Explosive composition and method for producing the same, and method for producing heteroatom-doped nanodiamonds

Abstract

The present invention provides an explosive composition containing at least one explosive and at least one heteroatom compound, the heteroatom compound including at least one type of heteroatom selected from the group consisting of B, P, Si, S, Cr, Sn, Al, Ge, Li, Na, K, Cs, Mg, Ca, Sr, Ba, Ti, Zr, V, Nb, Ta, Mo, W, Mn, Ni, Cu, Ag, Cd, Hg, Ga, In, Tl, As, Sb, Bi, Se, Te, Co, Xe, F, Y, and lanthanoids.

Description

[Technical Field]

[0001] This invention relates to explosive compositions and methods for producing the same, as well as to methods for producing heteroatom-doped nanodiamonds. [Background technology]

[0002] The luminescence centers of diamonds are nanoscale, chemically stable fluorescent chromophores that do not exhibit the degradation, fading, or flashing behaviors in vivo often seen in organic phosphors, making them promising probes for fluorescence imaging. Furthermore, because the spin information of electrons excited within the luminescence centers can sometimes be measured externally, their use in ODMR (Optically Detected Magnetic Resonance) and as qubits is also anticipated.

[0003] SiV centers, a type of luminescence center in diamond, have a sharp peak in their emission spectrum called a ZPL (Zero Phonon Level) (Non-Patent Literature 1).

[0004] Silicon or boron-doped diamonds are manufactured by methods such as CVD (Patent Documents 1-4).

[0005] Patent Document 5 discloses a diamond synthesis explosive composition comprising one or more high-performance explosives and diamond powder. [Prior art documents] [Patent Documents]

[0006] [Patent Document 1] Special Publication 2014-504254 [Patent Document 2] Japanese Patent Publication No. 2004-176132 [Patent Document 3] Japanese Patent Publication No. 2018-076216 [Patent Document 4] Japanese Patent Publication No. 2018-012612 [Patent Document 5] Japanese Patent Publication No. 2-241536 [Non-patent literature]

[0007] [Non-Patent Document 1] E. Neu et al. APPLIED PHYSICS LETTERS 98, 243107 (2011) [Overview of the Initiative] [Problems that the invention aims to solve]

[0008] The object of the present invention is to provide an explosive composition suitable for the production of heteroatom-doped nanodiamonds, a method for producing the same, and a method for producing heteroatom-doped nanodiamonds. [Means for solving the problem]

[0009] This invention provides the following explosive compositions and methods for producing the same, as well as a method for producing heteroatom-doped nanodiamonds. Item 1. An explosive composition comprising at least one explosive and at least one heteroatom compound, wherein the heteroatom compound comprises at least one heteroatom selected from the group consisting of B, P, Si, S, Cr, Sn, Al, Ge, Li, Na, K, Cs, Mg, Ca, Sr, Ba, Ti, Zr, V, Nb, Ta, Mo, W, Mn, Ni, Cu, Ag, Cd, Hg, Ga, In, Tl, As, Sb, Bi, Se, Te, Co, Xe, F, Y and lanthanides. Item 2. The explosive composition according to Item 1, wherein the explosive comprises at least one selected from the group consisting of trinitrotoluene (TNT), cyclotrimethylenetrinitramine (Hexogen, RDX), cyclotetramethylenetetranitramine (Octogen), trinitrophenylmethylnitramine (Tetril), pentaerythritol tetranitrate (PETN), tetranitromethane (TNM), triaminotrinitrobenzene, hexanitrostilbene, and diaminodinitrobenzofloxane. Item 3. The explosive composition according to Item 1 or 2, wherein the heteroatom compound is an organic heteroatom compound. Item 4. The explosive composition according to any one of Items 1 to 3, comprising 80 to 99.9999% by mass of an explosive and 0.0001 to 20% by mass of a heteroatom compound. Item 5. The explosive composition according to any one of Items 1 to 4, wherein the particle size of the explosive and / or the heteroatom compound is 10 mm or less. Item 6. A method for producing an explosive composition according to any one of Items 1 to 5, characterized in that an explosive and a heteroatom compound are mixed in a dry powder state, a molten state or using a solvent, and molded by a pressing method or a casting method. Item 7. The method for producing an explosive composition according to Item 6, wherein an explosive composition is prepared by mixing in a dry powder state or a molten state using an explosive and / or a heteroatom compound having a particle size of 10 mm or less. Item 8. A method for producing heteroatom-doped nanodiamond, comprising a step of exploding the explosive composition according to any one of Items 1 to 5 in a sealed container.

Advantages of the Invention

[0010] By using the explosive composition of the present invention, nanodiamond doped with at least one heteroatom can be obtained by a detonation method.

Brief Description of the Drawings

[0011] [Figure 1] (a) 738 nm bright point imaging image, (b) fluorescence measurement results of the bright point in Fig. 1(a), and (c) XRD measurement results of the sample after treatment with mixed acid and alkali of silicon-doped nanodiamond obtained by using triphenylsilanol as a silicon compound and having an addition amount of 1% by mass on an external basis. In Fig. 1(b), there is a fluorescence side band (shoulder peak) near 750 nm, but this side band may not exist depending on the sample.

Embodiments for Carrying Out the Invention

[0012] The explosive composition of the present invention comprises at least one explosive and at least one heteroatom compound.

[0013] The explosives used are not particularly limited, and a wide range of known explosives can be used. Specific examples include trinitrotoluene (TNT), cyclotrimethylenetrinitramine (Hexogen, RDX), cyclotetramethylenetetranitramine (Octogen), trinitrophenylmethylnitramine (Tetrill), pentaerythritol tetranitrate (PETN), tetranitromethane (TNM), triaminotrinitrobenzene, hexanitrostilbene, and diaminodinitrobenzofloxane, which can be used individually or in combination of two or more.

[0014] A heteroatomic compound is a compound containing at least one heteroatom (an atom other than carbon), and may be either an organic compound or an inorganic compound.

[0015] The heteroatoms are selected from the group consisting of B, P, Si, S, Cr, Sn, Al, Ge, Li, Na, K, Cs, Mg, Ca, Sr, Ba, Ti, Zr, V, Nb, Ta, Mo, W, Mn, Ni, Cu, Ag, Cd, Hg, Ga, In, Tl, As, Sb, Bi, Se, Te, Co, Xe, F, Y, and lanthanides, preferably selected from the group consisting of Si, Ge, Sn, B, P, Ni, Ti, Co, Xe, Cr, W, Ta, Zr, Ag, and lanthanides, and even more preferably selected from the group consisting of Si, Ge, Sn, B, P, Ni, Ti, Co, Xe, Cr, W, Ta, Zr, and Ag.

[0016] The heteroatomic compounds listed below are merely illustrative examples, and a wide range of known heteroatomic compounds can be used.

[0017] When the heteroatom is silicon, the organic silicon compounds are: Silanes having lower alkyl groups such as acetoxytrimethylsilane, diacetoxydimethylsilane, triacetoxymethylsilane, acetoxytriethylsilane, diacetoxydiethylsilane, triacetoxyethylsilane, acetoxytripropylsilane, methoxytrimethylsilane, dimethoxydimethylsilane, trimethoxymethylsilane, ethoxytrimethylsilane, diethoxydimethylsilane, triethoxymethylsilane, ethoxytriethylsilane, diethoxydiethylsilane, triethoxyethylsilane, and trimethylphenoxysilane.

[0018] Trichloromethylsilane, dichlorodimethylsilane, chlorotrimethylsilane, trichloroethylsilane, dichlorodiethylsilane, chlorotriethylsilane, trichlorophenylsilane, dichlorodiphenylsilane, chlorotriphenylsilane, dichlorodiphenylsilane, dichloromethylphenylsilane, dichloroethylphenylsilane, chlorodifluoromethylsilane, dichlorofluoromethylsilane, chlorofluorodimethylsilane, chloroethyldifluorosilane, dichloroethylfluorosilane, chlorodifluoropropylsilane, dichlorofluoropropyl Silanes containing halogen atoms, such as pyrusilane, trifluoromethylsilane, difluorodimethylsilane, fluorotrimethylsilane, ethyltrifluorosilane, diethyldifluorosilane, triethylfluorosilane, trifluoropropylsilane, fluorotripropylsilane, trifluorophenylsilane, difluorodiphenylsilane, fluorotriphenylsilane, tribrommethylsilane, dibromdimethylsilane, bromtrimethylsilane, bromtriethylsilane, bromtripropylsilane, dibromdiphenylsilane, and bromtriphenylsilane.

[0019] Polysilanes such as hexamethyldisilane, hexaethyldisilane, hexapropyldisilane, hexaphenyldisilane, and octaphenylcyclotetrasilane. Silazanes such as triethylsilazane, tripropylsilazane, triphenylsilazane, hexamethyldisilazane, hexaethyldisilazane, hexaphenyldisilazane, hexamethylcyclotrisilazane, octamethylcyclotetrasilazane, hexaethylcyclotrisilazane, octaethylcyclotetrasilazane, and hexaphenylcyclotrisilazane. Aromatic silanes, such as silabenzene and disilabenzene, have silicon atoms incorporated into their aromatic rings. Hydroxyl group-containing silanes such as trimethylsilanol, dimethylphenylsilanol, triethylsilanol, diethylsilanediol, tripropylsilanol, dipropylsilanediol, triphenylsilanol, and diphenylsilanediol.

[0020] Alkyl or aryl-substituted silanes such as tetramethylsilane, ethyltrimethylsilane, trimethylpropylsilane, trimethylphenylsilane, diethyldimethylsilane, triethylmethylsilane, methyltriphenylsilane, tetraethylsilane, triethylphenylsilane, diethyldiphenylsilane, ethyltriphenylsilane, and tetraphenylsilane. • Carboxyl group-containing silanes such as triphenylsilylcarboxylic acid, trimethylsilylacetic acid, trimethylsilylpropionic acid, and trimethylsilylbutyric acid.

[0021] Siloxanes such as hexamethyldisiloxane, hexaethyldisiloxane, hexapropyldisiloxane, and hexaphenyldisiloxane. Silanes having an alkyl or aryl group and a hydrogen atom, such as methylsilane, dimethylsilane, trimethylsilane, diethylsilane, triethylsilane, tripropylsilane, diphenylsilane, and triphenylsilane. Tetrakis(chloromethyl)silane, tetrakis(hydroxymethyl)silane, tetrakis(trimethylsilyl)silane, tetrakis(trimethylsilyl)methane, tetrakis(dimethylsilanolyl)silane, tetrakis(tri(hydroxymethyl)silyl)silane, tetrakis(nitratemethyl)silane, These are some examples.

[0022] Inorganic silicon compounds include silicon oxide, silicon oxynitride, silicon nitride, silicon carbide oxide, silicon carbide nitride, silane, or silicon-doped carbon materials. Examples of silicon-doped carbon materials include graphite, activated carbon, carbon black, Ketjenblack, coke, soft carbon, hard carbon, acetylene black, carbon fiber, and mesoporous carbon.

[0023] Examples of boron compounds include inorganic boron compounds and organoboron compounds.

[0024] Examples of inorganic boron compounds include orthoboric acid, diboron dioxide, diboron trioxide, tetraboron trioxide, tetraboron pentoxide, boron tribromide, tetrafluoroboric acid, ammonium borate, and magnesium borate.

[0025] Examples of organoboron compounds include triethylborane, (R)-5,5-diphenyl-2-methyl-3,4-propano-1,3,2-oxazaborolidine, triisopropyl borate, 2-isopropoxy-4,4,5,5-tetramethyl-1,3,2-dioxaborolane, bis(hexyleneglycolato)diborone, 4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolane-2-yl)-1H-pyrazole, tert-butyl-N-[4-(4,4,5,5-tetramethyl-1,2,3-dioxaborolane-2-yl)phenyl]carbamate, phenylboronic acid, 3-acetylphenylboronic acid, borotetraacetic acid trifluoride complex, boron trifluoride sulfolane complex, 2-thiopheneboronic acid, and tris(trimethylsilyl)borate.

[0026] Examples of phosphorus compounds include inorganic phosphorus compounds and organic phosphorus compounds. Examples of inorganic phosphorus compounds include ammonium polyphosphate.

[0027] Examples of organophosphorus compounds include trimethyl phosphate, triethyl phosphate, tripropyl phosphate, tributyl phosphate, tripentyl phosphate, trihexyl phosphate, dimethylethyl phosphate, methyl dibutyl phosphate, ethyl dipropyl phosphate, 2-ethylhexyl di(p-tolyl) phosphate, bis(2-ethylhexyl)p-tolyl phosphate, trityl phosphate, di(dodecyl)p-tolyl phosphate, tris(2-butoxyethyl) phosphate, tricyclohexyl phosphate, triphenyl phosphate, ethyl diphenyl phosphate, and dibutyl phosphate. Phosphate esters such as phenyl phosphate, phenylbisdodecyl phosphate, cresyldiphenyl phosphate, tricresyl phosphate, p-tolylbis(2,5,5'-trimethylhexyl) phosphate, cresyl-2,6-xylenyl phosphate, trixylenyl phosphate, hydroxyphenyldiphenyl phosphate, tris(t-butylphenyl) phosphate, tris(i-propylphenyl) phosphate, 2-ethylhexyldiphenyl phosphate, bis(2-ethylhexyl)phenyl phosphate, tri(nonylphenyl) phosphate, phenylbisneopentyl phosphate, etc. Condensed phosphate esters such as 1,3-phenylene bis(diphenyl phosphate), 1,4-phenylene bis(dixylenyl phosphate), 1,3-phenylene bis(3,5,5'-trimethylhexyl phosphate), bisphenol A bis(diphenyl phosphate), 4,4'-biphenyl bis(dixylenyl phosphate), and 1,3,5-phenylene tris(dixylenyl phosphate) Phosphite esters such as trimethyl phosphite, triethyl phosphite, triphenyl phosphite, and tricresyl phosphite, Examples of phosphite esters include 1,3-phenylene bis(diphenyl phosphite), 1,3-phenylene bis(dixylenyl phosphite), 1,4-phenylene bis(3,5,5'-trimethylhexyl phosphite), bisphenol A bis(diphenyl phosphite), 4,4'-biphenyl bis(dixylenyl phosphite), and 1,3,5-phenylene tris(dixylenyl phosphite).

[0028] Examples of germanium compounds include organic germanium compounds such as methylgermane, ethylgermane, trimethylgermanium methoxide, dimethylgermanium diacetate, tributylgermanium acetate, tetramethoxygermanium, tetraethoxygermanium, isobutylgermane, alkylgermanium trichloride, and dimethylaminogermanium trichloride. Examples of germanium complexes include nitrotriphenol complexes (Ge2(ntp)2O), catechol complexes (Ge(cat)2), or aminopyrene complexes (Ge2(ap)2Cl2), as well as germanium alkoxides such as germanium ethoxide and germanium tetrabutoxide.

[0029] Examples of tin compounds include inorganic tin compounds such as tin(II) oxide, tin(IV) oxide, tin(II) sulfide, tin(IV) sulfide, tin(II) chloride, tin(IV) chloride, tin(II) bromide, tin(II) fluoride, tin acetate, and tin sulfate; alkyl tin compounds such as tetramethyltin; monoalkyl tin oxide compounds such as monobutyltin oxide; dialkyl tin oxide compounds such as dibutyltin oxide; aryl tin compounds such as tetraphenyltin; and organotin compounds such as dimethyl tin maleate, hydroxybutyltin oxide, and monobutyltin tris(2-ethylhexanoate).

[0030] Examples of nickel compounds include divalent nickel halides such as nickel(II) chloride, nickel(II) bromide, and nickel(II) iodide; inorganic nickel compounds such as nickel(II) acetate and nickel(II) carbonate; and organic nickel compounds such as nickelbis(ethyl acetate) and nickelbis(acetylacetonate).

[0031] Examples of titanium compounds include inorganic titanium compounds such as titanium dioxide, titanium nitride, strontium titanate, barium titanate, and potassium titanate; tetraalkoxy titanium compounds such as tetraethoxytitanium, tetraisopropoxytitanium, and tetrabutyroxytitanium; tetraethylene glycol titanate, di-n-butylbis(triethanolamine) titanate, diisopropoxytitanium bis(acetylacetone)ate, isopropoxytitanium octanoate, isopropyl titanium trimethacrylate, isopropyl titanium triacrylate, isopropyl triisostearoyl titanate, isopropyl tridecylbenzenesulfonyl titanate, isopropyl tris(butylmethyl pyrophosphate) titanate, tetraisopropyl di(dilauryl phosphite) titanate, dimethacrylate acetate titanate, diacryloxyacetate titanate, di(dioctyl phosphate)ethylene titanate, and tri(dioctyl phosphate) ethylene titanate. Isopropoxytitanium (Cutyl Phosphate), Isopropyltris(Dioctyl Pyrophosphate) Titanate, Tetraisopropylbis(Dioctyl Phosphate) Titanate, Tetraoctylbis(Ditridecyl Phosphate) Titanate, Tetra(2,2-Diallyloxymethyl-1-butyl)bis(Di-Tridecyl) Phosphate Titanate, Bis(Dioctyl Pyrophosphate) Oxyacetate Titanate, Tris(Dioctyl Pyrophosphate) Ethylene Examples include organotitanium compounds such as titanate, isopropyl tri-n-dodecylbenzenesulfonyl titanate, isopropyl trioctanoyl titanate, isopropyl dimethacryloyl isostearoyl titanate, isopropyl isostearoyl diacrylic titanate, isopropyl tri(dioctyl phosphate) titanate, isopropyl tricumylphenyl titanate, and isopropyl tri(N-aminoethyl-aminoethyl) titanate.

[0032] Examples of cobalt compounds include inorganic cobalt compounds such as cobalt inorganic salts, cobalt halides, cobalt oxide, cobalt hydroxide, dicobalt octacarbonyl, cobalt hydrogen tetracarbonyl, tetracobalt dodecacarbonyl, alkylidine tricobalt nonacarbonyl, cobalt tris(ethyl acetate), cobalt tris(acetylacetonate), organic cobalt salts (e.g., acetate, propionate, cyanide, naphthenate, stearate; alkyl sulfonates such as methanesulfonate, ethanesulfonate, octanesulfonate, dodecanesulfonate, etc. 6-18 Alkyl sulfonates; Aryl sulfonates that may be substituted with alkyl groups such as benzenesulfonates, p-toluenesulfonates, naphthalenesulfonates, decylbenzenesulfonates, and dodecylbenzenesulfonates (e.g., C 6-18 Examples include alkyl-aryl sulfonates and organic cobalt complexes. Ligands that make up the complexes include OH (hydroxo), alkoxy (methoxy, ethoxy, propoxy, butoxy, etc.), acyl (acetyl, propionyl, etc.), alkoxycarbonyl (methoxycarbonyl, ethoxycarbonyl, etc.), acetylacetonate, cyclopentadienyl group, halogen atoms (chlorine, bromine, etc.), CO, CN, oxygen atom, H2O (ac), phosphorus compounds such as phosphine (triarylphosphine such as triphenylphosphine), NH3 (ammine), NO, NO2 (nitro), NO3 (nitrate), ethylenediamine, diethylenetriamine, pyridine, phenanthroline, and other nitrogen-containing compounds.

[0033] Examples of xenon compounds include fluorides such as XeF2, XeF4, XeF6, XeOF2, XeOF4, and XeO2F4; oxides such as XeO3 and XeO4; xenonic acid Xe(OH)6 and its salt Ba3XeO6; perxenonic acid H4XeO6 and its salt Na4XeO6; complexes with metal carbonyls M(CO)5Xe(M=Cr,Mo,W); and hydrates.

[0034] Examples of chromium compounds include chromium acetylacetone complexes such as acetylacetone chromium, chromium alkoxides such as chromium(III) isopropoxide, organic acid chromium such as chromium(II) acetate and hydroxychromium(III) diacetate, tris(allyl)chromium, tris(methallyl)chromium, tris(clotyl)chromium, bis(cyclopentadienyl)chromium (i.e., chromosene), bis(pentamethylcyclopentadienyl)chromium (i.e., decamethylchromosene), bis(benzene)chromium, Examples of organochromium compounds include bis(ethylbenzene)chromium, bis(mesitylene)chromium, bis(pentadienyl)chromium, bis(2,4-dimethylpentadienyl)chromium, bis(allyl)tricarbonylchromium, (cyclopentadienyl)(pentadienyl)chromium, tetra(1-norbornyl)chromium, (trimethylenemethane)tetracarbonylchromium, bis(butadiene)dicarbonylchromium, (butadiene)tetracarbonylchromium, and bis(cyclooctatetraene)chromium.

[0035] Examples of tungsten compounds include inorganic tungsten compounds such as tungsten trioxide, ammonium tungstate, and sodium tungstate; boron atom-coordinated tungsten complexes such as those with ethylborylethylidene ligands; carbon atom-coordinated tungsten complexes such as those with carbonyl ligands, cyclopentadienyl ligands, alkyl ligands, and olefin ligands; nitrogen atom-coordinated tungsten complexes such as pyridine ligands and acetonitrile ligands; phosphorus atom-coordinated tungsten complexes coordinated with phosphine ligands, phosphine ligands, and phosphite ligands; and organic tungsten compounds such as sulfur atom-coordinated tungsten complexes coordinated with diethylcarbamodithiolat ligands.

[0036] Examples of thallium compounds include inorganic thallium compounds such as thallium nitrate, thallium sulfate, thallium fluoride, thallium chloride, thallium bromide, and thallium iodide; trialkylthallium compounds such as trimethylthallium, triethylthallium, and triisobutylthallium; arylthallium compounds such as dialkylthallium halides, alkenyldialkylthallium, alkynyldialkylthallium, triphenylthallium, and tritolylthallium; diarylthallium halides; thallium 2-ethylhexanoate, thallium malonate, thallium formate, thallium ethoxide, and thallium acetylacetonate.

[0037] Examples of zirconium compounds include inorganic zirconium compounds such as zirconium nitrate, zirconium sulfate, zirconium carbonate, zirconium hydroxide, zirconium fluoride, zirconium chloride, zirconium bromide, and zirconium iodide, as well as organic zirconium compounds such as zirconium n-propoxide, zirconium n-butoxide, zirconium t-butoxide, zirconium isopropoxide, zirconium ethoxide, zirconyl acetate, zirconium acetylacetonate, zirconium butoxyacetylacetonate, zirconium bisacetylacetonate, zirconium ethylacetoacetate, zirconium acetylacetonate bisethylacetoacetate, zirconium hexafluoroacetylacetonate, and zirconium trifluoroacetylacetonate.

[0038] Examples of silver compounds include organosilver compounds such as silver acetate, silver pivalate, silver trifluoromethanesulfonate, and silver benzoate; and inorganic silver compounds such as silver nitrate, silver fluoride, silver chloride, silver bromide, silver iodide, silver sulfate, silver oxide, silver sulfide, silver tetrafluoroborate, silver hexafluorophosphate (AgPF6), and silver hexafluoroantimonate (AgSbF6).

[0039] Examples of aluminum compounds include inorganic aluminum compounds such as aluminum oxide, alkoxy compounds such as trimethoxyaluminum, triethoxyaluminum, isopropoxyaluminum, isopropoxydiethoxyaluminum, and tributoxyaluminum; acyloxy compounds such as triacetoxyaluminum, tristearatealuminum, and tributyratealuminum; aluminum isopropylate, aluminum sec-butyrate, aluminum tert-butyrate, aluminum tris(ethylacetate), tris(hexafluoroacetylacetonate)aluminum, tris(ethylacetate), and tris(n-propylacetate). Examples include trialkylaluminum compounds such as trimethylaluminum, triethylaluminum, triisobutylaluminum, tris(isopropylacetate)aluminum, tris(n-butylacetate)aluminum, trissalicyaldehydealuminum, tris(2-ethoxycarbonylphenolate)aluminum, tris(acetylacetonate)aluminum, trimethylaluminum, triethylaluminum, triisobutylaluminum, arylaluminum compounds such as dialkylaluminum halides, alkenyldialkylaluminum, alkynyldialkylaluminum, triphenylaluminum, tritolylaluminum, and diarylaluminum halides.

[0040] Examples of vanadium compounds include vanadic acid and metavanadic acid, as well as their alkali metal salts (inorganic vanadium compounds), alkoxides such as triethoxyvanadyl, pentaethoxyvanadium, triamyloxyvanadyl, and triisopropoxyvanadyl; acetonates such as bisacetylacetonate vanadyl, vanadium acetylacetonate, vanadyl acetylacetonate, and vanadium oxyacetylacetonate; and organic vanadium compounds such as vanadium stearate, vanadium pivalate, and vanadium acetate.

[0041] Examples of niobium compounds include halides such as niobium pentachloride and niobium pentafluoride, inorganic niobium compounds such as niobium sulfate, niobic acid, and niobate salts, and organic niobium compounds such as niobium alkoxides.

[0042] Examples of tantalum compounds include inorganic tantalum compounds such as TaCl5 and TaF5, and organic tantalum compounds such as Ta(OC2H5)5, Ta(OCH3)5, Ta(OC3H7)5, Ta(OC4H9)5, (C5H5)2TaH3, and Ta(N(CH3)2)5.

[0043] Examples of molybdenum compounds include inorganic molybdenum compounds such as molybdenum trioxide, ammonium molybdate, magnesium molybdate, calcium molybdate, barium molybdate, sodium molybdate, potassium molybdate, phosphomolybdate, ammonium phosphomolybdate, sodium phosphomolybdate, silicic acid, molybdenum disulfide, molybdenum diselenium, molybdenum ditelluride, molybdenum boride, molybdenum disilicate, molybdenum nitride, and molybdenum carbide, as well as organic molybdenum compounds such as molybdenum dialkyldithiophosphate and molybdenum dialkyldithiocarbamate.

[0044] Examples of manganese compounds include inorganic manganese compounds such as manganese hydroxide, nitrate, acetate, sulfate, chloride, and carbonate; manganese oxalate, acetylacetonate compounds; and organic manganese compounds including manganese alkoxides such as methoxide, ethoxide, and butoxide.

[0045] Examples of copper compounds include organocopper compounds such as copper oxalate, copper stearate, copper formate, copper tartrate, copper oleate, copper acetate, copper gluconate, and copper salicylate, as well as inorganic copper compounds such as copper carbonate, copper chloride, copper bromide, copper iodide, copper phosphate, hydrotalcite, stichtite, and pyrolite.

[0046] Examples of cadmium compounds include inorganic cadmium compounds such as cadmium fluoride, cadmium chloride, cadmium bromide, cadmium iodide, cadmium oxide, and cadmium carbonate, as well as organic cadmium compounds such as cadmium phthalate and cadmium naphthalate.

[0047] Examples of mercury compounds include inorganic mercury compounds such as mercuric chloride, mercuric sulfate, and mercuric nitrate, and organic mercury compounds such as methylmercury, methylmercury chloride, ethylmercury, ethylmercury chloride, phenylmercury acetate, thimerosal, mercury parachlorobenzoate, and fluorescein mercury acetate.

[0048] Examples of gallium compounds include organic gallium compounds such as tetraphenylgallium and tetrakis(3,4,5-trifluorophenyl)gallium, and inorganic gallium compounds such as gallium oxoate, gallium halide, gallium hydroxide, and gallium cyanide.

[0049] Examples of indium compounds include organic indium compounds such as triethoxyindium, indium 2-ethylhexanoate, and indium acetylacetonate, and inorganic indium compounds such as indium cyanide, indium nitrate, indium sulfate, indium carbonate, indium fluoride, indium chloride, indium bromide, and indium iodide.

[0050] Examples of arsenic compounds include inorganic arsenic compounds such as arsenic trioxide, arsenic pentoxide, arsenic trichloride, arsenic pentachloride, arsenous acid, arsenic acid, and their salts, such as sodium arsenous acid, ammonium arsenous acid, potassium arsenous acid, ammonium arsenate, and potassium arsenate; and organic arsenic compounds such as cacodylic acid, phenylarsonic acid, diphenylarsonic acid, p-hydroxyphenylarsonic acid, p-aminophenylarsonic acid, and their salts, such as sodium cacodylate and potassium cacodylate.

[0051] Examples of antimony compounds include inorganic antimony compounds such as antimony oxide, antimony phosphate, KSb(OH), and NH4SbF6, as well as organic antimony compounds such as antimony esters with organic acids, cyclic alkyl antimonite esters, and triphenylantimony.

[0052] Examples of bismuth compounds include organic bismuth compounds such as triphenylbismuth, bismuth 2-ethylhexanoate, and bismuth acetylacetonate, and inorganic bismuth compounds such as bismuth nitrate, bismuth sulfate, bismuth acetate, bismuth hydroxide, bismuth fluoride, bismuth chloride, bismuth bromide, and bismuth iodide.

[0053] Examples of selenium compounds include organic selenium compounds such as selenomethionine, selenocysteine, and selenocystin, as well as alkali metal selenates such as potassium selenate and inorganic selenium compounds including alkali metal selenites such as sodium selenite.

[0054] Examples of tellurium compounds include telluric acid and its salts, tellurium oxide, tellurium chloride, tellurium bromide, tellurium iodide, and tellurium alkoxides.

[0055] Examples of magnesium compounds include organomagnesium compounds such as ethyl acetacetate magnesium monoisopropylate, magnesium bis(ethyl acetacetate), alkyl acetacetate magnesium monoisopropylate, and magnesium bis(acetylacetonate), as well as inorganic magnesium compounds such as magnesium oxide, magnesium sulfate, magnesium nitrate, and magnesium chloride.

[0056] Examples of calcium compounds include organocalcium compounds such as calcium 2-ethylhexanoate, calcium ethoxide, calcium methoxide, calcium methoxyethoxide, and calcium acetylacetonate, as well as inorganic calcium compounds such as calcium nitrate, calcium sulfate, calcium carbonate, calcium phosphate, calcium hydroxide, calcium cyanide, calcium fluoride, calcium chloride, calcium bromide, and calcium iodide.

[0057] Heteratomic compounds containing different atoms such as Li, Na, K, Cs, S, Sr, Ba, F, Y, and lanthanides can be any known organic or inorganic compounds.

[0058] Heteratomic compounds may be used individually or in combination of two or more.

[0059] The proportion of explosives in an explosive composition containing at least one explosive and at least one heteroatomic compound is preferably 80 to 99.9999% by mass, more preferably 85 to 99.999% by mass, even more preferably 90 to 99.99% by mass, and particularly preferably 95 to 99.9% by mass. The proportion of heteroatomic compounds is preferably 0.0001 to 20% by mass, more preferably 0.001 to 15% by mass, even more preferably 0.01 to 10% by mass, and particularly preferably 0.1 to 5% by mass. Furthermore, the heteroatomic content in the explosive composition containing the explosive and heteroatomic compound is preferably 0.000005 to 10% by mass, more preferably 0.00001 to 8% by mass, even more preferably 0.0001 to 5% by mass, particularly preferably 0.001 to 3% by mass, and most preferably 0.01 to 1% by mass.

[0060] The mixture of at least one explosive and at least one heteroatom compound may be performed by powder mixing, melting, or dissolving or dispersing in a suitable solvent if both are solids. Mixing can be carried out by stirring, bead milling, ultrasound, etc.

[0061] In one preferred embodiment, an explosive composition comprising at least one explosive and at least one heteroatomic compound further comprises at least one cooling medium. The cooling medium may be a solid, liquid, or gas. One method of using the cooling medium is to detonate the explosive composition comprising the explosive and the heteroatomic compound in the cooling medium. Examples of cooling mediums include inert gases (nitrogen, argon, CO), water, ice, liquid nitrogen, aqueous solutions of heteroatom-containing salts, and crystalline hydrates. Examples of heteroatom-containing salts, when the heteroatom is silicon, include ammonium hexafluorosilicate, ammonium silicate, and tetramethylammonium silicate. When the cooling medium is, for example, water or ice, it is preferable to use about five times the weight of the explosive.

[0062] In one preferred embodiment of the present invention, an explosive composition comprising at least one explosive and at least one heteroatomic compound is converted into heteroatom-doped nanodiamonds by compression due to a shock wave under high pressure and high temperature conditions generated by the explosion of the explosive (detonation method). During the explosion of the explosive, at least one heteroatom is incorporated into the diamond lattice. The carbon source of the heteroatom-doped nanodiamonds may be the explosive and the organic heteroatomic compound, but if the explosive composition comprising the explosive and at least one heteroatomic compound further contains a carbon material that does not contain heteroatoms, this carbon material can also serve as a carbon source for the heteroatom-doped nanodiamonds.

[0063] Heteratom-doped nanodiamonds produced using the explosive composition of the present invention contain heteratom V (vacancy) centers, thereby having fluorescence emission peaks. The wavelength of the fluorescence emission peak is preferably 720-770 nm, more preferably 730-760 nm, when the heteratom contains silicon; preferably 580-630 nm, more preferably 590-620 nm, when the heteratom contains germanium; and preferably 590-650 nm, more preferably 600-640 nm, when the heteratom contains tin. In one more preferred embodiment of the present invention, the fluorescence emission peak of nanodiamonds with Group 14 element Si includes a sharp peak at approximately 738 nm, referred to as the ZPL (Zero Phonon Level).

[0064] The concentration of heteroatom V centers in heteroatom-doped nanodiamonds produced using the explosive composition of the present invention is preferably 1×10 10 / cm 3 or more, more preferably 2×10 10 to 1×10 19 / cm 3 . The concentration of heteroatom V centers is presumed to be able to be specified, for example, by using a confocal laser microscope or a fluorescence absorption spectroscopic device. Note that the determination of the concentration of heteroatom V centers by fluorescence absorption analysis can refer to the literature (DOI 10.1002 / pssa.201532174).

[0065] The BET specific surface area of heteroatom-doped nanodiamonds produced using the explosive composition of the present invention is preferably 20 to 900 m 2 / g, more preferably 25 to 800 m 2 / g, still more preferably 30 to 700 m 2 / g, particularly preferably 35 to 600 m 2 / g. The BET specific surface area can be measured by nitrogen adsorption. Examples of the measuring apparatus for the BET specific surface area include BELSORP-miniII (manufactured by MicrotracBEL Corporation), and the BET specific surface area can be measured, for example, under the following conditions. · Amount of measurement powder: 40 mg · Preliminary drying: Treatment at 120°C under vacuum for 3 hours · Measurement temperature: -196°C (liquid nitrogen temperature) The average size of primary particles of heteroatom-doped nanodiamonds produced using the explosive composition of the present invention is preferably 2 to 70 nm, more preferably 2.5 to 60 nm, still more preferably 3 to 55 nm, and particularly preferably 3.5 to 50 nm. The average size of primary particles can be determined by the Scherrer's formula from the analysis results of powder X-ray diffraction method (XRD). Examples of the measuring apparatus for XRD include a fully automatic multi-purpose X-ray diffractometer (manufactured by Rigaku Corporation).

[0066] The carbon content of heteroatom-doped nanodiamonds produced using the explosive composition of the present invention is preferably 70-99% by mass, more preferably 75-98% by mass, and even more preferably 80-97% by mass.

[0067] The hydrogen content of heteroatom-doped nanodiamonds produced using the explosive composition of the present invention is preferably 0.1 to 5% by mass, more preferably 0.2 to 4.5% by mass, and even more preferably 0.3 to 4.0% by mass.

[0068] The nitrogen content of heteroatom-doped nanodiamonds produced using the explosive composition of the present invention is preferably 0.1 to 5% by mass, more preferably 0.2 to 4.5% by mass, and even more preferably 0.3 to 4.0% by mass.

[0069] The carbon, hydrogen, and nitrogen content of heteroatom-doped nanodiamonds can be measured by elemental analysis.

[0070] The heteroatom content of heteroatom-doped nanodiamonds produced using the explosive composition of the present invention is preferably 0.0001 to 10.0 mass%, more preferably 0.0001 to 5.0 mass%, and even more preferably 0.0001 to 1.0 mass%. The heteroatom content can be measured, for example, by inductively coupled plasma emission spectrometry (ICP-AES), XRF, or SIMS (secondary ion mass spectrometry), and heteroatom-doped nanodiamonds can be quantified as an acidic solution after alkali fusion.

[0071] In one preferred embodiment of the present invention, heteroatom-doped nanodiamonds produced using the explosive composition of the present invention can be subjected to Raman spectroscopy, which allows for the identification of characteristic peaks for diamond, graphite, surface hydroxyl groups (OH), and surface carbonyl groups (CO) in the Raman shift chart. The peak characteristic of diamond in the Raman shift chart is at 1100-1400 cm⁻¹. -1 The characteristic peak of graphite is 1450-1700cm. -1 The peak characteristic of surface hydroxyl groups (OH) is at 1500-1750 cm⁻¹.-1 The peak characteristic of surface carbonyl groups (CO) is at 1650-1800 cm⁻¹. -1 The characteristic peak areas for diamond, graphite, surface hydroxyl groups (OH), and surface carbonyl groups (CO) are shown by a Raman spectrometer. The laser wavelength of the Raman light source is, for example, 325 nm or 488 nm. A confocal micro-Raman spectrometer (for example, product name: Micro-Laser Raman Spectrophotometer LabRAM HR Evolution, manufactured by Horiba, Ltd.) can be used as the Raman spectrometer.

[0072] In one preferred embodiment of the present invention, in heteroatom-doped nanodiamonds produced using the explosive composition of the present invention, the ratio (D / G) of the peak area of ​​diamond (D) to the peak area of ​​graphite (G) is preferably 0.2 to 9, more preferably 0.3 to 8, and even more preferably 0.5 to 7.

[0073] In one preferred embodiment of the present invention, the ratio (H / D) of the peak area (H) of the surface hydroxyl groups (OH) of heteroatom-doped nanodiamonds produced using the explosive composition of the present invention to the peak area (D) of diamonds is preferably 0.1 to 5, more preferably 0.1 to 4.0, and even more preferably 0.1 to 3.0.

[0074] In one preferred embodiment of the present invention, the ratio (C / D) of the peak area (C) of the surface carbonyl group (CO) to the peak area (D) of the diamond in heteroatom-doped nanodiamonds produced using the explosive composition of the present invention is preferably 0.01 to 1.5, more preferably 0.03 to 1.2, and even more preferably 0.05 to 1.0.

[0075] For Raman analysis techniques of nanodiamonds, refer to the literature (e.g., Vadym N. Mochalin et. al, NATURE NANOTECHNOLOGY, 7(2012)11-23, especially Figure 3).

[0076] In another preferred embodiment of the present invention, heteroatom-doped nanodiamonds produced using the explosive composition of the present invention may have at least one oxygen functional group terminator and / or at least one hydrogen terminator on their surface. Examples of oxygen functional group terminators include OH, COOH, CONH2, C=O, and CHO, with OH, C=O, and COOH being preferred. Examples of hydrogen terminators include alkyl groups having 1 to 20 carbon atoms.

[0077] The presence of at least one oxygen functional group terminator on the surface of heteroatom-doped nanodiamonds is preferable because it suppresses aggregation of nanodiamond particles. The presence of at least one hydrogen terminator on the surface of heteroatom-doped nanodiamonds is also preferable because it results in a positive zeta potential, leading to stability and high dispersion in acidic aqueous solutions.

[0078] In another preferred embodiment of the present invention, heteroatom-doped nanodiamonds produced using the explosive composition of the present invention may have a core-shell structure. The core of the heteroatom-doped nanodiamonds with a core-shell structure is a nanodiamond particle doped with heteroatoms. Preferably, this core has SiV centers and emits fluorescence. The shell is a non-diamond coating layer, which may contain sp2 carbon atoms and more preferably oxygen atoms. The shell may also be a graphite layer. The thickness of the shell is preferably 5 nm or less, more preferably 3 nm or less, and even more preferably 1 nm or less. The shell may have hydrophilic functional groups on its surface.

[0079] Heteratomic-doped nanodiamonds can preferably be produced by detonation using the explosive composition of the present invention. The shape of the heteratomic-doped nanodiamonds is preferably spherical, ellipsoidal, or a polyhedron close to these shapes.

[0080] In this specification, circularity is a numerical value used to represent the complexity of a shape drawn in an image or other image. With a maximum value of 1, the more complex the shape, the smaller the value. For example, circularity can be determined by analyzing a TEM image of silicon-doped nanodiamond using image analysis software (e.g., winROOF) and using the following formula. Roundness = 4π × (area) ÷ (perimeter)^2 For example, in the case of a perfect circle with a radius of 10, the calculation formula is "4π × (10 × 10 × π) ÷ (10 × 2 × π)^2", resulting in a circularity of 1 (the maximum value). In other words, a perfect circle is the simplest shape in terms of circularity. The circularity of heteroatom-doped nanodiamonds produced using the explosive composition of the present invention is preferably 0.2 or higher, more preferably 0.3 or higher, and even more preferably 0.35 or higher.

[0081] In one preferred embodiment of the present invention, heteroatom-doped nanodiamond particles produced using the explosive composition of the present invention have a diamond structure at their core containing sp3 carbon and doped heteroatoms, and their surface is covered with an amorphous layer composed of sp2 carbon. In a more preferred embodiment, the outside of the amorphous layer may be covered with a graphite oxide layer. Furthermore, a hydration layer may be formed between the amorphous layer and the graphite oxide layer.

[0082] In one preferred embodiment of the present invention, heteroatom-doped nanodiamonds produced using the explosive composition of the present invention have a positive or negative zeta potential. The zeta potential of the heteroatom-doped nanodiamonds is preferably -70 to 70 mV, more preferably -60 to 30 mV.

[0083] Heteratomic-doped nanodiamonds are produced by a manufacturing method that includes the steps of mixing an explosive composition containing at least one explosive and at least one heteroatomic compound, and detonating the resulting explosive composition in a sealed container. Examples of containers include metal containers and synthetic resin containers. The explosive and heteroatomic compound are preferably formed by pressing or casting. Methods for producing particles (dry powders) of the explosive and heteroatomic compound include crystallization, crushing, and spray flash evaporation. When forming the explosive composition by pressing or casting, the explosive and heteroatomic compound are mixed using dry powder, a molten state, or a solvent. The state of the mixture of the explosive and heteroatomic compound may be any of the following four combinations: • Explosives (dried powder) and heteroatomic compounds (dried powder) • Explosives (dry powder) and heteroatomic compounds (molten state) • Explosives (molten state) and heteroatomic compounds (dried powder) • Explosives (molten state) and heteroatomic compounds (molten state) The mixture of explosives and heteroatomic compounds may be prepared in the presence or absence of a solvent, and the mixture can be formed by compression or pouring after mixing.

[0084] The average particle size of the explosive and heteroatomic compound is preferably 10 mm or less, more preferably 5 mm or less, and even more preferably 1 mm or less. These average particle sizes can be measured by laser diffraction / scattering, optical microscopy, or Raman spectroscopy. The products obtained from the explosion can be further subjected to purification and post-processing steps. The purification step may include either or both mixed acid treatment and alkali treatment. The preferred purification step is mixed acid treatment.

[0085] When an explosive composition containing at least one type of explosive and at least one type of heteroatomic compound is detonated in a sealed container, heteroatomic-doped nanodiamonds are produced, along with graphite, metallic impurities, individual heteroatoms, and heteroatomic oxides. Graphite and metallic impurities can be removed by mixed acid treatment, while individual heteroatoms and heteroatomic oxides can be removed by alkali treatment.

[0086] The mixed acid can be a mixture of concentrated sulfuric acid and concentrated nitric acid, preferably a mixture of concentrated sulfuric acid and concentrated nitric acid in a volume ratio of 1:1. The temperature for the mixed acid treatment is 50 to 200°C, and the treatment time is 0.5 to 24 hours.

[0087] Examples of alkalis include alkali metal hydroxides such as sodium hydroxide and potassium hydroxide. The alkali treatment temperature is 30 to 150°C, and the treatment time is 0.5 to 24 hours.

[0088] Post-processing steps may include annealing and gas-phase oxidation. Annealing allows doped heteroatoms and vacancies in heteroatom-doped nanodiamonds to meet, forming heteroatom V-centers. Gas-phase oxidation can thin or remove the graphite layer formed on the surface of the heteroatom-doped nanodiamonds. An optional vacancy formation step may be performed before annealing. The vacancy formation step is performed by irradiation with an ion beam or electron beam. Although heteroatom V-centers can be formed by annealing even without the vacancy formation step, performing annealing after the vacancy formation step can form more heteroatom V-centers. The vacancy density introduced by ion beam irradiation or electron beam irradiation should be limited to a concentration where the diamond is destroyed (>1 × 10⁻⁶). 21 / cm 3 It is limited by the vacancy concentration, but the lower limit is, for example, 1 × 10⁻⁶ 16 / cm 3 In addition to the above, 1 x 10 18 / cm 3That concludes the explanation. The ion beam is preferably a hydrogen (H) or helium (He) ion beam. For example, the energy of the hydrogen ion beam is preferably 10 to 1500 keV, and the energy of the helium ion beam is preferably 20 to 2000 keV. The energy of the electron beam is preferably 500 to 5000 keV.

[0089] The annealing temperature is preferably 800°C or higher, and the annealing time is 30 minutes or longer.

[0090] Gas-phase oxidation can be carried out in an atmospheric environment, the gas-phase oxidation temperature is preferably 300°C or higher, and the gas-phase oxidation time is 2 hours or more.

[0091] In one preferred embodiment of the present invention, an explosive composition comprising at least one explosive and at least one heteroatomic compound is converted into diamond by compression due to a shock wave under high pressure and high temperature conditions generated by the explosion of the explosive (detonation method). Heteroatoms are incorporated into the diamond lattice during the explosion of the explosive. The carbon source of the nanodiamonds may be the explosive and the organic heteroatomic compound, but if the explosive composition comprising the explosive and the heteroatomic compound further contains a carbon material that does not contain heteroatoms, this carbon material can also serve as a carbon source for heteroatom-doped nanodiamonds. [Examples]

[0092] The present invention will be described more specifically below with reference to examples, but the present invention is not limited to these examples. Examples 1-6 When TNT is used as the explosive, and the dopants shown in Table 1, which are compounds in which the other atom is silicon, are used in the number of moles shown in Table 1 per mole of TNT, silicon-doped nanodiamonds are produced by detonation according to a conventional method under the temperature (K) and pressure (GPa) conditions shown in Table 1, silicon-doped nanodiamonds can be obtained in the proportions shown in Table 1.

[0093] The names and structural formulas of the dopant molecules (heteroatomic compounds) 1-6 used to dope with silicon are shown below. Dopant molecule 1: Silline Dopant molecule 2: Tetramethylsilane (SiMe4) Dopant molecule 3: Tetrakis(nitratemethyl)silane (SiPETN) Dopant molecule 4: Tetrakis(dimethylsilanolyl)silane(Si(SiMe2OH)4) Dopant molecule 5: Tetrakis(trimethylsilyl)silane(Si(SiMe3)4) Dopant molecule 6: Tetrakis(trimethylsilyl)methane (C(SiMe3)4)

[0094] [ka]

[0095] [Table 1]

[0096] As is clear from Table 1, it is evident that the present invention can yield nanodiamonds with a large amount of silicon atoms incorporated into them.

[0097] Example 7 Approximately 60 g of an explosive composition prepared by adding 100 parts by mass of trinitrotoluene (TNT) and cyclotrimethylenetrinitramine (RDX) to triphenylsilanol as a silicon compound, in amounts of 10 parts by mass, 1 part by mass, or 0.1 parts by mass, respectively, was used to produce silicon-doped nanodiamonds according to a conventional method for nanodiamond production. The obtained silicon-doped nanodiamonds were subjected to the following treatments. The amount of triphenylsilanol added to the explosive was 10% by mass, 1% by mass, or 0.1% by mass. (i) Mixed acid treatment 2800g of a mixed acid in a concentrated sulfuric acid:concentrated nitric acid ratio of 11:1 (by weight) was mixed with 15g of nanodiamonds obtained from a detonation test, and the mixture was treated at 150°C for 10 hours while stirring. (ii) Alkali treatment 1 g of mixed acid-treated nanodiamonds was added to 100 mL of 8N sodium hydroxide aqueous solution and treated at 100°C for 10 hours while stirring. (iii) Annealing The alkali-treated nanodiamonds were annealed at 800°C for 30 minutes under a vacuum atmosphere. (iv) gas-phase oxidation The silicon-doped nanodiamonds of the present invention were obtained by subjecting annealed nanodiamonds to gas-phase oxidation treatment at 300°C for 2 hours in an atmospheric environment. (v) Fluorescence analysis A 10 w / v% aqueous suspension of the silicon-doped nanodiamond of the present invention, obtained by gas-phase oxidation, was dropped onto a glass substrate and dried to prepare evaluation samples. The obtained evaluation samples were subjected to high-speed mapping using a micro-Raman spectrometer (product name: Micro-Laser Raman Spectrophotometer LabRAM HR Evolution, manufactured by Horiba, Ltd.), and 738 nm bright spot imaging was performed. Figure 1(a) shows the 738 nm bright spot imaging image of silicon-doped nanodiamond obtained with triphenylsilanol as the silicon compound, with an external addition amount of 1 mass. Figure 1(b) shows the fluorescence spectrum of the bright spot in Figure 1(a). The zero phonon line (fluorescence peak) of the SiV center can be confirmed. The Si content of the obtained silicon-doped nanodiamond was 3.2 mass% when the amount of triphenylsilanol added to the explosive was 10 mass%, 0.15 mass% when it was 1 mass%, and 0.03 mass% when it was 0.1 mass%. Figure 1(b) confirms that the silicon-doped nanodiamonds of the present invention have fluorescence at 738 nm originating from SV centers. Furthermore, the average size of primary particles and the BET specific surface area of ​​the obtained silicon-doped nanodiamonds, measured by XRD, are shown in Table 2 below.

[0098] [Table 2]

[0099] • Measurement of BET specific surface area Device: BELSORP-miniII (Microtrac, manufactured by Bell Corporation) Measured amount of powder: 40mg Pre-drying: Process at 120°C under vacuum for 3 hours. Measurement temperature: -196°C (liquid nitrogen temperature) • Measurement of the average size of primary particles (powder X-ray diffraction (XRD)) Equipment: Fully automated multi-purpose X-ray diffractometer (manufactured by Rigaku Corporation) • Measurement method for silicon content (XRF) Equipment: X-ray fluorescence analyzer ZSX Primus IV, manufactured by Rigaku Corporation.

[0100] Example 8 Boron-doped nanodiamonds can be obtained in the same manner as in Example 7, except that 1 part by mass of phenylboronic acid is used instead of 1 part by mass of triphenylsilanol.

[0101] Example 9 Phosphorus-doped nanodiamonds can be obtained in the same manner as in Example 7, except that 1 part by mass of triphenylphosphine is used instead of 1 part by mass of triphenylsilanol.

[0102] Example 10 Nickel-doped nanodiamonds can be obtained in the same manner as in Example 7, except that 1 part by mass of nickel bis(acetylacetonate) is used instead of 1 part by mass of triphenylsilanol.

[0103] Example 11 Nanodiamonds doped with silicon and boron can be obtained in the same manner as in Example 7, except that 0.5 parts by mass of triphenylsilanol and 0.5 parts by mass of phenylboronic acid are used instead of 1 part by mass of triphenylsilanol as in Example 7.

[0104] Example 12 Nanodiamonds doped with silicon and phosphorus can be obtained in the same manner as in Example 7, except that 0.5 parts by mass of triphenylsilanol and 0.5 parts by mass of triphenylphosphine are used instead of 1 part by mass of triphenylsilanol as in Example 7.

Claims

1. An explosive composition comprising at least one explosive and at least one organic heteroatom compound, wherein the organic heteroatom compound comprises at least one heteroatom selected from the group consisting of Si, Ge, and Sn, wherein the proportion of the explosive in the explosive composition is 90 to 99.99% by mass, and the proportion of the organic heteroatom compound is 0.01 to 10% by mass, and the explosive composition has a fluorescence emission peak based on heteroatom V (vacancy) centers, for the production of nanodiamonds.

2. The explosive composition according to claim 1, wherein the explosive comprises at least one selected from the group consisting of trinitrotoluene (TNT), cyclotrimethylenetrinitramine (Hexogen, RDX), cyclotetramethylenetetranitramine (Octogen), trinitrophenylmethylnitramine (Tetril), pentaerythritol tetranitrate (PETN), tetranitromethane (TNM), triaminotrinitrobenzene, hexanitrostilbene, and diaminodinitrobenzofloxane.

3. The explosive composition according to claim 1 or 2, wherein the particle size of the explosive and / or organic heteroatomic compound is 10 mm or less.

4. The explosive composition according to any one of claims 1 to 3, wherein the organic heteroatom compound comprises an aryl heteroatom compound.

5. A method for producing an explosive composition according to any one of claims 1 to 4, characterized by mixing an explosive and an organic heteroatom compound using a dry powder, a molten state, or a solvent, and forming it by a pressing method or a pouring method.

6. A method for producing an explosive composition according to claim 5, comprising mixing an explosive and / or an organic heteroatom compound having a particle size of 10 mm or less in a dry powder or molten state to produce the explosive composition.

7. A method for producing heteroatom-doped nanodiamonds, comprising the step of detonating an explosive composition according to any one of claims 1 to 6 in a sealed container.

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