JPH0339497A - Tin plating method - Google Patents
Tin plating methodInfo
- Publication number
- JPH0339497A JPH0339497A JP17307089A JP17307089A JPH0339497A JP H0339497 A JPH0339497 A JP H0339497A JP 17307089 A JP17307089 A JP 17307089A JP 17307089 A JP17307089 A JP 17307089A JP H0339497 A JPH0339497 A JP H0339497A
- Authority
- JP
- Japan
- Prior art keywords
- tin
- anode
- platinum
- plating
- oxide
- 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
- 238000007747 plating Methods 0.000 title claims abstract description 40
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 title claims abstract description 24
- 238000000034 method Methods 0.000 title claims abstract description 13
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims abstract description 36
- 239000011248 coating agent Substances 0.000 claims abstract description 18
- 238000000576 coating method Methods 0.000 claims abstract description 18
- HTXDPTMKBJXEOW-UHFFFAOYSA-N dioxoiridium Chemical compound O=[Ir]=O HTXDPTMKBJXEOW-UHFFFAOYSA-N 0.000 claims abstract description 17
- 229910052697 platinum Inorganic materials 0.000 claims abstract description 17
- 229910000457 iridium oxide Inorganic materials 0.000 claims abstract description 16
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 claims abstract description 13
- 229910001887 tin oxide Inorganic materials 0.000 claims abstract description 13
- 238000005260 corrosion Methods 0.000 claims abstract description 7
- 230000007797 corrosion Effects 0.000 claims abstract description 7
- 230000002378 acidificating effect Effects 0.000 claims abstract description 4
- 238000009713 electroplating Methods 0.000 claims abstract description 3
- 229910052751 metal Inorganic materials 0.000 claims description 7
- 239000002184 metal Substances 0.000 claims description 7
- 239000000758 substrate Substances 0.000 claims description 5
- 238000011109 contamination Methods 0.000 abstract 1
- 230000001105 regulatory effect Effects 0.000 abstract 1
- 239000010936 titanium Substances 0.000 description 15
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 8
- 229910052719 titanium Inorganic materials 0.000 description 8
- 239000002253 acid Substances 0.000 description 5
- TXUICONDJPYNPY-UHFFFAOYSA-N (1,10,13-trimethyl-3-oxo-4,5,6,7,8,9,11,12,14,15,16,17-dodecahydrocyclopenta[a]phenanthren-17-yl) heptanoate Chemical compound C1CC2CC(=O)C=C(C)C2(C)C2C1C1CCC(OC(=O)CCCCCC)C1(C)CC2 TXUICONDJPYNPY-UHFFFAOYSA-N 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 229910021626 Tin(II) chloride Inorganic materials 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 239000001119 stannous chloride Substances 0.000 description 4
- 235000011150 stannous chloride Nutrition 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- 229910052741 iridium Inorganic materials 0.000 description 3
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 3
- -1 stannous chloride Chemical class 0.000 description 3
- NGNBDVOYPDDBFK-UHFFFAOYSA-N 2-[2,4-di(pentan-2-yl)phenoxy]acetyl chloride Chemical compound CCCC(C)C1=CC=C(OCC(Cl)=O)C(C(C)CCC)=C1 NGNBDVOYPDDBFK-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 2
- 229910000978 Pb alloy Inorganic materials 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005530 etching Methods 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- AMQJEAYHLZJPGS-UHFFFAOYSA-N N-Pentanol Chemical compound CCCCCO AMQJEAYHLZJPGS-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 150000002504 iridium compounds Chemical class 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 229910052758 niobium Inorganic materials 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
- 235000006408 oxalic acid Nutrition 0.000 description 1
- CTSLXHKWHWQRSH-UHFFFAOYSA-N oxalyl chloride Substances ClC(=O)C(Cl)=O CTSLXHKWHWQRSH-UHFFFAOYSA-N 0.000 description 1
- 150000003058 platinum compounds Chemical class 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 238000005488 sandblasting Methods 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 229910052715 tantalum Inorganic materials 0.000 description 1
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 150000003606 tin compounds Chemical class 0.000 description 1
- DANYXEHCMQHDNX-UHFFFAOYSA-K trichloroiridium Chemical compound Cl[Ir](Cl)Cl DANYXEHCMQHDNX-UHFFFAOYSA-K 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Abstract
Description
【発明の詳細な説明】
（産業上の利用分野）
本発明は酸性スズメッキ浴から電気メツキ法によってス
ズメー／キを行なう方法に関する。DETAILED DESCRIPTION OF THE INVENTION (Industrial Field of Application) The present invention relates to a method of tin-plating by electroplating from an acid tin plating bath.
（従来の技術）
鉄鋼業における表面処理としての酸性スズメッキ裕から
ｆｌＬ％スズメッキを行なう場合、近年までは可溶性ス
ズ陽極が用いられていたが、このスズ陽極は消耗が早く
寸法安定性が悪いばかりでなく、摺電圧が高い、メツキ
液の管理が難しい等の欠点を有していた。(Prior art) Until recently, soluble tin anodes have been used when performing flL% tin plating from acid tin plating as a surface treatment in the steel industry, but these tin anodes wear out quickly and have poor dimensional stability. However, it had drawbacks such as high sliding voltage and difficulty in managing the plating solution.
このため最近では不溶性陽極が用いられるようになり、
主として鉛合金あるいは白金電気メツキ−チタン陽極（
ＰＬ−Ｔｉ陽極）が用いられている。For this reason, insoluble anodes have recently been used,
Mainly lead alloy or platinum electrometallic titanium anode (
PL-Ti anode) is used.
しかし鉛合金ＰＩｉ極は有害な鉛がメツキ液中に多量に
入る、スズメッキ皮膜中に鉛が合金として析出して悪影
響を与える等の欠点があるため、次第にＰｔ−Ｔｉ陽極
が多く用いられるようになってきた。However, the lead alloy PIi electrode has drawbacks such as a large amount of harmful lead entering the plating solution and lead precipitating as an alloy in the tin plating film, which has an adverse effect, so Pt-Ti anodes are gradually being used more and more. It has become.
（発明が解決しようとする問題点）
上記Ｐｔ−Ｔｉ陽極は高価であるため、陽極コスト高の
原因となるので、安価かつ長寿命でメツキ液を汚染する
ことの無いスズメッキ方法の開発が望まれていた。(Problems to be Solved by the Invention) The above-mentioned Pt-Ti anode is expensive, which causes high anode costs. Therefore, it is desired to develop a tin plating method that is inexpensive, has a long life, and does not contaminate the plating solution. was.
（問題点を解決するための手段）
本発明者らはスズメッキ方法において、使用する陽極の
面から検討した。熱分解法によりチタン上に白金Ｍ金属
酸化物を被覆した陽極について検討したが、価格として
は上記Ｐ Ｌ −Ｔ ｉ陽極よりも低価格であるが、寿
命の点ではＰｔ−Ｔｉ陽極より僅かに艮い程度なので満
足できず、更に他の不溶性陽極について検討し、本発明
を完成するに至った。(Means for Solving the Problems) The present inventors investigated the tin plating method from the aspect of the anode used. We investigated an anode in which platinum M metal oxide was coated on titanium using a pyrolysis method. Although the price was lower than the P L -Ti anode mentioned above, its lifespan was slightly longer than that of the Pt-Ti anode. Since the result was only a small amount, we were not satisfied with the results, so we further investigated other insoluble anodes and completed the present invention.
すなわち本発明は、酸性スズメッキ浴から型式メツキ法
によってスズメッキを行なうにあたり、耐食性金属基体
上に、スズ酸化物と、イリジウム酸化物および／または
白金とからなる被覆を有する電極を陽極として用いるこ
とを特徴とするスズメッキ方法である。That is, the present invention is characterized in that when performing tin plating by the type plating method from an acidic tin plating bath, an electrode having a coating of tin oxide, iridium oxide and/or platinum on a corrosion-resistant metal substrate is used as an anode. This is a tin plating method.
スズ酸化物とイリジウム酸化物および／または白金とか
らなる被覆中のスズ酸化物の量が多すぎるとＰ！Ｊ電圧
の上昇をまねき、逆に少なすぎると電極寿命が短くなる
ので、スズ酸化物の含有量は３〜８０ｍｏｌ％が好まし
く、より好ましくは５〜７０輪０１％である。If the amount of tin oxide in the coating consisting of tin oxide and iridium oxide and/or platinum is too large, P! If it is too small, the J voltage will increase, and if it is too small, the electrode life will be shortened. Therefore, the tin oxide content is preferably 3 to 80 mol%, more preferably 5 to 70 mol%.
耐食性金属として、バルブ金属が最適であり、チタン、
ニオブ、タンタルまたはジルコニウムを使用するが、チ
タンが安価であり好ましい。Valve metals are the best corrosion-resistant metals, including titanium,
Niobium, tantalum or zirconium is used, but titanium is preferred because it is inexpensive.
耐食性金属基体上にスズ酸化物と、イリジウム酸化物お
よび／または白金とからなる被覆を設ける方法は、例え
ば熱分解法による。すなわち塩化第一スズ等のスズ化合
物、塩化イリジウム等のイリジウム化合物、塩化白金酸
等の白金化合物をアルコールに溶解した塗布液を、予め
サンドブラストあるいは塩酸、７フ化水素酸等によりエ
ツチングした耐食性金属基体上に塗布して電気炉等によ
り大気雰囲気中で４００〜６００℃で加熱する。A method for providing a coating made of tin oxide, iridium oxide and/or platinum on a corrosion-resistant metal substrate is, for example, a thermal decomposition method. That is, a corrosion-resistant metal substrate is prepared by sandblasting or etching with hydrochloric acid, heptahydrofluoric acid, etc., in advance with a coating solution in which a tin compound such as stannous chloride, an iridium compound such as iridium chloride, or a platinum compound such as chloroplatinic acid is dissolved in alcohol. It is coated on top and heated at 400 to 600°C in an air atmosphere using an electric furnace or the like.
この操作を必要な回数だけ繰り返すことによりスｘｐａ
化物とイリジウム酸化物および／または白金とからなる
被覆を有する′？ｒｉ極を得る。By repeating this operation as many times as necessary,
with a coating consisting of iridium oxide, iridium oxide and/or platinum? Obtain ri pole.
（実施例）
以下実施例により本発明を具体的に説明するが、これら
は本発明を何等限定するものではない。(Examples) The present invention will be specifically explained below with reference to Examples, but these are not intended to limit the present invention in any way.
Ｘ棗鮭Ｌ
１５Ｘ２００Ｘ１ｍ曽のチタン板をトリクレンで脱脂し
た後、熱シュウ酸でエツチングして粗面化した基体に、
Ｉｒ：５ｎ＝３：７（モル比）となるように塩化イリジ
ウム酸と塩化第一スズを秤量して、ブタノールを適量加
えた塗布液を塗布して、大気雰囲気中で電気炉により５
００℃で１時間加熱処理する操作を酸化イリジウムの量
がイリジウム換算で６ｇ／ｌとなるまで繰り返して、イ
リジウム酸化物とスズ酸化物とからなる被覆を有する電
極を得た。X Natsume L
Weighed iridic acid chloride and stannous chloride so that Ir:5n=3:7 (molar ratio), applied a coating solution containing an appropriate amount of butanol, and heated in an electric furnace in the air for 50 minutes.
The operation of heat treatment at 00° C. for 1 hour was repeated until the amount of iridium oxide became 6 g/l in terms of iridium, thereby obtaining an electrode having a coating made of iridium oxide and tin oxide.
この電極を陽極とし、チタン板を陰極として、酸化スズ
２５ｇ／ｌ、フェノールスルホンａａ Ｏｇ／ｌ、５０
℃の酸性スズメッキ液を用いて、電流重度３ＯＡ／ｄ＋
ａ”でメツキ試験を行なった。７０日経過後に摺電圧が
ＩＯＶを越えたので陽極寿命と判断してメツキ試験を中
断した。Using this electrode as an anode and a titanium plate as a cathode, tin oxide 25g/l, phenol sulfone aa Og/l, 50
Using acidic tin plating solution at ℃, current severity 3OA/d+
A plating test was carried out on "a". After 70 days, the sliding voltage exceeded IOV, so the anode life was judged to have come to an end and the plating test was discontinued.
笈凰１又
１５Ｘ２００Ｘ１ｍｍのチタン板をサンドプラス１処理
した基体に、Ｉｒ：Ｓｎ：Ｐｔ＝４：４：２（モル比）
となるように塩化イリジウム酸、塩化第一スズおよび塩
化白金酸を秤量して、エタノールを適量加えた塗布液を
塗布して、大気雰囲気中で？！！％炉により５００℃で
２０分間加熱処理する操作を酸化イリジウムの量がイリ
ジウム換算で９ｇ／ｌとなるまで繰り返して、イリジウ
ム酸化物と白金とからなる被覆を有する電極を得た。Ir:Sn:Pt=4:4:2 (molar ratio) was applied to the base of a 15 x 200 x 1 mm titanium plate treated with Sand Plus 1.
Weigh out iridic acid chloride, stannous chloride, and platinic chloride so that the coating solution containing an appropriate amount of ethanol is applied in an atmospheric atmosphere. ! ! The operation of heat treatment at 500° C. for 20 minutes in a furnace was repeated until the amount of iridium oxide became 9 g/l in terms of iridium, thereby obtaining an electrode having a coating made of iridium oxide and platinum.
この電極を陽極とし、実施例１と同一の条件でメツキ試
験を行なった。７５日経過後に摺電圧が１０Ｖを越えた
ので陽極寿命と判断してメツキ試験を中断した。Using this electrode as an anode, a plating test was conducted under the same conditions as in Example 1. After 75 days, the sliding voltage exceeded 10V, so it was judged that the anode life was over, and the plating test was interrupted.
Ｘ遣１」−
１５Ｘ２００Ｘ１ｍ鵠のチタン板を熱濃塩酸によりエツ
チングした基体に、Ｉ ｒ：ｓｏ：Ｐｔ＝ ７ ： １
：２（モル比）となるように実施例２と同じ方法で作
製した塗布液を塗布して、大気雰囲気中で電気炉によ１
）５００℃で１時間加熱処理する操作を酸化イリジウム
の量がイリジウム換算で１４１／ｍ”となるまで繰り返
して、イリジウム酸化物、スズ酸化物および白金とから
なるｔｌｌを有する電極を得た。Ir:so:Pt=7:1 on a substrate made by etching a 15x200x1m titanium plate with hot concentrated hydrochloric acid.
:2 (molar ratio) by applying the coating solution prepared in the same manner as in Example 2, and heating it in an electric furnace in the air atmosphere.
) The operation of heat treatment at 500°C for 1 hour was repeated until the amount of iridium oxide became 141/m'' in terms of iridium, thereby obtaining an electrode having a tll composed of iridium oxide, tin oxide and platinum.
この電極を陽極とし、実施例１と同一の条件でメツキ試
験を行なった。７９日経過後に摺電圧が１０Ｖを越えた
ので陽極寿命と判断してメツキ試験を中断した。Using this electrode as an anode, a plating test was conducted under the same conditions as in Example 1. After 79 days, the sliding voltage exceeded 10 V, so it was judged that the anode life was over, and the plating test was discontinued.
笈逼男」−
１５ Ｘ ２００ Ｘ １ ｍ−のチタン板を熱シュウ
酸１こよりエツチングした基体に、Ｓｎ：ＰＬ＝３：マ
（モル比）となるように塩化第一スズと塩化白金酸を秤
量して、アミルアルコールを適量加えた塗布液を塗布し
て、大気雰囲気中で電気炉により５００℃で２０分間加
熱処理する操作を白金の量が１４ｇ ／ ｍ ２となる
まで繰り返して、スズ酸化物と白金とからなる被覆を有
する電極を得た。A titanium plate measuring 15 x 200 x 1 m was etched with 1 part of hot oxalic acid, and stannous chloride and chloroplatinic acid were added to the base so that the molar ratio of Sn:PL was 3:M. Weigh the platinum, apply a coating solution containing an appropriate amount of amyl alcohol, and heat treat it at 500°C for 20 minutes in an electric furnace in the air until the amount of platinum reaches 14 g/m 2 to oxidize tin. An electrode with a coating consisting of metal and platinum was obtained.
この電極を陽極とし、実施例１と同一の条件でメツキ試
験を行なった。７１日経過後に摺電圧が１０Ｖを越えた
ので陽極寿命と判断してメツキ試験を中断した。Using this electrode as an anode, a plating test was conducted under the same conditions as in Example 1. After 71 days, the sliding voltage exceeded 10 V, so it was judged that the anode life was over, and the plating test was interrupted.
思上」１一
実施例１と同一寸法の市販のＰｔ−Ｔｉ電極（白金被覆
厚み３．５μＩＩＩ）を陽極とし、実施例１と同一の条
件でメツキ試験を行なった。１８日経過後に摺電圧がＩ
ＯＶを越えたので陽極寿命とｔｑ断してメツキ試験を中
断した。A plating test was conducted under the same conditions as in Example 1, using a commercially available Pt-Ti electrode (platinum coating thickness: 3.5 μIII) having the same dimensions as in Example 1 as an anode. After 18 days, the sliding voltage becomes I
Since the OV was exceeded, the anode life was terminated and the plating test was interrupted.
思上」１虹
実施例１と同一寸法の市販のＩ ｒ Ｏ２−Ｔ ｉ電極
（Ｉ ｒ０２ ２０ｇ／ｍ’）をｐａｉとし、実施例１
と同一の条件でメツキ試験を行なった。２５日Ｕ過後に
摺電圧がＩＯＶを越えたので陽極寿命とＮＩしてメツキ
試験を中断した。A commercially available IrO2-Ti electrode (Ir02 20g/m') having the same dimensions as Example 1 was used as pai, and Example 1
A plating test was conducted under the same conditions. After 25 days, the sliding voltage exceeded IOV, so the anode life was reached and the plating test was interrupted.
（発明の効果）
本発明のスズメッキ方法で使用する陽極は安価であり、
スズメッキ浴中で優れた耐久性を示すので、メツキ浴を
汚染することなく艮ＩＨＩ’ｌ／、ンキを行なうことが
できる。(Effects of the invention) The anode used in the tin plating method of the invention is inexpensive;
Since it exhibits excellent durability in a tin plating bath, tin plating can be carried out without contaminating the plating bath.
Claims (1)
ッキを行なうにあたり、耐食性金属基体上に、スズ酸化
物と、イリジウム酸化物および／または白金とからなる
被覆を有する電極を陽極として用いることを特徴とする
スズメッキ方法。 ２ スズ酸化物と、イリジウム酸化物および／または白
金とからなる被覆のスズの含有量が３〜８０ｍｏｌ％で
ある請求項１記載のスズメッキ方法。[Claims] 1. In carrying out tin plating by electroplating from an acidic tin plating bath, an electrode having a coating of tin oxide, iridium oxide and/or platinum on a corrosion-resistant metal substrate is used as an anode. A tin plating method featuring: 2. The tin plating method according to claim 1, wherein the tin content of the coating consisting of tin oxide, iridium oxide and/or platinum is 3 to 80 mol%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP17307089A JPH0339497A (en) | 1989-07-06 | 1989-07-06 | Tin plating method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP17307089A JPH0339497A (en) | 1989-07-06 | 1989-07-06 | Tin plating method |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH0339497A true JPH0339497A (en) | 1991-02-20 |
Family
ID=15953650
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP17307089A Pending JPH0339497A (en) | 1989-07-06 | 1989-07-06 | Tin plating method |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0339497A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| AU2004262666B2 (en) * | 2003-07-28 | 2009-07-16 | Industrie De Nora S.P.A. | Electrode for electrochemical processes and method for producing the same |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5230790A (en) * | 1975-09-04 | 1977-03-08 | Kyocera Corp | Anode made of ceramics for electrolysis |
-
1989
- 1989-07-06 JP JP17307089A patent/JPH0339497A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5230790A (en) * | 1975-09-04 | 1977-03-08 | Kyocera Corp | Anode made of ceramics for electrolysis |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| AU2004262666B2 (en) * | 2003-07-28 | 2009-07-16 | Industrie De Nora S.P.A. | Electrode for electrochemical processes and method for producing the same |
| US7695755B2 (en) * | 2003-07-28 | 2010-04-13 | De Nora Elettrodi S.P.A. | Electrode for electrochemical processes and method for producing the same |
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