WO2009122139A1 - Procédé de dépôt chimique en phase vapeur - Google Patents
Procédé de dépôt chimique en phase vapeur Download PDFInfo
- Publication number
- WO2009122139A1 WO2009122139A1 PCT/GB2009/000787 GB2009000787W WO2009122139A1 WO 2009122139 A1 WO2009122139 A1 WO 2009122139A1 GB 2009000787 W GB2009000787 W GB 2009000787W WO 2009122139 A1 WO2009122139 A1 WO 2009122139A1
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- WIPO (PCT)
- Prior art keywords
- chamber
- carbon
- substrate
- continuous
- process according
- Prior art date
Links
- 238000000034 method Methods 0.000 title claims abstract description 67
- 230000008569 process Effects 0.000 title claims abstract description 49
- 238000005229 chemical vapour deposition Methods 0.000 title description 44
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 66
- 239000000758 substrate Substances 0.000 claims abstract description 65
- 238000000151 deposition Methods 0.000 claims abstract description 28
- 230000008021 deposition Effects 0.000 claims abstract description 24
- 239000002717 carbon nanostructure Substances 0.000 claims abstract description 19
- 238000002230 thermal chemical vapour deposition Methods 0.000 claims abstract description 16
- 239000000203 mixture Substances 0.000 claims abstract description 15
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- 239000000835 fiber Substances 0.000 claims description 19
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- 238000010924 continuous production Methods 0.000 abstract description 6
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- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 16
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- 230000008901 benefit Effects 0.000 description 3
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- 229910017052 cobalt Inorganic materials 0.000 description 3
- 239000010941 cobalt Substances 0.000 description 3
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 3
- KTWOOEGAPBSYNW-UHFFFAOYSA-N ferrocene Chemical compound [Fe+2].C=1C=C[CH-]C=1.C=1C=C[CH-]C=1 KTWOOEGAPBSYNW-UHFFFAOYSA-N 0.000 description 3
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- 229910052723 transition metal Inorganic materials 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 101100194816 Caenorhabditis elegans rig-3 gene Proteins 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 238000001505 atmospheric-pressure chemical vapour deposition Methods 0.000 description 2
- 230000004888 barrier function Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
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- MVFCKEFYUDZOCX-UHFFFAOYSA-N iron(2+);dinitrate Chemical compound [Fe+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MVFCKEFYUDZOCX-UHFFFAOYSA-N 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
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- XMWRBQBLMFGWIX-UHFFFAOYSA-N C60 fullerene Chemical class C12=C3C(C4=C56)=C7C8=C5C5=C9C%10=C6C6=C4C1=C1C4=C6C6=C%10C%10=C9C9=C%11C5=C8C5=C8C7=C3C3=C7C2=C1C1=C2C4=C6C4=C%10C6=C9C9=C%11C5=C5C8=C3C3=C7C1=C1C2=C4C6=C2C9=C5C3=C12 XMWRBQBLMFGWIX-UHFFFAOYSA-N 0.000 description 1
- 101100493711 Caenorhabditis elegans bath-41 gene Proteins 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- 206010010144 Completed suicide Diseases 0.000 description 1
- 229910000608 Fe(NO3)3.9H2O Inorganic materials 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 1
- 239000002250 absorbent Substances 0.000 description 1
- 230000002745 absorbent Effects 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 101150062523 bath-39 gene Proteins 0.000 description 1
- 150000001721 carbon Chemical group 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 239000002134 carbon nanofiber Substances 0.000 description 1
- 239000007833 carbon precursor Substances 0.000 description 1
- 239000012018 catalyst precursor Substances 0.000 description 1
- 238000003421 catalytic decomposition reaction Methods 0.000 description 1
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- 238000011109 contamination Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- KZHJGOXRZJKJNY-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Si]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O KZHJGOXRZJKJNY-UHFFFAOYSA-N 0.000 description 1
- 235000012489 doughnuts Nutrition 0.000 description 1
- 238000011143 downstream manufacturing Methods 0.000 description 1
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- 230000000694 effects Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 229940117927 ethylene oxide Drugs 0.000 description 1
- 229910003472 fullerene Inorganic materials 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
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- 210000004209 hair Anatomy 0.000 description 1
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- 150000002431 hydrogen Chemical class 0.000 description 1
- 230000004941 influx Effects 0.000 description 1
- 239000003863 metallic catalyst Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical class C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 229910052863 mullite Inorganic materials 0.000 description 1
- 239000002048 multi walled nanotube Substances 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 239000002109 single walled nanotube Substances 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82B—NANOSTRUCTURES FORMED BY MANIPULATION OF INDIVIDUAL ATOMS, MOLECULES, OR LIMITED COLLECTIONS OF ATOMS OR MOLECULES AS DISCRETE UNITS; MANUFACTURE OR TREATMENT THEREOF
- B82B3/00—Manufacture or treatment of nanostructures by manipulation of individual atoms or molecules, or limited collections of atoms or molecules as discrete units
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/15—Nano-sized carbon materials
- C01B32/158—Carbon nanotubes
- C01B32/16—Preparation
- C01B32/162—Preparation characterised by catalysts
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/15—Nano-sized carbon materials
- C01B32/158—Carbon nanotubes
- C01B32/16—Preparation
- C01B32/164—Preparation involving continuous processes
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/02—Pretreatment of the material to be coated
- C23C16/0272—Deposition of sub-layers, e.g. to promote the adhesion of the main coating
- C23C16/0281—Deposition of sub-layers, e.g. to promote the adhesion of the main coating of metallic sub-layers
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
- C23C16/26—Deposition of carbon only
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
- C23C16/54—Apparatus specially adapted for continuous coating
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
- C23C16/54—Apparatus specially adapted for continuous coating
- C23C16/545—Apparatus specially adapted for continuous coating for coating elongated substrates
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F9/00—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments
- D01F9/08—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments of inorganic material
- D01F9/12—Carbon filaments; Apparatus specially adapted for the manufacture thereof
- D01F9/127—Carbon filaments; Apparatus specially adapted for the manufacture thereof by thermal decomposition of hydrocarbon gases or vapours or other carbon-containing compounds in the form of gas or vapour, e.g. carbon monoxide, alcohols
- D01F9/133—Apparatus therefor
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
- D06M11/73—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with carbon or compounds thereof
- D06M11/74—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with carbon or compounds thereof with carbon or graphite; with carbides; with graphitic acids or their salts
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
- D06M2101/40—Fibres of carbon
Definitions
- This invention relates to a process for growing carbon structures on the surface of a substrate, and especially to such a process for growing carbon structures using chemical vapour deposition (CVD ) on continuous substrates, especially moving, continuous fibres.
- CVD chemical vapour deposition
- the invention relates to a process for growing carbon nanostructures on the surface of continuous, moving substrates using thermal CVD.
- the carbon-bearing substrates, especially when fibres, find particular application as reinforcing members in composites.
- CVD processes for depositing carbon onto continuous fibres are known.
- the mechanical behaviour of the carbon fibre/carbon matrix is improved by the presence of the pyrolytic carbon coating, which acts as an interphase between fibre and matrix.
- US 4859503 describes continuous coating of a strand of carbon filaments with a refractory carbide in a hermetic enclosure, by a reactive CVD deposition technique.
- US 5547512 describes deposition of a barrier coating of an oxide, carbide, boride, nitride, suicide, carbon or metal onto a continuous fibre tow, such as, for example, aluminium borosilicate and mullite fibres, alumina-zirconia fibres or carbon fibres, by CVD, in a horizontal cylindrical furnace tube having one end through which the reactive gas and an inert carrier gas are fed and the fibre tow is also introduced.
- the total flux when subjected to the high temperature of the furnace, deposits a continuous coating by CVD onto the filaments of the moving tow.
- the other end of the furnace tube is unconstricted, and the flux exiting through the unconstricted outlet is sufficient to minimize the back diffusion of air such than non-oxide coatings can be attained with acceptable levels of oxygen contamination.
- a reactive gas flow of 190cc/min and a high inert argon gas flow rate of 2100cc/min are exemplified.
- the barrier coating is required so that when the fibres are incorporated into a matrix and used at high operating temperatures, the matrix does not chemically react with or dissolve the fibres. Similar methods for fabricating carbon nanostructures by chemical vapour deposition are also known.
- Carbon nanostructures are discrete, ordered structures grown from specific catalytic sites on a substrate and include carbon nanotubes, nanostacks, nanofibres and the like, which group of structures grow axially along their respective lengths away from the substrate surface.
- the carbon nanotubes (CNT's) which may be single wall or multi-wall carbon nanotubes, and carbon nanostacks or graphite nanofibres, may have dimensions, for example, of from 1nm to 500nm wide and 1 ⁇ m to several mm long.
- each carbon atom is bound to three neighbouring carbon atoms to form a flat plane of repeating hexagonal rings resembling a honeycomb.
- this honeycomb is rolled to form a cylinder or tube.
- CVD methods for growing nanocarbons usually rely on the presence of a specific metal powder catalyst, such as iron, cobalt or nickel, to initiate growth of the carbon nanostructures and to control their subsequent morphology.
- a specific metal powder catalyst such as iron, cobalt or nickel
- PCT/GB03/00674 describes a process for growing carbon nanostructures, in which the nanostructures are grown on a continuous, elongate, heated, catalytic filament, wire, ribbon or tape passing through a sealed CVD chamber, the carbon nanostructures being scraped off upon their exit from the chamber.
- Nitrogen and argon are the most extensively used inert gases.”
- the flow rate of the carbon source gas is described as being typically 10-30 ml per minute, with the flow rate of the inert gas being typically 100ml per minute.
- WO2007/026213 describes a static process for the continuous production of CNT's using a fluidized mixture of a floating catalyst (comprising ferrocene in a carrier gas, xylene) and a hydrocarbon feed gas, in a CVD chamber having stainless steel or glass lined walls.
- a floating catalyst comprising ferrocene in a carrier gas, xylene
- a hydrocarbon feed gas in a CVD chamber having stainless steel or glass lined walls.
- the article "Production of Controlled Architectures of Aligned Carbon Nanotubes by an Injection Chemical Vapour Deposition Method", Carbon 41 (2003) 359- 368 also describes a static CNT growth process using an injection CVD method in which ferrocene as catalyst is introduced by injection into a CVD chamber and CNT growth on a quartz substrate or chamber walls is achieved.
- the article "Long Bundles of Aligned Carbon Nanofibers Obtained by Vertical Floating Catalyst Method", Materials Chemistry and Physics 87 (2004) 241-245 is a further example of a static CNT growth process and uses a vertical quartz reactor.
- the present invention provides a process for growing carbon structures on a continuous substrate by thermal CVD, wherein the continuous substrate is moved along its length into and out of a deposition chamber through one or more non-airtight openings located in one end or portion of an otherwise sealed deposition chamber, into which a reactive gas mixture for generating the carbon structures is also introduced in a sealed manner.
- Such a set-up permits the substrate to be movable along its length without needing to seal its entry and exit points yet still retaining a relatively oxygen-free i.e. substantially inert atmosphere.
- the reactive gas mixture for generating the carbon structures is introduced at a location remote from the one end or portion, although it could be introduced from a plurality of well spaced positions.
- the reactive gas mixture is introduced from the bottom or a lower part of the chamber so that it flows upwards.
- the mixture will usually include an inert gas component and the mixture will be continuously supplied for the entire duration of the process, the intention being to prevent air or moisture ingress.
- a process for growing carbon nanostructures on a continuous substrate by thermal CVD wherein the continuous substrate is moved through a deposition chamber, entering and exiting it through one or more non-airtight openings located at or near one end of the deposition chamber, and a reactive gas mixture is fed in from an opposing end of the deposition chamber.
- the one or more substrate inlet/outlet openings are substantially the only non-airtight openings in the chamber, so that the other end or portion of the chamber is sealed. All the gases in the chamber are therefore forced to exit through those opening(s), and given they are introduced at the opposite end or portion of the chamber, generally leads to a one-way flow of gases within the chamber.
- Those openings will usually only be slightly larger in cross-section than the substrate and may even be constricted so as to minimise air ingress.
- APCVD atomic layer deposition
- the continuous substrate is moved through a deposition chamber, entering and exiting it through one or more (e.g. a pair of) non-airtight openings located at or near one end of the deposition chamber, and a reactant gas mixture is fed in from an opposing end of the deposition chamber.
- the reactive gas mixture will comprise one or more reactant (carbon source) gases and one or more inert gases in a desired ratio, as well as any required reductant gases or catalytic gases.
- any reactant/reductant/inert or catalytic gases are all introduced in an airtight manner and forced to exit through the non-airtight openings.
- the substrate may enter and exit through a single non-airtight opening, separate respective unsealed inlet and outlet openings, but in the same portion of the chamber, are usually needed to facilitate transfer to adjacent spooling mechanisms.
- the substrate needs to stay in the chamber for a sufficient duration to enable growth of carbon structures to occur.
- the substrate may follow a path whereby it reverses its direction inside the chamber, so as to allow it to enter and exit the chamber from that one end or portion. While the substrate could follow a path where it is redirected by passing around the inner periphery of a reaction chamber of a particular shape (e.g. a drum or ring-shaped, i.e. a solid or hollow doughnut shaped chamber), conveniently, the substrate follows a path whereby it reverses its direction of movement inside the chamber.
- At least one reversing device may be provided in the chamber.
- the device is preferably located at or near the remote location or the opposing end or portion of the chamber.
- the chamber is an elongate tubular chamber.
- the substrate is set up to follow a path where it reverses its direction, then this may be achieved using at least one reversing device located at or near the opposing end or portion of the chamber.
- reversing devices may be static devices including loops, channels or guides or the like, but to minimise damage to the deposited carbon coating are preferably mobile devices including rotating wheels, guides, pulleys, or the like, or may include resilient mechanisms such as springs that attach guides or pulleys, etc. to the chamber walls.
- the substrate will completely reverse its path so as to follow the same or a closely aligned path.
- the substrate may be guided around two or more devices so that the return path is spaced from the initial path. In any event, the substrate reverses such that it exits and enters the chamber in the same vicinity, through which all gases must exit, thereby ensuring a clear gas flow direction in the chamber and minimising oxygen ingress.
- the reversing device is normally either fixedly or flexibly attached to the interior of the chamber. However, it may hang freely (e.g. a weighted pulley); the latter arrangement would suffice, for example, where the substrate reverses its direction at its lowermost end, as in a vertically arranged deposition chamber.
- the non-airtight opening(s) of the chamber are located in the uppermost part of the chamber, so as to take advantage of upward convection.
- the CVD chamber may be any suitable shape.
- An especially preferred shape is an elongate chamber, for example an elongate cylindrical chamber.
- the chamber is an elongate, vertically aligned (i.e. upright) chamber with the openings located uppermost through which the hot gases exit.
- the substrate moves in a direction along its length through the chamber, usually with a continuous motion at a calculated spool rate that gives the correct residence time in the chamber. Continuous movement provides for a more uniform coverage of carbon structures.
- the substrate is moved semi-continuously, i.e. batchwise through the chamber, for example, equal lengths are successively moved on into the chamber at selected intervals. Preferably, such lengths will be short enough for each section to reside in the chamber for multiple residences (e.g. four or more) for improved uniformity of coverage.
- a length of substrate approximately equal to the length of the chamber may be introduced into the chamber and held stationary for a first residence period, and then advanced around the reversing device for a second stationary residence period, before exiting the chamber.
- a length double the length of the chamber may be introduced into the chamber for a single stationary residence period before exiting the chamber.
- the continuous substrate may take any suitable form, but may be, for example, a yarn, ribbon, wire, filament or fibre, a tow of filaments or fibres, a fabric or a narrow fabric strip. Similarly a number of different materials are suitable for the continuous substrate, for example, ceramic such as alumina or silane, carbon, glass or iron wire.
- the substrate material must be sufficiently heat resistant to resist the high temperatures (typically 600-800 0 C) typically used in the thermal CVD process.
- the continuous substrate comprises a continuous tow of reinforcing fibres for use in a composite.
- a process for preparing a continuous substrate having carbon nanostructures deposited thereon which process includes moving the substrate continuously or semi-continuously along its length through successive processing stages including:- i) an optional pre-treatment stage; ii) an optional catalytic pre-treatment stage to facilitate carbon nanostructure deposition; and, iii) a thermal CVD deposition stage comprising a process as described above.
- a pre-treatment stage will usually be required.
- carbon fibres are generally unreactive, non-absorbent materials and usually require some surface treatment to improve the fibre surface wettability or to increase the quantity of surface functional groups.
- the pre-treatment stage may comprise an oxidation stage.
- Stage ii) may comprise passing the substrate through at least one bath containing a catalytic agent, for example, where the incipient wetness impregnation technique is used.
- a catalytic treatment may form part of stage iii), such as, for example, the injection technique, which is used to introduce catalytic gas-borne particles into the chamber during carbon growth.
- a further downstream process may involve removing the carbon structures from the substrate.
- the present invention further provides a process for depositing carbon structures on a continuous substrate by thermal CVD, wherein the continuous substrate is moved into and out of a deposition chamber through one or more non-airtight openings located at or near one end or portion of the deposition chamber, and a reactive gas mixture is fed in from an opposing end or portion of the deposition chamber.
- Figs. 1A and 1B are respective schematic front views of two alternative CVD rigs in accordance with the present invention.
- Fig. 2 is a schematic front view of a third alternative CVD rig in accordance with the present invention.
- Fig. 3 is a pair of scanning electron micrographs (SEMs), at two different magnifications, of CNT's growth on continuous carbon fibres;
- Figs. 4A and 4B are respective schematic front views of two alternative, comparative CVD rigs (i.e. not according to the present invention).
- Fig. 5 is a schematic side view of a continuous production process for generating CNT coated carbon fibre tows.
- the following example describes a process for growing carbon nanotubes on continuous carbon fibres using a CVD process according to the invention.
- polyacrylonitrile (PAN) based carbon fibres were used in a tow comprising about 12,000 continuous fibres of average diameter 7 ⁇ m.
- the tow fibres were surface treated to improve their absorption and interaction properties.
- This surface treatment process comprised oxidation by refluxing in nitric acid, washing of the fibres, and then soaking of the fibres in sodium hydroxide solution at ambient temperature, and finally refluxing in the same solution.
- Carbon nanotubes (CNT's) synthesis usually requires the introduction of a catalyst often in the form of gas particulates or as a solid support. (Otherwise, amorphous or pyrolytic carbon coatings will result.)
- a variety of catalytic methods may be used with thermal CVD, and these include the incipient wetness impregnation technique and the injection technique.
- the incipient wetness technique the substrate is uniformly impregnated with a catalyst containing solution prior to CVD, while the injection technique involves injecting a metal containing solution into a preheated chamber where it is vaporised and the catalyst carried into the CVD chamber.
- the incipient wetness technique was used on the carbon fibres.
- the choice of metallic catalyst may affect the morphology and growth of the CNTs.
- transition metals iron, cobalt and nickel (or titanium) alone or in bimetallic combinations is well known for catalysing nanotubes growth by thermal CVD.
- the incipient wetness technique was used to incorporate an iron catalyst onto the surface treated PAN-based fibres.
- Iron nitrate nanohydrate (Fe(NO 3 ) 3 .9H 2 O) as a catalyst precursor, was dissolved in propan-2-ol, and the surface treated PAN-based fibres were impregnated with this solution, and then washed in fresh propan-2-ol to remove the excess nitrate solution, and then dried at 200- 300 0 C.
- the final stage in the incipient wetness technique, calcination involves treating the samples at a high temperature of about 750 0 C to form the Fe catalyst particles. Since this calcination step needs to be carried out at the same temperature as is required for CNT growth, it was decided to attempt to carry out this final stage simultaneously with growing the carbon nanostructures on the iron catalyst coated fibres. This would result in less physical damage to the lengthy fibre tow and lead to a shorter and more cost effective process.
- the fibres 1 were subjected to thermal CVD in the CVD rig 3 shown schematically in Figure 1B.
- the rig 3 comprises a CVD quartz tube 5 housed within a furnace 7. Heating to a temperature in the range 600-800 0 C, preferably about 75O 0 C, is provided by a heating element 9 surrounding the tube 5.
- the tube 5 is arranged vertically within the furnace 7, and has an upper end that is only open to the atmosphere through lateral openings 13 and 15, as well as a sealed lower end that is contiguous with a gas entry pipe 1 1 , so that no air from the atmosphere can enter the tube at its lower end.
- a seed carbon tow is pre-threaded through the CVD tube 5. It enters through opening 13 at the upper end of the tube 5, extends down the tube and then passes around reversing device in the form of a freely rotating yarn guide 17, and passes back upwards through the tube 5 to pass out of opening 15 at the same upper end level with opening 13. (Separate openings were preferred to accommodate the respective spooling arrangements and because entry and exit vertically out of a single opening would have been difficult in practice.) The tow is then wound via a tow guide 19 onto a take-up roller 21. The yarn guide 17 is fixed to the inner walls of the work tube 5 by fixing strips so as to maintain a constant effective length and dwell time for the tow in the tube 5.
- the dried, catalyst pre-coated carbon tow was wound up on a delivery spool (not shown) and the end tied to the seed carbon tow.
- the rate of passage of the tow through the tube can be anything from 1 to 6 cm/minute, but the take-up roller 21 was usually set to move at a very slow rate of 1 - 3 cm/min.
- the tube 5 was 40cm long (effective process length 80cm), so the dwell time for most runs was between 30 min to 1.5 h.
- the reversing device is fixedly attached to the tube walls to ensure uniform runs.
- an alternative rig is shown with a freely hanging reversing device 17". This may be more convenient and entirely acceptable for some types of substrates or for experimental trials. It does, however, have the disadvantages that it may drop and break the tube when tension is removed from the substrate, and that variation in tow tension can cause it to move up and down in the tube, leading to variable effective dwell times.
- this shows a further reversal device where a yarn guide 17" is connected by two or more flexible links to the tube 5, so as to give some play and minimise damage to the nanocarbons.
- a gas system consisting of argon acting as a carrier gas, hydrogen, acting as a reductant/morphology control gas and ethylene or carbon dioxide, acting as a carbon source gas, were fed into the tube 5 via the gas entry pipe 11.
- Average flow rates for the ethylene, argon and hydrogen were 5, 50 and 5 mls/min respectively (i.e. 1 :10:1). It will be noted that these are very moderate flushing rates, despite the presence of unsealed openings 13 and 15. (This is in contrast to the excessive flushing rates needed in some prior art set-ups that are open to the atmosphere.)
- the actual pressure may be close to or of the order of atmospheric pressure but it is the inertness of the atmosphere rather than the actual pressure which is important.
- the reactant gas: inert gas ratio will usually be between 1 : 6 to 1: 15. Inert gas flow rates usually will not need to exceed 0.5l/min, more preferably not more than 0.2l/min.
- Figure 3 shows a pair of SEMs at different magnifications of the tow removed from the take-up reel after one continuous trial run and shows a good growth of CNTs on the surface of the tow.
- the CNTs exhibited random orientation and coiling. While growth is not as dense as might be achieved in a static environment, it is still encouraging that despite the substrate moving around various guides, reasonable coverage is achieved.
- Such CNT coated carbon fibres otherwise known as "hairy fibres" inherently give rise to improved properties when incorporated as reinforcing fibres in composites, due to the enhanced fibre-matrix interactions caused by the numerous tiny CNT "hairs”.
- the process has the potential to be a single overall continuous process, including the oxidation treatment, catalytic impregnation and drying treatment and calcination/CVD treatment.
- the two experimental rigs depicted in Figs. 4a and 4b were tried out, each involving the tow passing in one end of the CVD tube and out of the opposite end.
- the flow rate of argon was not high enough to prevent the influx.
- the apparatus can be adapted to the CVD rig shown in Fig. 2, which allows the floating catalyst technique, as mentioned in the above acknowledged prior art, to be used instead of the incipient wetness technique.
- a glass fibre tow 25 can be exposed in the reaction chamber simultaneously to reactant gases and catalytic gases.
- this rig differs from those in Figs. 1A and 1 B in that it has an additional pre-heated chamber 23 for introducing heated catalytic gases into the CVD tube, which pre-heated chamber is interposed between the feed gas supply and the gas inlet to the CVD tube.
- a ferrocene Fe(CsHs) 2 solution in toluene would be injected using controlled delivery means 24 into the pre-heated chamber 23 (heater jacket not shown) maintained at around 200 0 C, and would be turned into vapour.
- the feed gases pass through the pre-heated chamber 23 and into the CVD tube 5 they would carry that vapour into the CVD tube, to be deposited on the glass fibre substrate 25.
- the controlled delivery means i.e. whether it injects solution continuously or periodically
- a flexibly mounted yarn guide 17" could be used.
- Figure 5 shows a possible scaled up continuous (or semi-continuous) production process for coating carbon fibre tows with CNT's.
- the entire process since the surface pre- treatment stage and the incipient wetness impregnation treatment and the intervening washing and rinsing steps all involve solution baths, it is possible for the entire process to be automated and carried out on continuously or semi-continuously moving continuous fibre tow. If desired, this could incorporate the CVD process at the end, although the fibre may instead be transferred manually to the CVD rig for separate processing at a preferred spooling rate.
- Section A would be the pre-treatment stage (about 3m in length), while section B (about 5m) would be the catalytic treatment stage, before automated or manual transfer to the CVD rig.
- Section A commences with the carbon fibre tow travelling over and around bobbins 31 successively through a nitric acid bath 33, then a de-ionised water wash bath 37, a sodium hydroxide bath 39 and a de-ionised water wash bath 41 , with water sprays 35 being located above transfer bobbins 43 located between each of the baths, and the water spray being collected by a drain bench (not shown).
- An extraction hood 45 would be provided above the water sprays 35.
- the tow 29 would then transfer into Section B and through an oven 47 maintained at 100 0 C to be dried, variable speed air blowers 49 being provided overhead upon entry and exit from the oven.
- the tow 29 would then pass successively through a bath 51 of transition metal salt catalyst solution or similar catalytic agent solution (e.g. iron nitrate nanohydrate) and a solvent rinse bath 53, before passing under another variable speed blower 49 and through a further oven 55 maintained at 100-300 0 C, where the catalytically treated fibres would be dried, before being collected on a wind-up bobbin 57.
- transition metal salt catalyst solution or similar catalytic agent solution e.g. iron nitrate nanohydrate
- the tow 29 could then be manually or automatically transferred to a CVD rig 5 ⁇ set up and operating in accordance with the invention (as described, for example, in
- Example 1 underneath another extraction hood 45, before finally being collected on winder 61.
- a continuous production scheme with appropriate modifications for glass fibre substrates could similarly be designed based on Example 2.
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Abstract
L'invention porte sur un procédé de dépôt chimique en phase vapeur thermique pour faire croître des structures de carbone (par exemple, des nanotubes de carbone) sur un substrat continu (1) qui est déplacé dans et hors d'une chambre de dépôt (5) à travers une ou plusieurs ouvertures non étanches à l'air (13, 15) situées à une extrémité ou au voisinage d'une extrémité de celle-ci, un mélange de gaz réactif étant délivré à l'intérieur de celle-ci à partir d'une extrémité opposée (1). Le substrat peut inverser sa direction à l'intérieur de la chambre, et au moins un dispositif d'inversion (17) peut être situé à l'extrémité opposée. Ce procédé peut former une étape d'un processus semi-continu ou continu pour la fabrication de fibres composites de renfort revêtues de nanostructures de carbone.
Applications Claiming Priority (2)
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GBGB0805837.2A GB0805837D0 (en) | 2008-03-31 | 2008-03-31 | Chemical Vapour Deposition Process |
GB0805837.2 | 2008-03-31 |
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PCT/GB2009/000787 WO2009122139A1 (fr) | 2008-03-31 | 2009-03-25 | Procédé de dépôt chimique en phase vapeur |
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WO (1) | WO2009122139A1 (fr) |
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CN103103493A (zh) * | 2012-11-07 | 2013-05-15 | 山东鑫汇铜材有限公司 | 一种石墨烯铜线生产装置 |
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DE102014104009A1 (de) | 2014-03-24 | 2015-09-24 | Aixtron Se | Auf seinen beiden voneinander wegweisenden Breitseiten je ein Substrat tragender Substratträger |
GB201412656D0 (en) | 2014-07-16 | 2014-08-27 | Imp Innovations Ltd | Process |
WO2017055618A1 (fr) * | 2015-10-02 | 2017-04-06 | O'flynn Donal Paul | Procédé de production de structures de graphène |
Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE1093164B (de) * | 1953-10-02 | 1960-11-17 | Roederstein Kondensatoren | Vorrichtung zum Gasplattieren mit Metallkarbonylverbindungen |
US20060118242A1 (en) * | 2001-02-12 | 2006-06-08 | Anthony Herbert | Atmospheric pressure plasma system |
Family Cites Families (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH0835069A (ja) * | 1994-07-22 | 1996-02-06 | Kao Corp | 成膜装置 |
GB2385864A (en) * | 2002-02-28 | 2003-09-03 | Qinetiq Ltd | Production of nanocarbons |
US20060083927A1 (en) * | 2004-10-15 | 2006-04-20 | Zyvex Corporation | Thermal interface incorporating nanotubes |
KR20070116866A (ko) * | 2005-03-10 | 2007-12-11 | 테일러드 매터리얼스 코포레이션 | 박막 제조방법 및 제조장치 |
-
2008
- 2008-03-31 GB GBGB0805837.2A patent/GB0805837D0/en not_active Ceased
-
2009
- 2009-03-25 WO PCT/GB2009/000787 patent/WO2009122139A1/fr active Application Filing
- 2009-03-25 GB GB0905047A patent/GB2458776B/en not_active Expired - Fee Related
Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE1093164B (de) * | 1953-10-02 | 1960-11-17 | Roederstein Kondensatoren | Vorrichtung zum Gasplattieren mit Metallkarbonylverbindungen |
US20060118242A1 (en) * | 2001-02-12 | 2006-06-08 | Anthony Herbert | Atmospheric pressure plasma system |
Non-Patent Citations (2)
Title |
---|
CHEMISTRY OF MATERIALS 20080311 AMERICAN CHEMICAL SOCIETY US, vol. 20, no. 5, 11 March 2008 (2008-03-11), pages 1862 - 1869, XP002529241 * |
DATABASE COMPENDEX [online] ENGINEERING INFORMATION, INC., NEW YORK, NY, US; QIAN H ET AL: "Hierarchical composites reinforced with carbon nanotube grafted fibers: The potential assessed at the single fiber level", XP002529242, Database accession no. E20081711223756 * |
Cited By (36)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US8815709B2 (en) | 2008-10-03 | 2014-08-26 | Veeco Instruments Inc. | Chemical vapor deposition with energy input |
US9556031B2 (en) | 2009-04-17 | 2017-01-31 | Seerstone Llc | Method for producing solid carbon by reducing carbon oxides |
US8679444B2 (en) | 2009-04-17 | 2014-03-25 | Seerstone Llc | Method for producing solid carbon by reducing carbon oxides |
US10500582B2 (en) | 2009-04-17 | 2019-12-10 | Seerstone Llc | Compositions of matter including solid carbon formed by reducing carbon oxides |
US10808321B2 (en) | 2010-02-08 | 2020-10-20 | Graphene Square Inc. | Graphene roll-to-roll coating apparatus and graphene roll-to-roll coating method using the same |
KR101371286B1 (ko) * | 2010-02-08 | 2014-03-07 | 그래핀스퀘어 주식회사 | 그래핀 롤투롤 코팅 장치 및 이를 이용한 그래핀 롤투롤 코팅 방법 |
US10266948B2 (en) | 2010-02-08 | 2019-04-23 | Graphene Square Inc. | Graphene roll-to-roll coating apparatus and graphene roll-to-roll coating method using the same |
WO2011106624A1 (fr) * | 2010-02-26 | 2011-09-01 | Alliance For Sustainable Energy, Llc | Dépôt chimique en phase vapeur assisté par filament chaud (hwcvd) utilisant des filaments de carbure |
JP2013538780A (ja) * | 2010-09-22 | 2013-10-17 | アプライド ナノストラクチャード ソリューションズ リミテッド ライアビリティー カンパニー | その上で成長するカーボンナノチューブを含有する炭素繊維基材及びその製造方法 |
KR101168259B1 (ko) | 2012-03-05 | 2012-07-30 | 한국기계연구원 | 롤투롤 기반의 그래핀 연속 합성 장치 |
US9221685B2 (en) | 2012-04-16 | 2015-12-29 | Seerstone Llc | Methods of capturing and sequestering carbon |
US9796591B2 (en) | 2012-04-16 | 2017-10-24 | Seerstone Llc | Methods for reducing carbon oxides with non ferrous catalysts and forming solid carbon products |
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US9637382B2 (en) | 2012-04-16 | 2017-05-02 | Seerstone Llc | Methods for producing solid carbon by reducing carbon dioxide |
US10106416B2 (en) | 2012-04-16 | 2018-10-23 | Seerstone Llc | Methods for treating an offgas containing carbon oxides |
US9731970B2 (en) | 2012-04-16 | 2017-08-15 | Seerstone Llc | Methods and systems for thermal energy recovery from production of solid carbon materials by reducing carbon oxides |
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US10358346B2 (en) | 2012-07-13 | 2019-07-23 | Seerstone Llc | Methods and systems for forming ammonia and solid carbon products |
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US9779845B2 (en) | 2012-07-18 | 2017-10-03 | Seerstone Llc | Primary voltaic sources including nanofiber Schottky barrier arrays and methods of forming same |
CN103103493A (zh) * | 2012-11-07 | 2013-05-15 | 山东鑫汇铜材有限公司 | 一种石墨烯铜线生产装置 |
US9650251B2 (en) | 2012-11-29 | 2017-05-16 | Seerstone Llc | Reactors and methods for producing solid carbon materials |
US9993791B2 (en) | 2012-11-29 | 2018-06-12 | Seerstone Llc | Reactors and methods for producing solid carbon materials |
US10086349B2 (en) | 2013-03-15 | 2018-10-02 | Seerstone Llc | Reactors, systems, and methods for forming solid products |
US10115844B2 (en) | 2013-03-15 | 2018-10-30 | Seerstone Llc | Electrodes comprising nanostructured carbon |
US10322832B2 (en) | 2013-03-15 | 2019-06-18 | Seerstone, Llc | Systems for producing solid carbon by reducing carbon oxides |
US9783416B2 (en) | 2013-03-15 | 2017-10-10 | Seerstone Llc | Methods of producing hydrogen and solid carbon |
US9783421B2 (en) | 2013-03-15 | 2017-10-10 | Seerstone Llc | Carbon oxide reduction with intermetallic and carbide catalysts |
US9586823B2 (en) | 2013-03-15 | 2017-03-07 | Seerstone Llc | Systems for producing solid carbon by reducing carbon oxides |
JP2015533760A (ja) * | 2013-06-18 | 2015-11-26 | エルジー・ケム・リミテッド | カーボンナノチューブ繊維の製造装置及びこれを用いたカーボンナノチューブ繊維の製造方法 |
US9556542B2 (en) | 2013-06-18 | 2017-01-31 | Lg Chem, Ltd. | Device for manufacturing carbon nanotube fibers and method for manufacturing carbon nanotube fibers using same |
US11752459B2 (en) | 2016-07-28 | 2023-09-12 | Seerstone Llc | Solid carbon products comprising compressed carbon nanotubes in a container and methods of forming same |
US11951428B2 (en) | 2016-07-28 | 2024-04-09 | Seerstone, Llc | Solid carbon products comprising compressed carbon nanotubes in a container and methods of forming same |
TWI682047B (zh) * | 2018-10-02 | 2020-01-11 | 大永真空科技股份有限公司 | 適用於紗線鍍膜的腔體 |
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GB0805837D0 (en) | 2008-06-04 |
GB2458776B (en) | 2010-06-02 |
GB0905047D0 (en) | 2009-05-06 |
GB2458776A (en) | 2009-10-07 |
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