阅读说明：本技术 超导电线及其形成方法 (Superconduction electric wire and forming method thereof ) 是由 张申甲 S·K·兰加纳坦 于 2019-05-27 设计创作，主要内容包括：本公开涉及一种超导电线及其形成方法。公开了一种具有增强导电率的超导电线。使用冷拉和退火来增强超导电线的导电率。还公开了制造超导电线的方法。(This disclosure relates to a kind of superconduction electric wire and forming method thereof.Disclose a kind of superconduction electric wire with enhancing conductivity.Enhance the conductivity of superconduction electric wire using cold drawing and annealing.Also disclose the method for manufacture superconduction electric wire.)

1. a kind of method that manufacture has the superconduction electric wire of enhancing conductivity, this method comprises:

Cold drawing is carried out to form bracing wire to the prewire product formed by superconduction electric metal, wherein described superconduct metal by proof gold Belong to and nano-sized carbon additive is formed, the pure metal is copper；And

It is annealed to the bracing wire to form superconduction electric wire；And

It is wherein described to superconduct the International Annealed Copper Standard conductivity i.e. IACS conductivity that line shows 100% or bigger.

2. according to the method described in claim 1, wherein, cold drawing steps are reduced by about the cross-sectional area of the prewire product 25% or more.

3. according to the method described in claim 1, wherein, the nano-sized carbon additive includes carbon nanotube, graphene or its group It closes.

4. according to the method described in claim 1, wherein, annealing steps include that the bracing wire is heated to about to 300 DEG C~about 700 DEG C temperature and for about 2 hours or more.

5. according to the method described in claim 1, wherein the copper-clad is containing about 99.99% or bigger absolute purity.

6. according to the method described in claim 1, wherein, the superconduction electric wire includes by weight about 0.0005%~by weight The nano-sized carbon additive of meter about 0.1%.

7. according to the method described in claim 1, wherein, the superconduction electric wire show about 100.5% or the bigger world move back Fiery copper standard conductivity, that is, IACS conductivity.

8. according to the method described in claim 1, wherein, the superconduction electric wire is straight with about 0.01 inch~about 0.2 inch Diameter.

9. according to the method described in claim 1, wherein, the superconduction electric metal is by depositing operation, deformation technique, gas phase work Skill, solidifying process or powder metallurgical technique are formed.

10. being formed according to the method described in claim 9, superconducting metal described in wherein by chemical vapor deposition process.

11. according to the method described in claim 10, wherein, by stack formed by the chemical vapor deposition process it is multiple Sheet metal is superconducted to form the prewire product.

12. a kind of cable, comprising:

One or more conducting elements respectively include method according to claim 1 superconduction electric wire obtained；And

Surround one or more cable coatings of one or more of conducting elements.

Technical field

The present invention relates generally to superconduction electric wires.

Background technique

Superconduction electric metal refers to the alloy that bigger conductivity is shown for the pure metal for forming superconduction electric metal Or compound.By by certain high conductivity additives mix pure metal in is formed with improved conductivity alloy or answer It closes object and superconducts metal to produce.For example, can be by by the high conductivity nano-sized carbon of carbon nanotube and/or graphene etc. Superconduction electrolytic copper is formed in particle incorporation high-purity copper.It is known superconduct metal needs will be comprising a large amount of this high conductivity additions Object is to improve the conductivity of pure metal significantly.

PCT Patent Application discloses WO 2018/064137 and describes a kind of method for forming metal-graphite alkene compound, packet It includes: coating metal assembly (10) using graphene (14) to form graphene coating metal assembly, combine multiple graphenes and apply Metal assembly is covered to be formed precursor workpiece (26), and precursor workpiece (26) is processed into blocky (30) to form metal-graphite Alkene compound.Metal-graphite alkene compound includes the graphene (14) in metal matrix, and wherein graphene (14) is distributed across whole In a metal matrix and mainly (but not exclusively) with level in the plane orientation of the axial direction of metal-graphite alkene compound Monoatomic layer or multi-layer graphene (14).

Patent application publication US 2016/0168693 A1 describes the graphene in a kind of customization conductive structure The method of amount, including baseplate material is arranged in multiple strands and is arranged at least one graphene layer circumferentially coated On one or more strands in multiple strands, graphene layer is with the carbon atom of the single atom thick of hexagonal shaped pattern arrangement Layer, baseplate material and at least one graphene layer have axial direction.Along the axial direction side of substrate and at least one graphene layer Include multiple substrate material layers to the first cross section of interception and is disposed alternately between multiple substrate material layers at least One internal graphene layer.

Summary of the invention

According to one embodiment, it includes: to by superconduction electric metal that manufacturing, which has the method for the superconduction electric wire of enhancing conductivity, The prewire product of formation carries out cold drawing (cold wire drawing) to form bracing wire；And it anneals to the bracing wire To form superconduction electric wire.The superconduction electric metal is formed by pure metal and nano-sized carbon additive.The pure metal is copper.It is described super Conductor wire shows 100% or bigger International Annealed Copper Standard (" IACS ") conductivity.

Specific embodiment

Compared with conventional metallic alloys (it shows with metal purity decline and reduced conductivity), such as superconduct The superconduction electric metal of copper etc. shows the conductivity bigger than pure metal by mixing nano-sized carbon additive.For example, although copper Purity reduce (will usually conductivity be made to decline), but superconduction electrolytic copper can show the International Annealed Copper Standard greater than 100% (" IACS ") conductivity.It is appreciated that traditional copper has the conductivity of about 100%IACS, ultrapure copper rises to about 101% IACS, and copper alloy has the IACS less than 100%IACS.

However, being difficult to produce the superconduction electric metal of commercial quantities in practice for certain applications, the conduction of such as electric wire Element.Alternatively, most known superconduction electric wire has shown lower conductivity and/or only can be with limited Amount production.It has now been discovered that the conductivity of superconduction electric wire can be improved by suitably handling superconduction electric metal.Advantageously, The nano-sized carbon that can only need to have trace in superconduction electric metal to the improvement of superconduction electric wire described here, which has limited productions Time needed for superconduction electric wire and difficulty.

Specifically, it has been surprisingly found that, superconduction electric metal can be handled by continuous cold drawing steps and annealing steps To enhance conductivity.Generally speaking, these steps can improve the conductivity of superconduction electric metal when forming superconduction electric wire, and nothing It needs specially treated and is commercially difficult to the nano-sized carbon additive of the amount maintained without the incorporation of superconduction electric metal.

It is believed that cold drawing can improve the arrangement of the nano-sized carbon additive in superconduction electric metal, and annealing can improve gold The crystal structure of category.It is appreciated that nano-sized carbon additive is high anisotropy conductor, it means that they are planar arranged When, ratio had higher current-carrying capacity when arranging outside plane.Cold drawing can elongate superconduction electric metal, and can make nano-sized carbon Additive along prewire product length longitudinal arrangement.Then, the annealing of prewire product can be by tying pure metal again Brilliant and reparation is any caused by cold-drawing process to be damaged to enhance the conductivity of obtained superconduction electric wire.

IACS can be shown according to the conductivity that method described here has carried out the superconduction electric wire of cold drawing and annealing to lead The pact of about 0.5% or bigger raising, about 0.75% or the bigger raising, IACS conductivity of IACS conductivity of electric rate 1.00% or bigger raising, about the 1.25% of IACS conductivity or bigger raising or IACS conductivity about 1.5% or Bigger raising.Improving for the IACS conductivity of this superconduction electric wire can be greater than its for only carrying out one of cold drawing or annealing The additive of the IACS conductivity of its line improves.

Generally, the step of cold drawing and annealing can be carried out as known in the art.For example, can be at room temperature Cold drawing is carried out by mold or a series of progressive dies by drawing the prewire product formed by superconduction electric metal, to reduce The circumferential area of prewire product.In a particular embodiment, suitable cold drawing steps can subtract the gross area of prewire product Small about 30% or bigger, about 35% or bigger, about 40% or bigger, about 45% or bigger or about 50% or bigger.It can manage Solution, bigger area reduce the more longer spread that can lead to the high conductivity additive in metal phase.

It is also possible to by the temperature of the recrystallization temperature for the pure metal being heated to above bracing wire in superconduction electric metal, The temperature is kept to cool down pure metal for a period of time, then to anneal.For example, the case where superconduction electric metal is superconduction electrolytic copper Under, annealing can about 300 DEG C~about 700 DEG C at a temperature of carry out, and can keep at such temperatures about 1 hour~ About 5 hours.It can be by enabling thermally treated pure metal to be cooled down at any time or by quenching cooling.

Valuably, cold-drawing process described here and annealing process are applicable to superconducting by incorporation nano-sized carbon additive Any material that metal is formed.In a particular embodiment, superconduction electric metal can be superconduction electrolytic copper.It is appreciated that superconduction electrolytic copper The traditional copper application for having needed high conductivity and having will benefit from even more big conductivity can easily be replaced.For example, super Conductive copper can be used to form line/cable conducting element, electric interconnection part and any component (such as cable formed by it Transmission line accessory and integrated circuit etc.).Replace the copper in these applications can permit to improve immediately, is without redesigning System.For example, the power transmission line formed by improvement superconduction electrolytic copper described here and the similar power transmission formed by traditional copper Line, which is compared, can transmit bigger electricity (current-carrying capacity).

It generally, can be by suitable to manufacture for nano-sized carbon additive to be mixed any known technique in pure metal Superconduction electric metal.As used herein, pure metal means there is such as about 99% or bigger purity, about 99.5% or more Big purity, about 99.9% or bigger purity or about 99.99% or bigger purity etc. high-purity metal.It is appreciated that pure Degree can be measured alternatively using substitution marking system.For example, in a particular embodiment, suitable metal can be 4N or 5N It is pure, respectively refer to the metal with 99.99% and 99.999% purity.As used herein, purity can refer to particular implementation Absolute purity or metal foundation purity in example.When assessing purity, metal foundation purity has ignored nonmetalloid.It can manage Solution, any impurity other than required nano-sized carbon additive all decline the conductivity of superconduction electric metal.

Being formed for the known method of method described here and the suitable superconduction electric metal of improvement may include deformation work Skill, gas phase process, solidifying process and the compound assembling from powder metallurgical technique.In a particular embodiment, deposition method can Superconduction electric metal is formed to be advantageously used in, because this technique forms a large amount of superconduction electric metal and can be with proper amount of Nano-sized carbon additive forms this superconduction electric metal.Generally, nano-sized carbon can be deposited to gold by deposition method described here Belong on piece, processes these sheet metals together then to form the superconduction electric metal of bigger quality.

It is appreciated that deposition method described here can be modified in various ways.For example, original metal part can be gold Belong to the cross-sectional slices of plate, thin slice or stick and item etc..Generally, this sheet metal can be prepared by high purity metal, then Cleaning is to remove pollutant and any oxidation.For example, the oxidative damage to copper, this oxidative damage can be removed by immersing acetic acid The conductivity of obtained superconduction electrolytic copper will otherwise declined.

In the specific embodiment of disclosed deposition method, chemical vapor deposition (" CVD ") technique can be used by stone Black alkene is deposited directly on the surface of sheet metal.In such embodiments, sheet metal can be placed in the vacuum chamber of heating, Then the appropriate graphite alkene precursor gases of methane etc. can be pumped into.The decomposition of methane can form graphene.However, it is possible to Understand, can alternatively use other depositing operations.It is, for example, possible to use other known chemical vapor deposition processes to deposit Other nano-sized carbon additives of graphene or carbon nanotube etc..Alternatively, other depositing operations can be used.For example, Nano carbon particle can be deposited alternatively in a solvent from the suspension of nano-sized carbon additive.

It can be by the related other details of the illustrative methods of the improved superconduction electric metal of method described here with being formed It is disclosed in PCT Publication WO 2018/064137, above-mentioned document is incorporated by reference into this.It is appreciated that superconducting Metal can be obtained alternatively in the form of manufacture.In such embodiments, cold drawing described here and annealing process can be with Improve conductivity.

In a particular embodiment, superconduction electric metal may include any of nano-sized carbon additive.For example, in particular implementation In example, nano-sized carbon additive can be carbon nanotube or graphene.High conductivity additive can with any suitable amount (including By weight about 0.0005% or bigger, by weight about 0.0010% or bigger, by weight about 0.0015% or bigger or Person by weight about 0.0020% is bigger) comprising in a metal.Superconduct it is appreciated that technique described here can be improved The conductivity of metal, to reduce the needs for mixing the nano-sized carbon additive of high load level (for example, 10% or bigger).

Example

Production superconducts copper wire to assess the improvement of the conductivity of cold drawing and annealing process described here.Use depositing operation Then it extrudes (extrusion) and superconducts copper wire to be formed.Specifically, by being deposited on graphene by 99.99% purity Copper wire is superconducted in the cross-sectional slices of the copper rod for 0.625 inch diameter that copper (10100 bronze medal of UNS) is formed to be formed.Cross section Slice or disk with a thickness of 0.00070 inch.Cross-sectional slices are cleaned 1 minute in acetic acid bath.

Graphene is deposited in cross-sectional slices using chemical vapor deposition (" CVD ") technique.It is horizontal for CVD technique Cross-sectional slice is placed in the vacuum chamber with 50mTorr or smaller vacuum pressure, then with hydrogen with 100cm³/min Purging 15 minutes, to purge any remaining oxygen.Then within 16~25 minutes time by vacuum chamber be heated to 900 DEG C~ 1100 DEG C of temperature.Then the temperature is kept 15 minutes further to ensure that cross-sectional slices reach equilibrium temperature.Then with The rate of 0.1L/min introduces methane and inert carrier gas and continues 5~10 minutes, and graphene is deposited on cross-sectional slices Surface on.

By stacked graphene cover cross-sectional slices and they are wrapped in copper foil, multiple graphenes are covered Cross-sectional slices are formed as line.Then using 29000psi pressure in about 30 minutes by the stacked body of package in inert nitrogen It is extruded under atmosphere with 700 DEG C~800 DEG C.The diameter for extruding line is 0.808 inch, and being by weight is 0.000715% Graphene.

Table 1 depicts the electrical properties for superconducting copper wire processed using method described here.Example 1 is by surpassing Conductive metal extrudes the line to be formed.Example 2 is formed and 1 middle line of example is cold drawn to 0.0670 inch of diameter.Show Example 3 is the line in the example 2 after annealing 2 hours at 430 DEG C.Example 4 is in the example 1 after annealing 2 hours at 430 DEG C Line.Example 4 is without cold drawing.IACS conductivity is measured at 20 DEG C.

Table 1

As discribed in table 1, the line in example 3 shows 100.5% IACS conductivity, and in example 1,2 and 4 Each line respectively shows the IACS conductivity less than 100%.Dual with the conductivity of the greatly splicing thread in example 3 adds Work is different, and only cold drawing or annealing steps will not increase the conductivity for extruding line significantly.

It should be appreciated that each greatest measure limitation provided in this specification includes each lower numerical value limitation, as These lower numerical value limitations are clearly write out the same herein.The each minimum value limitation provided throughout the specification will packet Each higher numerical value limitation is included, as these higher numerical value limitations are clearly write out herein.It is provided in this specification Each numberical range will include each of falling into this wider numberical range relatively narrow numberical range, such as these relatively narrow numbers Value range is all clearly write out the same herein.

It limits unless expressly excluded or in other ways, otherwise (including any cross reference of incorporated herein every document Or relevant patent or application) be integrally incorporated by reference in this.The reference of any document is not an admission that it is about this In disclosed or claimed any invention the prior art, or individually or with any with any other bibliography Combined form instructs, implies or disclose any such invention.In addition, any meaning with regard to the term in the literature or definition with For any meaning for the same term in document being incorporated by reference into or definition mutually conflict, to be endowed being somebody's turn to do in the literature Subject to the meaning or definition of term.

For the purpose of description, embodiment and exemplary foregoing description are had been presented for.It is not intended to exhaustion or limitation institute The form of description.In view of above-mentioned introduction, many modifications can be carried out.Some modifications in these modifications have been discussed, and It will be appreciated by those skilled in the art that other modifications.Those of ordinary skill in the art in order to illustrate and these implementations are chosen and described Example.On the contrary, being therefore intended to limit range by the claim with each embodiment.Certainly, range is not limited to illustrate here Example or embodiment, but can be used for accordingly it is any amount of application and equivalent in.

Cross reference to related applications

This application claims " ULTRA-CONDUCTIVE WIRES AND submitting, entitled on May 25th, 2018 The priority of the U.S. Provisional Patent Application Serial Article 62/676,610 of METHODS OF FORMING THEREOF ", and pass through The full text of this application is incorporated into this by reference.