JP2012234681A - Wiring material for superconducting magnet - Google Patents
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Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01F—MAGNETS; INDUCTANCES; TRANSFORMERS; SELECTION OF MATERIALS FOR THEIR MAGNETIC PROPERTIES
- H01F6/00—Superconducting magnets; Superconducting coils
- H01F6/06—Coils, e.g. winding, insulating, terminating or casing arrangements therefor
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
- H01B1/02—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of metals or alloys
- H01B1/023—Alloys based on aluminium
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01F—MAGNETS; INDUCTANCES; TRANSFORMERS; SELECTION OF MATERIALS FOR THEIR MAGNETIC PROPERTIES
- H01F41/00—Apparatus or processes specially adapted for manufacturing or assembling magnets, inductances or transformers; Apparatus or processes specially adapted for manufacturing materials characterised by their magnetic properties
- H01F41/02—Apparatus or processes specially adapted for manufacturing or assembling magnets, inductances or transformers; Apparatus or processes specially adapted for manufacturing materials characterised by their magnetic properties for manufacturing cores, coils, or magnets
- H01F41/04—Apparatus or processes specially adapted for manufacturing or assembling magnets, inductances or transformers; Apparatus or processes specially adapted for manufacturing materials characterised by their magnetic properties for manufacturing cores, coils, or magnets for manufacturing coils
- H01F41/048—Superconductive coils
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- Engineering & Computer Science (AREA)
- Power Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Conductive Materials (AREA)
- Non-Insulated Conductors (AREA)
Abstract
Description
本発明は、例えば77K以下の低温、特に20K以下の極低温において優れた導電性を示す超電導磁石用配線材、とりわけ例えば1T以上の強磁場中で用いても優れた導電性を示す超電導磁石用配線材に関する。 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.
例えば、医療用のMRI(磁気共鳴画像診断装置)や分析用のNMR(核磁気共鳴分析
装置)あるいはリニアモーターカー等、多くの分野で超電導磁石が用いられている。液体ヘリウムを用いてその沸点4.2K(ケルビン)に冷却された低温超電導コイルや、冷凍機で20K程度に冷却された高温超電導コイルが超電導磁石として使われている。
これら超電導コイルは、効率的かつ均一に冷却した状態で、電流を供給される必要があるため、その周辺には液体窒素の沸点77K以下の極低温に冷却された配線材(超電導磁石用配線材)が配置されている。そして、この超電導磁石用配線材を介して超電導コイルに電力を供給している。
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.
そして、いうまでもなくこのような超電導磁石用配線材は、極低温において電気抵抗が低いものが好ましい。
例えば特許文献1には、部材同士を電気的に結合するための配線材として銀(Ag)、金(Au)、レニウム(Re)、白金(Pt)、銅(Cu)、亜鉛(Zn)、アルミニウム(Al)、鉄(Fe)等を用いる超電導装置について記載されている。このような金属のなかでも、比較的安価で取り扱いが容易なことから、銅が最も広く用いられ、続いてアルミニウムが用いられることが多い。そして充分な電気伝導性を確保するために、銅として純度99.99質量%以上(以下、「4N」(4ナイン)と表記する場合がある。同様に例えば純度99.9999質量%以上を「6N」(6ナイン)と、純度を示す質量パーセント表記において、先頭から連続する9の数の後にNをつけて表記する場合がある。)の無酸素銅が用いられ、アルミニウムとしては純度99質量%以上(2N)から99.99質量%以上(4N)程度の純度のものが従来から用いられてきた。
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.
また、特許文献2、3は、極低温で繰り返し歪を受けても電気抵抗増加が小さい純度99.98質%以上の極低温用高純度アルミニウム導体が示されている。
しかしながら、このような超電導磁石用配線材の中でも超電導コイルの近傍でも用いられるものは、例えば磁束密度1T(テスラ)以上の強磁場が印加された状態で使用される。このため、磁場が印加されていない状態では、充分な導電性を有する上記材料も、このような強磁場中では磁気抵抗効果により、導電特性が低下するという問題がある。
そして、導電性が低下すると、配線材内の導電経路で発熱を生じ、その結果、極低温容器内の液体ヘリウム蒸発量が多くなる等の弊害を生じていた。
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.
銅は顕著な磁気抵抗効果(すなわち磁場中で電気抵抗が著しく増大する)ことが知られており、また、アルミニウムも銅ほどではないが、大きな磁気抵抗効果を示すことが知られている。 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.
このため、銅やアルミニウムのような取り扱いの容易な金属を用い、かつ例えば磁束密度1T以上のような強磁場中でも優れた導電性を示す電気配線材への強い要望が有る。
そこで、本願発明は取り扱いが容易でかつ、かつ例えば磁束密度1T以上のような強磁場中でも優れた導電性を示す電気配線材を提供することを目的とする。
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.
本発明の態様1は、磁束密度1T以上の磁場中で用いる電気配線材であって、純度が99.999質量%以上のアルミニウムを含んで成ることを特徴とする電気配線材である。 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.
本願発明者らは、アルミニウム(Al)でも純度を99.999質量%以上にすることで磁気抵抗効果を著しく抑制できることを見出した。そして、このようなアルミニウムからなる電気配線材は、喩え磁束密度1T以上の強磁場中で用いても優れた電気伝導性を維持することができる。 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.
このような、本願発明に係る電気配線材を用いることにより、超電導コイルから磁束密度1T以上の磁場が印加された状態でも、電気配線材内での電気抵抗による発熱を少なくすることが可能になる。これにより、例えば液体ヘリウム等の冷却剤の蒸発を抑制でき、また電気配線材の断面積を小さくできるため超電導装置を用いる各種装置を小型化することが可能となる。
また、従来の純度の低いアルミニウムの電気配線材と同様の取り扱いができることから、本願発明に係る電気配線材は取り扱いが容易である。
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.
本発明の態様2は、前記アルミニウムの鉄の含有量が1質量ppm以下であることを特徴とする態様1に記載の電気配線材である。
鉄の含有量を1質量ppm以下にすることにより、より確実に強磁場中での導電性を確保することができる。 By setting the iron content to 1 mass ppm or less, conductivity in a strong magnetic field can be more reliably ensured.
本発明の態様3は、前記アルミニウムの純度が99.9999質量%以上であることを特徴とする態様1または2に記載の電気配線材である。
Aspect 3 of the present invention is the electrical wiring material according to
本発明の態様4は、前記アルミニウムの純度が99.99998質量%以上であることを特徴とする態様1または2に記載の電気配線材である。
本発明の態様5は、前記アルミニウムが金属間化合物Al3Feを含むことを特徴とする態様1〜4のいずれかに記載の電気配線材である。 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.
本願発明により、取り扱いが容易でかつ、かつ例えば磁束密度1T以上のような強磁場中でも優れた導電性を示す電気配線材を提供することができる。 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.
本願発明に係る電気配線材は磁束密度1T以上の磁場中でも用いるために、純度が99.999質量%以上であるアルミニウムを含んで成ることを特徴としている。
本願発明者らは、純度を99.999質量%以上のアルミニウムは1T以上の磁場が印加されても磁気抵抗効果が顕著には出現せず、従って導電性が低下しないことを初めて見出し、本願発明に至ったものである。
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.
例えば、特開2009−242865号公報および特開2009−242866号公報に示されるように、アルミニウムは、5N(純度99.999質量%以上)および6N(純度99.9999質量%以上)のように純度が高くなるほど、例えば液体ヘリウム温度のような極低温での電気抵抗が減少することが知られていた。 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.
また、例えば特開2010−106329号公報に示されるように、純度が99.999質量%以上であり、かつ鉄の含有量が1質量ppm以下であるアルミニウムも知られていた。 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.
しかし、アルミニウムは4N程度まで純度を上げることで磁場を印加しない状態では、極低温の電気伝導性を向上できるものの、磁束密度1T以上の強磁場を印加すると顕著な磁気抵抗効果が現れて導電性が低下することが知られており、5Nおよび6Nレベルの高純度材においても、4Nレベル材と同様に強磁場下では高い導電性を得ることができないと考えられていた。
このため、磁束密度1T以上の磁場中でも用いる電気配線材に純度が99.999質量%以上であるアルミニウムが用いられることがなかったと考えられる。
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.
そして、5Nレベル以上の高純度アルミニウムにおいては、従来、考えられていたような強磁場下での導電性の低下が生じないことを本願発明者が初めて見出したのは上述の通りである。
なお、詳細は後述の実施例で述べるが、磁場を印加しない状態ではアルミニウム以上の導電性を示す銅については、5Nあるいは6N以上の高純度材であっても強磁場中では顕著な導電性の低下が認められることから、アルミニウムを5N以上の高純度にすることで強磁場中でも高い導電性を維持するという本願発明者が見出した現象は、アルミニウムに特有のものである。
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.
さらに本願発明に係る電気配線材では、アルミニウム中に含まれる鉄の量を1質量ppm以下とすることが好ましい。
これは、詳細を後述するように、強磁性元素である鉄の量を制御することにより、より確実に磁気抵抗効果を抑制し、強磁場中での(強磁場が印加されたことによる)導電性の低下を確実に抑制できるからである。
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.
なお、本願発明に係る電気配線材は、温度が77K(−196℃)以下の低温、より好ましくは20K(−253℃)以下の極低温でかつ磁束密度1T以上の磁場が印加される状態で用いることでその効果を顕著に示す。 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.
以下の本願発明に係る電気配線材の詳細を説明する。
(1)不純物レベル
上述のように本願に係る電気配線材は、純度が99.999質量%以上であるアルミニウムを含んで成ることを特徴としている。純度は好ましくは99.9999質量%以上であり、より好ましくは99.99998質量%以上(以下、「6N8」という場合がある)である。純度が高いほど、強磁場下において導電性の低下が少ないからである。さらに、99.9999質量%以上の純度では、磁場を印加しない場合よりも1T以上の強磁場中の方が、比抵抗が小さくなる場合があるからである。
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.
また、好ましくはアルミニウム中に含まれる鉄の含有量は1質量ppm以下であり、より好ましくは0.1質量ppm以下である。
上述のようにより確実に強磁場中での導電性の低下を抑制できるからである。
鉄を1質量ppm以下にすることにより、強磁場中での導電性の低下を抑制できるメカニズムについては、未だ不明な点も多いが、現時点で推測可能なメカニズムは、鉄が強磁性元素であるために強磁場の影響を受けやすく、この結果、1質量ppmを超えて存在すると導電性に与える影響が大きくなり、強磁場下での導電性を低下させるおそれがあるためであり、0.1ppmでは強磁性体であることによる影響をほぼ完全に排除できるためであると推定される。ただし、この推定されるメカニズムは本願発明の技術的範囲を制約するものではない。
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.
また、鉄以外の強磁性元素としてNiおよびCoが知られているが、これらは既知のアルミニウム高純度化プロセスにおいて容易に除去されるため、その数値があまり問題とされることがない。ただし、これらNiおよびCoも1ppm以下であることが好ましく、0.1ppm以下であることがより好ましい。 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.
なお、アルミニウムの純度については、いくつかの方法において定義可能である。例えばアルミニウムの含有量の測定により求めてもよい。しかし、比較的簡便にかつ高精度にアルミニウムの純度を求める方法として、超高純度アルミニウムに不純物として含まれ得る以下の33元素の含有量(質量パーセント)を測定し、これらの含有量の合計を100パーセントから引くことにより求めるのが好ましい。 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.
ここで不純物として含まれ得る33元素とは、リチウム(Li)、ベリリウム(Be)、ボロン(B)、ナトリウム(Na)、マグネシウム(Mg)、シリコン(Si)、カリウム(K)、カルシウム(Ca)、チタン(Ti)、バナジウム(V)、クロム(Cr)、マンガン(Mn)、鉄(Fe)、ニッケル(Ni)、コバルト(Co)、銅(Cu)、亜鉛(Zn)、ガリウム(Ga)、ヒ素(As)、ジルコニウム(Zr)、モリブデン(Mo)、銀(Ag)、カドミウム(Cd)、インジウム(In)、錫(Sn)、アンチモン(Sb)、バリウム(Ba)、ランタン(La)、セリウム(Ce)、白金(Pt)、水銀(Hg)、鉛(Pb)およびビスマス(Bi)である。
これらの元素の含有量は、例えばグロー放電質量分析法により求めることができる。
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)精製方法
このような高純度のアルミニウムは、任意の精製(精錬)方法を用いて得てよい。以下に、本願発明に係る高純度アルミニウムを得るための精製方法をいくつか例示する。ただし、これらの方法に限定されるものではないことはいうまでもない。
(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.
・三層電解法
高純度のアルミニウムを得る方法の1つとして、Al−Cu合金層に市販の比較的純度の低いアルミニウム(例えば純度99.9%のJIS−H2102の特1種程度のグレード)を投入し、溶融状態で陽極とし、その上に例えばフッ化アルミニウムおよびフッ化バリウム等を含む電解浴を配置し、陰極に高純度のアルミニウムを析出させる三層電解法を用いることができる。
三層電解法では主に純度99.999質量%以上の純度のアルミニウムを得ることができる。またアルミニウム中の鉄の含有量を比較的容易に1質量ppm以下に抑制することができる。
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.
・一方向凝固法
例えば三層凝固法により得た高純度アルミニウムの純度をさらに高めるために一方向凝固法を用いることができる。
一方向凝固法によって、Feの含有量とTi、V、CrおよびZrの各含有量とを選択的に低減することができる。
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.
一方向凝固法とは、例えば炉体移動式管状炉を用い、炉心管内でアルミニウムを溶解させた後、炉体を炉心管から引き抜くことにより、端部から一方向に凝固させる方法であり、凝固開始端側ではTi、V、CrおよびZrの各元素の含有量が選択的に多くなることが知られており、かつ、凝固終了端側(凝固開始端の反対側)ではFeの含有量が選択的に多くなる。よって、得られた鋳塊の凝固開始端側と凝固終了端側とを切り取ることにより、FeとTi、V、CrおよびZrの各元素の含有量を確実に低減することが可能になる。具体的に、一方向凝固法で得られた鋳塊のどの部分を切り取るかについては、例えば、凝固方向に沿って適当な間隔で元素含有量を分析するなどして、Feの含有量とTi、V、CrおよびZrの合計含有量とが充分に低減された部分のみを残すように決定すればよい。 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.
三層電解法による精製と一方向凝固法による精製の実施順序は、特に制限されないが、通常は、まず三層電解法で精製し、その後、一方向凝固法で精製される。また、三層電解法による精製と一方向凝固法による精製は、例えば、交互に繰り返し行ってもよいし、いずれか一方もしくは両方を各々繰り返し行ってもよいが、特に、一方向凝固法による精製
は、繰り返し行うことが好ましい。
このように三層凝固法と一方向凝固法を組み合わせることにより純度99.9999質量%以上の純度のアルミニウムを得ることができる。また、アルミニウム中の鉄の含有量を比較的容易に1質量ppm以下、更には0.1質量ppm以下に抑制することができる。
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.
・帯溶融法
さらに、純度の高い、例えば純度99.99998質量%以上のアルミニウムを得るのに帯溶融法を用いることができる。また帯溶融法を適切に用いるとアルミニウム中の鉄の含有量をより確実に、1質量ppm以下、更には0.1質量ppm以下に抑制することができる。
とりわけ、本願発明者らが発明した帯溶融法によるアルミニウムの精製方法(特願2010−064544に記載の方法)を用いることが効果的である。
-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.
すなわち、アルミニウム中の不純物を帯溶融精製(zone melting process)により除去する際に、不純物が加熱したアルミニウム中に拡散するのを防止するために、アルミニウムが配置されるボートの表面に予めアルミナ層を形成し、かつ溶融したアルミニウムからの不純物の分離を確実に行うために帯溶融精製を圧力3×10−5Pa以下、より好ましくは3×10−6Pa〜2×10−5Paの真空中で行うことが好ましい。 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.
さらに、帯溶融精製を行う前に、帯溶融精製を行うアルミニウム原料の表面層を予め溶解除去する前処理を実施することが好ましい。前処理の方法は特に限定されるものでなく、アルミニウム原料の表面層を除去するために当該技術分野で用いられている各種の処理を用いることができる。
前処理として、例えば酸処理、電解研磨などが挙げられる。
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.
また、帯溶融精製(帯溶融法)で使用する上述のボートは、グラファイトボートが好ましく、上述のアルミナ層を形成後不活性ガスまたは真空中でベーキングしておくことが好ましい。 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.
さらに、帯溶融精製時にアルミニウムが溶融している溶融部の幅は、アルミニウム原料の断面寸法wに対して、w×1.5以上w×6以下とすることが好ましい 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.
また、精製に用いる原料のアルミニウムは例えば上述の三層凝固法と一方向凝固法を組み合わせることにより得る等、例えば純度99.9999質量以上の高純度アルミニウムを用いることが好ましい。 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.
帯溶融は例えば、高周波加熱のための高周波コイルを移動することで、溶融部を原料アルミニウムの一方の端部から他方の端部に向けて移動させ、原料アルミウム全体を帯溶融精製することができる。不純物金属元素成分のうち包晶系成分(Ti、V、Cr、As、Se、Zr、Mo)は溶融開始部に、共晶系成分(上述の不純物元素33元素から包晶系7元素を除いた26元素)は溶解終了部に濃縮する傾向があるため、アルミニウム原料の両端部を除く領域で高純度アルミニウムを得ることが可能である。 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.
溶融部を例えばアルミニウム原料の長手方向の一端から他端までの間のように所定の間移動させた後は、高周波加熱を終了し、溶融部を凝固させる。凝固後、アルミニウム材を切り出す(例えば両端部を切り落とす)ことにより、精製された高純度のアルミニウム材が得られる。 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.
長手方向(溶融部の移動方向)に複数本のアルミニウム原料を配置している場合は、長手方向のアルミニウム原料を接触させて、長手方向に1個のアルミニウム原料として、一方の端部(すなわち、複数のアルミニウム原料の端部のうち長手方向に隣接するアルミニウム原料がない2つの端部の一方)から他方の端部(すなわち、複数のアルミニウム原料の端部のうち長手方向に隣接するアルミニウム原料がない2つの端部の他方)に移動させるのが好ましい。
接触するアルミニウム原料の端部同士が帯溶融時に接合し、長い一本のアルミウム材を得ることができるからである。
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.
なお、上述したようにアルミニウム原料の一方の端から他方の端まで帯溶融(帯溶融精製)した後、再度、一方の端から他方の端まで帯溶融を繰り返すことができる。
繰り返し数(パス数)は通常1以上20以下である。パス数をこれ以上多くしても、精製効果の向上は限定的である。
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.
包晶系7元素を効果的に精製するため、パス数は3以上が好ましく、5以上がさらに好ましい。パス数がこれより少ないと、包晶系7元素は移動しにくいため、十分な精製効果が得られない。
また、長手方向に複数のアルミニウム原料を互いに接触させて配置した場合、パス数が3より少ないと接合後の精製材(アルミニウム材)の形状(特に高さ寸法)が不均一となって、精製中に溶融幅が変動して均一な精製効果が得られにくい場合があるからである。
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)成形方法
上述の精製方法により得られた高純度アルミニウムの鋳塊は、各種の方法を用いて所望の形状に成形される。
以下に成形方法を例示する。なお成形方法はこれらに限定されるものではない。
(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.
・圧延
例えば、得ようとする電気配線材が板材や線材である場合に圧延は効果的な成形方法である。
圧延加工は、例えば、鋳塊を一対のロールの間に挟み込むことにより圧力を加えながら、これらロール間に鋳塊を通過させる方法など、通常の方法を採用して行えばよい。圧延加工を行う際の具体的な手法や条件(処理温度、処理時間、加工率など)は、特に制限されるものではなく、本発明の効果を損なわない範囲で適宜設定すればよい。
-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.
圧延加工により最終的に得られる板材および線材のサイズは限定されるものではないが、好ましいサイズとして、板であれば厚さ0.1mm〜3mm、線材であれば直径0.1mm〜3mmを例示することができる。
0.1mmより薄いと断面積が小さくなり配線材としての十分な導電性を有しにくくなる場合がある。また3mmより厚いと可撓性を利用して変形させることが難しくなる場合がある。厚さ0.1mm〜3mmの場合に可撓性を利用して曲面状の容器側面に配置できるなど、取り扱いが容易であるという利点を有する。
なお、言うまでもないが圧延加工により得ることができる形状は、板材や線材(ワイヤー)に限定されるものではなく、例えばパイプやH型形状も圧延により得ることができる。
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.
鋳塊を予め加熱し、室温以上の温度にした状態で圧延を行う熱間圧延または温間圧延でもよく、また鋳塊を予め加熱しない冷間圧延でもよい。また、熱間または温間圧延と冷間圧延を組み合わせてもよい。 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.
なお、前記圧延するに際しては、あらかじめ所望の形状に鋳造し、切削するなどの処理を施すこともできる。鋳造を行うには、例えば、超高純度アルミニウムを加熱溶融して溶湯とし、得られた超高純度アルミニウム溶湯を鋳型内で冷却固化させるといった通常の方法を採用すればよいが、これに限定されるものではない。鋳造の際の条件等も特に制限されないが、加熱温度は通常700〜800℃であり、加熱溶融は通常、真空中あるいは不活性ガス(窒素ガス、アルゴンガス等)雰囲気下で、黒鉛製等のルツボ内で行なわれる。 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.
・圧延以外の成形方法
また、圧延以外の成形方法として、引き抜き(伸線)または押出しを行ってもよい。引き抜きまたは押出しにより得る形状は限定されないが、例えば断面が円形のワイヤーを得るのに引き抜きまたは押出しは適している。
-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.
引き抜きを行う前に圧延により圧延線材(圧延ロッド)を得て、圧延線材を引き抜くことで所望のワイヤー形状を得てもよい。
なお、得られるワイヤーの断面は円形に限定されるものではなく、例えば、楕円、方形等の異形断面を有していてもよい。
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.
また、引き抜きまたは押出し以外に鋳塊を切削することで所望の形状を得てもよい。
(4)焼鈍
さらに、上記圧延加工等の成形方法により得られた本発明の成形品は必要に応じて焼鈍処理を施してもよい。焼鈍処理を施すことにより、通常、鋳塊から被成形材を切り出す際や成形加工の際に生じることがある歪みを除去することができる。
焼鈍処理の条件は特に制限されないが、400〜600℃で1時間以上保持する方法が好ましい。
温度が400℃より低いと鋳塊に含まれる歪(転位)が十分に低減されない。そして、歪(転位)は電気抵抗を高める要因となるため、優れた導電特性を発揮できない場合があるからである。熱処理温度が600℃より高いと、不純物、特に鉄のマトリックスへの固溶が進行する。固溶した鉄は電気抵抗を高める効果が大きいため、導電特性が低下する場合
がある。
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.
より好ましくは、430〜550℃で1時間以上保持する。
この温度範囲であれば、充分に歪を除去できるとともに、鉄がマトリクスに固溶することなく、アルミニウムとの金属間化合物として存在するからである。
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.
さらに、以下の理由にもよる。
鉄とアルミニウムの金属間化合物としては、Al6Fe、Al3FeおよびAlmFe(m〜4.5)等の複数の種類が知られている。そして、この温度範囲(430〜550℃)で焼鈍後の高純度アルミニウム材に存在する鉄とアルミニウムの金属間化合物の過半(例えば体積比で50%以上、好ましくは70%以上)がAl3Feであると考えられる。 Al3Feの存在及びその体積比は、化学溶媒による基体溶解およびろ過収集を行い、ろ過収集された残渣を分析電子顕微鏡(分析TEM)で観察および分析することにより確認および測定することができる。
このAl3Feは、析出物として存在していても、ほとんど導電性に悪影響を与えることがないという利点を有する。
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.
なお、本願発明に係る電気配線材は、上述の99.999質量%以上の高純度アルミニウムのみから成ってもよいが、例えば、保護被覆を設ける等、各種の機能を持たせるために当該高純度アルミニウム以外の部分を含んでもよい。 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.
実施例サンプルとして、詳細を以下に示す実施例1(純度99.999質量%以上、5N−Al)、実施例2(純度99.9999質量%以上、6N−Al)および実施例3(純度99.99998質量%以上、6N8−Al)を作製した後、比抵抗を測定した。
また、比較例として純度が4Nレベルのアルミニウムである比較例1(4N−Al)および、純度が3Nレベルのアルミニウムである比較例2(3N−Al)を以下に示す。比較例1および2の比抵抗は計算により求めた。
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.
また、銅については純度が5Nレベルの銅である比較例3(5N−Cu)の比抵抗を測定した。 Moreover, about copper, the specific resistance of the comparative example 3 (5N-Cu) whose purity is 5N level copper was measured.
また、銅についてはさらに文献値データを比較例として用いた。比較例4は4Nレベルの銅サンプルであり、比較例5は5Nレベルの銅サンプルであり、比較例6は6Nレベルの銅サンプルである。 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)高純度アルミニウム材の作成
最初に実施例1〜3に用いた高純度アルミニウム材の作製方法を以下に示す。
・実施例1
純度99.92質量%の市販のアルミニウムを三層電解法により精製して、純度99.999質量%以上の高純度アルミニウムを得た。
詳しくは、Al−Cu合金層に99.92質量%の市販のアルミニウムを投入し、電解浴の組成を41%AlF3−35%BaF2−14%CaF2−10%NaFとして、760℃で電気を流し、陰極側に析出した高純度アルミニウムを採取した。
この高純度アルミニウム中の各元素含有量について、グロー放電質量分析法(サーモエレクトロン社製「VG9000」を使用)にて分析したところ、表1に示す通りであった。
(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).
・実施例2
上記三層溶解法で得られた高純度アルミニウムを一方向凝固法により精製して、純度99.9999質量%以上の高純度アルミニウムを得た。
詳しくは、ルツボ(内寸法:幅65mm×長さ400mm×高さ35mm)の中に2kgの三層溶解法で得た高純度アルミニウムを入れ、これを、炉体移動式管状炉の炉心管(石英製、内径100mm×長さ1000mm)の内部に収容し、1×10−2Paの真空雰囲気にて炉体(ルツボ)を700℃に温度制御して、高純度アルミニウムを溶解させた後、炉体を30mm/時の速度で炉心管から引き抜くことにより端部から一方向に凝固させた。そして、長さ方向において凝固開始端より50mmの位置から凝固開始端より150mmの位置までを切り出し、幅65mm×長さ100mm×厚さ30mmの塊状の超高純度アルミニウムを得た。
この超高純度アルミニウム中の各元素含有量について、上記と同様、グロー放電質量分
析法にて分析したところ、表1に示す通りであった。
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
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.
・実施例3
上記の一方向凝固法で得られた6Nアルミニウム塊から、約18mm×18mm×100mmの四角柱あるいは類似形状に切削加工で切出し、純水で希釈した20%塩酸水溶液で3時間酸洗浄したアルミニウム原料を得た。
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.
このアルミニウム原料を用いて以下の方法で帯溶融法を実施した。
帯溶融精製装置の真空チャンバ(外径50mm、内径46mm、長さ1400mmの石英管)内部に、グラファイトボートを配置した。グラファイトボートの原料配置部には、住友化学株式会社製の高純度アルミナ粉末AKPシリーズ(純度99.99%)を押圧しながら塗布してアルミナ層を形成した。
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.
グラファイトボートを真空下にて高周波加熱しベーキングした。
ベーキングは10−5〜10−7Paの真空中で、帯溶融に用いる高周波加熱コイル(加熱コイル巻数3、内径70mm、周波数約100kHz)にて加熱し、100mm/時間の速度でボートの一端から他端まで移動して、グラファイトボート全体を順に加熱して行った。
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.
上記のアルミニウム原料9本、合計重量約780gを、グラファイトボートに設けた20×20×1000mmの原料配置部に配置した。アルミニウム原料は9本全体で概ね四角柱とみなせるように配置した、アルミニウム原料の断面寸法w=18mm、長さL=900mm、L=w×50であった。 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.
チャンバ内を密閉し、ターボ分子ポンプおよび油回転ポンプにより圧力が1×10−5Pa以下になるまで排気した。その後、高周波加熱コイル(高周波コイル)によりアルミニウム原料の長手方向の一端を加熱し溶融させ溶融部を形成した。
溶融部の溶融幅が約70mmとなるように高周波電源(周波数100kHz、最大出力5kW)の出力を調整した。そして高周波コイルを毎時100mmの速度で移動させ、溶融部を約900mm移動させた。このときのチャンバ内の圧力は5×10−6〜9×10−6Paであった。溶融部の温度を放射温度計にて測定した結果、660℃〜800℃であった。
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 (
その後、徐々に高周波出力を下げて溶融部を凝固させた。
そして、高周波コイルを溶融開始位置(最初に溶融部を形成した位置)まで移動させ、チャンバ内を真空に維持したまま、溶融開始位置で再度アルミニウム原料を加熱溶融させて溶融部を形成した。この溶融部を移動させて帯溶融精製を繰り返した。溶融幅約70mm、溶融部の移動速度毎時100mmでの帯溶融精製を、合計3回(3パス)行った時点で、溶融開始部から終了部まで形状がほぼ均一となり、それ以降(以下に示す7パスの間)は均一な形状を維持した。
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).
次に、溶融幅約50mm、溶融部の移動速度毎時60mmにて帯溶融精製を7パス実施した。溶融幅は精製原料(アルミニウム原料)の断面寸法wに対し、w×2.8〜w×3.9であった。
合計10パス終了後にチャンバを大気開放し、アルミニウムを取り出し、長さ約950mmの精製アルミニウム材を得た。
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.
得られたアルミニウム材を切出して、上記と同様にグロー放電質量分析法組成分析を行った結果を表1に示す。 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.
次いで、上記で得られた実施例1〜3の高純度アルミニウム材それぞれを切削加工し、幅6mm×厚さ6mm×長さ100mmの伸線用素材を得た。伸線用素材表面の切削加工による汚染元素を除去するために、塩酸:純水=1:1の比率で作製した酸にて1時間の酸洗浄を行い、30分以上流水洗浄した。 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.
得られた伸線用素材を溝付きロール圧延および線引きにより、0.5φまで伸線(引き抜き)した。伸線した試料を石英治具に固定し、真空中にて500℃で3時間保持した後炉冷したものを比抵抗測定用のサンプルとした。
さらに、比較例3のサンプルとして市販の5Nレベルの高純度銅(NewMet Koch社製99.999%Cu、0.5φ)を石英治具に固定し、有機溶剤洗浄し、真空中にて500℃で3時間保持した後炉冷したものを比抵抗測定用のサンプルとした。
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)比抵抗の導出
・比抵抗の測定
実施例1〜3および比較例3のサンプルについては比抵抗を実際に測定した。
測定は、得られた上記のサンプルを液体ヘリウム(4.2K)中に浸漬した後、サンプルに印加する磁場を磁束密度0T(磁場を印加せず)〜15Tまで変化させて、4端子法で測定した。
磁場はサンプルの長手方向に平行な方向に印加した。
(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.
・比抵抗の算出
表1に示す組成を有する比較例1および比較例2については、文献:R.J.Corruccini, NBS Technical Note,218(1964)に記載の以下の(1)式を用いて計算した。(1)式では、ΔρHが磁場中での比抵抗の増加量である。ρRTは磁場が印加されないときの室温での比抵抗であり、3N以上の高純度Alではほぼ一定値として扱えるため2753nΩcmとした。ρは磁場が印加されないときの4.2Kでの比抵抗であり、純度により大きく変化するので、今回4N−Alでは9.42nΩcm(RRR=285)、3N−Alでは117nΩcm(RRR=23)の実験値を用いた。これらの式は磁場がサンプルの長手方向に垂直な場合に得られた式であるが、平行な場合の同様の式が得られていないため、今回比較のために使用した。RRRは残留抵抗比とも呼ばれ、297Kでの比抵抗とヘリウム温度(4.2K)での比抵抗の比である。
-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).
・比抵抗の文献からの引用
比較例4〜6については、その比抵抗を文献:Fujiwara S. et.al.,Int. Conf. Process. Mater. Prop., 1st (1993),909-912.より得た。なお、これらの文献値では、磁場の印可方向とサンプルの長手方向の関係は記載されていない。
このようにして導出した実施例1〜3および比較例1〜6の比抵抗を表2に示す。
RRRについては、実施例1〜3および比較例1〜3が測定値であり、比較例4〜6は文献値である。
-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.
表2より、従来のアルミニウム製(4Nレベル)の配線部材に相当する比較例2のサンプルは磁場のない時(0T)に比べ、磁場の強度(磁束密度)の増加とともに比抵抗が増えて、15Tでは、3倍程度にまで増加していることが判る。 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.
これに対して、実施例1〜3は、そもそも磁場のない状態で、比較例2と比べ10分の1以上と比抵抗が小さい上に、磁場が増加しても比抵抗の増加が小さい。
実施例1(5Nレベル)では、15Tの比抵抗は、磁場のない場合に比べ約1.5倍と比較例2と比べ明らかに増加が小さい。
実施例2(6Nレベル)では、磁場のない場合と比べ、15Tでもその比抵抗の増加は10%以内と非常に小さくなっている。また、磁束密度が1〜12Tの範囲では、その比抵抗の値は、磁場を印加しない場合より小さくなっており磁気抵抗抑制効果が顕著に表れている。
実施例3(6N8レベル)に至っては1〜15Tのいずれの磁束密度においても比抵抗が磁場のない場合より低くなっており磁気抵抗抑制効果が極めて顕著に表れている。
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.
図1は、導電性指数と印加した磁場(磁束密度)との関係を示すグラフである。導電性指数は4Nのアルミニウムの強磁場中での比抵抗を示す比較例2を基準として、それぞれのサンプルの導電性の大小を示す指数である。すなわち、それぞれの磁束密度において、比較例2の比抵抗の値をそれぞれのサンプルの比抵抗の値で割ることにより求める。この指数の値が大きいほど、比較例2サンプルと比べて、その磁束密度(強磁場)下での導電性が優れていることを示す。
実施例サンプルが極めて顕著な効果を示すことから、縦軸の導電性指数は対数で示した。
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.
図1から判るように実施例サンプルは、磁場がない場合で、比較例2と比べ導電性が13〜28倍程度高い。そして磁場が印加されるとともに、比較例2と比べた導電性が増加し、1Tでは16倍(実施例1)〜65倍(実施例3)であり、15Tでは、26倍(実施例1)〜96倍(実施例1)とさらに増加している。 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).
また、図1からは銅のサンプル(比較例3〜6)がいずれも右肩下がりの曲線を示しており、比較例2と比べ、磁場の強度が増加するほど磁気抵抗の効果が強くなることを示している。すなわち、銅の場合は、喩え6Nレベルまで純度を高めても磁気抵抗による導電性の低下を抑制することができないことを示しており(表1からも比較例3〜6のサンプルは15Tでの比抵抗が磁場のないときの比抵抗に比べ5〜18倍程度高くなっていることが判る)、本願発明者らが見出した、純度を99.999質量%以上まで高めることにより、磁場中での導電性の低下を抑制できるという効果がアルミニウムに特有のものであることを示している。 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.
なぜ、高純度化による磁気抵抗抑制効果がアルミニウムに出現し、銅に出現しないかは、不明であるが、電気抵抗要因の違いに起因していると推定できる。つまり、高純度銅の主要な電気抵抗要因は結晶粒界や転位による伝導電子の散乱であり、高純度化しても電気抵抗要因の変化は小さく、従って磁気抵抗も変化が小さいと考えられる。一方、高純度アルミニウムの主要な電気抵抗要因は不純物原子による伝導電子の散乱であり、高純度化するほど電気抵抗要因が減るため、5N以上のアルミニウムでは磁場中での電気抵抗増加が小さいという優れた特性が現れたのではないかと思われる。ただし、この推定のメカニズムは、本願発明の技術的範囲を制限するものではない。 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.
本願発明により、取り扱いが容易でかつ、かつ例えば磁束密度1T以上のような強磁場中でも優れた導電性を示す電気配線材を提供することができる。 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.
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JP2011101774A JP5749558B2 (en) | 2011-04-28 | 2011-04-28 | Wiring material for superconducting magnets |
US13/458,095 US20120275948A1 (en) | 2011-04-28 | 2012-04-27 | Wiring material for superconducting magnet |
FR1253958A FR2974658A1 (en) | 2011-04-28 | 2012-04-27 | WIRING MATERIAL FOR SUPERCONDUCTING MAGNET |
DE102012008605A DE102012008605A1 (en) | 2011-04-28 | 2012-04-27 | Cabling material for superconducting magnets |
CN2012101298841A CN102760507A (en) | 2011-04-28 | 2012-04-27 | Wiring material for superconducting magnet |
GB1207377.1A GB2490585A (en) | 2011-04-28 | 2012-04-27 | High purity aluminium material wire for strong magnetic field operation |
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