EP0041638B1 - Method for the pretreatment of stainless steel for the direct electrodeposition of gold - Google Patents
Method for the pretreatment of stainless steel for the direct electrodeposition of gold Download PDFInfo
- Publication number
- EP0041638B1 EP0041638B1 EP81103983A EP81103983A EP0041638B1 EP 0041638 B1 EP0041638 B1 EP 0041638B1 EP 81103983 A EP81103983 A EP 81103983A EP 81103983 A EP81103983 A EP 81103983A EP 0041638 B1 EP0041638 B1 EP 0041638B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- gold
- stainless steel
- pretreatment
- bath
- process according
- 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.)
- Expired
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
- C25D5/34—Pretreatment of metallic surfaces to be electroplated
- C25D5/36—Pretreatment of metallic surfaces to be electroplated of iron or steel
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25F—PROCESSES FOR THE ELECTROLYTIC REMOVAL OF MATERIALS FROM OBJECTS; APPARATUS THEREFOR
- C25F1/00—Electrolytic cleaning, degreasing, pickling or descaling
Definitions
- the invention relates to a process for the pretreatment of stainless steel, in particular of chromium-nickel steels for direct galvanic gold plating with strongly acid baths.
- stainless steel objects can be incorporated from z. B. nickel silver or copper can be treated. They can then be gilded with adherence while maintaining the surface quality.
- the pretreatment baths preferably contain alkali cyanide in a concentration of 2-100 g / l.
- alkali cyanide in a concentration of 2-100 g / l.
- you can also other additives such.
- the activation advantageously takes place at temperatures from 20 ° to 70 ° C. and is carried out predominantly at room temperature. It consists of an initial cathodic treatment, preferably at 2-40 A / dm 2, for 15 seconds to 5 minutes and a subsequent anodic treatment under the same conditions.
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Electroplating Methods And Accessories (AREA)
- Electroplating And Plating Baths Therefor (AREA)
Abstract
Description
Die Erfindung betrifft ein Verfahren zur Vorbehandlung von Edelstahl, insbesondere von Chromnickelstählen für eine direkte galvanische Vergoldung mit stark sauren Bädern.The invention relates to a process for the pretreatment of stainless steel, in particular of chromium-nickel steels for direct galvanic gold plating with strongly acid baths.
Die galvanische Abscheidung gut haftender Metallüberzüge auf rostfreien, hochlegierten Stählen bereitet durch die dichte, schwer zu entfernende Passivschicht seit jeher größere Schwierigkeiten. Bestimmend für das passive Verhalten dieser Stähle ist eine sich rasch ausbildende Deckschicht, vorwiegend aus Cr203, einem sehr schwer löslichen Oxid. Aus diesem Grund muß zur Vorbereitung des Edelstahls vor dem Galvanisieren eine Entfernung der Passivschicht durch Beizen in aggressiven Mineralsäuren, zum Teil unter Stromeinwirkung, vorgenommen werden. So wird zum Beispiel empfohlen, 10-20 Vol.-% HN03konz. mit 1-2 Vol.-% H2F2konz. bei 50° hierfür zu verwenden, oder H2S04, Cr03 und H2F2 bei Raumtemperatur einzusetzen oder kathodisch die Teile in verschiedenen Säuren zu aktivieren. Fast alle Verfahren greifen jedoch das Grundmaterial an, was besonders bei hochglanzpolierten Teilen unerwünscht ist. Weitere Probleme ergeben sich bei diesen bekannten Verfahren, wenn Edelstahlgegenstände mit eingearbeiteten z. B. Neusilber- oder Kupferteilen vorliegen. Fast alle diese Verfahren verursachen auch nicht unerhebliche Korrosionsprobleme in den Galvanisieranlagen.The galvanic deposition of well-adhering metal coatings on rustproof, high-alloy steels has always been more difficult due to the dense, difficult-to-remove passive layer. The determining factor for the passive behavior of these steels is a rapidly developing cover layer, predominantly made of Cr 2 0 3 , a very poorly soluble oxide. For this reason, in order to prepare the stainless steel, the passive layer must be removed by pickling in aggressive mineral acids, partly under the influence of electricity, before galvanizing. For example, 10-20 vol .-% HN0 3 conc. Is recommended. with 1-2 vol .-% H 2 F 2 conc. Use at 50 ° for this, or use H 2 S0 4 , Cr0 3 and H 2 F 2 at room temperature or activate the parts cathodically in different acids. However, almost all processes attack the base material, which is particularly undesirable for highly polished parts. Further problems arise with these known methods when stainless steel objects with incorporated z. B. nickel silver or copper parts. Almost all of these processes also cause considerable corrosion problems in the electroplating systems.
Bekannt sind auch Aktivierungsverfahren unter Abscheidung einer Zwischenschicht, meist Nickel, aus stark salzsaurer Lösung. Diesen haften aber ebenfalls deutliche Nachteile an. Neben Korrosionsproblemen bei Anwendung dieser Bäder sind die so aktivierten und anschließend vergoldeten Teile wesentlich anfälliger gegen Korrosion als direkt vergoldete. Ausgehend von Fehlstellen korrodiert die Nikkelzwischenschicht bis zur völligen Ablösung der Goldauflage. Bei Schmuckteilen, die direkt auf der Haut getragen werden, ist eine Unternickelung auf Grund allergischer Reaktionen einzelner Personen und eventueller canzerogener Wirkung meist unerwünscht.Activation processes involving the deposition of an intermediate layer, usually nickel, from a strongly hydrochloric acid solution are also known. However, these also have clear disadvantages. In addition to corrosion problems when using these baths, the parts activated and subsequently gold-plated are much more susceptible to corrosion than directly gold-plated parts. Starting from defects, the intermediate layer of nickel corrodes until the gold plating is completely detached. For jewelry that is worn directly on the skin, under-nickeling is usually undesirable due to allergic reactions by individual people and possible cancerogenic effects.
Zur Vermeidung der Unternickelung wurde versucht, Edelstahlteile direkt im Goldbad zu aktivieren. Die US-PS 4168214 beschreibt ein Goldbad auf Basis eines »verdünnten Königswassers«, das in der Lage ist, Edelstahl direkt im Bad zu aktivieren. Das Bad hat jedoch ebenfalls den Nachteil, daß es die Oberfläche, besonders an Lötstellen, angreift. Außerdem ist das Bad schlecht zu führen, da die Agressivität mit der Betriebsdauer ansteigt. Andere zur direkten Beschichtung von Edelstahl bekannte stark saure Goldbäder ergeben nur in wenigen Fällen eine ausreichende Haftung der Goldschicht. Wenn die zu beschichtenden Edelstahlteile, zum Beispiel Uhrenarmbänder, zuvor einer Behandlung unterzogen worden waren, die eine stärkere Passivschicht entstehen ließ, wie zum Beispiel Tempern, Löten, Polieren unter Hitzeentwicklung, Behandlung in passivierenden Beizen oder Elektropolieren, konnte durch direktes Vergolden keine ausreichende Haftfestigkeit erzielt werden.In order to avoid nickel plating, attempts were made to activate stainless steel parts directly in the gold bath. The US-PS 4168214 describes a gold bath based on a "diluted aqua regia", which is able to activate stainless steel directly in the bath. However, the bath also has the disadvantage that it attacks the surface, particularly at solder joints. In addition, the bathroom is difficult to manage because the aggressiveness increases with the operating time. Other strongly acidic gold baths known for the direct coating of stainless steel only result in sufficient adhesion of the gold layer in a few cases. If the stainless steel parts to be coated, for example watch straps, had previously been subjected to a treatment that gave rise to a thicker passive layer, such as tempering, soldering, polishing under heat, treatment in passivating pickling or electropolishing, sufficient gold plating could not achieve sufficient adhesive strength will.
Es war daher Aufgabe der vorliegenden Erfindung, ein Verfahren zur Vorbehandlung von Edelstahl für eine direkte galvanische Vergoldung in einem stark sauren Goldbad zu finden, das die Metalloberfläche möglichst wenig angreift und eine gute Haftfestigkeit der abgeschiedenen Goldschichten erzielt.It was therefore an object of the present invention to find a process for the pretreatment of stainless steel for direct galvanic gold plating in a strongly acidic gold bath, which attacks the metal surface as little as possible and achieves good adhesion of the deposited gold layers.
Diese Aufgabe wurde erfindungsgemäß dadurch gelöst, daß die Edelstahlteile in eine cyanidhaltige wäßrige Lösung gebracht und zuerst kathodisch und anschließend anodisch behandelt werden.This object has been achieved according to the invention in that the stainless steel parts are brought into an aqueous solution containing cyanide and treated first cathodically and then anodically.
Überraschenderweise zeigte es sich, daß bei Behandlung von Edelstahlteilen, die in einem stark passiven Zustand vorlagen, in einer Lösung eines Alkalicyanids nach zunächst kathodischer, dann anodischer Polung bei Raumtemperatur selbst bei niedrigen Stromdichten eine gute Aktivierung erzielt wurde. Nach direkter anschließender Vergoldung in einem handelsüblichen stark sauren Goldbad wurden sehr gute Haftfestigkeiten erzielt. Gleiche Aktivierungsergebnisse konnten selbst bei sichtbaren Anlaufschichten erreicht werden, wenn das Cyanid vorteilhafterweise direkt in einem handelsüblichen Entfettungsbad eingesetzt und die genannte Polungsreihenfolge eingehalten wurde.Surprisingly, it was found that when stainless steel parts which were in a highly passive state were treated in a solution of an alkali metal cyanide, after first cathodic then anodic polarization at room temperature, good activation was achieved even at low current densities. After subsequent gilding in a commercially available, strongly acidic gold bath, very good adhesive strengths were achieved. The same activation results could be achieved even with visible tarnish layers if the cyanide was advantageously used directly in a commercially available degreasing bath and the polarity sequence mentioned was observed.
Nach dem erfindungsgemäßen Verfahren können selbst Edelstahlgegenstände eingearbeiteten Teilen aus z. B. Neusilber oder Kupfer behandelt werden. Sie können anschließend unter voller Erhaltung der Oberflächengüte haftfest vergoldet werden.According to the method of the invention, even stainless steel objects can be incorporated from z. B. nickel silver or copper can be treated. They can then be gilded with adherence while maintaining the surface quality.
Vorzugsweise enthalten die Vorbehandlungsbäder Alkalicyanid in einer Konzentration 2-100 g/I. Daneben können sie noch weitere Zusätze, wie z. B. Phosphate, kondensierte Phosphate, Carbonate und Silikate der Alkalimetalle in verschiedenen Konzentrationen enthalten. Diese Badbestandteile dienen vorwiegend der Entfettung und haben auf die Aktivierung keinen Einfluß. Höhere Konzentrationen an Alkalihydroxid sind zu vermeiden.The pretreatment baths preferably contain alkali cyanide in a concentration of 2-100 g / l. In addition, you can also other additives such. B. phosphates, condensed phosphates, carbonates and silicates of alkali metals in various concentrations. These bath components are mainly used for degreasing and have no influence on the activation. Higher concentrations of alkali hydroxide should be avoided.
Die Aktivierung erfolgt vorteilhafterweise bei Temperaturen von 20° bis 70° C und wird vorwiegend bei Raumtemperatur ausgeführt. Sie besteht aus einer zunächst kathodischen Behandlung von vorzugsweise bei 2-40 A/dm2 während 15 sec bis 5 min und einer anschließenden anodischen Behandlung unter denselben Bedingungen.The activation advantageously takes place at temperatures from 20 ° to 70 ° C. and is carried out predominantly at room temperature. It consists of an initial cathodic treatment, preferably at 2-40 A / dm 2, for 15 seconds to 5 minutes and a subsequent anodic treatment under the same conditions.
Die Anwendung höherer Temperatur bis ca. 70° C und höherer Stromdichte ist möglich, aber nicht erforderlich. Zur anschließenden direkten Vergoldung eignet sich jedes handelsübliche stark saure Goldbad mit pH kleiner 3. Eine Dekapierung nach der Aktivierung, z. B. in 10%iger Schwefelsäure, wirkt sich günstig auf die Zwischenspülung aus, ist aber für die eigentliche Aktivierung ohne Einfluß.The use of higher temperatures up to approx. 70 ° C and higher current density is possible, but not necessary. Any commercially available strongly acidic gold bath with a pH of less than 3 is suitable for the subsequent direct gold plating Pickling after activation, e.g. B. in 10% sulfuric acid, has a favorable effect on the intermediate rinse, but is without influence for the actual activation.
Die folgenden Beispiele sollen das erfindungsgemäße Vorbehandlungsverfahren näher erläutern:
- 1. 10 g KCN, 10 g NaOH, 30 g Na2C03 und 50 g Na3PO4 . 12 H2O werden in Wasser zu 1 gelöst. Eine auf Hochglanz polierte Probe aus V4A (Chromnickelstahl mit 18% Cr, 11% Ni, 2% Mo nach DIN 17440) wird 1 min bei Raumtemperatur und 10 A/dm2 kathodisch, anschließend unter gleichen Bedingungen anodisch in diesem Bad behandelt, gut zwischengespült und in einem handelsüblichen stark sauren Goldbad vergoldet. Die abgeschiedene Goldschicht ist hochglänzend und haftet gut. Sie läßt sich selbst durch Bürsten nach scharfem Knicken der Probe nicht entfernen.
- 2. Eine Probe aus V4A wird durch einstündiges Tempern bei 300°C an Luft bewußt passiviert.
Nach Behandlung der Probe in einem Bad nach Beispiel 1 unter den dort genannten Bedingungen wurde ebenfalls sehr gute Haftfestigkeit bei der Vergoldung erzielt. - 3. 20 g NaCN, 10 g NaOH, 10 g Na4P2O7 . 10 H2O, 30 g Na2SiO3 · 5 H2O und 0,5 g Netzmittel werden in Wasser zu 1 Liter gelöst.
Ein elektropoliertes Edelstahlgeflechtarmband mit einem Uhrengehäuse aus Neusilber wird bei Raumtemperatur 1 min bei 5 A/dm2 kathodisch, anschließend unter gleichen Bedingungen anodisch aktiviert, gut zwischengespült und in einem handelsüblichen stark sauren Goldbad vergoldet. Die Goldschicht läßt sich auch durch starkes Kratzen nicht entfernen.
- 1. 10 g KCN, 10 g NaOH, 30 g Na 2 CO 3 and 50 g Na 3 PO 4 . 12 H 2 O are dissolved in water to 1. A specularly polished sample made of V4A (chromium-nickel steel with 18% Cr, 11% Ni, 2% Mo according to DIN 17440) is rinsed cathodically for 1 min at room temperature and 10 A / dm 2 , then anodically treated in this bath under the same conditions, and rinsed well and gilded in a commercially available strong acid gold bath. The deposited gold layer is high-gloss and adheres well. It cannot be removed even by brushing after the sample has been sharply bent.
- 2. A sample of V4A is deliberately passivated in air for 1 hour at 300 ° C.
After treatment of the sample in a bath according to Example 1 under the conditions mentioned there, very good adhesive strength was also achieved in the gold plating. - 3. 20 g NaCN, 10 g NaOH, 10 g Na 4 P 2 O 7 . 10 H 2 O, 30 g Na 2 SiO 3 .5 H 2 O and 0.5 g wetting agent are dissolved in 1 liter water.
An electropolished stainless steel braided bracelet with a nickel silver watch case is cathodic at room temperature for 1 min at 5 A / dm 2 , then anodically activated under the same conditions, rinsed well and gold-plated in a commercially available, strongly acidic gold bath. The gold layer cannot be removed even by heavy scratching.
Claims (5)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| AT81103983T ATE4602T1 (en) | 1980-05-29 | 1981-05-23 | METHOD OF PREPARING STAINLESS STEEL FOR DIRECT GOLD PLATING. |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE3020371A DE3020371C2 (en) | 1980-05-29 | 1980-05-29 | Process for the pretreatment of stainless steel for direct galvanic gold plating |
| DE3020371 | 1980-05-29 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| EP0041638A1 EP0041638A1 (en) | 1981-12-16 |
| EP0041638B1 true EP0041638B1 (en) | 1983-09-07 |
Family
ID=6103493
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP81103983A Expired EP0041638B1 (en) | 1980-05-29 | 1981-05-23 | Method for the pretreatment of stainless steel for the direct electrodeposition of gold |
Country Status (5)
| Country | Link |
|---|---|
| US (1) | US4659438A (en) |
| EP (1) | EP0041638B1 (en) |
| JP (1) | JPS5719395A (en) |
| AT (1) | ATE4602T1 (en) |
| DE (1) | DE3020371C2 (en) |
Families Citing this family (24)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0631469B2 (en) * | 1987-02-06 | 1994-04-27 | 株式会社関西プラント工業 | Manufacturing method of gold plating containers |
| JPH0631463B2 (en) * | 1987-02-06 | 1994-04-27 | 株式会社関西プラント工業 | Gold plated plate manufacturing method |
| JPH0754865Y2 (en) * | 1989-03-07 | 1995-12-18 | 株式会社ソキア | Light intensity adjustment mechanism and lightwave rangefinder in lightwave rangefinder |
| US6878932B1 (en) * | 2003-05-09 | 2005-04-12 | John D. Kroska | Mass spectrometer ionization source and related methods |
| US20090114345A1 (en) * | 2007-11-07 | 2009-05-07 | Sumitomo Metal Mining Co., Ltd. | Method for manufacturing a substrate for mounting a semiconductor element |
| US8542465B2 (en) | 2010-03-17 | 2013-09-24 | Western Digital Technologies, Inc. | Suspension assembly having a microactuator electrically connected to a gold coating on a stainless steel surface |
| US8885299B1 (en) | 2010-05-24 | 2014-11-11 | Hutchinson Technology Incorporated | Low resistance ground joints for dual stage actuation disk drive suspensions |
| US8665567B2 (en) | 2010-06-30 | 2014-03-04 | Western Digital Technologies, Inc. | Suspension assembly having a microactuator grounded to a flexure |
| WO2013138619A1 (en) | 2012-03-16 | 2013-09-19 | Hutchinson Technology Incorporated | Mid-loadbeam dual stage actuated (dsa) disk drive head suspension |
| US9093117B2 (en) | 2012-03-22 | 2015-07-28 | Hutchinson Technology Incorporated | Ground feature for disk drive head suspension flexures |
| JP6251745B2 (en) | 2012-09-14 | 2017-12-20 | ハッチンソン テクノロジー インコーポレイテッドＨｕｔｃｈｉｎｓｏｎ Ｔｅｃｈｎｏｌｏｇｙ Ｉｎｃｏｒｐｏｒａｔｅｄ | Gimbal-type flexible member having two-stage starting structure and suspension |
| WO2014059128A2 (en) | 2012-10-10 | 2014-04-17 | Hutchinson Technology Incorporated | Co-located gimbal-based dual stage actuation disk drive suspensions with dampers |
| US8941951B2 (en) | 2012-11-28 | 2015-01-27 | Hutchinson Technology Incorporated | Head suspension flexure with integrated strain sensor and sputtered traces |
| US8891206B2 (en) | 2012-12-17 | 2014-11-18 | Hutchinson Technology Incorporated | Co-located gimbal-based dual stage actuation disk drive suspensions with motor stiffener |
| US8896969B1 (en) | 2013-05-23 | 2014-11-25 | Hutchinson Technology Incorporated | Two-motor co-located gimbal-based dual stage actuation disk drive suspensions with motor stiffeners |
| US8717712B1 (en) | 2013-07-15 | 2014-05-06 | Hutchinson Technology Incorporated | Disk drive suspension assembly having a partially flangeless load point dimple |
| US8896970B1 (en) | 2013-12-31 | 2014-11-25 | Hutchinson Technology Incorporated | Balanced co-located gimbal-based dual stage actuation disk drive suspensions |
| US8867173B1 (en) | 2014-01-03 | 2014-10-21 | Hutchinson Technology Incorporated | Balanced multi-trace transmission in a hard disk drive flexure |
| US9070392B1 (en) | 2014-12-16 | 2015-06-30 | Hutchinson Technology Incorporated | Piezoelectric disk drive suspension motors having plated stiffeners |
| US9318136B1 (en) | 2014-12-22 | 2016-04-19 | Hutchinson Technology Incorporated | Multilayer disk drive motors having out-of-plane bending |
| US9296188B1 (en) | 2015-02-17 | 2016-03-29 | Hutchinson Technology Incorporated | Partial curing of a microactuator mounting adhesive in a disk drive suspension |
| WO2017003782A1 (en) | 2015-06-30 | 2017-01-05 | Hutchinson Technology Incorporated | Disk drive head suspension structures having improved gold-dielectric joint reliability |
| US9646638B1 (en) | 2016-05-12 | 2017-05-09 | Hutchinson Technology Incorporated | Co-located gimbal-based DSA disk drive suspension with traces routed around slider pad |
| CN106637047A (en) * | 2016-12-22 | 2017-05-10 | 机械科学研究总院青岛分院 | Surface passivation film removing method for plate-shaped stainless steel piece |
Family Cites Families (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DD94539A (en) * | ||||
| US2915444A (en) * | 1955-12-09 | 1959-12-01 | Enthone | Process for cleaning and plating ferrous metals |
| US2973307A (en) * | 1956-11-16 | 1961-02-28 | Lyon Inc | Method of treating stainless steel |
| US3551302A (en) * | 1967-09-19 | 1970-12-29 | Roger M Woods | Gold-plating process |
| US3694326A (en) * | 1969-11-03 | 1972-09-26 | Allegheny Ludlum Steel | Pretreatment of stainless steel for electroplating |
| US3642586A (en) * | 1970-05-12 | 1972-02-15 | Republic Steel Corp | Anodic treatment for stainless steel |
| IT1047584B (en) * | 1975-09-26 | 1980-10-20 | Centro Speriment Metallurg | METHOD FOR IMPROVING THE SUSCETTI BILITA OF STEEL TO COATINGS |
| US4078977A (en) * | 1976-09-13 | 1978-03-14 | Fountain Laurence R | Surface preparation of a damaged braze for rebrazing |
| US4168214A (en) * | 1978-06-14 | 1979-09-18 | American Chemical And Refining Company, Inc. | Gold electroplating bath and method of making the same |
-
1980
- 1980-05-29 DE DE3020371A patent/DE3020371C2/en not_active Expired
-
1981
- 1981-05-14 US US06/263,705 patent/US4659438A/en not_active Expired - Fee Related
- 1981-05-23 AT AT81103983T patent/ATE4602T1/en not_active IP Right Cessation
- 1981-05-23 EP EP81103983A patent/EP0041638B1/en not_active Expired
- 1981-05-27 JP JP7945881A patent/JPS5719395A/en active Pending
Also Published As
| Publication number | Publication date |
|---|---|
| JPS5719395A (en) | 1982-02-01 |
| EP0041638A1 (en) | 1981-12-16 |
| ATE4602T1 (en) | 1983-09-15 |
| DE3020371A1 (en) | 1981-12-03 |
| US4659438A (en) | 1987-04-21 |
| DE3020371C2 (en) | 1985-12-19 |
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