US20070026231A1 - Method of coating an anode/collector with carbon nanotubes - Google Patents

Method of coating an anode/collector with carbon nanotubes Download PDF

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US20070026231A1
US20070026231A1 US10/445,976 US44597603A US2007026231A1 US 20070026231 A1 US20070026231 A1 US 20070026231A1 US 44597603 A US44597603 A US 44597603A US 2007026231 A1 US2007026231 A1 US 2007026231A1
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anode
collector
coating method
coating
vapor deposition
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US7169437B1 (en
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Donald Shiffler
Michael Haworth
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y10/00—Nanotechnology for information processing, storage or transmission, e.g. quantum computing or single electron logic
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
    • H01J1/00—Details of electrodes, of magnetic control means, of screens, or of the mounting or spacing thereof, common to two or more basic types of discharge tubes or lamps
    • H01J1/02—Main electrodes
    • H01J1/36—Solid anodes; Solid auxiliary anodes for maintaining a discharge
    • H01J1/38—Solid anodes; Solid auxiliary anodes for maintaining a discharge characterised by the material
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
    • H01J23/00—Details of transit-time tubes of the types covered by group H01J25/00
    • H01J23/02—Electrodes; Magnetic control means; Screens
    • H01J23/027—Collectors
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
    • H01J29/00—Details of cathode-ray tubes or of electron-beam tubes of the types covered by group H01J31/00
    • H01J29/02—Electrodes; Screens; Mounting, supporting, spacing or insulating thereof
    • H01J29/08—Electrodes intimately associated with a screen on or from which an image or pattern is formed, picked-up, converted or stored, e.g. backing-plates for storage tubes or collecting secondary electrons
    • H01J29/085—Anode plates, e.g. for screens of flat panel displays
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
    • H01J9/00—Apparatus or processes specially adapted for the manufacture, installation, removal, maintenance of electric discharge tubes, discharge lamps, or parts thereof; Recovery of material from discharge tubes or lamps
    • H01J9/02—Manufacture of electrodes or electrode systems
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
    • H01J9/00—Apparatus or processes specially adapted for the manufacture, installation, removal, maintenance of electric discharge tubes, discharge lamps, or parts thereof; Recovery of material from discharge tubes or lamps
    • H01J9/02—Manufacture of electrodes or electrode systems
    • H01J9/14—Manufacture of electrodes or electrode systems of non-emitting electrodes
    • 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
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S977/00—Nanotechnology
    • Y10S977/70—Nanostructure
    • Y10S977/734—Fullerenes, i.e. graphene-based structures, such as nanohorns, nanococoons, nanoscrolls or fullerene-like structures, e.g. WS2 or MoS2 chalcogenide nanotubes, planar C3N4, etc.
    • Y10S977/742—Carbon nanotubes, CNTs
    • 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
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S977/00—Nanotechnology
    • Y10S977/84—Manufacture, treatment, or detection of nanostructure
    • Y10S977/842—Manufacture, treatment, or detection of nanostructure for carbon nanotubes or fullerenes
    • Y10S977/847—Surface modifications, e.g. functionalization, coating
    • 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
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/30—Self-sustaining carbon mass or layer with impregnant or other layer

Definitions

  • the invention is in the field of vacuum tubes, and more particularly relates to a coated anode designed to reduce out-gassing, plasma formation, and secondary electron production.
  • Every vacuum electronics device ranging from radio frequency tubes to microwaves tubes, must have some region in which the cathode emitted electrons impact after participating in the desired interactions.
  • these structures consist of stainless steel, oxygen free high conductivity (OFHC) copper or some other metal.
  • OFHC oxygen free high conductivity
  • the metal is coated with an insulating material such as titanium nitride.
  • Metals are generally the optimum structures due to the good electrical and thermal conductivity as well as the superior vacuum performance.
  • Secondary electrons are electrons produced by the impact of the primary electron beam. A single primary electron can produce several or as many as hundreds of secondary electrons. These secondary electrons then cause the formation of plasmas and result in further out-gassing from the metal anode or collector.
  • anode/collector that can significantly reduce the production of secondary electrons, plasma formation, and out-gassing of neutral gases.
  • the anode/collector surface of a vacuum tube is coated with a carbon nanotube material having the longitudinal axis of at least a portion of the nanotubes running parallel to the surface.
  • the anode/collector surface initially is comprised of carbon or a metal surface coated with a thin film of carbon. It is then coated with a carbonizable resin.
  • the final coating can be a carbon nanotube felt-like material that is pyro-bonded to the anode surface, or nanotubes can be deposited on the anode by chemical vapor deposition or by evaporation and then pyro-bonded.
  • FIG. 1 illustrates a typical cylindrical anode/cathode configuration.
  • FIG. 2 is an end view of the cylindrical anode/cathode of FIG. 1
  • FIG. 3 is an end view of a portion of the cylindrical anode/cathode at 475 kV with the anode coated.
  • FIG. 4 is a low gain end view of a portion of the cylindrical anode/cathode at 475 kV with an uncoated anode.
  • Carbon nanotubes are very small tube-shaped molecules having the structure of a graphite molecule rolled into a tube. Nanotubes have high conductivity along their longitudinal direction (z) and low conductivity in the transverse (r) direction. The carbon bonds are such that electrons are tightly bound in the p-orbits in the transverse direction and not readily dislodged. Thus, an anode coated with a carbon nanotube material that has at least a portion of the nanotubes lying parallel to the anode surface will produce few secondary electrons. Processes for fabricating single-walled carbon nanotubes into fibers and ribbon-like materials with preferentially oriented nanotubes are known in the art (Vigolo, Brigitte, et. al, “Macroscopic Fibers and Ribbons of Oriented Carbon Nanotubes,” Science, Vol. 290, pp. 1331-1334, 17 Nov. 2000).
  • Nanotubes can be placed on an anode/collector surface coated with a carbonizable resin using chemical vapor deposition (CVD) or evaporation.
  • CVD chemical vapor deposition
  • Carbon nanotubes are commercially available in a power form, e.g., Carbon Nanotechnologies, Inc., Houston, Tex.
  • the coating is then pyro-bonded to the anode/collector surface.
  • a carbon surface or a metal surface coated with a thin film of carbon is obtained in the shape of the desired anode.
  • the electron impact surface is then coated with a carbonizable resin.
  • a carbonizable resin e.g. phenolic, is any resin that when heated sufficiently hot leaves only carbon in a solid state, generally a powder.
  • the carbon nanotubes can be secured to the anode/collector surface using CVD onto the surface, which has been coated with a carbonizable resin.
  • the anode/collector part is then baked to greater than 7000 centigrade in a non-oxidizing atmosphere, decomposing the resin, and releasing volatile components.
  • a porous carbon “char” residue embedded with carbon nanotubes is left on the surface.
  • chemical vapor deposition (CVD) is used to infiltrate carbon into the porous char, creating a non-porous, rigid surface.
  • This pyrocarbon material coating consists of a layer of carbon derived using pyrolysis through chemical vapor deposition (CVD). Pyrolysis through CVD is a process in which a low pressure hydrocarbon gas, methane for example, flows onto the part to be coated, is thermally decomposed, and deposits carbon on the part while releasing hydrogen.
  • the carbonized part is heated to over 1000° centigrade while a low-pressure hydrocarbon gas is flowed onto it.
  • the gas thermally decomposes, depositing carbon layers and releasing hydrogen.
  • the length of the process depends on the size of the part to be coated, the number of layers required, and the gas flow rate.
  • the thickness of the CVD film added depends on the thickness of the carbon nanotube coating, which depends on the degree of reduction required. The degree of reduction required depends on the exact parameters of the device to be used.
  • the entire assembly is then placed in a vacuum bakeout at over 100° centigrade to remove any remaining water.
  • the coating retains sufficient conductivity to conduct the incident electrons to the remainder of the pulsed circuit.
  • Carbon nanotubes can also be produced in a “felt” material, in which a significant portion of the nanotubes that form the fabric of the felt lie in the plane of the material.
  • the felt consists of a polymer fabric into which ribbon-like carbon nanotube strips have been woven.
  • the source of this felt material is Dr. Otto Chou, Physics and Astronomy Department, University of North Carolina at Chapel Hill.
  • a carbon surface or a metal surface coated with a thin film of carbon is obtained in the shape of the desired anode.
  • the electron impact surface is then coated with a carbonizable resin as previously described.
  • the felt can be secured to the anode/collector surface by placing the felt on the surface which has been coated with a carbonizable resin and then heating the entire structure to greater than 1000° C.
  • the felt is thus pyro-bonded to the anode/collector surface, forming a coating.
  • FIG. 1 An anode structure having a cylindrical geometry is depicted in FIG. 1 with an end view shown in FIG. 2 .
  • a cathode 2 emits electrons that are accelerated to high energy towards the anode/collector 1 .
  • the cylindrical cathode is held in position within the cylindrical anode by a support 3 . Electrons impact the anode at very high energy, leading to the production of neutral gas, plasma, and secondary electrons.
  • FIG. 3 is a scanned photograph of a portion of the cylindrical anode/cathode (approximately encompassed by the FIG. 2 dashed line 4 ) where the anode 1 has been coated with the carbon nanotube material as described above.
  • the potential difference between the cathode and the anode is 475 kV. No plasma formation can be seen.
  • the same cylindrical anode/cathode at 475 kV is shown in FIG. 4 but with an uncoated anode.
  • This low-gain photo clearly shows the plasma formation 5 .
  • the plasma brightness in FIG. 4 necessitated the much-reduced gain of FIG. 4 relative to FIG. 3 .
  • the carbon nanotube-based anode/collector coating has several advantages over previous metals and coatings.
  • This coating can be used in high and low vacuum.
  • the coating can be applied in a complex range of shapes. Secondary electron production, neutral gas (out-gassing) production, and plasma production are greatly reduced, permitting microwave and radio frequency vacuum electronics to be run with higher efficiency due to lower pumping requirements. Many devices have been limited in peak power and pulse duration by these effects.
  • These coated anodes have applications ranging from cathode ray tubes in computers, televisions, and displays to microwave tubes in radar, communications, and cooking.

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  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Chemical & Material Sciences (AREA)
  • Nanotechnology (AREA)
  • Physics & Mathematics (AREA)
  • Mathematical Physics (AREA)
  • Theoretical Computer Science (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Carbon And Carbon Compounds (AREA)
  • Chemical Or Physical Treatment Of Fibers (AREA)
  • Cold Cathode And The Manufacture (AREA)
  • Battery Electrode And Active Subsutance (AREA)

Abstract

A vacuum tube having its anode/collector coated with carbon nanotube-based material in which five percent or more of the carbon nanotubes are aligned parallel to the anode/collector's surface.

Description

    STATEMENT OF GOVERNMENT INTEREST
  • The conditions under which this invention was made are such as to entitle the Government of the United States under paragraph I(a) of Executive Order 10096, as represented by the Secretary of the Air Force, to the entire right, title and interest therein, including foreign rights.
    • BACKGROUND
  • The invention is in the field of vacuum tubes, and more particularly relates to a coated anode designed to reduce out-gassing, plasma formation, and secondary electron production.
  • Every vacuum electronics device, ranging from radio frequency tubes to microwaves tubes, must have some region in which the cathode emitted electrons impact after participating in the desired interactions. Generally these structures consist of stainless steel, oxygen free high conductivity (OFHC) copper or some other metal. Occasionally the metal is coated with an insulating material such as titanium nitride. Metals are generally the optimum structures due to the good electrical and thermal conductivity as well as the superior vacuum performance.
  • One major drawback with these materials is the production of secondary electrons, plasmas, and neutral gasses upon electron impact. Neutral gasses contribute to raising the pressure in the tube, reducing the vacuum. Plasmas not only increase the pressure but also cause the tube to short electrically, limiting the duration of microwave or radio frequency output. Plasmas can also cause damage other components, e.g., the cathode or other metallic structures. Secondary electrons are electrons produced by the impact of the primary electron beam. A single primary electron can produce several or as many as hundreds of secondary electrons. These secondary electrons then cause the formation of plasmas and result in further out-gassing from the metal anode or collector.
  • These problems are amplified when the collector is biased to allow energy recovery from the primary electron beam. Here, the secondary electrons can easily be re-accelerated back into the collector, causing a cascading process producing more secondary electrons. One method to reduce this effect is to coat the anode/collector with a carbon film. The carbon reduces, but does not eliminate the effects discussed above.
  • Accordingly, there is a need for an anode/collector that can significantly reduce the production of secondary electrons, plasma formation, and out-gassing of neutral gases.
    • SUMMARY
  • In a preferred embodiment, the anode/collector surface of a vacuum tube is coated with a carbon nanotube material having the longitudinal axis of at least a portion of the nanotubes running parallel to the surface. The anode/collector surface initially is comprised of carbon or a metal surface coated with a thin film of carbon. It is then coated with a carbonizable resin. The final coating can be a carbon nanotube felt-like material that is pyro-bonded to the anode surface, or nanotubes can be deposited on the anode by chemical vapor deposition or by evaporation and then pyro-bonded.
  • Other aspects and advantages of the present invention will become apparent from the following detailed description, taken in conjunction with the accompanying drawing, illustrating by way of example the principles of the invention.
    • BRIEF DESCRIPTION OF THE DRAWINGS
  • FIG. 1 illustrates a typical cylindrical anode/cathode configuration.
  • FIG. 2 is an end view of the cylindrical anode/cathode of FIG. 1
  • FIG. 3 is an end view of a portion of the cylindrical anode/cathode at 475 kV with the anode coated.
  • FIG. 4 is a low gain end view of a portion of the cylindrical anode/cathode at 475 kV with an uncoated anode.
    • DETAILED DESCRIPTION
  • Conventional vacuum tube anodes/collectors produce secondary electrons from the impact of electrons from the cathode, along with plasmas and neutral gasses that degrade the performance of the tube. The carbon nanotube anode coating of the present invention significantly reduces these problems.
  • Carbon nanotubes are very small tube-shaped molecules having the structure of a graphite molecule rolled into a tube. Nanotubes have high conductivity along their longitudinal direction (z) and low conductivity in the transverse (r) direction. The carbon bonds are such that electrons are tightly bound in the p-orbits in the transverse direction and not readily dislodged. Thus, an anode coated with a carbon nanotube material that has at least a portion of the nanotubes lying parallel to the anode surface will produce few secondary electrons. Processes for fabricating single-walled carbon nanotubes into fibers and ribbon-like materials with preferentially oriented nanotubes are known in the art (Vigolo, Brigitte, et. al, “Macroscopic Fibers and Ribbons of Oriented Carbon Nanotubes,” Science, Vol. 290, pp. 1331-1334, 17 Nov. 2000).
  • Nanotubes can be placed on an anode/collector surface coated with a carbonizable resin using chemical vapor deposition (CVD) or evaporation. (Carbon nanotubes are commercially available in a power form, e.g., Carbon Nanotechnologies, Inc., Houston, Tex.) After the nanotubes have been deposited, the coating is then pyro-bonded to the anode/collector surface.
  • First, a carbon surface or a metal surface coated with a thin film of carbon is obtained in the shape of the desired anode. The electron impact surface is then coated with a carbonizable resin. A carbonizable resin, e.g. phenolic, is any resin that when heated sufficiently hot leaves only carbon in a solid state, generally a powder. The carbon nanotubes can be secured to the anode/collector surface using CVD onto the surface, which has been coated with a carbonizable resin.
  • The anode/collector part is then baked to greater than 7000 centigrade in a non-oxidizing atmosphere, decomposing the resin, and releasing volatile components. A porous carbon “char” residue embedded with carbon nanotubes is left on the surface. Next, chemical vapor deposition (CVD) is used to infiltrate carbon into the porous char, creating a non-porous, rigid surface. This pyrocarbon material coating consists of a layer of carbon derived using pyrolysis through chemical vapor deposition (CVD). Pyrolysis through CVD is a process in which a low pressure hydrocarbon gas, methane for example, flows onto the part to be coated, is thermally decomposed, and deposits carbon on the part while releasing hydrogen. In particular, the carbonized part is heated to over 1000° centigrade while a low-pressure hydrocarbon gas is flowed onto it. The gas thermally decomposes, depositing carbon layers and releasing hydrogen. The length of the process depends on the size of the part to be coated, the number of layers required, and the gas flow rate. The thickness of the CVD film added depends on the thickness of the carbon nanotube coating, which depends on the degree of reduction required. The degree of reduction required depends on the exact parameters of the device to be used. The entire assembly is then placed in a vacuum bakeout at over 100° centigrade to remove any remaining water. The coating retains sufficient conductivity to conduct the incident electrons to the remainder of the pulsed circuit.
  • Carbon nanotubes can also be produced in a “felt” material, in which a significant portion of the nanotubes that form the fabric of the felt lie in the plane of the material. The felt consists of a polymer fabric into which ribbon-like carbon nanotube strips have been woven. (The source of this felt material is Dr. Otto Chou, Physics and Astronomy Department, University of North Carolina at Chapel Hill.) First, a carbon surface or a metal surface coated with a thin film of carbon is obtained in the shape of the desired anode. The electron impact surface is then coated with a carbonizable resin as previously described. The felt can be secured to the anode/collector surface by placing the felt on the surface which has been coated with a carbonizable resin and then heating the entire structure to greater than 1000° C. The felt is thus pyro-bonded to the anode/collector surface, forming a coating.
  • A significant reduction in secondary electrons was measured for carbon nanotube material having as little as five percent of the nanotubes parallel to the anode surface. At the same time, the cathode-produced electrons are conducted away by the anode parallel to the anode surface. Plasmas that normally would form due to secondary electron emission at 80 keV electron energies did not form until the electron energy exceeded 475 keV. For example, an anode structure having a cylindrical geometry is depicted in FIG. 1 with an end view shown in FIG. 2. A cathode 2 emits electrons that are accelerated to high energy towards the anode/collector 1. The cylindrical cathode is held in position within the cylindrical anode by a support 3. Electrons impact the anode at very high energy, leading to the production of neutral gas, plasma, and secondary electrons.
  • FIG. 3 is a scanned photograph of a portion of the cylindrical anode/cathode (approximately encompassed by the FIG. 2 dashed line 4) where the anode 1 has been coated with the carbon nanotube material as described above. The potential difference between the cathode and the anode is 475 kV. No plasma formation can be seen. For comparison, the same cylindrical anode/cathode at 475 kV is shown in FIG. 4 but with an uncoated anode. This low-gain photo clearly shows the plasma formation 5. The plasma brightness in FIG. 4 necessitated the much-reduced gain of FIG. 4 relative to FIG. 3.
  • The carbon nanotube-based anode/collector coating has several advantages over previous metals and coatings. This coating can be used in high and low vacuum. The coating can be applied in a complex range of shapes. Secondary electron production, neutral gas (out-gassing) production, and plasma production are greatly reduced, permitting microwave and radio frequency vacuum electronics to be run with higher efficiency due to lower pumping requirements. Many devices have been limited in peak power and pulse duration by these effects. These coated anodes have applications ranging from cathode ray tubes in computers, televisions, and displays to microwave tubes in radar, communications, and cooking.

Claims (21)

1-4. (canceled)
5. A method of coating an anode/collector with carbon nanotubes comprising the steps of:
forming a coating comprised of carbon nanotubes onto an anode/collector by applying a carbonizable resin to the anode/collector and depositing carbon nanotubes onto the cabonizable resin:
pyrobonding the coating onto the anode/collector by heating the anode/collector in a non-oxidizing atmosphere to a temperature sufficient to decompose the carbonizable resin and release volatile components;
infiltrating the coating with carbon by pyrolysis through chemical vapor deposition; and
removing any residual water from the coating.
6. (canceled)
7. An anode/collector coating method as defined in claim 5 wherein the pyrolysis through chemical vapor deposition includes directing a flow of low pressure hydrocarbon gas over the coating while heating the anode/collector to a temperature of over 1000° C.
8. (canceled)
9. An anode/collector coating method as defined in claim 5 wherein the anode/collector is heated to a temperature of over 700° C.
10. An anode/collector coating method as defined in claim 5 wherein the water removing step includes evaporating any residual water by baking the anode/collector in a vacuum oven.
11. An anode/collector coating method as defined in claim 5 wherein the water removing step includes heating the anode/collector to at least 100° C. in a vacuum.
12. (canceled)
13. An anode/collector coating method as defined in claim 10 wherein the pyro-bonding step includes heating the anode/collector to a temperature of over 700° C.
14. An anode/collector coating method as defined in claim 10 wherein the pyrolysis through chemical vapor deposition includes directing a flow of low pressure hydrocarbon gas over the coating while heating the anode/collector to a temperature of over 1000° C.
15. (canceled)
16. An anode/collector coating method as defined in claim 5 wherein the depositing step is obtained through vapor deposition.
17. An anode/collector coating method as defined in claim 16 further comprising, before the pyro-bonding step, the steps of:
applying a carbonizable resin to the anode/collector, and
depositing carbon nanotubes onto the carbonizable resin.
18. An anode/collector coating method as defined in claim 5 wherein the depositing step is obtained through chemical vapor deposition.
19. An anode/collector coating method as defined in claim 10 wherein the depositing step is obtained through vapor deposition.
20. An anode/collector coating method as defined in claim 18 wherein the pyro-bonding step is comprised of heating the anode/collector to a temperature of over 700° C. in a non-oxidizing atmosphere.
21. An anode/collector coating method as defined in claim 7 wherein the depositing step is obtained by means of chemical vapor deposition.
22. (canceled)
23. An anode/collector coating method as defined in claim 9 wherein the pyrolysis through chemical vapor deposition includes directing a flow of low pressure hydrocarbon gas over the coating while heating the anode/collector to a temperature of over 1000° C.
24. An anode/collector coating method as defined in claim 5 wherein the carbonizable resin is phenolic.
US10/445,976 2001-11-13 2003-05-27 Method of coating an anode/collector with carbon nanotubes Expired - Fee Related US7169437B1 (en)

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Families Citing this family (77)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6706402B2 (en) 2001-07-25 2004-03-16 Nantero, Inc. Nanotube films and articles
US7259410B2 (en) * 2001-07-25 2007-08-21 Nantero, Inc. Devices having horizontally-disposed nanofabric articles and methods of making the same
US7563711B1 (en) * 2001-07-25 2009-07-21 Nantero, Inc. Method of forming a carbon nanotube-based contact to semiconductor
US6919592B2 (en) 2001-07-25 2005-07-19 Nantero, Inc. Electromechanical memory array using nanotube ribbons and method for making same
US6835591B2 (en) * 2001-07-25 2004-12-28 Nantero, Inc. Methods of nanotube films and articles
US20050182056A9 (en) * 2002-02-21 2005-08-18 Seth Pawan Modified release formulations of at least one form of tramadol
US7162308B2 (en) 2002-11-26 2007-01-09 Wilson Greatbatch Technologies, Inc. Nanotube coatings for implantable electrodes
US7666382B2 (en) * 2004-12-16 2010-02-23 Nantero, Inc. Aqueous carbon nanotube applicator liquids and methods for producing applicator liquids thereof
CA2512387A1 (en) * 2003-01-13 2004-08-05 Nantero, Inc. Methods of using thin metal layers to make carbon nanotube films, layers, fabrics, ribbons, elements and articles
US7858185B2 (en) 2003-09-08 2010-12-28 Nantero, Inc. High purity nanotube fabrics and films
US8937575B2 (en) 2009-07-31 2015-01-20 Nantero Inc. Microstrip antenna elements and arrays comprising a shaped nanotube fabric layer and integrated two terminal nanotube select devices
US9574290B2 (en) 2003-01-13 2017-02-21 Nantero Inc. Methods for arranging nanotube elements within nanotube fabrics and films
US9422651B2 (en) 2003-01-13 2016-08-23 Nantero Inc. Methods for arranging nanoscopic elements within networks, fabrics, and films
US7045421B2 (en) * 2003-04-22 2006-05-16 Nantero, Inc. Process for making bit selectable devices having elements made with nanotubes
EP1631812A4 (en) 2003-05-14 2010-12-01 Nantero Inc Sensor platform using a horizontally oriented nanotube element
US8039961B2 (en) * 2003-08-25 2011-10-18 Samsung Electronics Co., Ltd. Composite carbon nanotube-based structures and methods for removing heat from solid-state devices
US8211593B2 (en) * 2003-09-08 2012-07-03 Intematix Corporation Low platinum fuel cells, catalysts, and method for preparing the same
US7375369B2 (en) 2003-09-08 2008-05-20 Nantero, Inc. Spin-coatable liquid for formation of high purity nanotube films
US7416993B2 (en) * 2003-09-08 2008-08-26 Nantero, Inc. Patterned nanowire articles on a substrate and methods of making the same
US7351444B2 (en) * 2003-09-08 2008-04-01 Intematix Corporation Low platinum fuel cell catalysts and method for preparing the same
US20050112450A1 (en) * 2003-09-08 2005-05-26 Intematix Corporation Low platinum fuel cell catalysts and method for preparing the same
US20050260412A1 (en) * 2004-05-19 2005-11-24 Lockheed Martin Corporation System, method, and apparatus for producing high efficiency heat transfer device with carbon nanotubes
CN1309770C (en) * 2004-05-19 2007-04-11 中国航空工业第一集团公司北京航空材料研究院 High volume fraction carbon nanotube array - resin base composite materials and method for preparing same
US7709880B2 (en) * 2004-06-09 2010-05-04 Nantero, Inc. Field effect devices having a gate controlled via a nanotube switching element
US8471238B2 (en) 2004-09-16 2013-06-25 Nantero Inc. Light emitters using nanotubes and methods of making same
US7365632B2 (en) * 2004-09-21 2008-04-29 Nantero, Inc. Resistive elements using carbon nanotubes
CA2586120A1 (en) * 2004-11-02 2006-12-28 Nantero, Inc. Nanotube esd protective devices and corresponding nonvolatile and volatile nanotube switches
US8941094B2 (en) 2010-09-02 2015-01-27 Nantero Inc. Methods for adjusting the conductivity range of a nanotube fabric layer
US9287356B2 (en) 2005-05-09 2016-03-15 Nantero Inc. Nonvolatile nanotube diodes and nonvolatile nanotube blocks and systems using same and methods of making same
US8513768B2 (en) 2005-05-09 2013-08-20 Nantero Inc. Nonvolatile nanotube diodes and nonvolatile nanotube blocks and systems using same and methods of making same
US9196615B2 (en) 2005-05-09 2015-11-24 Nantero Inc. Nonvolatile nanotube diodes and nonvolatile nanotube blocks and systems using same and methods of making same
US7781862B2 (en) 2005-05-09 2010-08-24 Nantero, Inc. Two-terminal nanotube devices and systems and methods of making same
US8013363B2 (en) * 2005-05-09 2011-09-06 Nantero, Inc. Nonvolatile nanotube diodes and nonvolatile nanotube blocks and systems using same and methods of making same
US7782650B2 (en) * 2005-05-09 2010-08-24 Nantero, Inc. Nonvolatile nanotube diodes and nonvolatile nanotube blocks and systems using same and methods of making same
US8183665B2 (en) * 2005-11-15 2012-05-22 Nantero Inc. Nonvolatile nanotube diodes and nonvolatile nanotube blocks and systems using same and methods of making same
US7835170B2 (en) 2005-05-09 2010-11-16 Nantero, Inc. Memory elements and cross point switches and arrays of same using nonvolatile nanotube blocks
US7479654B2 (en) 2005-05-09 2009-01-20 Nantero, Inc. Memory arrays using nanotube articles with reprogrammable resistance
US8217490B2 (en) 2005-05-09 2012-07-10 Nantero Inc. Nonvolatile nanotube diodes and nonvolatile nanotube blocks and systems using same and methods of making same
US9911743B2 (en) 2005-05-09 2018-03-06 Nantero, Inc. Nonvolatile nanotube diodes and nonvolatile nanotube blocks and systems using same and methods of making same
US7598127B2 (en) 2005-05-12 2009-10-06 Nantero, Inc. Nanotube fuse structure
TWI264271B (en) * 2005-05-13 2006-10-11 Delta Electronics Inc Heat sink
US7915122B2 (en) * 2005-06-08 2011-03-29 Nantero, Inc. Self-aligned cell integration scheme
US7538040B2 (en) * 2005-06-30 2009-05-26 Nantero, Inc. Techniques for precision pattern transfer of carbon nanotubes from photo mask to wafers
DE102005039188B4 (en) * 2005-08-18 2007-06-21 Siemens Ag X-ray tube
DE102005039187B4 (en) * 2005-08-18 2012-06-21 Siemens Ag X-ray tube
AU2006347609A1 (en) * 2005-09-06 2008-05-08 Nantero, Inc. Carbon nanotubes for the selective transfer of heat from electronics
US8525143B2 (en) * 2005-09-06 2013-09-03 Nantero Inc. Method and system of using nanotube fabrics as joule heating elements for memories and other applications
EP1929276B1 (en) * 2005-09-06 2011-07-27 Nantero, Inc. Nanotube sensor system and method of use
KR20080078879A (en) * 2005-12-19 2008-08-28 어드밴스드 테크놀러지 머티리얼즈, 인코포레이티드 Production of carbon nanotubes
DE102006010232A1 (en) * 2006-03-02 2007-09-06 Schunk Kohlenstofftechnik Gmbh Method for producing a heat sink and heat sink
US20080238882A1 (en) * 2007-02-21 2008-10-02 Ramesh Sivarajan Symmetric touch screen system with carbon nanotube-based transparent conductive electrode pairs
EP2126954A1 (en) * 2007-02-24 2009-12-02 E. I. Du Pont de Nemours and Company Field emission device with anode coating
WO2008112764A1 (en) 2007-03-12 2008-09-18 Nantero, Inc. Electromagnetic and thermal sensors using carbon nanotubes and methods of making same
WO2009005908A2 (en) * 2007-05-22 2009-01-08 Nantero, Inc. Triodes using nanofabric articles and methods of making the same
WO2009043344A1 (en) 2007-10-02 2009-04-09 Hans-Henning Reis X-ray rotating anode plate, and method for the production thereof
CN101576423B (en) * 2008-05-07 2010-12-29 清华大学 Ionization gauge
US8587989B2 (en) * 2008-06-20 2013-11-19 Nantero Inc. NRAM arrays with nanotube blocks, nanotube traces, and nanotube planes and methods of making same
US7915637B2 (en) 2008-11-19 2011-03-29 Nantero, Inc. Switching materials comprising mixed nanoscopic particles and carbon nanotubes and method of making and using the same
US8574673B2 (en) 2009-07-31 2013-11-05 Nantero Inc. Anisotropic nanotube fabric layers and films and methods of forming same
US8128993B2 (en) * 2009-07-31 2012-03-06 Nantero Inc. Anisotropic nanotube fabric layers and films and methods of forming same
US20110034008A1 (en) * 2009-08-07 2011-02-10 Nantero, Inc. Method for forming a textured surface on a semiconductor substrate using a nanofabric layer
WO2011050331A2 (en) * 2009-10-23 2011-04-28 Nantero, Inc. Method for passivating a carbonic nanolayer
US8351239B2 (en) * 2009-10-23 2013-01-08 Nantero Inc. Dynamic sense current supply circuit and associated method for reading and characterizing a resistive memory array
US8895950B2 (en) 2009-10-23 2014-11-25 Nantero Inc. Methods for passivating a carbonic nanolayer
US8222704B2 (en) * 2009-12-31 2012-07-17 Nantero, Inc. Compact electrical switching devices with nanotube elements, and methods of making same
KR101709823B1 (en) 2010-02-12 2017-02-23 난테로 인크. Methods for controlling density, porosity, and/or gap size within nanotube fabric layers and films
US20110203632A1 (en) * 2010-02-22 2011-08-25 Rahul Sen Photovoltaic devices using semiconducting nanotube layers
US10661304B2 (en) 2010-03-30 2020-05-26 Nantero, Inc. Microfluidic control surfaces using ordered nanotube fabrics
CN103896244B (en) * 2012-12-29 2016-08-10 清华大学 Reactor and the method for growth CNT
US9650732B2 (en) 2013-05-01 2017-05-16 Nantero Inc. Low defect nanotube application solutions and fabrics and methods for making same
US10654718B2 (en) 2013-09-20 2020-05-19 Nantero, Inc. Scalable nanotube fabrics and methods for making same
US9299430B1 (en) 2015-01-22 2016-03-29 Nantero Inc. Methods for reading and programming 1-R resistive change element arrays
US9934848B2 (en) 2016-06-07 2018-04-03 Nantero, Inc. Methods for determining the resistive states of resistive change elements
US9941001B2 (en) 2016-06-07 2018-04-10 Nantero, Inc. Circuits for determining the resistive states of resistive change elements
US11373833B1 (en) 2018-10-05 2022-06-28 Government Of The United States, As Represented By The Secretary Of The Air Force Systems, methods and apparatus for fabricating and utilizing a cathode
RU2745976C1 (en) * 2020-04-13 2021-04-05 Федеральное государственное бюджетное образовательное учреждение высшего образования "Московский государственный университет имени М.В. Ломоносова" (МГУ) Anti-dynatron coating based on a polymer matrix with the inclusion of carbon nanotubes and a method for its preparation
CN114646689A (en) * 2020-12-17 2022-06-21 清华大学 Secondary electron probe and secondary electron detector

Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4417175A (en) * 1981-05-15 1983-11-22 The United States Of America As Represented By The Administrator Of The National Aeronautics And Space Administration Ion sputter textured graphite electrode plates
US4607193A (en) * 1984-10-10 1986-08-19 The United States Of America As Represented By The Administrator Of The National Aeronautics And Space Administration Textured carbon surfaces on copper by sputtering
US5786666A (en) * 1996-03-22 1998-07-28 Lockheed Martin Energy Systems, Inc. Collector surface for a microwave tube comprising a carbon-bonded carbon-fiber composite
US5916642A (en) * 1995-11-22 1999-06-29 Northwestern University Method of encapsulating a material in a carbon nanotube
US6265466B1 (en) * 1999-02-12 2001-07-24 Eikos, Inc. Electromagnetic shielding composite comprising nanotubes
US6322713B1 (en) * 1999-07-15 2001-11-27 Agere Systems Guardian Corp. Nanoscale conductive connectors and method for making same
US6331690B1 (en) * 1997-12-22 2001-12-18 Nec Corporation Process for producing single-wall carbon nanotubes uniform in diameter and laser ablation apparatus used therein
US6361861B2 (en) * 1999-06-14 2002-03-26 Battelle Memorial Institute Carbon nanotubes on a substrate
US20040043219A1 (en) * 2000-11-29 2004-03-04 Fuminori Ito Pattern forming method for carbon nanotube, and field emission cold cathode and method of manufacturing the cold cathode
US6914372B1 (en) * 1999-10-12 2005-07-05 Matsushita Electric Industrial Co., Ltd. Electron-emitting element and electron source, field emission image display device, and fluorescent lamp utilizing the same and methods of fabricating the same

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP3421549B2 (en) 1996-09-18 2003-06-30 株式会社東芝 Vacuum micro device
JP4069532B2 (en) 1999-01-11 2008-04-02 松下電器産業株式会社 Carbon ink, electron-emitting device, method for manufacturing electron-emitting device, and image display device
US6521324B1 (en) 1999-11-30 2003-02-18 3M Innovative Properties Company Thermal transfer of microstructured layers
EP1276132A1 (en) * 2001-07-10 2003-01-15 VA TECH Transmission & Distribution GmbH & Co. KEG Method and device for collecting electrons

Patent Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4417175A (en) * 1981-05-15 1983-11-22 The United States Of America As Represented By The Administrator Of The National Aeronautics And Space Administration Ion sputter textured graphite electrode plates
US4607193A (en) * 1984-10-10 1986-08-19 The United States Of America As Represented By The Administrator Of The National Aeronautics And Space Administration Textured carbon surfaces on copper by sputtering
US5916642A (en) * 1995-11-22 1999-06-29 Northwestern University Method of encapsulating a material in a carbon nanotube
US5786666A (en) * 1996-03-22 1998-07-28 Lockheed Martin Energy Systems, Inc. Collector surface for a microwave tube comprising a carbon-bonded carbon-fiber composite
US6331690B1 (en) * 1997-12-22 2001-12-18 Nec Corporation Process for producing single-wall carbon nanotubes uniform in diameter and laser ablation apparatus used therein
US6265466B1 (en) * 1999-02-12 2001-07-24 Eikos, Inc. Electromagnetic shielding composite comprising nanotubes
US6361861B2 (en) * 1999-06-14 2002-03-26 Battelle Memorial Institute Carbon nanotubes on a substrate
US6322713B1 (en) * 1999-07-15 2001-11-27 Agere Systems Guardian Corp. Nanoscale conductive connectors and method for making same
US6914372B1 (en) * 1999-10-12 2005-07-05 Matsushita Electric Industrial Co., Ltd. Electron-emitting element and electron source, field emission image display device, and fluorescent lamp utilizing the same and methods of fabricating the same
US20040043219A1 (en) * 2000-11-29 2004-03-04 Fuminori Ito Pattern forming method for carbon nanotube, and field emission cold cathode and method of manufacturing the cold cathode

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