JP2012234681A - Wiring material for superconducting magnet - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an electric wiring material which is easy to handle and exhibits excellent conductivity even in a strong magnetic field having a magnetic flux density of 1 T, for example.SOLUTION: There is provided an electric wiring material used in a magnetic field having a magnetic flux density of 1 T or more, containing aluminum with purity of 99.999% by mass or more.

Description

  The present invention relates to a wiring material for a superconducting magnet that exhibits excellent conductivity at a low temperature of, for example, 77K or less, particularly at an extremely low temperature of 20K or less, particularly for a superconducting magnet that exhibits excellent conductivity even when used in a strong magnetic field of, for example, 1T or more. It relates to wiring materials.

For example, superconducting magnets are used in many fields such as medical MRI (magnetic resonance imaging apparatus), analytical NMR (nuclear magnetic resonance analyzer) or linear motor car. A low-temperature superconducting coil cooled to a boiling point of 4.2 K (Kelvin) using liquid helium or a high-temperature superconducting coil cooled to about 20 K by a refrigerator is used as a superconducting magnet.
Since these superconducting coils need to be supplied with an electric current efficiently and uniformly cooled, a wiring material (wiring material for a superconducting magnet) that is cooled to an extremely low temperature of the boiling point of liquid nitrogen of 77 K or less is formed around it. ) Is arranged. Then, electric power is supplied to the superconducting coil through the superconducting magnet wiring material.

Needless to say, such a superconducting magnet wiring material preferably has a low electrical resistance at an extremely low temperature.
For example, Patent Document 1 discloses silver (Ag), gold (Au), rhenium (Re), platinum (Pt), copper (Cu), zinc (Zn), and a wiring material for electrically coupling members together. A superconducting device using aluminum (Al), iron (Fe) or the like is described. Among these metals, copper is the most widely used because it is relatively inexpensive and easy to handle, and then aluminum is often used. In order to ensure sufficient electrical conductivity, the purity of copper may be expressed as 99.99 mass% or more (hereinafter referred to as “4N” (4 nines). Similarly, for example, the purity of 99.9999 mass% or more is expressed as “ 6N "(6 nines), oxygen-free copper of 9 in the mass percentage notation indicating purity may be indicated by adding N after the number of consecutive 9 from the top), and aluminum has a purity of 99 mass % Or more (2N) to a purity of about 99.99 mass% or more (4N) has been conventionally used.

  Patent Documents 2 and 3 show a high-purity aluminum conductor for cryogenic use having a purity of 99.98% by mass or less with a small increase in electrical resistance even when subjected to repeated strain at a cryogenic temperature.

JP 2009-212522 A Japanese Patent Laid-Open No. 7-15208 JP 7-166283 A

However, among such superconducting magnet wiring materials, those used in the vicinity of the superconducting coil are used in a state where a strong magnetic field having a magnetic flux density of 1 T (Tesla) or more is applied, for example. For this reason, in the state where the magnetic field is not applied, the above-mentioned material having sufficient conductivity has a problem that the conductive characteristics are deteriorated due to the magnetoresistance effect in such a strong magnetic field.
When the conductivity is lowered, heat is generated in the conductive path in the wiring material, and as a result, the amount of evaporation of liquid helium in the cryogenic container is increased.

  Copper is known to have a significant magnetoresistance effect (i.e., electrical resistance increases significantly in a magnetic field), and aluminum is known to exhibit a large magnetoresistance effect, although not as much as copper.

For this reason, there is a strong demand for an electrical wiring material that uses an easily handled metal such as copper or aluminum and exhibits excellent conductivity even in a strong magnetic field such as a magnetic flux density of 1 T or more.
Therefore, an object of the present invention is to provide an electrical wiring material that is easy to handle and exhibits excellent conductivity even in a strong magnetic field such as a magnetic flux density of 1 T or more.

  Aspect 1 of the present invention is an electrical wiring material used in a magnetic field having a magnetic flux density of 1 T or more, and is an electrical wiring material characterized by comprising aluminum having a purity of 99.999% by mass or more.

  The present inventors have found that the magnetoresistive effect can be remarkably suppressed by making the purity of aluminum (Al) 99.999% by mass or more. Such an electrical wiring material made of aluminum can maintain excellent electrical conductivity even when used in a strong magnetic field having a magnetic flux density of 1 T or more.

By using such an electrical wiring material according to the present invention, it is possible to reduce heat generation due to electrical resistance in the electrical wiring material even when a magnetic field having a magnetic flux density of 1 T or more is applied from the superconducting coil. . Thereby, for example, evaporation of a coolant such as liquid helium can be suppressed, and the cross-sectional area of the electric wiring member can be reduced, so that various devices using the superconducting device can be miniaturized.
Moreover, since it can handle similarly to the conventional electrical wiring material of low purity aluminum, the electrical wiring material according to the present invention is easy to handle.

  Aspect 2 of the present invention is the electrical wiring material according to aspect 1, wherein the iron content of the aluminum is 1 mass ppm or less.

  By setting the iron content to 1 mass ppm or less, conductivity in a strong magnetic field can be more reliably ensured.

  Aspect 3 of the present invention is the electrical wiring material according to aspect 1 or 2, wherein the purity of the aluminum is 99.9999% by mass or more.

  Aspect 4 of the present invention is the electrical wiring material according to aspect 1 or 2, wherein the purity of the aluminum is 99.99998% by mass or more.

Aspect 5 of the present invention is the electrical wiring material according to any one of aspects 1 to 4, wherein the aluminum contains an intermetallic compound Al ₃ Fe.

  According to the present invention, it is possible to provide an electrical wiring material that is easy to handle and exhibits excellent conductivity even in a strong magnetic field such as a magnetic flux density of 1 T or more.

It is a graph which shows the relationship between a conductivity index and the applied magnetic field (magnetic flux density).

The electrical wiring material according to the present invention is characterized by comprising aluminum having a purity of 99.999 mass% or more in order to be used even in a magnetic field having a magnetic flux density of 1 T or more.
The inventors of the present invention have found for the first time that aluminum having a purity of 99.999% by mass or more does not exhibit a remarkable magnetoresistance effect even when a magnetic field of 1T or more is applied, and therefore does not lower the conductivity. Has been reached.

  For example, as disclosed in Japanese Patent Application Laid-Open Nos. 2009-242865 and 2009-242866, aluminum has a purity of 5N (purity 99.999% by mass or more) and 6N (purity 99.9999% by mass or more). It has been known that the higher the purity, the lower the electrical resistance at cryogenic temperatures, such as liquid helium temperature.

  Further, for example, as disclosed in JP 2010-106329 A, aluminum having a purity of 99.999 mass% or more and an iron content of 1 mass ppm or less has been known.

However, although aluminum can improve the electrical conductivity at a very low temperature in a state where a magnetic field is not applied by increasing the purity to about 4N, when a strong magnetic field having a magnetic flux density of 1 T or more is applied, a remarkable magnetoresistance effect appears and becomes conductive. It has been known that a high conductivity material of 5N and 6N levels cannot obtain high conductivity under a strong magnetic field as in the case of 4N level materials.
For this reason, it is thought that the aluminum whose purity is 99.999 mass% or more was not used for the electrical wiring material used also in the magnetic field of magnetic flux density 1T or more.

As described above, the inventor of the present application has found for the first time that high-purity aluminum of 5N level or higher does not cause a decrease in conductivity under a strong magnetic field as conventionally considered.
Although details will be described later in Examples, copper exhibiting conductivity higher than that of aluminum in a state where no magnetic field is applied has a remarkable conductivity in a strong magnetic field even if it is a high purity material of 5N or 6N or higher. Since a decrease is observed, the phenomenon found by the present inventor that high conductivity is maintained even in a strong magnetic field by making aluminum high purity of 5N or more is peculiar to aluminum.

Furthermore, in the electrical wiring material which concerns on this invention, it is preferable that the quantity of iron contained in aluminum shall be 1 mass ppm or less.
As will be described in detail later, by controlling the amount of iron, which is a ferromagnetic element, the magnetoresistive effect is more reliably suppressed, and conduction in a strong magnetic field (by applying a strong magnetic field) It is because the fall of property can be suppressed reliably.

  The electrical wiring material according to the present invention is a low temperature of 77K (−196 ° C.) or less, more preferably a very low temperature of 20K (−253 ° C.) or less and a magnetic field having a magnetic flux density of 1T or more. The effect is remarkably shown by using.

Details of the electrical wiring material according to the present invention will be described below.
(1) Impurity Level As described above, the electrical wiring material according to the present application is characterized by comprising aluminum having a purity of 99.999% by mass or more. The purity is preferably 99.9999% by mass or more, more preferably 99.99998% by mass or more (hereinafter sometimes referred to as “6N8”). This is because the higher the purity, the less the decrease in conductivity under a strong magnetic field. Furthermore, when the purity is 99.9999% by mass or more, the specific resistance may be smaller in a strong magnetic field of 1 T or more than in the case where a magnetic field is not applied.

The content of iron contained in aluminum is preferably 1 ppm by mass or less, more preferably 0.1 ppm by mass or less.
This is because a decrease in conductivity in a strong magnetic field can be suppressed more reliably as described above.
There are still many unclear points about the mechanism that can suppress the decrease in conductivity in a strong magnetic field by setting iron to 1 ppm by mass or less, but the mechanism that can be guessed at present is that iron is a ferromagnetic element. For this reason, it is easily affected by a strong magnetic field. As a result, if it exceeds 1 mass ppm, the effect on conductivity is increased, and there is a possibility that the conductivity under a strong magnetic field may be reduced. It is estimated that this is because the influence of the ferromagnetic material can be almost completely eliminated. However, this estimated mechanism does not limit the technical scope of the present invention.

  Further, Ni and Co are known as ferromagnetic elements other than iron. However, since these are easily removed in the known aluminum purification process, the numerical values are not so problematic. However, these Ni and Co are also preferably 1 ppm or less, and more preferably 0.1 ppm or less.

  The purity of aluminum can be defined by several methods. For example, it may be determined by measuring the aluminum content. However, as a method of obtaining the purity of aluminum relatively easily and with high accuracy, the content (mass percent) of the following 33 elements that can be contained as impurities in ultrahigh purity aluminum is measured, and the total of these contents is calculated. It is preferably determined by subtracting from 100 percent.

Here, the 33 elements that can be included as impurities include lithium (Li), beryllium (Be), boron (B), sodium (Na), magnesium (Mg), silicon (Si), potassium (K), calcium (Ca ), Titanium (Ti), vanadium (V), chromium (Cr), manganese (Mn), iron (Fe), nickel (Ni), cobalt (Co), copper (Cu), zinc (Zn), gallium (Ga) ), Arsenic (As), zirconium (Zr), molybdenum (Mo), silver (Ag), cadmium (Cd), indium (In), tin (Sn), antimony (Sb), barium (Ba), lanthanum (La) ), Cerium (Ce), platinum (Pt), mercury (Hg), lead (Pb) and bismuth (Bi).
The content of these elements can be determined, for example, by glow discharge mass spectrometry.

(2) Purification method Such high-purity aluminum may be obtained using any purification (refining) method. Hereinafter, several purification methods for obtaining high-purity aluminum according to the present invention will be exemplified. However, it goes without saying that the method is not limited to these methods.

Three-layer electrolytic method As one of the methods for obtaining high-purity aluminum, a commercially available relatively low-purity aluminum (for example, a grade of about 1 kind of JIS-H2102 having a purity of 99.9%) is used for the Al-Cu alloy layer. Can be used as a positive electrode in a molten state, an electrolytic bath containing, for example, aluminum fluoride and barium fluoride is disposed thereon, and high-purity aluminum is deposited on the cathode.
In the three-layer electrolytic method, aluminum having a purity of 99.999% by mass or more can be obtained. Further, the iron content in aluminum can be suppressed to 1 ppm by mass or less relatively easily.

Unidirectional solidification method A unidirectional solidification method can be used to further increase the purity of high-purity aluminum obtained by, for example, a three-layer solidification method.
By the unidirectional solidification method, the Fe content and the Ti, V, Cr, and Zr contents can be selectively reduced.

  The unidirectional solidification method is a method in which, for example, a furnace body moving tube furnace is used, aluminum is melted in the core tube, and then the furnace body is pulled out from the core tube to solidify in one direction from the end. It is known that the content of each element of Ti, V, Cr, and Zr is selectively increased on the start end side, and the Fe content is on the solidification end end side (opposite side of the solidification start end). Selectively increase. Therefore, by cutting off the solidification start end side and the solidification end end side of the obtained ingot, it is possible to reliably reduce the content of each element of Fe and Ti, V, Cr, and Zr. Specifically, as to which part of the ingot obtained by the unidirectional solidification method is to be cut, for example, by analyzing the element content at appropriate intervals along the solidification direction, the Fe content and Ti The total content of V, Cr, and Zr may be determined so as to leave only a part that is sufficiently reduced.

The order of performing the purification by the three-layer electrolysis method and the purification by the unidirectional solidification method is not particularly limited, but usually the purification is first performed by the three-layer electrolysis method and then purified by the unidirectional solidification method. Further, the purification by the three-layer electrolysis method and the purification by the unidirectional solidification method may be repeated alternately, for example, or either one or both may be repeated. Is preferably repeated.
Thus, aluminum with a purity of 99.9999% by mass or more can be obtained by combining the three-layer solidification method and the unidirectional solidification method. Moreover, the iron content in aluminum can be suppressed to 1 mass ppm or less, and further to 0.1 mass ppm or less, relatively easily.

-Band melting method Furthermore, the band melting method can be used to obtain aluminum having a high purity, for example, a purity of 99.99998% by mass or more. Further, when the band melting method is appropriately used, the iron content in aluminum can be more reliably suppressed to 1 mass ppm or less, and further to 0.1 mass ppm or less.
In particular, it is effective to use the aluminum refining method (the method described in Japanese Patent Application No. 2010-064544) by the band melting method invented by the present inventors.

That is, when removing impurities in aluminum by a zone melting process, an alumina layer is previously formed on the surface of the boat on which the aluminum is placed in order to prevent the impurities from diffusing into the heated aluminum. In order to ensure separation of impurities from the formed and molten aluminum, the zone melting purification is performed in a vacuum of 3 × 10 ⁻⁵ Pa or less, more preferably 3 × 10 ⁻⁶ Pa to 2 × 10 ⁻⁵ Pa. It is preferable to carry out with.

Furthermore, it is preferable to carry out a pretreatment for dissolving and removing the surface layer of the aluminum raw material to be subjected to the band melting and refining before the band melting and refining. The pretreatment method is not particularly limited, and various treatments used in the technical field for removing the surface layer of the aluminum raw material can be used.
Examples of the pretreatment include acid treatment and electrolytic polishing.

  Further, the above-mentioned boat used in the zone melting refining (zone melting method) is preferably a graphite boat, and is preferably baked in an inert gas or vacuum after forming the above-mentioned alumina layer.

  Furthermore, it is preferable that the width of the melted portion in which aluminum is melted during zone melting and purification is w × 1.5 or more and w × 6 or less with respect to the cross-sectional dimension w of the aluminum raw material.

  Moreover, it is preferable to use high-purity aluminum having a purity of, for example, 99.9999 mass or more, for example, by using the above-mentioned three-layer solidification method and unidirectional solidification method as the raw material aluminum used for purification.

  For example, band melting can be performed by moving a high-frequency coil for high-frequency heating to move the melting part from one end part of the raw material aluminum toward the other end part, and the whole raw material aluminum can be melt-purified. . Among the impurity metal element components, peritectic components (Ti, V, Cr, As, Se, Zr, Mo) are added to the eutectic component (excluding the peritectic seven elements from the above-mentioned impurity elements 33 elements) at the melting start part. Therefore, it is possible to obtain high-purity aluminum in the region excluding both ends of the aluminum raw material.

  After the molten part is moved for a predetermined time, for example, from one end to the other end in the longitudinal direction of the aluminum raw material, the high-frequency heating is terminated and the molten part is solidified. After solidification, the aluminum material is cut out (for example, both end portions are cut off) to obtain a purified high-purity aluminum material.

In the case where a plurality of aluminum raw materials are arranged in the longitudinal direction (moving direction of the molten portion), the aluminum raw material in the longitudinal direction is brought into contact with each other as one aluminum raw material in the longitudinal direction (i.e., Among the end portions of the plurality of aluminum raw materials, one of the two end portions having no aluminum raw material adjacent in the longitudinal direction to the other end portion (that is, the aluminum raw material adjacent in the longitudinal direction among the end portions of the plurality of aluminum raw materials is It is preferable to move to the other of the two ends not present.
This is because the end portions of the aluminum raw materials that are in contact with each other are joined at the time of band melting, and a single long aluminum material can be obtained.

As described above, after melting from one end of the aluminum raw material to the other end (band melting refining), the band melting can be repeated from one end to the other end again.
The number of repetitions (number of passes) is usually 1 or more and 20 or less. Even if the number of passes is increased further, the improvement of the purification effect is limited.

In order to effectively purify the peritectic 7 elements, the number of passes is preferably 3 or more, more preferably 5 or more. If the number of passes is less than this, the peritectic 7 elements are difficult to move, so that a sufficient purification effect cannot be obtained.
Also, when a plurality of aluminum raw materials are arranged in contact with each other in the longitudinal direction, if the number of passes is less than 3, the shape (particularly the height dimension) of the refined material (aluminum material) after joining becomes non-uniform and refined This is because the melt width may fluctuate and a uniform purification effect may not be obtained.

(3) Molding method The ingot of high-purity aluminum obtained by the above-described purification method is molded into a desired shape using various methods.
Examples of the molding method will be described below. The molding method is not limited to these.

-Rolling For example, when the electric wiring material to be obtained is a plate material or a wire material, rolling is an effective forming method.
The rolling process may be performed by adopting a normal method such as a method of passing the ingot between these rolls while applying pressure by sandwiching the ingot between a pair of rolls. Specific methods and conditions (processing temperature, processing time, processing rate, etc.) when performing the rolling process are not particularly limited, and may be appropriately set within a range not impairing the effects of the present invention.

The sizes of the plate and wire finally obtained by rolling are not limited, but preferred sizes include a thickness of 0.1 mm to 3 mm for a plate and a diameter of 0.1 mm to 3 mm for a wire. can do.
If it is thinner than 0.1 mm, the cross-sectional area becomes small and it may be difficult to have sufficient conductivity as a wiring material. If it is thicker than 3 mm, it may be difficult to deform using flexibility. In the case of a thickness of 0.1 mm to 3 mm, there is an advantage that handling is easy, for example, it can be arranged on the side surface of a curved container using flexibility.
Needless to say, the shape that can be obtained by rolling is not limited to a plate or wire (wire), and for example, a pipe or an H-shape can also be obtained by rolling.

  Hot rolling or warm rolling in which the ingot is preheated and rolled at a temperature equal to or higher than room temperature may be used, or cold rolling in which the ingot is not preheated may be used. Also, hot or warm rolling and cold rolling may be combined.

  In addition, when rolling, it is possible to perform a process such as casting into a desired shape and cutting in advance. For casting, for example, an ordinary method may be employed in which ultra high purity aluminum is heated and melted to form a molten metal, and the obtained ultra high purity aluminum molten metal is cooled and solidified in a mold, but is not limited thereto. It is not something. The conditions for casting are not particularly limited, but the heating temperature is usually 700 to 800 ° C., and the heating and melting is usually performed in a vacuum or under an inert gas (nitrogen gas, argon gas, etc.) atmosphere made of graphite or the like. Performed in a crucible.

-Forming method other than rolling As a forming method other than rolling, drawing (drawing) or extrusion may be performed. Although the shape obtained by drawing or extruding is not limited, for example, drawing or extruding is suitable for obtaining a wire having a circular cross section.

Before drawing, a rolled wire rod (rolled rod) may be obtained by rolling, and a desired wire shape may be obtained by drawing the rolled wire rod.
In addition, the cross section of the obtained wire is not limited to a circle, and may have an irregular cross section such as an ellipse or a square.

Moreover, you may obtain a desired shape by cutting an ingot other than drawing or extrusion.
(4) Annealing Furthermore, the molded product of the present invention obtained by a molding method such as rolling may be annealed as necessary. By performing the annealing treatment, it is usually possible to remove distortion that may occur when the material to be molded is cut out from the ingot or during the molding process.
The conditions for the annealing treatment are not particularly limited, but a method of holding at 400 to 600 ° C. for 1 hour or more is preferable.
When the temperature is lower than 400 ° C., the strain (dislocation) contained in the ingot is not sufficiently reduced. And since distortion (dislocation) becomes a factor which raises electrical resistance, it is because it may be unable to exhibit the outstanding electroconductivity. When the heat treatment temperature is higher than 600 ° C., the solid solution of impurities, particularly iron, proceeds. Since solid solution iron has a large effect of increasing electric resistance, the conductive characteristics may be deteriorated.

More preferably, hold | maintain at 430-550 degreeC for 1 hour or more.
This is because, within this temperature range, strain can be sufficiently removed and iron exists as an intermetallic compound with aluminum without being dissolved in the matrix.

Furthermore, it depends on the following reasons.
As an intermetallic compound of iron and aluminum, a plurality of types such as Al ₆ Fe, Al ₃ Fe, and Al _m Fe ( _{m to} 4.5) are known. In this temperature range (430 to 550 ° C.), the majority of the intermetallic compound of iron and aluminum existing in the high-purity aluminum material after annealing (for example, 50% or more by volume, preferably 70% or more) is Al ₃ Fe. It is thought that. The presence of Al ₃ Fe and the volume ratio thereof can be confirmed and measured by dissolving the substrate with a chemical solvent and collecting by filtration, and observing and analyzing the residue collected by filtration with an analytical electron microscope (analysis TEM).
This Al ₃ Fe has an advantage that even if it exists as a precipitate, it hardly affects the conductivity.

  In addition, although the electrical wiring material which concerns on this invention may consist only of the above-mentioned 99.999 mass% or more high-purity aluminum, it is the said high-purity in order to give various functions, such as providing a protective coating, for example. Parts other than aluminum may be included.

Example 1 (purity 99.999 mass% or more, 5N-Al), Example 2 (purity 99.9999 mass% or more, 6N-Al) and Example 3 (purity 99) are shown in detail below as sample samples. , 99998% by mass or more, 6N8-Al), and then the specific resistance was measured.
Further, as Comparative Examples, Comparative Example 1 (4N—Al), which is aluminum with a purity of 4N, and Comparative Example 2 (3N—Al), which is aluminum with a purity of 3N, are shown below. The specific resistances of Comparative Examples 1 and 2 were obtained by calculation.

  Moreover, about copper, the specific resistance of the comparative example 3 (5N-Cu) whose purity is 5N level copper was measured.

  Further, for copper, literature data was used as a comparative example. Comparative Example 4 is a 4N level copper sample, Comparative Example 5 is a 5N level copper sample, and Comparative Example 6 is a 6N level copper sample.

(1) Preparation of high-purity aluminum material First, the manufacturing method of the high-purity aluminum material used for Examples 1-3 is shown below.
Example 1
Commercially available aluminum having a purity of 99.92% by mass was purified by a three-layer electrolysis method to obtain high-purity aluminum having a purity of 99.999% by mass or more.
Specifically, 99.92 mass% of commercially available aluminum is added to the Al—Cu alloy layer, and the electrolytic bath composition is 41% AlF ₃ -35% BaF ₂ -14% CaF ₂ -10% NaF at 760 ° C. Electricity was applied to collect high-purity aluminum deposited on the cathode side.
Each element content in the high-purity aluminum was analyzed by glow discharge mass spectrometry (using “VG9000” manufactured by Thermo Electron).

Example 2
The high-purity aluminum obtained by the above three-layer dissolution method was purified by a unidirectional solidification method to obtain high-purity aluminum having a purity of 99.9999 mass% or more.
Specifically, in a crucible (inner dimensions: width 65 mm × length 400 mm × height 35 mm), 2 kg of high-purity aluminum obtained by the three-layer melting method is placed, and this is put into a core tube ( It is housed in a quartz, inside diameter 100 mm × length 1000 mm), and the furnace body (crucible) is temperature controlled at 700 ° C. in a vacuum atmosphere of 1 × 10 ⁻² Pa to dissolve high purity aluminum, The furnace body was solidified in one direction from the end by being pulled out of the core tube at a speed of 30 mm / hour. And in the length direction, it cut out from the position of 50 mm from the coagulation start end to the position of 150 mm from the coagulation start end, to obtain a massive ultra high purity aluminum of 65 mm width × 100 mm length × 30 mm thickness.
The content of each element in this ultra-high purity aluminum was analyzed by glow discharge mass spectrometry as described above, and as shown in Table 1.

Example 3
Aluminum raw material cut from a 6N aluminum lump obtained by the above-mentioned unidirectional solidification method into a square column of approximately 18mm x 18mm x 100mm or similar shape by cutting and acid-washed with 20% aqueous hydrochloric acid diluted with pure water for 3 hours Got.

The zone melting method was implemented by the following method using this aluminum raw material.
A graphite boat was placed inside a vacuum chamber (quartz tube having an outer diameter of 50 mm, an inner diameter of 46 mm, and a length of 1400 mm) of the zone melting purification apparatus. A high-purity alumina powder AKP series (purity: 99.99%) manufactured by Sumitomo Chemical Co., Ltd. was applied to the raw material placement portion of the graphite boat while being pressed to form an alumina layer.

The graphite boat was baked by heating at high frequency under vacuum.
Baking is performed in a vacuum of 10 ⁻⁵ to 10 ⁻⁷ Pa using a high-frequency heating coil (heating coil winding number 3, inner diameter 70 mm, frequency about 100 kHz) used for band melting, and from one end of the boat at a speed of 100 mm / hour. It moved to the other end and the whole graphite boat was heated in order.

  Nine aluminum raw materials and a total weight of about 780 g were placed in a 20 × 20 × 1000 mm raw material placement portion provided on a graphite boat. A total of nine aluminum raw materials were arranged so that they could be regarded as square pillars in general, and the cross-sectional dimensions of the aluminum raw material were w = 18 mm, length L = 900 mm, and L = w × 50.

The inside of the chamber was sealed and evacuated by a turbo molecular pump and an oil rotary pump until the pressure became 1 × 10 ⁻⁵ Pa or less. Thereafter, one end in the longitudinal direction of the aluminum raw material was heated and melted by a high-frequency heating coil (high-frequency coil) to form a molten portion.
The output of the high frequency power source (frequency 100 kHz, maximum output 5 kW) was adjusted so that the melt width of the melted portion was about 70 mm. Then, the high frequency coil was moved at a speed of 100 mm per hour, and the melting part was moved about 900 mm. The pressure in the chamber at this time was 5 × 10 ^{−6 to} 9 × 10 ⁻⁶ Pa. It was 660 degreeC-800 degreeC as a result of measuring the temperature of a fusion | melting part with the radiation thermometer.

Thereafter, the high frequency output was gradually lowered to solidify the melted portion.
Then, the high-frequency coil was moved to the melting start position (the position where the melted portion was first formed), and the aluminum raw material was heated and melted again at the melting start position while the inside of the chamber was maintained at a vacuum to form a melted portion. This melting portion was moved to repeat the zone melting purification. When zone melting and refining at a melting width of about 70 mm and a moving speed of the melting part of 100 mm per hour was performed a total of three times (three passes), the shape became almost uniform from the melting start part to the end part, and thereafter (shown below A uniform shape was maintained for 7 passes).

Next, zone melting and refining was performed 7 passes at a melt width of about 50 mm and a moving speed of the melted part of 60 mm per hour. The melt width was w × 2.8 to w × 3.9 with respect to the cross-sectional dimension w of the refined material (aluminum material).
After a total of 10 passes, the chamber was opened to the atmosphere and aluminum was taken out to obtain a purified aluminum material having a length of about 950 mm.

  The obtained aluminum material was cut out and the results of glow discharge mass spectrometry composition analysis as described above are shown in Table 1.

  Next, each of the high-purity aluminum materials of Examples 1 to 3 obtained above was cut to obtain a wire drawing material having a width of 6 mm, a thickness of 6 mm, and a length of 100 mm. In order to remove contaminating elements due to cutting of the surface of the wire drawing material, acid cleaning was performed for 1 hour with an acid prepared at a ratio of hydrochloric acid: pure water = 1: 1, and running water was washed for 30 minutes or more.

The obtained wire drawing material was drawn (drawn) to 0.5φ by grooved roll rolling and wire drawing. The drawn sample was fixed to a quartz jig, held in a vacuum at 500 ° C. for 3 hours, and then furnace-cooled to obtain a specific resistance measurement sample.
Furthermore, as a sample of Comparative Example 3, a commercially available high purity copper of 5N level (99.999% Cu, 0.5φ manufactured by NewMet Koch) was fixed to a quartz jig, washed with an organic solvent, and 500 ° C. in vacuum. Then, the sample which was held for 3 hours and then cooled in the furnace was used as a sample for measuring specific resistance.

(2) Derivation of specific resistance / Measurement of specific resistance With respect to the samples of Examples 1 to 3 and Comparative Example 3, the specific resistance was actually measured.
In the measurement, after the obtained sample is immersed in liquid helium (4.2K), the magnetic field applied to the sample is changed from a magnetic flux density of 0T (no magnetic field applied) to 15T, and the four-terminal method is used. It was measured.
A magnetic field was applied in a direction parallel to the longitudinal direction of the sample.

-Calculation of specific resistance About the comparative example 1 and the comparative example 2 which have a composition shown in Table 1, it computed using the following (1) formulas described in literature: RJCorruccini, NBS Technical Note, 218 (1964). In the equation (1), Δρ _H is an increase in specific resistance in the magnetic field. ρ _RT is a specific resistance at room temperature when no magnetic field is applied, and it is set to 2753 nΩcm because it can be treated as a substantially constant value in high purity Al of 3N or higher. ρ is a specific resistance at 4.2 K when no magnetic field is applied, and varies greatly depending on the purity. Therefore, this time, 9.42 nΩcm (RRR = 285) for 4N-Al and 117 nΩcm (RRR = 23) for 3N-Al. Experimental values were used. These formulas are obtained when the magnetic field is perpendicular to the longitudinal direction of the sample. However, similar formulas are not obtained when they are parallel, and are used for comparison. RRR is also called the residual resistance ratio, and is the ratio of the specific resistance at 297K to the specific resistance at the helium temperature (4.2K).

-Citation from the literature of specific resistance About Comparative Examples 4-6, the specific resistance is literature: Fujiwara S. et.al., Int. Conf. Process. Mater. Prop., 1st (1993), 909-912. Got more. Note that these literature values do not describe the relationship between the magnetic field application direction and the sample longitudinal direction.
Table 2 shows specific resistances of Examples 1 to 3 and Comparative Examples 1 to 6 derived as described above.
About RRR, Examples 1-3 and Comparative Examples 1-3 are measured values, and Comparative Examples 4-6 are literature values.

  From Table 2, the specific resistance of the sample of Comparative Example 2 corresponding to a conventional aluminum (4N level) wiring member increases as the magnetic field strength (magnetic flux density) increases, compared to when there is no magnetic field (0T), It can be seen that 15T has increased to about three times.

On the other hand, in Examples 1 to 3, in the first place, the specific resistance is as small as 1/10 or more as compared with Comparative Example 2, and the increase in specific resistance is small even when the magnetic field is increased.
In Example 1 (5N level), the resistivity of 15T is about 1.5 times that of the case without a magnetic field, and the increase is clearly smaller than that of Comparative Example 2.
In Example 2 (6N level), the increase in specific resistance is very small at 10 T, even within 15%, compared to the case without a magnetic field. In addition, in the range where the magnetic flux density is 1 to 12T, the value of the specific resistance is smaller than that in the case where no magnetic field is applied, and the magnetoresistive suppression effect is prominent.
In Example 3 (6N8 level), at any magnetic flux density of 1 to 15 T, the specific resistance is lower than that in the absence of a magnetic field, and the magnetoresistive suppression effect is very remarkable.

FIG. 1 is a graph showing the relationship between the conductivity index and the applied magnetic field (magnetic flux density). The conductivity index is an index indicating the magnitude of conductivity of each sample on the basis of Comparative Example 2 showing the specific resistance of 4N aluminum in a strong magnetic field. That is, at each magnetic flux density, the specific resistance value of Comparative Example 2 is obtained by dividing by the specific resistance value of each sample. It shows that the electrical conductivity under the magnetic flux density (strong magnetic field) is excellent, so that the value of this index | exponent is large compared with the comparative example 2 sample.
Since the sample of Example shows a very remarkable effect, the conductivity index on the vertical axis is shown in logarithm.

  As can be seen from FIG. 1, the example sample has no magnetic field and is about 13 to 28 times higher in conductivity than Comparative Example 2. As the magnetic field is applied, the conductivity compared to Comparative Example 2 increases, and is 16 times (Example 1) to 65 times (Example 3) at 1T and 26 times (Example 1) at 15T. It is further increased to -96 times (Example 1).

  Also, from FIG. 1, all of the copper samples (Comparative Examples 3 to 6) show a downward-sloping curve. Compared with Comparative Example 2, the effect of magnetoresistance increases as the magnetic field strength increases. Is shown. That is, in the case of copper, it is shown that even if the purity is increased to a level of 6N, the decrease in conductivity due to the magnetic resistance cannot be suppressed (from Table 1, the samples of Comparative Examples 3 to 6 are 15T). The specific resistance is found to be about 5 to 18 times higher than the specific resistance in the absence of a magnetic field), and the inventors have found that the purity is increased to 99.999 mass% or more in the magnetic field. This indicates that the effect of suppressing the decrease in conductivity is unique to aluminum.

  The reason why the magnetoresistance suppression effect due to the high purity appears in aluminum and does not appear in copper is unknown, but it can be presumed that it is caused by the difference in electrical resistance factors. In other words, the main electrical resistance factor of high-purity copper is scattering of conduction electrons due to grain boundaries and dislocations, and even if the purity is increased, the change in electrical resistance factor is small, and therefore the magnetic resistance is also considered to be small. On the other hand, the main electrical resistance factor of high-purity aluminum is the scattering of conduction electrons by impurity atoms, and the electrical resistance factor decreases as the purity increases, so that the increase in electrical resistance in a magnetic field is small for aluminum of 5N or more. It seems that the characteristic has appeared. However, this estimation mechanism does not limit the technical scope of the present invention.

  According to the present invention, it is possible to provide an electrical wiring material that is easy to handle and exhibits excellent conductivity even in a strong magnetic field such as a magnetic flux density of 1 T or more.

Claims (5)

  An electrical wiring material used in a magnetic field having a magnetic flux density of 1 T or more, comprising aluminum having a purity of 99.999% by mass or more.   The electric wiring material according to claim 1, wherein the iron content of the aluminum is 1 mass ppm or less.   The electrical wiring material according to claim 1, wherein the aluminum has a purity of 99.9999% by mass or more.   The electrical wiring material according to claim 1, wherein the aluminum has a purity of 99.99999% by mass or more. The electrical wiring material according to claim 1, wherein the aluminum contains an intermetallic compound Al ₃ Fe.

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