JPH03260083A - Production of high purity copper - Google Patents
Production of high purity copperInfo
- Publication number
- JPH03260083A JPH03260083A JP2060477A JP6047790A JPH03260083A JP H03260083 A JPH03260083 A JP H03260083A JP 2060477 A JP2060477 A JP 2060477A JP 6047790 A JP6047790 A JP 6047790A JP H03260083 A JPH03260083 A JP H03260083A
- Authority
- JP
- Japan
- Prior art keywords
- copper
- purity
- purity copper
- electrolytic
- current
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 70
- 229910052802 copper Inorganic materials 0.000 title claims abstract description 70
- 239000010949 copper Substances 0.000 title claims abstract description 70
- 238000004519 manufacturing process Methods 0.000 title claims description 9
- 238000000034 method Methods 0.000 claims description 19
- 238000005868 electrolysis reaction Methods 0.000 claims description 17
- 239000003792 electrolyte Substances 0.000 claims description 9
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 abstract description 8
- 239000000654 additive Substances 0.000 abstract description 3
- YDLQKLWVKKFPII-UHFFFAOYSA-N timiperone Chemical compound C1=CC(F)=CC=C1C(=O)CCCN1CCC(N2C(NC3=CC=CC=C32)=S)CC1 YDLQKLWVKKFPII-UHFFFAOYSA-N 0.000 abstract 1
- 229950000809 timiperone Drugs 0.000 abstract 1
- 239000012535 impurity Substances 0.000 description 15
- 238000007670 refining Methods 0.000 description 13
- 238000004857 zone melting Methods 0.000 description 4
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 239000008151 electrolyte solution Substances 0.000 description 3
- 239000010936 titanium Substances 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000007667 floating Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000010287 polarization Effects 0.000 description 2
- 238000005477 sputtering target Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 239000010409 thin film Substances 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- 229910001200 Ferrotitanium Inorganic materials 0.000 description 1
- 108010010803 Gelatin Proteins 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 239000005018 casein Substances 0.000 description 1
- BECPQYXYKAMYBN-UHFFFAOYSA-N casein, tech. Chemical compound NCCCCC(C(O)=O)N=C(O)C(CC(O)=O)N=C(O)C(CCC(O)=N)N=C(O)C(CC(C)C)N=C(O)C(CCC(O)=O)N=C(O)C(CC(O)=O)N=C(O)C(CCC(O)=O)N=C(O)C(C(C)O)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=O)N=C(O)C(CCC(O)=O)N=C(O)C(COP(O)(O)=O)N=C(O)C(CCC(O)=N)N=C(O)C(N)CC1=CC=CC=C1 BECPQYXYKAMYBN-UHFFFAOYSA-N 0.000 description 1
- 235000021240 caseins Nutrition 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229910000365 copper sulfate Inorganic materials 0.000 description 1
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 210000001787 dendrite Anatomy 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 239000012776 electronic material Substances 0.000 description 1
- 238000004993 emission spectroscopy Methods 0.000 description 1
- 229920000159 gelatin Polymers 0.000 description 1
- 239000008273 gelatin Substances 0.000 description 1
- 235000019322 gelatine Nutrition 0.000 description 1
- 235000011852 gelatine desserts Nutrition 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 238000009499 grossing Methods 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 238000009616 inductively coupled plasma Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000007788 roughening Methods 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
Landscapes
- Electrolytic Production Of Metals (AREA)
Abstract
Description
【発明の詳細な説明】
［産業上の利用分野］
本発明は、パルス電流電解による純度
９９．９９９ないし９９．９９９９９６程度の高純度銅
の製造方法に関する。DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to a method for producing high purity copper with a purity of about 99.999 to 99.999996 by pulsed current electrolysis.
［従来の技術］
一般に、銅はその加工性の良さ、導電性の良さのために
電子材料として広く使用されている。山でも表面実装技
術におけるボンディングワイヤや薄膜形成技術における
スパッタリングターゲットへの使用か注目されている。[Prior Art] Generally, copper is widely used as an electronic material due to its good workability and good conductivity. Attention is also being paid to its use in bonding wires in surface mount technology and sputtering targets in thin film formation technology.
通常、電気分解で得られた銅、すなわち電気銅は、不純
物元素としてＰｂＳＳｎ、Ａｇ５Ｆｅ。Usually, copper obtained by electrolysis, that is, electrolytic copper, contains PbSSn and Ag5Fe as impurity elements.
Ｎ１等の重金属元素、およびＳ、Ｃ，Ｏ等の元素を１な
いし２０ ｐｐｍの範囲で含有しており、その純度は９
９．９％程度である。このような電気銅を用いて作製さ
れたボンディングワイヤヤスバッタリングターゲットは
、その中に含有する不純物元素がそれぞれ表面実装工程
、薄膜形成工程において悪影響を及ぼす。このため、ボ
ンディングヮイヤやスパッタリングターゲット等に用い
られる銅は、不純物元素濃度をできるたけ低くすること
か望ましい。したかって、電気銅を９９．９９９００以
上の純度を（−ｊ゛するものに精錬する必要かある。Contains heavy metal elements such as N1 and elements such as S, C, and O in the range of 1 to 20 ppm, and its purity is 9.
It is about 9.9%. The impurity elements contained in the bonding wire sheath battering target produced using such electrolytic copper have an adverse effect on the surface mounting process and the thin film forming process, respectively. For this reason, it is desirable that the concentration of impurity elements in copper used for bonding wires, sputtering targets, etc. be as low as possible. Therefore, is it necessary to refine electrolytic copper to a purity of 99.99900 or higher (-j゛)?
従来の高純度銅の製造ｈ′法は、次のようにして行う。The conventional method h' for producing high-purity copper is carried out as follows.
まず、一般にＴ業的に製造された電気銅（純度９９．９
？ｏ）を陽極とし、純銅、チタンまたはステンレスのい
ずれかを陰極として電解液中に浸漬させる。電解液には
、銅分４０ないし５５ｇ／、１１゜遊離硫酸１００ない
し２２ Ｑ ｇ ／ １１を含有する酸性硫酸銅溶液を
用いる。次に、電解液温度４０ないし７０ ℃、電流密
度１ないし５ Ａ ／ ｄ ｍ ２の条件下で電解液を
直流電流による電解精錬（以下、直流電解精錬と呼ぶ）
を行い、陰極に銅を析出させる。その後、析出した銅に
ゾーンメルティング法、フローティングメルティング法
等の乾式精製を施して高純度銅を得る。First, electrolytic copper (purity 99.9
? o) is used as an anode, and pure copper, titanium, or stainless steel is used as a cathode and immersed in an electrolytic solution. As the electrolytic solution, an acidic copper sulfate solution containing 40 to 55 g/11 of copper and 100 to 22 Q g/11 of free sulfuric acid is used. Next, the electrolyte is electrolytically refined using a direct current (hereinafter referred to as DC electrolytic refining) under the conditions of an electrolyte temperature of 40 to 70°C and a current density of 1 to 5 A/dm2.
to deposit copper on the cathode. Thereafter, the precipitated copper is subjected to dry refining such as a zone melting method or a floating melting method to obtain high purity copper.
［発明か解決しようとする課題］
しかしなから、上記の直流電解精錬により得られた銅は
、？ｊ＆視的に見て表面か粗い。このため、残Ｈする不
純物元素か銅表面の四部に入り込み純度を低下させる。[Problem to be solved by the invention] However, what about the copper obtained by the above-mentioned DC electrolytic refining? j& Visually, the surface is rough. Therefore, the remaining H impurity elements enter the four parts of the copper surface and reduce the purity.
このように凹部に入り込んだ不純物は、１回の乾式精製
では除去できないので、多数回の乾式精製で除去しなく
てはならない。その結果、製造コストが非常に高くなる
。The impurities that have entered the recesses cannot be removed by one dry refining process, so they must be removed by multiple dry refining processes. As a result, manufacturing costs become very high.
この問題を解決するために、あらかしめニカワ、カゼイ
ン、ゼラチン、千オ尿素、ポリビニルアルコール、およ
び脂肪族スルホン化物の１種またはそれ以上を添加した
電解液を直流電解精錬して下漬な表面を持つ銅を得る方
法が行われている。しかし、この方法は、添加した有機
物質に含有されている硫黄元素が直流電解精錬中に銅に
析出して、得られる銅の純度を低下させる。このため、
この方法では９９．９９９％以上の純度の銅を得ること
ができない。In order to solve this problem, an electrolytic solution containing one or more of rough glue, casein, gelatin, 1,000 urea, polyvinyl alcohol, and aliphatic sulfonated substances was subjected to direct current electrolytic refining to obtain a rough surface. There are ways to get copper with. However, in this method, the sulfur element contained in the added organic substance is deposited on the copper during DC electrolytic refining, reducing the purity of the obtained copper. For this reason,
Copper with a purity of 99.999% or higher cannot be obtained by this method.
本発明はかかる点に鑑みてなされたものであり、９９．
９９９％以上の純度を有し、しかも表面の平滑度が高い
高純度銅を効率よく製造することができる高純度銅の製
造方法を提供することを目的とする。The present invention has been made in view of this point, and is based on 99.
It is an object of the present invention to provide a method for producing high-purity copper that can efficiently produce high-purity copper having a purity of 999% or more and a high surface smoothness.
［課題を解決するための手段］
本発明は、下記式Ｉて示されるデユーティ−サイクルが
０．０１ないし１〕、５、通電時間が１サイクル当たり
１０μｓｅｃないし１ｓｅｃｓ下記式ＩＩで示される平
均電流密度がし）、５〜５．０Ａ／ｄｍ２である条件下
で無添加物電解液をパルス電流電解することを特徴とす
る高純度銅の製造方法である。[Means for Solving the Problems] The present invention provides a duty cycle represented by the following formula I of 0.01 to 1]; This method of producing high-purity copper is characterized by subjecting an additive-free electrolyte to pulse current electrolysis under conditions of 5 to 5.0 A/dm2.
デユーティ−サイクル−Ｔ（／ （Ｔ＋ ＋Ｔ＞ ）・
・・ （１）
平均電流密度−１，・７１ ／ （Ｔ Ｉ ＋ Ｔ ２
）（ＩＩ）
（式１．Ｕ中、１１１．を通電電流、Ｔ ｒ ハＡ ’
４ ”ｉ ＆”）、Ｔ２は非通電時間である）
ここで、パルス電流電解後に得られた電解銅の乾式精製
を行うことが好ましい。なお、乾式精製には、ゾーンメ
ルティング法、フローティングメルティング法等が用い
られる。Duty cycle-T(/(T+ +T>)・
... (1) Average current density -1, 71 / (T I + T 2
)(II) (In formula 1.U, 111. energizing current, T r A'
4 "i &"), T2 is the non-current application time) Here, it is preferable to carry out dry refining of the electrolytic copper obtained after pulsed current electrolysis. In addition, a zone melting method, a floating melting method, etc. are used for dry refining.
デユーティ−サイクルは、０．０１ないしｒ〕、５に設
定する。これは、デユーティ−サイクルか０．０１未満
であると電流効率か低すぎて生産性か悪＜、デユーティ
−サイクルか０．５を超えると得られる銅の表面か粗く
なるからである。The duty cycle is set to 0.01 to 5. This is because when the duty cycle is less than 0.01, the current efficiency is too low and productivity is poor, and when the duty cycle is more than 0.5, the surface of the resulting copper becomes rough.
通電時間は、］サイクル当たり１０μｓｅｃないし１
ｓｅｃに設定する。これは、通電時間か１サイクル当た
り１０μｓｅｃ未満であると電流効率が低すぎて生産性
か悪く、通電時間が１サイクル当たり１ ｓｅｃを超え
ると得られる銅の表面が粗くなるからである。なお、１
サイクルは、１回の通電状態と１回の非通電状態で構成
される。The energization time is 10 μsec to 1 per cycle.
Set to sec. This is because if the energization time is less than 10 μsec per cycle, the current efficiency will be too low and productivity will be poor, and if the energization time exceeds 1 sec per cycle, the surface of the resulting copper will become rough. In addition, 1
A cycle consists of one energized state and one non-energized state.
平均電流密度は、０．５〜５．０Ａ／ｄｍ２に設定する
。これは、平均電流密度か０．５Ａ／ｄｍ２未満である
と銅が析出せず、平均電流密度か５．０Ａ／ｄｍ２を超
えると得られる銅の表面が粗くなるからである。The average current density is set to 0.5 to 5.0 A/dm2. This is because copper does not precipitate when the average current density is less than 0.5 A/dm2, and when the average current density exceeds 5.0 A/dm2, the surface of the resulting copper becomes rough.
また、電解液の温度は特に定めないが、３５ないし６５
℃が好ましい。In addition, the temperature of the electrolyte is not particularly determined, but is between 35 and 65
°C is preferred.
［作用］
本発明の高純度銅の製造方法は、デューティーサイクル
か０．０１ないし０．５、通電■、１間か１サイクル当
たり１０μＳｅｅないし１ ｓｅｃ 、平均電流密度が
０．５〜５．０Ａ／ｄｍ’である条件下におけるパルス
電流電解法を用いる。パルス電流電解法は、第１図に示
すような波形１のパルスで電流を通電して電解を行うも
のである。すなわち、第１図においで、電流量■１を時
間Ｔまたけ通電する状態と、時間Ｔ２だけ通電しない状
態を繰り返して行うものである。[Function] The method for producing high-purity copper of the present invention has a duty cycle of 0.01 to 0.5, electrification (1), 10 μSee to 1 sec per cycle, and an average current density of 0.5 to 5.0 A. A pulsed current electrolysis method under the condition of /dm' is used. In the pulsed current electrolysis method, electrolysis is performed by applying a current with pulses having a waveform 1 as shown in FIG. That is, in FIG. 1, a state in which the current amount 1 is applied for a time T and a state in which the current is not applied for a time T2 are repeated.
この方法において、非通電時間Ｔ２内に、陰極表面濃度
の低下、すなわち濃度分極が減少される。In this method, the cathode surface concentration decreases, that is, the concentration polarization is reduced during the non-current application time T2.
このため、陰極の濃度分極による高純度銅表面の粗面化
を防止し、針状晶や樹枝状結晶（デンドライト）の発生
を抑制する。Therefore, roughening of the high-purity copper surface due to concentration polarization of the cathode is prevented, and generation of needle crystals and dendrites is suppressed.
また、上記のような条件設定を行うことにより、９９．
９９９％以上の高純度であり、しかも表面が平滑である
高純度銅を得ることができる。Also, by setting the conditions as described above, 99.
High purity copper with a purity of 999% or more and a smooth surface can be obtained.
さらに、得られた高純度銅を乾式精製することにより、
より高純度の銅を製造することができる。Furthermore, by dry refining the obtained high purity copper,
Higher purity copper can be produced.
［実施例］
以下、本発明の高純度銅の製造方法を具体的に説明する
。[Example] Hereinafter, the method for producing high-purity copper of the present invention will be specifically described.
実施例１
電気銅を陽極とし、チタン板を陰極として、５０ ｇ
／ Ｉの銅分および１５０ｇ／ｇの遊離硫酸を金白゛す
る電解液中に浸漬して、パルス電流電解を総通電時間、
２０時間で行った。ここで、電気銅は、工業的に製造さ
れたもので純度が９９．９％であり、Ａｇを１６ｐｐｍ
ＳＳを８ｐｐＩＩＳＦｅを４ ｐｐ＋ａ含有するもので
ある。また、電解液には表面平滑剤等の添加物を加えな
かった。なお、パルス電流電解は、デユーティ−サイク
ルがＱ、２、通電時間が１サイクル当たり１１１ｓｅｅ
、平均電流密度が２Ａ／ｄｍ”、電解液温度が５５℃の
条件下で行った。なお、パルス電流電解の条件はド記第
１表に示す。このようにして、高純度銅を製造した。Example 1 Electrolytic copper as an anode and a titanium plate as a cathode, 50 g
/ I copper content and 150 g/g free sulfuric acid were immersed in a gold-plated electrolyte, and pulsed current electrolysis was carried out for a total energizing time,
I did it in 20 hours. Here, electrolytic copper is industrially produced and has a purity of 99.9%, and contains 16 ppm of Ag.
It contains 8 pp of SS and 4 pp+a of IISFe. Furthermore, no additives such as surface smoothing agents were added to the electrolyte. In addition, in pulse current electrolysis, the duty cycle is Q, 2, and the current application time is 111sees per cycle.
The electrolysis was carried out under the conditions of an average current density of 2 A/dm'' and an electrolyte temperature of 55°C.The conditions for pulsed current electrolysis are shown in Table 1.In this way, high purity copper was produced. .
得られた高純度銅の表面の平滑性、不純物元素濃度、電
流効率を調べた。その結果を下記第１表に併記する。な
お、表面の平滑度は、ルーペを用いて１０倍に拡大して
目蜆により観察し、・ｌソ滑な結晶の場合を良、樹脂状
もしくは粉状結晶の場合を不良とした。また、不純物元
素濃度は、高周波誘導結合プラズマ（ＩＣＰ）発光分光
分析により測定した。電流効率は、通電した総電流員に
対する実際に銅の析出に寄与した電流の割合を算出した
値を示した。The surface smoothness, impurity element concentration, and current efficiency of the obtained high-purity copper were investigated. The results are also listed in Table 1 below. The smoothness of the surface was observed using a magnifying glass at 10 times magnification, and was evaluated as good in the case of smooth crystals and poor in the case of resin-like or powdery crystals. Further, the impurity element concentration was measured by high frequency inductively coupled plasma (ICP) emission spectrometry. The current efficiency was a calculated value of the ratio of the current that actually contributed to the deposition of copper to the total current that was applied.
実施例２〜５．比較例１〜６
下記第１表に示す条件でパルス電流電解を行うことを除
いて、実施例１と同様にして高純度銅を製造した。Examples 2-5. Comparative Examples 1 to 6 High purity copper was produced in the same manner as in Example 1, except that pulse current electrolysis was performed under the conditions shown in Table 1 below.
得られた高純度銅の表面の平滑性、不純物元素濃度、電
流効率を実施例１と同様にして調べた。The surface smoothness, impurity element concentration, and current efficiency of the obtained high-purity copper were examined in the same manner as in Example 1.
その結果を下記第１表に併記する。The results are also listed in Table 1 below.
実施例６
実施例１と同様にして高純度銅を製造した。次に、得ら
れた高純度銅にゾーンメルティング法により乾式精製を
１回行った。Example 6 High purity copper was produced in the same manner as in Example 1. Next, the obtained high-purity copper was subjected to one dry refining process using a zone melting method.
精製後の高純度銅の不純物元素濃度を実施例１と同様に
して調べた。その結果を下記第１表に併記する。The concentration of impurity elements in the purified high-purity copper was investigated in the same manner as in Example 1. The results are also listed in Table 1 below.
従来例１
電気銅を陽極とし、チタン板を陰極として、５０ｇ／ｌ
）の銅分および１’５０ｇ／Ｄの遊離硫酸を含有する電
解液中に浸漬して、電流密度が２Ａ／ｄｍ２、電解液温
度が５５℃の条件下で直流電解を２０時間行った。ここ
で、電気銅は、工業的に製造されたもので純度が９９．
９％であり、Ａｇを１６ｐｐｍ、ＳをｇｐｐＨ，Ｆｅを
４ ｐｐｎ＋含有するものである。このようにして、電
解銅を製造した。Conventional example 1 Electrolytic copper is used as an anode, titanium plate is used as a cathode, 50 g/l
) and 1'50 g/D of free sulfuric acid, and DC electrolysis was performed for 20 hours at a current density of 2 A/dm2 and an electrolyte temperature of 55°C. Here, electrolytic copper is industrially produced and has a purity of 99.
It contains 16 ppm of Ag, gppH of S, and 4 ppn+ of Fe. In this way, electrolytic copper was produced.
得られた電解銅の表面の平滑性、不純物元素濃度、電流
効率を実施例１と１６１様にして調べた。その結果を下
記第１表に併記する。The surface smoothness, impurity element concentration, and current efficiency of the obtained electrolytic copper were examined in the same manner as in Examples 1 and 161. The results are also listed in Table 1 below.
従来例２
従来例１と同様にして電解銅を製造した。次に、得られ
た電解銅にゾーンメルティング法により乾式精製を１回
行った。Conventional Example 2 Electrolytic copper was produced in the same manner as in Conventional Example 1. Next, the obtained electrolytic copper was subjected to one dry refining process using a zone melting method.
精製後の電解銅の不純物元素濃度を実施例１と同様にし
て調べた。その結果を下記第１表に併記する。The concentration of impurity elements in the purified electrolytic copper was investigated in the same manner as in Example 1. The results are also listed in Table 1 below.
第１表から明らかなように、本発明の方法により製造さ
れた高純度銅（実施例１〜６）は、パルス電流電解を行
ったにもかかわらず７０％以上の電流効率であり、不純
物量が少なく高純度（９９゜９９９％以上）のものであ
り、表面の平滑性も良好であった。特に乾式精製を行っ
た高純度銅（実施例６）は、かなりの高純度のものであ
った。また、本発明にかかる方法により製造された高純
度銅（実施例１〜６）は導電性および低温軟化特性に優
れ、比較的軟質のものであった。As is clear from Table 1, the high-purity copper produced by the method of the present invention (Examples 1 to 6) had a current efficiency of 70% or more even though pulsed current electrolysis was performed, and the amount of impurities was It was of high purity (99°999% or more) with little oxidation and had good surface smoothness. In particular, the high purity copper that was dry refined (Example 6) was of considerably high purity. Moreover, the high-purity copper produced by the method according to the present invention (Examples 1 to 6) had excellent conductivity and low-temperature softening properties, and was relatively soft.
これに対して、従来の方法により製造された電解銅（従
来例１）は、不純物量か多く、しかも表面の平滑性も悪
いものであった。また、得られた電解銅に乾式精製を行
ったもの（従来例２）も、不純物量が多かった。On the other hand, electrolytic copper produced by the conventional method (Conventional Example 1) contained a large amount of impurities and had poor surface smoothness. Furthermore, the obtained electrolytic copper that was subjected to dry refining (Conventional Example 2) also had a large amount of impurities.
また、本発明の範囲外のデユーティ−サイクル、通電時
間、平均電流密度等のパルス電流電界条件で製造された
電解銅（比較例１〜６）は、不純物量、表面平滑性、電
流効率等が劣るものであった。In addition, electrolytic copper (Comparative Examples 1 to 6) manufactured under pulsed current electric field conditions such as duty cycle, energization time, and average current density that are outside the range of the present invention has poor impurity content, surface smoothness, current efficiency, etc. It was inferior.
［発明の効果］
以上説明した如く、本発明の高純度銅の製造方法は、９
９．９９９％ないし９９．９９９９％の純度を有し、し
かも表面の平滑度が高い高純度銅を効率よく製造するこ
とができるものである。[Effect of the invention] As explained above, the method for producing high-purity copper of the present invention has 9
High purity copper having a purity of 9.999% to 99.9999% and a highly smooth surface can be efficiently produced.
第１図は本発明に使用されるパルス電流電解におけるパ
ルス波形を示す特性図である。
１・・・パルス波形。FIG. 1 is a characteristic diagram showing a pulse waveform in pulsed current electrolysis used in the present invention. 1...Pulse waveform.
Claims (2)
．０１ないし０．５、通電時間が１サイクル当たり１０
μｓｃｃないし１ｓｃｃ、下記式IIで示される平均電流
密度が０．５〜５．０Ａ／ｄｍ＾２である条件下で無添
加物電解液をパルス電流電解することを特徴とする高純
度銅の製造方法。 デューティーサイクル＝Ｔ＿１／（Ｔ＿１＋Ｔ２）・・
・（ I ） 平均電流密度＝Ｉ＿１・Ｔ＿１／（Ｔ＿１＋Ｔ＿２）・
・・（II） （式 I 、II中、Ｉ＿１は通電電流、Ｔ＿１は通電時間
、Ｔ＿２は非通電時間である）(1) The duty cycle shown by the formula I below is 0.
．． 01 to 0.5, energizing time is 10 per cycle
Production of high-purity copper characterized by pulse current electrolysis of an additive-free electrolyte under conditions of μscc to 1scc and an average current density of 0.5 to 5.0 A/dm^2 represented by the following formula II. Method. Duty cycle = T_1/(T_1+T2)...
・(I) Average current density=I_1・T_1/(T_1+T_2)・
...(II) (In formulas I and II, I_1 is the energizing current, T_1 is the energizing time, and T_2 is the non-energizing time)
行うものである請求項１記載の高純度銅の製造方法。(2) The method for producing high-purity copper according to claim 1, wherein the electrolytic copper obtained after pulsed current electrolysis is dry-refined.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2060477A JPH03260083A (en) | 1990-03-12 | 1990-03-12 | Production of high purity copper |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2060477A JPH03260083A (en) | 1990-03-12 | 1990-03-12 | Production of high purity copper |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH03260083A true JPH03260083A (en) | 1991-11-20 |
Family
ID=13143395
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2060477A Pending JPH03260083A (en) | 1990-03-12 | 1990-03-12 | Production of high purity copper |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH03260083A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2014533778A (en) * | 2011-11-22 | 2014-12-15 | ナノメタルルギ スプウカ アクツィーナ | Process for industrial copper electrorefining |
| CN104694978A (en) * | 2013-12-05 | 2015-06-10 | 阳谷祥光铜业有限公司 | Waste electrolyte treatment method and device |
-
1990
- 1990-03-12 JP JP2060477A patent/JPH03260083A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2014533778A (en) * | 2011-11-22 | 2014-12-15 | ナノメタルルギ スプウカ アクツィーナ | Process for industrial copper electrorefining |
| CN104694978A (en) * | 2013-12-05 | 2015-06-10 | 阳谷祥光铜业有限公司 | Waste electrolyte treatment method and device |
| CN104694978B (en) * | 2013-12-05 | 2018-03-23 | 阳谷祥光铜业有限公司 | The processing method and processing unit of a kind of waste electrolyte |
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