JPS6396298A - Insoluble anode made of lead alloy - Google Patents
Insoluble anode made of lead alloyInfo
- Publication number
- JPS6396298A JPS6396298A JP24141886A JP24141886A JPS6396298A JP S6396298 A JPS6396298 A JP S6396298A JP 24141886 A JP24141886 A JP 24141886A JP 24141886 A JP24141886 A JP 24141886A JP S6396298 A JPS6396298 A JP S6396298A
- Authority
- JP
- Japan
- Prior art keywords
- anode
- alloy
- insoluble anode
- insoluble
- lead
- 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.)
- Granted
Links
- 229910000978 Pb alloy Inorganic materials 0.000 title claims description 15
- 238000005260 corrosion Methods 0.000 claims abstract description 27
- 230000007797 corrosion Effects 0.000 claims abstract description 27
- 239000000463 material Substances 0.000 claims abstract description 24
- 229910052738 indium Inorganic materials 0.000 claims abstract description 8
- 229910052716 thallium Inorganic materials 0.000 claims abstract description 4
- 239000012535 impurity Substances 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 abstract description 18
- 238000007747 plating Methods 0.000 abstract description 13
- 238000009713 electroplating Methods 0.000 abstract description 10
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 abstract description 7
- 229910052751 metal Inorganic materials 0.000 abstract description 7
- 239000002184 metal Substances 0.000 abstract description 7
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 abstract description 6
- 229910000846 In alloy Inorganic materials 0.000 abstract description 5
- 229910052802 copper Inorganic materials 0.000 abstract description 4
- 239000010949 copper Substances 0.000 abstract description 4
- 239000011889 copper foil Substances 0.000 abstract description 4
- 239000000203 mixture Substances 0.000 abstract description 4
- 239000011248 coating agent Substances 0.000 abstract description 3
- 238000000576 coating method Methods 0.000 abstract description 3
- 239000003792 electrolyte Substances 0.000 abstract description 3
- 229910052719 titanium Inorganic materials 0.000 abstract description 3
- 229910052742 iron Inorganic materials 0.000 abstract description 2
- 229910052758 niobium Inorganic materials 0.000 abstract description 2
- 229910052715 tantalum Inorganic materials 0.000 abstract description 2
- 239000007769 metal material Substances 0.000 abstract 1
- 239000011888 foil Substances 0.000 description 16
- 238000002844 melting Methods 0.000 description 9
- 229910045601 alloy Inorganic materials 0.000 description 7
- 239000000956 alloy Substances 0.000 description 7
- 230000008018 melting Effects 0.000 description 7
- YADSGOSSYOOKMP-UHFFFAOYSA-N dioxolead Chemical compound O=[Pb]=O YADSGOSSYOOKMP-UHFFFAOYSA-N 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- 229910000831 Steel Inorganic materials 0.000 description 5
- 239000010959 steel Substances 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 230000004580 weight loss Effects 0.000 description 5
- 230000008901 benefit Effects 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 230000001965 increasing effect Effects 0.000 description 4
- 238000012423 maintenance Methods 0.000 description 4
- 238000005096 rolling process Methods 0.000 description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- 238000003466 welding Methods 0.000 description 3
- 229910020174 Pb-In Inorganic materials 0.000 description 2
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- 239000010953 base metal Substances 0.000 description 2
- 238000005266 casting Methods 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000000151 deposition Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000005246 galvanizing Methods 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 239000010970 precious metal Substances 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 238000004062 sedimentation Methods 0.000 description 2
- 239000010802 sludge Substances 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- 239000013585 weight reducing agent Substances 0.000 description 2
- 239000007832 Na2SO4 Substances 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 229910001007 Tl alloy Inorganic materials 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000000052 comparative effect Effects 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
- 238000005520 cutting process Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000010828 elution Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 229910052745 lead Inorganic materials 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000010446 mirabilite Substances 0.000 description 1
- 239000010955 niobium Substances 0.000 description 1
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 238000005476 soldering Methods 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Abstract
Description
【発明の詳細な説明】
本発明は、鉛合金製不溶性陽極に関するものであシ、特
には硫酸系浴にて優れた耐食性を有するＰｂ−ＴノーＩ
ｎ系不溶性陽極に関する。本発明陽極は高電流密度下で
さえも優れた耐食性を示すので、近時採用される傾向に
ある高電流密度に対応しうる機能型１１極であシ、特に
金属電気メツキ用途や電解金属箔製造用途、電解精錬用
途等に好適に用いられる。特定的には、電気亜鉛厚メッ
キや電解鋼箔製造に有用に用いられる。本発明Ｎ極の使
用によシ生産ライン速度の上昇、メッキ説或いは金Ｎ箔
形成のスピードアップ等の生産性の向上が図れると同時
に、腐食猷の減少に伴う！！極寿命の延長、浴管理及び
保守の容易化といった多くのメリットが得られる。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to an insoluble anode made of lead alloy, and in particular to an insoluble anode made of lead alloy.
This invention relates to an n-based insoluble anode. The anode of the present invention exhibits excellent corrosion resistance even under high current densities, so it can be used as a functional 11-pole type that can handle the high current densities that have recently been adopted, especially for metal electroplating applications and electrolytic metal foil applications. Suitable for use in manufacturing, electrolytic refining, etc. Specifically, it is usefully used in electrolytic thick plating and electrolytic steel foil production. By using the N-pole of the present invention, it is possible to improve productivity by increasing production line speed, speeding up plating process or gold N foil formation, and at the same time, reduce corrosion. ! Many benefits can be obtained, such as extended service life and easier bath management and maintenance.
発明の背景
電気メツキ技術は、云うまでもなく、耐食性付与その他
機々の目的のために工業界に不可欠の重要な技術であ）
、鉄鋼材料ストリップ、銅板等の被メッキ材にＺｎｓ
Ｓ ｎｑ Ｎ Ｌ ＣｕＮ Ｆ ｅその他並びにその合
金を電気メッキすることが広く行われている。Background of the Invention Electroplating technology is, needless to say, an important technology indispensable to the industrial world for imparting corrosion resistance and other purposes.)
, Zns on materials to be plated such as steel material strips and copper plates.
Electroplating of S nq N L CuN Fe, etc. and alloys thereof is widely practiced.
中でも、鉄鋼材料の電気亜鉛メッキの普及は著しく、自
動車、家電製品等の分野で需要が増大している。Among these, electrolytic galvanizing of steel materials has become extremely popular, and demand is increasing in the fields of automobiles, home appliances, etc.
とシわけ、自動車の車体の電気亜鉛メッキにおいては亜
鉛付＠量の多い厚亜鉛メッキが求められ、高電流密度を
使用しての電気メツキ操業が実施されつつある。従来、
可溶性＠極が用いられていたが、上記のような高電流密
度化に対応するべくまた可溶性陽極の使用に伴うメッキ
液管理の困難さ、極間ピッチの拡大による保守の面倒さ
といった難点を解消するため、現在では不溶性＠極が脚
光をあび、可溶性陽極から不溶性陽極への転換が進行中
である。In particular, in the electrogalvanizing of automobile bodies, thick galvanizing with a large amount of zinc is required, and electroplating operations using high current densities are being implemented. Conventionally,
Soluble @ electrodes were used, but in order to cope with the high current density mentioned above, we also solved the difficulties associated with the use of soluble anodes, such as the difficulty in managing the plating solution and the troublesome maintenance due to the increased pitch between the electrodes. Therefore, insoluble @ electrodes are currently in the spotlight, and the transition from soluble anodes to insoluble anodes is underway.
更に、電解金属箔、特に銅箔の製造においても不溶性陽
極が用いられる。電解鋼箔の製造は、例えばチタン製の
ドラムのほぼ３時〜６時及び６時〜９時の位置に一定の
間隔を置いて不溶性陽極を対置せしめ、ドラムと不溶性
陽極間の間隙に硫酸銅液を循回せしめ、陰極としてのド
ラム周囲に銅を尼着せしめ、連続的に電層した銅箔をド
ラムから剥ぎ取ることによって為されている。鋼箔はエ
レクトロニクス産業において大組に用いられ、その生産
性を高めるために従来よシ高電流密度での操業が検討さ
れつつある。Furthermore, insoluble anodes are also used in the production of electrolytic metal foils, especially copper foils. In the production of electrolytic steel foil, for example, insoluble anodes are placed on a titanium drum at regular intervals at approximately 3 o'clock to 6 o'clock and 6 o'clock to 9 o'clock positions, and copper sulfate is placed in the gap between the drum and the insoluble anode. This is done by circulating a liquid, depositing copper around the drum as a cathode, and then peeling off the continuous conductive layer of copper foil from the drum. Steel foils are used extensively in the electronics industry, and in order to increase productivity, operations at higher current densities than conventionally are being considered.
このように、不溶性陽極はメッキ及び箔製造等において
瓜要な地位を占めている。Thus, insoluble anodes occupy an important position in plating, foil manufacturing, and the like.
従来技術とその問題点
不溶性陽極としては、従来、鉛製のものが主と、して使
用されていた。その理由は、鉛はメッキ液や箔製造電解
液に対して耐食性があシ、そしてメッキ通電によってそ
の表面に二〇化鉛が生成され、この二酸化鉛が放電面と
して好適に作用するからである。Prior Art and Its Problems Conventionally, insoluble anodes have been mainly made of lead. The reason for this is that lead has poor corrosion resistance against plating solutions and foil manufacturing electrolytes, and lead dioxide is generated on the surface when the plating current is applied, and this lead dioxide acts suitably as a discharge surface. .
しかしながら、生成する二酸化鉛は内部歪を有するため
鉛表面から剥離しやすく、不溶性陽極の耐久力が乏しい
という重大な欠点が９ｆｌされるようになった。However, since the lead dioxide produced has internal strain, it easily peels off from the lead surface, and the insoluble anode has a serious drawback of poor durability.
主として電気メッキを例にとって従来技術を検討してみ
ると、この剥離対策として、船中に種々の合金成分を含
有させた鉛合金の使用が提唱されている。そうした中で
、Ｐｂ−Ｉｎ及びＰｂ−’ｒ！の鉛合金は基本的に良好
な挙動を示す。例えば特開昭５９−２８５９８号はｐｂ
−１５−１０％Ｉｎ或いはｐｂ−α５〜１０％Ｉｎ−１
５〜１０％Ａｇを開示する。特公昭６〇−４５７ｔ８号
は、Ｐｂ−ｃＬ８〜６％Ｔｊ或いはＰｂ−［１８〜６％
Ｔ７−ＣＬ３〜６％Ａ、９ を開示する。両者ともＰｂ
−Ｉｎ或いはＰｂ−Ｔｊの耐食性を改善するためにＡｇ
の添加を記載している。Examining the prior art, mainly taking electroplating as an example, the use of lead alloys containing various alloy components has been proposed as a countermeasure against this peeling. Under such circumstances, Pb-In and Pb-'r! Lead alloys exhibit basically good behavior. For example, JP-A No. 59-28598 is pb
-15-10%In or pb-α5-10%In-1
5-10% Ag is disclosed. Special Publication No. 60-457t8 is Pb-cL8~6%Tj or Pb-[18~6%
T7-CL3-6%A,9 is disclosed. Both are Pb
-Ag to improve the corrosion resistance of In or Pb-Tj
The addition of
しかしながら、Ａｇの添加は
（イ） Ａｇは高価な貴金属である
（口） Ａｇはｐｂに比較して融点が高い点で不溶性
陽極用添加元素として必ずしも好ましいものでなく、ま
たその耐食性増大効果も充分とは云えない。特に、高電
流密度下ではＰｂ−Ｉｎ−（Ａｇ）及びＰｂ−Ｔｊ−（
Ａｇ） いずれも所期の耐食性を示さない。However, the addition of Ag is not necessarily preferable as an additive element for insoluble anodes because (a) Ag is an expensive noble metal (2) Ag has a higher melting point than PB, and its corrosion resistance increasing effect is not sufficient I cannot say that. In particular, under high current density, Pb-In-(Ag) and Pb-Tj-(
Ag) None of them showed the expected corrosion resistance.
最初に述べた通電、斯界では、電気メッキ、電解箔製造
等において高電流密度化操業採用の傾向にあシ、従って
低電流密度下のみならず高電流密度下でも優れた耐食性
を示し、しかも製造加工等を容易ならしめる低融点型の
不溶性陽極の開発が要望されている。In the electrical conduction industry mentioned at the beginning, there is a trend toward high current density operation in electroplating, electrolytic foil manufacturing, etc., and therefore it shows excellent corrosion resistance not only under low current density but also under high current density. There is a need for the development of a low melting point insoluble anode that can be easily processed.
発明の目的
こうした状況に鑑み、本発明は、金属メッキ、電解箔製
造等の各種電解操業において、高価な貴金属を含まず、
鉛よシ融点の高い成分を含まず、そして高電流密度下で
も優れた耐食性を示す鉛合金製不溶性陽極の開発を目的
とする。Purpose of the Invention In view of these circumstances, the present invention aims to provide a method that does not contain expensive precious metals in various electrolytic operations such as metal plating and electrolytic foil production.
The objective is to develop an insoluble lead alloy anode that does not contain components with higher melting points than lead and exhibits excellent corrosion resistance even under high current densities.
上記目的に向は鋭意研究の結果、ＴｌとＩｎとの併用が
上記目的に対してきわめて有益であるとの知見を得た。As a result of intensive research aimed at the above-mentioned purpose, it has been found that the combination of Tl and In is extremely beneficial for the above-mentioned purpose.
これ亥でＰｂ−Ｉｎ或いはＰｂ−Ｔｊと１或いはＩｎ
の単独添加は為されていたが、その組合せ添加の試みは
為されたことはなかった。ＴｊとＩｎ の併用が高′
＃１ｔＮ、密度下での耐食性に有益に寄与することは先
行技術からは全く示唆されず、新たな意＠ある知見であ
る。実験の結果、重量％で、ａ５〜９％Ｔ７とＱ、０１
〜６％Ｉｎ との組合せが効果的であることが判明し
た。In this case, Pb-In or Pb-Tj and 1 or In
have been added individually, but no attempt has been made to add them in combination. Combined use of Tj and In is high
The prior art does not suggest that #1tN contributes beneficially to corrosion resistance under high density conditions, and this is a new and interesting finding. As a result of the experiment, in weight%, a5-9%T7 and Q,01
A combination with ~6% In was found to be effective.
斯くして、本発明は、重量％で表わしてα５〜９％ＴＩ
及び１０１〜６％Ｉｎを含有し、残部が鉛と不可避的
不純物から成る鉛合金を放電部とする不溶性陽極を提供
するものである。Thus, the present invention provides α5-9% TI expressed in weight percent.
and 101 to 6% In, with the remainder being lead and inevitable impurities, as a discharge part.
本発明において、「高電流密度」とは、１００Ａ／ｄｍ
２以上、通常は１６０ Ａ／ｄｍ２以上、最適には２０
０Ａ７ｄｍ２のオーダの電流密度を云う。箔製造の場合
＆′１５０Ａ／’ｄｍ２以上を一般に指す。In the present invention, "high current density" means 100A/dm
2 or more, usually 160 A/dm2 or more, optimally 20
It refers to a current density on the order of 0A7dm2. In the case of foil manufacturing, it generally refers to >&'150 A/'dm2.
不溶性陽極は、
（イ）機能面から見ると、
ｔ 高ＴＩＥ ’ｔＡ Ｎ度に対応しうるので、メッキ
や箔製造ライン速度の上昇＜’ａ造２インの短縮）及び
メッキ膜及び箔形成のスピードアップを図ることが出来
、厚メッキや電解銅箔製造にきわめて適応性を示すこと
、
２、 合金メッキの同時析出に適すること、五 メッキ
膜及び箔の均質、均一化を為しうろこと、
４、 浴中への溶出速度量を減少しうること（ロ）操業
面から見ると、
（１）極間ピッチがほとんど変らないので保守が容易で
あること、
（２）浴組成管理が簡易化すること
（５）スラッジ沈降剤等の添加ｆｆ１ｔ−減少しうるこ
と
の点で電気メッキ用或いは箔製造用等の電解操業用陽極
として優れたものであ）、これによシメツキ製品品質の
向上とコストダウンが可能となる０不溶性陽極の耐食性
が増大する程こうしたメリットは増々増大する。(a) From a functional point of view, insoluble anodes can handle high TIE'tAN degrees, so they can increase plating and foil production line speeds <shorten 2-in. 2. Suitable for simultaneous deposition of alloy plating; 5. Scales that can make the plating film and foil homogeneous; 4. The rate of elution into the bath can be reduced (b) From an operational perspective, (1) maintenance is easy as the pitch between electrodes hardly changes, (2) bath composition management is simplified. (5) Addition of sludge sedimentation agent, etc. It is excellent as an anode for electrolytic operations such as electroplating or foil manufacturing in that it can reduce ff1t), thereby improving the quality of the shimetsu product. These advantages will increase as the corrosion resistance of the zero-insoluble anode increases, making it possible to reduce costs.
本発明に従えば、ｐｂに、ＴＩが（Ｌ５〜９重量噂、好
ましくは３〜９創りそしてＩｎが００１〜６重量％、好
ましくは（１５〜３重世％添加される。ＰｂにＴＩ ’
Ｉｔ添加すると耐食性が向上し、更に各Ｔｌ水準のＰｂ
−Ｔｌ合金にＩｎを添加すると成るＩｎ添加社範囲で耐
食性が格段に向上する。従って、ＴＩ 添加水準に応
じて最適のＩｎ 添加量が選定される。According to the present invention, to Pb, TI is added (L5-9% by weight, preferably 3-9% by weight, and In is added by 001-6% by weight, preferably 15-3% by weight.TI' is added to Pb.
Addition of It improves corrosion resistance, and further improves Pb at each Tl level.
- When In is added to the Tl alloy, corrosion resistance is significantly improved within the range of In addition. Therefore, the optimum amount of In to be added is selected depending on the TI addition level.
後に実施例に示すように例えば次のような耐食性向上効
果が得られる（比較基準純ｐｂの重量減−８，５■／Ａ
−ｈｒ）：
Ｔｚ（％） Ｉｎ（％） 重量減（ａｐ／Ａ−
ｈｒ）α５ ３ α９２
１ １〜５ α７〜α９１５
α５へ５ α１９〜α５３５
α５〜５ ［１２〜α４６
９ １２５〜３ ０．２〜α９３Ｔｌ
が効果を奏するには最小限α５％必要である。他方
Ｉｎとの併添の下ではＴ）は９％を越えると効果が飽和
する。Ｉｎは最適ＴＩとの組合せにおいて１０１％で効
果を奏するが、６％を越えて添加すると逆効果となる。As shown in the examples later, the following corrosion resistance improvement effect can be obtained (weight reduction of comparison standard pure PB -8.5 /A
-hr): Tz (%) In (%) Weight loss (ap/A-
hr) α5 3 α92
1 1~5 α7~α915
To α5 5 α19 to α535
α5~5 [12~α46
9 125~3 0.2~α93Tl
For this to be effective, a minimum of α5% is required. On the other hand, when combined with In, the effect is saturated when T) exceeds 9%. In is effective at 101% in combination with the optimum TI, but if added in excess of 6%, it will have the opposite effect.
本発明によるＰｂ−ＴＪ−Ｉｎ合金は、前述したように
、次の点で特徴づけられる：
（イ）高電流密度下でさえ優れた耐食性を示し、純ｐｂ
に較べて１／４０〜１／２０ の重量減に基く耐食性
の向上を示しうろこと、
（ロ）Ｔｌ及びＩｎというＰｂよシ低融点の金属のみの
添加によ）構成される低融点材であること、（低融点材
から成る不溶性陽極は、合金の製造を容易ならしめ、母
材被覆型陽極の場合母材への溶接、肉盛シ等による母材
の変形を防止し、回収後の再溶解における酸化損失を減
少し、圧延等の加工を容易とする等の点で非常に大きな
メリットを与える。）
（ハ）従来使用されたような高価な貴金属を含まないこ
と。As mentioned above, the Pb-TJ-In alloy according to the present invention is characterized by the following points: (a) It exhibits excellent corrosion resistance even under high current density, and is pure Pb-TJ-In alloy.
(b) A low melting point material composed of Tl and In, which are low melting point metals (in addition to Pb), which exhibit improved corrosion resistance due to a weight reduction of 1/40 to 1/20 compared to Pb. (An insoluble anode made of a low-melting point material makes it easier to manufacture the alloy, and in the case of a base metal-coated anode, it prevents deformation of the base metal due to welding, overlaying, etc.) It has great advantages in terms of reducing oxidation loss during remelting and facilitating processing such as rolling.) (c) It does not contain expensive precious metals that were conventionally used.
本発明陽極は、所定の成分の鉛合金を溶解し、それを鋳
造・圧延等によシミ極に仕上げた陽極全体が当該鉛合金
から成るもの、表面をチタン、ニオブ、タンタル等の高
耐食性を持つ金属を被覆したクラッド材（Ｆ；材は鉄、
銅等で良い）又は耐食性材料単体から成る母材の片面或
いは両面に当該鉛合金を被覆したものを含み、被覆する
方法についてはＴＩＧ方式等で直接母材に溶着するか、
母材表面にへンダ付け、電気メッキ、等表面処理をした
後鉛を溶層肉盛シするその他を包括する。The anode of the present invention is made by melting a lead alloy with predetermined components and finishing it into a smeared electrode by casting, rolling, etc. The entire anode is made of the lead alloy, and the surface is coated with highly corrosion-resistant material such as titanium, niobium, tantalum, etc. Clad material coated with metal (F; material is iron,
Copper, etc.) or a base material made of a single corrosion-resistant material coated with the lead alloy on one or both sides, and the method of coating includes directly welding to the base material using the TIG method, etc.
It includes soldering, electroplating, etc. on the surface of the base material, and other methods in which lead is deposited on the surface after surface treatment.
要は電極の放電部が本発明合金で作製されれは良い。In short, it is good if the discharge part of the electrode is made of the alloy of the present invention.
実施例及び比較例
通常の溶解法にて表１に示される成分組成金有する鉛合
金溶湯ｔ−調製し、鋳造復圧延にて厚さ５鴎の板材とし
た。この板材から厚さ３ ａｓ ｘ巾１０ｆｆｉ１１１
×長さ１５０鴎の寸法を持つ試験材を切出し、これを陽
極とした。電解面積はＬ５ｃ！ｌである。一方、陰極と
しては純鉛製の厚さ５鴎×巾６０關×長さ１５０器の板
を使用し、陰極２板ｔ−ＶＸ！ｈ極を挾むよう対峠させ
た。EXAMPLES AND COMPARATIVE EXAMPLES A molten lead alloy having the composition shown in Table 1 was prepared by a conventional melting method, and a plate material having a thickness of 5 mm was made by casting and back rolling. From this board material thickness 3 as x width 10ffi111
A test material having dimensions of 150 x length was cut out and used as an anode. The electrolytic area is L5c! It is l. On the other hand, as the cathode, we used a board made of pure lead with a thickness of 5 mm x width of 60 mm x length of 150 mm, and 2 cathode plates t-VX! The two were placed opposite each other to sandwich the h-pole.
耐食性試験は次のようにして行った：陽極及び陰極を、
Ｎａ２ＳＯ４を７１９／ｌの割合で溶解し更に硫酸（１
＋１）を加えることにより調製した硫ｒ４１歳性芒硝溶
液（ｐＨ＝ｔｌ）中に浸漬し、浴温−４０〜６０℃、印
加電流；３Ａ１電流密度２００ Ａ／ｄｍ２、通電時間
＝１００時間の条件下で電解試験を行った。試ｇｉ！ｌ
後陽極を乾燥炉に入れて乾燥し、試験片の重量減を計測
した。計測した試験片の重量減から単位電位量当夛の重
量減を算出した。結果を表１に併せて示す。第１図はそ
のグラフ表示である０表 １
表 １ （胱き ）
発明の効果
高電流密度対応の高耐食性・低融点合金製不溶性陽極の
提供により、高い生産性の下でしかも浴の保守管理を容
易にして高品質のメッキ及び箔製品の製造を可能ならし
める。これらは次のようにまとめることが出来る：
ｔ 腐食量の減少による１！極寿命の延長（コストダウ
ン）
２、腐食量の減少による極間調整日数の減少５、ｌ
浴組成管理の簡易化
４、 スラッジ沈降剤等の添加量の減少（コストダウン
）
５、製品品質の向上
６ 合金製造の容易化・コストダウン
Ｚ 母材への溶接・肉盛りに際しての母材の変形防止
＆ 回収再溶解において酸化による損失減少９ 圧延、
押出、切断、溶接等の加工の容易化ＩＣＬ 腐食量の
減少による薄肉軽量化の実現これらメリットの下で、均
質な厚メッキや箔製造が可能となる。The corrosion resistance test was carried out as follows: the anode and cathode were
Dissolve Na2SO4 at a ratio of 719/l and add sulfuric acid (1
The conditions were immersed in a 41-year-old mirabilite solution (pH = tl) prepared by adding sulfur solution (pH = tl), bath temperature -40 to 60°C, applied current: 3A1 current density 200 A/dm2, current application time = 100 hours. Electrolytic tests were conducted below. Trial gi! l
The post-anode was placed in a drying oven and dried, and the weight loss of the test piece was measured. The weight loss per unit electric potential was calculated from the measured weight loss of the test piece. The results are also shown in Table 1. Figure 1 is a graphical representation of the results.Table 1 Effects of the Invention By providing an insoluble anode made of a highly corrosion-resistant, low-melting point alloy that is compatible with high current density, bath maintenance and management can be achieved with high productivity. To facilitate the production of high quality plating and foil products. These can be summarized as follows: t 1 due to reduction in corrosion amount! Extended electrode life (cost reduction) 2. Reduced number of electrode gap adjustment days due to reduced amount of corrosion 5.
Simplifying bath composition management 4. Reducing the amount of sludge sedimentation agents, etc. added (reducing costs) 5. Improving product quality 6. Easier manufacturing of alloys and reducing costs Z. Prevention of deformation & reduction of loss due to oxidation in recovery and remelting 9 Rolling,
Easier processing such as extrusion, cutting, welding, etc. ICL Realization of thinner walls and lighter weight by reducing the amount of corrosion These advantages make it possible to manufacture uniformly thick plating and foil.
第１図は、幾つかのＴ！含有量に対してＩｎ含有量（重
量％）と重量減（ｍ９／Ａ・ｈｒ） との関係を示す
グラフである。Figure 1 shows several T! It is a graph showing the relationship between In content (wt%) and weight loss (m9/A·hr).
手続補正書
昭和６２年６月１０
特許庁長官 黒 １）明 雄 殿
事件の表示 昭和６１年 特願第２４１４１８ 号発明
の名称 鉛合金製不溶性陽極
補正をする者
事件との関係 特許出願人名 称
芳沢機工東部株式会社Procedural Amendment June 10, 1988 Commissioner of the Patent Office Black 1) Indication of the case of Yu Akira 1988 Japanese Patent Application No. 241418 Title of the invention Relationship to the case of person who corrects lead alloy insoluble anode Name of patent applicant Title
Yoshizawa Kiko Tobu Co., Ltd.
Claims (1)
〜６％Ｉｎを含有し、残部が鉛と不可避的不純物から成
る鉛合金を放電部とする不溶性陽極。 ２）陽極全体が前記鉛合金から成る特許請求の範囲第１
項記載の不溶性陽極。 ３）表面を耐食性材料で被覆したクラッド材を母材とし
、その少くとも片面に前記鉛合金を被覆した特許請求の
範囲第１項記載の不溶性陽極。 ４）耐食性材料製母材の少くとも片面に前記鉛合金を被
覆した特許請求の範囲第１項記載の不溶性陽極。[Claims] 1) 0.5 to 9% Tl and 0.01% by weight
An insoluble anode whose discharge portion is a lead alloy containing ~6% In, with the balance consisting of lead and unavoidable impurities. 2) Claim 1 in which the entire anode is made of the lead alloy
Insoluble anode as described in section. 3) The insoluble anode according to claim 1, wherein the base material is a clad material whose surface is coated with a corrosion-resistant material, and at least one side of which is coated with the lead alloy. 4) The insoluble anode according to claim 1, wherein at least one side of a base material made of a corrosion-resistant material is coated with the lead alloy.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61241418A JP2529557B2 (en) | 1986-10-13 | 1986-10-13 | Lead alloy insoluble anode |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61241418A JP2529557B2 (en) | 1986-10-13 | 1986-10-13 | Lead alloy insoluble anode |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS6396298A true JPS6396298A (en) | 1988-04-27 |
| JP2529557B2 JP2529557B2 (en) | 1996-08-28 |
Family
ID=17073998
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP61241418A Expired - Lifetime JP2529557B2 (en) | 1986-10-13 | 1986-10-13 | Lead alloy insoluble anode |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2529557B2 (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH028386A (en) * | 1988-06-27 | 1990-01-11 | Mitsui Toatsu Chem Inc | Method for electrolytically reducing m-hydroxybenzoic acid |
| CN106191930A (en) * | 2016-07-04 | 2016-12-07 | 北京有色金属研究总院 | A kind of electrification is metallurgical with alloy lead anode plate and preparation method thereof |
| CN110133707A (en) * | 2016-07-11 | 2019-08-16 | 浜松光子学株式会社 | Radiation detector |
-
1986
- 1986-10-13 JP JP61241418A patent/JP2529557B2/en not_active Expired - Lifetime
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH028386A (en) * | 1988-06-27 | 1990-01-11 | Mitsui Toatsu Chem Inc | Method for electrolytically reducing m-hydroxybenzoic acid |
| CN106191930A (en) * | 2016-07-04 | 2016-12-07 | 北京有色金属研究总院 | A kind of electrification is metallurgical with alloy lead anode plate and preparation method thereof |
| CN110133707A (en) * | 2016-07-11 | 2019-08-16 | 浜松光子学株式会社 | Radiation detector |
| US11555934B2 (en) | 2016-07-11 | 2023-01-17 | Hamamatsu Photonics K.K. | Radiation detector |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2529557B2 (en) | 1996-08-28 |
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