CN1080779A - The copper alloy that the very thin multi-core low-temp superconducting wire band is used - Google Patents
The copper alloy that the very thin multi-core low-temp superconducting wire band is used Download PDFInfo
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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Abstract
The invention belongs to the copper alloy that the very thin multi-core low-temp superconducting wire band is used, it is made up of copper and rare earth element, and the addition of rare earth element is 0.05-0.7 (weight %).Said rare earth element is a kind of among Gd, Er, Nd, the Dy.Copper alloy of the present invention not only has certain initial susceptibility value, and can significantly not increase its residual resistance ratio under low temperature (4.2K).Copper alloy of the present invention is especially suitable for use as the matrix of the very thin multi-core superconductor that uses at low temperatures.
Description
The invention belongs to copper alloy, especially the copper alloy of using with the low-temperature superconducting tape is relevant.
The superconductor that uses in practical application area at present mainly is the low temperature superconducting material at the liquid helium warm area, wherein the NbTi superconductor accounts for more than 90% of annual practical superconductor consumption, reach hundreds of tons the order of magnitude, requirement to the NbTi superconductor continues to improve its critical current density except need, and the core line diameter in the split conductor also requires more and more thinner.Core filament diameter in the multicore NbTi line of using as the Superconducting Super Collider engineering will carefully reach about 2.5 microns, about 0.38 micron of distance between the core silk, want to make well behaved multi-core superconducting materials, except the performance that requires NbTi core silk itself, should have excellent conducting performance and magnetic property as the copper material of basis material.
The most frequently used basis material is a fine copper, and fine copper is nonmagnetic, has fabulous conductivity again, promptly extremely low resistivity and higher the residual resistance ratio ratio of 4.2K resistivity (the R.R.R. room temperature resistivity with).The fine copper that has these two kinds of performances concurrently is with in its very thin multi-core superconducting wire band of making tangible contiguous coupling effect being arranged as the weak point of the basis material of superconducting wire band.This coupling meeting obviously reduces the stability of superconductor.In order to overcome this coupling, people such as E.W.Collings propose to add (Advances in Cryogenic Engineering Materials.Vol.34 such as a small amount of magnetic medium Mn.Fe.Cr in the copper matrix, 1988.P.867 the counter-rotating that～878), utilizes these magnetic element atomic spin magnetic moments overcomes this contiguous coupling effect for the scattering of superelectron.Though this class copper alloy can obviously overcome the coupling of proximity effect, but its low-temperature resistivity under 4.2K is significantly increased than fine copper, as in fine copper, adding the copper alloy of 0.5% manganese, its low-temperature resistivity under 4.2K has increased an order of magnitude than fine copper, thermal conductivity is variation thereupon also, this obviously is unfavorable for the stabilization of copper matrix to superconductor, when using this Albatra metal-as the copper matrix of very thin multi-core superconducting wire band, for satisfying to its stable requirement, must answer fine copper again in the outside of this copper matrix, simultaneously for preventing the diffusion between fine copper and cupromanganese, also to set up the non-proliferation interlayer, this will certainly increase the cost of superconducting wire band, increase the copper ratio of tape, reduce the current capacity of tape, also make the structure and the complex manufacturingization of superconducting wire band simultaneously.
The objective of the invention is to design the copper alloy that a kind of suitable very thin multi-core low-temp superconducting wire band is used, this Albatra metal-has magnetic, but its low temperature electrical property obviously is better than the copper alloy of a small amount of magnetic medium of existing interpolation.
Copper alloy of the present invention is by copper and 0.05-0.7%(weight) rare earth element forms, rare earth element is the Gd(gadolinium), the Er(erbium), the Nd(neodymium), the Dy(dysprosium) in a kind of.
Gd, Er, Nd, Dy belong to the rare earth element of magnetic, and the copper alloy of being made up of rare earth element and copper has the initial susceptibility that uses meaning, promptly have the ability of carrying out scattering by the counter-rotating of spin magnetic torque for superelectron at low temperatures.Adding all can reduce conduction, the heat conductivility of fine copper after adding element to some extent in the fine copper generally speaking, so must control its addition, to obtain the combination property of electric preferably and magnetic.The parameter of weighing the electromagnetic performance of copper alloy of the present invention has initial susceptibility X, room temperature resistivity ρ r, low-temperature resistivity ρ 4.2K and residual resistance ratio R, R, R.
In order to make the copper alloy of the present invention of uniform ingredients, rare earth element all adds with the form of intermediate alloy, and intermediate alloy can be according to the fragility of the various compositions in the binary phase diagraml of rare earth element and copper mutually, so that broken.Copper alloy of the present invention adopts smelting copper alloy, casting and manufacturing procedure commonly used to can be made into villous themeda, rod, line, the material of all size.
The rare earth element that adds 0.05 weight % in fine copper just makes copper alloy of the present invention have the initial susceptibility that uses meaning, increase along with the rare earth element addition, initial susceptibility also increase thereupon, the resistivity of alloy also increases thereupon simultaneously, residual resistance ratio descends thereupon, residual resistance ratio R, R, the R. of fine copper matrix commonly used generally are not less than 30 in the very thin multi-core superconducting wire band, so the addition of rare earth element is no more than 0.7 weight %.Wherein to add 0.1-0.5(weight %) copper alloy of rare earth element has better comprehensive performance.
Copper alloy of the present invention has the combination property of good electricity and magnetic.Just has the initial susceptibility value of using meaning even add the copper alloy of the present invention of the rare earth element of 0.05 weight %, especially add the Gd(gadolinium) copper alloy, the initial susceptibility that adds the copper alloy of 0.05Gd weight % just can be suitable with the value of the copper alloy of interpolation 0.3 weight % manganese.In addition, less again to the influence of its resistivity when giving the initial susceptibility of alloy of the present invention, for example in copper, behind the interpolation 0.1Gd weight %, the low-temperature resistivity of copper under 4.2K almost there is not any influence.Even the Er(erbium to the resistivity effects maximum), add in the copper with 0.1 weight % after, its low-temperature resistivity also only increases by 18%, and same addition, manganese is just big many to the influence of copper, its resistivity under 4.2K is about 16 times of fine copper.Because copper alloy of the present invention has above-mentioned advantage, therefore this Albatra metal-is especially suitable for use as very thin multi-core NbTi superconducting wire band or the Nb3Sn that uses under 4.2K, the copper matrix of superconducting wire bands such as V3Ga is particularly useful for the superconducting core filament diameter less than 10 microns, the minimum at interval multicore tape of core silk.
To be further described embodiments of the present invention and effect thereof by indefiniteness embodiment below.
1. be Nd＞99.0, rare earth impurities≤1.0, non-rare earth impurity≤0.9 with cathode copper, a granularity less than its composition weight of rare earth neodymium Nd-4(% of 3 millimeters), technical pure manganese is raw material, preparation is equivalent to fine copper, copper-manganese alloy, the copper-neodymium alloy of T2 respectively, and measures its electromagnetic performance.
(1) technology of preparation copper-neodymium alloy is to make copper-neodymium intermediate alloy earlier, and then is that raw material makes alloy with intermediate alloy and cathode copper, presses Cu
6The ratio weighing and burden of copper and rare earth in the Nd compound, adopt conventional smelting copper alloy technology, promptly earlier place vacuum medium frequency induction furnace to melt a cathode copper, in the copper liquid of fusion, add granularity again less than 3 millimeters rare earth neodymium, treat to pour in the swage after the fusing evenly, promptly obtain copper-neodymium intermediate alloy ingot.Determine its accurate composition through chemical analysis, be broken into granularity less than 3 millimeters particle, be raw material with cathode copper and the above-mentioned copper that makes-neodymium intermediate alloy again, in composition (weight %) is the ratio weighing and burden of Cu-0.05Nd, adopt copper alloy founding commonly used with the furnace charge that the prepares copper alloy that contains rare earth neodymium 0.05 that founding makes in the induction furnace frequently in a vacuum, in casting simultaneously, also be the round ingot casting of 30 * 100 millimeters of φ of specimen casting, this ingot casting is through forge hot, it is that 6 * 6 millimeters sample is as the magnetic susceptibility specimen that the cold back car of swaging becomes diameter * length; The bar that diameter is 6 millimeters is made the wire rod of 0.4 millimeter of diameter again through cold working, after 500 ℃ of vacuum heat of 1 hour promptly can be used as the resistivity measurement sample.
(2) preparation be equivalent to T2 fine copper be to be raw material with a cathode copper, adopt above-mentioned similar process conditions to obtain.
(3) technology of preparation copper-manganese alloy is to be raw material with cathode copper, a technical pure manganese, according to composition (weight %) Cu-0.1Mn, Cu-0.3Mn, Cu-0.5Mn weighing and burden, frequently earlier copper is melted in the induction material in a vacuum respectively then, in molten copper liquid, add manganese again, wait to melt and evenly water later the copper-manganese alloy that in swage, obtains different components.
Conventional four leads method are adopted in the measurement of resistivity, measure and calculate its room temperature resistivity ρ r, liquid nitrogen temperature electricalresistivity 77K and liquid helium temperature electricalresistivity 4.2K in room temperature, liquid nitrogen temperature, liquid helium warm area respectively, calculate ρ r/ ρ 77K and R.R.R(ρ r/ ρ 4.2K again) value.
The method of measurement of initial susceptibility is: measuring samples is the cylinder of 6 * 6 millimeters of φ, this samples vertical is placed search coil center two anti-phase serial connections, that have identical geometrical factor and move up and down, measuring samples in measuring coil induced electromotive force and its time integrates in motion can be recorded magnetic moment, with the weight of this value divided by sample, then obtain the magnetic moment in the Unit Weight sample, unit is e.m.u/g.The search coil that uses in the test is of a size of 20 millimeters of internal diameters, and 40 millimeters of external diameters are high 40 millimeters, and with 0.03 millimeter enamel covered wire coiling of diameter, the coil total number of turns of pair of series reversal connection is 200,000 circles.The standard sample that the demarcation unit uses is the monocrystalline Ni ball of 3 millimeters of diameters, and its magnetic moment is 58.53e, m, u/g.The integrator that uses in the test is 7066 digital voltmeters, and its resolution is 1 μ v, and the measurement sensitivity of whole system is 5.7 * 10 after demarcating
-4E.m.u/ μ v. multiply by the magnetic moment that this measurement sensitivity is institute's test sample product with the integrated value that records.The magnetic field intensity of magnetic moment when measuring can be obtained corresponding magnetic susceptibility.The magnetic susceptibility that records during with 0.5T magnetic field is defined as the said initial susceptibility (x) among the present invention.The ratio (x/c) of initial susceptibility and interpolation concentration can characterize the size of the element atomic magnetic moment that arc stood when element was added in the copper matrix under the 4.2K.
The data that the sample of the different-alloy that makes obtains after are after measured listed in table 1.
Measurement result shows that the copper alloy of the Nd that only adds 0.05 weight % in fine copper just can make the initial susceptibility of this alloy reach 2.4 * 10
-7E.m.u/g.Its influence to the room temperature electrical property of copper is also not obvious, also can reduce the resistivity to 4.2K, so the R.R.R value of gained copper alloy also is better than fine copper (T2).
2. making raw material and technology in the use-case 1 produce copper-neodymium alloy, is that the content of neodymium is different in the alloy with the difference of example 1, and its composition (weight %) is respectively: Cu-0.1Nd, and Cu-0.3Nd, Cu-0.5Nd, Cu-0.7Nd, the electricity, the magnetic property that record see Table 2.
Listed data are as can be seen along with the increase of neodymium content in the copper from table, the initial susceptibility of alloy increases thereupon, resistivity under each temperature all increases thereupon simultaneously, R.R.R decreases, when but neodymium content was increased to 0.7 weight % in the copper, the initial susceptibility of this alloy but increased to 32.8 * 10
-7E.m.u/g, its R.R.R also remains on 37.2, and the R.R.R value of Cu-0.1Mn alloy has dropped to 4.77; This is favourable to the stability that improves the superconduction band, the coupling of eliminating proximity effect obviously.
In addition, from table, also can find out, add the alloy of neodymium, although its initial susceptibility can increase along with the increasing of neodymium content in the alloy, but the ratio x/c of the number of initial susceptibility and interpolation pantogen does not change with the variation of neodymium concentration, thereby available x/c ratio characterizes the size of the element atomic magnetic moment that arc stood when rare element neodymium was added in the copper under the 4.2K.Otherwise, when adding manganese element (seeing Table 1), addition is in 0.1-0.5 weight % scope, the ratio x/c of the initial susceptibility of alloy and manganese element atomicity is along with the variation of adding concentration but presents obvious variation, this explanation add manganese to the contribution of alloy magnetic moment except the magnetic moment of isolated atom, the contribution that also exists their each other relevant and cause to the alloy magnetic moment, this addition that certainly will will increase manganese just can reach identical initial susceptibility, will inevitably cause electrical property further to descend and increase addition.
3. be raw material with cathode copper and granularity less than 3 millimeters rare earth element er Er-4, adopt similar technology in the example 1, make copper-erbium Cu earlier
5The Er intermediate alloy is made copper-erbium alloy of different content (weight %) again.The composition of copper-erbium alloy (weight %) is respectively Cu-0.05Er, Cu-0.1Er, Cu-0.3Er, Cu-0.5Er and Cu-0.7Er.Method identical in the use-case 1 is measured its electromagnetic performance respectively, the results are shown in Table 3.
The data of the Cu-Mn alloy in table 3 a routine data and the table 1 and the Cu-Nd alloy data in the table 2 are compared as can be seen, rare earth erbium is different to the influence of the resistivity of copper and neodymium, erbium is similar to neodymium to the influence of the room temperature resistivity of copper, but the resistivity effects under the 4.2K is greater than neodymium, therefore contain more obvious that the R.R.R of the copper-erbium alloy of erbium reduces, even but the addition of erbium is up to 0.7 weight %, the R.R.R value of its alloy is still up to 30.4, and only add the copper alloy of 0.1Mn weight %, its R.R.R value only is 4.77.In addition, erbium is better than rare earth neodymium and manganese metal to the contribution of the initial susceptibility of giving fine copper, erbium and manganese and x/c value are respectively the amount that this explanation of 2.2-2.3 and 0.35-0.58 will reach the erbium of the identical required adding of initial susceptibility and can significantly reduce, and for example its initial susceptibility of Cu-0.3Er is 3.89 * 10
-5E.m.u/g, and the initial susceptibility of the alloy of Cu-0.5Mn is 3.19 * 10
-5E.m.u/g, the initial susceptibility of Cu-0.7Nd only are 32.8 * 10
-7E.m.u/g promptly will reach suitable initial susceptibility, and the addition of rare earth erbium obviously can reduce; Its corresponding R.R.R value is respectively 38.3,3.62 and 37.2.Cu-0.3Er alloy and Cu-0.7Nd alloy phase ratio, its R.R.R value of Cu-0.3Er that reduces addition is basic identical with Cu-0.7Nd, but the Cu-0.3Er initial susceptibility is roughly 100 times of Cu-0.7Nd.
4. be raw material with cathode copper and granularity less than 3 millimeters dysprosium doping Dy-4, adopt similar technology in the example 1, make copper-dysprosium Cu earlier
5The Dy intermediate alloy is made copper-disprosium alloy of different content (weight %) again, and the composition of copper-disprosium alloy (weight %) is respectively Cu-0.05Dy, Cu-0.1Dy, Cu-0.3Dy, Cu-0.5Dy and Cu-0.7Dy.Method identical in the use-case 1 is measured its electromagnetic performance respectively, the results are shown in Table 4.
Add the copper alloy of dysprosium as can be seen from Table 4, add 0.1 weight %Mn to this Effect on Performance when the addition of dysprosium also is significantly less than the influence of the room temperature resistivity of copper alloy and the resistivity under the 4.2K during up to 0.7 weight %, and its initial susceptibility is roughly suitable.That is to say in order to reach identical magnetic susceptibility (15.5 * 10
-6E.m.u/g), even the addition of dysprosium is increased to 0.7 weight %, the resistivity decreased that also can not make alloy is not to satisfying the requirement of superconductor to the resistivity of copper matrix, and still can keep R.R.R is 32.2.
5. be raw material with cathode copper and granularity less than 3 millimeters rare-earth element gadolinium Gd-4, adopt similar technology in the example 1, make Cu earlier
6The Gd intermediate alloy is copper-gadpolinium alloy that raw material is made different content (weight %) with cathode copper and Cu Gd intermediate alloy again, and the composition of copper-gadpolinium alloy (weight %) is respectively Cu-0.05Gd, Cu-0.1Gd, Cu-0.3Gd, Gu-0.5Gd and Cu-0.7Gd.Identical method records its room temperature resistivity ρ r respectively in the use-case 1, the electricalresistivity 77K under the 77K, and resistivity under the 4.2K and initial susceptibility X by calculating R.R.R value and x/c, the results are shown in Table 5.
Rare-earth element gadolinium has the highest initial susceptibility and the ratio (x/c) that adds concentration in interpolation element of the present invention as can be seen from Table 5, that is to say under same situation of adding concentration, might have than add other elements stronger for the right magnetic scattering process of superelectron.Another advantage of adding rare-earth element gadolinium simultaneously is that the influence that gadolinium adds in the copper the resistivity of copper is not again very big, just is worse than rear earth element nd slightly.Still can be even in copper, add like this, the residual resistance ratio R.R.R of its alloy of gadolinium of 0.1 weight % up to arriving 65.9 of fine copper; Add the gadolinium of 0.7 weight %, the residual resistance ratio R.R.R of its alloy also can remain on 31.8 level, compare with the copper alloy that adds manganese, the copper alloy that adds 0.1 weight %Mn, its residual resistance ratio only is 4.77, this cupromanganese can't be separately in the multi-core superconducting tape as basis material, must coat fine copper more outside.
By among the above embodiment as can be seen, the copper alloy of the rear earth element nd of adding 0.05-0.7 weight %, gadolinium, dysprosium, erbium in fine copper, had the initial susceptibility that uses meaning, thereby can play the magnetic scattering process right when making this Albatra metal-to superelectron as the copper matrix of superconducting multicore wire band, can overcome the contiguous coupling effect that causes because the superconduction heart yearn is too thin and/or the superconducting core distance between centers of tracks is too little in varying degrees, increase the stability of superconductor; Simultaneously, add this class rare earth element and can not make the room temperature resistivity of copper and the resistivity of 4.2K that too big increase is arranged again egregiously, still can satisfy the requirement of superconductor the electrical property of copper matrix.What just can make the copper alloy that contains rare earth element by the addition of selecting different rare earth elements, changing rare earth element has different room temperature resistivities and initial susceptibility to satisfy different superconductors, and the very thin multi-core low-temp superconducting wire band of different superconducting core linear diameters and different superconducting core distance between centers of tracks is to the requirement of copper basis material.Compare with the copper alloy that adds magnetic medium (as Mn, Fe, Cr), alloy of the present invention is when reaching similar initial susceptibility, and resistivity and residual resistance ratio have obvious minimizing and raising respectively, and the highest residual resistance ratio can reach 76.7.Compare with fine copper, copper alloy of the present invention be magnetic can overcome the coupling of the proximity effect between the superconduction heart yearn in, still have the electric conductivity that can satisfy instructions for use.Therefore, the copper alloy that contains rare earth element of the present invention is especially suitable for use as the basis material of low temperature superconducting material, especially be suitable as the basis material of core diameter, also can be used for the requirement of electromagnetic performance is met the other field of copper alloy performance of the present invention less than 10 microns very thin multi-core superconducting wire band.
Table 1
Table 3
Table 5
Claims (6)
1, an Albatra metal-is characterized in that described copper alloy is made up of copper and rare earth element, and the content (weight %) of said copper alloy middle rare earth element is 0.05-0.7, and all the other are copper.
2, according to the said copper alloy of claim 1, the content (weight %) that it is characterized in that said rare earth element is 0.1-0.5.
3, according to claim 1 or 2 said copper alloys, it is characterized in that said rare earth element is the Gd(gadolinium).
4, according to claim 1 or 2 said copper alloys, it is characterized in that said rare earth element is the Er(erbium).
5, according to claim 1 or 2 said copper alloys, it is characterized in that said rare earth element is the Nd(neodymium).
6, according to claim 1 or 2 said copper alloys, it is characterized in that said rare earth element is the Dy(dysprosium).
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