The present invention relates generally to ultra-conductive metal and methods of making same and, more specifically, to metal-graphene composite forms.
Commercially pure copper is the most widely used bulk electrical conductor in virtually all industrial and commercial sectors. It is overwhelmingly used for AC motors, generators, alternators, electronics, electrical transmission (i.e., wiring and bus bars), and more. Copper's unique combination of attributes, including high conductivity (second only to silver), high ampacity (electrical density, defined as current passing through a unit cross-sectional area), good strength, ductility, and oxidation/corrosion properties, at low cost make it ideal for most electrical applications. Copper is refined to a requisite amount of elemental purity to achieve the greatest practical electrical conductivity, from a performance-cost view point. As such, impurity elements, oxides, alloying or trace elements, and porosity all decrease the electrical properties of copper and metals in general.
The electrical conductivity of metals is typically related to that of copper via the International Annealed Copper Standard (IACS). The standard establishes 100% IACS as a conductivity of 58.001 Mega Siemens per meter (MS/m) at 20° C. Current (purer) grades of commercial copper wire achieve up to about 101% IACS. In contrast, silver has 107% IACS meaning an electrical conductivity of 62.1 MS/m.
Presently, ultra-conductive copper (UCC) is a highly sought after technology in the copper industry due to its readily evident material properties. UCC is defined as a copper (Cu) based material system, such as a composite or alloy, comprised predominantly of copper, with additives distributed in the copper matrix, such that the composite material exhibits electrical conductivity greater than 58.001 MS/m or 100% IACS.
Currently, UCC is envisioned to be synthesized as having copper with nanoscale carbon additives, in particular carbon nanotubes (CNTs) and graphene nano-particles (GNPs), such that the resultant material has ultrahigh electrical conductivity and thermal conductivity. Methods of synthesizing Cu/CNT or Cu/GNP have been attempted and include, for example, deformation processing, vapor phase processing, solidification processing, electrodeposition, electrophoretic deposition, and composite assembly through powder metallurgy. However, the material synthesized and referred to as UCC thus far in literature have not demonstrated at least 100% IACS, and have not been successfully made in a manner suitable for bulk scale commercial production. Per IACS, bulk scale UCC is defined to possess two specific features: (a) the dimensions of the forms synthesized have to be greater than 1.3 mm; and (b) the length of the specimen over which electrical resistivity or electrical conductivity is measured must be at least 1 m. The primary problems associated with contemporary UCC synthesis (failed) efforts include high energy expenditure during material processing, long processing time, process design and conditions that cause defects or introduce impurities in the additives, relatively high costs, and inability of processing methods for integration with existing copper form manufacturing units.
Considering these facts, there is a need for improved methods for synthesizing UCC and other ultra-conductive metals that address one or more of the drawbacks discussed above.
In an aspect of the present invention, a method of synthesizing a metal-graphene composite is provided and includes coating or otherwise introducing metal components with graphene, forming a precursor workpiece from the graphene-coated/inhibited metal components, and forming a bulk form of the metal-graphene composite from the precursor workpiece.
In an aspect of the present invention, a metal-graphene composite is provided and includes graphene in a metal matrix wherein the graphene is single-layer or multi-layer graphene sheets with nano-scale thickness, distributed throughout the metal matrix and primarily (but not exclusively) oriented with a plane horizontal to an axial direction of the metal-graphene composite.
The objects and advantages of present will be appreciated in light of the following detailed descriptions and drawings in which:
Embodiments of the present invention are directed to ultra-conductive metal-graphene composite forms. For example, a metal component (e.g., a wire, rod, bar, sheet, strip, film, or foil) may be coated with graphene and formed into a bulk form (e.g., a wire, rod, bar, sheet, strip, or foil). Further embodiments are directed to methods of synthesizing ultra-conductive metal-graphene composite forms. As used herein, a “metal-graphene composite” refers to both composites and nano-alloys of the metal and graphene. In various embodiments, the metal may be, without limitation, copper, aluminum, silver, gold, titanium, nickel, iron, magnesium, manganese, cobalt, zinc, and chromium. Thus, while the embodiments described below relate to ultra-conductive copper-graphene composites, the invention is not so limited.
In an aspect of the present invention, a metal-graphene composite may have enhanced electrical properties compared to a conventional metal component with commercial grade purity. Conventional material behavior demonstrates that electrical conductivity increases with metal purity and consequently decreases with alloy additions, second phase additives, and impurities. Such impurity elements manifest as solid solutions and/or second phases in the matrix metal during processing, all of which decrease electrical properties (i.e., electrical conductivity and ampacity) of the bulk metal. However, in graphene, three of the four outer shell electrons are used to covalently bond within the hexagonal graphene plane. The other electron is a pi (n) electron, which is highly mobile and is localized over the surface. The high inherent electrical properties of graphene may be attributed to the presence of this localized pi electron shell, which is somewhat analogous to the 4s1 electron in copper. These electrons may work in tandem in a metal-graphene composite, to produce enhanced electrical properties. Thus, an embodiment of the present invention includes a metal-graphene composite in bulk form, in which single- or multi-layer graphene is distributed in the metal matrix and primarily oriented with the plane horizontal to the axial direction (but not exclusively), which produces ultra-conductivity and ultra-ampacity (i.e., conductivity above 100% IACS and greater ampacity than commercial grades).
With reference to
Next, the copper profiles may be coated with graphene. As shown in
Next, the graphene coated copper profiles may be arranged to form a precursor workpiece, which may have various forms such as a billet, rod, plate, or sheet. As shown in
It should be recognized that other forms of depositing graphene on the copper may be used. For example, with reference to
The weight percentage of the graphene in the copper-graphene composite may vary. At a minimum, the amount of graphene must be sufficient to improve the electrical properties of the metal. For example, the weight percentage of the graphene may range from greater than 0 and up to and including 50%. In an embodiment, the copper-graphene composite may include 0.00000001% to 50% by weight of graphene, 0.05% to 30% by weight of graphene, 0.01% to 5% by weight of graphene, with a preferred range of from greater than zero up to and including 1%. The balance of the copper-graphene composite is primarily copper but may include trace amounts of other elements (such as impurity elements already present in the copper profile). The copper may include, without limitation, UNS 10100, UNS11000, UNS 12200, or ultra-pure copper as well as other copper alloys. Examples of the bulk forms of the copper-graphene composite, with embedded graphene include, without limitation, a wire, a rod, a tube, a strand, a strip, a foil, a plate, or a bar.
The resulting ultra-conductive metal-graphene composite form (e.g., the wire 30) may have a similar or increased electrical conductivity compared to the IACS standard and may have an increased ampacity. For example, an ultra-conductive copper wire or other bulk form according to the present invention may have an electrical conductivity of from about 57.6 MS/m (99.3% IACS) to about 60.90 MS/m (105% IACS) or greater, and an ampacity of about 19.1 MA/m2 at a temperature of 60° C., or greater. The ultra-conductive copper bulk form may have a higher ampacity compared to the IACS standard at temperatures of from 20° C. to 150° C. The corresponding values for commercially available copper wire procured from CerroWire LLC are 57.82 MS/m (99.69% IACS) and 3 to 4 MA/m2 at a temperature of 20° C. and 15.9 MA/m2 at 60° C. The corresponding values for commercially available copper wire procured from SouthWire LLC are 56.91 MS/m (98.11% IACS) and 3 to 4 MA/m2 at a temperature of 20° C. and 15.9 MA/m2 at 60° C. For another example, an ultra-conductive aluminum wire or other bulk form according to the present invention may have an electrical conductivity of greater than 34.5 MS/m (59.58% IACS), or about 34.76 MS/m (59.93% IACS). The corresponding values for an aluminum wire made from commercially available AA1100 was 34.5 MS/m (59.58% IACS).
In order to facilitate a more complete understanding of the embodiments of the invention, the following non-limiting examples are provided.
A copper rod that was 0.625 inch in diameter and made of 4N purity (or typical UNS 10100 copper) was cut into discs with circular cross section and approximately 0.125 in thickness. Next, the copper discs were placed in a bath of acetic acid for 1 minute to clean the surface of the copper discs.
Next, a graphene layer was deposited directly onto the face of the copper discs via chemical vapor deposition (CVD). The copper discs were placed flat on the sides of a quartz holder and introduced into the CVD chamber. A vacuum of less than 50 milliTorrs (mTorr) was achieved in the CVD chamber. The quartz chamber was then flooded with hydrogen gas for another 15 minutes at 100 cm3/min to purge any remaining oxygen, while periodically checking for hydrogen leaks. The furnace was heated to a range of about 900° C. to 1100° C. for 16 to 25 minutes. During this heating, the quartz holder with copper discs was positioned in the center of the CVD chamber for heating. Once the final temperature was reached in the furnace, it was maintained for an additional 15 to 30 minutes to ensure the copper discs reached equilibrium temperature with the furnace environment. A graphene precursor gas, comprising of processed methane along with carrier gases (e.g., hydrogen, methane, carbon monoxide, noble gases) was then introduced into the CVD chamber at a rate of at 0.1 liters per minute (I/min) for 5 to 10 minutes during which graphene was deposited onto the copper disc surfaces. Oxides and impurities were removed from the copper disc surfaces in the CVD chamber prior to graphene deposition facilitated by the high temperature and reducing atmosphere in the CVD chamber. Additionally, the deposition of graphene sealed the surfaces of the copper disc, thereby minimizing any further oxidation prior to subsequent processing. The copper discs were then reclaimed, stacked, and wrapped in copper foil to assemble a billet of approximately 1 to 2 in in length.
The billet was placed in an experimental extrusion apparatus at 700° C. to 800° C. and hot-pressed for about 30 minutes with a force of 10,000 lb (providing a pressure of about 29,000 psi) prior to extrusion. It should be recognized that the force can be increased for larger billet sizes. A continuous flow of nitrogen gas was maintained to the apparatus during this step to minimize oxidation of the billet. The billet was then extruded at that temperature into a nitrogen gas environment to form the consolidated copper-graphene composite wire. The billet was formed into a wire of approximately 0.0808 in diameter (12 AWG wire) and approximately 24 in length (limited by the length of the billet).
The electrical conductivity and ampacity of the hot-extruded 12 AWG copper-graphene composite wire was measured according to ASTM standards and was reported to be 60.73 MS/m (104.7% IACS) at 20° C. and 19.1 MA/m2 at 60° C., respectively. The corresponding values for commercially available copper wire procured from CerroWire LLC are 57.82 MS/m (99.69% IACS) and 3 to 4 MA/m2 at a temperature of 20° C. and 15.9 MA/m2 at 60° C. The corresponding values for commercially available copper wire procured from SouthWire LLC are 56.91 MS/m (98.11% IACS) and 3 to 4 MA/m2 at a temperature of 20° C. and 15.9 MA/m2 at 60° C.
Copper discs were prepared according to the method described in Example 1. Next, graphene ink was coated on the transverse circular surfaces of the discs. The copper-graphene composite included 0.5% by weight of graphene. To create the graphene ink, 2 mL of isopropanol was mixed with the graphene sheets to achieve a mixture. The copper discs were coated with the graphene-isopropanol ink and placed in a fume hood at room temperature to evaporate the isopropanol. The coated discs were then reclaimed, stacked, and wrapped in a copper foil to assemble a billet with a length of approximately 1 to 2 in. The billet was extruded into a wire according to the method described in Example 1.
The electrical conductivity and ampacity of the hot-extruded 12 AWG copper-graphene composite wire was measured according to ASTM standards, and is reported to be 57.6 MS/m (99.3% IACS) and 19.1 MA/m2 at 60° C., respectively. The corresponding values for commercially available copper wire procured from CerroWire LLC are 57.82 MS/m (99.69% IACS) and 3 to 4 MA/m2 at a temperature of 20° C. and 15.9 MA/m2 at 60° C. The corresponding values for commercially available copper wire procured from SouthWire LLC are 56.91 MS/m (98.11% IACS) and 3 to 4 MA/m2 at a temperature of 20° C. and 15.9 MA/m2 at 60° C.
While specific embodiments have been described in considerable detail to illustrate the present invention, the description is not intended to restrict or in any way limit the scope of the appended claims to such detail. The various features discussed herein may be used alone or in any combination. Additional advantages and modifications will readily appear to those skilled in the art. The invention in its broader aspects is therefore not limited to the specific details, representative apparatus and methods and illustrative examples shown and described. Accordingly, departures may be made from such details without departing from the scope of the general inventive concept.
Discs of 0.625 in diameter were punched from an aluminum alloy sheet made of AA1100. Next, graphene ink was coated on the transverse circular surfaces of the discs. The aluminum-graphene composite included 0.25% by weight of graphene. To create the graphene ink, 2 mL of isopropanol was mixed with the graphene sheets to achieve a mixture. The aluminum discs were coated with the graphene-isopropanol ink and placed in a fume hood at room temperature to evaporate the isopropanol. The coated discs were then reclaimed, stacked, and wrapped in a pure aluminum foil to assemble a billet with a length of approximately 1 to 2 in. The billet was placed in an experimental extrusion apparatus at 350° C. to 550° C. and hot-pressed for about 30 minutes with a force of 3,000 lb (providing a pressure of about 8,500 psi) prior to extrusion. It should be recognized that the force can be increased for larger billet sizes. A continuous flow of nitrogen gas was maintained to the apparatus during this step to minimize oxidation of the billet. The billet was then extruded at that temperature into a nitrogen gas environment to form the consolidated aluminum-graphene composite wire. The billet was formed into a wire of approximately 0.0808 in diameter (12 AWG wire) and approximately 24 in length (limited by the length of the billet).
The electrical conductivity and ampacity of the hot-extruded 12 AWG aluminum-graphene composite wire was measured according to ASTM standards and was reported to be 34.76 MS/m (59.93% IACS). Control wires made of AA1100 without graphene measured to have an electrical conductivity of 34.5 MS/m (59.58% IACS).
While specific embodiments have been described in considerable detail to illustrate the present invention, the description is not intended to restrict or in any way limit the scope of the appended claims to such detail. The various features discussed herein may be used alone or in any combination. Additional advantages and modifications will readily appear to those skilled in the art. The invention in its broader aspects is therefore not limited to the specific details, representative apparatus and methods and illustrative examples shown and described. Accordingly, departures may be made from such details without departing from the scope of the general inventive concept.
Filing Document | Filing Date | Country | Kind |
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PCT/US2017/053664 | 9/27/2017 | WO | 00 |
Number | Date | Country | |
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62406587 | Oct 2016 | US | |
62400260 | Sep 2016 | US |