EP0195995B1 - Process for the electrodeposition of composite tin-graphite or tin-lead graphite layers, and baths used therefor - Google Patents

Process for the electrodeposition of composite tin-graphite or tin-lead graphite layers, and baths used therefor Download PDF

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Publication number
EP0195995B1
EP0195995B1 EP86103563A EP86103563A EP0195995B1 EP 0195995 B1 EP0195995 B1 EP 0195995B1 EP 86103563 A EP86103563 A EP 86103563A EP 86103563 A EP86103563 A EP 86103563A EP 0195995 B1 EP0195995 B1 EP 0195995B1
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Prior art keywords
tin
graphite
electroplating bath
lead
acid
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German (de)
French (fr)
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EP0195995A1 (en
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Georg Behringer
Klaus Otto
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Siemens AG
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Siemens AG
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    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D15/00—Electrolytic or electrophoretic production of coatings containing embedded materials, e.g. particles, whiskers, wires
    • C25D15/02—Combined electrolytic and electrophoretic processes with charged materials

Definitions

  • the invention relates to a process for the production of tin-graphite or tin / lead-graphite layers, which are electrodeposited in a single operation with graphite powder particles embedded in an electroplating bath.
  • the invention relates to the associated bath for the electrodeposition of tin-graphite or tin / lead-graphite dispersion coatings, with a galvanizing bath from an aqueous solution of tin-II salts or tin-II and lead-II salts , in which graphite powder is distributed.
  • Tin layers can be applied by hot-dip tinning or also by means of galvanic baths. From DE-A 2 413 402 slidable tin layers for electrical sliding contacts on plug-in elements are known, in which the tin or lead layers, in particular galvanically applied, in the ball polishing process with the addition of substances which promote the sliding, such as graphite powder, in the border area incorporated into the surface and solidified at the same time cold.
  • the graphite is therefore only mechanically incorporated into the interface up to a depth of about 0.5 ⁇ m, for which purpose a separate operation is required.
  • the shape of the parts to be treated is important here, and an optimal distribution on all interfaces of the contact cannot be achieved.
  • the object of the invention is to provide an improved method for applying layers based on tin-graphite or tin / lead-graphite and the associated means.
  • the object is achieved in that a plating bath with a pH of 2 in which the graphite powder is dispersed by means of an acid-resistant substance which promotes the wetting of the powder particles by the plating bath is used, and in that temperatures of 35 ° C. are used .
  • the galvanic separation takes place at current densities of 1 to 15 A / dm 2.
  • the electroplating bath suitable for carrying out the method according to the invention has a pH s 2 and contains an acid-resistant, organic substance which promotes the wetting of the graphite powder particles.
  • the organic substance can be one or more substances from the group consisting of phenol and dibutylaniline, gelatin and cresol, cresol sulfonic acid and 2-methylpentyl sulfate, dibutyl sodium naphthalene sulfonate or sodium lauryl sulfate and sodium xanthate.
  • the graphite powder dispersed in the wetting agent preferably has a grain size distribution ⁇ 5 ⁇ m, in particular with grain sizes ⁇ 1 ⁇ m, 70% of the graphite particles being smaller than 1 ⁇ m.
  • DE-C 2 634 128 has already disclosed a bath and a process for the electrodeposition of nickel-graphite dispersion coatings from an aqueous solution of nickel sulfamate, which works on an acidic basis and contains a wetting agent suitable for acidic nickel baths.
  • nickel there are other requirements for nickel than for tin. So far it has been assumed that layers based on tin-graphite cannot be produced galvanically.
  • tin and tin-lead layers electroplated on contact pins which can also have a low antimony content, which increases the hardness of the coating, can considerably improve the abrasion resistance.
  • the required insertion force is reduced despite the high contact pressure. It could be demonstrated in detail that the resistance to abrasion in the electroplated dispersion coatings of tin-graphite or tin / lead-graphite is increased by 10 to 25 times compared to the previously known tin or tin / lead layers.
  • the metallic contacts are first subjected to a pretreatment customary in electroplating and then coated with a tin-graphite or tin / lead-graphite dispersion coating in one of the electrolytes of the composition specified below.
  • the grain size distributions given in the examples ⁇ 1-5 ⁇ m mean that 70% of the graphite particles are smaller than 1 ⁇ m.
  • the deposited tin layer contained 1.6% by weight of graphite. Abrasion resistance increased tenfold.
  • the deposited layer contained 2% by weight of graphite.
  • the abrasion resistance increased 18 times.
  • the deposited tin layer contained 1.8% by weight of C.
  • the abrasion resistance compared to a pure tin layer was increased 20 times.
  • the deposited tin / lead layer (90/10) contained 1.8% by weight of graphite and 1% by weight of antimony.
  • the abrasion resistance compared to pure tin / lead layers is increased 25 times.
  • the deposited tin / lead layer (60/40) contained 1% by weight of graphite and 1% by weight of antimony.
  • the abrasion resistance increases tenfold compared to a pure tin / lead layer.

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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 And Plating Baths Therefor (AREA)
  • Electroplating Methods And Accessories (AREA)
  • Manufacturing Of Electrical Connectors (AREA)

Description

Die Erfindung bezieht sich auf ein Verfahren zur Herstellung von Zinn-Graphit- oder Zinn/Blei-Graphit-Schichten, die galvanisch mit in einem Galvanisierbad eingelagerten Graphit-Pulverteilchen in einem einzigen Arbeitsgang abgeschieden werden. Daneben bezieht sich die Erfindung auf das zugehörige Bad zum galvanischen Abscheiden von Zinn-Graphit- oder Zinn/Blei-Graphit-Dispersionsüberzügen, mit einem Galvanisierbad aus einer wäßrigen Lösung von Zinn-II-Salzen oder Zinn-II- und Blei-II-Salzen, in dem Graphitpulver verteilt ist.The invention relates to a process for the production of tin-graphite or tin / lead-graphite layers, which are electrodeposited in a single operation with graphite powder particles embedded in an electroplating bath. In addition, the invention relates to the associated bath for the electrodeposition of tin-graphite or tin / lead-graphite dispersion coatings, with a galvanizing bath from an aqueous solution of tin-II salts or tin-II and lead-II salts , in which graphite powder is distributed.

Für den Einsatz von mehrpoligen Steckkontaktleisten werden bisher vorwiegend edelmetallüberzogene Kontaktstifte bzw. -messer und Kontaktbuchsen verwendet, die ausschließlich galvanisch aufgebracht werden. Es ist bekannt, zu Standzeitverlängerungen dabei Graphiteinlagerungen in die Edelmetallüberzüge vorzusehen: Beispielsweise aus der DE-C 2 543 082 ist ein cyanidischer Silberelektrolyt und ein Verfahren zur galvanischen Abscheidung von Silber-Graphit-Dispersionsüberzügen und seine Anwendung für Kontakte bekannt, bei denen der Graphit als Festschmierstoff dient.To date, the use of multipole plug contact strips has predominantly been made of noble metal-coated contact pins or knives and contact sockets, which are applied exclusively by electroplating. It is known to provide graphite deposits in the noble metal coatings to extend the service life: for example from DE-C 2 543 082 a cyanide silver electrolyte and a method for the electrodeposition of silver-graphite dispersion coatings and its use for contacts in which the graphite is known Solid lubricant is used.

Seit einiger Zeit ist man bemüht, für die oben angegebenen Kontakte die Edelmetallschichten durch Zinn- bzw. Zinn/Blei-Schichten zu ersetzen. Zinn-Schichten können durch Feuerverzinnung oder ebenfalls mittels galvanischer Bäder aufgebracht werden. Aus der DE-A 2 413 402 sind gleitfähige Zinn-Schichten für elektrische Gleitkontakte an Steckelementen bekannt, bei denen die insbesondere galvanisch aufgebrachten Zinn- oder auch Zinn/Blei-Schichten im Kugelpolierverfahren unter Zugabe von die Gleitung förderlichen Stoffen, wie Graphitpuder, im Grenzbereich der Oberfläche inkorporiert und gleichzeitig kalt verfestigt werden.For some time now, efforts have been made to replace the noble metal layers with tin or tin / lead layers for the contacts specified above. Tin layers can be applied by hot-dip tinning or also by means of galvanic baths. From DE-A 2 413 402 slidable tin layers for electrical sliding contacts on plug-in elements are known, in which the tin or lead layers, in particular galvanically applied, in the ball polishing process with the addition of substances which promote the sliding, such as graphite powder, in the border area incorporated into the surface and solidified at the same time cold.

Beim Stand der Technik erfolgt der Einbau des Graphits in die Zinnschicht also nur mechanisch in die Grenzfläche bis zu etwa 0,5 µm Tiefe, wozu ein separater Arbeitsgang erforderlich ist. Dabei ist die Form der zu behandelnden Teile von Bedeutung, wobei eine optimale Verteilung auf allen Grenzflächen des Kontaktes nicht erreicht werden kann.In the prior art, the graphite is therefore only mechanically incorporated into the interface up to a depth of about 0.5 μm, for which purpose a separate operation is required. The shape of the parts to be treated is important here, and an optimal distribution on all interfaces of the contact cannot be achieved.

Aufgabe der Erfindung ist es demgegenüber, ein verbessertes Verfahren zum Aufbringen von Schichten auf Zinn-Graphit- bzw. Zinn/Blei-Graphit-Basis und die zugehörigen Mittel anzugeben.In contrast, the object of the invention is to provide an improved method for applying layers based on tin-graphite or tin / lead-graphite and the associated means.

Gemäß der Erfindung ist die Aufgabe dadurch gelöst, daß ein Galvanisierbad mit einem pH-Wert 2, in dem das Graphitpulver mittels einer die Benetzung der Pulverteilchen durch das Galvanisierbad fördernden, säurebeständigen Substanz dispergiert ist, verwendet wird und daß bei Temperaturen 35°C gearbeitet wird. Dabei erfolgt die galvanische Abscheidung bei Stromdichten von 1 bis 15 A/dm2. According to the invention, the object is achieved in that a plating bath with a pH of 2 in which the graphite powder is dispersed by means of an acid-resistant substance which promotes the wetting of the powder particles by the plating bath is used, and in that temperatures of 35 ° C. are used . The galvanic separation takes place at current densities of 1 to 15 A / dm 2.

Aus der US-A 2 489 523 war es zwar bereits bekannt zur galvanischen Abscheidung von Zinn- oder Blei-Zinn-Schichten ein stark saures Bad mit einem pH-Wert zwischen 1,4 und 2,4 zu verwenden. Graphit als leitbeständiger Zusatz war dabei allerdings nicht vorgesehen. Demgegenüber sollen bei der GB-A 1 265 472 auf Werkstücke harte Verschleißschichten aus Nickel oder Kobalt aufgebracht werden, in denen Kohlenstoff in Form von Fasern oder Whiskern vorhanden ist. Hierbei erfolgt die galvanische Abscheidung bei einem pH-Wert > 4. Erst die Erfindung hat gezeigt, daß ein Einbringen von Graphitpulver beim galvanischen Abscheiden in einem einzigen Arbeitsgang möglich ist, wenn in einem stark sauren Bad das Graphitpulver mittels einer die Benetzung der Pulverteilchen fördernden Substanz dispergiert ist.From US Pat. No. 2,489,523, it was already known to use a strongly acidic bath with a pH between 1.4 and 2.4 for the electrodeposition of tin or lead-tin layers. However, graphite was not intended as a conductive additive. In contrast, in GB-A 1 265 472 hard wear layers of nickel or cobalt are to be applied to workpieces, in which carbon is present in the form of fibers or whiskers. Here, the galvanic deposition takes place at a pH value> 4. Only the invention has shown that it is possible to introduce graphite powder during the electrodeposition in a single operation if the graphite powder is used in a strongly acidic bath by means of a substance which promotes the wetting of the powder particles is dispersed.

Das für die Ausführung des erfindungsgemäßen Verfahrens geeignete Galvanisierbad hat einen pH-Wert s 2 und enthält eine säurebeständige, organische Substanz, die die Benetzung der Graphit-Pulverteilchen fördert. Dabei können die organische Substanz ein oder mehrere Stoffe aus der Gruppe Phenol und Dibutylanilin, Gelatine und Kresol, Kresol-Sulfonsäure und 2-Methyl-Pentylsulfat, Dibutyl-Natriumnaphthalinsulfonat oder Natriumlaurylsulfat und Natriumxanthogenat sein. Das im Netzmittel dispergierte Graphitpulver hat vorzugsweise eine Korngrößenverteilung < 5 jim, insbesondere mit Korngrößen < 1 µm, wobei 70% der Graphitteilchen kleiner als 1 um sind.The electroplating bath suitable for carrying out the method according to the invention has a pH s 2 and contains an acid-resistant, organic substance which promotes the wetting of the graphite powder particles. The organic substance can be one or more substances from the group consisting of phenol and dibutylaniline, gelatin and cresol, cresol sulfonic acid and 2-methylpentyl sulfate, dibutyl sodium naphthalene sulfonate or sodium lauryl sulfate and sodium xanthate. The graphite powder dispersed in the wetting agent preferably has a grain size distribution <5 μm, in particular with grain sizes <1 μm, 70% of the graphite particles being smaller than 1 μm.

Im Rahmen der Erfindung wurden also geeignete Mittel gefunden, die in der Lage sind, die feinen Graphitkömer zu dispergieren und gleichzeitig deren Einbau in die galvanisch abgeschiedenen Zinn- bzw. Zinn/Blei-Schichten in hinreichendem Maße zu garantieren.In the context of the invention, therefore, suitable agents have been found which are capable of dispersing the fine graphite grains and at the same time guaranteeing their incorporation to a sufficient extent in the electrodeposited tin or tin / lead layers.

Aus der DE-C 2 634 128 war zwar bereits ein Bad und ein Verfahren zum galvanischen Abscheiden von Nickel-Graphit-Dispersionsüberzügen aus einer wäßrigen Lösung von Nickelsulfamat bekannt, das auf saurer Basis arbeitet und ein für saure Nickelbäder geeignetes Netzmittel enthält. Allerdings liegen bei Nickel andere Voraussetzungen wie bei Zinn vor. Bislang wurde davon ausgegangen, daß Schichten auf Zinn-Graphit-Basis galvanisch nicht herstellbar sind.DE-C 2 634 128 has already disclosed a bath and a process for the electrodeposition of nickel-graphite dispersion coatings from an aqueous solution of nickel sulfamate, which works on an acidic basis and contains a wetting agent suitable for acidic nickel baths. However, there are other requirements for nickel than for tin. So far it has been assumed that layers based on tin-graphite cannot be produced galvanically.

Aufgrund der Erfindung läßt sich bei auf Kontaktstiften galvanisch abgeschiedenen Zinn- und ZinNBlei-Schichten, die auch einen geringen Antimongehalt aufweisen können, welcher die Härte des Überzuges erhöht, die Abriebbeständigkeit erheblich verbessern. Dabei wird die notwendige Steckkraft trotz hohen Kontaktdruckes vermindert. Es konnte im einzelnen nachgewiesen werden, daß bei den galvanisch hergestellten Dispersionsüberzügen aus Zinn-Graphit- bzw. Zinn/Blei-Graphit die Abriebbeständigkeit um das 10 bis 25fache gegenüber den bisher bekannten Zinn- bzw. Zinn/Blei-Schichten erhöht ist.According to the invention, tin and tin-lead layers electroplated on contact pins, which can also have a low antimony content, which increases the hardness of the coating, can considerably improve the abrasion resistance. The required insertion force is reduced despite the high contact pressure. It could be demonstrated in detail that the resistance to abrasion in the electroplated dispersion coatings of tin-graphite or tin / lead-graphite is increased by 10 to 25 times compared to the previously known tin or tin / lead layers.

Weitere Einzelheiten und Vorteile der Erfindung ergeben sich aus der nachfolgenden Beschreibung von Ausführungsbeispielen:Further details and advantages of the invention result from the following description of exemplary embodiments:

Bei den einzelnen Beispielen werden die metallischen Kontakte zunächst einer in der Galvanotechnik üblichen Vorbehandlung unterzogen und anschließend in einem der Elektrolyten der nachfolgend angegebenen Zusammensetzung mit einem Zinn-Graphit- bzw. Zinn/Blei-Graphit-Dispersionsüberzug beschichtet.In the individual examples, the metallic contacts are first subjected to a pretreatment customary in electroplating and then coated with a tin-graphite or tin / lead-graphite dispersion coating in one of the electrolytes of the composition specified below.

Die in den Beispielen angegebenen Korngrößenverteilungen < 1-5 um bedeuten, daß 70% der Graphitteilchen kleiner als 1 µm sind.

Figure imgb0001
The grain size distributions given in the examples <1-5 µm mean that 70% of the graphite particles are smaller than 1 µm.
Figure imgb0001

Die abgeschiedene Zinnschicht enthielt 1,6 Gew.-% Graphit. Die Abriebbeständigkeit stieg um das 10fache.

Figure imgb0002
The deposited tin layer contained 1.6% by weight of graphite. Abrasion resistance increased tenfold.
Figure imgb0002

Die abgeschiedene Schicht enthielt 2 Gew.-% Graphit. Die Abriebbeständigkeit stieg um das 18fache.

Figure imgb0003
The deposited layer contained 2% by weight of graphite. The abrasion resistance increased 18 times.
Figure imgb0003

Die abgeschiedene Zinnschicht enthielt 1,8 Gew.-% C. Die Abriebbeständigkeit gegenüber einer reinen Zinnschicht wurde um das 20fache erhöht.

Figure imgb0004
The deposited tin layer contained 1.8% by weight of C. The abrasion resistance compared to a pure tin layer was increased 20 times.
Figure imgb0004

Die abgeschiedene Zinn/Blei-Schicht (90/10) enthielt 1,8 Gew.-% Graphit und 1 Gew.-% Antimon. Die Abriebbeständigkeit gegenüber reinen Zinn/Blei-Schichten ist um das 25fache gesteigert.

Figure imgb0005
The deposited tin / lead layer (90/10) contained 1.8% by weight of graphite and 1% by weight of antimony. The abrasion resistance compared to pure tin / lead layers is increased 25 times.
Figure imgb0005

Die abgeschiedene Zinn/Blei-Schicht (60/40) enthielt 1 Gew.-% Graphit und 1 Gew.-% Antimon. Die Abriebbeständigkeit steigt um das 10fiache gegenüber einer reinen Zinn/Blei-Schicht.The deposited tin / lead layer (60/40) contained 1% by weight of graphite and 1% by weight of antimony. The abrasion resistance increases tenfold compared to a pure tin / lead layer.

Claims (14)

1. A process for the production of tin-graphite or tin/lead graphite layers which are electrodeposited in a single step using an electroplating bath in which graphite powder particles are incorporated, characterised in that an electroplating bath having a pH value ≤ 2 in which the graphite powder is dispersed by means of an acid-resistant substance that promotes the wetting of the particles by the electroplating bath is used and that the process is carried out at ≤35°C.
2. A process according to claim 1, characterised in that the electrodeposition takes place at current densities of 1 to 15 A/dm2.
3. A bath for electrodeposition of tin-graphite or tin/lead-graphite dispersion coatings with an electroplating bath comprising an aqueous solution of tin-II salts or tin-II and lead-II salts in which graphite powder is dispersed, characterised in that the electroplating bath has a pH of ≤ 2 and contains an acid-resistant organic substance that promotes the wetting of the graphite powder particles.
4. An electroplating bath according to claim 3, characterised in that the organic substance is one or more substances from the group
phenol and dibutylaniline,
gelatine and cresol,
cresol sulphonic acid and 2-methyl pentyl sulphate,
dibutyl sodium naphthalene sulphonate, or
sodium lauryl sulphate and sodium xanthogenate.
5. An electroplating bath according to claim 3, characterised in that the graphite powder has a grain size distribution < 5 µm, in particular with grain sizes < 1 µm.
6. An electroplating bath according to claim 3, characterised in that the tin-II salt is stannous sulphate, stannous fluoborate, tin methane sulphonate or tin methacryl sulphonate.
7. An electroplating bath according to claim 3, characterised in that the lead-II salt is lead methacryl sulphonate or lead methane sulphonate.
8. An electroplating bath according to claim 3, characterised in that in addition an antimony salt, for example potassium antimony-III oxide tartrate, is present.
9. An electroplating bath according to claim 3, characterised in that the acid solution contains sulphuric acid, fluoboric acid, methane sulphonic acid or methacryl sulphonic acid.
10. An electroplating bath according to claim 3, characterised in that it contains tin sulphate corresponding to 26 g Sn/I, 140 g/I sulphuric acid, 5 g/I phenol, 1 g/I dibutylaniline and 100 g/I graphite.
11. An electroplating bath according to claim 3, characterised in that it contains tin fluoborate corresponding to 66 g Sn/I, 120 g/I fluoboric acid, 20 g/I boric acid, 4 g/l gelatine, 6 g/I cresol and 100 g/I graphite.
12. An electroplating bath according to claim 3, characterised in that it contains tin-II-methane sulphonate corresponding to 70 g Sn/I, 300 g/I methane sulphonic acid, 6 g/l cresol sulphonic acid, 8 g/l 2-methylpentyl sulphate and 100 g/l graphite.
13. An electroplating bath according to claim 3, characterised in that it contains tin-II-methacryl sulphonate corresponding to 70 g Sn/l, lead-II methacryl sulphonate corresponding to 6 g Pb/l, 110 g/l methacryl sulphonic acid, 3 g/I potassium antimony-III-oxide tartrate, 0.5 g/l dibutyl sodium naphthalene sulphonate and 100 g/l graphite.
14. An electroplating bath according to claim 3, characterised in that it contains tin-II methane sulphonate corresponding to 9 g Sn/I, lead-II methane sulphonate corresponding to 4.5 g Pb/I, 250 g/l methane sulphonic acid, 0.5 g/I sodium lauryl sulphate, 0.1 g/I sodium xanthogenate and 60 g/I graphite.
EP86103563A 1985-03-29 1986-03-17 Process for the electrodeposition of composite tin-graphite or tin-lead graphite layers, and baths used therefor Expired EP0195995B1 (en)

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DE3511621 1985-03-29
DE3511621 1985-03-29

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EP1369504A1 (en) * 2002-06-05 2003-12-10 Hille &amp; Müller Metal strip for the manufacture of components for electrical connectors
DE10261303B3 (en) * 2002-12-27 2004-06-24 Wieland-Werke Ag Electrically conducting composite material used in automotive applications as electrical contact components, such as connectors or connections, comprises a metal strip and a contact layer containing carbon powder and a further additive
JP4783954B2 (en) * 2004-06-21 2011-09-28 Ｄｏｗａメタルテック株式会社 Composite plating material and method for producing the same
JP4813785B2 (en) * 2004-09-29 2011-11-09 Ｄｏｗａメタルテック株式会社 Tin plating material
JP4749746B2 (en) * 2005-03-24 2011-08-17 Ｄｏｗａメタルテック株式会社 Tin plating material and method for producing the same
JP4704132B2 (en) * 2005-07-04 2011-06-15 Ｄｏｗａメタルテック株式会社 Composite plating material and method for producing the same
JP4855032B2 (en) * 2005-09-29 2012-01-18 Ｄｏｗａメタルテック株式会社 Composite plating material and method for producing the same
JP2011017066A (en) * 2009-07-10 2011-01-27 Kyushu Nogeden:Kk Tin plated film and tin-plating bath for forming the same
DE102010040469B3 (en) * 2010-09-09 2012-01-12 Federal-Mogul Wiesbaden Gmbh Laminated material for sliding elements, process for its production and use
JP6173595B2 (en) 2013-11-19 2017-08-02 アクア メタルズ インコーポレーテッドＡｑｕａ Ｍｅｔａｌｓ Ｉｎｃ． Apparatus and method for non-smelting recycling of lead acid batteries
DE102015202631B4 (en) * 2015-02-13 2018-02-15 Schaeffler Technologies AG & Co. KG Bearings and procedures
US11028460B2 (en) 2015-05-13 2021-06-08 Aqua Metals Inc. Systems and methods for recovery of lead from lead acid batteries
EP3294931A4 (en) * 2015-05-13 2018-12-26 Aqua Metals Inc. Electrodeposited lead composition, methods of production, and uses
CN107889511B (en) 2015-05-13 2020-07-14 艾库伊金属有限公司 Closed loop system and method for recycling lead acid batteries
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DE3665886D1 (en) 1989-11-02
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US4652349A (en) 1987-03-24

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