WO2011087526A1 - 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
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- WO2011087526A1 WO2011087526A1 PCT/US2010/041873 US2010041873W WO2011087526A1 WO 2011087526 A1 WO2011087526 A1 WO 2011087526A1 US 2010041873 W US2010041873 W US 2010041873W WO 2011087526 A1 WO2011087526 A1 WO 2011087526A1
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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
- B82Y40/00—Manufacture or treatment of nanostructures
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J19/18—Stationary reactors having moving elements inside
- B01J19/22—Stationary reactors having moving elements inside in the form of endless belts
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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
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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- 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
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J2219/00049—Controlling or regulating processes
- B01J2219/00051—Controlling the temperature
- B01J2219/00121—Controlling the temperature by direct heating or cooling
- B01J2219/00123—Controlling the temperature by direct heating or cooling adding a temperature modifying medium to the reactants
Definitions
- the present invention relates in general to an apparatus and method for the production of carbon nanotubes on a continuously moving substrate.
- CNT carbon nanotube
- Vapor grown carbon fiber is produced by contacting a gas phase hydrocarbon gas mixture with the preform at a temperature between about 500 °C to 1200 °C. According to the patent, the fibers grow on the composite preform resulting in a tangled mass of carbon fiber. The reaction time for growth varies between 15 minutes and 2 hours, primarily as a function of feed gas composition and temperature.
- 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, 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, wherein the apparatus is open to an atmospheric environment during operation.
- the CNT growth is carried out at ambient or near ambient pressures.
- 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 CNTs in a continuous process in accordance with an embodiment of the present invention.
- 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.
- the present invention relates in general to an apparatus and method for the production of carbon nanotubes on a continuously moving substrate.
- carbon nanotube CNT, plural CNTs 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.
- 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 °C to about 800 °C) in a multi-zone apparatus 100.
- elevated temperature typically in the range of about 550 °C to about 800 °C
- 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.
- CNT growth occurs in 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 110a, 110b, 110c, llOd of Figure 4). Apparatus 100 optionally includes pre-heater 132 that pre-heats feed gas 128 and feed gas diffuser 136 to evenly 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.
- 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 atmospheric environment 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.
- the catalyst activation zone can be placed just before first purge zone 114, with its own pre-purge zone.
- 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 15 cm/min to about 1 m/min or greater.
- the process can be run with a linespeed of about 2 m/min to about 11 m/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 30 cm/min to about 2 m/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 15 cm/min to about 30 cm/min to produce, for example, CNTs having a length between about 100 microns to about 200 microns.
- a linespeed of up to at least 60 m/min can be used for a continuous process for infusion.
- the CNT length is not tied only to linespeed and growth temperature, however, the flow rate of both the feed gas and inert purge gases can also influence CNT length. For example, a flow rate consisting of less than 1% carbon feedstock in inert gas at high linespeeds (2 m/min to 11 m/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 (2 m/min to 11 m/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 an enclosure such as stainless steel, titanium, carbon steel, INCONEL®, INVAR®, other high temperature metals, non-porous ceramics, 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.
- the volume of CNT growth zone 108 is less than or equal to about 10000% of the volume of substrate 106 being fed therethrough. Without being bound by theory, reducing the size of CNT growth zone 108 ensures high probability interactions between feed gas 128 and substrates coated with catalyst particles. Larger volumes result in excessive unfavorable reactions as the treated substrate is only a small fraction of the available volume.
- 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 240 cm to as large as 8000 cm .
- 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 between about 550 °C and about 900 °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 atmospheric environment, 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 atmospheric environment through ports 142. This also prevents gas mixing which is important in situations where multiple CNT growth zones 108 (e.g., 108a, 108b, 108c, in Figure 6) 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 5) and into CNT growth zone 108 via feed gas diffusers 136 (shown in Figure 5). Feed gas 128 can react with catalyst particles 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 inlet manifold 134 shown in Figure 5
- Feed gas 128 can react with catalyst particles 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.
- 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 gas flow, 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 °C to about 850 °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 128 can be added after the preheating process to ensure that the preheater is not clogged with soot over long time operation of the system.
- 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. As illustrated in Figure 4, gas diffusers 136 are used in series to create "gas stagnation" regions therebetween, where the larger volumes slow down the gas flow rate. Gas diffusers 136 are used to speed up gas between each zone to create a "billowing effect" as gas accelerates to the new stagnation region. 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.
- heaters 110 can apply an even temperature generation source.
- a gas diffusing element of the growth system can also exist as an embodiment where instead of a diffuser plate, feed gas inlet manifold 134 is packed with a high temperature porous material such as alumina or silica ceramic or sintered metal foams to diffuse and spread the gas which can be introduced through a diffuser plate that has a simple slot which runs along the width of the chamber.
- feed gas inlet manifold 134 is packed with a high temperature porous material such as alumina or silica ceramic or sintered metal foams to diffuse and spread the gas which can be introduced through a diffuser plate that has a simple slot which runs along the width of the chamber.
- 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 gas 130 may be relatively cool, such that purge zones 114 and 116 optionally act as a cooling zone, e.g., by helping reduce the temperature of the process gases before they exit the system.
- 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.
- 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 12 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.
- illustrative rectangular CNT growth zone 108 there is quite a bit of excess volume— olume 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 quartz tube 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 can be introduced at the ends of, the center of, or within CNT growth zone 108 (e.g., symmetrically, either through the sides or through the top and bottom plates of CNT growth zone 108). This can improve 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 temperature 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. Purge zones 114, 116 can also provide a buffer to prevent oxidation at the interface between the internal system and external environments.
- metal e.g., stainless steel, INVAR®, INCONEL®, etc.
- 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.
- 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).
- a clean one - too much carbon can adhere to catalyst particles, compromising their ability to synthesize CNTs.
- the inventors thus intentionally run the apparatus "dirty.” Once carbon deposits to a monolayer on the walls of CNT growth zone 108, carbon will readily deposit over itself. Since some of the available carbon is "withdrawn” due to this mechanism, the remaining carbon radicals react with the catalyst at a more acceptable rate - a rate that does not poison the catalyst.
- soot inhibiting coatings e.g., MgO, Silica, Alumina
- 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, in some embodiments, 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.
- the reduction process can be affected by a variety of factors including, but not limited to, the temperature, the catalyst composition, feed gas composition, and the component flow rates.
- the feed gas composition may determine the amount of hydrogen available upon dissociation to reduce the catalyst.
- hydrogen e.g., H 2
- H 2 hydrogen
- 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.
- 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.
- Such 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.
- 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. In some embodiments, the infused carbon nanotubes are multi-wall nanotubes. In some embodiments, 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.
- the continuous processing line for CNT growth is used to provide an improved filament winding process.
- 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.
- 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. Specifically, in the process disclosed herein, 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.
- 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.
- 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 lb. spools, although larger spools are usable.
- a pre-process operation can be incorporated that divides very large spoolable lengths, for example 100 lb. or more, into easy to handle dimensions, such as two 50 lb spools.
- feed gas refers to any carbon compound gas (e.g., acetylene), 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.
- feed gas also includes an inert gas, e.g., nitrogen, and can also contain an auxiliary gas such as hydrogen used to aid in soot inhibition and catalyst reduction
- the feed gas can therefore consist of a mixture of 95% nitrogen, 3% hydrogen, and 2% acetylene by volume and can be fed into the system via the various methods described hereinabove.
- purge gas refers to any gas capable of displacing another gas. Purge gas can optionally be cooler than corresponding feed gas. In some embodiments, purge gas can include an inert gas such as nitrogen, argon, or helium.
- nanoparticle or NP (plural NPs), or grammatical equivalents thereof 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.
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Priority Applications (4)
Application Number | Priority Date | Filing Date | Title |
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CA2801186A CA2801186A1 (en) | 2010-01-15 | 2010-07-13 | Apparatus and method for the production of carbon nanotubes on a continuously moving substrate |
EP10843384.8A EP2558623A4 (en) | 2010-01-15 | 2010-07-13 | Apparatus and method for the production of carbon nanotubes on a continuously moving substrate |
AU2010341769A AU2010341769A1 (en) | 2010-01-15 | 2010-07-13 | Apparatus and method for the production of carbon nanotubes on a continuously moving substrate |
ZA2013/00495A ZA201300495B (en) | 2010-01-15 | 2013-01-18 | Apparatus and method for the production of carbon nanotubes on a continuously moving susbtrate |
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US29562410P | 2010-01-15 | 2010-01-15 | |
US61/295,624 | 2010-01-15 | ||
US12/714,389 | 2010-02-26 | ||
US12/714,389 US20100260933A1 (en) | 2009-04-10 | 2010-02-26 | Apparatus and method for the production of carbon nanotubes on a continuously moving substrate |
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EP (1) | EP2558623A4 (en) |
AU (1) | AU2010341769A1 (en) |
CA (1) | CA2801186A1 (en) |
WO (1) | WO2011087526A1 (en) |
ZA (1) | ZA201300495B (en) |
Cited By (3)
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---|---|---|---|---|
WO2019040468A1 (en) * | 2017-08-22 | 2019-02-28 | Ntherma Corporation | Methods and devices for synthesis of carbon nanotubes |
RU191901U1 (en) * | 2017-11-14 | 2019-08-28 | Федеральное государственное бюджетное образовательное учреждение высшего образования "Московский государственный технологический университет "СТАНКИН" (ФГБОУ ВО "МГТУ "СТАНКИН") | Reactor for producing carbon nanomaterials by gas-phase chemical deposition |
US10640384B2 (en) | 2017-08-22 | 2020-05-05 | Ntherma Corporation | Graphene nanoribbons, graphene nanoplatelets and mixtures thereof and methods of synthesis |
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2010
- 2010-07-13 AU AU2010341769A patent/AU2010341769A1/en not_active Abandoned
- 2010-07-13 WO PCT/US2010/041873 patent/WO2011087526A1/en active Application Filing
- 2010-07-13 EP EP10843384.8A patent/EP2558623A4/en not_active Withdrawn
- 2010-07-13 CA CA2801186A patent/CA2801186A1/en not_active Abandoned
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2013
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Cited By (5)
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WO2019040468A1 (en) * | 2017-08-22 | 2019-02-28 | Ntherma Corporation | Methods and devices for synthesis of carbon nanotubes |
US10640382B2 (en) | 2017-08-22 | 2020-05-05 | Ntherma Corporation | Vertically aligned multi-walled carbon nanotubes |
US10640384B2 (en) | 2017-08-22 | 2020-05-05 | Ntherma Corporation | Graphene nanoribbons, graphene nanoplatelets and mixtures thereof and methods of synthesis |
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RU191901U1 (en) * | 2017-11-14 | 2019-08-28 | Федеральное государственное бюджетное образовательное учреждение высшего образования "Московский государственный технологический университет "СТАНКИН" (ФГБОУ ВО "МГТУ "СТАНКИН") | Reactor for producing carbon nanomaterials by gas-phase chemical deposition |
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Publication number | Publication date |
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EP2558623A4 (en) | 2014-03-05 |
EP2558623A1 (en) | 2013-02-20 |
AU2010341769A1 (en) | 2013-03-28 |
ZA201300495B (en) | 2013-09-25 |
CA2801186A1 (en) | 2011-07-21 |
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