEB ZrB ₂ is formed of - example powdered sample of the composition prepared as in 9 (114.8850 mg) the TGA chamber under a stream of argon (110cc / min) to weighed by TGA pan and packed into a flat surface and 250 ℃ per minute 10 ℃ Lt; RTI ID = 0.0 > 250 C < / RTI > for 1 hour to bond to the molded solid thermosetting polymer. Ethynyl units in TPEB were reacted at 250 < 0 > C by isothermal heat treatment and converted to molded solid thermosetting polymers. The resulting thermoset polymer contained homogeneously distributed ZrH ₂ and boron, embedded in the domain of the polymer. The solid thermoset polymer sample is slowly heated to 1300 占 폚 at 3 占 폚 per minute and left at this temperature for 3 hours to obtain a ceramic solid having structural integrity of 98.01% by weight. By heating from 500 ° C to 1300 ° C, the highly reactive Zr nanoparticles were reacted with the resulting carbon atoms formed from decomposition of boron and TPEB present in smaller amounts compared to the precursor compositions of Examples 4 and 7. The refractory metal ceramic carbon matrix composition was formed in one step. XRD analysis showed relatively pure and high yield of ZrB ₂ nanoparticles on the ZrC nanoparticles embedded in the amorphous carbon matrix as the product formed during the heat treatment. The XRD study showed about 85% yield of ZrB ₂ nanoparticles and 15% yield of ZrC nanoparticles with average particle sizes of 29.3 nm and 27.9 nm for ZrB ₂ and ZrC, respectively.

Example 11

HfH _2, boron and TPEB formulated in a precursor composition of a (1:: 2.1 0.01) - TPEB (0.035 g; 0.073 mmol), boron (0.126 g, 11.6 mmol), and HfH _2; a (1.00 g 5.56 mmol) completely mixed and used as the precursor composition for the formation of excess carbon and the embedded or bonded refractory nanoparticles HfB ₂ which acts as a matrix material. The ratio of the two reactants can easily be varied by the above-described formulation methods.

Example 12

A preliminary TGA-DSC thermal analysis study to determine the conditions for the formation of refractory HfB ₂ ceramic solids in one step by heating to 1400 ° C at 10 ° C / min under an argon atmosphere - a sample of the precursor composition prepared in Example 11 30.9100 mg) were weighed out with a ceramic pan and packed in a flat plane and cleaned with argon stream (110 cc / min) for 15 minutes followed by a Q600 TGA-DSC TA instrument to produce a solid ceramic material having 98.47% Lt; RTI ID = 0.0 > 10 C < / RTI > The DSC thermogram showed a small melting endothermic reaction (TPEB) at about 194 ° C and an exothermic transition peak at about 282 ° C (reaction / cure of the ethynyl group of TPEB to form a molded thermoset polymer). The DSC thermogram showed two exothermic reaction transition peaks at about 535 ° C and 728 ° C. As the heating continued, the DSC thermogram was flat to about 1142 ° C, but began to exhibit an exothermic transition, which continued to a final temperature of 1400 ° C. During this heat treatment to 1400 占 폚, the sample only lost a small amount of weight at 1400 占 폚 and retained 98.47% by weight. The ceramic carbon solid composition was formed in one step and exhibited structural integrity.

Example 13

Nanoparticles refractory HfB ₂ solid ceramic formed in one step by a controlled heating of a 3 ℃ / min under an argon atmosphere up to 1300 ℃ - the powdered sample (115.7420 mg) of the composition prepared as in Example 11 ceramic pan And heated in a TGA chamber under argon flow (110 cc / min) to 10O < 0 > C / minute to 250 < 0 > C and heated at 250 [deg.] C for 1 hour to bond with the molded solid thermosetting polymer. During the heat treatment, the sample showed an endothermic reaction transition at about 195 캜 due to the melting point of TPEB. Ethynyl units in TPEB were reacted at 250 < 0 > C by isothermal heat treatment and converted to molded solid thermosetting polymers. The obtained thermosetting polymer contained homogeneously distributed HfH ₂ and boron, embedded in the domain of the polymer. Further heated at the above 500 ℃ and H ₂ as the HfH ₂ described decomposition and formed from a Hf nanoparticles and H _2, on the other hand to be evaporated from the sample, a highly reactive Hf nanoparticles carbon formed from the carbonization of the boron element, and TPEB Interact with atoms. The solid thermoset polymer sample was slowly heated to 1300 占 폚 at 3 占 폚 / minute and heated at 1300 占 폚 for 3 hours to obtain a ceramic solid having structural integrity retained at 98.49% by weight. The new refractory metal ceramic carbon matrix composition was formed in one step. XRD analysis (Figure 9) showed pure high yield HfB ₂ (87%) and HfC (13%) nanoparticles embedded in amorphous carbon matrix as the product formed during the heat treatment. The XRD study showed an average particle size of 31.3 nm and 30.5 nm for HfB ₂ and HfC, respectively. Figure 10 shows a photograph of a typical sample.

Example 14

(0.018 g; 0.038 mmol), boron (0.035 g, 3.24 mmol), and tungsten (0.500 g; 2.72 mmol) powder were thoroughly mixed with each other to form a precursor composition of tungsten, boron and TPEB And used as a precursor composition for the formation of refractory nanoparticles WB that are buried or bound with an excess of carbon acting as a matrix material. The ratio of the three reactants can easily be varied by the above-described formulation method.

Example 15

A preliminary TGA-DSC thermal analysis study to determine the conditions for the formation of refractory WB ceramic solids in one step by heating to 1400 ° C at 10 ° C / min under an argon atmosphere - a sample of the precursor composition prepared in Example 14 (16.8960 mg) were weighed out with a ceramic pan and packed in a flat plane and rinsed with argon stream (110 cc / min) for 15 minutes followed by heating in a TGA chamber to 10O < 0 > C / min to 1400 [deg.] C using a Q600 TGA- % ≪ / RTI > retained solid ceramic material. During the heat treatment to 1400 ° C, the sample showed a small exothermic reaction peak at about 1100 ° C and a stronger exothermic reaction at about 1188 ° C. The ceramic carbon solid composition exhibited structural integrity.

Example 16

Formation of a nanoparticulate refractory WB solid ceramic in one step by controlled heating at 2 DEG C / min to 1300 DEG C under an argon atmosphere - A sample of the powdered composition (115.7420 mg) prepared as in Example 14 was placed in a ceramic pan Packed with a weighed flat surface and heated in a TGA chamber to 10O < 0 > C / minute to 250 < 0 > C under argon flow (110 cc / min) and heated at 250 [deg.] C for 1 hour to bond to the molded solid thermoset polymer. During the heat treatment, the sample showed an endothermic reaction transition at about 195 캜 due to the melting point of TPEB. Ethynyl units in TPEB were reacted at 250 < 0 > C by isothermal heat treatment and converted to molded solid thermosetting polymers. The obtained thermosetting polymer contained uniformly distributed tungsten and boron elements embedded in the domain of the polymer. The thermosetting polymer composition was further heated to obtain micronized tungsten particles interacting with the boron element and carbon atoms formed from the carbonization of TPEB. The solid thermoset polymer sample is heated slowly to 1300 占 폚 at 2 占 폚 per minute and heated at 1300 占 폚 for 3 hours to obtain a carbon ceramic solid retained at 97.31% by weight. The refractory metal ceramic carbon matrix composition was formed in one step and retained its structural integrity. XRD analysis (Figure 11) showed very pure WB nanoparticles with a high average yield of 24 nm with a small amount of WC nanoparticles embedded in the amorphous carbon matrix.

Example 17

Formulation of a precursor composition of tantalum, boron and TPEB (1: 2.1: 0.01) TPEB (0.018 g; 0.038 mmol), boron (0.063 g, 5.83 mmol), and tantalum (0.500 g; 2.76 mmol) Was used as a precursor composition for the formation of refractory nanoparticles TaB ₂ , embedded or bound with excess carbon serving as a matrix material. The ratio of the three reactants can easily be varied by the above-described formulation method.

Example 18

Nano in one step by a controlled heating under an argon atmosphere up to 1400 ℃ particulate refractory TaB ₂ ceramic formation of a solid-in Example 17 was weighed samples (100.3100 mg) of the resulting precursor composition as in the ceramic pan and packed into a flat surface Deg.] C and argon stream (110 cc / min) for 15 minutes and then heated to 10 < 0 > C / minute in a TGA chamber to 250 < 0 > C and heated at 250 [deg.] C for 1 hour. The solid thermosetting polymer obtained was then heated to 1300 ° C at 2 ° C per minute and heated at 1300 ° C for 3 hours, followed by 1 ° C per minute to 1400 ° C and at 1400 ° C for 1 hour. XRD analysis (FIG. 12) showed high yields of TaB ₂ (93.8%) and small amounts of TaC (6.2%) nanoparticles in the solid ceramic composition. The XRD study showed average particle sizes of 24 nm and 20 nm for TaB ₂ and TaC, respectively. Figure 13 shows a photograph of a typical sample.

Example 19

Formation of nanoparticle refractory TiB ₂ and ZrB ₂ solid ceramic compositions in one step by heating to 1300 ° C. The same amounts (55 mg) of TiH ₂ / boron / TPEB and ZrH ₂ / The boron / TPEB was thoroughly mixed. A sample of this mixture (83.9220 mg) was weighed with a ceramic pan, packed onto a flat surface and rinsed with argon stream (110 cc / min) for 15 minutes and then heated in a TGA chamber to 10 & / RTI > The solid thermosetting polymer was then heated to 1300 캜 at 2 캜 / minute and heated at 1300 캜 for 3 hours to obtain a molded solid ceramic solid retained at 97.24% by weight. Removing the carbon ceramic solids and exhibiting structural integrity. XRD analysis (Figure 14) shows that ZrB ₂ (74%, particle size of 19.3 nm), TiB ₂ (12.3%), TiC (~3.5%) and ZrC (~10% ), A very complex mixture of formed ceramic nanoparticle materials. The above% is the crystalline material in the sample. The XRD was too complex to measure nanoparticle size for some ceramics.

Example 20

Formation of nanoparticle refractory HfB ₂ and TaB ₂ solid ceramic compositions in one step by heating to 1400 ° C. The same amounts (77 mg) of HfH ₂ / boron / TPEB and Ta powder / The boron / TPEB was thoroughly mixed. A sample of the mixture (143.3430 mg) was weighed with a ceramic pan, packed onto a flat surface and rinsed with argon stream (110 cc / min) for 15 minutes and then heated in a TGA chamber to 10 & / RTI > The solid thermoset polymer is then heated to 1300 ° C at 2 ° C per minute and heated at 1300 ° C for 3 hours, followed by heating to 1400 ° C per minute at 1 ° C and 1 hour at 1400 ° C to obtain a molded solid A ceramic solid was obtained. Removing the carbon ceramic solids and exhibiting structural integrity. The XRD analysis (Figure 15) revealed that a very high percentage of the formed ceramic nanoparticle material, including TaB ₂ (61.8%, 26.5 nm particle size), HfB ₂ (26.5%), TiC (8.2%), and HaTaC Complex mixtures. The above% is the crystalline material in the sample. The XRD was too complex to measure nanoparticle size for some ceramics.

Example 21

TiH _2, boron and DEBP (1: 2.1: 0.03) formulation of the precursor composition screen of - DEBP (0.108 g; 0.534 mmol ), boron (0.455 g, 42.1 mmol), and TiH _2; a (1.00 g 20.0 mmol) completely Was used as a precursor composition for the formation of refractory nanoparticle titanium boride (TiB ₂ ) which was mixed and overburdened with carbon to act as a matrix material. The ratio of the three reactants can easily be varied by the above-described formulation method.

Example 22

Formation of nanoparticle TiB ₂ solid ceramic composition from DEBP as TiH ₂ , boron, and carbon source in one step by heating to 1300 ° C - Samples (68.1378 mg) of the powdered composition prepared as in Example 21, Packed with a flat surface and bound to the molded solid thermosetting polymer by heating in a TGA chamber at 40 DEG C per minute to 250 DEG C under an argon stream (110 cc / min) and heating at 250 DEG C for 1 hour. A thermoset polymer thus obtained is contained within the buried, uniformly distributed titanium hydride (TiH _2), and boron element domain of the polymer. The solid thermoset polymer sample was slowly heated to 1300 占 폚 at 2 占 폚 per minute and heated at 1300 占 폚 for 3 hours to obtain a 93,89 weight% retained carbon ceramic solid. The refractory metal ceramic carbon matrix composition was formed in one step and retained its structural integrity.

Example 23

Formulation of TiH ₂ , Boron, and TPEB Carbon Fiber Polymer Hybrids - The precursor composition (1.8567 g of TiH ₂ , boron, and TPEB mixture) prepared as in Example 1 was placed into a mold of diameter 0.5 formed from aluminum foil A small amount of cleaved carbon fiber was added and mixed. The mixture was heated to 240 DEG C to melt the TPEB and the melted composition was pressed to a flat surface to bond to a flat surface. The resulting carbon fiber-precursor composition is then heated at 260-270 ° C for 1 hour in an argon stream to solidify it into a shaped carbon fiber-containing polymeric thermoset material, where TiH ₂ and boron are fiber-reinforced polymer thermoset And embedded in the hybrid water. The molded solid carbon fiber polymeric hybrid was removed from the mold.

Example 24

TiH ₂ and boron, carbon fiber polymeric mixed water TiB ₂ carbon fiber ceramic mixed transition to the water-heat-curable polymer fibers with a TiH ₂ and boron, in the reinforced hybrid uniformly distributed embodiment, the solid prepared in Example 23, molded carbon fiber The polymeric hybrids were placed in an oven and heated to 3O < 0 > C / minute and 1200 < 0 > C / minute under an argon stream and left at this temperature for 2 hours. The obtained ceramic-carbon reinforced hybrid was cooled to 3 캜 / minute and returned to room temperature. The solid fiber reinforced hybrid sample was characterized by XRD and found to contain buried refractory TiB ₂ nanoparticles and small amounts of TiC nanoparticles in a carbon matrix and carbon fiber.

Example 25

Placing an embodiment as a template for the 0.5 diameter assembled from aluminum foil Example 7 The precursor prepared as in composition (2.145 g of ZrH _2, boron, and TPEB mixture) - ZrH _2, boron and TPEB carbon fiber polymeric hybrid formation of A small amount of cleaved carbon fiber was added and mixed. The mixture was heated to 240 DEG C to melt the TPEB and the molten composition was squeezed to a flat surface and tied to a flat surface. The obtained carbon fiber-precursor composition was heated at 260 to 270 ° C for 1 hour under an argon stream to solidify the carbon fiber-containing polymeric thermoset material into a molded carbon fiber-containing polymeric thermosetting material. The solid molded carbon fiber polymeric homogeneously distributed ZrH ₂ and boron was removed from the mold.

Example 26

ZrH ₂ and boron, carbon fiber polymeric mixed water ZrB ₂ carbon fiber ceramic conversion to mixed with a water-minute 3 ℃ position the embodiment, the solid molded carbon fiber polymeric hybrid prepared in Example 25 in the oven and placed under an argon stream 1200 ℃ And allowed to stand at the above temperature for 3 hours. The resultant ceramic-carbon fiber-reinforced hybrid was cooled to room temperature while cooling to 3 캜 / minute.

Example 27

Formation of HfH ₂ , Boron, and TPEB Carbon Fiber Polymeric Composites - The precursor composition (2.8558 g of HfH ₂ , boron, and TPEB mixture) prepared as in Example 11 was placed into a 0.5 diameter mold assembled from aluminum foil And a small amount of cleaved carbon fiber was added and mixed. The composition was heated to 240 DEG C to melt the TPEB and the melted composition was pressed to a flat surface to bond to a flat surface. The obtained carbon fiber-precursor composition was heated at 260 to 270 ° C for 1 hour under an argon stream to solidify the carbon fiber-containing polymeric thermoset material into a molded carbon fiber-containing polymeric thermosetting material. The solid molded carbon fiber polymeric hybrid with homogeneously distributed HfH ₂ and boron was removed from the mold.

Example 28

Conversion of HfH ₂ and boron-carbon fiber polymeric hybrids to HfB ₂ carbon fiber ceramic hybrids The solid molded carbon fiber polymeric hybrids prepared in Example 27 were placed in an oven and heated to ₃ ° C./minute at 1200 ° C. And left at this temperature for 4 hours. The resultant ceramic-carbon fiber-reinforced hybrid was cooled to room temperature while cooling to 3 캜 / minute.

Example 29

Formulation of the precursor polymer composition of TPEB TPEB (10.30 g; 21.5 mmol) was placed on aluminum sheet and heated at 260 占 폚 for 40 minutes or until the mixture was viscous to stir with a metal spatula. The mixture was cooled and crushed into small pieces and ball milled for 2 minutes to obtain a fine black powder.

Example 30

TiH _2, boron, TPEB formulation of the precursor composition of the bulb the polymerization and formation of the molded pellets - Example TPEB prepolymers of 29 origin (0.129 g; 0.270 mmol), boron (0.455 g, 42.1 mmol), and TiH ₂ ( 1.00 g; 42.1 mmol) was ball-milled for 5 minutes to obtain a crimson-black fine powder. The powder was placed in a 13 mm pellet press and squeezed at 10,000 pounds for 1 minute.

Example 31

TiH _2, boron, and TPEB bulb transition to a solid molded thermoset material of the precursor composition of the polymer-position of the pellets of Example 30 originating in the furnace and heated to 200 ℃ under per minute argon atmosphere per minute 20 ℃ and at the temperature 10 (Overnight) to form a rigid molded polymeric thermosetting solid. TiH ₂ and the boron is uniformly dispersed in a solid thermoplastic material.

Example 32

Conversion of the precursor composition of TiH ₂ , boron, and TPEB precursor polymers to solid molded thermoset materials - Another pellet prepared as in Example 30 was placed in a furnace and heated to 250 ° C at 20 ° C per minute under an argon atmosphere And allowed to stand at that temperature for 2 hours to form a rigid molded polymeric thermosetting solid.

Example 33

Refractory TiB ₂ is formed of solid ceramic in one step by heating to 10 ℃ / min under an argon atmosphere up to 1400 ℃ - a polymeric thermoset solid (1.55 g) formed in Example 31 origin 3 and "position in the tube furnace, argon Heated to 1400 DEG C at 2 DEG C per minute and left for 2 hours at 1400 DEG C to obtain a solid densified ceramic holding 97.8 wt%. The solid ceramic was removed from the furnace and characterized by XRD to yield an excess of carbon in combination with a small amount of TiC it was found to form a TiB ₂ nano-particle size. the TiB ₂ -TiC carbon solid composition was formed in one step exhibited greater structural integrity, hard and rigid.

Example 34

Formulation of precursor compositions of TiH ₂ , boron and TPEB precursor polymers, formation of molded pellets and direct conversion to refractory TiC solid ceramic carbon composition in one step - TPEB precursor polymer prepared in Example 29 (0.129 g; 0.270 mmol ), Boron (0.455 g, 42.1 mmol), and TiH2 (1.00 g; 42.1 mmol) were ball milled for 5 minutes to obtain a crimson-black fine powder. The powder was placed in a 13 mm pellet press and squeezed at 10,000 pounds for 1 minute. The pellet was then placed in a furnace and heated to 250 ° C at 20 ° C per minute under an argon atmosphere and allowed to stand at this temperature for 30 minutes and then heated to 1200 ° C at 2 ° C per minute under an argon stream (100 cc / min) And left for 3 hours to obtain a solid dense ceramic holding 97.1% by weight. Upon cooling, the solid ceramic was removed from the furnace and characterized by XRD and found to form nanoparticle-sized TiB ₂ with a small amount of TiC in the excess carbon as matrix. The TiB ₂ -TiC carbon solid composition was formed in one step and exhibited large structural integrity, rigidity and stiffness.

Example 35

Formulation and Pellet Formation of a Precursor Composition of Tungsten Powder, Boron, and TPEB Precursor Polymers - TPEB precursor polymer from Example 29 (0.018 g; 0.038 mmol), boron (0.035 g, 3.24 mmol), and tungsten powder ; 2.72 mmol) was ball-milled for 5 minutes to obtain a crimson-black fine powder. The powder was placed in a 13 mm pellet press and squeezed at 10,000 pounds for 10 seconds.

Example 36

Tungsten powder. Conversion of the precursor composition of boron and TPEB precursor polymers to solid molded thermoset materials - The pellets of Example 35 were placed in a furnace and heated to 20 ° C at 215 ° C per minute under an argon atmosphere and at this temperature for 10 hours (overnight) And allowed to stand to obtain a rigid molded polymeric solid. The tungsten and boron powder are uniformly dispersed in the solid thermosetting material.

Example 37

Formation of refractory WB solid ceramic in one step by heating to 2O < 0 > C / min under argon atmosphere to 2O < 0 > C / min- Example 36. Place the cured thermoset pellets (0.525 g) from Example 36 in a 3 "tube furnace, / Min) at 2 [deg.] C per minute to 1500 [deg.] C and left at 1500 [deg.] C for 2 hours to obtain a solid densified ceramic retained at 99.5% by weight. Upon cooling, the solid ceramic was removed from the furnace, The WB-WC carbon solid composition was formed in one step and was characterized by structural integrity, rigidity, and mechanical strength. The WB-WC carbon solid composition was found to form pure WB with nanoparticles in excess of carbon size and WC with a small amount of nanoparticle size. And stiffness.

Example 38

(0.070 g; 0.146 mmol), boron (0.252 g, 23.3 mmol), and hafnium hydride (2.00 g; 11.1 mmol) were added to a solution of the precursor composition of HfH2, boron, and TPEB precursor polymer ) Was ball milled for 5 minutes to obtain a crimson-black fine powder. The powder was placed in a 13 mm pellet press and squeezed at 10,000 pounds for 10 seconds.

Example 39

Conversion of the precursor composition of HfH ₂ , boron, and TPEB precursor polymers to solid molded thermoset materials - the pellets of Example 38 were placed in a furnace and heated to 210 ° C at 20 ° C per minute under an argon atmosphere and heated at this temperature for 10 hours (Overnight) to give a rigid molded polymeric solid. The hafnium hydride and the boron powder are uniformly dispersed in the solid thermosetting material.

Example 40

Formation of refractory HfB ₂ solid ceramic in one step by heating to 2 ° C per minute and up to 1500 ° C under an argon atmosphere- cured thermosetting pellets (2.29 g) from Example 39 were placed in a 3 "tube furnace and argon stream / Min) at 2 [deg.] C per minute to 1500 [deg.] C and left at 1500 [deg.] C for 2 hours to obtain a solid densified ceramic holding 99.4% by weight. Upon cooling, the solid ceramic was removed from the furnace and characterized by XRD It has been found that the HfB ₂ -HfC carbon solid composition is formed in one step and is characterized by structural integrity, rigidity and elasticity, and as a matrix it is found to form predominantly pure nanoparticle size HfB ₂ with a small amount of nanoparticle size HfC in excess of carbon. Respectively.

Example 41

(0.050 g; 0.105 mmol), boron (0.116 g, 10.7 mmol), and zirconium hydride (0.500 g; 5.36 mmol) were added to a solution of the precursor composition of ZrH ₂ , boron, and TPEB precursor polymer . mmol) was ball-milled for 5 minutes to obtain a crimson-black fine powder. The powder was placed in a 13 mm pellet press and squeezed at 8,000 pounds for 10 seconds.

Example 42

ZrH _2, boron, and TPEB transition to a precursor polymer precursor composition of the solid molded thermosetting material-heated to the pellets of Example 41 origin per minute 20 ℃ was placed in a furnace under an argon atmosphere 210 ℃ and 10 hours at the temperature (Overnight) to form a rigid molded polymeric solid. The zirconium hydrate and the boron powder are uniformly dispersed in the solid thermosetting material.

Example 43

Refractory ZrB ₂ is formed of solid ceramic in one step by heating under an argon atmosphere per minute 2 ℃ to 1400 ℃ - the thermosetting pellets (0.625 g) hardening of Example 42 origin 3 and "position in the tube furnace, a stream of argon (100cc / Min) to 1400 DEG C at 2 DEG C per minute and left at 1400 DEG C for 2 hours to obtain a solid densified ceramic having 98.5 wt% retention. Upon cooling, the solid ceramic was removed from the furnace and characterized by XRD as a matrix has been found to form a pure ZrB ₂ and a small amount of nano-particle size of ZrC in the nanoparticle size excess carbon. the ZrB ₂ -ZrC carbon solid composition has been formed by step 1, the structural integrity, hard and rigid Respectively.

Example 44

Formulation of a precursor composition of TiH ₂ , boron, and TPEB precursor polymers containing cleaved fibers- TPEB precursor polymer from Example 29 (1.29 g; 2.70 mmol), boron (4.55 g, 42.1 mmol), and TiH ₂ 10.00 g; 200 mmol) was ball-milled for 5 minutes to obtain a crimson-black fine powder. The solids mixture was removed and the solid mixture was placed in a 2½ " pellet die and compressed at 10,000 pounds for 1 minute. ≪ RTI ID = 0.0 > .

Example 45

Conversion of precursor compositions of TiH ₂ , boron, and TPEB precursor polymers containing cleaved fibers to thermoset materials - 2½ "pellets of Example 44 were placed in a furnace and heated to 210 ° C at 20 ° C per minute under an argon atmosphere, At room temperature for 10 hours (overnight) to form a rigid molded polymeric carbon fiber reinforced thermoset solid. The titanium hydride and boron powder are uniformly dispersed in a solid thermoset-carbon fiber hybrid.

Example 46

Formation of Refractory Carbon Fiber Reinforced TiB ₂ Solid Ceramics in One Step by Heating to 2 ° C / min and 1400 ° C / min under argon atmosphere- Carbon fiber-containing molded polymeric thermosetting pellets of Example 45 (15.7g) Heated to 1400 DEG C at 2 DEG C per minute under an argon stream (100 cc / min) to obtain a solid densified carbon fiber-reinforced ceramic having 97.2 wt% retained. It was found that the TiB ₂ -TiC carbon-carbon fiber solid composition was removed from the furnace and characterized by XRD and forming nanoparticle size TiB ₂ and nanoparticle size TiC _{2 in} the carbon-carbon fiber hybrid. Which is a significant structural integration.

Example 47

ZrH _2, boron, and TPEB bulb formulated in a precursor composition of a polymer containing a cleaved fiber - TPEB precursor polymer of Example 29 the origin (1.00 g; 2.09 mmol), boron (2.32 g, 21.5 mmol), and ZrH ₂ ( 10.00 g; 107 mmol) was ball-milled for 5 minutes to obtain a crimson-black fine powder. The solids mixture was removed and the solid mixture was placed in a 2 "pellet die and pelletized at 10,000 pounds per minute (1 < RTI ID = 0.0 >Lt; / RTI >

Example 48

Conversion of precursor compositions of TiH ₂ , boron, and TPEB precursor polymers containing cleaved fibers to thermoset materials - 2½ "pellets of Example 47 were placed in a furnace and heated to 210 ° C at 20 ° C per minute under an argon atmosphere, At room temperature for 10 hours (overnight) to form a rigid molded carbon fiber reinforced polymeric solid. The zirconium hydride and boron powder are uniformly dispersed in a solid thermoset-carbon fiber hybrid.

Example 49

Formation of refractory ZrB ₂ solid carbon fiber reinforced ceramic in one step by heating to 2O < 0 > C / min under argon atmosphere to 1500 [deg.] C - Example 12 Carbon fiber- Heated to 1500 DEG C at 2 DEG C per minute under an argon stream (100 cc / min) to obtain a solid densified carbon fiber reinforced ceramic retained at 97.5 wt%. The solid carbon fiber reinforced ceramic was removed from the furnace And characterized by XRD and forming ZrB ₂ of nanoparticle size and ZrC of nanoparticle size in the carbon-carbon fiber hybrid. The ZrB ₂ -ZrC carbon-carbon fiber solid composition was found to have a large Structural integrity.

Example 50

Formulation of ZrH ₂ and boron precursor composition Zirconium hydride (0.500 g; 5.36 mmol) and boron (0.116 g, 10.7 mmol) were ball milled for one minute to give a gray fine powder. The powder was placed in a 6 mm pellet press and squeezed at 4,000 pounds for 10 seconds.

Example 51

The ZrH ₂ prepared as in Example 50 - - Pure nanoparticles refractory ZrB formation of _two ceramic solid in one step by a controlled heating under an argon atmosphere up to 1300 ℃ to 3 ℃ / min, boron pellets (133.187 mg) TGA chamber position and heated to 250 ℃ as then the solid ceramic material, 97.77% by weight is retained by heating to 1300 ℃ per minute 3 ℃ and allowed to stand at 1300 ℃ under an argon stream of 100cc / min for 3 hours per 5 ℃ (pure ZrB ₂ ). Highly reactive Zr nanoparticles formed from the decomposition of ZrH ₂ were reacted with boron by heating from 500 ° C to 1300 ° C to form nanoparticles ZrB ₂ . The new refractory metal ceramic ZrB ₂ was formed in one step. XRD (FIG. 16) of the ceramic pellets showed pure ZrB ₂ with an average particle size of 36.7 nm. The ceramic pellets exhibited large structural integrity, rigidity and rigidity.

Example 52

TiH _2, boron, and TPEB a precursor composition in the formulations of the bulb the polymerization and formation of the molded pellets - TPEB precursor polymer of Example 29 the origin (0.129 g; 0.270 mmol), boron (0.455 g, 42.1 mmol), and TiH ₂ (1.00 g; 42.1 mmol) was ball-milled for 1 minute to obtain a crimson-black fine powder. The powder was placed in a 6 mm pellet press and squeezed at 4,000 pounds per second.

Example 53

Formation of nanoparticles refractory TiB _2, TiN, and TiC ceramic solid in one step by a controlled heating under a nitrogen atmosphere up to 1300 ℃ - positioning the pellets (198.992 mg) prepared in Example 52 to the TGA chamber and a nitrogen gas flow 100cc / Min to 5O < 0 > C / min and 250 < 0 > C for 1 hour to bind the molded solid thermosetting polymer. Ethynyl units were reacted and converted to molded thermoset polymers in TPEB by isothermal heat treatment at 250 캜. Then the polymeric said solid polymeric sample consisting of thermosetting material within the buried TiH ₂ and boron per minute 3 ℃ slowly heated to 1300 ℃ and by heating at 1300 ℃ for 3 hours to give the solid ceramic material, and this is compared to the initial weight And increased by about 12% by weight. Above 400 ℃, TiH Ti nanoparticles and H ₂ in _second decomposition of the H ₂ is generated and is evaporated from the sample. With additional heating from above 500 ° C to 1300 ° C, highly reactive Ti nanoparticles were reacted with the resulting carbon atoms formed from boron, nitrogen and carbonization of TPEB during the heat treatment. Upon cooling, the solid ceramic was removed from the furnace and characterized by XRD and found to contain large amounts of TiN nanoparticles along with small amounts of TiB ₂ and Tic nanoparticles embedded in excess carbon formed during the simple carbonization process. The TiB ₂ -TiN-TiC carbon solid composition was formed in one step and exhibited large structural integrity, rigidity and rigidity.

Example 54

(0.050 g; 0.105 mmol), boron (0.116 g, 10.7 mmol), and zirconium hydride (0.500 g; 5.36 mmol) were added dropwise over 1 min to a solution of the precursor composition of ZrH ₂ , boron and TPEB precursor polymer Followed by ball milling to obtain a crimson-black fine powder. The powder was placed in a 6 mm pellet press and squeezed at 4,000 pounds for 10 seconds.

Example 55

Formation of nanoparticle refractory ZrB ₂ , ZrN, and ZrC ceramic solids in one step by heating to 1300 ° C under a nitrogen atmosphere- The pellet precursor composition (200.819 mg) prepared in Example 54 was placed in a TGA chamber and heated to 100 cc / Heated to 250 ° C at a rate of 5 ° C per minute and allowed to stand at 250 ° C for 1 hour and then heated to 1300 ° C at 3 ° C per minute and left at 1300 ° C for 3 hours to obtain a solid dense ceramic, The weight was increased due to the reaction (the final weight of the sample was 220.755 mg). By removing the cooling during the solid ceramic from the furnace and containing a large amount of ZrN in with XRD (FIG. 17) to the characterization and simple carbonization process, a small amount of ZrB ₂ and ZrC nanoparticles within the buried excess of carbon formed during the It turned out. The ZrB ₂ -ZrN-ZrC carbon solid composition was formed in one step exhibited a greater structural integrity, hard and rigid.

Obviously many modifications and variations are possible in view of the above teachings. It is therefore to be understood that the claimed subject matter may be practiced other than as specifically described. For example, references to claimed elements using articles "a,""an,""the," or "said" should not be construed as limiting the element in a singular.

Claims (41)

Refractory - nanoparticles of metal boride; And
Wherein the composition comprises an elastomeric matrix and is not present in powder form. The composition of claim 1, wherein the nanoparticles comprise titanium boride. The composition of claim 1, wherein the nanoparticles comprise zirconium boride, hafnium boride, tungsten boride, or tantalum boride. The composition of claim 1, wherein the refractory metal is an IV-VI transition metal, niobium, molybdenum, chromium, or vanadium. The composition of claim 1, wherein the composition comprises at least 5% by weight of nanoparticles. The composition of claim 1, wherein the composition comprises at least 99% by weight of nanoparticles. 2. The composition of claim 1, wherein the average diameter of the nanoparticles is less than 100 nm. The composition of claim 1, wherein the elastomeric matrix comprises graphite carbon, carbon nanotubes, or amorphous carbon. The composition of claim 1, wherein the composition comprises nanoparticles comprising carbide or nitride of a refractory metal. The composition of claim 1, wherein the composition further comprises fibers, carbon fibers, ceramic fibers or metal fibers. The composition of claim 1, wherein the composition contains a void volume of less than 20% by weight. 10. An article comprising a composition according to claim 1 in solid form as an unbreakable mass having a minimum size of at least 1 mm at all dimensions. 13. The article of claim 12, wherein the surface of the article comprises an oxide of refractory metal. Nanoparticles or particles of refractory metal, and
A refractory metal component that can be decomposed into refractory metal nanoparticles;
boron; And
An organic compound having a char yield of at least 60% by weight, and
An organic component selected from a thermosetting material prepared from the organic compound
≪ / RTI > 15. The composition of claim 14, wherein the refractory metal is titanium. 15. The composition of claim 14, wherein the refractory metal is an IV-VI transition metal, zirconium, hafnium, tungsten, niobium, molybdenum, chromium, tantalum or vanadium. 15. The method of claim 14, wherein the metal component is selected from the group consisting of salts, hydrides, carbonyl compounds or halides of refractory metals; Particles of refractory metal, tungsten powder or tantalum powder; Or a titanium hydride, a zirconium hydride or a hafnium hydride. 15. The method according to claim 14,
Containing only carbon and hydrogen;
Aromatic and acetylene groups;
Containing only carbon, hydrogen and nitrogen or oxygen;
Oxygen-free;
Lt; RTI ID = 0.0 > oxygen. ≪ / RTI > The method of claim 14, wherein the organic compound is selected from the group consisting of 1,2,4,5-tetrakis (phenylethynyl) benzene or a precursor polymer thereof, 4,4'-diethynylbiphenyl, N, N ' - phenylenedimethylidene) -bis- (3-ethynyl aniline), dianilphthalonitrile, or resorcinol phthalonitrile or a precursor polymer thereof. 15. The composition of claim 14, wherein the metal component and the organic component are the same compound. 15. The composition of claim 14, wherein the boron and particles of the refractory-metal compound or refractory metal are dispersed in a thermoset material. 15. The composition of claim 14, wherein the composition comprises fibers, carbon fibers, ceramic fibers or metal fibers. Metal compound, boron, and an organic compound having a Charge yield of at least 60 wt%, which are capable of decomposing or reacting with particles of refractory metal or refractory-metal nanoparticles to form a precursor mixture / RTI > 24. The method of claim 23, further comprising positioning the precursor mixture in a mold or a shaped reactor. 24. The method of claim 23, further comprising heating the precursor mixture under inert atmosphere or vacuum at a temperature that causes decomposition or reaction of the refractory-metal compound or particles to form refractory-metal nanoparticles to form the metal nanoparticle composition ≪ / RTI > 26. The method of claim 25, wherein heating of the precursor mixture results in polymerization of the organic compound into a thermoset material. 26. The method of claim 25, wherein heating of the precursor mixture is performed at 150 to 600 < 0 > C. 26. The method of claim 25 further comprising heating the metal nanoparticle composition under inert atmosphere, argon, nitrogen, or vacuum at a temperature that causes formation of a ceramic comprising refractory-metal boride nanoparticles in the elastomeric matrix How to. 29. The method of claim 28, wherein the heating of the metal nanoparticle composition is performed at 500-1900 < 0 > C. 29. The method of claim 28, wherein heating of the metal nanoparticle composition results in the formation of nanoparticles comprising carbide or nitride of the refractory metal. 29. The method of claim 28, further comprising heating the ceramic in an oxygen-containing atmosphere to form an oxide of the refractory metal on the surface of the ceramic. Providing a precursor mixture of refractory metal nanoparticles, boron and particles of a refractory-metal compound or refractory metal that can be decomposed into an organic compound;
Heating the precursor mixture in an inert atmosphere or in a vacuum at elevated pressures and temperatures to form refractory-metal nanoparticles to cause decomposition of the refractory-metal compound to form a metal nanoparticle composition;
Heating the metal nanoparticle composition in an inert atmosphere, argon, nitrogen or vacuum at a temperature which causes formation of a ceramic comprising nanoparticles of refractory metal boride in the elastomeric matrix,
Wherein the organic compound has a Tertiary yield of at least 60% by weight when heated at elevated pressure. Wherein the composition comprises nanoparticles of a refractory metal boride and is not present in powder form. 34. The composition of claim 33, wherein the nanoparticles comprise a zirconium boride. 34. The composition of claim 33, wherein the refractory metal is an IV-VI transition metal, titanium, hafnium, tungsten, tantalum, niobium, molybdenum, chromium, or vanadium. 34. The composition of claim 33, wherein the composition comprises at least 99% by weight of nanoparticles. 33. An article comprising a composition according to claim 33, wherein the article is in solid form as unbreakable mass having a minimum size of at least 1 mm at all dimensions. Nanoparticles or particles of refractory metal, and
A refractory metal component that can be decomposed into refractory metal nanoparticles; And
boron
≪ / RTI > Metal particles or particles of refractory metal capable of reacting with or decomposing with boron and refractory-metal nanoparticles to form a precursor mixture; And
Heating the precursor mixture in an inert atmosphere or vacuum at a temperature that causes formation of nanoparticles having a boride of the refractory metal. 40. The method of claim 39, further comprising the step of placing the precursor mixture in a mold or molded reactor prior to heating. 40. The method of claim 39, wherein heating of the precursor mixture is performed at 500 to 1900 占 폚.

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