Composition and aggregate containing boron nitride nanotube structure and method for producing the same

Abstract

To provide a novel composition and aggregate that contain an independent boron nitride nanotube and have novel features.SOLUTION: A composition (or aggregate) comprises an epitaxial h-BN / BNNT structure comprising a hexagonal boron nitride structure that is epitaxial to a boron nitride nanotube structure. The composition (or aggregate) comprises an independent boron nitride nanotube wherein a total mass percentage of the independent hexagonal boron nitride and the residual boron in the composition is 35% or less. In the composition (or aggregate), 1% or less of the independent boron nitride nanotube and the boron nitride nanotube structure has dixie cup defects or bamboo defects. In the composition, at least 50% of the independent boron nitride nanotube and the boron nitride nanotube structure is a single layer. A method for producing a composition comprising an epitaxial h-BN / BNNT structure is also provided.SELECTED DRAWING: Figure 1

Description

[Technical field]

[0001] CROSS-REFERENCE TO RELATED APPLICATIONS This application claims priority to U.S. Patent Application Publication No. 15 / 928,969, filed March 22, 2018, the entire contents of which are incorporated herein by reference.

[0002] Subject matter of the present invention The present subject matter relates to novel and unexpected materials each comprising an arrangement of atoms including a first region of an arrangement of atoms that corresponds (at least to a specified degree) to an idealized boron nitride nanotube, the arrangement of atoms also including at least a second region (different from the first region), such novel and unexpected materials having a unique combination of properties.

[0003] In one aspect, the inventive subject matter therefore provides new and unexpected materials that possess a unique combination of properties. The present subject matter also provides novel compositions and aggregates that include such novel and unexpected materials.

[0004] The present subject matter also provides novel compositions and aggregates comprising boron nitride nanotubes and having novel characteristics. The present subject matter also provides novel methods of producing new and unexpected materials, compositions, and aggregates. [Background technology]

[0005] Boron nitride nanotubes are nanoscale hollow tubes with typical diameters in the range of 2-20 nanometers and typical lengths in the range of tens of nanometers to tens of microns. The expression "boron nitride nanotubes" (or "boron nitride nanotubes") encompasses structures consisting of a single generally tubular wall (i.e., single-walled boron nitride nanotubes) as well as structures consisting of multiple generally tubular concentric walls (i.e., multi-walled boron nitride nanotubes).

[0006] A hypothetical idealized boron nitride nanotube is comprised of one or more layers (i.e., walls), each layer consisting of a roughly tubular arrangement of boron and nitrogen atoms, the boron and nitrogen atoms being arranged in a repeating hexagonal pattern of alternating boron and nitrogen atoms. As is well known to those skilled in the art, an idealized boron nitride nanotube can be conceptualized as a structure that would result from taking a layer (or layers) of boron and nitrogen atoms, the boron and nitrogen being arranged in an alternating hexagonal repeating pattern, and curving the layer (or layers) such that two sides of the layer (or each layer) meet and connect along a seam such that the alternating boron / nitrogen hexagonal repeating pattern meets at the seam to provide a one-walled (or a number of walls corresponding to the number of layers) hollow cylindrical array of boron and nitrogen atoms in a continuous alternating hexagonal pattern (i.e., no seams are discernible).

[0007] Boron nitride nanotubes are often compared to carbon nanotubes with respect to their corresponding chemical structure and their corresponding properties. While similarities exist (e.g., superior mechanical strength), many differences are also known to exist, including (among other differences) that boron nitride nanotubes are electrically insulating (whereas carbon nanotubes are electrically conducting) and that boron nitride nanotubes are stable up to much higher temperatures.

[0008] Boron nitride nanotubes have many distinctively favorable properties, including strength to mass ratio (high strength / low density), toughness, stiffness, thermal conductivity, flame retardancy, corrosion resistance, neutron radiation absorption / protection, friction and wear resistance, oxidation resistance, hydrophobicity, hydrogen storage capacity, nanoparticle carrier effectiveness, among others.

[0009] There are several forms of defective boron nitride nanotubes known to those skilled in the art, such as dixie cup defects and bamboo defects. . Summary of the Invention

[0010] As noted above, the present subject matter provides, in one aspect, novel and unexpected materials (defined herein as epitaxial h-BN / BNNT structures) each comprising an arrangement of atoms that includes a first region of an arrangement of atoms that corresponds (at least to a specified extent) to an idealized boron nitride nanotube, the arrangement of atoms also including at least a second region (different from the first region), such novel and unexpected materials having a unique set of properties.

[0011] According to a first aspect of the present subject matter, there is provided a composition comprising at least a first epitaxial h-BN / BNNT structure (as defined herein), the first epitaxial h-BN / BNNT structure comprising at least a first boron nitride nanotube structure (also defined herein) and at least a first hexagonal boron nitride structure (also defined herein), the first hexagonal boron nitride structure being epitaxial to the first boron nitride nanotube structure (also defined herein).

[0012] According to a second aspect of the inventive subject matter, there is provided an aggregate comprising a monolithic structure comprising at least a first epitaxial h-BN / BNNT structure (as defined herein), the first epitaxial h-BN / BNNT structure comprising at least a first boron nitride nanotube structure (also defined herein) and at least a first hexagonal boron nitride structure (also defined herein), the first hexagonal boron nitride structure being epitaxial to the boron nitride nanotube structure (also defined herein), the monolithic structure having a first dimension of at least 100 nm and a second dimension of at least 100 nm, the second dimension being perpendicular to the first dimension.

[0013] The present subject matter also provides other novel compositions and aggregates comprising epitaxial h-BN / BNNT structures as defined herein. The novel and unexpected epitaxial h-BN / BNNT structures (as defined herein) provided by the present subject matter exhibit improved properties such as, for example, superior adhesion to matrix materials (enhanced physical / mechanical resistance to removal from the matrix material), provide superior nano-nucleation sites for metal crystallization (e.g., when casting one or more metals such as aluminum, magnesium, titanium, etc., that have melting points below the temperature at which the boron nitride nanotube structures decompose), and can provide favorable properties even after exposure to extremely high temperatures.

[0014] The present subject matter also provides novel compositions and aggregates comprising free-standing boron nitride nanotubes (as defined herein) and having novel characteristics. The present subject matter also relates to high purity compositions and aggregates comprising boron nitride nanotube structures and / or individual boron nitride nanotubes, e.g., compositions and aggregates comprising boron nitride nanotube structures and / or individual boron nitride nanotubes, and free of residual boron and individual nanotubes. Compositions and aggregates in which the total amount of hexagonal boron nitride (as defined herein) is limited to less than (or equal to) a particular weight percent.

[0015] According to a third aspect of the inventive subject matter, there is provided a composition comprising a plurality of independent boron nitride nanotubes (as defined herein), wherein the sum of [1] the total mass of all independent hexagonal boron nitride (also defined herein) in the composition and [2] the total mass of all residual boron (also defined herein) in the composition constitutes 35% or less by mass of the composition.

[0016] According to a fourth aspect of the present subject matter, there is provided an aggregate comprising a monolithic structure comprising a plurality of independent boron nitride nanotubes (as defined herein), the monolithic structure having a first dimension of at least 100 nm and a second dimension of at least 100 nm, the second dimension being perpendicular to the first dimension, and the sum of [1] the total mass of the independent hexagonal boron nitride (also defined herein) in the monolithic structure and [2] the total mass of all residual boron (also defined herein) in the monolithic structure accounts for 35% or less of the mass of the monolithic structure.

[0017] The subject matter of the present invention also relates to high quality compositions and aggregates comprising boron nitride nanotube structures and / or individual boron nitride nanotubes, for example compositions and aggregates comprising boron nitride nanotube structures and / or individual boron nitride nanotubes, in which the total amount of boron nitride nanotube structures and / or individual boron nitride nanotubes having Dixie cup defects (defined below) and boron nitride nanotube structures and / or individual boron nitride nanotubes having bamboo defects (defined below) is limited to less than (or equal to) a particular percentage.

[0018] According to a fifth aspect of the present subject matter, there is provided a composition comprising at least 10 individual boron nitride nanotubes (as defined herein) having a length of at least 50 nm: [1] Of the total of independent boron nitride nanotubes in the composition having a length of at least 50 nm and [2] boron nitride nanotube structures (also defined herein) in the composition having a length of at least 50 nm, no more than 1% of said total have at least one defect selected from among Dixie cup defects (also defined herein) and bamboo defects (also defined herein).

[0019] According to a sixth aspect of the inventive subject matter, there is provided an aggregate comprising a monolithic structure comprising a plurality of individual boron nitride nanotubes (as defined herein), the monolithic structure having a first dimension of at least 100 nm and a second dimension of at least 100 nm, the second dimension being perpendicular to the first dimension and including: Of the sum of [1] independent boron nitride nanotubes having a length of at least 50 nm in a monolithic structure and [2] boron nitride nanotube structures (also defined herein) having a length of at least 50 nm in a monolithic structure, 1% or less of said sum has at least one defect selected from among Dixie cup defects (also defined herein) and bamboo defects (also defined herein).

[0020] The present subject matter also relates to compositions and aggregates comprising boron nitride nanotube structures and / or individual boron nitride nanotubes, where the amount of single-walled boron nitride nanotube structures and / or individual boron nitride nanotubes relative to the amount of multi-walled boron nitride nanotube structures and / or individual boron nitride nanotubes is greater than (or equal to) a particular percentage.

[0021] According to a seventh aspect of the inventive subject matter, there is provided a composition comprising at least 10 individual boron nitride nanotubes (as defined herein): Of the sum of [1] individual boron nitride nanotubes in the composition having a length of at least 50 nm, and [2] boron nitride nanotube structures (also defined herein) in the composition having a length of at least 50 nm, at least 50% of said sum are each single-walled (also defined herein).

[0022] According to an eighth aspect of the inventive subject matter, there is provided an aggregate comprising a monolithic structure comprising at least one free-standing boron nitride nanotube (as defined herein), the monolithic structure having a first dimension of at least 100 nm and a second dimension of at least 100 nm, the second dimension being perpendicular to the first dimension, the monolithic structure comprising: Of the sum of [1] individual boron nitride nanotubes having a length of at least 50 nm in a monolithic structure and [2] boron nitride nanotube structures (also defined herein) having a length of at least 50 nm in a monolithic structure, at least 50% of said sum are each single-walled (also defined herein).

[0023] The present subject matter also provides novel methods of producing new and unexpected materials, compositions, and aggregates. According to a ninth aspect of the present inventive subject matter, there is provided a method of making a composition, the method comprising: providing a mixture of nitrogen gas and hydrogen gas to a first region of a chamber; converting at least a portion of the mixture of nitrogen gas and hydrogen gas into a plasma; providing a mixture of the at least one boron-containing material and the nitrogen gas to a second region of the chamber, thereby contacting the mixture of the at least one boron-containing material and the nitrogen gas with the plasma to form a reaction mixture; converting at least a portion of the mixture into an epitaxial h-BN / BNNT structure; Includes.

[0024] The present subject matter may be more fully understood with reference to the accompanying drawings and the following detailed description of the present subject matter. [Brief description of the drawings]

[0025] [Figure 1] FIG. 1 is a schematic diagram of an exemplary embodiment of an apparatus 10 that can be used to produce epitaxial h-BN / BNNT structures, as well as compositions and / or aggregates that include epitaxial h-BN / BNNT structures, in accordance with the first and second aspects of the present inventive subject matter. [Diagram 2] FIG. 2 is an enlarged view of a portion of FIG. [Diagram 3] FIG. 3 is a diagram of an epitaxial h-BN / BNNT structure. [Figure 4] FIG. 4 is a TEM image of a representative portion of the product of Example 1, where approximately 30% of the boron nitride nanotube structures were each at least 30% covered by epitaxial hexagonal boron nitride. [Diagram 5] FIG. 5 is a TEM image of a representative section of the product of Example 2, where approximately 90% of the boron nitride nanotube structures were each at least 30% covered by epitaxial hexagonal boron nitride. [Figure 6] FIG. 6 is a TEM image of a portion of the product of Example 2, which shows (among other things) the epitaxial h-BN / BNNT structures. [Figure 7] FIG. 7 is a TEM image of a portion of the product of Example 2, which shows (among other things) free-standing hexagonal boron nitride and epitaxial h-BN / BNNT structures, one of which contains an agglomerate of boron nitride nanotube structures. [Figure 8] FIG. 8 is a TEM image of a portion of the product of Example 2, which shows (among other things) agglomerates of boron nitride nanotube structures and epitaxial h-BN / BNNT structures. [Figure 9] FIG. 9 is a TEM image of a portion of the product of Example 2, which shows (among other things) the epitaxial h-BN / BNNT structures. [Figure 10]FIG. 10 is a TEM image of a portion of the product of Example 2, which shows (among other things) the remaining boron and epitaxial h-BN / BNNT structures. [Figure 11] FIG. 11 is a TEM image of a portion of the product of Example 2, which shows (among other things) the remaining boron and epitaxial h-BN / BNNT structures. [Figure 12] FIG. 12 is a TEM image of a portion of the product of Example 2, which shows (among other things) the epitaxial h-BN / BNNT structures. [Figure 13] FIG. 13 is a TEM image of a free-standing boron nitride nanotube. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0026] Unless otherwise specified, all terms (including technical and scientific terms) used herein have the same meaning as commonly understood by those skilled in the art to which the subject matter of the present invention belongs. Terms, such as those defined in commonly used dictionaries, should be interpreted as having a meaning consistent with their meaning in the relevant technical field and in the context of this disclosure, and are not to be interpreted in an ideal or overly formal sense unless expressly defined as such in this specification.

[0027] Terms such as "first", "second", and the like are used herein when referring to various structures, epitaxial h-BN / BNNT structures, boron nitride nanotube structures, hexagonal boron nitride structures, features, percentages, percentage ranges, dimensions, areas, and connection sections, but such structures, epitaxial h-BN / BNNT structures, boron nitride nanotube structures, hexagonal boron nitride structures, features, percentages, percentage ranges, dimensions, areas, connection sections are not limited by these numerical terms. These numerical terms are used merely to individually identify each structure, epitaxial h-BN / BNNT structure, boron nitride nanotube structure, hexagonal boron nitride structure, element, percentage, percentage range, dimension, area, or connection section and / or to distinguish between structures, epitaxial h-BN / BNNT structures, boron nitride nanotube structures, hexagonal boron nitride structures, elements, percentages, percentage ranges, dimensions, areas, or connection sections.

[0028] The term "each" is used in many places in this specification in connection with a feature (or features) in a plurality of items (or "at least one" item, etc.) to indicate that the feature (or features) are present in each of the specified items (or individual items), as opposed to a feature that is provided in some way by the plurality of items but not necessarily by any individual item, or as opposed to a feature that is an average of features for the plurality of items. Such use of the term "each" can take a variety of forms, for example: "Materials each containing an arrangement of atoms..." "A plurality of layers, each of which is generally tubular and concentric," "one or more layers (i.e., walls), each layer consisting of a roughly tubular array of boron and nitrogen atoms"; "At least 50% of said totals are each a single layer"; "Each of the at least one hexagonal boron nitride structure is epitaxial to the boron nitride nanotube structure," "Each epitaxial h-BN / BNNT structure includes a boron nitride nanotube structure and at least one hexagonal boron nitride structure," "Hexagonal boron nitride structures, each epitaxial to a boron nitride nanotube structure," "A structure that contains (or a number of structures that each contain)" "For each of at least 10% of the atoms in the outermost wall of the boron nitride nanotube structure, [1] there is an atom in a hexagonal boron nitride structure that is epitaxial to the boron nitride nanotube structure, and [2] within 10 nanometers of such an atom." "[1] each of the boron nitride nanotube structures in an amount that is at least 10% of the sum of the amount of individual boron nitride nanotubes having a length of at least 50 nm in the composition and the amount of the boron nitride nanotube structures having a length of at least 50 nm in the composition, "The boron nitride nanotube structure has a length of at least 50 nm, and at least 10% in total of the outermost wall of the boron nitride nanotube structure is covered by hexagonal boron nitride structures, each of which is epitaxial to the boron nitride nanotube structure," and "each of at least a portion of said totals" It is.

[0029] As noted above, in accordance with a first aspect of the present inventive subject matter, there is provided a composition comprising at least a first epitaxial h-BN / BNNT structure, the first epitaxial h-BN / BNNT structure comprising at least a first boron nitride nanotube structure and at least a first hexagonal boron nitride structure, the first hexagonal boron nitride structure being epitaxial to the first boron nitride nanotube structure.

[0030] The expression "epitaxial h-BN / BNNT structure" as used herein refers to a novel and unexpected structure provided by the subject matter of the present invention, i.e., a structure comprising a boron nitride nanotube structure (defined below) and at least one hexagonal boron nitride structure (defined below), each of the at least one hexagonal boron nitride structure being epitaxial to the boron nitride nanotube structure. Thus, each epitaxial h-BN / BNNT structure comprises a boron nitride nanotube structure and at least one hexagonal boron nitride structure.

[0031] As is well known to those skilled in the art, the term "epitaxial" is used broadly in reference to crystal nucleation and growth. A crystal is defined as atoms, molecules, or ions arranged in a regular repeating pattern, a crystal lattice, that spans all three spatial dimensions. Crystal growth is the process by which an existing crystal grows as more atoms, molecules, or ions are added to their defined positions in the crystal lattice. During crystal growth, atoms, molecules, or ions must fall into the correct lattice positions in order for a highly regular crystal to grow. If an atom, molecule, or ion falls into a position different from the position in the ideal crystal lattice, a defect is formed. Typically, atoms, molecules, or ions in a crystal lattice are held in place, i.e., they cannot easily move from their own positions, and thus crystal growth is often irreversible in the sense that the molecules or ions are fixed once they fall into a defined position in the growing lattice.

[0032] Crystallization is typically understood as consisting of two processes: crystal nucleation and crystal growth. Crystal nucleation is when a new crystal is formed (i.e., when no pre-existing crystal exists), and crystal growth is when atoms, molecules, or ions are added to an existing crystal, i.e., a nucleated (and optionally grown) crystal, i.e., addition to a nucleated crystal is referred to as crystal growth, and also addition to a crystal that has been nucleated and already grown to some extent is referred to as crystal growth).

[0033] Epitaxy refers to the nucleation of a crystal of a particular orientation on another crystal, the orientation being determined by the underlying crystal. A statement herein that a first structure (i.e., a hexagonal boron nitride structure) is epitaxial to a second structure (i.e., a boron nitride nanotube structure) means that [1] the atoms in the second structure and [2] the atoms in the first structure closest to the second structure are arranged relative to each other in the way that atoms in an idealized structure corresponding to the second structure are arranged relative to each other, i.e., they are arranged in such a way that they are (or will be) the result of the nucleation of the second structure on the first structure and the growth of the second structure on the nucleated second structure.

[0034] Thus, the phrase "hexagonal boron nitride structures that are epitaxial to a boron nitride nanotube structure" (and similar phrases, e.g., "hexagonal boron nitride structures that are each epitaxial to a boron nitride nanotube structure," "each of the at least one hexagonal boron nitride structure is epitaxial to a boron nitride nanotube structure," "hexagonal boron nitride that is epitaxial to a boron nitride nanotube structure," etc.) as used herein refers to each such hexagonal boron nitride structure. In this context, it means that [1] the atoms in the hexagonal boron nitride structure and [2] the atoms in the boron nitride nanotube structure closest to the hexagonal boron nitride structure are arranged relative to each other in the way that atoms in an idealized hexagonal boron nitride structure (discussed below) are arranged relative to each other, i.e., they are arranged in a way that is (or will be) the result of nucleation of the hexagonal boron nitride structure on the boron nitride nanotube structure and growth of the hexagonal boron nitride structure on the nucleated hexagonal boron nitride structure.

[0035] Hexagonal boron nitride is characterized by stacking of two-dimensional honeycomb lattices of boron and nitrogen atoms strongly bonded by highly polar BN bonds. The layers of hexagonal boron nitride are generally stacked in an AA' stacking mode, i.e., a boron atom with a partial positive charge in one layer sits on an oppositely charged nitrogen atom in the adjacent layer.

[0036] The expression "boron nitride nanotube structure" is used herein to mean a portion of an epitaxial h-BN / BNNT structure in which boron and nitrogen atoms are present in an atomic arrangement that has a defect rate of 10 percent or less relative to an idealized boron nitride nanotube of the same length, diameter, and number of walls (discussed above).

[0037] The expression "defect rate" as used herein means the percentage of atoms in a structure that are inappropriately positioned relative to an idealized structure, i.e., the expression "atomic arrangements with a defect rate of 10 percent or less relative to an idealized boron nitride nanotube" as used herein includes structures in which the percentage of deviation from an idealized boron nitride nanotube (of the same length, diameter, and number of walls) is 10 percent or less, such deviation being quantified by dividing the number of atoms in the actual boron nitride nanotube structure that are in positions that do not correspond to their respective positions in the idealized boron nitride nanotube by the total number of positions for atoms in the idealized boron nitride nanotube (or by subtracting from 100 percent the percentage of atoms in the actual boron nitride nanotube structure that are in positions that correspond to their respective positions in the idealized boron nitride nanotube relative to the total number of positions in the idealized boron nitride nanotube). A single deviation is when a single atom in the idealized boron nitride nanotube is replaced by a different atom or when a single shift occurs. For example, when comparing the atomic arrangement in an actual boron nitride nanotube structure to the atomic arrangement in an idealized boron nitride nanotube, a single set of deviations may include a series of atoms (one atom wide) extending around the circumference of the actual boron nitride nanotube structure, with the atoms on either side of each of the series of atoms (not including the series) being compared to the atomic arrangement in the idealized boron nitride nanotube.

[0038] As discussed above, a hypothetical idealized boron nitride nanotube consists of one or more layers (i.e., walls), each layer consisting of a roughly tubular array of boron and nitrogen atoms arranged in a repeating hexagonal pattern of alternating boron and nitrogen atoms.

[0039] The expression "hexagonal boron nitride structure," as used herein, refers to a portion of an epitaxial h-BN / BNNT structure in which boron and nitrogen atoms are present in an atomic arrangement that has a defect rate of 10 percent or less relative to an idealized hexagonal boron nitride structure of the same shape and number of layers (discussed below).

[0040] As stated above, the expression "defect rate" as used herein means the percentage of atoms in a structure that are inappropriately positioned relative to an idealized structure. In this context, i.e., in the expression "defect rate of 10 percent or less relative to an idealized hexagonal boron nitride structure of the same shape and number of layers (discussed below)", a defect rate of 10 percent or less encompasses structures that have a deviation rate of 10 percent or less from an idealized hexagonal boron nitride structure of the same shape and number of layers, and such deviation is quantified by dividing the number of atoms in the actual atomic arrangement that are in positions that do not correspond to their respective positions in the idealized hexagonal boron nitride structure by the total number of positions for atoms in the idealized hexagonal boron nitride structure (or by subtracting from 100 percent the percentage of atoms in the actual atomic arrangement that are in positions that correspond to their respective positions in the idealized hexagonal boron nitride structure relative to the total number of positions in the idealized hexagonal boron nitride structure) and expressed as a percentage. A single deviation is when a single atom in the idealized hexagonal boron nitride structure is replaced by a different atom, or when a single shift occurs. For example, when comparing the atomic arrangement in an actual material to the atomic arrangement in an idealized hexagonal boron nitride structure, a single set of deviations would involve a series of atoms (one atom wide) that spans the actual material, and the atoms on either side of each of the series (not including the series) are compared to the atomic arrangement in the idealized hexagonal boron nitride structure.

[0041] The expression "idealized hexagonal boron nitride structure" as used herein means a hypothetical ideal boron nitride structure consisting of one or more layers, each layer consisting of an arrangement of boron and nitrogen atoms corresponding to a defect-free hexagonal boron nitride crystal. As known to those skilled in the art, the boron and nitrogen atoms in a hexagonal boron nitride crystal are arranged in a repeating hexagonal pattern with alternating boron and nitrogen atoms.

[0042] The expression "hexagonal boron nitride region" as used herein means a region of a hexagonal boron nitride structure (eg, a region of an integral unitary structure). The expression "hexagonal boron nitride" is used herein to mean one or more hexagonal boron nitride structures.

[0043] The expression "boron and nitrogen atoms nucleated on the boron nitride nanotube structure", as used herein, means, among all the boron and nitrogen atoms in the hexagonal boron nitride structure, each of which is epitaxial to the boron nitride nanotube structure, only those boron and nitrogen atoms that are in contact with atoms in the boron nitride nanotube structure, i.e. only those boron and nitrogen atoms that are arranged in such a way that they are (or will be) the result of the nucleation of hexagonal boron nitride on the boron nitride nanotube structure. For example, if hexagonal boron nitride is nucleated and grown on the boron nitride nanotube structure, the expression "boron and nitrogen atoms nucleated on the boron nitride nanotube structure" means only the boron and nitrogen atoms nucleated on the boron nitride nanotube structure, and not the boron and nitrogen atoms that are subsequently grown on the nucleated boron and nitrogen atoms. do not have.

[0044] Thus, the expression "hexagonal boron nitride epitaxial to the boron nitride nanotube structure" (as defined above) differs from the expression "boron and nitrogen atoms nucleated on the boron nitride nanotube structure" in that the expression "hexagonal boron nitride epitaxial to the boron nitride nanotube structure" refers to all of the atoms in all of the hexagonal boron nitride structures that are epitaxial to the boron nitride nanotube structure (not just the boron and nitrogen atoms nucleated on the boron nitride nanotube).

[0045] The expression "free-standing boron nitride nanotubes" as used herein means structures comprising boron and nitrogen atoms in an atomic arrangement that: [1] has a defect rate of 10 percent or less relative to an idealized boron nitride nanotube of the same length, diameter, and number of walls (discussed above); and [2] there are no hexagonal boron nitride structures to which it is epitaxial (i.e., there are no hexagonal boron nitride structures that are epitaxial to the atomic arrangement of nitrogen and boron atoms that has a defect rate of 10 percent or less relative to the idealized boron nitride nanotube).

[0046] The expression "free-standing hexagonal boron nitride" as used herein means a structure (or structures each containing) that includes boron and nitrogen atoms in an atomic arrangement that: [1] has a defect rate of 10 percent or less relative to an idealized hexagonal boron nitride structure of the same shape and number of layers (discussed above); and [2] there is no boron nitride nanotube structure that is epitaxial to it (i.e., there is no boron nitride nanotube whose atomic arrangement is epitaxial to the idealized hexagonal boron nitride structure with a defect rate of 10 percent or less).

[0047] As discussed below, one of the features of the epitaxial h-BN / BNNT structures disclosed herein is that it is easily perceived (e.g., by normal human vision) that the hexagonal boron nitride structures (which are epitaxial to the boron nitride nanotube structures) "cover" (partially or completely) the boron nitride nanotube structures. This specification includes definitions that allow for quantification, as a percentage, of the extent to which the boron nitride nanotube structure is covered by the hexagonal boron nitride structures. In order to make such quantifications definitive (i.e., highly accurate), so that one of skill in the art can easily determine whether any particular structure satisfies expressions herein relating to such coverage and / or can easily determine whether any particular composition or aggregate satisfies expressions relating to at least certain percent of the boron nitride nanotube structures, each of which is covered by at least certain percent, this specification includes very detailed definitions (below) to make such calculations sufficiently accurate.

[0048] The phrase "at least 10% in total of the outermost wall of the boron nitride nanotube structure is covered by hexagonal boron nitride structures, each of which is epitaxial to the boron nitride nanotube structure," as used herein, means that for each of at least 10% of the atoms in the outermost wall of the boron nitride nanotube structure, there is [1] an atom in the hexagonal boron nitride structure that is epitaxial to the boron nitride nanotube structure, and [2] within 10 nanometers of such an atom.

[0049] The expression "outermost wall", as used herein in relation to a boron nitride nanotube structure, refers to the outermost wall of a multi-walled boron nitride nanotube structure (i.e., the wall that is furthest from the axis of the boron nitride nanotube structure and furthest from the space within the tube), or the wall of a (single-walled boron nitride nanotube structure). In the case of boron nanotube structures, this means a single wall.

[0050] The expression "outermost wall", when used herein in relation to free-standing boron nitride nanotubes, means the outermost wall of a free-standing multi-walled boron nitride nanotube (i.e. the wall furthest from the axis of the free-standing boron nitride nanotube and furthest from the space within the tube) or (in the case of a free-standing single-walled boron nitride nanotube) the single wall.

[0051] In addition to the above definitions regarding the calculation of the percentage of boron nitride nanotube structures covered by hexagonal boron nitride structures in an epitaxial h-BN / BNNT structure, there are also epitaxial h-BN / BNNT structures in which multiple boron nitride nanotube structures may form an agglomerate together, and the entire agglomerate (including multiple boron nitride nanotube structures) may be covered (at least to a certain percentage) by hexagonal boron nitride structures that are epitaxial to the boron nitride nanotube structures (e.g., the outermost one) in the agglomerate. In order to make such quantification sufficiently precise so that the skilled person can easily determine whether any particular structure satisfies the expressions herein related to such coverage and / or can easily determine whether any particular composition or aggregate satisfies the expressions related to such coverage, the present specification includes further definitions (starting with the definition of "agglomerate" and specific types of agglomerates) to make such calculations sufficiently precise.

[0052] The term "clump", as used herein (e.g., in the terms "independent boron nitride nanotube clump", "boron nitride nanotube structure clump" and "boron nitride nanotube structure / independent boron nitride nanotube clump") means a group of at least two independent boron nitride nanotubes that are all in contact with each other, a group of at least two boron nitride nanotube structures that are all in contact with each other, or a group of at least one independent boron nitride nanotube and at least one boron nitride nanotube structure that are all in contact with each other. A single "cluster" refers to a group in which each member of the group is in direct or indirect contact with every other member of the group (indirect contact between each member of a group refers to a series of directly contacted pairs of members that are not in direct contact with each other, but are spread among the members, i.e., a first and second member are in direct contact with each other, a third member is in direct contact with at least one of the first and second members, a fourth member is in direct contact with at least one of the first through third members, a fifth member is in direct contact with at least one of the first through fourth members, etc.). Representative examples where "clusters" are important in the context of the present subject matter are discussed below after the definition of "external atoms...".

[0053] The expression "independent boron nitride nanotube mass" as used herein means a mass that includes a plurality of independent boron nitride nanotubes and does not include a boron nitride nanotube structure.

[0054] The expression "agglomerate of boron nitride nanotube structures" as used herein means agglomerate that includes a plurality of boron nitride nanotube structures and does not include individual boron nitride nanotubes.

[0055] The expression "boron nitride nanotube structure / individual boron nitride nanotube agglomerate" as used herein refers to at least one boron nitride nanotube structure and agglomerate comprising at least one individual boron nitride nanotube. Similar expressions refer to similar structures, e.g., similarly, any specified number (or range) of boron nitride nanotube structures and / or individual boron nitride nanotube agglomerates may be expressed as any number (or range) of boron nitride nanotube structures and / or individual boron nitride nanotube agglomerates in which the sum of [1] the total number of boron nitride nanotube structures and [2] the total number of individual boron nitride nanotubes is greater than or equal to that number. This means that the structure is equal to the specified number (or is within the specified range).

[0056] "At least 10% of the total outer atoms of the boron nitride nanotube structure agglomerate, the boron nitride nanotube structure / independent boron nitride nanotube agglomerate, or the boron nitride nanotube structure that is not an agglomerate, The expression "covered by hexagonal boron nitride structures, each of which is epitaxial to the boron nitride nanotube structures in the boron nitride nanotube structure [2], boron nitride nanotube structure mass, [3] boron nitride nanotube structure / independent boron nitride nanotube mass, or [5] non-mass boron nitride nanotube structure" means As used herein, it means that for each of at least 10% of the outer atoms (as defined below) of a [2] boron nitride nanotube structure agglomerate, [3] boron nitride nanotube structure / freestanding boron nitride nanotube agglomerate, or [5] non-agglomerate boron nitride nanotube structure, there is an atom that is [a] in the hexagonal boron nitride structure that is epitaxial to the boron nitride nanotubes in the agglomerate, and [b] within 10 nanometers of such outer atom.

[0057] The expression "external atom of [2] boron nitride nanotube structure agglomerate, [3] boron nitride nanotube structure / independent boron nitride nanotube agglomerate, or [5] non-agglomerate boron nitride nanotube structure" as used herein includes any atom on [2] boron nitride nanotube structure agglomerate, [3] boron nitride nanotube structure / independent boron nitride nanotube agglomerate, or [5] non-agglomerate boron nitride nanotube structure for which there is a cylindrical region of radius 0.1 angstroms in contact with the atom and extending for at least 1 mm from the atom without intersecting with any other atom on [2] boron nitride nanotube structure agglomerate, [3] boron nitride nanotube structure / independent boron nitride nanotube agglomerate, or [5] non-agglomerate boron nitride nanotube structure.

[0058] A representative example where "agglomeration" is important in the context of the present subject matter is when one or more boron nitride nanotube structures and / or one or more individual boron nitride nanotubes in an agglomerate are substantially completely covered by other boron nitride nanotube structures and / or individual boron nitride nanotubes (e.g., such substantially completely covered boron nitride nanotube structures and / or one or more individual boron nitride nanotubes are within a larger agglomerate). In such a situation, the atoms of such substantially complete boron nitride nanotube structures and / or one or more individual boron nitride nanotubes do not meet the above definition of "external atoms" according to the description herein, and therefore such atoms are not considered to be "at least 10% in total of the external atoms of [2] the boron nitride nanotube structure agglomerate, [3] the boron nitride nanotube structure / individual boron nitride nanotube agglomerate, or [5] the boron nitride nanotube structure that is not an agglomerate" [2] a boron nitride nanotube structure mass, [3] a boron nitride nanotube structure / independent boron nitride nanotube mass, or [5] a boron nitride nanotube structure that is not a mass, each of which is covered by a hexagonal boron nitride structure that is epitaxial to the boron nitride nanotube structure. is not taken into account in determining whether the expression is satisfied.

[0059] The expression "residual boron" as used herein means a mass consisting (or consisting essentially) of boron and / or boron compounds. The expression "aggregate" as used herein means a unitary, monolithic structure, i.e., a structure that can be lifted by grasping any portion of the structure (i.e., such a portion can be grasped and lifted without any portion of the structure being disrupted by gravity from any other portion of the structure). (I).

[0060] The expression "integral unitary structure" as used herein means a structure that is one piece. The term "plurality" as used herein means two or more (e.g., "plurality of hexagonal boron nitride structures" means two or more hexagonal boron nitride structures).

[0061] As used herein, the phrase "or less than" a specified amount means the specified amount or less (e.g., "or less than 35% by weight of the composition" means 35% or less than 35% by weight of the composition).

[0062] As used herein, the phrase "at least" a specified amount means the specified amount or more (e.g., "at least 10 boron nitride nanotube structures" means 10 or more boron nitride nanotube structures), and vice versa (e.g., "two or more boron nitride nanotube structures" means at least two boron nitride nanotube structures).

[0063] A phrase such as "The "[composition or aggregate] comprises at least [a specified percentage] of [a type of material]" (e.g., "The composition comprises at least 10% by weight of hexagonal boron nitride") means that the specified type of material makes up the specified percentage (or range of percentages) of the entire composition or aggregate, and vice versa (i.e., "The "[specified material" makes up [a specified percentage] of the [composition or aggregate]" means that the specified percentage (or range of percentages) of the composition or aggregate is the specified material).

[0064] In expressions where the "total" is characterized as the sum of the respective values ​​for two or more items, for example the following expressions: "The sum of [1] the total mass of all independent hexagonal boron nitride in the composition and [2] the total mass of all residual boron in the composition," "The sum of [1] independent boron nitride nanotubes having a length of at least 50 nm in the composition and [2] boron nitride nanotube structures having a length of at least 50 nm in the composition," "The sum of the amounts of: [1] independent boron nitride nanotube clumps having a length of at least 50 nm in the composition; [2] boron nitride nanotube structure clumps having a length of at least 50 nm in the composition; [3] boron nitride nanotube structures / independent boron nitride nanotube clumps having a length of at least 50 nm in the composition; [4] independent boron nitride nanotubes that are not clumps and have a length of at least 50 nm in the composition; and [5] boron nitride nanotube structures that are not clumps and have a length of at least 50 nm in the composition." And, in similar expressions where "composition" is replaced by and / or included with "unitary structure," one or more of the values ​​may be zero, i.e., the inclusion of an item does not imply that the value for such item is necessarily other than zero.

[0065] The expressions "plasma" and "ionized gas" are used herein according to their well-known meaning and refer to the material obtained when sufficient energy is supplied to a gas to liberate electrons from atoms or molecules, thus allowing ions and electrons to coexist (also referred to as the fourth state of matter, i.e. solid, liquid, gas, plasma).

[0066] As mentioned above, according to a first aspect of the present subject matter: at least a first epitaxial h-BN / BNNT structure; A composition is provided comprising: the first epitaxial h-BN / BNNT structure includes at least a first boron nitride nanotube structure and at least a first hexagonal boron nitride structure; The first hexagonal boron nitride structure is epitaxial to the first boron nitride nanotube structure.

[0067] In some embodiments according to the first aspect of the inventive subject matter, which may or may not include any of the other features described herein, as appropriate: [1] The total of the amount of independent boron nitride nanotubes having a length of at least 50 nm in the composition and the amount of boron nitride nanotube structures having a length of at least 50 nm in the composition is at least 10; [1] For each of the boron nitride nanotube structures in an amount that is at least 10% of the sum of the amount of individual boron nitride nanotubes having a length of at least 50 nm in the composition and the amount of boron nitride nanotube structures having a length of at least 50 nm in the composition: the boron nitride nanotube structure has a length of at least 50 nm, and at least 10% in total of an outermost wall of the boron nitride nanotube structure is covered by hexagonal boron nitride structures, each of which is epitaxial to the boron nitride nanotube structure; And in some such embodiments: For each of the boron nitride nanotube structures in an amount that is at least a first percent (selected from among 20%, 30%, 40%, 50%, 60%, 70%, 80%, and 90%) or within a first percentage range (selected from among 10%-20%, 20%-30%, 30%-40%, 40%-50%, 50%-60%, 60%-70%, 70%-80%, and 80%-90%) of the sum of [1] the amount of individual boron nitride nanotubes having a length of at least 50 nm in the composition and [2] the amount of boron nitride nanotube structures having a length of at least 50 nm in the composition: the boron nitride nanotube structure has a length of at least 50 nm, and at least a second total percent (selected from among 10%, 20%, 30%, 40%, 50%, 60%, 70%, 80%, and 90%) of an outermost wall of the boron nitride nanotube structure, or within a second total percent range (selected from among 10%-20%, 20%-30%, 30%-40%, 40%-50%, 50%-60%, 60%-70%, 70%-80%, and 80%-90%) of the outermost wall of the boron nitride nanotube structure is covered by hexagonal boron nitride structures, each epitaxial to the boron nitride nanotube structure; Any combination of the first percentage (or range of first percentages) and the second percentage (or range of second percentages) is included.

[0068] In some embodiments according to the first aspect of the inventive subject matter, which may or may not include any of the other features described herein, as appropriate: the total amount of each of [1] independent boron nitride nanotube clumps having a length of at least 50 nm in the composition, [2] boron nitride nanotube structure clumps having a length of at least 50 nm in the composition, [3] boron nitride nanotube structures / independent boron nitride nanotube clumps having a length of at least 50 nm in the composition, [4] independent boron nitride nanotubes that are not clumps and have a length of at least 50 nm in the composition, and [5] boron nitride nanotube structures that are not clumps and have a length of at least 50 nm in the composition is at least 10; [2] boron nitride nanotube structure chunks having a length of at least 50 nm in the composition, [3] boron nitride nanotube structures / independent boron nitride nanotube chunks having a length of at least 50 nm in the composition, and [5] boron nitride nanotube structures in the composition that are not chunks and have a length of at least 50 nm, at least 30% of the total For each of the quantities: [2] At least 10% of the outer atoms of the boron nitride nanotube structure agglomerate, [3] the boron nitride nanotube structure / independent boron nitride nanotube agglomerate, or [5] the boron nitride nanotube structure that is not an agglomerate, in total, [2] a boron nitride nanotube structure mass, [3] a boron nitride nanotube structure / independent boron nitride nanotube mass, or [5] a boron nitride nanotube structure that is not a mass, each of which is covered by a hexagonal boron nitride structure that is epitaxial to the boron nitride nanotube structure; And in some such embodiments: the total amount of each of [1] independent boron nitride nanotube clumps having a length of at least 50 nm in the composition, [2] boron nitride nanotube structure clumps having a length of at least 50 nm in the composition, [3] boron nitride nanotube structures / independent boron nitride nanotube clumps having a length of at least 50 nm in the composition, [4] independent boron nitride nanotubes that are not clumps and have a length of at least 50 nm in the composition, and [5] boron nitride nanotube structures that are not clumps and have a length of at least 50 nm in the composition is at least 10; For each of the amounts of [2] boron nitride nanotube structure chunks having a length of at least 50 nm in the composition, [3] boron nitride nanotube structures / freestanding boron nitride nanotube chunks having a length of at least 50 nm in the composition, and [5] boron nitride nanotube structures in the composition that are not chunks and have a length of at least 50 nm, that is at least a first percentage (selected from among 40%, 50%, 60%, 70%, 80%, and 90%) of said total or within a first percentage range (selected from among 30%-40%, 40%-50%, 50%-60%, 60%-70%, 70%-80%, and 80%-90%): [2] the boron nitride nanotube structure agglomerates, [3] the boron nitride nanotube structure / independent boron nitride nanotube agglomerates, or [5] the boron nitride nanotube structure that is not an agglomerate, at least a second percent in total (selected from among 10%, 20%, 30%, 40%, 50%, 60%, 70%, 80%, and 90%) of the outer atoms, or a second percent in total within a range (selected from among 10%-20%, 20%-30%, 30%-40%, 40%-50%, 50%-60%, 60%-70%, 70%-80%, and 80%-90%) [2] a boron nitride nanotube structure mass, [3] a boron nitride nanotube structure / independent boron nitride nanotube mass, or [5] a boron nitride nanotube structure that is not a mass, each of which is covered by a hexagonal boron nitride structure that is epitaxial to the boron nitride nanotube structure; Any combination of the first percentage (or range of first percentages) and the second percentage (or range of second percentages) is included.

[0069] As mentioned above, according to a second aspect of the inventive subject matter: a monolithic structure including at least a first epitaxial h-BN / BNNT structure; An aggregate is provided, comprising: the first epitaxial h-BN / BNNT structure includes at least a first boron nitride nanotube structure and at least a first hexagonal boron nitride structure; the first hexagonal boron nitride structure is epitaxial to the boron nitride nanotube structure; The monolithic structure has a first dimension of at least 100 nm and a second dimension of at least 100 nm, the second dimension being perpendicular to the first dimension.

[0070] In some embodiments according to the second aspect of the inventive subject matter, which may or may not include any of the other features described herein, as appropriate: [1] For each of the boron nitride nanotube structures in the monolithic structure in an amount that is at least 10% of the sum of the amount of independent boron nitride nanotubes having a length of at least 50 nm in the monolithic structure and the amount of boron nitride nanotube structures having a length of at least 50 nm in the monolithic structure: a total of at least 10% of an outermost wall of the boron nitride nanotube structure is covered by hexagonal boron nitride structures, each of which is epitaxial to the boron nitride nanotube structure; And in some such embodiments: For each of the boron nitride nanotube structures in the monolithic structure in an amount that is at least a first percent (selected from among 20%, 30%, 40%, 50%, 60%, 70%, 80%, and 90%) of the sum of [1] the amount of individual boron nitride nanotubes having a length of at least 50 nm in the monolithic structure and [2] the amount of boron nitride nanotube structures having a length of at least 50 nm in the monolithic structure, or within a first percentage range (selected from among 10% to 20%, 20% to 30%, 30% to 40%, 40% to 50%, 50% to 60%, 60% to 70%, 70% to 80%, and 80% to 90%): a total of at least a second percent (selected from among 20%, 30%, 40%, 50%, 60%, 70%, 80%, and 90%) of an outermost wall of the boron nitride nanotube structure, or within a total range of a second percent (selected from among 10%-20%, 20%-30%, 30%-40%, 40%-50%, 50%-60%, 60%-70%, 70%-80%, and 80%-90%), are covered by hexagonal boron nitride structures, each epitaxial to the boron nitride nanotube structure; Any combination of the first percentage (or range of first percentages) and the second percentage (or range of second percentages) is included.

[0071] In some embodiments according to the second aspect of the inventive subject matter, which may or may not include any of the other features described herein, as appropriate: [2] A boron nitride nanotube structure mass having a length of at least 50 nm in a monolithic structure, [3] A boron nitride nanotube structure / independent boron nitride nanotube mass having a length of at least 50 nm in a monolithic structure, and [5] A boron nitride nanotube structure that is not a mass and has a length of at least 50 nm in a monolithic structure. For each of the amounts that is at least 10% of the sum of the respective amounts of [1] individual boron nitride nanotube chunks having a length of at least 50 nm in a monolithic structure, [2] boron nitride nanotube structure chunks having a length of at least 50 nm in a monolithic structure, [3] boron nitride nanotube structure / individual boron nitride nanotube chunks having a length of at least 50 nm in a monolithic structure, [4] individual boron nitride nanotubes that are not chunks and have a length of at least 50 nm in a monolithic structure, and [5] boron nitride nanotube structure that is not chunks and has a length of at least 50 nm in a monolithic structure: [2] At least 10% of the outer atoms of the boron nitride nanotube structure agglomerate, [3] the boron nitride nanotube structure / independent boron nitride nanotube agglomerate, or [5] the boron nitride nanotube structure that is not an agglomerate, in total, [2] a boron nitride nanotube structure mass, [3] a boron nitride nanotube structure / independent boron nitride nanotube mass, or [5] a boron nitride nanotube structure that is not a mass, each of which is covered by a hexagonal boron nitride structure that is epitaxial to the boron nitride nanotube structure; And in some such embodiments: [2] A boron nitride nanotube structure mass having a length of at least 50 nm in a monolithic structure, [3] A boron nitride nanotube structure / independent boron nitride nanotube mass having a length of at least 50 nm in a monolithic structure, and [5] A boron nitride nanotube structure that is not a mass and has a length of at least 50 nm in a monolithic structure. [1] Individual boron nitride nanotubes with lengths of at least 50 nm in a monolithic structure.

[0023] For each of the amounts of

[0023] boron nitride nanotube structure agglomerates having a length of at least 50 nm in a monolithic structure, [1] boron nitride nanotube structure agglomerates having a length of at least 50 nm in a monolithic structure, [2] boron nitride nanotube structure agglomerates having a length of at least 50 nm in a monolithic structure, [3] boron nitride nanotube structure / independent boron nitride nanotube agglomerates having a length of at least 50 nm in a monolithic structure, [4] independent boron nitride nanotubes in a monolithic structure that are not agglomerates and have a length of at least 50 nm, and [5] boron nitride nanotube structure in a monolithic structure that are not agglomerates and have a length of at least 50 nm, [2] the boron nitride nanotube structure agglomerates, [3] the boron nitride nanotube structure / independent boron nitride nanotube agglomerates, or [5] the boron nitride nanotube structure that is not an agglomerate, at least a second percent in total (selected from among 20%, 30%, 40%, 50%, 60%, 70%, 80%, and 90%) of the outer atoms, or a second percent in total within a range (selected from among 10% to 20%, 20% to 30%, 30% to 40%, 40% to 50%, 50% to 60%, 60% to 70%, 70% to 80%, and 80% to 90%) [2] a boron nitride nanotube structure mass, [3] a boron nitride nanotube structure / independent boron nitride nanotube mass, or [5] a boron nitride nanotube structure that is not a mass, each of which is covered by a hexagonal boron nitride structure that is epitaxial to the boron nitride nanotube structure; Any combination of the first percentage (or range of first percentages) and the second percentage (or range of second percentages) is included.

[0072] As mentioned above, according to a third aspect of the inventive subject matter: Multiple independent boron nitride nanotubes, A composition is provided comprising: [1] The total mass of all independent hexagonal boron nitride in the composition and [2] the total mass of all residual boron in the composition together constitute 35% or less of the mass of the composition.

[0073] In some embodiments according to the third aspect of the inventive subject matter, which may or may not include any of the other features described herein, as appropriate: [1] The sum of the total mass of all independent hexagonal boron nitride in the composition and [2] the total mass of all residual boron in the composition comprises less than or equal to a first percentage (selected from among 30%, 25%, 20%, 15%, 10%, and 5%) of the mass of the composition, or comprises a percentage within a first percentage range (selected from among 30%-350%, 25%-30%, 20%-25%, 15%-20%, 10%-15%, and 5%-10%).

[0074] As mentioned above, according to a fourth aspect of the inventive subject matter: a monolithic structure comprising a plurality of independent boron nitride nanotubes; An aggregate is provided, comprising: the monolithic structure has a first dimension of at least 100 nm and a second dimension of at least 100 nm, the second dimension being perpendicular to the first dimension; [1] The total mass of the free-standing hexagonal boron nitride in the monolithic structure and [2] the total mass of all residual boron in the monolithic structure constitute no more than 35% of the mass of the monolithic structure.

[0075] In some embodiments according to the fourth aspect of the inventive subject matter, which may or may not include any of the other features described herein, as appropriate: [1] The total mass of all independent hexagonal boron nitride crystals in the monolithic structure and [2] The total mass of all independent hexagonal boron nitride crystals in the monolithic structure and the total mass of all residual boron constitutes less than or equal to a first percentage (selected from among 30%, 25%, 20%, 15%, 10%, and 5%) of the mass of the monolithic structure, or constitutes a percentage within a first percentage range (selected from among 30%-350%, 25%-30%, 20%-25%, 15%-20%, 10%-15%, and 5%-10%).

[0076] As mentioned above, according to a fifth aspect of the inventive subject matter: at least 10 independent boron nitride nanotubes having a length of at least 50 nm; A composition is provided comprising: [1] Of the total of independent boron nitride nanotubes having a length of at least 50 nm in the composition and [2] boron nitride nanotube structures having a length of at least 50 nm in the composition, 1% or less of the total has at least one defect selected from Dixie cup defects and bamboo defects.

[0077] Those skilled in the art are familiar with Dixie cup defects and bamboo defects. For clarity, the term "bamboo defects" as used herein with respect to boron nitride nanotubes means that the boron nitride nanotubes have a plurality of regions in which the diameter of the boron nitride nanotube increases by at least 10% over a length of 5 nm or less (i.e., the respective diameters (i.e., the diameter perpendicular to the axis of the boron nitride nanotube) of the boron nitride nanotube at intervals of 5 nm or less along the length of the boron nitride nanotube differ by at least 10% (i.e., one diameter is at least 1.1 times the other diameter)).

[0078] For clarity, the expression "Dixie cup defect", when used herein with respect to a boron nitride nanotube (or a plurality of boron nitride nanotubes), means that the boron nitride nanotube (or each of the boron nitride nanotubes) is tapered in the sense that it has a first (wide) end and a second (narrow) end (separated from one another along the axis of the boron nitride nanotube or wall), the second (narrow) end having a diameter (perpendicular to the axis) that is 65% or less of the diameter of the first (wide) end, and the narrow end of one boron nitride nanotube is recessed within the wide end of another tapered boron nitride nanotube (i.e., a plane perpendicular to the axis of the boron nitride nanotube and in the "Dixie cup overlap" region will pass through both boron nitride nanotubes).

[0079] In some embodiments according to the fifth aspect of the inventive subject matter, which may or may not include any of the other features described herein, as appropriate: Of the sum of [1] the individual boron nitride nanotubes having a length of at least 50 nm in the composition and [2] the boron nitride nanotube structures having a length of at least 50 nm in the composition, less than or equal to a first percentage (selected from among 0.8%, 0.6%, 0.4%, 0.3%, 0.2%, and 0.1%) of the sum, or within a first percentage range (selected from among 0.0% to 0.1%, 0.1% to 0.2%, 0.2% to 0.3%, 0.3% to 0.4%, 0.4% to 0.6%, 0.6% to 0.8%, and 0.8% to 1.0%), the sum has at least one defect selected from Dixie cup defects and bamboo defects.

[0080] As mentioned above, according to a sixth aspect of the inventive subject matter: a monolithic structure comprising a plurality of independent boron nitride nanotubes; An aggregate is provided, comprising: the monolithic structure has a first dimension of at least 100 nm and a second dimension of at least 100 nm, the second dimension being perpendicular to the first dimension; [1] Of the total of independent boron nitride nanotubes having a length of at least 50 nm in a monolithic structure and [2] boron nitride nanotube structures having a length of at least 50 nm in a monolithic structure, 1% or less of the total has at least one defect selected from Dixie cup defects and bamboo defects.

[0081] In some embodiments according to the sixth aspect of the inventive subject matter, which may or may not include any of the other features described herein, as appropriate: Of the sum of [1] independent boron nitride nanotubes having a length of at least 50 nm in a monolithic structure and [2] boron nitride nanotube structures having a length of at least 50 nm in a monolithic structure, a first percentage (selected from among 0.8%, 0.6%, 0.4%, 0.3%, 0.2%, and 0.1%) or a percentage within a first percentage range (selected from among 0.0% to 0.1%, 0.1% to 0.2%, 0.2% to 0.3%, 0.3% to 0.4%, 0.4% to 0.6%, 0.6% to 0.8%, and 0.8% to 1.0%) of the sum has at least one defect selected from Dixie cup defects and bamboo defects.

[0082] As mentioned above, according to a seventh aspect of the inventive subject matter: at least 10 independent boron nitride nanotubes; A composition is provided comprising: [1] Of the total of independent boron nitride nanotubes in the composition having a length of at least 50 nm, and [2] of boron nitride nanotube structures in the composition having a length of at least 50 nm, at least 50% of said total are each single-walled.

[0083] In some embodiments according to the seventh aspect of the present inventive subject matter, which may or may not include any of the other features described herein, as appropriate, at least a portion of the sum of [1] individual boron nitride nanotubes in the composition having a length of at least 50 nm and [2] boron nitride nanotube structures in the composition having a length of at least 50 nm that is single-walled is present in an individual boron nitride nanotube agglomerate, a boron nitride nanotube structure agglomerate, or a boron nitride nanotube structure / individual boron nitride nanotube agglomerate.

[0084] In some embodiments according to the seventh aspect of the present inventive subject matter, which may or may not include any of the other features described herein, between 50 and 60 percent of the sum of [1] the individual boron nitride nanotubes in the composition having a length of at least 50 nm and [2] the boron nitride nanotube structures in the composition having a length of at least 50 nm are each single-walled.

[0085] As mentioned above, according to an eighth aspect of the inventive subject matter: a monolithic structure comprising at least one free-standing boron nitride nanotube; An aggregate is provided, comprising: the monolithic structure has a first dimension of at least 100 nm and a second dimension of at least 100 nm, the second dimension being perpendicular to the first dimension; [1] Of the sum of independent boron nitride nanotubes having a length of at least 50 nm in a monolithic structure and [2] boron nitride nanotube structures having a length of at least 50 nm in a monolithic structure, at least 50% of said sum are each single-walled.

[0086] In some embodiments according to an eighth aspect of the inventive subject matter, which may or may not include any of the other features described herein, optionally, of the sum of [1] independent boron nitride nanotubes having a length of at least 50 nm in a monolithic structure, and [2] boron nitride nanotube structures having a length of at least 50 nm in a monolithic structure, At least some of the single walls are present in individual boron nitride nanotube masses, boron nitride nanotube structure masses, or boron nitride nanotube structure / individual boron nitride nanotube masses.

[0087] In some embodiments according to an eighth aspect of the present inventive subject matter, which may or may not include any of the other features described herein, of the sum of [1] independent boron nitride nanotubes having a length of at least 50 nm in a monolithic structure and [2] boron nitride nanotube structures having a length of at least 50 nm in a monolithic structure, between 50 and 60 percent of said sum are each single-walled.

[0088] In some embodiments according to any of the first, second, fifth, sixth, seventh, and eighth aspects of the inventive subject matter, which may or may not include any of the other features described herein, as appropriate, the combined mass of the epitaxial h-BN / BNNT structures in the composition comprises at least 65% of the mass of the composition or monolithic structure (i.e., the compositions according to the first, third, fifth, and seventh aspects, and the monolithic structures according to the second, fourth, sixth, and eighth aspects, as well as other occurrences of "composition or monolithic structure" below); In some of such embodiments, the combined mass of the epitaxial h-BN / BNNT structures in the composition comprises at least a first percent (selected from among 70%, 75%, 80%, 85%, 90%, 95%, 97%, and 99%) of the mass of the composition or monolithic structure, or a percentage that is within a first percentage range (selected from among among 65%-70%, 70%-75%, 75%-80%, 80%-85%, 85%-90%, 90%-95%, 95%-97%, and 97%-99%).

[0089] In some embodiments according to any of the first, second, third, fourth, fifth, sixth, seventh, and eighth aspects of the present inventive subject matter, which may or may not include any of the other features described herein, at least 10% by weight of the composition or monolithic structure comprises hexagonal boron nitride structures, each epitaxial to the boron nitride nanotube structures.

[0090] In some embodiments according to any of the first, second, third, fourth, fifth, sixth, seventh, and eighth aspects of the present inventive subject matter, which may or may not include any of the other features described herein, for each of at least 10% of the atoms in the composition or monolithic structure, the atoms are present in a hexagonal boron nitride structure that is epitaxial to a boron nitride nanotube structure in the composition.

[0091] In some embodiments according to any of the first and second aspects of the inventive subject matter, which may or may not include any of the other features described herein, as appropriate, the combined mass of all independent hexagonal boron nitride in the composition or monolithic structure, and [2] the combined mass of all amorphous boron in the composition or monolithic structure, constitute less than 35% of the mass of the composition or monolithic structure; In some of such embodiments, the combined mass of all independent hexagonal boron nitride in the composition or monolithic structure and[2] the combined mass of all amorphous boron in the composition or monolithic structure constitute less than a first percentage (selected from among 30%, 25%, 20%, 15%, 10%, and 5%) or constitute a percentage within a first percentage range (selected from among 10%-20%, 20%-30%, 30%-40%, 40%-50%, 50%-60%, 60%-70%, 70%-80%, and 80%-90%) of the mass of the composition or monolithic structure.

[0092] Some embodiments according to any of the first, second, third, and fourth aspects of the inventive subject matter may or may not include any of the other features described herein, as appropriate. [1] A composition or a monolithic structure having independent boron nitride nanotubes with a length of at least 50 nm, and [2] a composition or a monolithic structure having a length of at least 50 nm, wherein 1% or less of the total of the boron nitride nanotube structures with a length of at least 50 nm has at least one defect selected from Dixie cup defects and bamboo defects; In some of such embodiments, a percentage of the combined total of [1] the individual boron nitride nanotubes having a length of at least 50 nm in the composition or monolithic structure and [2] the boron nitride nanotube structures having a length of at least 50 nm in the composition or monolithic structure, less than or equal to a first percentage (selected from among 0.8%, 0.6%, 0.4%, 0.3%, 0.2%, and 0.1%), or within a first percentage range (selected from among 0.0%-0.1%, 0.1%-0.2%, 0.2%-0.3%, 0.3%-0.4%, 0.4%-0.6%, 0.6%-0.8%, and 0.8%-1.0%) of said combined total has at least one defect selected from Dixie cup defects and bamboo defects.

[0093] In some embodiments according to any of the first, second, third, fourth, fifth, and sixth aspects of the present inventive subject matter, which may or may not include any of the other features described herein, optionally, at least 50% of the total of [1] individual boron nitride nanotubes having a length of at least 50 nm in the composition or monolithic structure and [2] boron nitride nanotube structures having a length of at least 50 nm in the composition or monolithic structure are each single-walled.

[0094] In some embodiments according to any of the third and fourth aspects of the inventive subject matter, which may or may not include any of the other features described herein, as appropriate, the independent hexagonal boron nitride comprises 1 weight percent or less of the composition or aggregate; In some of such embodiments, the independent hexagonal boron nitride comprises at least a first percent (selected from among 0.8%, 0.6%, 0.4%, 0.3%, 0.2%, and 0.1%) of the mass of the composition or aggregate, or a percentage that is within a first percentage range (selected from among 0.0%-0.1%, 0.1%-0.2%, 0.2%-0.3%, 0.3%-0.4%, 0.4%-0.6%, 0.6%-0.8%, and 0.8%-1.0%).

[0095] Figure 1 is a schematic diagram of a representative embodiment of an apparatus 10 that can be used to produce epitaxial h-BN / BNNT structures, as well as compositions and / or aggregates that include epitaxial h-BN / BNNT structures, in accordance with the first and second aspects of the present subject matter. Figure 2 is an enlarged view of a portion of Figure 1, showing a portion of the apparatus 10.

[0096] The apparatus 10 comprises a plasma generation device 11, a collar region 12, a first reaction section 13 (defining a first reaction chamber region), and a second reaction section 14 (defining a second reaction chamber region).

[0097] The plasma generator 11 comprises a wall 15, an electromagnetic wave generator and waveguide 16, and a sparker 17. The waveguide is an inductor, for example in the form of a coil (1 / 4" or larger) of copper tubing with several turns (usually 3-6). The copper coil is a non-magnetic coil that provides high electrical conductivity. The number of turns is scaled to match the inductance and electrical resistance of the inductor providing compatibility with the high frequency power supply output.

[0098] The wall 15 of the plasma-generating device 11 comprises an RF-transparent region 18 that is radio frequency transparent (i.e., RF transparent), electrically conductive, and non-magnetic. A representative example of a suitable material from which the RF-transparent region 18 can be fabricated is alumina.

[0099] An AC power source 19 supplies high frequency energy to an electromagnetic wave generator 16 which generates electromagnetic waves at multiple frequencies selected from the range of tens of kilohertz to thousands of gigahertz, and such electromagnetic waves pass through an RF transparent portion 18 of a wall 15 of the plasma generation region 11.

[0100] Inside the plasma generator 11, there is a plasma generator space 21. The sparker 17 comprises a moving electrode 29 and a discharge protrusion 30. The moving electrode 29 is configured to controllably extend into the region of the plasma generator volume 21 containing the maximum magnetic field density and maximum electric field density. The discharge protrusion 30 is fabricated from an electrically conductive, non-magnetic material and is configured to create a discharge point when the moving electrode 29 approaches, such a discharge generating a plasma. The moving electrode 29 is configured to be withdrawn from the region of maximum magnetic field density and maximum electric field density after such a discharge.

[0101] The plasma generator 11 has one or more ports 20 through which material (eg, nitrogen gas) can be introduced into the plasma generator volume 21 . The plasma generating device 11 has a plume opening 22 through which a plume of plasma generated by the plasma generating device 11 passes and enters a color space 23 inside the color region 12 .

[0102] The collar region 12 includes at least one reactant feed opening 24 through which a feedstock (e.g., boron powder, boron nitride, boron carbide, boron trioxide, boric acid, etc.) can be introduced (e.g., injected) into the collar space 23 (and into the plasma plume), optionally with a carrier gas therethrough.

[0103] First reaction vessel section 13 may include one or more access ports 25 providing access to a first reaction chamber region 26 within first reaction vessel section 13. The one or more access ports 25 (if included) may provide access for diagnostics (such as optical monitoring of the reaction), for inserting structures into the reaction chamber (e.g., quench modifiers such as wires or mesh), or for removing product.

[0104] Similarly, the second reactor vessel section 14 may include one or more access ports 27 providing access to a second reaction chamber region 28 within the second reactor vessel section 14. The one or more access ports 27 (if included) may provide access for diagnostics (such as optical monitoring of the reaction), for inserting structures into the reaction chamber (e.g., quench modifiers such as wires or meshes), or for removing product.

[0105] The apparatus 10 further comprises an outer shell 31 on the outside of the plasma generator 11 to allow cooling and / or provide a gas-liquid seal. In the embodiment shown in FIG. 1, the outer shell 31 is substantially concentric with the plasma generator 11, with the plasma generator 11 being the inner tube and the outer shell being the outer tube. Holes 32 at the end of the outer shell 31 allow a coolant, such as water, to flow (in the direction shown) to the bottom of the chamber 33 within the outer shell 31 and out the top of the chamber 33. The outer shell 31 also helps seal the plasma generator 11, thereby helping to avoid or reduce any leakage of plasma and gas. The outer shell 31 is preferably RF transparent. Representative examples of suitable materials from which the outer shell 31 can be manufactured include quartz and ceramic materials.

[0106] In some embodiments, product may be continuously or semi-continuously removed from the first reaction chamber region 26 and / or the second reaction chamber region 28 (e.g., removing product from the first reaction chamber region 26 and / or the second reaction chamber region 28). conveyor) (i.e. not a batch operation).

[0107] An outlet port 34 is formed in the second reaction vessel section 14, and a first exhaust line 35 is connected to the outlet port 34. A pressure regulator 36 is connected to the first exhaust line 35, and a second exhaust line 37 is connected to the pressure regulator 36, thereby allowing gases (e.g., nitrogen, argon, and hydrogen) to be exhausted and controlling the internal pressure of the first and second reaction chamber regions 26 and 28. Any suitable pressure regulator (e.g., a needle valve) may be used as the pressure regulator 36.

[0108] In the above discussion, the plasma generator is an inductively coupled plasma generator. Alternatively, as an alternative, the plasma generator may be a DC arc plasma generator (i.e., a plasma generator powered by a DC power source). Those skilled in the art are familiar with DC arc plasma generators, and any such plasma generator may be used. In some embodiments, in the production of compositions and / or aggregates including boron nitride nanotubes having a hexagonal boron nitride structure that is epitaxial to the boron nitride nanotubes, an inductively coupled plasma generator is advantageous (compared to a DC arc plasma generator) because it provides a larger plasma volume, a lower plasma gas velocity, and a longer reaction time. In addition, since there are no electrodes in an inductively coupled plasma generator, the inductively coupled plasma generator may be relatively maintenance-free and no contaminants are introduced from the electrodes into the material being produced (unlike a DC arc plasma generator that must include electrodes).

[0109] The power density and volume of the plasma plume can be adjusted by varying the input power to the plasma generator, by varying the pressure within the plasma generator volume 21, and / or by varying the flow rate of materials (e.g., nitrogen gas, boron powder with nitrogen carrier gas, etc.) supplied to the apparatus 10.

[0110] The apparatus 10 shown in FIG. According to a third aspect (or a fourth aspect) of the present inventive subject matter, a composition (or aggregate) comprising a plurality of independent boron nitride nanotubes, wherein the sum of [1] the total mass of all independent hexagonal boron nitride nanotubes in the composition (or aggregate) and [2] the total mass of all residual boron in the composition (or aggregate) accounts for 35% or less of the mass of the composition (or aggregate); According to a fifth aspect (or sixth aspect) of the present subject matter, a composition (or aggregate) comprising at least 10 independent boron nitride nanotubes having a length of at least 50 nm, wherein 1% or less of the total of [1] independent boron nitride nanotubes having a length of at least 50 nm in the composition (or aggregate) and [2] boron nitride nanotube structures having a length of at least 50 nm in the composition (or aggregate) has at least one defect selected from Dixie cup defects and bamboo defects; and According to a seventh aspect (or an eighth aspect) of the subject matter of the present invention, there is provided a composition (or aggregate) comprising at least 10 individual boron nitride nanotubes, each of which is single-walled, of the sum of [1] individual boron nitride nanotubes having a length of at least 50 nm in the composition (or aggregate) and [2] boron nitride nanotube structures having a length of at least 50 nm in the composition (or aggregate); wherein at least 50% of said sum is single-walled. can be used to prepare

[0111] One specific exemplary embodiment of a method by which epitaxial h-BN / BNNT structures according to the first aspect of the inventive subject matter can be fabricated comprises: 1. The apparatus further comprises: supplying 50 liters per minute of a mixture of nitrogen and hydrogen (96 parts by weight nitrogen and 4 parts by weight hydrogen) to a plasma generator volume 21 of the apparatus 10 shown in FIG. 1 (through a port 20 of the apparatus 10 shown in FIG. 1); the apparatus further comprises a plasma generator 11 having an outer diameter of 3.5 inches; 1, the inner diameter of the plasma generator 11 is 2.0 inches, the length (longitudinal in the orientation shown in FIG. 1) of the plasma generator 11 is 10.0 inches, the outer diameter of the collar region 12 is 3.5 inches, the inner diameter of the collar region 12 is 1.40 inches, the length (longitudinal in the orientation shown in FIG. 1) of the collar region 12 is 3.0 inches, the diameter of the plume opening 22 (the connection section between the plasma generator space 21 and the collar space 23) is 1.38 inches, the reactant feed opening 24 is midway along the length of the collar region 12, the inner diameter of the first reactor section 13 is 8.0 inches, and the first reactor section 14 is 1.2 inches. 1 ) is 24 inches, the inside diameter of second reactor vessel section 14 is 8.0 inches, the length (longitudinal in the orientation shown in FIG. 1 ) of second reactor vessel section 14 is 24 inches (i.e., first reactor vessel section 13 and second reactor vessel section 14 together define a cylindrical chamber area of ​​uniform diameter which, combined with first reaction chamber area 26 and second reaction chamber area 28, is 8 inches in diameter and 48 inches in length), and the diameter of reactant feed opening 24 is 1 / 16 inch; Ionizing the nitrogen and hydrogen in the plasma generating device space 21 by supplying 35 to 45 kW to the electromagnetic wave generating device 16; and feeding 20-90 mg / min of solid elemental boron powder (which is at room temperature prior to entering apparatus 10) entrained in nitrogen gas (e.g., 0.1-10.0 liters per minute) into the color space (through reactant feed opening 24 at the hottest location within apparatus 10); while maintaining the pressure in the first reactor section 13 and the second reactor section 14 within the range of 10 psi to 20 psi (the pressure may vary within this range).

[0112] In this exemplary embodiment, the temperature in at least a portion of the collar region 12 is approximately 8000 K due to the heat provided by the plasma, while the temperatures in the first reactor section 13 and the second reactor section 14 are lower the further away from the collar region 12.

[0113] Epitaxial h-BN / BNNT structures in accordance with the present subject matter are similar to rock candy; continuing the analogy, the boron nitride nanotube structures are the strings and the nucleated and grown hexagonal boron nitride is the sugar.

[0114] The boron and nitrogen ions that are not converted to boron nitride nanotube structures in the hottest zone of the device become supersaturated in the device and accumulate on the boron nitride nanotube structures where they nucleate hexagonal boron nitride structures on the boron nitride nanotube structures (i.e., produce structures having boron and nitrogen atoms nucleated on the boron nitride nanotube structures) and / or grow on the already nucleated boron nitride structures.

[0115] The boron nitride nanotube structures formed according to the exemplary embodiments above generally (eg, 90% or more) have diameters in the range of 3-30 nm. The boron nitride nanotube structures formed according to the exemplary embodiments above generally (eg, 90% or more) have lengths in the range of 10 nm to 50 micrometers.

[0116] The boron nitride nanotube structures formed according to the exemplary embodiments described above and the epitaxially covering hexagonal boron nitride nodules are generally (e.g., 90% or more) between 1 nm and 200 nm thick (and are readily identifiable, e.g., in TEM images).

[0117] The portions of the boron nitride nanotube structure that are not covered by the hexagonal boron nitride structure, and the free-standing boron nitride nanotubes (if present), are very smooth and easily identifiable (e.g., in transmission electron microscope images (i.e., TEM images)).

[0118] The remaining boron portion (in the product of the exemplary embodiment described above) is generally amorphous (and easily identifiable, for example, in a TEM image). A typical product contains 65 parts by weight of epitaxial h-BN / BNNT structures and 35 parts by weight of remaining boron and / or free-standing hexagonal boron nitride (typically containing less than 1 part by weight of free-standing hexagonal boron nitride).

[0119] Products according to the present inventive subject matter exhibit numerous properties that make them useful in a variety of applications. For example, epitaxial h-BN / BNNT structures may be thicker and / or have a rougher exterior than corresponding free-standing boron nitride nanotubes, which allows them to adhere more readily to matrix materials, i.e., provide enhanced physical / mechanical resistance to removal from the matrix material (FIG. 3 is a diagram of an epitaxial h-BN / BNNT structure).

[0120] In addition, the epitaxial h-BN / BNNT structure provides nanonucleation sites for metals to crystallize (e.g., when casting metals with melting points lower than the temperature at which the BNNTs decompose, such as aluminum, magnesium, or titanium).

[0121] In addition, epitaxial h-BN / BNNT structures offer exceptional properties after being subjected to extremely high temperatures (in some cases, hexagonal boron nitride can act as a sacrificial layer for the boron nitride structure it overlies).

[0122] Some embodiments of epitaxial h-BN / BNNT structures according to the present inventive subject matter provide any combination of the advantageous properties described above. Generally, increasing the percentage of hydrogen in the mixture of nitrogen and hydrogen supplied to port 20 of apparatus 10 (i.e., greater than 4 weight percent) increases the amount of epitaxial hexagonal boron nitride structures formed, and decreasing the percentage of hydrogen in the mixture of nitrogen and hydrogen supplied to port 20 of apparatus 10 (i.e., less than 4 weight percent) decreases the amount of epitaxial hexagonal boron nitride structures formed. Although the present subject matter is not limited to any particular theory, it is believed that the hydrogen supplied in the mixture supplied to port 20 provides energy that assists in the nucleation of the hexagonal boron nitride structures on the boron nitride nanotube structures.

[0123] Entraining solid elemental boron powder with nitrogen gas at 0.1 to 10.0 liters per minute and feeding it to the color space through reactant feed opening 24 (having a 1 / 16 inch diameter) equates to a nitrogen gas flow rate of about 53.3 cm / sec to 5330 cm / sec. Although the present subject matter is not limited to any particular theory, it is believed that this high nitrogen gas flow rate allows a significant amount of boron to pass unreacted through the region where the boron nitride nanotube structures are being formed, thereby providing boron that can participate in the nucleation of hexagonal boron nitride on the boron nitride nanotube structures so formed.

[0124] If a larger apparatus is used, the flow rate of the nitrogen gas entrained with the boron feed will be increased to accommodate for the larger reaction zone through which the hydrogen and boron pass unreacted. Similarly, if a larger flow rate of nitrogen and hydrogen is fed to the plasma generator volume 21 (e.g., in a larger apparatus), the power supplied to the electromagnetic wave generator 16 will be increased sufficiently to ionize the nitrogen and hydrogen.

[0125] While the present subject matter is not limited to any particular theory, it is believed that the shrinkage due to the reduced diameter of the plume opening creates flow characteristics that result in the formation of epitaxial h-BN / BNNT structures. It is believed that the small diameter compared to the larger diameter of 26 also contributes to (or provides) the flow properties that lead to the formation of epitaxial h-BN / BNNT structures.

[0126] The above-described exemplary embodiment of the method comprises: According to a third aspect (or a fourth aspect) of the present inventive subject matter, a composition (or aggregate) comprising a plurality of independent boron nitride nanotubes, wherein the sum of [1] the total mass of all independent hexagonal boron nitride nanotubes in the composition (or aggregate) and [2] the total mass of all residual boron in the composition (or aggregate) accounts for 35% or less of the mass of the composition (or aggregate); According to a fifth aspect (or sixth aspect) of the subject matter of the present invention, a composition (or aggregate) comprising at least 10 independent boron nitride nanotubes having a length of at least 50 nm, wherein 1% or less of the total of [1] independent boron nitride nanotubes having a length of at least 50 nm in the composition (or aggregate) and [2] boron nitride nanotube structures having a length of at least 50 nm in the composition (or aggregate) has at least one defect selected from Dixie cup defects and bamboo defects; and / or According to a seventh aspect (or an eighth aspect) of the subject matter of the present invention, there is provided a composition (or aggregate) comprising at least 10 individual boron nitride nanotubes, each of which is single-walled, of the sum of [1] individual boron nitride nanotubes having a length of at least 50 nm in the composition (or aggregate) and [2] boron nitride nanotube structures having a length of at least 50 nm in the composition (or aggregate); wherein at least 50% of said sum is single-walled. It can also be used to prepare

[0127] Thus, in addition, the subject of the invention is: a composition (or aggregate) having an advantageously high purity, e.g., the sum of [1] the total mass of all independent hexagonal boron nitride in the composition (or aggregate) and [2] the total mass of all residual boron in the composition (or aggregate) accounts for 35% or less of the mass of the composition (or aggregate); [1] A composition (or aggregate) having an advantageously high quality in which, of the total of the independent boron nitride nanotubes having a length of at least 50 nm in the composition (or aggregate) and the boron nitride nanotube structures having a length of at least 50 nm in the composition (or aggregate), 1% or less of said total has at least one defect selected from Dixie cup defects and bamboo defects; and / or A composition (or aggregate) having an advantageously high percentage of independent boron nitride nanotubes and boron nitride nanotube structures that are single-walled, e.g., at least 50% of the total of [1] independent boron nitride nanotubes having a length of at least 50 nm in the composition (or aggregate) and [2] boron nitride nanotube structures having a length of at least 50 nm in the composition (or aggregate) are each single-walled; to provide.

[0128] Such compositions or aggregates may have any combination of the advantageous features described above, and may have any of the advantageous features described above of the epitaxial h-BN / BNNT structures according to the present inventive subject matter.

[0129] As noted above, according to a ninth aspect of the present inventive subject matter, there is provided a method of making a composition, the method comprising: providing a mixture of nitrogen gas and hydrogen gas to a first region of the chamber; converting at least a portion of the mixture of nitrogen gas and hydrogen gas into a plasma; providing a mixture of the at least one boron-containing material and the nitrogen gas to a second region of the chamber, thereby contacting the mixture of the at least one boron-containing material and the nitrogen gas with the plasma to form a reaction mixture; converting at least a portion of the mixture into an epitaxial h-BN / BNNT structure; Includes.

[0130] In some embodiments according to the ninth aspect of the present inventive subject matter, which may or may not include any of the other features described herein, as appropriate, the chamber comprises: The first area; Second area; At least the third area; a first connection section providing a connection between the first region and the second region; and a second connection section providing a connection between the second region and the third region; Equipped with the first region has at least one first region cross-sectional area perpendicular to an axis of the chamber extending through the first region, the second region, and the third region; the second region has at least one second region cross-sectional area perpendicular to an axis of the chamber; the third region has at least one third region cross-sectional area perpendicular to an axis of the chamber; the first connection section has at least one first connection section cross-sectional area perpendicular to an axis of the chamber; the second connection section has at least one second connection section cross-sectional area perpendicular to the axis of the chamber; Each first juncture section cross-sectional area is smaller than the first area cross-sectional area and smaller than the second area cross-sectional area; Each second connection section cross-sectional area is smaller than the third region cross-sectional area; And in some such embodiments: the pressure within at least a portion of the third region is at least 10 psi; the pressure within at least a portion of the third region is in the range of 10 to 20 psi; and / or The pressure within at least a portion of the third region is in the range of 15 to 20 psi.

[0131] In some embodiments according to the ninth aspect of the present inventive subject matter, which may or may not include any of the other features described herein, the weight percent of hydrogen gas in the mixture of nitrogen gas and hydrogen gas is in the range of 1 weight percent to 7 weight percent (in some embodiments, at least 2 weight percent, in some embodiments, in the range of 2 weight percent to 7 weight percent, and in some embodiments, 4 weight percent or about 4.0 weight percent).

[0132] In some embodiments according to the ninth aspect of the present inventive subject matter, which may or may not include any of the other features described herein, the weight percent of hydrogen gas in the mixture of nitrogen gas and hydrogen gas is at least 3 mass percent.

[0133] In some embodiments according to the ninth aspect of the present inventive subject matter, which may or may not include any of the other features described herein, the weight percent of hydrogen gas in the mixture of nitrogen gas and hydrogen gas is at least 4 mass percent.

[0134] In some embodiments according to the ninth aspect of the present inventive subject matter, which may or may not include any of the other features described herein, the mixture of nitrogen gas and hydrogen gas is supplied to the first region at a rate of at least 30 liters per minute.

[0135] In some embodiments according to the ninth aspect of the present inventive subject matter, which may or may not include any of the other features described herein, the mixture of nitrogen gas and hydrogen gas is supplied to the first region at a rate of at least 40 liters per minute.

[0136] In some embodiments according to the ninth aspect of the present inventive subject matter, which may or may not include any of the other features described herein, the mixture of nitrogen gas and hydrogen gas is supplied to the first region at a rate of at least 50 liters per minute.

[0137] In some embodiments according to the ninth aspect of the present inventive subject matter, which may or may not include any of the other features described herein, the providing of the mixture of at least one boron-containing material and nitrogen gas to the second region of the chamber comprises providing boron at a rate of at least 20 mg / min.

[0138] In some embodiments according to the ninth aspect of the present inventive subject matter, which may or may not include any of the other features described herein, the providing of the mixture of at least one boron-containing material and nitrogen gas to the second region of the chamber comprises providing boron at a rate in a range of 20 mg / min to 90 mg / min.

[0139] In some embodiments according to the ninth aspect of the present inventive subject matter, which may or may not include any of the other features described herein, the providing of the mixture of at least one boron-containing material and nitrogen gas to the second region of the chamber comprises providing the nitrogen gas at a rate in a range of 0.1 liters per minute to 1.3 liters per minute.

[0140] In some embodiments according to the ninth aspect of the present inventive subject matter, which may or may not include any of the other features described herein, the providing of the mixture of at least one boron-containing material and nitrogen gas to the second region of the chamber comprises providing the nitrogen gas at a rate in a range of 1.3 liters per minute to 8.4 liters per minute.

[0141] In some embodiments according to the ninth aspect of the present inventive subject matter, which may or may not include any of the other features described herein, the converting of at least a portion of the mixture of nitrogen gas and hydrogen gas into a plasma comprises generating electromagnetic waves in a first region.

[0142] In some embodiments according to the ninth aspect of the present inventive subject matter, which may or may not include any of the other features described herein as appropriate, said generating electromagnetic waves comprises supplying high frequency energy to an electromagnetic wave generating device at a power rate of at least 35 kW (in some embodiments, 35-45 kW).

[0143] In some embodiments according to the ninth aspect of the present inventive subject matter, which may or may not include any of the other features described herein as appropriate, said generating electromagnetic waves comprises supplying radio frequency energy to an electromagnetic wave generating device at a power of at least 39 (in some embodiments, 39-45 kW).

[0144] In some embodiments according to the ninth aspect of the present inventive subject matter, which may or may not include any of the other features described herein, the pressure in at least a portion of the chamber is at least 10 psi.

[0145] In some embodiments according to the ninth aspect of the present inventive subject matter, which may or may not include any of the other features described herein, the pressure in at least a portion of the chamber is in the range of 10 to 20 psi.

[0146] In some embodiments according to the ninth aspect of the present inventive subject matter, which may or may not include any of the other features described herein, the pressure in at least a portion of the chamber is in the range of 15 to 20 psi.

[0147] In some embodiments according to the ninth aspect of the inventive subject matter, which may or may not include any of the other features described herein, optionally, the method further comprises contacting at least some of the epitaxial h-BN / BNNT structures with nitric acid; In some such embodiments, the method further includes subjecting at least some of the epitaxial h-BN / BNNT structures to a temperature in the range of 700-900°C.

[0148] In some embodiments according to the ninth aspect of the present inventive subject matter, which may or may not include any of the other features described herein, as appropriate, the method further includes subjecting at least some of the epitaxial h-BN / BNNT structures to a temperature in the range of 700-900° C.

[0149] Example 1 50 liters per minute of a mixture of nitrogen and hydrogen (96 parts by weight nitrogen and 4 parts by weight hydrogen) was fed (through a port) into the plasma generator space of the apparatus shown in Figure 1. The apparatus is further characterized in that the plasma generator outer diameter is 3.5 inches, the plasma generator inner diameter is 2.0 inches, the plasma generator length is 10.0 inches, the collar area outer diameter is 3.5 inches, the collar area inner diameter is 1.40 inches, the collar area length is 3.0 inches, the plume opening (the connection section between the plasma generator space and the collar space) has a diameter of 1.38 inches, a reactant feed opening is midway along the length of the collar area, the first reactor section has an inner diameter of 8.0 inches, the first reactor section has a length of 24 inches, the second reactor section has an inner diameter of 8.0 inches, the second reactor section has a length of 24 inches, and the reactant feed opening has a diameter of 1 / 16 inch; Supply 39 kW to the electromagnetic wave generator to ionize the nitrogen and hydrogen in the plasma generator space. 22 mg / min of solid elemental boron powder (at room temperature prior to entering the apparatus) was fed into the color space through the reactant feed opening in 1.3 liters / min of nitrogen gas; The pressure in the first reactor section and the second reactor section was maintained within a range of 15 psi to 20 psi (i.e., the pressure was varied within this range), and the temperature in at least a portion of the collar region was approximately 8000K.

[0150] FIG. 4 is a TEM image of a representative portion of the product of Example 1, where approximately 30% of the boron nitride nanotube structures were each at least 30% covered by epitaxial hexagonal boron nitride.

[0151] Over 50% of the total free standing boron nitride nanotubes and boron nitride nanotube structures were single walled, with the remainder being double walled and multi walled. Less than 1% of the combined free standing boron nitride nanotubes and boron nitride nanotube structures had Dixie cup or bamboo defects.

[0152] The combined mass of residual boron and free-standing hexagonal boron nitride was less than 35% by mass of the product. Example 2 A mixture of nitrogen and hydrogen (96 parts by weight of nitrogen and 4 parts by weight of hydrogen) at 50 liters per minute Supply (through a port) into the plasma generator space of the same device used in Example 1, Supply 39 kW to the electromagnetic wave generator to ionize the nitrogen and hydrogen in the plasma generator space. 22 mg / min of solid elemental boron powder (at room temperature prior to entering the apparatus) was fed into the color space through the reactant feed opening in 8.4 liters / min of nitrogen gas; The pressure in the first reactor section and the second reactor section was maintained within a range of 15 psi to 20 psi (i.e., the pressure was varied within this range), and the temperature in at least a portion of the collar region was approximately 8000K.

[0153] FIG. 5 is a TEM image of a representative section of the product of Example 2, where approximately 90% of the boron nitride nanotube structures were each at least 30% covered by epitaxial hexagonal boron nitride.

[0154] FIG. 6 is a TEM image of a portion of the product of Example 2, which shows the epitaxial h-BN / BNNT structure. Reference number 61 in the TEM image of FIG. 6 denotes an example of high purity and high quality boron nitride nanotubes.

[0155] Reference number 62 in the TEM image of FIG. 6 indicates an example of unreacted amorphous boron. References 63, 64, and 65 in the TEM image of FIG. 6 refer to examples of epitaxial h-BN / BNNT structures.

[0156] FIG. 7 is a TEM image of a portion of the product of Example 2, showing free-standing hexagonal boron nitride, epitaxial h-BN / BNNT structures, one of which contains an agglomerate of boron nitride nanotube structures.

[0157] Reference number 71 in the TEM image of FIG. 7 indicates examples of free-standing hexagonal boron nitride structures. Reference numeral 72 in the TEM image of FIG. 7 denotes an example of an epitaxial h-BN / BNNT structure (comprising an agglomerate of boron nitride nanotube structures).

[0158] Reference numeral 73 in the TEM image of FIG. 7 denotes an example of an epitaxial h-BN / BNNT structure (containing a single boron nitride nanotube structure). Reference number 74 in the TEM image of FIG. 7 indicates an example of an epitaxial h-BN / BNNT structure (comprising two clusters of boron nitride nanotube structures).

[0159] FIG. 8 is a TEM image of a portion of the product of Example 2, showing bulk boron nitride nanotube structures and epitaxial h-BN / BNNT structures. Reference number 81 in the TEM image of FIG. 8 refers to an example of a free-standing agglomerate of boron nitride nanotubes (ie, agglomerates without nucleation or growth of epitaxial hexagonal boron nitride).

[0160] Reference numeral 82 in the TEM image of FIG. 8 refers to an example of an epitaxial h-BN / BNNT structure (containing boron nitride nucleations on the sides of a bundle of boron nitride nanotube structures).

[0161] FIG. 9 is a TEM image of a portion of the product of Example 2, which shows the epitaxial h-BN / BNNT structure. Reference numeral 91 in the TEM image of FIG. 9 denotes an example of an epitaxial h-BN / BNNT structure (containing a single boron nitride nanotube structure).

[0162] Reference numeral 92 in the TEM image of FIG. 9 denotes an example of an epitaxial h-BN / BNNT structure (comprising an agglomerate of boron nitride nanotube structures). FIG. 10 is a TEM image of a portion of the product of Example 2, showing the remaining boron and epitaxial h-BN / BNNT structures.

[0163] Reference numerals 101 and 102 in the TEM image of FIG. 10 refer to examples of remaining amorphous boron. Reference numeral 103 in the TEM image of FIG. 10 denotes an example of an epitaxial h-BN / BNNT structure.

[0164] Reference numeral 104 in the TEM image of FIG. 10 denotes an example of an epitaxial h-BN / BNNT structure (comprising an agglomerate of boron nitride nanotube structures). FIG. 11 is a TEM image of a portion of the product of Example 2, showing the remaining boron and epitaxial h-BN / BNNT structures.

[0165] Reference numbers 111 and 112 in the TEM image of FIG. 11 refer to examples of remaining amorphous boron. References 113 and 114 in the TEM image of FIG. 11 refer to examples of epitaxial h-BN / BNNT structures.

[0166] FIG. 12 is a TEM image of a portion of the product of Example 2, which shows the epitaxial h-BN / BNNT structure. References 121 and 122 in the TEM image of FIG. 12 refer to examples of epitaxial h-BN / BNNT structures.

[0167] Over 50% of the total free standing boron nitride nanotubes and boron nitride nanotube structures were single walled, with the remainder being double walled and multi walled. Less than 1% of the combined free standing boron nitride nanotubes and boron nitride nanotube structures had Dixie cup or bamboo defects.

[0168] The combined mass of residual boron and free-standing hexagonal boron nitride was less than 35% by mass of the product. FIG. 13 is a TEM image of a free-standing boron nitride nanotube.

[0169] Below is a series of numbered paragraphs, each defining subject matter within the scope of the present subject matter. Section 1. At least a first epitaxial h-BN / BNNT structure; Including, the first epitaxial h-BN / BNNT structure includes at least a first boron nitride nanotube structure and at least a first hexagonal boron nitride structure; the first hexagonal boron nitride structure is epitaxial to the first boron nitride nanotube structure; composition.

[0170] Section 2. [1] The total of the amount of independent boron nitride nanotubes having a length of at least 50 nm in the composition and the amount of boron nitride nanotube structures having a length of at least 50 nm in the composition is at least 10; [1] For each of the boron nitride nanotube structures in an amount that is at least 10% of the sum of the amount of independent boron nitride nanotubes having a length of at least 50 nm in the composition and the amount of the boron nitride nanotube structures in the composition having a length of at least 50 nm, hand: the boron nitride nanotube structure has a length of at least 50 nm, and at least 10% in total of an outermost wall of the boron nitride nanotube structure is covered by hexagonal boron nitride structures, each of which is epitaxial to the boron nitride nanotube structure; 2. The composition of claim 1.

[0171] Section 3. [1] For each of the boron nitride nanotube structures in an amount that is at least 30% of the sum of the amount of individual boron nitride nanotubes having a length of at least 50 nm in the composition and the amount of boron nitride nanotube structures having a length of at least 50 nm in the composition: the boron nitride nanotube structure has a length of at least 50 nm, and at least 30% in total of an outermost wall of the boron nitride nanotube structure is covered by hexagonal boron nitride structures, each of which is epitaxial to the boron nitride nanotube structure; Item 2. The composition of claim 2.

[0172] Section 4. [1] For each of the boron nitride nanotube structures in an amount that is at least 80% of the sum of the amount of individual boron nitride nanotubes having a length of at least 50 nm in the composition and the amount of boron nitride nanotube structures having a length of at least 50 nm in the composition: the boron nitride nanotube structure has a length of at least 50 nm, and at least 30% in total of an outermost wall of the boron nitride nanotube structure is covered by hexagonal boron nitride structures, each of which is epitaxial to the boron nitride nanotube structure; Item 2. The composition of claim 2.

[0173] Clause 5. The total amount of each of [1] independent boron nitride nanotube agglomerates having a length of at least 50 nm in the composition, [2] boron nitride nanotube structure agglomerates having a length of at least 50 nm in the composition, [3] boron nitride nanotube structure / independent boron nitride nanotube agglomerates having a length of at least 50 nm in the composition, [4] independent boron nitride nanotubes that are not agglomerates and have a length of at least 50 nm in the composition, and [5] boron nitride nanotube structure that are not agglomerates and have a length of at least 50 nm in the composition is at least 10; [2] boron nitride nanotube structure chunks having a length of at least 50 nm in the composition, [3] boron nitride nanotube structures / independent boron nitride nanotube chunks having a length of at least 50 nm in the composition, and [5] boron nitride nanotube structures in the composition that are not chunks and have a length of at least 50 nm, each in an amount that is at least 30% of the total: [2] At least 10% of the outer atoms of the boron nitride nanotube structure agglomerate, [3] the boron nitride nanotube structure / independent boron nitride nanotube agglomerate, or [5] the boron nitride nanotube structure that is not an agglomerate, in total, [2] a boron nitride nanotube structure mass, [3] a boron nitride nanotube structure / independent boron nitride nanotube mass, or [5] a boron nitride nanotube structure that is not a mass and is covered by a hexagonal boron nitride structure that is epitaxial to the boron nitride nanotube structure. 2. The composition of claim 1.

[0174] Section 6. [2] Boron nitride nanotube structure chunks having a length of at least 50 nm in the composition, [3] Boron nitride nanotube structure / independent boron nitride nanotube chunks having a length of at least 50 nm in the composition, and [5] Boron nitride nanotube structure that is not agglomerated and has a length of at least 50 nm in the composition, for each of the amounts that are at least 30% of the total: [2] a boron nitride nanotube structure agglomerate, [3] a boron nitride nanotube structure / independent boron nitride nanotube agglomerate, or [5] a boron nitride nanotube structure that is not an agglomerate, at least 30% of the outer atoms are [2] a boron nitride nanotube structure mass, [3] a boron nitride nanotube structure / independent boron nitride nanotube mass, or [5] a boron nitride nanotube structure that is not a mass and is covered by a hexagonal boron nitride structure that is epitaxial to the boron nitride nanotube structure. Item 5. The composition of claim 5.

[0175] Section 7. [2] Boron nitride nanotube structure chunks having a length of at least 50 nm in the composition, [3] Boron nitride nanotube structures / independent boron nitride nanotube chunks having a length of at least 50 nm in the composition, and [5] Boron nitride nanotube structures that are not chunks and have a length of at least 50 nm in the composition, each in an amount that is at least 80% of the total: [2] a boron nitride nanotube structure agglomerate, [3] a boron nitride nanotube structure / independent boron nitride nanotube agglomerate, or [5] a boron nitride nanotube structure that is not an agglomerate, at least 30% of the outer atoms are [2] a boron nitride nanotube structure mass, [3] a boron nitride nanotube structure / independent boron nitride nanotube mass, or [5] a boron nitride nanotube structure that is not a mass and is covered by a hexagonal boron nitride structure that is epitaxial to the boron nitride nanotube structure. Item 5. The composition of claim 5.

[0176] Clause 8. A monolithic structure comprising at least a first epitaxial h-BN / BNNT structure; the first epitaxial h-BN / BNNT structure includes at least a first boron nitride nanotube structure and at least a first hexagonal boron nitride structure; the first hexagonal boron nitride structure is epitaxial to the boron nitride nanotube structure; The monolithic structure has a first dimension of at least 100 nm and a second dimension of at least 100 nm, the second dimension being perpendicular to the first dimension. Aggregates.

[0177] Section 9. For each boron nitride nanotube structure in the monolithic structure in an amount that is at least 10% of the sum of [1] the amount of independent boron nitride nanotubes having a length of at least 50 nm in the monolithic structure and [2] the amount of boron nitride nanotube structures having a length of at least 50 nm in the monolithic structure: a total of at least 10% of the outermost wall of the boron nitride nanotube structure is covered by hexagonal boron nitride structures, each of which is epitaxial to the boron nitride nanotube structure; 9. The aggregate according to clause 8.

[0178] Section 10. For each boron nitride nanotube structure in the monolithic structure in an amount that is at least 30% of the sum of the amount of independent boron nitride nanotubes having a length of at least 50 nm in the monolithic structure and the amount of boron nitride nanotube structures having a length of at least 50 nm in the monolithic structure: a total of at least 30% of the outermost wall of the boron nitride nanotube structure is covered by hexagonal boron nitride structures, each of which is epitaxial to the boron nitride nanotube structure; Item 9. The aggregate according to item 9.

[0179] Section 11. For each boron nitride nanotube structure in the monolithic structure in an amount that is at least 80% of the sum of the amount of independent boron nitride nanotubes having a length of at least 50 nm in the monolithic structure and the amount of boron nitride nanotube structures having a length of at least 50 nm in the monolithic structure: a total of at least 30% of the outermost wall of the boron nitride nanotube structure is covered by hexagonal boron nitride structures, each of which is epitaxial to the boron nitride nanotube structure; Item 9. The aggregate according to item 9.

[0180] Section 12. [2] Boron nitride nanotube structure mass having a length of at least 50 nm in a monolithic structure, [3] Boron nitride nanotube structure / independent boron nitride nanotube mass having a length of at least 50 nm in a monolithic structure, and [5] Boron nitride nanotube structure not massed and having a length of at least 50 nm in a monolithic structure, For each of the amounts that is at least 10% of the sum of the respective amounts of [1] individual boron nitride nanotube chunks having a length of at least 50 nm in a monolithic structure, [2] boron nitride nanotube structure chunks having a length of at least 50 nm in a monolithic structure, [3] boron nitride nanotube structure / individual boron nitride nanotube chunks having a length of at least 50 nm in a monolithic structure, [4] individual boron nitride nanotubes that are not chunks and have a length of at least 50 nm in a monolithic structure, and [5] boron nitride nanotube structure that is not chunks and has a length of at least 50 nm in a monolithic structure: [2] At least 10% of the outer atoms of the boron nitride nanotube structure agglomerate, [3] the boron nitride nanotube structure / independent boron nitride nanotube agglomerate, or [5] the boron nitride nanotube structure that is not an agglomerate, in total, [2] a boron nitride nanotube structure mass, [3] a boron nitride nanotube structure / independent boron nitride nanotube mass, or [5] a boron nitride nanotube structure that is not a mass and is covered by a hexagonal boron nitride structure that is epitaxial to the boron nitride nanotube structure. 9. The aggregate according to clause 8.

[0181] Section 13. [2] Boron nitride nanotube structure mass having a length of at least 50 nm in a monolithic structure, [3] Boron nitride nanotube structure / independent boron nitride nanotube mass having a length of at least 50 nm in a monolithic structure, and [5] Boron nitride nanotube structure not massed and having a length of at least 50 nm in a monolithic structure, For each of the amounts that is at least 30% of the sum of the respective amounts of [1] individual boron nitride nanotube chunks having a length of at least 50 nm in a monolithic structure, [2] boron nitride nanotube structure chunks having a length of at least 50 nm in a monolithic structure, [3] boron nitride nanotube structure / individual boron nitride nanotube chunks having a length of at least 50 nm in a monolithic structure, [4] individual boron nitride nanotubes that are not chunks and have a length of at least 50 nm in a monolithic structure, and [5] boron nitride nanotube structure that is not chunks and has a length of at least 50 nm in a monolithic structure: [2] a boron nitride nanotube structure agglomerate, [3] a boron nitride nanotube structure / independent boron nitride nanotube agglomerate, or [5] a boron nitride nanotube structure that is not an agglomerate, at least 30% of the outer atoms are [2] a boron nitride nanotube structure mass, [3] a boron nitride nanotube structure / independent boron nitride nanotube mass, or [5] a boron nitride nanotube structure that is not a mass and is covered by a hexagonal boron nitride structure that is epitaxial to the boron nitride nanotube structure. 13. The aggregate of claim 12.

[0182] Section 14. [2] Boron nitride nanotube structure mass having a length of at least 50 nm in a monolithic structure, [3] Boron nitride nanotube structure / independent boron nitride nanotube mass having a length of at least 50 nm in a monolithic structure, and [5] Boron nitride nanotube structure not massed and having a length of at least 50 nm in a monolithic structure, For each of the amounts that is at least 80% of the sum of the respective amounts of [1] individual boron nitride nanotube chunks having a length of at least 50 nm in a monolithic structure, [2] boron nitride nanotube structure chunks having a length of at least 50 nm in a monolithic structure, [3] boron nitride nanotube structure / individual boron nitride nanotube chunks having a length of at least 50 nm in a monolithic structure, [4] individual boron nitride nanotubes that are not chunks and have a length of at least 50 nm in a monolithic structure, and [5] boron nitride nanotube structure that is not chunks and has a length of at least 50 nm in a monolithic structure: [2] a boron nitride nanotube structure agglomerate, [3] a boron nitride nanotube structure / independent boron nitride nanotube agglomerate, or [5] a boron nitride nanotube structure that is not an agglomerate, at least 30% of the outer atoms are [2] a boron nitride nanotube structure mass, [3] a boron nitride nanotube structure / independent boron nitride nanotube mass, or [5] a boron nitride nanotube structure that is not a mass and is covered by a hexagonal boron nitride structure that is epitaxial to the boron nitride nanotube structure. 13. The aggregate of claim 12.

[0183] Clause 15. A composition comprising: Multiple independent boron nitride nanotubes, Including, [1] The sum of the total mass of all independent hexagonal boron nitride in the composition and [2] the total mass of all residual boron in the composition accounts for 35% or less of the mass of the composition; composition.

[0184] Clause 16. The composition of clause 15, wherein the sum of [1] the total mass of all independent hexagonal boron nitride in the composition and [2] the total mass of all residual boron in the composition constitutes 25% or less by mass of the composition.

[0185] Section 17. A monolithic structure comprising a plurality of independent boron nitride nanotubes; Including, the monolithic structure has a first dimension of at least 100 nm and a second dimension of at least 100 nm, the second dimension being perpendicular to the first dimension; [1] The total mass of independent hexagonal boron nitride in the monolithic structure and [2] the total mass of all residual boron in the monolithic structure constitute 35% or less of the mass of the monolithic structure; Aggregates.

[0186] Clause 18. The aggregate of clause 17, wherein the sum of the total mass of all independent hexagonal boron nitride in the aggregate and the total mass of all residual boron in the aggregate constitutes 25% or less of the mass of the aggregate.

[0187] Clause 19. A composition comprising: at least 10 independent boron nitride nanotubes having a length of at least 50 nm; Including, [1] Among the total of the independent boron nitride nanotubes having a length of at least 50 nm in the composition and [2] the boron nitride nanotube structures having a length of at least 50 nm in the composition, 1% or less of the total is selected from Dixie cup defects and bamboo defects. having at least one defect selected from the group consisting of composition.

[0188] Section 20. A monolithic structure comprising a plurality of independent boron nitride nanotubes; Including, the monolithic structure has a first dimension of at least 100 nm and a second dimension of at least 100 nm, the second dimension being perpendicular to the first dimension; [1] Among the total of independent boron nitride nanotubes having a length of at least 50 nm in a monolithic structure and [2] boron nitride nanotube structures having a length of at least 50 nm in a monolithic structure, 1% or less of the total has at least one defect selected from Dixie cup defects and bamboo defects. Aggregates.

[0189] Clause 21. A composition comprising: at least 10 independent boron nitride nanotubes; Including, [1] Among the total of independent boron nitride nanotubes having a length of at least 50 nm in the composition and [2] boron nitride nanotube structures having a length of at least 50 nm in the composition, at least 50% of said total are each single-walled; composition.

[0190] Clause 22. The composition of clause 21, wherein at least a portion of said sum of [1] independent boron nitride nanotubes in the composition having a length of at least 50 nm and [2] boron nitride nanotube structures in the composition having a length of at least 50 nm that is single-walled is present in an independent boron nitride nanotube agglomerate, a boron nitride nanotube structure agglomerate, or a boron nitride nanotube structure / independent boron nitride nanotube agglomerate.

[0191] Clause 23. The composition of clause 21, wherein between 50 and 60 percent of the total of [1] the individual boron nitride nanotubes in the composition having a length of at least 50 nm and [2] the boron nitride nanotube structures in the composition having a length of at least 50 nm are each single-walled.

[0192] Clause 24. A monolithic structure comprising at least one free-standing boron nitride nanotube; Including, the monolithic structure has a first dimension of at least 100 nm and a second dimension of at least 100 nm, the second dimension being perpendicular to the first dimension; [1] Among the total of independent boron nitride nanotubes having a length of at least 50 nm in a monolithic structure and [2] boron nitride nanotube structures having a length of at least 50 nm in a monolithic structure, at least 50% of the total are each single-walled; Aggregates.

[0193] Clause 25. The aggregate of clause 24, wherein at least a portion of said sum of [1] independent boron nitride nanotubes having a length of at least 50 nm in a monolithic structure and [2] boron nitride nanotube structures having a length of at least 50 nm in a monolithic structure that is a single wall is present in an independent boron nitride nanotube agglomerate, a boron nitride nanotube structure agglomerate, or a boron nitride nanotube structure / independent boron nitride nanotube agglomerate.

[0194] Section 26. [1] Of the total of independent boron nitride nanotubes having a length of at least 50 nm in a monolithic structure and [2] of boron nitride nanotube structures having a length of at least 50 nm in a monolithic structure, 50 to 60 percent of said total are single-walled. 25. The aggregate according to claim 24.

[0195] Clause 27. The composition of any one of clauses 1-7, 19, and 21, wherein the combined mass of the epitaxial h-BN / BNNT structures in the composition accounts for at least 65% of the mass of the composition.

[0196] Clause 28. The composition of clause 27, wherein the combined mass of the epitaxial h-BN / BNNT structures in the composition accounts for at least 75% of the mass of the composition. Clause 29. The aggregate of any one of clauses 8-14, 20, and 24, wherein the combined mass of the epitaxial h-BN / BNNT structures in the composition accounts for at least 65% of the mass of the monolithic structure.

[0197] Clause 30. The aggregate of clause 29, wherein the combined mass of the epitaxial h-BN / BNNT structures in the composition accounts for at least 75% of the mass of the monolithic structure. Clause 31. The composition of any one of clauses 1-7, 15, 16, 19, 21-23, 27, and 28, wherein at least 10 wt.% of the composition comprises hexagonal boron nitride structures that are each epitaxial to the boron nitride nanotube structures.

[0198] Clause 32. The aggregate of any one of clauses 8-14, 17, 18, 20, 24-26, 29, and 30, wherein at least 10% by weight of the monolithic structure comprises hexagonal boron nitride structures that are each epitaxial to the boron nitride nanotube structures.

[0199] Clause 33. The composition of any one of clauses 1-7, 15, 16, 19, 21-23, 27, 28, and 31, wherein for each of at least 10% of the atoms in the composition, the atoms are present in a hexagonal boron nitride structure that is epitaxial to a boron nitride nanotube structure in the composition.

[0200] Clause 34. The aggregate of any one of clauses 8-14, 17, 18, 20, 24-26, 29, 30, and 32, wherein for each of at least 10% of the atoms in the monolithic structure, the atoms are present in a hexagonal boron nitride structure that is epitaxial to a boron nitride nanotube structure in the composition.

[0201] Clause 35. The composition of any one of clauses 1-7, 27, 28, 31, and 33, wherein the sum of [1] the combined mass of all independent hexagonal boron nitride in the composition and [2] the combined mass of all amorphous boron in the composition accounts for less than 35% by mass of the composition.

[0202] Clause 36. The aggregate of any one of clauses 8-14, 29, 30, 32, and 34, wherein the sum of the combined mass of all of the free-standing hexagonal boron nitride in the monolithic structure and the combined mass of all of the amorphous boron in the monolithic structure constitutes less than 35% of the mass of the monolithic structure.

[0203] Clause 37. The composition of any one of clauses 1-7, 15, 16, 27, 28, 31, 33, and 35, wherein 1% or less of the sum of [1] the independent boron nitride nanotubes in the composition having a length of at least 50 nm and [2] the boron nitride nanotube structures in the composition having a length of at least 50 nm has at least one defect selected from Dixie cup defects and bamboo defects.

[0204] Section 38. [1] Individual boron nitride nanotubes having a length of at least 50 nm in a monolithic structure and [2] Individual boron nitride nanotubes having a length of at least 50 nm in a monolithic structure 37. The aggregate of any one of clauses 8-14, 17, 18, 29, 30, 32, 34, and 36, wherein 1% or less of the aggregate, together with the tube structure, has at least one defect selected from among Dixie cup defects and bamboo defects.

[0205] Clause 39. The composition of any one of clauses 1-7, 15, 16, 19, 27, 28, 31, 33, 35, and 37, wherein at least 50 percent of the sum of [1] independent boron nitride nanotubes in the composition having a length of at least 50 nm and [2] boron nitride nanotube structures in the composition having a length of at least 50 nm are each single-walled.

[0206] Clause 40. The aggregate of any one of clauses 8-14, 17, 18, 20, 29, 30, 32, 34, 36, and 38, wherein at least 50 percent of the sum of [1] independent boron nitride nanotubes having a length of at least 50 nm in the monolithic structure and [2] boron nitride nanotube structures having a length of at least 50 nm in the monolithic structure are each single-walled.

[0207] Clause 41. The composition of any one of clauses 15, 16, 27, 28, 31, 33, 35, 37, and 39, wherein the free-standing hexagonal boron nitride comprises 1 weight percent or less of the composition.

[0208] Clause 42. The aggregate of any one of clauses 17, 18, 29, 30, 32, 34, 36, 38, and 40, wherein the independent hexagonal boron nitride particles comprise 1 mass percent or less of the aggregate.

[0209] Clause 43. A method for producing a composition comprising: providing a mixture of nitrogen gas and hydrogen gas to a first region of the chamber; converting at least a portion of the mixture of nitrogen gas and hydrogen gas into a plasma; providing a mixture of the at least one boron-containing material and the nitrogen gas to a second region of the chamber, thereby contacting the mixture of the at least one boron-containing material and the nitrogen gas with the plasma to form a reaction mixture; converting at least a portion of the mixture into an epitaxial h-BN / BNNT structure; A method comprising:

[0210] Section 44. Chambers: The first area; Second area; At least the third area; a first connection section providing a connection between the first region and the second region; and a second connection section providing a connection between the second region and the third region; Equipped with the first region has at least one first region cross-sectional area perpendicular to an axis of the chamber extending through the first region, the second region, and the third region; the second region has at least one second region cross-sectional area perpendicular to an axis of the chamber; the third region has at least one third region cross-sectional area perpendicular to an axis of the chamber; the first connection section has at least one first connection section cross-sectional area perpendicular to an axis of the chamber; The second connection section has at least one second axially extending perpendicular to the axis of the chamber. A connection section cross-sectional area, Each first juncture section cross-sectional area is smaller than the first area cross-sectional area and smaller than the second area cross-sectional area; Each second connection section cross-sectional area is smaller than the third region cross-sectional area; 44. The method according to claim 43.

[0211] Clause 45. The method of clause 44, wherein the pressure within at least a portion of the third region is at least 10 psi. Clause 46. The method of clause 44, wherein the pressure within at least a portion of the third region is within the range of 10 to 20 psi.

[0212] Clause 47. The method of clause 44, wherein the pressure within at least a portion of the third region is within the range of 15 to 20 psi. Clause 48. The method of any one of clauses 43-47, wherein the weight percentage of hydrogen gas in the mixture of nitrogen gas and hydrogen gas is at least 2 weight percent.

[0213] Clause 49. The method of any one of clauses 43-47, wherein the weight percentage of hydrogen gas in the mixture of nitrogen gas and hydrogen gas is at least 3 weight percent. Clause 50. The method of any one of clauses 43-47, wherein the weight percent of hydrogen gas in the mixture of nitrogen gas and hydrogen gas is at least 4 weight percent.

[0214] Clause 51. The method of any one of clauses 43-50, wherein the mixture of nitrogen gas and hydrogen gas is supplied to the first region at a rate of at least 30 liters per minute. Clause 52. The method of any one of clauses 43-50, wherein the mixture of nitrogen gas and hydrogen gas is supplied to the first region at a rate of at least 40 liters per minute.

[0215] Clause 53. The method of any one of clauses 43-50, wherein the mixture of nitrogen gas and hydrogen gas is supplied to the first region at a rate of at least 50 liters per minute. Clause 54. The method of any one of clauses 43-53, wherein said providing a mixture of at least one boron-containing material and nitrogen gas to the second region of the chamber includes providing boron at a rate of at least 20 mg / min.

[0216] Clause 55. The method of any one of clauses 43-53, wherein said providing a mixture of at least one boron-containing material and nitrogen gas to the second region of the chamber includes providing boron at a rate in the range of 20 mg / min to 90 mg / min.

[0217] Clause 56. The method of any one of clauses 43-55, wherein said providing the mixture of at least one boron-containing material and nitrogen gas to the second region of the chamber comprises providing nitrogen gas at a rate in the range of 0.1 liters per minute to 1.3 liters per minute.

[0218] Clause 57. The method of any one of clauses 43-55, wherein said providing the mixture of at least one boron-containing material and nitrogen gas to the second region of the chamber includes providing nitrogen gas at a rate in the range of 1.3 liters per minute to 8.4 liters per minute.

[0219] Clause 58. The method of any one of clauses 43-57, wherein said converting at least a portion of the mixture of nitrogen gas and hydrogen gas into a plasma comprises generating electromagnetic waves in a first region.

[0220] Clause 59. The method of clause 58, wherein said generating electromagnetic waves comprises supplying high frequency energy to an electromagnetic wave generator at a power amount of at least 35 kW. Clause 60. The method of clause 58, wherein said generating electromagnetic waves comprises supplying high frequency energy to an electromagnetic wave generating device with a power amount of at least 39 kW.

[0221] Clause 61. The method of any one of clauses 43-60, wherein the method further comprises contacting at least some of the epitaxial h-BN / BNNT structures with nitric acid. Clause 62. The method of any one of clauses 43-61, wherein the method further comprises subjecting at least some of the epitaxial h-BN / BNNT structures to a temperature in the range of 700-900°C.

Claims

1. A composition comprising at least a first h-BN / BNNT structure, the first h-BN / BNNT structure includes at least a first boron nitride nanotube structure and at least a first hexagonal boron nitride structure; Where: [1] The total of the amount of independent boron nitride nanotubes having a length of at least 50 nm in the composition and the amount of boron nitride nanotube structures having a length of at least 50 nm in the composition is at least 10; [1] for each of the boron nitride nanotube structures in an amount that is at least 10% of the sum of the amount of individual boron nitride nanotubes having a length of at least 50 nm in the composition and the amount of boron nitride nanotube structures having a length of at least 50 nm in the composition, The boron nitride nanotube structure has a length of at least 50 nm, and at least 10% in total of the outermost wall of the boron nitride nanotube structure is covered by the hexagonal boron nitride structure. composition.

2. [1] for each of the boron nitride nanotube structures in an amount that is at least 30% of the sum of the amount of individual boron nitride nanotubes having a length of at least 50 nm in the composition and the amount of boron nitride nanotube structures having a length of at least 50 nm in the composition, The boron nitride nanotube structure has a length of at least 50 nm, and at least 30% in total of the outermost wall of the boron nitride nanotube structure is covered by the hexagonal boron nitride structure. The composition of claim 1.

3. [1] for each of the boron nitride nanotube structures in an amount that is at least 80% of the sum of the amount of independent boron nitride nanotubes having a length of at least 50 nm in the composition and the amount of boron nitride nanotube structures having a length of at least 50 nm in the composition, The boron nitride nanotube structure has a length of at least 50 nm, and at least 30% in total of the outermost wall of the boron nitride nanotube structure is covered by the hexagonal boron nitride structure. The composition of claim 1.

4. the total amount of each of the following in the composition is at least 10: [1] independent boron nitride nanotube clumps having a length of at least 50 nm; [2] boron nitride nanotube structure clumps having a length of at least 50 nm; [3] boron nitride nanotube structure / independent boron nitride nanotube clumps having a length of at least 50 nm; [4] independent boron nitride nanotubes that are not clumps and have a length of at least 50 nm in the composition; and [5] boron nitride nanotube structure that are not clumps and have a length of at least 50 nm in the composition; [2] boron nitride nanotube structure chunks having a length of at least 50 nm in the composition, [3] boron nitride nanotube structures / independent boron nitride nanotube chunks having a length of at least 50 nm in the composition, and [5] boron nitride nanotube structures in the composition that are not chunks and have a length of at least 50 nm, each of which is at least 30% of the total, [2] a boron nitride nanotube structure mass, [3] a boron nitride nanotube structure / independent boron nitride nanotube mass, or [5] at least 10% in total of the outer atoms of a boron nitride nanotube structure that is not a mass is covered by a hexagonal boron nitride structure; A composition according to any one of claims 1 to 3.

5. 11. An aggregate comprising a monolithic structure comprising a composition comprising at least a first h-BN / BNNT structure according to claim 1, the monolithic structure has a first dimension of at least 100 nm and a second dimension of at least 100 nm, the second dimension being perpendicular to the first dimension; Aggregates.

6. [2] A boron nitride nanotube structure mass having a length of at least 50 nm in a monolithic structure, [3] A boron nitride nanotube structure / independent boron nitride nanotube mass having a length of at least 50 nm in a monolithic structure, and [5] A boron nitride nanotube structure that is not a mass and has a length of at least 50 nm in a monolithic structure, For each of the amounts that is at least 10% of the sum of the respective amounts of [1] independent boron nitride nanotube chunks in a monolithic structure having a length of at least 50 nm, [2] boron nitride nanotube structure chunks in a monolithic structure having a length of at least 50 nm, [3] boron nitride nanotube structure / independent boron nitride nanotube chunks in a monolithic structure having a length of at least 50 nm, [4] independent boron nitride nanotubes that are not clumps and have a length of at least 50 nm in a monolithic structure, and [5] boron nitride nanotube structure that is not clumps and has a length of at least 50 nm in a monolithic structure: [2] a boron nitride nanotube structure mass, [3] a boron nitride nanotube structure / independent boron nitride nanotube mass, or [5] a boron nitride nanotube structure that is not a mass, the total of at least 10% of the outer atoms of the boron nitride nanotube structure is [2] A boron nitride nanotube structure mass, [3] A boron nitride nanotube structure / independent boron nitride nanotube mass, or [5] A boron nitride nanotube structure that is not a mass and is covered by a hexagonal boron nitride structure. The aggregate of claim 5.

7. At least a first epitaxial h-BN / BNNT structure; and At least one metal, A composition comprising: the first epitaxial h-BN / BNNT structure includes at least a first boron nitride nanotube structure and at least a first hexagonal boron nitride structure; the first hexagonal boron nitride structure is epitaxial to the first boron nitride nanotube structure; wherein atoms in the first hexagonal boron nitride structure are epitaxially arranged with respect to atoms in the first boron nitride nanotube structure closest to the first hexagonal boron nitride structure; the at least one metal is adhered to the first epitaxial h-BN / BNNT structure; composition.

8. 8. The composition of claim 7, wherein the at least one metal comprises at least one atom selected from aluminum, magnesium, and titanium.

9. [1] The total of the amount of independent boron nitride nanotubes having a length of at least 50 nm in the composition and the amount of boron nitride nanotube structures having a length of at least 50 nm in the composition is at least 10; [1] for each of the boron nitride nanotube structures in an amount that is at least 10% of the sum of the amount of individual boron nitride nanotubes having a length of at least 50 nm in the composition and the amount of boron nitride nanotube structures having a length of at least 50 nm in the composition, the boron nitride nanotube structure has a length of at least 50 nm, and at least 10% in total of an outermost wall of the boron nitride nanotube structure is covered by hexagonal boron nitride structures, each of which is epitaxial to the boron nitride nanotube structure; 9. The composition according to claim 7 or 8.

10. [1] The total of the amount of independent boron nitride nanotubes having a length of at least 50 nm in the composition and the amount of boron nitride nanotube structures having a length of at least 50 nm in the composition is at least 10; [1] for each of the boron nitride nanotube structures in an amount that is at least 30% of the sum of the amount of individual boron nitride nanotubes having a length of at least 50 nm in the composition and the amount of boron nitride nanotube structures having a length of at least 50 nm in the composition, the boron nitride nanotube structure has a length of at least 50 nm, and a total of at least 30% of an outermost wall of the boron nitride nanotube structure is covered by hexagonal boron nitride structures, each of which is epitaxial to the boron nitride nanotube structure; 9. The composition according to claim 7 or 8.

11. the total amount of each of the following in the composition is at least 10: [1] independent boron nitride nanotube clumps having a length of at least 50 nm; [2] boron nitride nanotube structure clumps having a length of at least 50 nm; [3] boron nitride nanotube structure / independent boron nitride nanotube clumps having a length of at least 50 nm; [4] independent boron nitride nanotubes that are not clumps and have a length of at least 50 nm in the composition; and [5] boron nitride nanotube structure that are not clumps and have a length of at least 50 nm in the composition; [2] boron nitride nanotube structure chunks having a length of at least 50 nm in the composition, [3] boron nitride nanotube structures / independent boron nitride nanotube chunks having a length of at least 50 nm in the composition, and [5] boron nitride nanotube structures in the composition that are not chunks and have a length of at least 50 nm, each of which is at least 30% of the total, [2] a boron nitride nanotube structure mass, [3] a boron nitride nanotube structure / independent boron nitride nanotube mass, or [5] a boron nitride nanotube structure that is not a mass, the total of at least 10% of the outer atoms of the boron nitride nanotube structure is [2] the boron nitride nanotube structure mass, [3] the boron nitride nanotube structure / independent boron nitride nanotube mass, or [5] the boron nitride nanotube structure in the non-mass boron nitride nanotube structure is covered by a hexagonal boron nitride structure, each of which is epitaxial to the boron nitride nanotube structure. A composition according to any one of claims 7 to 10.

12. 12. An aggregate comprising a composition comprising at least a first monolithic structure comprising a composition comprising at least a first epitaxial h-BN / BNNT structure according to any one of claims 7 to 11, the monolithic structure has a first dimension of at least 100 nm and a second dimension of at least 100 nm, the second dimension being perpendicular to the first dimension; Aggregates.

13. [2] A boron nitride nanotube structure mass having a length of at least 50 nm in a monolithic structure, [3] A boron nitride nanotube structure / independent boron nitride nanotube mass having a length of at least 50 nm in a monolithic structure, and [5] A boron nitride nanotube structure that is not a mass and has a length of at least 50 nm in a monolithic structure, For each of the amounts that is at least 10% of the sum of the respective amounts of [1] independent boron nitride nanotube chunks in a monolithic structure having a length of at least 50 nm, [2] boron nitride nanotube structure chunks in a monolithic structure having a length of at least 50 nm, [3] boron nitride nanotube structure / independent boron nitride nanotube chunks in a monolithic structure having a length of at least 50 nm, [4] independent boron nitride nanotubes that are not clumps and have a length of at least 50 nm in a monolithic structure, and [5] boron nitride nanotube structure that is not clumps and has a length of at least 50 nm in a monolithic structure: [2] a boron nitride nanotube structure mass, [3] a boron nitride nanotube structure / independent boron nitride nanotube mass, or [5] a boron nitride nanotube structure that is not a mass, the total of at least 10% of the outer atoms of the boron nitride nanotube structure is [2] A boron nitride nanotube structure mass, [3] A boron nitride nanotube structure / independent boron nitride nanotube mass, or [5] A boron nitride nanotube structure that is not a mass and is covered by a hexagonal boron nitride structure. The aggregate of claim 12.

14. 1. A material comprising at least a first hexagonal boron nitride structure and at least a first boron nitride nanotube structure, Atoms in the first hexagonal boron nitride structure are epitaxially arranged with respect to atoms in the first boron nitride nanotube structure closest to the first hexagonal boron nitride structure. material.

15. [1] The total of the amount of independent boron nitride nanotubes having a length of at least 50 nm in the composition and the amount of boron nitride nanotube structures having a length of at least 50 nm in the composition is at least 10; [1] for each of the boron nitride nanotube structures in an amount that is at least 10% of the sum of the amount of individual boron nitride nanotubes having a length of at least 50 nm in the composition and the amount of boron nitride nanotube structures having a length of at least 50 nm in the composition, the boron nitride nanotube structure has a length of at least 50 nm, and at least 10% in total of an outermost wall of the boron nitride nanotube structure is covered by hexagonal boron nitride structures, each of which is epitaxial to the boron nitride nanotube structure; The composition of claim 14.

16. [1] The total of the amount of independent boron nitride nanotubes having a length of at least 50 nm in the composition and the amount of boron nitride nanotube structures having a length of at least 50 nm in the composition is at least 10; [1] for each of the boron nitride nanotube structures in an amount that is at least 30% of the sum of the amount of individual boron nitride nanotubes having a length of at least 50 nm in the composition and the amount of boron nitride nanotube structures having a length of at least 50 nm in the composition, the boron nitride nanotube structure has a length of at least 50 nm, and a total of at least 30% of an outermost wall of the boron nitride nanotube structure is covered by hexagonal boron nitride structures, each of which is epitaxial to the boron nitride nanotube structure; The composition of claim 14.

17. the total amount of each of the following in the composition is at least 10: [1] independent boron nitride nanotube clumps having a length of at least 50 nm; [2] boron nitride nanotube structure clumps having a length of at least 50 nm; [3] boron nitride nanotube structure / independent boron nitride nanotube clumps having a length of at least 50 nm; [4] independent boron nitride nanotubes that are not clumps and have a length of at least 50 nm in the composition; and [5] boron nitride nanotube structure that are not clumps and have a length of at least 50 nm in the composition; [2] boron nitride nanotube structure chunks having a length of at least 50 nm in the composition, [3] boron nitride nanotube structures / independent boron nitride nanotube chunks having a length of at least 50 nm in the composition, and [5] boron nitride nanotube structures in the composition that are not chunks and have a length of at least 50 nm, each of which is at least 30% of the total, [2] a boron nitride nanotube structure mass, [3] a boron nitride nanotube structure / independent boron nitride nanotube mass, or [5] a boron nitride nanotube structure that is not a mass, the total of at least 10% of the outer atoms of the boron nitride nanotube structure is [2] the boron nitride nanotube structure mass, [3] the boron nitride nanotube structure / independent boron nitride nanotube mass, or [5] the boron nitride nanotube structure in the non-mass boron nitride nanotube structure is covered by a hexagonal boron nitride structure, each of which is epitaxial to the boron nitride nanotube structure.

17. The composition according to any one of claims 14 to 16.

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