WO2010117515A1 - Apparatus and method for the production of carbon nanotubes on a continuously moving substrate - Google Patents
Apparatus and method for the production of carbon nanotubes on a continuously moving substrate Download PDFInfo
- Publication number
- WO2010117515A1 WO2010117515A1 PCT/US2010/025660 US2010025660W WO2010117515A1 WO 2010117515 A1 WO2010117515 A1 WO 2010117515A1 US 2010025660 W US2010025660 W US 2010025660W WO 2010117515 A1 WO2010117515 A1 WO 2010117515A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- substrate
- carbon nanotube
- zone
- growth zone
- nanotube growth
- Prior art date
Links
Classifications
-
- 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
-
- 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
- C01B32/164—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
- C23C16/44—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
- C23C16/448—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 characterised by the method used for generating reactive gas streams, e.g. by evaporation or sublimation of precursor materials
- C23C16/452—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 characterised by the method used for generating reactive gas streams, e.g. by evaporation or sublimation of precursor materials by activating reactive gas streams before their introduction into the reaction chamber, e.g. by ionisation or addition of reactive species
-
- 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
- C23C16/455—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 characterised by the method used for introducing gases into reaction chamber or for modifying gas flows in reaction chamber
- C23C16/45519—Inert gas curtains
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/64—Nanometer sized, i.e. from 1-100 nanometer
Definitions
- the present invention relates in general to an apparatus and method for the production of carbon nanotubes on a continuously moving substrate.
- carbon nanotube refers to any of a number of cylindrically-shaped allotropes of carbon of the fullerene family including single- walled carbon nanotubes (SWNTs), double-walled carbon nanotubes (DWNTs), multi-walled carbon nanotubes (MWNTs).
- SWNTs single- walled carbon nanotubes
- DWNTs double-walled carbon nanotubes
- MWNTs multi-walled carbon nanotubes
- CNTs can be capped by a fullerene-like structure or open- ended.
- CNTs include those that encapsulate other materials.
- Carbon nanotubes exhibit impressive physical properties. The strongest CNTs exhibit roughly eighty times the strength, six times the toughness (i.e., Young's Modulus), and one-sixth the density of high carbon steel.
- CNT carbon nanotube
- Vapor grown carbon fiber i.e., CNTs
- CNTs Vapor grown carbon fiber
- the fibers grow on the composite preform resulting in a tangled mass of carbon fiber (carbon nanotubes).
- the reaction time for growth varies between 15 minutes and 2 hours, primarily as a function of feed gas composition and temperature.
- the processing times for the approach disclosed in 7,338,684 are too long for efficient processing. Furthermore, due to the extreme variation in the processing time for various steps, the process is unsuitable for implementation as a continuous processing line for the production of carbon nanotubes on a continuously moving substrate.
- inventions disclosed herein relate to an apparatus capable of linear and/or continuous CNT synthesis on spoolable length substrates.
- the apparatus includes at least one carbon nanotube growth zone having a substrate inlet sized to allow a spoolable length substrate to pass therethrough
- the apparatus also includes at least one heater in thermal communication with the carbon nanotube growth zone; and at least one feed gas inlet in fluid communication with the carbon nanotube growth zone.
- the apparatus is open to the atmosphere during operation.
- the CNT growth is carried out at ambient or near ambient pressures.
- the apparatus optionally includes one or more purge zones, on opposing sides of the carbon nanotube growth zone.
- the apparatus is designed to be integrated into a system for the continuous growth of carbon nanotubes.
- Figure 1 shows a simplified perspective view of an apparatus for the synthesis of
- Figure 2 shows a simplified cross-sectional side view of an apparatus for the synthesis of CNTs in a continuous process in accordance with an illustrative embodiment of the present invention.
- Figure 3 shows a cross-sectional side view of an embodiment of an apparatus in accordance with the present invention.
- Figure 4 shows a cross-sectional side view of an embodiment of an apparatus in accordance with the present invention.
- Figure 5 shows a top cross-sectional view of the apparatus of Figure 3 in accordance with the present invention.
- Figure 6 shows a top cross-sectional view of an embodiment of an apparatus in accordance with the present invention.
- Figure 7 shows a transverse side view of another embodiment of an apparatus in accordance with the present invention.
- Figure 8 shows a transverse top view of the embodiment of Figure 7.
- Figure 9 shows a longitudinal top cross sectional view of the embodiment of
- Figure 10 shows a longitudinal side cross sectional view of the embodiment of
- Figure 11 shows a longitudinal top view of the embodiment of Figure 7.
- Figure 12 is a side cross-sectional view of the embodiment of Figure 7.
- apparatus 100 is used to grow, produce, deposit, or otherwise generate CNTs in situ directly onto or into moving substrate 106 and takes the form of an open ended, atmospheric, to slightly higher than atmospheric pressure, small cavity, chemical vapor deposition (CVD) CNT growth system.
- CNTs are grown via CVD at atmospheric pressure and at elevated temperature (typically in the range of about 550 0 C to about 800 0 C in a multi-zone apparatus 100.
- the fact that the synthesis occurs at atmospheric pressure is one factor that facilitates the incorporation of apparatus 100 into a continuous processing line for CNT-on-fiber synthesis.
- the fact that CNT growth occurs in a seconds, as opposed to minutes (or longer) in the prior art, is another feature that enables using the apparatus disclosed herein in a continuous processing line.
- CNT-synthesis can be performed at a rate sufficient to provide a continuous process for functionalizing spoolable substrates. Numerous apparatus configurations facilitate such continuous synthesis.
- Apparatus 100 includes at least one CNT growth zone 108 equipped with growth heaters 110 disposed between two quench or purge zones 114, 116. Any number of growth heaters can be included, (e.g., heaters HOa, HOb, HOc, HOd of Figure 4). Apparatus 100 optionally includes pre-heater 132 that pre-heats feed gasl28 and feed gas diffuser 136 to distribute feed gas 128.
- CNTs applied directly on substrate surfaces improves overall CNT dispersion, placement, and alignment in the completed structure.
- the incorporation of CNTs on the fiber or fabric level improves CNT loading by having the CNTs preordered and placed in the composite structure, instead of having to dope resins with loose CNTs.
- To grow CNTs directly on a substrate in a continuous process improves not only these physical characteristics but also reduces overall CNT cost. By having CNTs grown directly on the final useful substrate surface, the auxiliary costs involved with CNT purification and doping/mixing/placement/dispersion are removed.
- apparatus 100 can include substrate inlet 118 sized to allow spoolable length substrate 106 to continually pass therethrough, allowing for the synthesis and growth of CNTs directly on substrate 106.
- Apparatus 100 can be a multi-zone apparatus with seed or CNT growth zone 108 between a pre-process purge or first purge zone 114 and a post-process purge or second purge zone 116.
- Apparatus 100 can be open to the atmosphere during operation, with first end 120 and second end 124, such that substrate 106 enters apparatus 100 through substrate inlet 118 in first end 120, passes through first purge zone 114, CNT growth zone 108, second purge zone 116 and out through substrate outlet 122 (shown in Figure 2) in second end 124.
- the CNT growth system can include additional zones that are specifically designed to activate catalyst particles via reduction reactions.
- a catalyst activation zone can be placed between first purge zone 114 and CNT growth zone 108.
- Apparatus 100 allows for the seamless transfer of substrate 106 into and out of CNT growth zone 108, obviating the need for batch runs.
- Spoolable length substrate 106 effectively passes through an equilibrated growth system which has established optimal conditions for rapid CNT growth in real time as substrate 106 continually moves through a system that begins with spoolable length substrate 106 and winds the finished product at the end at CNT infusion on substrate 106.
- the ability to do this continuously and efficiently, while controlling parameters such as CNT length, density, and other characteristics has not been previously achieved.
- a continuous process for infusion of CNTs on spoolable substrates can achieve a linespeed between about 0.5 ft/min to about 36 ft/min.
- the process can be run with a linespeed of about 6 ft/min to about 36 ft/min to produce, for example, CNTs having a length between about 1 micron to about 10 microns.
- the process can also be run with a linespeed of about 1 ft/min to about 6 ft/min to produce, for example, CNTs having a length between about 10 microns to about 100 microns.
- the process can be run with a linespeed of about 0.5 ft/min to about 1 ft/min to produce, for example, CNTs having a length between about 100 microns to about 200 microns.
- the CNT length is not tied only to linespeed and growth temperature, however, the flow rate of both the feed gas and inert carrier gases can also influence CNT length.
- a flow rate consisting of less than 1% carbon feedstock in inert gas at high linespeeds (6 ft/min to 36 ft/min) will result in CNTs having a length between 1 micron to about 5 microns.
- a flow rate consisting of more than 1% carbon feedstock in inert gas at high linespeeds (6 ft/min to 36 ft/min) will result in CNTs having length between 5 microns to about 10 microns. Resulting growth rates for this continuous CNT growth system range depending on temperature, gases used, substrate residence time, and catalyst, however, growth rates on the range of 0.01-10 microns/second are possible.
- CNT growth zone 108 can be an open-air continuous operation, flow-through chamber.
- CNT growth zone 108 can be formed or otherwise bound by a metal enclosure such as stainless steel, titanium, carbon steel, or other high temperature metal or mixtures thereof, with additional features added to improve structural rigidity as well as reduce thermal warping due to repeated heat cycling.
- CNT growth zone 108 can be circular, rectangular, oval, or any number of polygonal or other geometrical variant cross-section based on the profile and size of substrate passing therethrough.
- An internal volume of CNT growth zone 108 can be compared with a volume of substrate 106 having a length substantially equal to a length of CNT growth zone 108.
- CNT growth zone 108 is designed to have an internal volume of no more than about 10000 times greater than the volume of substrate 106 disposed within CNT growth zone 108. In most embodiments, this number is greatly reduced to no more than about 4000 times. In other embodiments, this can be reduced to about 3000 times or less.
- cross sectional areas of CNT growth zone 108 can be limited to about 10000, 4000, or 3000 times greater than a cross sectional area of substrate 106.
- CNT growth zone 108 can range from dimensions as small as millimeters wide to as large as over 1600 mm wide.
- CNT growth zone 108 can have a rectangular cross-section and a volume of about 0.27 cubic feet.
- Temperature in CNT growth zone 108 can be controlled with imbedded thermocouples strategically placed on an interior surface thereof. Since CNT growth zone 108 is so small, the temperature of the enclosure is nearly the same temperature as the CNT growth zone 108 and gases inside. CNT growth zone 108 can be maintained at about 550° C.
- both purge zones 114, 116 provide the same function.
- purge zones 114, 116 supply a continuous flow of purge gas 130 (shown in Figure 2) to buffer CNT growth zone 108 from the external environment.
- This can include optionally preheating purge zone 114 and/or cooling purge zone 116. This helps to prevent unwanted mixing of feed gas 128 with the outside atmosphere, which could cause unintended oxidation and damage to substrate 106 (shown in Figure 3 and Figure 4) or CNT material.
- Purge zones 114, 116 are insulated from CNT growth zone 108 to prevent excessive heat loss or transfer from heated CNT growth zone 108.
- one or more exhaust ports 142 are placed between purge zones 114, 116 and CNT growth zone 108.
- gas does not mix between CNT growth zone 108 and purge zones 114, 116, but instead exhausts to the atmosphere through ports 142.
- This also prevents gas mixing which is important in situations where multiple CNT growth zones 108 (e.g., 108a, 108b in Figure 4) can be used in series, attached, or otherwise utilized together to extend the overall effective CNT growth zone.
- Purge zones 114, 116 in this embodiment still provide a cool gas purge to ensure reduced temperatures as substrate 106 enters/exits CNT growth zone 108.
- Feed gas 128 can enter CNT growth zone 108 of apparatus 100 via one or more feed gas inlets 112 (e.g., 112a and 112b of Figure 4). Feed gas 128 can pass through feed gas inlet manifold 134 (shown in Figure 4) and into CNT growth zone 108 via feed gas diffusers 136 (shown in Figure 4). Feed gas 128 can react with seeds present on or in substrate 106 to create CNTs, with any leftover feed gas 128 passing through exhaust manifold 140 (shown in Figure 6) or otherwise exit CNT growth zone 108.
- feed gas inlets 112 e.g., 112a and 112b of Figure 4
- Feed gas 128 can pass through feed gas inlet manifold 134 (shown in Figure 4) and into CNT growth zone 108 via feed gas diffusers 136 (shown in Figure 4). Feed gas 128 can react with seeds present on or in substrate 106 to create CNTs, with any leftover feed gas 128 passing through exhaust manifold 140 (show
- Purge gas 130 can be used to prevent the hot gases inside CNT growth zone 108 from mixing with the oxygen rich gas outside CNT growth zone 108 and creating local oxidizing conditions that could adversely affect substrate 106 entering or exiting CNT growth zone 108.
- Purge gas 130 can enter purge zones 114, 116 of apparatus 100 at purge gas inlets 126, 127 (shown in Figure 2), allowing for a buffer between CNT growth zone 108 and the external environment.
- Purge gas 130 can prevent ambient gasses from entering CNT growth zone 108, and can either exit through substrate inlet 118 or substrate outlet 122 at respective ends 120, 124 of apparatus 100 as indicated in Figure 2, or purge gas 130 can exit through exhaust manifold 140 (shown in Figure 6).
- Purge gas preheater 132 can preheat purge gas 130 prior to introduction into first purge zone 114.
- CNT growth zone 108 can be further heated by heaters 110 (shown in Figure 3) contained within CNT growth zone 108.
- heaters 110 are on either side of substrate 106.
- heaters 110 can be anywhere within CNT growth zone 108, either placed along the length or in cases of wide systems, along the width of CNT growth zone 108, to ensure isothermal heating for well controlled CNT growth processes.
- Heaters 110 can heat CNT growth zone 108 and maintain an operational temperature at a pre-set level. Heaters 110 can be controlled by a controller (not shown).
- Heaters 110 can be any suitable device capable of maintaining CNT growth zone 108 at about the operating temperature.
- heaters 111 shown in Figure 5 and Figure 6) can preheat feed gas 128. Any of heaters 110, 111, 132 can be used in conjunction with CNT growth zone 108, so long as the particular heater is in thermal communication with CNT growth zone 108.
- Heaters 110, 111, 132 can include long coils of gas line heated by a resistively heated element, and/or series of expanding tubes to slow down and which is then heated via resistive heaters (e.g., infrared heaters). Regardless of the method, gas can be heated from about room temperature to a temperature suitable for CNT growth, e.g.
- heaters 110, 111, and/or 132 can provide heat such that the temperature within CNT growth zone 108 is about 550 0 C to about 850 0 C or up to about 1000 °C.
- Temperature controls (not shown) can provide monitoring and/or adjustment of temperature within CNT growth zone 108. Measurement can be made at points (e.g., probe 160 of Figure 9) on plates or other structures defining CNT growth zone 108. Because the height of CNT growth zone 108 is relatively small, the temperature gradient between the plates can be very small, and thus, measurement of temperature of the plates can accurately reflect the temperature within CNT growth zone 108.
- substrate 106 has a small thermal mass, as compared with CNT growth zone 108, substrate 106 can assume the temperature of CNT growth zone 108 almost immediately. Thus, preheat can be left off to allow room temperature gas to enter the growth zone for heating by heaters 110. In some embodiments, only purge gas is preheated. Other feed gas can be added to purge gas after purge gas preheater 132. This can be done to reduce long term sooting and clogging conditions that can occur in purge gas preheater 132 over long times of operations. Preheated purge gas can then enter feed gas inlet manifold 134.
- Feed gas inlet manifold 134 provides a cavity for further gas mixing as well as a means for dispersing and distributing gas to all gas insertion points in CNT growth zone 108. These points of insertion are built into one or more feed gas diffusers 136, e.g. gas diffuser plates with a series of patterned holes. These strategically placed holes ensure a consistent pressure and gas flow distribution. Feed gas enters CNT growth zone 108, where heaters 110 can apply an even temperature generation source.
- substrate 106 enters first purge zone 114, where purge gas 130, which has been preheated by purge gas preheater 132 warms substrate 106 while simultaneously preventing ambient air from entering CNT growth zone 108. Substrate 106 then passes through substrate inlet 118 in first end 120 of CNT growth zone 108. As illustrated in Figure 5 and Figure 6, substrate 106 enters CNT growth zone 108, is heated by heaters 110 (shown in Figure 6) and exposed to feed gas 128 (shown in Figure 2).
- feed gas 128 Before entering CNT growth zone 108, feed gas 128 can move from any of heaters 111, through any of feed gas inlets 112, through feed gas inlet manifold 134, and through feed gas diffusers 136. Feed gas 128 and/or purge gas 130 can exit first purge zone 114 and/or CNT growth zone 108 via exhaust ports 142 and/or exhaust manifold 140, maintaining atmospheric or slightly above atmospheric pressure. Substrate 106 can continue through additional CNT growth zones 108 as desired until sufficient CNT growth has occurred. As illustrated in Figure 5, substrate 106 passes through substrate outlet 122 in second end 124 of CNT growth zone 108 and into second purge zone 116.
- first purge zone 114 and second purge zone 116 can be the same zone and substrate 106 can turn around within apparatus 100 and pass out of CNT growth zone 108 via substrate inlet 118. In either event, substrate passes into a purge zone and out of apparatus 100.
- Purge zones 114 and 116 can each have purge gas introduced through purge gas inlet 126 and 127 (shown in Figure 2), such that purge gas 130 therein acts as a buffer and prevents feed gas 128 from contacting ambient air.
- Purge zones 114 and 116 can each have exhaust ports 142 (shown in Figure 2) and/or exhaust manifolds 140 (shown in Figure 6) to accomplish appropriate buffering.
- Access plate 138 (shown in Figure 5) can provide access to CNT growth zone 108, for cleaning and other maintenance.
- CNT growth zone 108 can be constructed from skirt 144, piped connection 146, and plugged connection 148. Insulation, such as gas seal insulation 150 can provide a barrier to the external environment. Stainless steel standoffs 152 can support copper plate 154, which can in turn support quartz lens 156. As with the embodiments described above, feed gas can enter CNT growth zone 108 via gas ports 158 and temperature can be monitored by probe 160. While the embodiment illustrated in Figures 7-12 is functional, the embodiments described above are preferred at the time of filing.
- multiple substrates 106 can pass through apparatus 100 at any given time.
- any number of heaters can be used either inside or outside a particular CNT growth zone 108.
- Some of potential advantages of the apparatus and method of the present teachings can include, without limitation: improved cross-sectional area; improved zoning; improved materials; and combined catalyst reduction and CNT synthesis.
- the conventional circular cross-section is an inefficient use of volume.
- Such circular cross-section can create difficulties with maintaining a sufficient system purge, because an increased volume requires increased purge gas flow rates to maintain the same level of gas purge.
- the conventional circular cross-section is inefficient for high volume production of CNTs in an open environment.
- Further such circular cross-section can create a need for increased feed gas flow.
- the relative increase in purge gas flow requires increased feed gas flows.
- the volume of a 12K fiber is 2000 times less than the total volume of exemplary CNT growth zone 108 having a rectangular cross-section.
- an equivalent growth cylindrical chamber e.g., a cylindrical chamber having a width that accommodates the same planarized fiber as the rectangular cross-section CNT growth zone 108
- the volume of the fiber is 17,500 times less than the volume of CNT growth zone 108.
- gas deposition processes e.g., CVD, etc.
- pressure and temperature are typically governed by pressure and temperature alone
- volume has a significant impact on the efficiency of deposition.
- excess volume volume in which unwanted reactions occur (e.g., gasses reacting with themselves or with chamber walls); and a cylindrical chamber has about eight times that volume.
- CNT growth zone 108 having a cross-section more closely matched to corresponding substrate 106 (e.g., rectangular).
- CNT growth zone 108 can have a height maintained constant as the size of substrate 106 scales upward. Temperature gradients between the top and bottom of CNT growth zone 108 are essentially negligible and, consequently, thermal issues and the product-quality variations that result are avoided.
- the conventional circular cross-sectional chamber also requires feed gas introduction. Because tubular furnaces are used, conventional CNT synthesis chambers introduce feed gas at one end and draw it through the chamber to the other end.
- feed gas is introduced at the center of or within CNT growth zone 108 (symmetrically, either through the sides or through the top and bottom plates of CNT growth zone 108). This improves the overall CNT growth rate because the incoming feed gas in continuously replenishing at the hottest portion of the system, which is where CNT growth is most active. This constant feed gas replenishment can be an important aspect to the increased growth rate exhibited by CNT growth zone(s) 108 in accordance with the present teachings.
- Purge zones 114, 116 on either or both ends of CNT growth zone 108 disclosed herein provide a buffer between the internal system and external environments. Purge zone 116 achieves the cooling in a short period of time, as may be required for the continuous processing line.
- metal e.g., stainless steel
- Metal, and stainless steel in particular is more susceptible to carbon deposition (i.e., soot and by-product formation). Quartz, on the other hand, is easier to clean, with fewer deposits. Quartz also facilitates sample observation.
- soot and carbon deposition on stainless steel can result in more consistent, faster, more efficient, and more stable CNT growth. It is believed that, in conjunction with atmospheric operation, the CVD process occurring in CNT growth zone 108 is diffusion limited. That is, the catalyst is "overfed;" too much carbon is available in the system due to its relatively higher partial pressure (than if operating under partial vacuum).
- Using apparatus 100 allows for both a catalyst reduction and CNT growth to occur within CNT growth zone 108. This is significant because the reduction step cannot be accomplished timely enough for use in a continuous process if performed as a discrete operation. Conventionally, the reduction step typically takes 1-12 hours to perform. Both operations occur in CNT growth zone 108 in accordance with the present invention due, at least in part, to the fact that feed gas is introduced the center of CNT growth zone 108, not the end. The reduction process occurs as the fibers enter the heated zone; by this point, the gas has had time to react with the walls and cool off prior to reacting with the catalyst and causing the oxidation reduction (via hydrogen radical interactions). It is this transition region where the reduction occurs. At the hottest isothermal zone in the system, the CNT growth occurs, with the greatest growth rate occurring proximal to the feed gas inlets near the center of the CNT growth zone.
- substrate is intended to include any material upon which CNTs can be synthesized and can include, but is not limited to, a carbon fiber, a graphite fiber, a cellulosic fiber, a glass fiber, a metal fiber (e.g., steel, aluminum, etc.), a metallic fiber, a ceramic fiber, a metallic-ceramic fiber, an aramid fiber, or any substrate comprising a combination thereof.
- the substrate can include fibers or filaments arranged, for example, in a fiber tow (typically having about 1000 to about 12000 fibers) as well as planar substrates such as fabrics, tapes, or other fiber broadgoods, and materials upon which CNTs can be synthesized.
- a fiber tow typically having about 1000 to about 12000 fibers
- planar substrates such as fabrics, tapes, or other fiber broadgoods, and materials upon which CNTs can be synthesized.
- the apparatus of the present invention results in the production of carbon-nanotube infused fiber.
- infused means chemically or physically bonded and "infusion” means the process of bonding.
- bonding can involve direct covalent bonding, ionic bonding, pi-pi, and/or van der Waals force-mediated physisorption.
- the CNTs can be directly bonded to the substrate. Additionally, it is believed that some degree of mechanical interlocking occurs as well. Bonding can be indirect, such as the CNT infusion to the substrate via a barrier coating and/or an intervening transition metal nanoparticle disposed between the CNTs and substrate.
- the carbon nanotubes can be "infused" to the substrate directly or indirectly as described above. The particular manner in which a CNT is "infused" to a substrate is referred to as a "bonding motif.”
- CNTs useful for infusion to substrates include single- walled CNTs, double-walled CNTs, multi-walled CNTs, and mixtures thereof.
- the exact CNTs to be used depends on the application of the CNT-infused substrate.
- CNTs can be used for thermal and/or electrical conductivity applications, or as insulators.
- the infused carbon nanotubes are single-wall nanotubes.
- the infused carbon nanotubes are multi-wall nanotubes.
- the infused carbon nanotubes are a combination of single- wall and multi-wall nanotubes.
- single-wall and multi-wall nanotubes differ in the characteristic properties of single-wall and multi-wall nanotubes that, for some end uses of the fiber, dictate the synthesis of one or the other type of nanotube.
- single- walled nanotubes can be semi-conducting or metallic, while multi-walled nanotubes are metallic.
- CNTs are formed on substrates (e.g., graphite tow, glass roving, etc.) using the system and process described above, and are then passed through a resin bath to produce resin- impregnated, CNT-infused substrate. After resin impregnation, the substrate is positioned on the surface of a rotating mandrel by a delivery head. The substate then winds onto the mandrel in a precise geometric pattern in known fashion. These additional sub operations can be performed in continuous fashion, extending the basic continuous process.
- the filament winding process described above provides pipes, tubes, or other forms as are characteristically produced via a male mold. But the forms made from the filament winding process disclosed herein differ from those produced via conventional filament winding processes.
- the forms are made from composite materials that include CNT-infused substrates. Such forms will therefore benefit from enhanced strength, etc., as provided by the CNT-infused substrates.
- the term “spoolable dimensions” refers to substrates having at least one dimension that is not limited in length, allowing for the material to be stored on a spool or mandrel. Substrates of “spoolable dimensions” have at least one dimension that indicates the use of either batch or continuous processing for CNT infusion as described herein.
- Commercial carbon fiber tow in particular, can be obtained in 5, 10, 20, 50, and 100 Ib. (for spools having high weight, usually a 3k/12K tow) spools, for example, although larger spools may require special order.
- Processes of the invention operate readily with 5 to 20 Ib. spools, although larger spools are usable.
- a pre-process operation can be incorporated that divides very large spoolable lengths, for example 100 Ib. or more, into easy to handle dimensions, such as two 50 Ib spools.
- feed gas refers to any carbon compound gas, solid, or liquid that can be volatilized, nebulized, atomized, or otherwise fluidized and is capable of dissociating or cracking at high temperatures into at least some free carbon radicals and which, in the presence of a catalyst, can form CNTs on the substrate.
- feed gas can comprise acetylene, ethylene, methanol, methane, propane, benzene, natural gas, or any combination thereof.
- purge gas refers to any gas, solid, or liquid that can be volatilized, nebulized, atomized, or otherwise fluidized and is capable of displacing another gas.
- Purge gas can optionally be cooler than corresponding feed gas.
- purge gas can include a mass flow controlled mixture of inert gas such as nitrogen, argon, or helium and carbon feedstock, such as acetylene, ethylene, ethane, methane, carbon monoxide, and similar carbon-containing gases, typically mixed from between about 0 to about 10% feed gas with the remainder consisting of inert gas.
- additional gases such as ammonia, hydrogen, and/or oxygen can be mixed as a third process gas as well in ranges of between about 0 to aboutl0%.
- the term “nanoparticle” or NP refers to particles sized between about 0.1 to about 100 nanometers in equivalent spherical diameter, although the NPs need not be spherical in shape. Transition metal NPs, in particular, serve as catalysts for CNT growth on the substrates.
- the term “material residence time” refers to the amount of time a discrete point along a substrate of spoolable dimensions is exposed to CNT growth conditions during the CNT infusion processes described herein. This definition includes the residence time when employing multiple CNT growth zones.
- linespeed refers to the speed at which a substrate of spoolable dimensions can be fed through the CNT infusion processes described herein, where linespeed is a velocity determined by dividing CNT growth zone(s) length by the material residence time.
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Nanotechnology (AREA)
- General Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Crystallography & Structural Chemistry (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Inorganic Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Composite Materials (AREA)
- Carbon And Carbon Compounds (AREA)
Abstract
Description
Claims
Priority Applications (9)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
AU2010235123A AU2010235123A1 (en) | 2009-04-10 | 2010-02-26 | Apparatus and method for the production of carbon nanotubes on a continuously moving substrate |
BRPI1010288A BRPI1010288A2 (en) | 2009-04-10 | 2010-02-26 | apparatus and method for producing carbon nanotubes on a continuously moving substrate |
DK10762037.9T DK2417286T3 (en) | 2009-04-10 | 2010-02-26 | Device and method for producing carbon nanotubes on a substrate that moves continuously |
KR1020117022125A KR101696212B1 (en) | 2009-04-10 | 2010-02-26 | Apparatus and method for the production of carbon nanotubes on a continuously moving substrate |
CN201080016238.3A CN102388171B (en) | 2009-04-10 | 2010-02-26 | Apparatus and method for the production of carbon nanotubes on a continuously moving substrate |
EP20100762037 EP2417286B1 (en) | 2009-04-10 | 2010-02-26 | Apparatus and method for the production of carbon nanotubes on a continuously moving substrate |
CA2756852A CA2756852A1 (en) | 2009-04-10 | 2010-02-26 | Apparatus and method for the production of carbon nanotubes on a continuously moving substrate |
JP2012504678A JP5629756B2 (en) | 2009-04-10 | 2010-02-26 | Apparatus and method for producing carbon nanotubes on a continuously moving substrate |
ZA2011/06735A ZA201106735B (en) | 2009-04-10 | 2011-09-14 | Apparatus and method for the production of carbon nanotubes on a continuously moving substrate |
Applications Claiming Priority (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US16851609P | 2009-04-10 | 2009-04-10 | |
US61/168,516 | 2009-04-10 | ||
US29562410P | 2010-01-15 | 2010-01-15 | |
US61/295,624 | 2010-01-15 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2010117515A1 true WO2010117515A1 (en) | 2010-10-14 |
Family
ID=42934604
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/US2010/025660 WO2010117515A1 (en) | 2009-04-10 | 2010-02-26 | Apparatus and method for the production of carbon nanotubes on a continuously moving substrate |
Country Status (11)
Country | Link |
---|---|
US (1) | US20100260933A1 (en) |
EP (1) | EP2417286B1 (en) |
JP (1) | JP5629756B2 (en) |
KR (1) | KR101696212B1 (en) |
CN (1) | CN102388171B (en) |
AU (1) | AU2010235123A1 (en) |
BR (1) | BRPI1010288A2 (en) |
CA (1) | CA2756852A1 (en) |
DK (1) | DK2417286T3 (en) |
WO (1) | WO2010117515A1 (en) |
ZA (1) | ZA201106735B (en) |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN102774825A (en) * | 2012-07-25 | 2012-11-14 | 清华大学 | Method for preparing ultra-long carbon nanotube by mobile constant temperature region method |
JP2013032248A (en) * | 2011-08-03 | 2013-02-14 | Hitachi Zosen Corp | Cvd apparatus for carbon nanotube formation |
Families Citing this family (20)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US8951632B2 (en) | 2007-01-03 | 2015-02-10 | Applied Nanostructured Solutions, Llc | CNT-infused carbon fiber materials and process therefor |
US9005755B2 (en) | 2007-01-03 | 2015-04-14 | Applied Nanostructured Solutions, Llc | CNS-infused carbon nanomaterials and process therefor |
US8951631B2 (en) | 2007-01-03 | 2015-02-10 | Applied Nanostructured Solutions, Llc | CNT-infused metal fiber materials and process therefor |
CN102333906B (en) | 2009-02-27 | 2015-03-11 | 应用纳米结构方案公司 | Low temperature CNT growth using gas-preheat method |
US20100227134A1 (en) | 2009-03-03 | 2010-09-09 | Lockheed Martin Corporation | Method for the prevention of nanoparticle agglomeration at high temperatures |
AU2010279709A1 (en) | 2009-08-03 | 2012-01-19 | Applied Nanostructured Solutions, Llc. | Incorporation of nanoparticles in composite fibers |
EP2354272B1 (en) | 2010-02-08 | 2016-08-24 | Graphene Square Inc. | Roll-to-roll apparatus for coating simultaneously internal and external surfaces of a pipe and graphene coating method using the same |
KR101870844B1 (en) | 2010-09-14 | 2018-06-25 | 어플라이드 나노스트럭처드 솔루션스, 엘엘씨. | Glass substrates having carbon nanotubes grown thereon and methods for production thereof |
BR112013005529A2 (en) | 2010-09-22 | 2016-05-03 | Applied Nanostructured Sols | carbon fiber substrates having carbon nanotubes developed therein, and processes for producing them |
KR101806916B1 (en) * | 2011-03-17 | 2017-12-12 | 한화테크윈 주식회사 | Apparatus for manufacturing graphene film and method for manufacturing graphene film |
US20120234240A1 (en) | 2011-03-17 | 2012-09-20 | Nps Corporation | Graphene synthesis chamber and method of synthesizing graphene by using the same |
US20130011578A1 (en) * | 2011-07-07 | 2013-01-10 | Hass Derek D | Method and apparatus for applying a coating at a high rate onto non-line-of-sight regions of a substrate |
US20130071565A1 (en) * | 2011-09-19 | 2013-03-21 | Applied Nanostructured Solutions, Llc | Apparatuses and Methods for Large-Scale Production of Hybrid Fibers Containing Carbon Nanostructures and Related Materials |
US9506194B2 (en) | 2012-09-04 | 2016-11-29 | Ocv Intellectual Capital, Llc | Dispersion of carbon enhanced reinforcement fibers in aqueous or non-aqueous media |
JP6168911B2 (en) * | 2013-08-20 | 2017-07-26 | 日立造船株式会社 | Carbon nanotube production equipment |
JP6138017B2 (en) * | 2013-10-02 | 2017-05-31 | 日立造船株式会社 | CVD device for carbon nanotube |
GB201412656D0 (en) | 2014-07-16 | 2014-08-27 | Imp Innovations Ltd | Process |
US20160229758A1 (en) * | 2015-02-11 | 2016-08-11 | United Technologies Corporation | Continuous chemical vapor deposition/infiltration coater |
US10745280B2 (en) | 2015-05-26 | 2020-08-18 | Department Of Electronics And Information Technology (Deity) | Compact thermal reactor for rapid growth of high quality carbon nanotubes (CNTs) produced by chemical process with low power consumption |
CN109748261A (en) * | 2019-03-25 | 2019-05-14 | 深圳市梅莎新能源科技有限公司 | The continuous preparation method and preparation facilities of carbon nano pipe array |
Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20040037767A1 (en) * | 2002-08-21 | 2004-02-26 | First Nano, Inc. | Method and apparatus of carbon nanotube fabrication |
US20080178924A1 (en) * | 2007-01-30 | 2008-07-31 | Solasta, Inc. | Photovoltaic cell and method of making thereof |
WO2009155451A1 (en) * | 2008-06-20 | 2009-12-23 | Sakti3, Inc. | High volume manufacture of electrochecmicals cells using physical vapor deposition |
WO2010081769A1 (en) * | 2009-01-13 | 2010-07-22 | Nokia Corporation | A process for producing carbon nanostructure on a flexible substrate, and energy storage devices comprising flexible carbon nanostructure electrodes |
Family Cites Families (106)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3304855A (en) * | 1963-05-15 | 1967-02-21 | H G Molenaar & Company Proprie | Extractor means for extracting liquid from a liquids containing mass |
US4566969A (en) * | 1981-09-29 | 1986-01-28 | Crane & Co., Inc. | Rolling filter apparatus |
US4515107A (en) * | 1982-11-12 | 1985-05-07 | Sovonics Solar Systems | Apparatus for the manufacture of photovoltaic devices |
US5310687A (en) * | 1984-10-31 | 1994-05-10 | Igen, Inc. | Luminescent metal chelate labels and means for detection |
US4797378A (en) * | 1986-02-18 | 1989-01-10 | Minnesota Mining And Manufacturing Company | Internally modified ceramic fiber |
US4920917A (en) * | 1987-03-18 | 1990-05-01 | Teijin Limited | Reactor for depositing a layer on a moving substrate |
DE68914120T2 (en) * | 1988-11-29 | 1994-09-01 | Tonen Corp | Process for the surface treatment of reinforcing fibers with sulfones and the surface-treated fibers thus obtained. |
EP0677989B1 (en) * | 1991-08-09 | 1998-09-16 | E.I. Du Pont De Nemours And Company | Antimicrobial compositions, process for preparing the same and use |
JPH09111135A (en) * | 1995-10-23 | 1997-04-28 | Mitsubishi Materials Corp | Conductive polymer composition |
US6683783B1 (en) * | 1997-03-07 | 2004-01-27 | William Marsh Rice University | Carbon fibers formed from single-wall carbon nanotubes |
US6863942B2 (en) * | 1998-06-19 | 2005-03-08 | The Research Foundation Of State University Of New York | Free-standing and aligned carbon nanotubes and synthesis thereof |
US6346189B1 (en) * | 1998-08-14 | 2002-02-12 | The Board Of Trustees Of The Leland Stanford Junior University | Carbon nanotube structures made using catalyst islands |
US6692717B1 (en) * | 1999-09-17 | 2004-02-17 | William Marsh Rice University | Catalytic growth of single-wall carbon nanotubes from metal particles |
US6265466B1 (en) * | 1999-02-12 | 2001-07-24 | Eikos, Inc. | Electromagnetic shielding composite comprising nanotubes |
US6221154B1 (en) * | 1999-02-18 | 2001-04-24 | City University Of Hong Kong | Method for growing beta-silicon carbide nanorods, and preparation of patterned field-emitters by chemical vapor depositon (CVD) |
US20030091496A1 (en) * | 2001-07-23 | 2003-05-15 | Resasco Daniel E. | Method and catalyst for producing single walled carbon nanotubes |
US6333016B1 (en) * | 1999-06-02 | 2001-12-25 | The Board Of Regents Of The University Of Oklahoma | Method of producing carbon nanotubes |
US6361861B2 (en) * | 1999-06-14 | 2002-03-26 | Battelle Memorial Institute | Carbon nanotubes on a substrate |
KR100360470B1 (en) * | 2000-03-15 | 2002-11-09 | 삼성에스디아이 주식회사 | Method for depositing a vertically aligned carbon nanotubes using thermal chemical vapor deposition |
US6653005B1 (en) * | 2000-05-10 | 2003-11-25 | University Of Central Florida | Portable hydrogen generator-fuel cell apparatus |
EP1182272A1 (en) * | 2000-08-23 | 2002-02-27 | Cold Plasma Applications C.P.A. | Process and apparatus for continuous cold plasma deposition of metallic layers |
KR100382879B1 (en) * | 2000-09-22 | 2003-05-09 | 일진나노텍 주식회사 | Method of synthesizing carbon nanotubes and apparatus being used therein. |
JP3981566B2 (en) * | 2001-03-21 | 2007-09-26 | 守信 遠藤 | Method for producing expanded carbon fiber body |
JP2004529840A (en) * | 2001-03-26 | 2004-09-30 | エイコス・インコーポレーテッド | Carbon nanotubes in structures and repair compositions |
RU2184086C1 (en) * | 2001-04-02 | 2002-06-27 | Петрик Виктор Иванович | Method of removing crude oil, petroleum products and/or chemical pollutant from liquid and/or gas, and/or from surface |
AUPR421701A0 (en) * | 2001-04-04 | 2001-05-17 | Commonwealth Scientific And Industrial Research Organisation | Process and apparatus for the production of carbon nanotubes |
US7160531B1 (en) * | 2001-05-08 | 2007-01-09 | University Of Kentucky Research Foundation | Process for the continuous production of aligned carbon nanotubes |
US7157068B2 (en) * | 2001-05-21 | 2007-01-02 | The Trustees Of Boston College | Varied morphology carbon nanotubes and method for their manufacture |
US7341498B2 (en) * | 2001-06-14 | 2008-03-11 | Hyperion Catalysis International, Inc. | Method of irradiating field emission cathode having nanotubes |
EP1414894B1 (en) * | 2001-08-06 | 2012-06-13 | Showa Denko K.K. | Conductive curable resin composition and separator for fuel cell |
US7070472B2 (en) * | 2001-08-29 | 2006-07-04 | Motorola, Inc. | Field emission display and methods of forming a field emission display |
US6837928B1 (en) * | 2001-08-30 | 2005-01-04 | The Board Of Trustees Of The Leland Stanford Junior University | Electric field orientation of carbon nanotubes |
US6528572B1 (en) * | 2001-09-14 | 2003-03-04 | General Electric Company | Conductive polymer compositions and methods of manufacture thereof |
US7022776B2 (en) * | 2001-11-07 | 2006-04-04 | General Electric | Conductive polyphenylene ether-polyamide composition, method of manufacture thereof, and article derived therefrom |
CA2470025C (en) * | 2001-12-21 | 2012-02-21 | Battelle Memorial Institute | Carbon nanotube-containing structures, methods of making, and processes using same |
JP4404961B2 (en) * | 2002-01-08 | 2010-01-27 | 双葉電子工業株式会社 | A method for producing carbon nanofibers. |
US20070035226A1 (en) * | 2002-02-11 | 2007-02-15 | Rensselaer Polytechnic Institute | Carbon nanotube hybrid structures |
JP4168676B2 (en) * | 2002-02-15 | 2008-10-22 | コニカミノルタホールディングス株式会社 | Film forming method |
JP2006502322A (en) * | 2002-02-25 | 2006-01-19 | ジェンテックス コーポレーション | Multifunctional protective fabric and decontamination method (cross-reference of related applications) This patent application claims the priority date benefit of US Provisional Application 60 / 360,050, filed February 25,2002. |
US7405854B2 (en) * | 2002-03-21 | 2008-07-29 | Cornell Research Foundation, Inc. | Fibrous micro-composite material |
US20060165914A1 (en) * | 2002-04-03 | 2006-07-27 | John Abrahamson | Continuous method for producing inorganic nanotubes |
WO2003106030A1 (en) * | 2002-06-13 | 2003-12-24 | National University Of Singapore | Selective area growth of aligned carbon nanotubes on a modified catalytic surface |
US6852410B2 (en) * | 2002-07-01 | 2005-02-08 | Georgia Tech Research Corporation | Macroscopic fiber comprising single-wall carbon nanotubes and acrylonitrile-based polymer and process for making the same |
US6979947B2 (en) * | 2002-07-09 | 2005-12-27 | Si Diamond Technology, Inc. | Nanotriode utilizing carbon nanotubes and fibers |
US20040089237A1 (en) * | 2002-07-17 | 2004-05-13 | Pruett James Gary | Continuous chemical vapor deposition process and process furnace |
US7378347B2 (en) * | 2002-10-28 | 2008-05-27 | Hewlett-Packard Development Company, L.P. | Method of forming catalyst nanoparticles for nanowire growth and other applications |
KR100704795B1 (en) * | 2002-11-01 | 2007-04-09 | 미츠비시 레이온 가부시키가이샤 | Composition containing carbon nanotubes, composite having coating thereof and process for producing them |
US7656027B2 (en) * | 2003-01-24 | 2010-02-02 | Nanoconduction, Inc. | In-chip structures and methods for removing heat from integrated circuits |
CN1286716C (en) * | 2003-03-19 | 2006-11-29 | 清华大学 | Method for growing carbon nano tube |
WO2005005033A2 (en) * | 2003-06-30 | 2005-01-20 | New Jersey Institute Of Technology | Catalysts and methods for making same |
US7354988B2 (en) * | 2003-08-12 | 2008-04-08 | General Electric Company | Electrically conductive compositions and method of manufacture thereof |
WO2005044723A2 (en) * | 2003-10-16 | 2005-05-19 | The University Of Akron | Carbon nanotubes on carbon nanofiber substrate |
AU2005230961B2 (en) * | 2004-01-15 | 2010-11-11 | Nanocomp Technologies, Inc. | Systems and methods for synthesis of extended length nanostructures |
US7338684B1 (en) * | 2004-02-12 | 2008-03-04 | Performance Polymer Solutions, Inc. | Vapor grown carbon fiber reinforced composite materials and methods of making and using same |
EP2113302A4 (en) * | 2004-05-13 | 2009-12-23 | Univ Hokkaido Nat Univ Corp | Fine carbon dispersion |
WO2006076036A2 (en) * | 2004-05-25 | 2006-07-20 | The Trustees Of The University Of Pennsylvania | Nanostructure assemblies, methods and devices thereof |
US8075863B2 (en) * | 2004-05-26 | 2011-12-13 | Massachusetts Institute Of Technology | Methods and devices for growth and/or assembly of nanostructures |
WO2006004599A2 (en) * | 2004-06-04 | 2006-01-12 | The Trustees Of Columbia University In The City Of New York | Methods for preparing single-walled carbon nanotubes |
KR20050121426A (en) * | 2004-06-22 | 2005-12-27 | 삼성에스디아이 주식회사 | Method for preparing catalyst for manufacturing carbon nano tubes |
US7838165B2 (en) * | 2004-07-02 | 2010-11-23 | Kabushiki Kaisha Toshiba | Carbon fiber synthesizing catalyst and method of making thereof |
US7938991B2 (en) * | 2004-07-22 | 2011-05-10 | William Marsh Rice University | Polymer / carbon-nanotube interpenetrating networks and process for making same |
US8080487B2 (en) * | 2004-09-20 | 2011-12-20 | Lockheed Martin Corporation | Ballistic fabrics with improved antiballistic properties |
US20060083927A1 (en) * | 2004-10-15 | 2006-04-20 | Zyvex Corporation | Thermal interface incorporating nanotubes |
MX2007005798A (en) * | 2004-11-16 | 2007-10-03 | Hyperion Catalysis Int | Method for preparing single walled carbon nanotubes. |
US7727504B2 (en) * | 2004-12-01 | 2010-06-01 | William Marsh Rice University | Fibers comprised of epitaxially grown single-wall carbon nanotubes, and a method for added catalyst and continuous growth at the tip |
US7494639B2 (en) * | 2004-12-28 | 2009-02-24 | William Marsh Rice University | Purification of carbon nanotubes based on the chemistry of fenton's reagent |
US7871591B2 (en) * | 2005-01-11 | 2011-01-18 | Honda Motor Co., Ltd. | Methods for growing long carbon single-walled nanotubes |
KR100664545B1 (en) * | 2005-03-08 | 2007-01-03 | (주)씨엔티 | Carbon nano tubes mass fabrication device and mass fabrication method |
US7501750B2 (en) * | 2005-05-31 | 2009-03-10 | Motorola, Inc. | Emitting device having electron emitting nanostructures and method of operation |
AU2006312250B2 (en) * | 2005-06-28 | 2011-07-07 | The Board Of Regents Of The University Of Oklahoma | Methods for growing and harvesting carbon nanotubes |
JP2007051058A (en) * | 2005-08-12 | 2007-03-01 | Samsung Electronics Co Ltd | Method for manufacturing carbon nanotube |
US8313723B2 (en) * | 2005-08-25 | 2012-11-20 | Nanocarbons Llc | Activated carbon fibers, methods of their preparation, and devices comprising activated carbon fibers |
CN1927988A (en) * | 2005-09-05 | 2007-03-14 | 鸿富锦精密工业(深圳)有限公司 | Heat interfacial material and method for making the same |
WO2008054379A2 (en) * | 2005-10-25 | 2008-05-08 | Massachusetts Institute Of Technology | Shape controlled growth of nanostructured films and objects |
US20070099527A1 (en) * | 2005-11-01 | 2007-05-03 | General Electric Company | Method and reactor to coat fiber tows and article |
US8148276B2 (en) * | 2005-11-28 | 2012-04-03 | University Of Hawaii | Three-dimensionally reinforced multifunctional nanocomposites |
KR100745735B1 (en) * | 2005-12-13 | 2007-08-02 | 삼성에스디아이 주식회사 | Method for growing carbon nanotubes and manufacturing method of field emission device therewith |
US7465605B2 (en) * | 2005-12-14 | 2008-12-16 | Intel Corporation | In-situ functionalization of carbon nanotubes |
WO2008045109A2 (en) * | 2005-12-19 | 2008-04-17 | University Of Virginia Patent Foundation | Conducting nanotubes or nanostructures based composites, method of making them and applications |
WO2008048313A2 (en) * | 2005-12-19 | 2008-04-24 | Advanced Technology Materials, Inc. | Production of carbon nanotubes |
FR2895398B1 (en) * | 2005-12-23 | 2008-03-28 | Saint Gobain Vetrotex | GLASS YARN COATED WITH AN ENSIMAGE COMPRISING NANOPARTICLES. |
FR2895397B1 (en) * | 2005-12-23 | 2008-03-28 | Saint Gobain Vetrotex | GLASS YARN AND STRUCTURES OF GLASS YARNS HAVING A COATING COMPRISING NANOPARTICLES |
KR20080092934A (en) * | 2006-02-01 | 2008-10-16 | 오츠카 가가쿠 가부시키가이샤 | Process and apparatus for producing carbon nanotube |
US7687981B2 (en) * | 2006-05-05 | 2010-03-30 | Brother International Corporation | Method for controlled density growth of carbon nanotubes |
US8337979B2 (en) * | 2006-05-19 | 2012-12-25 | Massachusetts Institute Of Technology | Nanostructure-reinforced composite articles and methods |
US20080020193A1 (en) * | 2006-07-24 | 2008-01-24 | Jang Bor Z | Hybrid fiber tows containning both nano-fillers and continuous fibers, hybrid composites, and their production processes |
US8389119B2 (en) * | 2006-07-31 | 2013-03-05 | The Board Of Trustees Of The Leland Stanford Junior University | Composite thermal interface material including aligned nanofiber with low melting temperature binder |
US20080053922A1 (en) * | 2006-09-01 | 2008-03-06 | Honsinger Charles P Jr | Nanostructured materials comprising support fibers coated with metal containing compounds and methods of using the same |
WO2008153609A1 (en) * | 2007-02-07 | 2008-12-18 | Seldon Technologies, Inc. | Methods for the production of aligned carbon nanotubes and nanostructured material containing the same |
CN101049927B (en) * | 2007-04-18 | 2010-11-10 | 清华大学 | Method for producing Nano carbon tubes continuously and equipment |
JP4811690B2 (en) * | 2007-07-06 | 2011-11-09 | 独立行政法人産業技術総合研究所 | Carbon nanotube film forming method and film forming apparatus |
US7785498B2 (en) * | 2007-07-19 | 2010-08-31 | Nanotek Instruments, Inc. | Method of producing conducting polymer-transition metal electro-catalyst composition and electrodes for fuel cells |
WO2009023644A1 (en) * | 2007-08-13 | 2009-02-19 | Smart Nanomaterials, Llc | Nano-enhanced smart panel |
WO2009023643A1 (en) * | 2007-08-13 | 2009-02-19 | Smart Nanomaterials, Llc | Nano-enhanced modularly constructed composite panel |
KR100916330B1 (en) * | 2007-08-21 | 2009-09-11 | 세메스 주식회사 | Method and apparatus of collecting carbon nano tube |
US20090081441A1 (en) * | 2007-09-20 | 2009-03-26 | Lockheed Martin Corporation | Fiber Tow Comprising Carbon-Nanotube-Infused Fibers |
US20090081383A1 (en) * | 2007-09-20 | 2009-03-26 | Lockheed Martin Corporation | Carbon Nanotube Infused Composites via Plasma Processing |
US7666915B2 (en) * | 2007-09-24 | 2010-02-23 | Headwaters Technology Innovation, Llc | Highly dispersible carbon nanospheres in a polar solvent and methods for making same |
US7867468B1 (en) * | 2008-02-28 | 2011-01-11 | Carbon Solutions, Inc. | Multiscale carbon nanotube-fiber reinforcements for composites |
GB0805837D0 (en) * | 2008-03-31 | 2008-06-04 | Qinetiq Ltd | Chemical Vapour Deposition Process |
US20110159270A9 (en) * | 2008-06-02 | 2011-06-30 | Texas A & M University System | Carbon nanotube fiber-reinforced polymer composites having improved fatigue durability and methods for production thereof |
US20100059243A1 (en) * | 2008-09-09 | 2010-03-11 | Jin-Hong Chang | Anti-electromagnetic interference material arrangement |
KR101420680B1 (en) * | 2008-09-22 | 2014-07-17 | 삼성전자주식회사 | Apparatus and method for surface treatment of carbon fiber using resistive heating |
US8585934B2 (en) * | 2009-02-17 | 2013-11-19 | Applied Nanostructured Solutions, Llc | Composites comprising carbon nanotubes on fiber |
JP2012523677A (en) * | 2009-04-13 | 2012-10-04 | アプライド マテリアルズ インコーポレイテッド | Composite materials including metallized carbon nanotubes and nanofibers |
BRPI1014711A2 (en) * | 2009-04-27 | 2016-04-12 | Applied Nanostrctured Solutions Llc | cnt-based resistance heating to defrost composite structures |
-
2010
- 2010-02-26 JP JP2012504678A patent/JP5629756B2/en active Active
- 2010-02-26 WO PCT/US2010/025660 patent/WO2010117515A1/en active Application Filing
- 2010-02-26 US US12/714,389 patent/US20100260933A1/en not_active Abandoned
- 2010-02-26 CN CN201080016238.3A patent/CN102388171B/en active Active
- 2010-02-26 BR BRPI1010288A patent/BRPI1010288A2/en not_active IP Right Cessation
- 2010-02-26 DK DK10762037.9T patent/DK2417286T3/en active
- 2010-02-26 CA CA2756852A patent/CA2756852A1/en not_active Abandoned
- 2010-02-26 AU AU2010235123A patent/AU2010235123A1/en not_active Abandoned
- 2010-02-26 KR KR1020117022125A patent/KR101696212B1/en active IP Right Grant
- 2010-02-26 EP EP20100762037 patent/EP2417286B1/en active Active
-
2011
- 2011-09-14 ZA ZA2011/06735A patent/ZA201106735B/en unknown
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20040037767A1 (en) * | 2002-08-21 | 2004-02-26 | First Nano, Inc. | Method and apparatus of carbon nanotube fabrication |
US20080178924A1 (en) * | 2007-01-30 | 2008-07-31 | Solasta, Inc. | Photovoltaic cell and method of making thereof |
WO2009155451A1 (en) * | 2008-06-20 | 2009-12-23 | Sakti3, Inc. | High volume manufacture of electrochecmicals cells using physical vapor deposition |
WO2010081769A1 (en) * | 2009-01-13 | 2010-07-22 | Nokia Corporation | A process for producing carbon nanostructure on a flexible substrate, and energy storage devices comprising flexible carbon nanostructure electrodes |
Non-Patent Citations (4)
Title |
---|
ANDREWS ET AL.: "Continuous production of aligned carbon nanotubes: a step closer to commercial realization.", CHEMICAL PHYSICS LETTERS, vol. 303, no. 5, 16 April 1999 (1999-04-16), pages 467 - 474, XP002232174 * |
CAO ET AL.: "MEDIUM-SCALE CARBON NANOTUBE THIN-FILM INTEGRATED CIRCUITS ON FLEXIBLE PLASTIC SUBSTRATES", NATURE, vol. 454, no. 7203, 24 July 2008 (2008-07-24), pages 495 - 500, XP055068838 * |
HART ET AL.: "Rapid Growth and Flow-Mediated Nucleation of Millimeter-Scale Aligned Carbon Nanotube Structures from a Thin-Film Catalyst.", JOURNAL OF PHYSICAL CHEMISTRY: B, vol. 110, no. ISS 6, 11 March 2006 (2006-03-11), pages 8250 - 8257, XP002458344 * |
SINGH ET AL.: "Production of controlled architectures of aligned carbon nanotubes by an injection chemical vapour déposition method.'", CARBON, vol. 41, no. 2, 7 December 2002 (2002-12-07), pages 359 - 368, XP004397239 * |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2013032248A (en) * | 2011-08-03 | 2013-02-14 | Hitachi Zosen Corp | Cvd apparatus for carbon nanotube formation |
CN102774825A (en) * | 2012-07-25 | 2012-11-14 | 清华大学 | Method for preparing ultra-long carbon nanotube by mobile constant temperature region method |
Also Published As
Publication number | Publication date |
---|---|
JP5629756B2 (en) | 2014-11-26 |
BRPI1010288A2 (en) | 2016-03-22 |
JP2012523363A (en) | 2012-10-04 |
KR20120014116A (en) | 2012-02-16 |
EP2417286B1 (en) | 2015-05-20 |
AU2010235123A1 (en) | 2011-10-06 |
EP2417286A1 (en) | 2012-02-15 |
EP2417286A4 (en) | 2012-08-15 |
US20100260933A1 (en) | 2010-10-14 |
ZA201106735B (en) | 2012-08-28 |
CN102388171A (en) | 2012-03-21 |
CN102388171B (en) | 2015-02-11 |
CA2756852A1 (en) | 2010-10-14 |
DK2417286T3 (en) | 2015-08-17 |
KR101696212B1 (en) | 2017-01-13 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
EP2417286B1 (en) | Apparatus and method for the production of carbon nanotubes on a continuously moving substrate | |
US20100272891A1 (en) | Apparatus and method for the production of carbon nanotubes on a continuously moving substrate | |
US20200010983A1 (en) | Apparatuses and Methods for Large-Scale Production of Hybrid Fibers Containing Carbon Nanostructures and Related Materials | |
EP2401416B1 (en) | Low temperature carbon nanotube growth using gas-preheat method | |
EP2616189B1 (en) | Glass substrates having carbon nanotubes grown thereon and methods for production thereof | |
AU2012326007B2 (en) | Systems and methods for continuously producing carbon nanostructures on reusable substrates | |
De Villoria et al. | High-yield growth of vertically aligned carbon nanotubes on a continuously moving substrate | |
KR20160146300A (en) | Apparatus for preparing carbon nanotube fiber and process for preparing carbon nanotube fiber using same | |
EP2558623A1 (en) | Apparatus and method for the production of carbon nanotubes on a continuously moving substrate | |
JP6422779B2 (en) | An improved method for synthesizing carbon nanotubes on multiple supports | |
US20100279010A1 (en) | Method and system for close proximity catalysis for carbon nanotube synthesis | |
Rohmund et al. | Production and derivatisation of carbon nanotubes | |
de Villoria et al. | CONTINUOUS GROWTH OF VERTICALLY ALIGNED CARBON NANOTUBES | |
KR20170062267A (en) | Carbon nanotube fiber, apparatus and method for preparing the same |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
WWE | Wipo information: entry into national phase |
Ref document number: 201080016238.3 Country of ref document: CN |
|
121 | Ep: the epo has been informed by wipo that ep was designated in this application |
Ref document number: 10762037 Country of ref document: EP Kind code of ref document: A1 |
|
WWE | Wipo information: entry into national phase |
Ref document number: 2010235123 Country of ref document: AU |
|
WWE | Wipo information: entry into national phase |
Ref document number: 2010762037 Country of ref document: EP |
|
ENP | Entry into the national phase |
Ref document number: 20117022125 Country of ref document: KR Kind code of ref document: A |
|
WWE | Wipo information: entry into national phase |
Ref document number: 2756852 Country of ref document: CA |
|
WWE | Wipo information: entry into national phase |
Ref document number: 7459/DELNP/2011 Country of ref document: IN |
|
WWE | Wipo information: entry into national phase |
Ref document number: 2012504678 Country of ref document: JP |
|
ENP | Entry into the national phase |
Ref document number: 2010235123 Country of ref document: AU Date of ref document: 20100226 Kind code of ref document: A |
|
NENP | Non-entry into the national phase |
Ref country code: DE |
|
REG | Reference to national code |
Ref country code: BR Ref legal event code: B01A Ref document number: PI1010288 Country of ref document: BR |
|
ENP | Entry into the national phase |
Ref document number: PI1010288 Country of ref document: BR Kind code of ref document: A2 Effective date: 20110927 |