EP2852552A1 - Formation of boron carbide-boron nitride carbon compositions - Google Patents
Formation of boron carbide-boron nitride carbon compositionsInfo
- Publication number
- EP2852552A1 EP2852552A1 EP13784805.7A EP13784805A EP2852552A1 EP 2852552 A1 EP2852552 A1 EP 2852552A1 EP 13784805 A EP13784805 A EP 13784805A EP 2852552 A1 EP2852552 A1 EP 2852552A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- composition
- boron
- carbon
- thermoset
- solid
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Withdrawn
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Definitions
- the present disclosure is generally related to synthesis of boron carbide and boron nitride.
- Boron carbide is a highly refractory material that is of great interest for both its structural and electronic properties. Of particular importance are its lo w density, high- temperature stability, high hardness, high chemical stability, high cross-section for neutron capture, and excellent high-temperature thermoelectric properties. Boron carbide is the third hardest material next to diamond and cubic boron nitride, having a Vickers hardness of 3770 kg/mm 2 , Combined with its low density (2.52 g/cnr), it is the premier material for personal armor, typically in the form of front and back inserts into flak jackets in which B 4 C plates are bonded to a polymer backing. The combination of properties gives rise to numerous
- boron carbide (commercial and mi litary applications ⁇ . Nuclear ap lications of boron carbide include shielding, and control rod and shut down pellets. Boron carbide, m co unction with other materials, also finds use as ballistic armor (including body or personal armor) where the combination of high hardness, high elastic modulus, and low density give the material an exceptionally high specific stopping power to defeat high velocity projectiles. Due to its high hardness, boron carbide powder is used as an abrasrvs m polishing and lapping applications, and also as a loose abrasive in culling applications snch as water jet cutting. It can also be used for dressing diamond tools. Other applications include ceramic tooling dies, precision toil parts, evaporating boats for materials testing and mortars and pestles.
- Boron carbide powder is mainly produced by reacting carbon with ⁇ ⁇ -( > : in an electric arc furnace, through carbothermal reaction of boric acid or boron oxide at high temperatures and the magiiesiotliermal reaction of boron oxide with Mg metal.
- B 4 C powders usual ly need to be mil led and purified to remove metallic impurities
- boron carbide is difficult to sinter to full density, with hot pressing or sinter hot isostatic pressing (HIP) being required to achieve greater tha 95% of theoretical density.
- HIP hot pressing or sinter hot isostatic pressing
- small quantities of additives such as fine carbon or silicon carbide are usually required.
- the best known additive for B C is carbon, most successfully added in the form of phenolic resin, which distributes carbon around the B 4 C particles, and also serves as a pressing agent. Up to 98% of near-theoretical density (TD) has been obtained using this additive.
- Boron nitride can be synthesized in hexagonal and cubic forms. Hexagonal boron nitride has recei ved considerable attention because of its advantageous properties such as high thermal conductivity, chemical inertness, optical transparency, and electrical insulation.
- the hexagonal form (h-BN) corresponding to graphite is the most stable and softest among BN polymorphs and is therefore used as a lubricant (nonconductive relative to graphite) and an additive to cosmetic products.
- Cubic boron nitride (c-BN) has the same structure as diamond and its properties are similar. Indeed, the hardness of c-BN is inferior only to diamond but its thermal and chemical stability is superior.
- BN nanomaterials such as clusters, nanocapsuies, nanohorns, and nanotubes have been discovered and extensively studied in the powdered form. These BN lianostructures are expected to be useful as electronic devices, field- effect transistors, high heat-resistant semiconductors, insulator lubricants, nanowires, magnetic nanoparticles, and gas storage materials. Powdered BN nanomaterials are interesting material for many applications such as lubricants, protective and optical coatings, advanced ceramic composites, and mold release liners.
- Boron nitride is a white material produced synthetically from reaction of boric acid or boron tri oxide with ammonia or urea in a nitrogen atmosphere with the elimination of H 2 0 and
- BN contains 92-95% boron nitride and 5-8% boron trioxide, which is eliminated somewhat by heating at temperatures about 1500°C.
- BN is a powder, which is typically converted to crystalline h-BN during the heating in nitrogen flow above 1500°C, whereas c-BN is made by annealing h-BN powder at even higher temperatures under pressure above 5 GPa.
- Boron nitride components can be fabricated by sintering techniques at high pressure and temperatures over 2000°C with subsequent machining. Shaped parts are made from boron nitride powders containing some boron oxide for better compressibility. Thin films of boron nitride can be obtained by chemical vapor deposition from boron trichloride and nitrogen precursors.
- composition comprising nanoparticles of boron carbide and a carbonaceous matrix.
- the composition is not in the form of a powder.
- composition comprising boron and an organic component
- the organic component is selected from an organic compound having a char yield of at least 60% by weight and a thermoset made from the organic compound.
- Also disclosed herein is a method comprising combining boron and an organic compound having a char yield of at least 60% by weight to form a precursor mixture.
- Also disclosed herein is a method comprising: pro viding a precursor mixture boron and an organic compound; heating the precursor mixture in an inert atmosphere at elevated pressure and at a temperature that causes polymerizati on of the organic compound to a thermoset to form a boron-thernioset composition; and heating the boron-thermoset composition in an inert atmosphere, argon, nitrogen, or vacuum at a temperature that causes formation of a ceramic comprising nanoparticles of boron carbide in a carbonaceous matrix.
- the organic compound has a char yield of at least 60% by weight when heated at the elevated pressure.
- Fig. 1 schematically illustrates a process for forming the disclosed compositions.
- Fig. 2 schematically illustrates boron particles 10 embedded in a thermoset matrix 20.
- Fig. 3 schematically illustrates the transfer 40 of carbon atoms from the carbon matrix 30 to the boron 50.
- Fig. 4 schematically illustrates boron carbide nanoparticles 60 in a carbonaceous matrix
- Fig. 5 shows an X-ray diffraction analysis (XRD) of a sample containing B4C and BN nanoparticles.
- Fig. 6 shows an XRD of a sample containing B4C nanoparticles.
- Fig. 7 shows an XRD of another sample containing B4C nanoparticles.
- Fig. 8 shows an XRD of another sample containing B4C nanoparticles in a small amount of carbon matrix.
- Fig. 9 shows a photograph of a sample containing B 4 C nanoparticles.
- a method for the in situ formation of nanoparticle boron carbide (B 4 C) and nanoparticle boron nitride (BN) from reaction of elemental boron with a meltable carbon precursor with or without a carbon matrix in one step affording a shaped composition with structural integrity (2) various elemental boron-carbon precursor/tliermoset compositions at multiple stages, (3) various nanoparticle boron carbide-carbon matrix compositions, (4) various nanoparticle boron nitride-carbon matrix compositions, (5) various nanoparticle boron carbide- boron nitride-carbon matrix compositions (6) fiber reinforced boron-carbide and boron carbide- carbon matrix composites, and (7) fiber reinforced boron carbide and boron nitride-carbon matrix composites,
- elemental boron is combined with a carbon precursor.
- boron nitride outer surface
- boron carbide superior-carbon.
- matrix compositions are also formed in a stoichiometric array.
- the carbon precursors are compounds such as polymers or resins with functional unsaturation to permit the carbon precursor to undergo conversion from the melt to form shaped thermosets or crosslinked polymers.
- a typical composition includes the carbon precursor and the elemental boron. Upon heating the composition, the carbon precursor melts at its melting point and is thermally converted to a shaped solid thermoset through reaction of the unsaturated sites.
- Thermal treatment of the shaped thermoset above 500°C results in carbonization of the carbon precursor yielding carbon atoms that react in an argon atmosphere with the boron paiticies affording boron carbide nanoparticles, which are embedded in the excess carbon.
- the temperatures at which the synthetic process occurs are well below those normally associated with the formation of boron carbide and nitride ceramics from reaction of the boron source with graphitic carbon.
- the method permits the carbide or nitride and carbide- or nitride-carbon composites to be easily shaped by molding procedures (injection molding, vacuum molding, pressure molding, spreading, etc), which is a far less costly and involved process than machining a hot press sintered material.
- the present methods can create carbides or nitrides as nanoparticles from reaction of elemental boron with a meltable carbon precursor with fast reaction of the "hot" carbon atoms being formed during the carbonization process affording boron carbide nanoparticles (argon atmosphere) within a relatively narrow size range and with boron nitride nanoparticles (nitrogen atmosphere) being formed on the exterior portion of the solid ceramic exposed to nitrogen gas. Thin films of boron nitride nanoparticles within a carbon matrix can also be formed,
- An excess of carbon ensures the formation of a carbon matrix in which the boron carbide nanoparticles are embedded, or the reaction can be conducted stoichiometricaUy to yield only boride carbide nanoparticles or boride carbide nanoparticles with a trace of carbon matrix.
- the amount of boron carbide and carbon within the resulting composition can be varied based on the cjuantity of each individual component (elemental boron and melt processable carbon compound) mixed for usage in the precursor composition.
- the reaction is performed in a nitrogen atmosphere, the boron preferentially reacts with the nitrogen, especially on the exterior part of a shaped component, relative to the carbon affording the corresponding boron nitride in pure form. Nitrogen cannot progress very far into the solid shaped sample ensuring boride carbide formation in the interior portion of any solid component.
- the boron carbides or nitrides may form as nanopartic!es. This is a highly desirable result, as it is generally accepted tha t homogeneous nanoparticle composites of ceramics will have better properties than their much more common microparticle counterparts.
- Carbon, ceramic, and metal fibers may be incorporated into various mixtures of precursor compositions composed of elemental boron and the acetylenic-containing aromatic compounds or polymers (carbon source) and the resulting fiber-containing mixture is converted to a shaped solid at temperatures below 500°C followed by heating to temperatures around 1000- ! 3Q0°C yielding a carbon-fiber reinforced boron carbide-carbon matrix composite.
- the precursor compositions (elemental boron and carbon precursor) described above are mixed with continuous carbon fibers or chopped carbon fibers and heated until conversion to the shaped thermoset forms.
- the fibers may also be, for example, metal or ceramic.
- the tough, solid carbon fiber ceramic composite can be used for structural appl ications (e.g., flak jacket/bull et proof vest, armor components on tanks, ships, and aircraft, and nuclear reactors) for usage from room temperature to > 3000°C.
- the precursor composition can contain various combinations of elemental boron and carbon precursor that will lead to shaped ceramics with numerous amounts of boron carbide iianoparticles embedded in a carbon ma trix/composite.
- boron nitride iianoparticles form as a layer on the exterior portion of the ceramics. Therefore, another composition would be the formation of boron nitride-carbon matrix compositions, which is a direct interaction of nitrogen with the boron atoms of the precursor boron.
- the atmosphere for performing the reaction one can selectively form either the boron carbide carbon-matrix composition or the boron nitride carbon- matrix composition or combinations thereof.
- fiber reinforced boron nitride-carbon matrix composites may be formed. Regardless of the inert atmosphere (argon or nitrogen), the composite may have outstanding oxidative stability and temperature capabilities in excess of 3000°C.
- the synthetic method may produce boron carbides and boron nitrides in shaped solid configurations from reaction of elemental boron with a meltable carbon precursor at elevated temperatures above 600°C.
- Mixed phases of B 4 C and BN can also be produced.
- the B 4 C and BN can be produced as nanopartic!es from the reaction of the boron with carbon atoms and nitrogen, respectively, during the pyrolysis reaction.
- the combination can be (d) thermally converted to a solid shaped ceramic solid containing high yiel ds of pure boron carbide nanopariicles or boron nitride nanoparticle or combinations thereof depending on whether the reaction is performed in argon or nitrogen.
- the appropriate boron nanoparticle ceramics are formed in situ from the interaction of the boron particles with the carbon atoms of the carbon precursor or with nitrogen during the thermal treatment from 600- 1300°C.
- the carbon sources may be melt processable aromatic-containing acetylenes or low molecular weight polymers that exhibit extremely high char yields to ensure high density, void- free solid components.
- the carbon precursor may contain only C and H to insure that pure boron carbide and boron nitride are eontrollably produced during the reaction.
- the boron carbide and boron nitride form above 600°C with the reaction occurring faster at higher temperatures.
- the individually formed ceramic nanopariicles boron carbide or boron nitride
- the individually formed ceramic nanopariicles are glued or bound together with the resulting nanostructured or amorphous elastic carbon to afford structural integrity.
- Fig. 1 The process is outlined in Fig. 1 and schematically illustrated in Figs. 2-4. Any reactions described are not limiting of the presently claimed methods and compositions. Even though microsized boron powder is used in the reaction, the boron carbide and boron nitride may be produced as nanopariicles from the reaction of the highly rea ctive carbon atom, being produced during pyrolysis (carbonization) of the carbon precursor, with the activated boron surface, thereby lowering the temperature of B 4 C or BN formation.
- the amount of elemental boron, which forms reactive boron ceramic nanopariicles, relative to the carbon precursor can be readily changed with respect to the amount of carbon matrix in order to vary the properties of the resulting solid composition.
- nanoparticle-containing B 4 C or BN carbon-matrix composites are expected to exhibit unique physical properties such as hardness and toughness, owing to the high surface area of the nanopariicles and the presence of the relatively elastic carbon, which would exist in forms ranging from amorphous to nanotube to graphitic carbon.
- the native presence of an "elastic" carbon matrix may allow for toughening of the inherently brittle sintered ceramics.
- the carbon permits operation of the toughened ceramic at extremely high temperatures, owing to carbon's high melting point (>3000 °C).
- Ceramic/carbon- matrix compositions are currently being sought for these reasons, and the present method may permit straightforward preparation of shaped solid composites in a single step for the first time, in contrast to the traditional means of first forming the ceramic powder and then preparing the carbon-matrix composite under sintering conditions. Only trace or very small amounts of carbon matrix may be needed to achieve the effect. Also, the ratio of ceramic to carbon is easily tuned based only on the ratio of elemental boron to carbon-precursor.
- Fiber or carbon fiber-reinforced boron carbide and boron nitride carbon matrix composites may exhibit outstanding mechanical properties for usage under extreme
- Finely divided fiber reinforced boron ceramic carbon composites can allow the consolidation of fully dense shaped, low density, solid components with extreme fracture resistance for uses in high stress and temperature applications such as advanced engine components for hypersonic vehicles and automobiles, where increased operation temperature and mechanical integrity could translate into tremendous economic advantages.
- Such tough, easily shaped ceramic composites could be significant to the next generation of array tanks, which can be designed to be more energy efficient and lighter weight than those in current service, and in advanced automobile engines and supporting components.
- a more robust nuclear reactor could be readily iabricated for aircraft carriers needing the superior processability of tough structural rods and housing of the heat resistant boron carbide or boron nitride ceramic-carbon composites.
- lightweight, tough, and hard ceramics easily made in controllable forms could be very important for the fabrication of superior military armor; again fabricated in a mold in a shaped structure.
- the ability to fabricate tough, shaped boron carbide or boron nitride components in one step enhances their importance due to the economic advantages and the elimination of machining to a shaped component.
- the first component is boron in elemental form. Suitable boron is readily available in powder form, A 95-97 % boron is suitable with a higher pure boron powder (99%) being preferred.
- the boron powder may be milled to reduce its particle size.
- the second component is an organic compound that has a char yield of at least 60% by weight.
- the char yield may also be as high as at least 70%, 80%, 90%, or 95°/» by weight.
- the char yield of a potential compound may be determined by comparing die weight of a sample before and after heating to at least 1000°C for at least 1 hr in an inert atmosphere such as nitrogen or argon. Any such compounds with high char yields may be used as the charring may play a role in the mechanism of the reactions.
- This char yield may be measured at an elevated pressure to be used when a heating step is also performed at such pressure.
- a compound having a low char yield at atmospheric pressure but ha ving a high char yield under external pressure or the conditions that the disclosed methods are performed may be suitable for producing boron carbides and nitrides.
- Certain organic compounds may exhibit any of the following characteristics, including mutually consistent combinations of characteristics: containing only carbon and hydrogen;
- containing aromatic and acetylene groups containing only carbon, hydrogen, and nitrogen or oxygen; containing no oxygen; and containing a heteroatom other than oxygen, it may have a melting point of at most 400 C 'C, 350°C, 300°C, 250°C, 200°C or 150 C 'C and the melting may occur before polymerization or degradation of the compound or it may be a liquid.
- organic compounds include, but are not limited to, l,2,4,5-tetrakis(phenylethynyi)benzene (TPEB), 4,4'-diethyny!biphenyl (DEBP), N, '-( l ,4-pheny!enedimethylidyne)-bis(3- ethynyianiline) (PDEA), N,N'-( 1 ,4-phenyienedimethyiidyne)-bis(3 ,4-dicyanoaniline)
- dianiiphthalonitrile dianiiphthalonitrile
- l,3-bis(3,4-dicyanophenoxy)benzene resorcinol phthaionitrile
- a prepolymer thereof More than one organic compound may be used. Prepolymers may also be used, such as a prepolymer of TPEB or other suitable organic compounds. Different compounds can be blended together and/or reacted to a prepolymer stage before usage as the organic compound of the precursor composition. The presence of nitrogen atoms in the organic compound may produce boron nitrides in the ceramic without the use of a nitrogen atmosphere.
- An optional component in the precursor materials is a plurality of fibers or other fillers.
- fibers include, but are not limited to, carbon fibers, ceramic fibers, and metal fibers.
- the fibers may be of any dimension that can be incorporated into the mixture and may be cut or chopped to shorter dimensions.
- the precursor mixture including any fibers, may be formed into a shaped component.
- the component may be shaped under pressure, removed from the pressure, and heated to thermoset and ceramic components as described below.
- the precursor mixture which may be mixed in a melt stage, then undergoes a heating step to form a thermoset composition. This may be performed while the mixture is in a mold. This will allow the final product to have the same shape as the moid, as the organic component of the mixture will melt if not already liquid and the mixture will fill the mold during the heating, and retain its shape when the ceramic is formed.
- the precursor mixture is heated in an inert atmosphere at a temperature that causes pol ymerization of the organic compound to a thermoset. if the organic compound is volatile, the heating may be performed under pressure, either physical or gas pressure, to avoid evaporation of the organic compound. Suitable heating temperatures include, but are not limited to, 150-500°C or 700°C.
- Heating the precursor may also cause the polymeriza tion of the organic compound t o a thermoset.
- the boron particles 10 would then be dispersed throughout the thermoset 20 as shown in Fig, 2.
- a thermoset having the boron particles dispersed throughout may be used as a final product.
- the thermoset may also be machined to a desired shape, followed by heating to form a ceramic as described below.
- the boron may be homogeneously distributed or embedded in the thermoset as an intermediate shaped solid.
- the composition may have a shape that it will retain upon further heating and conversion to the ceramic from reaction of the boron with the developing carbon matrix.
- the precursor mixture may be consolidated to a shaped solid component under pressure to promote intimate contact of the reactants to pro vide a very dense ceramic solid or to densify the final product.
- the precursor mixture may be compacted under exterior pressure, removed from the pressure, and then heated to a thermoset followed by conversion to the ceramic.
- the precursor mixture may be compacted under exterior pressure and the pressure maintained while heating to the thermoset and ceramic.
- thermoset composition in a second heating step, is heated to form a ceramic.
- the hea ting is performed at a temperature tha t causes formation of nanoparticles of boron carbide 60 in a carbonaceous matrix 70 (Fig. 4).
- the carbonaceous matrix may comprise graphitic carbon, carbon nanotubes, and/or amorphous carbon. If nitrogen is present, boron nitride nanoparticles may be formed. There may be a higher concentration of nitrides on the surface than in the interior. Suitable heating temperatures include, but are not limited to 500-1900°C.
- the presence and composition of the boron carbide or boron nitride nanoparticles may be verified by any known technique for detecting nanoparticles such as SEM, TEM, or XRD.
- the nanoparticles may have an a verage diameter of less than 100 ran, 50 nm, or 30 nm. They may be generally spherical in shape or may be non-spherical, such as nanorods.
- the ceramic may include any amount of nanoparticles, including but not limited to, at least 5%, 10%, 20%, 30%, 40%, 50%, 60%, 70%, 80%, 90%, 95%, or 99% by weight of nanoparticles.
- the percentage of nanoparticles may be in part determined by the molar ratio of boron and carbon atoms in the precursor mixture. At a 1 : 1 ratio, nearly all of the boron and carbon may be incorporated into the nanoparticles, leaving a small amount or trace of carbonaceous matrix . With higher amounts of organic compound, the fraction of boron carbide nanoparticles is lower and the fraction of carbonaceous matrix is higher.
- variations in the ratio of boron to organic may be used, affording a mixture of boron carbide and carbon matrix when performed in an inert atmosphere such as argon and boron carbide, boron nitride, and carbon matrix when performed in a nitrogen atmosphere,
- an inert atmosphere such as argon and boron carbide, boron nitride, and carbon matrix when performed in a nitrogen atmosphere
- boron nitride is made, raising the amount of carbon in the precursor mixture may lo was the amount of boron nitride in the ceramic.
- the ceramic is not formed as a powder and may be in the form of a solid, unbroken mass. It may contain less than 20% by volume of voids or as low as 10%, 5%, or 1%. It may have the same shape as the precursor mixture (if solid) or it may take on the shape of a mold it was placed in during the heating. The ceramic may retain its shape in that it does not crumble when handled and may not change shape or break without the use of extreme force.
- the ceramic composition may be tough, hard, and have stnictural integrity . The degree of such properties may depend on the amount of ceramic to carbon in the solid ceramic composition. Any shape may be formed to make an article useful for incorporation into an apparatus.
- the axticle may be large enough to have a minimum size of at least 1 cm in all dimensions. That is, the entire surface of the article is at least 5 mm from the center of mass of the article. Larger articles may be made, such as having a minimum size of at least 10 cm in all dimensions. Also, the composition may have smaller sizes, such as 1 mm, 2 mm, or 5 mm.
- Formulation of precursor composition of TPEB and boron in ratio of 1 to 136 - TPEB (0.250 g; 0.523 mraol) and powdered boron (0.769 g, 71.1 mmol) were thoroughly mixed and used as the precursor composition for the formation of refractory iianoparticle B 4 C embedded or bonded with the excess of carbon that behaves as a matrix material.
- the ratio of the two reactants can be readily varied by the described formulation method.
- Example 5 composition by heating to 1300°C under an argon atmosphere ⁇ ⁇
- the solid polymeric thermoset of Example 5 was heated at 2°C/min to and held at 1300°C for 3 hr under flow (110 cc/min) of argon.
- the resulting solid ceramic sample retained 91 .17% of the original weight.
- XRD analysis showed the formation of pure boron carbide (B 4 C) nanoparticies of 11.9 nm average particle size.
- the boron nitride nanoparticles are multiple phases of boron nitride and are being mainly formed on the exterior part or outer surface of the sample, which was exposed to the nitrogen.
- the boron carbide nanoparticles are mainly formed on the interior portion of the sample.
- Formulation of precursor composition of TPEB and boron in molar ratio of 1 to 159 - TPEB) (0.500 g; 1 .05 mmol) and powdered boron (1.81 g, 167 mmol) were thoroughly mixed and used as the precursor composition for the formation of refractor ⁇ ' nanoparticle B 4 C embedded or bonded with the excess of carbon tha t behaves as a matrix material.
- the ratio of the two reactants can be readily varied by the described formulation method.
- Example 16 composition by heating to 1300°C under an argon atmosphere -
- the solid polymeric thermoset of Example 16 was heated at 3°C/min to and held at 1300°C for 3 hr under flow of argon at 110 cc/min.
- the resulting solid ceramic sample retained 87.80% of the original weight.
- XRD analysis (Fig. 7) showed the formation of pure boron carbide nanoparticles (60%) embedded in an excess of crystalline carbon (40% ⁇ .
- the average particle size for the boron carbide nanoparticles and crystalline carbon are 5,6 nm and 2.1 ran, respectively.
- the average particle size for the boron carbide/nitride nanoparticles and crystalline carbon are 5.6 nm and 2.1 nm, respectively.
- the boron nitride was mainly formed on the exterior part or outer surface of the sample, which was exposed to the nitrogen.
- TPEB prepolymer (0.200 g; 0,41 8 mmol) prepared as in Example 24 and boron (0.604 g, 55.9 mmol) were ball milled for 5 minutes resulting in a deep red-black fine powder. The powder was placed in a 13 mm pellet press and pressed to 10,000 pounds for 1 minute.
- the pellet was then placed in a furnace, heated at 20°C /min under an argon atmosphere to 250°C, and held at this temperature for 30 minutes followed by heating at 2°C/min nder a flow (100 cc/min) of argon to 1500°C and holding at 1500°C for 2 hr yielding a solid dense ceramic with weight retention of 83.4%.
- the solid ceramic was removed from the furnace, characterized by XRD, and found to form nanoparticle sized B 4 C in an excess of carbon as the matrix.
- the B C carbon solid composition was formed in one step and exhibited great structural integrity, hardness, and toughness.
- the pellet precursor composition (89.1460 mg) prepared in Example 29 was placed in a TGA chamber, heated at 5°C/min under a 100 cc/min flow of argon to 250°C, and held at 250°C for 1 hr, followed by heating at 3°C/min to 1300°C and holding at 1300°C for 3 hr yielding a solid dense ceramic with a final char yield of 93%.
- the solid ceramic was removed from the furnace, characterized by XRD, and found to contain pure boron carbide formed as nanopartieles in a small amount of carbon.
- the average size of the boron carbide nanoparticle was 4.2 nm.
- the boron carbide solid nanoparticle composition was formed in one step and exhibited great structural integrity, hardness, and toughness.
- Example 24 Formulation of precursor composition of boron and TPEB prepolymer and formation of shaped pellet - TPEB prepolymer form
- Example 24 (0.083 g, 0, 174 mmol) and boron (0.302 g, 27.9 mmol) were ball milled for 5 minutes resulting in a deep red-black fine powder. The powder was placed in a 6 mm pellet press and pressed to 4,000 pounds for 10 seconds.
- the pellet precursor composition (106.5130 mg) prepared in Example 31 was placed in a TGA chamber, heated at 5°C/niinunder a 100 cc/min flow of argon to 250°C, and held at 250°C for 1 hr, followed by heating at 3°C/min to 1300°C and holding at I 300°C for 3 hr yielding a solid dense ceramic with a final char yield of 94%.
- the solid ceramic was removed from the furnace, characterized by XRD, and found to contain pure boron carbide formed as nanoparticles in an extremely small amount of carbon.
- the average size of the boron carbide nanoparticle was 3.7 nm.
- the boron carbide solid nanoparticle composition was formed in one step and exhibited great structural integrity, hardness, and toughness.
- Example 24 Formulation of precursor composition of boron and TPEB prepolymer and formation of shaped pellet - TPEB prepolymer form
- Example 24 (0.090 g, 0.188 mmol) and boron (0.302 g, 27.9 mmol) were ball milled for 5 minutes resulting in a deep red-black fine powder. The powder was placed in a 6 mm pellet press and pressed to 4,000 pounds for 10 seconds.
- thermoset Conversion of precursor composition of boron and TPEB prepolymer containing chopped fibers to thermoset -
- the 2 1 ⁇ 2" pellet from Example 35 was placed in a furnace, heated at 20°C/min under an argon atmosphere to 210°C, and held at this temperature for 10 hr (overnight) resulting in the formation of a tough shaped polymeric carbon fiber reinforced thermoset solid.
- the boron powder was homogeneous dispersed in the solid thermoset-carbon fiber composite.
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Abstract
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US13/749,794 US8822023B2 (en) | 2012-01-26 | 2013-01-25 | Refractory metal ceramics and methods of making thereof |
US13/768,219 US8865301B2 (en) | 2012-01-26 | 2013-02-15 | Refractory metal boride ceramics and methods of making thereof |
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US4512946A (en) * | 1983-09-06 | 1985-04-23 | General Electric Company | Microcomposite of metal boride and ceramic particles |
US4582553A (en) * | 1984-02-03 | 1986-04-15 | Commonwealth Aluminum Corporation | Process for manufacture of refractory hard metal containing plates for aluminum cell cathodes |
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US4937101A (en) * | 1988-11-07 | 1990-06-26 | Rohr Industries, Inc. | Prereacted inhibitor powder for carbon-carbon composites |
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