US20100215960A1 - Hollow carbon spheres - Google Patents
Hollow carbon spheres Download PDFInfo
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- US20100215960A1 US20100215960A1 US12/391,794 US39179409A US2010215960A1 US 20100215960 A1 US20100215960 A1 US 20100215960A1 US 39179409 A US39179409 A US 39179409A US 2010215960 A1 US2010215960 A1 US 2010215960A1
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- United States
- Prior art keywords
- carbon
- hollow carbon
- sphere
- shell
- hollow
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 151
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 151
- 239000000463 material Substances 0.000 claims description 52
- 239000011162 core material Substances 0.000 claims description 28
- 238000000034 method Methods 0.000 claims description 25
- 230000008569 process Effects 0.000 claims description 20
- 238000000151 deposition Methods 0.000 claims description 18
- 230000003197 catalytic effect Effects 0.000 claims description 14
- 238000004090 dissolution Methods 0.000 claims description 9
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 6
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 6
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 6
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 6
- 230000002378 acidificating effect Effects 0.000 claims description 5
- 239000011149 active material Substances 0.000 claims description 5
- 229910045601 alloy Inorganic materials 0.000 claims description 4
- 239000000956 alloy Substances 0.000 claims description 4
- 125000004432 carbon atom Chemical group C* 0.000 claims description 4
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 3
- 229910017052 cobalt Inorganic materials 0.000 claims description 3
- 239000010941 cobalt Substances 0.000 claims description 3
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 3
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 3
- 229910052737 gold Inorganic materials 0.000 claims description 3
- 239000010931 gold Substances 0.000 claims description 3
- 229910052742 iron Inorganic materials 0.000 claims description 3
- 229910052759 nickel Inorganic materials 0.000 claims description 3
- 229910052763 palladium Inorganic materials 0.000 claims description 3
- 229910052697 platinum Inorganic materials 0.000 claims description 3
- 229910052702 rhenium Inorganic materials 0.000 claims description 3
- WUAPFZMCVAUBPE-UHFFFAOYSA-N rhenium atom Chemical compound [Re] WUAPFZMCVAUBPE-UHFFFAOYSA-N 0.000 claims description 3
- 229910052703 rhodium Inorganic materials 0.000 claims description 3
- 239000010948 rhodium Substances 0.000 claims description 3
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 claims description 3
- 229910052709 silver Inorganic materials 0.000 claims description 3
- 239000004332 silver Substances 0.000 claims description 3
- 238000005229 chemical vapour deposition Methods 0.000 claims description 2
- 238000009833 condensation Methods 0.000 claims description 2
- 230000005494 condensation Effects 0.000 claims description 2
- 238000010891 electric arc Methods 0.000 claims description 2
- 238000000608 laser ablation Methods 0.000 claims description 2
- 238000007614 solvation Methods 0.000 claims description 2
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- 239000011257 shell material Substances 0.000 description 48
- 239000002243 precursor Substances 0.000 description 33
- 239000000443 aerosol Substances 0.000 description 31
- 239000007789 gas Substances 0.000 description 31
- 239000002245 particle Substances 0.000 description 18
- 239000002105 nanoparticle Substances 0.000 description 15
- MWPLVEDNUUSJAV-UHFFFAOYSA-N anthracene Chemical compound C1=CC=CC2=CC3=CC=CC=C3C=C21 MWPLVEDNUUSJAV-UHFFFAOYSA-N 0.000 description 12
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 12
- 239000000843 powder Substances 0.000 description 12
- 239000011258 core-shell material Substances 0.000 description 11
- 230000037361 pathway Effects 0.000 description 11
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 10
- 239000007788 liquid Substances 0.000 description 9
- 229910052718 tin Inorganic materials 0.000 description 9
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 8
- 125000004429 atom Chemical group 0.000 description 8
- 239000011263 electroactive material Substances 0.000 description 7
- 238000003917 TEM image Methods 0.000 description 6
- -1 poly(alkylene glycol Chemical compound 0.000 description 6
- 239000000203 mixture Substances 0.000 description 5
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 229910052786 argon Inorganic materials 0.000 description 4
- 239000003814 drug Substances 0.000 description 4
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- 229910052744 lithium Inorganic materials 0.000 description 4
- 239000002253 acid Substances 0.000 description 3
- 239000011852 carbon nanoparticle Substances 0.000 description 3
- 239000000919 ceramic Substances 0.000 description 3
- 239000011261 inert gas Substances 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 102000008394 Immunoglobulin Fragments Human genes 0.000 description 2
- 108010021625 Immunoglobulin Fragments Proteins 0.000 description 2
- 238000005275 alloying Methods 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000012377 drug delivery Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 2
- 239000010453 quartz Substances 0.000 description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
- 229920002732 Polyanhydride Polymers 0.000 description 1
- 229920000954 Polyglycolide Polymers 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- RQMIWLMVTCKXAQ-UHFFFAOYSA-N [AlH3].[C] Chemical compound [AlH3].[C] RQMIWLMVTCKXAQ-UHFFFAOYSA-N 0.000 description 1
- QWJYDTCSUDMGSU-UHFFFAOYSA-N [Sn].[C] Chemical compound [Sn].[C] QWJYDTCSUDMGSU-UHFFFAOYSA-N 0.000 description 1
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- 239000002246 antineoplastic agent Substances 0.000 description 1
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- 229910052732 germanium Inorganic materials 0.000 description 1
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 description 1
- 150000004676 glycans Chemical class 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
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- 150000002632 lipids Chemical class 0.000 description 1
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- 239000002088 nanocapsule Substances 0.000 description 1
- 150000007523 nucleic acids Chemical class 0.000 description 1
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- 239000011368 organic material Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 229920000747 poly(lactic acid) Polymers 0.000 description 1
- 229920001606 poly(lactic acid-co-glycolic acid) Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920001282 polysaccharide Polymers 0.000 description 1
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- 230000008707 rearrangement Effects 0.000 description 1
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- 229910052710 silicon Inorganic materials 0.000 description 1
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Images
Classifications
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/18—Carbon
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J13/00—Colloid chemistry, e.g. the production of colloidal materials or their solutions, not otherwise provided for; Making microcapsules or microballoons
- B01J13/02—Making microcapsules or microballoons
- B01J13/04—Making microcapsules or microballoons by physical processes, e.g. drying, spraying
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- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/48—Silver or gold
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- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/74—Iron group metals
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- B01J35/51—
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- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
- B01J37/0018—Addition of a binding agent or of material, later completely removed among others as result of heat treatment, leaching or washing,(e.g. forming of pores; protective layer, desintegrating by heat)
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- C—CHEMISTRY; METALLURGY
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- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/05—Preparation or purification of carbon not covered by groups C01B32/15, C01B32/20, C01B32/25, C01B32/30
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- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/626—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B
- C04B35/628—Coating the powders or the macroscopic reinforcing agents
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- C04B38/00—Porous mortars, concrete, artificial stone or ceramic ware; Preparation thereof
- C04B38/009—Porous or hollow ceramic granular materials, e.g. microballoons
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- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
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- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/30—Constituents and secondary phases not being of a fibrous nature
- C04B2235/40—Metallic constituents or additives not added as binding phase
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y10T428/00—Stock material or miscellaneous articles
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y10T428/2991—Coated
Definitions
- the present invention relates to a hollow carbon sphere, and in particular to a hollow carbon sphere having a large inner free volume.
- Hollow carbon spheres are known. For example, Xiong et al. 1 have reported hollow carbon spheres having diameters between 400 to 600 nanometers made from CCl 4 at temperatures between 190 and 230° C., Zhang et al. 2 have reported hollow carbon spheres with a nominal diameter of 400 nanometers and made using metal zinc powder and ethanol, Su et al. 3 have reported hollow carbon spheres made by coating silica spheres with carbon, and Win et al. 4 have reported hollow carbon spheres with diameters between 300 nanometers and 1 micron.
- U.S. Pat. No. 7,156,958 discloses a method for producing hollow carbon nanocapsules with a diameter between 3 to 60 nanometers and U.S. Patent Application Publication Nos. 2005/0079354 and 2007/0220873 disclose hollow carbon spheres with diameters less than 20 nanometers. However, these references do not disclose the size of an inner core or cavity within the hollow carbon structures. In contrast, U.S. Patent Application Publication No. 2007/0080054 does disclose an inner cavity of 5 nanometers within hollow carbon nanoparticles with a diameter of 20 nanometers and Phillips et al. 5,6 reported producing hollow graphite particles as small as 30 nm in diameter.
- hollow carbon spheres having diameters of less than 200 nanometers have been disclosed, however hollow carbon spheres within this size range with a relatively large inner free volume have not. Therefore, a hollow carbon sphere having a diameter of less than 200 nanometers with a relatively large inner free volume would be desirable.
- a hollow carbon sphere having a carbon shell and an inner free volume is disclosed.
- the hollow carbon sphere has a total volume that is equal to a volume of the carbon shell plus an inner free volume within the carbon shell.
- the inner free volume is at least 25% of the total volume.
- a nominal diameter of the hollow carbon sphere is between 10 and 180 nanometers.
- the carbon shell can have a pathway therethrough, for example a pathway in the form of porosity and/or a pathway in the form of a misfit region between two adjacent carbon grains that form at least part of the carbon shell.
- the pathway can afford for a material to be encapsulated within the hollow carbon sphere, for example an electro-active material, a catalytic material and/or a biologically active.
- the catalytic material can be located on a surface of the carbon shell, and in some instances be on an outer surface of the carbon shell.
- the catalytic material can include materials such as platinum, palladium, rhodium, rhenium, iron, nickel, cobalt, silver, gold and alloys thereof.
- a process for making hollow carbon spheres is also disclosed, the process including supplying a sacrificial core material which carbon will encapsulate, thereby forming a carbon shell. Thereafter, the sacrificial material is removed from within the carbon shell in order to produce the hollow carbon sphere.
- the hollow carbon sphere has an inner volume that is at least 25% of the total volume of the sphere.
- the depositing of carbon onto the sacrificial material can include depositing by condensation of carbon atoms.
- carbon can be vaporized within a plasma to form carbon vapor, followed by rearrangement and/or deposition of the carbon atoms onto the sacrificial material.
- the deposition of carbon onto the sacrificial core material can include depositing by chemical vapor deposition, depositing by laser ablation, depositing by electric arc discharge and depositing by low temperature solvation.
- the sacrificial material can be removed from within the carbon shell by acidic dissolution or by alkaline dissolution.
- FIG. 1 is a schematic illustration of a plurality of hollow carbon spheres according to an embodiment of the present invention
- FIG. 2 is a schematic illustration of the embodiment shown in FIG. 1 with an electro-active material within the plurality of hollow carbon spheres;
- FIG. 3 is a schematic illustration of the embodiment shown in FIG. 1 with catalytic material on a surface of the plurality of hollow carbon spheres;
- FIG. 4 is a TEM image showing a potential pathway through a carbon shell
- FIG. 5 is a schematic diagram of a process for making hollow carbon spheres
- FIG. 6 is a schematic diagram of an apparatus for making a core material encapsulated by carbon
- FIG. 7 is a schematic illustration of a carbon outer shell on a sacrificial material
- FIG. 8 is a TEM image of an outer carbon shell on a sacrificial material
- FIG. 9 is a schematic illustration of an apparatus for forming a core material encapsulated by carbon.
- FIG. 10 is a TEM image of hollow carbon spheres.
- the present invention discloses a hollow carbon sphere having a carbon shell with an inner free volume.
- a process for making the hollow carbon sphere is disclosed.
- the hollow carbon sphere can be used to encapsulate a material therewithin and/or to support a catalytic material.
- the hollow carbon sphere has utility as a battery material, a catalytic support structure material and the like.
- the process has utility for making hollow carbon spheres.
- the hollow carbon sphere has a total volume that is equal to a volume of the carbon shell plus a volume of the inner free space within the carbon shell.
- the inner free volume is at least 25% of the total volume. In some instances, the inner free volume is at least 50% of the total volume, while in other instances, the inner free volume is at least 75% of the total volume, and in still other instances the inner volume is at least 90% of the total volume.
- a nominal diameter of the hollow carbon sphere can be between 10 and 180 nanometers, and in some instances is between 50 and 150 nanometers. In still other instances, the nominal diameter of the hollow carbon sphere is between 80 and 120 nanometers.
- the carbon shell can have a nominal thickness that is between 2 to 30 nanometers, and in some instances is between 5 and 20 nanometers. In still other instances, the nominal thickness of the carbon shell is between 7 and 10 nanometers.
- the carbon shell can have a pathway therethrough that affords for the passing of material through the shell and into or out of the carbon sphere.
- the pathway can be in the form of porosity and/or a misfit region between two adjacent carbon grains wherein the diffusivity of atoms and/or molecules is enhanced.
- the hollow carbon spheres can be used to encapsulate an electro-active material therein.
- the electro-active material can be a material that alloys with lithium and/or a material that contains lithium.
- the hollow carbon sphere can also serve as a support structure for a catalytic material, the catalytic material being on a surface of the carbon shell.
- the surface can be an outer surface of the carbon shell, or in the alternative an inner surface of the carbon shell.
- the catalytic material can be a material such as platinum, palladium, rhodium, rhenium, iron, nickel, cobalt, silver, gold and/or alloys thereof.
- hollow carbon sphere can be used for drug delivery by having a biologically active material within and/or on the carbon shell.
- the hollow carbon sphere can include a biologically active material or molecule therewithin to be delivered and optionally a polymer that is covalently bound to the biologically active molecule, for example, an antibody or antibody fragment.
- the biologically active molecule can be located within and/or on the outside surface of the hollow carbon sphere.
- the biologically active molecule can be any molecule used to treat a patient, illustratively including a protein, carbohydrate or polysaccharide, nucleic acid, lipid, a combination thereof, or a synthetic molecule, including organic and inorganic materials.
- the hollow carbon spheres can be used as injectable particles, the hollow carbon spheres having a substance to be delivered and a copolymer of poly(alkylene glycol) with poly(lactic-co-glycolic acid), poly(lactic-acid), poly(glycolic acid), or polyanhydride, wherein the poly(alkylene glycol) is covalently bound to an antibody or antibody fragment.
- the hollow carbon spheres can be used to release over long periods of time highly active and effective drugs, such as anticancer drugs, that produce significant side effects when administered systemically. It is appreciated that the controlled release generally decreases the toxic side effects associated with systemic administration of the non-encapsulated drug.
- the polymeric matrix can also provide protection of the drugs against degradation in the plasma for drugs with short biological half-lives.
- a process for making a hollow carbon sphere can include providing a sacrificial material, depositing carbon onto the sacrificial material in order to form a carbon shell and removing the sacrificial material in order to produce the hollow carbon sphere.
- the sacrificial material can be any material that is removable from within the carbon shell by acidic dissolution or alkaline dissolution.
- a precursor in the form of a dry precursor powder, a liquid and/or a vapor of a liquid can be provided, the precursor suspended in an aerosol gas to produce an aerosol containing the precursor.
- the aerosol can be passed through a plasma having a hot zone with at least part of the precursors in the aerosol being vaporized. New particles can be created in the hot zone by reorganization of atoms from the precursor, and sometimes atoms from the aerosol gas as well.
- the aerosol gas can carry the new particles out of the hot zone and into a plasma afterglow region where extremely rapid cooling occurs.
- the particles can then be carried into a zone that is near ambient temperature where the particles can be removed from the aerosol gas generally with a filter. Thereafter, acidic dissolution or alkaline dissolution can be used to remove the core material from within the carbon shell.
- the hot zone of the plasma can be a region of high electromagnetic energy that can be generated using radio frequency, microwave energy or direct current discharge.
- the plasma can be a non-oxidizing plasma and in some instances is a low power atmospheric or near-atmospheric pressure plasma with the plasma generated by focusing microwave energy within a coupler.
- the aerosol gas can be an inert gas, illustratively including helium, argon and combinations thereof.
- the process can further include passing a plasma gas in addition to the aerosol through the hot zone of the plasma, the plasma gas also being an inert gas.
- the core material is a lithium alloying material and can contain an element such as tin, silicon, aluminum, germanium, combinations thereof and the like.
- the embodiment 10 can include one or more hollow carbon spheres 100 , the hollow carbon sphere 100 having a carbon shell 110 and an inner free volume 120 .
- the hollow carbon sphere 100 can include a radius 112 that extends from a center 102 of the sphere to an outer surface 116 of the carbon shell 110 .
- the hollow carbon sphere 100 can have an inner radius 124 that extends from the center 102 of the sphere to an inner surface 118 .
- the hollow carbon sphere 100 can have a total volume equal to 4/3 ⁇ R t 3 wherein R t is equivalent to the radius 112 as shown in FIG. 1 .
- the hollow carbon sphere 100 can have an inner free space volume equal to 4/3 ⁇ R i 3 wherein R i is equal to the inner radius 124 as shown in FIG. 1 .
- the inner free space volume is equal to at least 25% of the total volume for the hollow carbon sphere 100 . In other instances, the inner free space volume is at least 50% of the total volume, while in still other instances, the inner free space volume is at least 75% of the total volume. In still yet other instances, the inner free space volume is at least 90% of the total volume.
- the carbon shell 110 can have a pathway therethrough.
- the pathway can be in the form of porosity 114 as shown in FIG. 1 .
- the porosity 114 can afford for the passing, migration and/or diffusion of atoms and/or molecules through the carbon shell 110 .
- the pathway can be afforded by a misfit region between adjacent carbon grains that are part of the carbon shell 110 .
- FIG. 4 shows a transmission electron microscopy (TEM) image of a hollow carbon sphere with two adjacent grains 111 having different orientations schematically shown at 113 .
- the grains 111 have lines schematically drawn thereon that corresponding to rows of carbon atoms, thereby illustrating that the two grains 111 do not have the same orientation.
- TEM transmission electron microscopy
- the region 113 located between the two adjacent grains 111 can afford for enhanced diffusivity of atoms and/or molecules therethrough.
- atoms and/or molecules from an acid or alkaline solution can pass through the carbon shell and come into contact with the sacrificial material.
- the sacrificial material that has been dissolved can exit the hollow carbon sphere 100 .
- the hollow carbon sphere 100 can have an electro-active material 135 encapsulated therewithin.
- the electro-active material 135 can include a lithium alloying material. It is appreciated that the electro-active material 135 is deposited within the hollow carbon sphere 100 by first passing through the pathway described above of the carbon shell 110 .
- the hollow carbon sphere 100 has a catalytic material 140 supported by the carbon shell 110 .
- the catalytic material 140 can be present on the outer surface 116 and/or the inner surface 118 of the carbon shell 110 . It is appreciated that a biologically active material or molecule can be located within and/or on the carbon shell 110 and thus afford for the hollow carbon sphere to be used for drug delivery.
- the process 20 includes providing a precursor in the form of a powder, a liquid and/or a vapor of a liquid at step 200 and passing the precursor through a plasma torch at step 202 .
- a plasma torch at step 202 .
- at least part of a shell material and at least part of a core material that is contained within the precursor is vaporized.
- the vaporized material then condenses to form a core-shell structured nanoparticle at step 204 .
- the sacrificial material that is within an outer shell is removed and a hollow carbon sphere is produced.
- FIG. 6 provides a schematic representation of an apparatus for producing the core-shell structured nanoparticles at reference numeral 30 .
- an aerosol gas 300 passes through an inlet tube 310 into a precursor container 320 that contains a precursor 322 .
- Flow of the aerosol gas 300 into the precursor container 320 at a sufficient flow rate results in the suspension of the precursor 322 within the aerosol gas 300 to produce an aerosol.
- the precursor 322 can contain core material and shell material.
- the precursor 322 can also contain elements that are not incorporated within the core and/or shell of any core/shell structured nanoparticles that are produced, but may be present to assist in the overall process in some manner.
- the exit tube 330 can pass or flow through the exit tube 330 with at least part of the exit tube 330 passing into a plasma torch 340 .
- the exit tube 330 has a ceramic portion 332 that terminates generally in the middle of a waveguide 360 .
- the waveguide 360 is used to couple microwave energy to the plasma torch 340 .
- a plasma gas 350 which passes within the plasma torch 340 , but exterior to the ceramic portion 332 of the exit tube 330 which has the aerosol passing therethrough.
- a plasma can be generated with a hot zone 342 located within the plasma torch 340 .
- the temperature of the hot zone 342 is such that at least part of the precursor 322 is vaporized.
- the vaporized precursor 322 exits the hot zone 342 of the plasma torch 340 and enters into a chimney region 370 .
- the atoms of the vaporized precursor condense into solid particles.
- the passing or flowing of the aerosol through the hot zone 342 of the plasma torch 340 results in the vaporization of at least part of the core material and at least part of the shell material. Thereafter, the core and shell material atoms condense into core-shell structured nanoparticles.
- the core-shell structured nanoparticles can be collected from a particle filter 390 , from the interior side walls of the chimney region 370 and/or from a particle trap (not shown).
- the core-shell structured nanoparticles After the core-shell structured nanoparticles have been collected, they can be placed within an acidic or alkaline bath.
- the acid or acid or alkaline bath comes into contact with the sacrificial material or inner core and results in dissolution thereof. As such, hollow carbon spheres are produced.
- dry precursor powders were provided by hand grinding a mixture of micrometer tin particles with crystalline anthracene particles to produce the dry precursor powder 322 .
- the weight ratio of tin to anthracene was 50:1, the tin particles had an average diameter of 50 microns and the mixture of tin particles and anthracene crystals was hand ground until the product appeared fully homogeneous.
- the dry precursor powder 322 was placed within the precursor powder container 320 .
- Argon with a flow rate of 200 cubic centimeters per minute (cc/min) at standard temperature and pressure (STP) was used for the plasma gas 350 and was passed through the plasma torch 340 .
- argon with a flow rate of 300 cc/min at STP was used as the aerosol gas 300 and allowed to pass or flow into the precursor powder container 320 .
- the aerosol gas 300 had tin particles and anthracene particles from the dry precursor powder 322 suspended therein, thereby producing an aerosol.
- the aerosol containing the tin and anthracene particles exited the ceramic portion 332 of the exit tube 330 and entered the hot zone of the plasma generally at the middle of the waveguide section 360 .
- the waveguide section 360 coupled microwave energy to the plasma torch 340 such that an absorbed power of approximately 900 watts was present.
- the plasma torch was made from a quartz tube.
- the plasma itself was confined within the quartz torch 340 and the residence time of the plasma gas and the aerosol was relatively short, for example less than 1 second. Thereafter, new particles passed from the hot zone to an afterglow region and finally to a zone that was at near ambient temperature.
- core-shell structured nanoparticles having a tin core and a carbon shell with a mean nanoparticle diameter of 50 nanometers and a relatively tight size distribution were produced.
- FIG. 7 illustrates such a nanoparticle generally at reference numeral 210 , the core-shell structured nanoparticle 210 having an inner core 212 and an outer shell 214 .
- FIG. 8 shows a transmission electron microscopy (TEM) image of actual tin core-carbon shell nanoparticles produced using the parameters disclosed above.
- TEM transmission electron microscopy
- the sacrificial material of the inner core was removed by using a dissolution method as disclosed in U.S. Pat. No. 3,986,970, which is incorporated herein by reference in its entirety.
- precursor powder materials can be used to produce other core-shell structured nanoparticles, for example and for illustrative purposes only, aluminum micron-sized particles and anthracene can be used as precursor materials to produce aluminum-carbon nanoparticles.
- the liquid carbon source 327 was placed in a container 325 with an aerosol gas 300 flowing into the container 325 and above the source 327 before exiting the container 325 .
- vapor of the carbon source is suspended in the aerosol gas 300 as it flowed out of the container 325 and towards the container 320 .
- approximately 900 watts of absorbed power was present at the plasma torch 340 argon was used as the plasma and aerosol gases.
- flow rates of 250 cc/min for the plasma gas 350 , 30 cc/min for the aerosol gas 300 and 160 cc/min for the aerosol gas 300 afforded tin core-carbon shell nanoparticles.
- the sacrificial material was removed as described in the previous example with FIG. 10 showing a TEM image of hollow carbon spheres produced in this manner.
- the present invention is not bound by or to specific flow stream rates, compositions or configurations.
- other gas flow and/or plasma systems are included within the scope of the present invention.
- a method using a direct current (DC) discharge plasma having a one flow gas system wherein an aerosol gas and a plasma gas are one in the same is within the scope of the disclosed inventive method. This method would result in all of the gas that flows through the plasma and the precursor being well mixed before reaching the hot zone, as opposed to the two gas flow system wherein the aerosol gas and the plasma gas mix with each other in the center of the hot zone as described in the examples above.
- DC direct current
Abstract
Description
- This invention was made with government support under Contract No. DE-AC52-06NA25396 ordered by the U.S. Department of Energy. The government has certain rights in the invention.
- The present invention relates to a hollow carbon sphere, and in particular to a hollow carbon sphere having a large inner free volume.
- Hollow carbon spheres are known. For example, Xiong et al.1 have reported hollow carbon spheres having diameters between 400 to 600 nanometers made from CCl4 at temperatures between 190 and 230° C., Zhang et al.2 have reported hollow carbon spheres with a nominal diameter of 400 nanometers and made using metal zinc powder and ethanol, Su et al.3 have reported hollow carbon spheres made by coating silica spheres with carbon, and Win et al.4 have reported hollow carbon spheres with diameters between 300 nanometers and 1 micron.
- Regarding hollow carbon spheres having diameters of less than 200 nanometers, U.S. Pat. No. 7,156,958 discloses a method for producing hollow carbon nanocapsules with a diameter between 3 to 60 nanometers and U.S. Patent Application Publication Nos. 2005/0079354 and 2007/0220873 disclose hollow carbon spheres with diameters less than 20 nanometers. However, these references do not disclose the size of an inner core or cavity within the hollow carbon structures. In contrast, U.S. Patent Application Publication No. 2007/0080054 does disclose an inner cavity of 5 nanometers within hollow carbon nanoparticles with a diameter of 20 nanometers and Phillips et al.5,6 reported producing hollow graphite particles as small as 30 nm in diameter.
- As such, hollow carbon spheres having diameters of less than 200 nanometers have been disclosed, however hollow carbon spheres within this size range with a relatively large inner free volume have not. Therefore, a hollow carbon sphere having a diameter of less than 200 nanometers with a relatively large inner free volume would be desirable.
- A hollow carbon sphere having a carbon shell and an inner free volume is disclosed. The hollow carbon sphere has a total volume that is equal to a volume of the carbon shell plus an inner free volume within the carbon shell. The inner free volume is at least 25% of the total volume. In some instances, a nominal diameter of the hollow carbon sphere is between 10 and 180 nanometers.
- The carbon shell can have a pathway therethrough, for example a pathway in the form of porosity and/or a pathway in the form of a misfit region between two adjacent carbon grains that form at least part of the carbon shell. The pathway can afford for a material to be encapsulated within the hollow carbon sphere, for example an electro-active material, a catalytic material and/or a biologically active. In addition, the catalytic material can be located on a surface of the carbon shell, and in some instances be on an outer surface of the carbon shell. The catalytic material can include materials such as platinum, palladium, rhodium, rhenium, iron, nickel, cobalt, silver, gold and alloys thereof.
- A process for making hollow carbon spheres is also disclosed, the process including supplying a sacrificial core material which carbon will encapsulate, thereby forming a carbon shell. Thereafter, the sacrificial material is removed from within the carbon shell in order to produce the hollow carbon sphere. The hollow carbon sphere has an inner volume that is at least 25% of the total volume of the sphere.
- The depositing of carbon onto the sacrificial material can include depositing by condensation of carbon atoms. For example, carbon can be vaporized within a plasma to form carbon vapor, followed by rearrangement and/or deposition of the carbon atoms onto the sacrificial material. In addition, the deposition of carbon onto the sacrificial core material can include depositing by chemical vapor deposition, depositing by laser ablation, depositing by electric arc discharge and depositing by low temperature solvation. The sacrificial material can be removed from within the carbon shell by acidic dissolution or by alkaline dissolution.
-
FIG. 1 is a schematic illustration of a plurality of hollow carbon spheres according to an embodiment of the present invention -
FIG. 2 is a schematic illustration of the embodiment shown inFIG. 1 with an electro-active material within the plurality of hollow carbon spheres; -
FIG. 3 is a schematic illustration of the embodiment shown inFIG. 1 with catalytic material on a surface of the plurality of hollow carbon spheres; -
FIG. 4 is a TEM image showing a potential pathway through a carbon shell; -
FIG. 5 is a schematic diagram of a process for making hollow carbon spheres; -
FIG. 6 is a schematic diagram of an apparatus for making a core material encapsulated by carbon; -
FIG. 7 is a schematic illustration of a carbon outer shell on a sacrificial material; -
FIG. 8 is a TEM image of an outer carbon shell on a sacrificial material; -
FIG. 9 is a schematic illustration of an apparatus for forming a core material encapsulated by carbon; and -
FIG. 10 is a TEM image of hollow carbon spheres. - The present invention discloses a hollow carbon sphere having a carbon shell with an inner free volume. In addition, a process for making the hollow carbon sphere is disclosed. The hollow carbon sphere can be used to encapsulate a material therewithin and/or to support a catalytic material. As such, the hollow carbon sphere has utility as a battery material, a catalytic support structure material and the like. In addition, the process has utility for making hollow carbon spheres.
- The hollow carbon sphere has a total volume that is equal to a volume of the carbon shell plus a volume of the inner free space within the carbon shell. The inner free volume is at least 25% of the total volume. In some instances, the inner free volume is at least 50% of the total volume, while in other instances, the inner free volume is at least 75% of the total volume, and in still other instances the inner volume is at least 90% of the total volume.
- A nominal diameter of the hollow carbon sphere can be between 10 and 180 nanometers, and in some instances is between 50 and 150 nanometers. In still other instances, the nominal diameter of the hollow carbon sphere is between 80 and 120 nanometers. The carbon shell can have a nominal thickness that is between 2 to 30 nanometers, and in some instances is between 5 and 20 nanometers. In still other instances, the nominal thickness of the carbon shell is between 7 and 10 nanometers.
- The carbon shell can have a pathway therethrough that affords for the passing of material through the shell and into or out of the carbon sphere. The pathway can be in the form of porosity and/or a misfit region between two adjacent carbon grains wherein the diffusivity of atoms and/or molecules is enhanced.
- The hollow carbon spheres can be used to encapsulate an electro-active material therein. The electro-active material can be a material that alloys with lithium and/or a material that contains lithium. The hollow carbon sphere can also serve as a support structure for a catalytic material, the catalytic material being on a surface of the carbon shell. The surface can be an outer surface of the carbon shell, or in the alternative an inner surface of the carbon shell. The catalytic material can be a material such as platinum, palladium, rhodium, rhenium, iron, nickel, cobalt, silver, gold and/or alloys thereof.
- In addition, hollow carbon sphere can be used for drug delivery by having a biologically active material within and/or on the carbon shell. For example and for illustrative purposes only, the hollow carbon sphere can include a biologically active material or molecule therewithin to be delivered and optionally a polymer that is covalently bound to the biologically active molecule, for example, an antibody or antibody fragment. The biologically active molecule can be located within and/or on the outside surface of the hollow carbon sphere. The biologically active molecule can be any molecule used to treat a patient, illustratively including a protein, carbohydrate or polysaccharide, nucleic acid, lipid, a combination thereof, or a synthetic molecule, including organic and inorganic materials.
- In some instances, the hollow carbon spheres can be used as injectable particles, the hollow carbon spheres having a substance to be delivered and a copolymer of poly(alkylene glycol) with poly(lactic-co-glycolic acid), poly(lactic-acid), poly(glycolic acid), or polyanhydride, wherein the poly(alkylene glycol) is covalently bound to an antibody or antibody fragment. As such, the hollow carbon spheres can be used to release over long periods of time highly active and effective drugs, such as anticancer drugs, that produce significant side effects when administered systemically. It is appreciated that the controlled release generally decreases the toxic side effects associated with systemic administration of the non-encapsulated drug. The polymeric matrix can also provide protection of the drugs against degradation in the plasma for drugs with short biological half-lives.
- A process for making a hollow carbon sphere can include providing a sacrificial material, depositing carbon onto the sacrificial material in order to form a carbon shell and removing the sacrificial material in order to produce the hollow carbon sphere. The sacrificial material can be any material that is removable from within the carbon shell by acidic dissolution or alkaline dissolution.
- In some instances, a precursor in the form of a dry precursor powder, a liquid and/or a vapor of a liquid can be provided, the precursor suspended in an aerosol gas to produce an aerosol containing the precursor. In addition, the aerosol can be passed through a plasma having a hot zone with at least part of the precursors in the aerosol being vaporized. New particles can be created in the hot zone by reorganization of atoms from the precursor, and sometimes atoms from the aerosol gas as well.
- The aerosol gas can carry the new particles out of the hot zone and into a plasma afterglow region where extremely rapid cooling occurs. The particles can then be carried into a zone that is near ambient temperature where the particles can be removed from the aerosol gas generally with a filter. Thereafter, acidic dissolution or alkaline dissolution can be used to remove the core material from within the carbon shell.
- The hot zone of the plasma can be a region of high electromagnetic energy that can be generated using radio frequency, microwave energy or direct current discharge. The plasma can be a non-oxidizing plasma and in some instances is a low power atmospheric or near-atmospheric pressure plasma with the plasma generated by focusing microwave energy within a coupler.
- The aerosol gas can be an inert gas, illustratively including helium, argon and combinations thereof. The process can further include passing a plasma gas in addition to the aerosol through the hot zone of the plasma, the plasma gas also being an inert gas. In some instances, the core material is a lithium alloying material and can contain an element such as tin, silicon, aluminum, germanium, combinations thereof and the like.
- Turning now to
FIG. 1 , an embodiment of a hollow carbon sphere is shown generally atreference numeral 10. Theembodiment 10 can include one or morehollow carbon spheres 100, thehollow carbon sphere 100 having acarbon shell 110 and an innerfree volume 120. Thehollow carbon sphere 100 can include aradius 112 that extends from acenter 102 of the sphere to anouter surface 116 of thecarbon shell 110. In addition, thehollow carbon sphere 100 can have aninner radius 124 that extends from thecenter 102 of the sphere to aninner surface 118. As such, thehollow carbon sphere 100 can have a total volume equal to 4/3πRt 3 wherein Rt is equivalent to theradius 112 as shown inFIG. 1 . Likewise, thehollow carbon sphere 100 can have an inner free space volume equal to 4/3πRi 3 wherein Ri is equal to theinner radius 124 as shown inFIG. 1 . - In some instances, the inner free space volume is equal to at least 25% of the total volume for the
hollow carbon sphere 100. In other instances, the inner free space volume is at least 50% of the total volume, while in still other instances, the inner free space volume is at least 75% of the total volume. In still yet other instances, the inner free space volume is at least 90% of the total volume. - The
carbon shell 110 can have a pathway therethrough. For example and for illustrative purposes only, the pathway can be in the form ofporosity 114 as shown inFIG. 1 . Theporosity 114 can afford for the passing, migration and/or diffusion of atoms and/or molecules through thecarbon shell 110. In addition, the pathway can be afforded by a misfit region between adjacent carbon grains that are part of thecarbon shell 110. For example,FIG. 4 shows a transmission electron microscopy (TEM) image of a hollow carbon sphere with twoadjacent grains 111 having different orientations schematically shown at 113. Thegrains 111 have lines schematically drawn thereon that corresponding to rows of carbon atoms, thereby illustrating that the twograins 111 do not have the same orientation. As such, it is appreciated that theregion 113 located between the twoadjacent grains 111 can afford for enhanced diffusivity of atoms and/or molecules therethrough. In this manner, atoms and/or molecules from an acid or alkaline solution can pass through the carbon shell and come into contact with the sacrificial material. Likewise, the sacrificial material that has been dissolved can exit thehollow carbon sphere 100. - Turning now to
FIG. 2 , thehollow carbon sphere 100 can have an electro-active material 135 encapsulated therewithin. The electro-active material 135 can include a lithium alloying material. It is appreciated that the electro-active material 135 is deposited within thehollow carbon sphere 100 by first passing through the pathway described above of thecarbon shell 110. - Looking now at
FIG. 3 , thehollow carbon sphere 100 has acatalytic material 140 supported by thecarbon shell 110. Thecatalytic material 140 can be present on theouter surface 116 and/or theinner surface 118 of thecarbon shell 110. It is appreciated that a biologically active material or molecule can be located within and/or on thecarbon shell 110 and thus afford for the hollow carbon sphere to be used for drug delivery. - Turning now to
FIG. 5 , an embodiment for producing the hollow carbon sphere is shown generally atreference numeral 20. Theprocess 20 includes providing a precursor in the form of a powder, a liquid and/or a vapor of a liquid atstep 200 and passing the precursor through a plasma torch atstep 202. Upon passing the precursor through the plasma torch atstep 202, at least part of a shell material and at least part of a core material that is contained within the precursor is vaporized. The vaporized material then condenses to form a core-shell structured nanoparticle atstep 204. Thereafter, the sacrificial material that is within an outer shell is removed and a hollow carbon sphere is produced. -
FIG. 6 provides a schematic representation of an apparatus for producing the core-shell structured nanoparticles atreference numeral 30. As shown in this figure, anaerosol gas 300 passes through aninlet tube 310 into aprecursor container 320 that contains aprecursor 322. Flow of theaerosol gas 300 into theprecursor container 320 at a sufficient flow rate results in the suspension of theprecursor 322 within theaerosol gas 300 to produce an aerosol. Theprecursor 322 can contain core material and shell material. Theprecursor 322 can also contain elements that are not incorporated within the core and/or shell of any core/shell structured nanoparticles that are produced, but may be present to assist in the overall process in some manner. - After the aerosol has been produced, it can pass or flow through the
exit tube 330 with at least part of theexit tube 330 passing into aplasma torch 340. In some instances, theexit tube 330 has aceramic portion 332 that terminates generally in the middle of awaveguide 360. Thewaveguide 360 is used to couple microwave energy to theplasma torch 340. Also included can be aplasma gas 350 which passes within theplasma torch 340, but exterior to theceramic portion 332 of theexit tube 330 which has the aerosol passing therethrough. Upon focusing microwave energy with thewaveguide 360 onto theplasma torch 340, a plasma can be generated with ahot zone 342 located within theplasma torch 340. As the aerosol with theprecursor 322 passes through thehot zone 342 of theplasma torch 340, the temperature of thehot zone 342 is such that at least part of theprecursor 322 is vaporized. The vaporizedprecursor 322 exits thehot zone 342 of theplasma torch 340 and enters into achimney region 370. Upon exiting thehot zone 342, the atoms of the vaporized precursor condense into solid particles. - If the
precursor 322 contains a core material and a shell material, the passing or flowing of the aerosol through thehot zone 342 of theplasma torch 340 results in the vaporization of at least part of the core material and at least part of the shell material. Thereafter, the core and shell material atoms condense into core-shell structured nanoparticles. The core-shell structured nanoparticles can be collected from aparticle filter 390, from the interior side walls of thechimney region 370 and/or from a particle trap (not shown). - After the core-shell structured nanoparticles have been collected, they can be placed within an acidic or alkaline bath. The acid or acid or alkaline bath comes into contact with the sacrificial material or inner core and results in dissolution thereof. As such, hollow carbon spheres are produced.
- In order to better illustrate an embodiment of the present invention, an example of a process wherein hollow carbon spheres were produced is provided below.
- With reference to
FIG. 6 , dry precursor powders were provided by hand grinding a mixture of micrometer tin particles with crystalline anthracene particles to produce thedry precursor powder 322. The weight ratio of tin to anthracene was 50:1, the tin particles had an average diameter of 50 microns and the mixture of tin particles and anthracene crystals was hand ground until the product appeared fully homogeneous. Thedry precursor powder 322 was placed within theprecursor powder container 320. Argon with a flow rate of 200 cubic centimeters per minute (cc/min) at standard temperature and pressure (STP) was used for theplasma gas 350 and was passed through theplasma torch 340. - In order to produce an aerosol containing the
dry precursor powder 322, argon with a flow rate of 300 cc/min at STP was used as theaerosol gas 300 and allowed to pass or flow into theprecursor powder container 320. Upon flowing into theprecursor powder container 320 and subsequently exiting therefrom through theexit tube 330, theaerosol gas 300 had tin particles and anthracene particles from thedry precursor powder 322 suspended therein, thereby producing an aerosol. The aerosol containing the tin and anthracene particles exited theceramic portion 332 of theexit tube 330 and entered the hot zone of the plasma generally at the middle of thewaveguide section 360. Thewaveguide section 360 coupled microwave energy to theplasma torch 340 such that an absorbed power of approximately 900 watts was present. In this example, the plasma torch was made from a quartz tube. The plasma itself was confined within thequartz torch 340 and the residence time of the plasma gas and the aerosol was relatively short, for example less than 1 second. Thereafter, new particles passed from the hot zone to an afterglow region and finally to a zone that was at near ambient temperature. Using these parameters, core-shell structured nanoparticles having a tin core and a carbon shell with a mean nanoparticle diameter of 50 nanometers and a relatively tight size distribution were produced.FIG. 7 illustrates such a nanoparticle generally atreference numeral 210, the core-shell structurednanoparticle 210 having aninner core 212 and anouter shell 214.FIG. 8 shows a transmission electron microscopy (TEM) image of actual tin core-carbon shell nanoparticles produced using the parameters disclosed above. - After the core-shell structured nanoparticles were produced, the sacrificial material of the inner core was removed by using a dissolution method as disclosed in U.S. Pat. No. 3,986,970, which is incorporated herein by reference in its entirety.
- Although the above example produced tin-carbon nanoparticles, it is appreciated that other precursor powder materials can be used to produce other core-shell structured nanoparticles, for example and for illustrative purposes only, aluminum micron-sized particles and anthracene can be used as precursor materials to produce aluminum-carbon nanoparticles.
- With reference to
FIG. 9 wherein like numerals correspond to like elements referenced inFIG. 6 , dry precursor powders were provided as described above for Example 1, in addition to aliquid carbon source 327 in the form of hexane (C6H14) and/or its vapor. It is appreciated that hexane is a colorless liquid at room temperature, melts at −95° C., boils at 69° C. and has a vapor pressure of 132 mmHg at 20° C. and 1 atmosphere pressure. It is further appreciated that other liquid carbon sources and other methods of incorporating liquid drops and/or its vapor into an inert gas (e.g. ultrasonic vibration of hexane to produce a direct hexane aerosol) can be used within the scope of the present invention. - As illustrated in
FIG. 9 , theliquid carbon source 327 was placed in acontainer 325 with anaerosol gas 300 flowing into thecontainer 325 and above thesource 327 before exiting thecontainer 325. In this manner, vapor of the carbon source is suspended in theaerosol gas 300 as it flowed out of thecontainer 325 and towards thecontainer 320. For this particular example, approximately 900 watts of absorbed power was present at theplasma torch 340 argon was used as the plasma and aerosol gases. In addition, flow rates of 250 cc/min for theplasma gas aerosol gas 300 and 160 cc/min for theaerosol gas 300 afforded tin core-carbon shell nanoparticles. - After the core-shell structured nanoparticles were produced, the sacrificial material was removed as described in the previous example with
FIG. 10 showing a TEM image of hollow carbon spheres produced in this manner. - It is appreciated that the present invention is not bound by or to specific flow stream rates, compositions or configurations. In addition, even though the above examples disclose a method having a dual gas flow system with each gas flow having a different overall composition and only joining and mixing at the plasma hot zone, other gas flow and/or plasma systems are included within the scope of the present invention. For example and for illustrative purposes only, a method using a direct current (DC) discharge plasma having a one flow gas system wherein an aerosol gas and a plasma gas are one in the same is within the scope of the disclosed inventive method. This method would result in all of the gas that flows through the plasma and the precursor being well mixed before reaching the hot zone, as opposed to the two gas flow system wherein the aerosol gas and the plasma gas mix with each other in the center of the hot zone as described in the examples above.
- The foregoing drawings, discussion and description are illustrative of specific embodiments of the present invention, but they are not meant to be limitations upon the practice thereof. Numerous modifications and variations of the invention will be readily apparent to those of skill in the art in view of the teaching presented herein. It is the following claims, including all equivalents, which define the scope of the invention.
- 1. Yujie Xiong, Yi Xie, Zhengquan Li, Changzheng Wu and Rong Zhang, Chem. Commun., Royal Society of Chemistry, 2003, 904-905.
- 2. Wu Zhang, Jianwei Liu, Zhen Huang, Dekun Ma, Jianbo Liang, and Yitai Qian, Chemistry Letters, The Chemical Society of Japan, 2004, Vol. 33, No. 10, 1346-1347.
- 3. Fabing Su, X. S, Zhao, Yong Wang, Likui Wang and Jim Yang Lee, J. Mater. Chem., Royal Society of Chemistry, 2006, 16, 4413-4419.
- 4. Zhenhai Wen, Qiang Wang, Qian Zhang, Jinghong Li, Electrochemistry Communications, Elsevier, 2007, 9, 1867-1872.
- 5. Jonathan Phillips, Toshi Shiina, Martin Nemer and Kelvin Lester, Langmuir 22, 2006, 9694.
- 6. Jonathan Phillips, Martin Nemer and John Weigle U.S. Patent Application Publication No. 2006/0198949, USPTO, published Sep. 7, 2006.
Claims (16)
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US12/391,794 US20100215960A1 (en) | 2009-02-24 | 2009-02-24 | Hollow carbon spheres |
JP2010038831A JP2010222239A (en) | 2009-02-24 | 2010-02-24 | Hollow carbon sphere |
CN2010101809833A CN101905875A (en) | 2009-02-24 | 2010-02-24 | Hollow carbon sphere |
US13/080,738 US8419998B2 (en) | 2009-02-24 | 2011-04-06 | Process for making hollow carbon spheres |
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US13/080,738 Expired - Fee Related US8419998B2 (en) | 2009-02-24 | 2011-04-06 | Process for making hollow carbon spheres |
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CN107572500A (en) * | 2017-10-20 | 2018-01-12 | 中南大学 | A kind of Nano/micron carbon hollow ball and its preparation method and application |
CN111410177A (en) * | 2020-04-23 | 2020-07-14 | 西北工业大学 | Hollow carbon sphere packaged superfine inorganic particle composite material and preparation method and application thereof |
Also Published As
Publication number | Publication date |
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US8419998B2 (en) | 2013-04-16 |
US20110180513A1 (en) | 2011-07-28 |
JP2010222239A (en) | 2010-10-07 |
CN101905875A (en) | 2010-12-08 |
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