DE2620963A1 - PROCESS AND BATH FOR THE PRODUCTION OF A GALVANIC COATING - Google Patents

Description

PATENT LAWYERS
D R. - 1 N GH FINCKE
DIP L. - IM GH DRILL
DiPL-ING. S. STAEGER
DR. Rer. η-ΐ. R. KNEISSL
MÜLLER S TRASSE 31
MUNICH 5

Folder 23 968
M&T Case 1126

M&T Chemicals Inc., Greenwich, Conn., USA

Method and bath for producing a galvanic coating

Priority USA from May 16, 1975

The invention relates to improved methods and baths for electroplating Deposition of iron alloys with nickel or with nickel-cobalt. The invention particularly relates to use a new additive to improve the electrodeposition of iron-containing nickel and nickel-cobalt alloys.

Because of the compared to nickel and cobalt and their salts At a significantly lower cost of iron it would be very beneficial to be able to use nickel or nickel-cobalt alloys Electrodeposited iron, which has a significant iron content, which reduces the costs for the metals and salts.

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6098A8 / 0885 OfiJGiNAL inspected

would be reduced. It has been shown that of the two common valence forms of iron, namely Fe ⁺ and Fe, the ferrous form of Fe ^{+ is} the optimal form to allow electrodeposition of these alloys, although the baths generally also tolerate low concentrations of Fe ~ ions. In the electrodeposition of these iron alloys, however, the problem is that due to the presence of excessively high concentrations of Fe ⁺ ions, which can be formed by air or anodic oxidation of Fe ⁺ ions, these Fe ^ ions are added tend to precipitate out as basic salts, which not only have a disruptive tendency to clog anode bags and filters, but also separate out together with them, as a result of which deposits of unsatisfactory quality are obtained. This is because these can show cloudiness or localized matting, especially in peripheral areas. It can also be that - if the concentration of the suspended basic iron (III) salt is too high - micro-hills form over the entire surface, which is often referred to as "orange skin". The problem of the precipitation of basic iron (III) salts has made it very difficult to control the technical electrodeposition of alloys of iron with nickel or with nickel and cobalt.

Various possibilities have already been tried to overcome the problems associated with the formation of basic iron (III) salt precipitates. One option is to use a reducing agent that ^{keeps practically all iron ions in the Fe +} state. Although there are such reducing agents, but most tend to be unstable to form reaction products disturbing or affecting the deposition characteristics or the general Bath control and the bath behavior adversely.

609848/0885

Another possibility is to add an additive to the electroplating bath to bring in the iron (IIQ ions by complexing or chelating effect is soluble. So that such an additive is suitable for this purpose, it must have the following properties:

1. It must be used against electrolysis, i.e. reducing (cathode) and oxidizing (anode) conditions should be relatively stable.

2. It must be compatible with other additives which are added individually or in combination as a grain refiner or as a brightener, ie it must not adversely affect the behavior of these other additives.

3. It must be relatively cheap and not critical within its allowable concentration limits and

4. There must be fairly wide fluctuations in the Fe concentration be pretty resistant in the bathroom.

While there are some complexing agents that have some of the characteristics above Have properties, but generally lack others of these properties.

It has now been found that monosaccharides, oligosaccharides and polysaccharides have favorable properties that they can be oxidized and that they have complex-forming effects on iron (III) ions exhibit.

The object of the invention is generally the electrodeposition of alloys of nickel and iron and alloys

60 9 848/0885

To improve nickel-cobalt-iron. In particular, according to the invention, methods and baths for producing flawless electrodepositions containing iron and nickel or iron and nickel and cobalt are to be made available over a wide range of additive concentrations without significant precipitation of basic iron (III) salts. A further aim of the invention is to deposit nickel, cobalt or nickel-cobalt by electroplating, the iron content of the deposit being very low, generally well below 1% by weight, and z.3. 0.025% iron due to the iron content in the bath as an impurity. A preferable range of iron content can be 1 to 70% . A very preferred alloy range can be 5 to 50-6 iron in the electrodeposition.

An object of the invention is a method for producing an electroplating coating, which nickel and / or cobalt and also contains iron, in which an electric current is passed from an anode to a cathode through an aqueous acidic galvanic Bath is conducted that contains cobalt and / or nickel compounds and also iron compounds in order to remove cobalt, Nickel and. Iron ions for the electrodeposition of cobalt or nickel or of alloys of these two elements or of iron alloys with one of these elements or with both elements, which is characterized in that one a bath is used which contains an effective amount of boric acid and 2 g / l to 100 g / l of at least one monosaccharide, oligosaccharide and / or contains water hydrolyzable polysaccharide and that the electrodeposition is carried out over a period of time which is sufficient to leave a defect-free surface on the cathode galvanic metal coating is formed. Saccharides reduce the unwanted iron (IIl) ions to Elsen (II) ions and they also prevent the oxidation of divalent iron too

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trivalent iron. This reducing power is due in large part to the presence of aldehyde or keto groups in these Attributed to saccharides. Furthermore "these form saccharides strong complexes with Fe ions and these complexes remain in solution.

Typical examples of such saccharides are the following compounds:

Monosaccharides:

glucose

Fructose

Xylose

Arabinose

Mannose

Erythrosis

Glyceraldehyde etc.

Oligosaccharides:

Maltose Cellobiose Gentiobiose etc.

Polysaccharides:

Lactose

strength

Cellulose.

The baths can also have an "effective amount of at least one Components from the following groups included:

(a) primary brighteners;

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(b) secondary brighteners;

(c) secondary auxiliary brighteners; and

(d) Anti-pitting agents.

The substrates on which the nickel-containing, cobalt-containing, nickel- and cobalt-containing, nickel- and iron-containing or nickel-, cobalt- and iron-containing according to the invention produced galvanic coatings can be applied, know metals or metal alloys, as they are usually provided with galvanic deposits and used in electroplating. Examples are nickel, cobalt, Nickel-cobalt alloys, copper, tin, brass etc. Other typical substrate base metals from which objects are made that are later electroplated are e.g. ferrous metals, like steel; Copper; Tin and its alloys, such as lead; Copper alloys such as brass, bronze, etc .; Zinc, in particular in the form of zinc-based shell castings; all of the platings from other metals, e.g. from copper etc. The parent metal substrates can have a variety of surface conditions depending on the final look desired; the latter depends on such factors as gloss, brilliance, the leveling, the thickness etc. of the electroplating on such substrates Coating that contains cobalt, nickel, or iron.

As used herein, "primary brightening agent ¹¹ is intended to include galvanic additive compounds such as reaction products of epoxides with a-Hydroxyacetylenalkoholen such diäthoxyliertes 2-butyn-1 _t 4-diol or dipropoxyliertes 2-butyne-1,4-diol, other acetylenic substances , N-heterocyclic substances, active sulfur compounds, dyes, etc. Specific examples of such galvanic additives are the following compounds:

1,4-di- (ß-hydroxyethoxy) -2-butyne 1,4-di- (ß-hydroxy-T-chloropropoxy) -2-butyne

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1,4-di- (β-y-epoxypropoxy) -2- * butir.

1,4-Di- (ß-hydroxy-iT-butenoxy) -2-l) utin 1,4-Bi- (2'-hydroxy-4 ^l -oxa-6'-heptenoxy) -2-butyne N-1 , 2-dichloropropene3 / pyridinium chloride 2 _T 4,6-trimethyl-N-propargylpyridinium bromide N-allyl quinaldinium bromide

2-butyne-1,4-diol

Propargyl alcohol

2-methyl-3-butyn-2-ol

Thiodiproprionitrile

, CH ₂ CH ₂ CN

Thiourea
Phenosafranine
Vixen.

If, they can be used alone or in combination the primary brighteners on the galvanic coating do not produce any visible effects or they can be semi-glossy, deliver fine-grained deposits. However, best results are obtained when primary brighteners are combined with a secondary Glass former, a secondary auxiliary brightener, or both are used in order to achieve optimal conditions with regard to the gloss of the deposit, the gloss rate, the leveling, the gloss current density range, the density coverage at low amperage etc.

As used herein, the term "secondary brighteners" is intended to include aromatic sulfonates, sulfonamides, sulfonimides, sulfinates, etc. lock in. Specific examples of such galvanic additives are the following compounds:

1. Saccharin

60984 8/0 8 85

2. Trisodium 1,3,6-naphthaliritrisulfonate

3. Sodium sulphate sulfate
H. Dibenzenesulfonimide

5. Sodium benzene monosulfinate.

Such galvanic additive advertising, individually or in suitable form Combinations that can be used have one or more of the following functions:

1. The production of semi-glossy deposits or the Creation of a significant grain refinement compared to the usual, non-glossy, matt, core-shaped, non-reflective deposits from additive-free baths,

2. The effect as a conductivity agent when used in combination used with other additives, such as primary brighteners,

3. The control of internal stresses in the deposits by compressing the stresses in a favorable manner will,

4. the introduction of controlled sulfur contents in the electrodeposition in order to reduce the chemical reactivity, To influence potential differences in composite coating systems etc. in a favorable manner, whereby the corrosion phenomena are reduced and a better corrosion protection of the base metal is achieved etc.

As used herein the term "secondary brighteners" shall be aliphatic ^ or aromatic-aliphatic, olefinic or acetylenically unsaturated sulfonates, sulfonamides, or sulfone

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denote imide. Specific examples of such galvanic Additives are the following compounds:

1. Sodium allyl sulfonate

2. Sodium 3-chloro-2-butene-1-sulfonate

3. Sodium C-β-styrene sulfonate

4. Sodium propargyl sulfonate

- 5. Monoallylsulfamide (H ₂ N-SO ₂ -NH-CH ₂ -CH = CH ₂ )

6. Diallylsulfamide

vNH allyl

^X NH-allyl

7. Allylsulfonamide

Such compounds, when used alone (which is common) or in combination, have all the functions of them for the secondary brighteners. They also have one or more of the following functions:

1. They work in such a way that pitting corrosion is prevented or reduced to a minimum value (probably, by acting as hydrogen acceptors).

2. You can use one or more secondary brighteners and one or more primary brighteners work together to give better rates of gloss and leveling than either or two compounds from all three of the following classes can be obtained:

(1) primary brighteners;

(2) secondary brighteners; and

(3) auxiliary secondary brighteners, either alone or in combination.

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ίο -

3. You can die from catalytic poisoning etc. Condition the cathode surface so that the consumption rates of the interacting additives (usually of the type of the primary brighteners) can be reduced considerably, making the operation more economical and becomes more controllable.

Ions can also be included in the class of secondary auxiliary brighteners or compounds of certain metals and of metalloids, such as zinc, cadmium, selenium, etc., which - although they are currently not generally used - already have been used to reduce the gloss of the deposit, etc. to reinforce. Other interacting additives of organic nature, which may be suitable are the hydroxysulfonate compounds U.S. Patent 3,697,391, i.e. typically sodium formaldehyde bisulfite, Its function is to make the baths more compatible with concentrations of the primary brighteners make, whereby the compatibility with metal impurities, e.g. zinc etc., is increased.

As used herein, the term "anti-pitting agents" is intended to refer to materials (in addition to the secondary auxiliary brighteners and different therefrom) which prevent gas pitting or reduce it to a minimum value. A means to prevent pitting corrosion can also act in such a way that it protects the baths against impurities such as oils and fats etc. makes it easier to tolerate, which is due to their emulsifying, dispersing and dissolving, etc. action occurs on such impurities, thereby obtaining flawless deposits is promoted. Agents against pitting are optional additives, optionally in combination with one or more Components from the group of primary brighteners, secondary brighteners and secondary auxiliary brighteners can be used

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609848 / 088S

can. Preferred agents against pitting corrosion are e.g. sodium lauryl sulfate, Sodium lauryl ether sulfate and ITodium dialkyl sulfosuccinate.

Typical nickel-containing, cobalt-containing, and nickel-cobalt-containing Bath compositions that are effective in combination with Kengen from about 2 g / l to 100 g / l monosaccharide, oligosaccharide and polysaccharide compounds and effective amounts of about 0.005 to 0.2 g / L primary brighteners, with about 1.0 up to 30 g / l secondary gloss builders, with about 0.5 to 10 g / l secondary auxiliary brightener and with about 0.05 to 1 g / l agents used against pitting are described in more detail below.

Typical aqueous nickel-containing electroplating baths (which in combination with effective amounts of the cooperating additives can be used) are for example the following mixtures, in which, unless otherwise stated, all concentrations are given as g / l:

Aqueous galvanic nickel baths Table I.

Component minimum maximum preferred

Salary salary

Nickel sulfate nickel chloride boric acid pH (electrometric)

The ratio of nickel ions to iron ions in the bath described above is from about 1: 1 to about 50: 1.

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50 500 300 7.5 80 45 10 - 55 45 3 5 4th

A typical STilfan-ttype galvanic nickel cad, d- ~ s for The invention can be used the following components contain:

Table TI

component

minimum raxir.aler tevorzupr-salary Geh? It "" er Gi- '

I - _ ■; J- ο

ITickelsulfanate jickel chloride boric acid pH (electrometric)

50 400 45 1.5 60 45 10 55 * 4th 3 5

The ratio of kickel ions to iron ions in the above described bath is about 1: 1 to about 50: 1.

A typical chloride-free sulphate-type nickel bath used for Can be used to practice the invention, the following can be used Components include:

Table III

component

minimum maximum preferred ~ - Salary salary

Ilickelsulfat Ecric acid pH (electrcmetric)

50 5 50c / - • -00 3.5 10 55 45 2, 4th 3 Ms

A typical chloride-free galvanic nickel bath of the sulfarate type, used in the practice of this invention can contain the following components:

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IMSPSCTED

Table IV

Component 'minimum maxir-sler preferred: -

Salary salary

: -; ickelsulfaraat 50 ^ C 2 350

Boric acid 10 55 ^ 5

ρ Ε (electr © metric) 2.5 4 ~ to 3.5

The ratio of nickel ions to iron ions in the above described bath is about 1: 1 to about 50: 1.

It will be appreciated that the above baths may contain compounds in amounts that may be outside of the specified :: more preferred, minimum and maximum ranges, but best and economical operation will normally be obtained when the compounds in the baths are in cen specified: quantities are included. A particular advantage of the chloride-free versions of Tables III and IV above is that the aboard coatings obtained are practically free of tensile strength and that they allow high-speed plating with the use of boiling-speed anodes.

The following are aqueous electroplating cobalt baths and cobalt-nickel baths indicated in which the combination of effective Kengen veη one or more additives according to the invention gives favorable results.

609848/0885 Orkwal inspected

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Aqueous zinc (~ irid All concentrations? Unless otherwise s- ^v '. ·? ~ Giver., In g / l indicated) ^ Kobaltba der.und cobalt-nickel-I ^ cer

i <.obaltbaa; maximum
salary 350 4CO All-chloride-cobalt bath: 500 Go »!"; •
» 25th .7 '3'.'ΟΓΖ i- ¹ ^ ^- -
-1-- "" r ^ V ,; -; + CoSO ₄ -7H ₂ O 4CO 350 225 CoCl ₂ -6H ₂ O 50 j ^l -j 25th : cc CoCl ₂ -6H ₂ O 75 50 75 5 10 to H ₃ SO ₃ 50 Cobalt-nickel alloy bath: 50 SuIfamat cobalt bath: 400 10 45 Cobalt bath: NiSO ₄ * 7H ₂ 0 Co (O ₇ SNH ₂ ) ₂ 75 50 CoSO ₄ -7H ₂ O 500 CoSO ₄ '7H ₂ O CoCl ₂ -SH ₂ O 50 50 5 LOO NaCl 50 NiCl ₂ -6H ₂ O H-J30-T ~ 5 30th 3 's> 50 H ₃ EC ₃ 10 10 45 Cobalt bath with high chloride content CoSO ₄ -7HpO 50 225 CcCl ₂ -SH ₂ O 10 225 H ₃ BO ₃ 45 50 3CO 10 80 60 L ₅ 300 45 2? 0 cO 45

The ratio of nickel ions to iron ions in the abovementioned baths is about 1: 1 to about 50: Λ

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Preferred ga3.vanische Eobaltbäder can at least about ^ O g / l * CcCIp -HoO more typical and / else 20 to 50 g / l CoCIp 6 ^T T _r .O contain *. Other compounds a kit the bath vertr-i.-r.isHPS cation own (ie, a cation which aen operation of T '^ os does not interfere), at least 7.5 g / l chloride ions, Cl "^ vo: rcu-sv-eise eir ⁵ Kiniirurj of about 9 g / l Cl ") can be verd et ^{τη :: '5 IIs.}

The pH of all of the above-mentioned aqueous Kicl-ielb ·; IzT ₁ Kotaltbäder, Nickel-Cobalt-Eäder and I? Ickel-Cobalt-Eggs, -2 * ider can be.1 'during the electroplating be.1' values from 2.5 to 5, C- preferably about 3jO to 4.0, being held. While the bath is in operation, the pH value normally rises and it cannot be readjusted with acids, e.g. hydrochloric acid and sulfuric acid, etc.

The operating temperature range for the large baths can be about J <0 to 7CC, at temperatures in the range of 4f> to 65 "C are preferred.

"• ta

A movement of the baths above during electroplating can consist of recirculating the solution, the. ? Cathode rod moves and / or performs an air movement. In applications where the deposition of ferrous alloys from baths in which iron weighs in wrong eggs. (II ^ state (bivalent) is present, it is preferred to use a very gentle agitation, i.e. movement of the catholic rod, apply to the air oxidation of iron (II) ions in iron (III) ions to be attributed to a minimum value.

For the electrodeposition of binary or ternary alloys, e.g. nickel-cobalt and nickel-iron or nickel-cobalt-iron alloys, the anodes may consist of the separate metals in question, suitably lsi bath in

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ORIGINAL INSPECTED

In the form of rods, strips or small pieces suspended in titanium bars. In such cases, the ratio of the anc ~ is aer.oberf laugh, the individual Ketalle set to do 2? Ε of reveils desired alloy additions ^ arrciensetzung dor Kathe I? is equivalent to. For the galvanic deposition of binary egg-ternary alloys, nan can also use as anode alloys of the respective metals in such a weight ratio of the individual metals expressed in percent by weight that the ratio of the same metals expressed in percent by weight is obtained in the desired cathode alloy deposits. These two types of anoic systems generally lead to a fairly constant concentration of the bath metal ions for the respective metals. If irregularities of the bath ions occur with a fixed metal ratio of the anode alloys, then occasional adjustments can be avenged by adding the individual metal salts in appropriate corrective amounts. All anodes are suitably covered with cloth or plastic bags of the desired shape to minimize introduction of metal particles, anode sludge and the like into the bath which could mechanically or electrophoretically migrate to the cathode and result in rough cathodic deposits.

The invention is illustrated in the examples. example 1

A nickel electroplating bath was prepared by adding the following ingredients with water to the indicated concentrations (in g / l, unless otherwise stated) were mixed:

KISO ^ 7H ₂ O

Concentration (g / l) • 6C

6098 48/0885 origwal Ispeoted

H ₃ BO ₃ ^ 5

Iron (II) sulfate (FeSO ^ -7H ₂ O) 40

Reaction product of butynediol with 2 KoI

Ethylene oxide 50 mg / 1

Sodium saccharinate (0.6 Hol H ₂ O) <k, 0

Sodium allyl sulfonate 2,3

Fructose 20

PH 3.3

A polished brass plaque was scratched with a single horizontal pass of 2/0 grain emery, whereby a band width of about 1 cm was obtained at a distance of about 2.5 cm from the bottom of the plate. After cleaning the surface, including the use of a thin cyanide copper layer to ensure excellent physical and chemical purity, it was stored in a Kull cell for 10 minutes at a cell strength of 2 A and at a temperature of 50 C and galvanized using a magnetic stirrer. The resulting deposit was uniformly fine grained, well leveled, and had a glossy appearance. There was excellent ductility and good coverage at low sr current density.

2 ^ i game 2

Example No. 1 was repeated using 40 g / l sucrose, i.e. a disaccharide, instead of fructose with the same results were used.

Example_ 3

Example Kr. 1 was repeated using 40 g / l of glucose, i.e. a; - "or.csaccharide instead of fructose with the same results were used.

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Example 4

Example No. 1 was repeated, using 20 g / l lactose., I.e. a disaccharide instead of fructose with the same. Results were used.

Example 5

A nickel-iron bath was made by mixing the following ingredients with water to the indicated consents became:

O JOO g / l

₂ pO 60 '■ /!

Boric acid 45 g / l

Sodium allyl sulfonate 2.3 f / l

Saccharin 4.0 ^ / l

FeSO ₄ -YH ₂ O $ 10.0 / l

Glucose 10.0 g / l

Proparg3r alcohol 20 mg / l

PE 3, c

Temperature 54 ° C "

The resulting deposit was glossy, fairly good eir-re paved and ductile.

Example 6

A nickel-iron bath was made indene; the following components six water were mixed to the specified concentrations:

NiSO ₄ -6H ₂ O -00 fr / 1

60 srjl

609848/0885

20th 5 g / l 45 J g / i Q 3 g / l 4th τ O p / l IG, 5/1 40 O r- «r / l

FeSO ₄ * 7H ₂ 0

Boric acid sodium allyl sulfate Saccharin starch eutindiol

The bath was filtered and tested in a Kull cell. the Deposit was glossy and leveled. The Buktilitst was bad.

Example 7

A nickel-iron bath was made using the following ingredients mixed with i ^. ?? sr to the specified concentrations became:

; 00 g / l 60 g / l

FeSO ₄ .7H ₂ O 40 g / l

Boric acid 40 g / l

Sodium allyl sulfonate 2.5 g / l

Saccharin 4.0 g / l

Galactose 10.0 g / l

2,3-dichloropropene pyridinium chloride 20.0 mg / l PH 3.5

Temperature 5 ^ ⁰ C

The resulting deposit was glossy, ductile, and had moderate planarization.

Ex iel 8

Sin Ilickel Iron Bath was made by doing the following

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INSPECTED

components at the specified concentrations ~ dt water mixed became:

KiSO ^ -OH ₂ O JCC g / l

0 6C s / l

20th g / l 45 ? g / l 2, 0 p / l 0 g / l 10, 0 rng / l 40,

FeSO ₄ "7H ₂ O

Boric acid sodium allylsuifonai Saccharin dextrose butynediol

The resulting deposit was glossy, well leveled, and ductile.

Example 9

Example Ur. 8 was repeated, but the amount of FeSO / -7H ₂ O was increased to 40 g / l. The resulting deposit was glossy, planarized, and had poor ductility.

Example 10

A nickel-iron bath was made by adding the following ingredients mixed with a drum to the specified concentrations became:

NiSO ₄ -6H ₂ O 300 g / l

NiCl ₂ -6H ₂ O 60 g / l

FeSO ₄ -7H ₂ O ^ O g / l

Sodium allyl sulfonate 2, ΐ g / l

Saccharin 4.0 g / l adduct of butynediol with 2 mol propyl oxide 20.0 mg / l

Sucrose 20.0 g / l

609848/0885

ORIGINAL iMSPECTHD

The resulting deposit was moderately leveled, glossy and ductile.

Example 11

Example Kr. 10 was repeated using a mixture of. 10 g / i Glucose and 10 g / l erythorbic acid used instead of starch became. The resulting deposit was glossy, fair leveled and ductile.

Example 12

Example Kr. 10 was repeated, a mixture s-.us 10 g / l Dextrose and 10 g / l sodium gluconate instead of Sts »: e vewen · it would. The resulting deposit was glossy / !, ductile and leveled.

Example ^ 5

Example Kr. 10 was repeated using a mixture c-.us 10 g / l glucose and 10 g / l of sodium citrate was used. The deposit was ductile, glossy, and well leveled.

^ Jf INAL IMSPECTED

609848/0885 '

Claims (1)

P a t e η t a η s ό γ ü ehe 1, method of making a galvanic. Coating containing nickel and / or cobalt and also sisen in the current from an anode to a cathode through a - ·, - £.? ri "s only it is conducted galvanic bath, which kicke Iv er-tir, ± \: n ~ an, cobalt compounds and / or iron (II) compounds e; v": h "ilt, υ.Ώ ions for the electrodeposition of nickel, Eotrlt,? C ~ .kkel-cobalt alloys, nickel-iron alloys or nickel-cobalt-iron alloys, thereby g eke η η denotes that nan uses a bath, vrelches a effective I-Tenge boric acid and 2 g / l to 100 g / l at least one conosaccharide, oligosaccharide and / or polysaccharide contains, 2. The method according to claim 1, characterized in that a bath is used, velchos as nickel compounds Contains nickel sulfate and? Ji disgusting chloride. 3 ♦ Method according to claim 1, characterized g e k e r. η draws that one uses a bath, which is used as a hook connection Contains kickelsulfamate and nickel chloride lt » 4. The method according to claim 1, characterized in that a bath is used which is used as cobalt compounds Contains cobalt sulphate and cobalt chloride, 5. The method according to claim 1, characterized in that a bath is used, vrelchsn as Ko balt compounds contains cobalt sulfamate and cobalt chloride. 6. The method according to claim 1, characterized in that ηεη uses a bath containing 3 ice egg (II) compound iron (II) sulfate or iron (II) chi erJd ent. 609848/0885 -> ^BAD 7 - Procedure according to. Claim 1, characterized in that g e; < e r. n- draws that a bath is used, velshüs «is honosaccharide Contains glucose. 8. The method according to claim 1, characterized in that g e k ε η η - draws that I am wasting a bath, rather than conosaccharide Contains fructose. 5. The method according to claim 1, characterized in that g s I: e η η - draws that one uses a bath, which as ITencsaccharid Contains xylose. 0O. Process according to claim 1, characterized in that a bath is used which contains arabinose as con no ε accharide, 11. The method according to claim 1, characterized in that there is used a bath which is used as I-Ioncsaccharid Contains mannose. 12. The method according to claim 1, characterized in that a bath is used, which as Γ · 1ο-nosaccharide Contains erythrosis. 13. Process according to Claim 1, characterized in that a bath is used which is used as a monocaccharide Contains glyceraldehyde. 14. The method nach.Anspruch 1, characterized in that a Bsd is used, which as Ol.igosaccharid Contains maltose. 15 - The method according to claim 1, characterized in that that one uses a bath, which as an oligosaccharide Contains cellobiose. -24-609848 / 0885 I ¹ S. Method according to claim 1, characterized in that άΰ.3 one uses an Ead, ve 1 ehe? sis contains glycosaccharide gentiobiose. 17. The method according to claim 1, characterized in that one uses a Sad, "rich as a polysaccharide Contains lactose. 18. The method according to claim 1, characterized in that a bath is used -which is used as a polysaccharide Contains starch. "9. The method according to claim 1, characterized in that ican uses a bath which is used as FoIypacche.rid Contains cellulose. 20. Aqueous galvanic bath with a content of nickel compounds, Cobalt compounds and / or iron (II) compounds, uro Ions for the galvanic deposition of nickel,? Iobalt, ITikkel-cobalt alloys, Nickel-iron alloys or nickel-cobalt-iron alloys to give, characterized in that there is also boric acid and at least one Contains monosaccharide, oligosaccharide and / or polysaccharide in single or combined concentrations of 10 g / l to 50 g / l. 21. Bath according to claim 20, characterized in that that there are nickel sulfate and nickel chloride as nickel compounds contains. 22. Bath according to claim 20, characterized in that that it contains nickel sulfamate and nickel chloride as nickel compounds. —25— 609848/0885 23. Bath according to claim 20, characterized in that it is cobalt sulf'ite and cobalt compounds. Cobalt chloride contains. 24. Bath according to claim 20, characterized in that it is cobalt sulfate and rr-ate as cobalt compounds. Cobalt chloride contains. 25. Sad according to claim 20, characterized in that it is the iron (II) compound and iron (II) sulfate
Contains iron (II) chloride. 26. Bath according to claim 20, characterized in that it contains glucose as the monosaccharide. 27. Bath according to claim 20, characterized in that that it contains fructose as a monosaccharide. 28. Bath according to claim 20, characterized in that that it contains xylose as a monosaccharide. 29. Bath according to claim 20, characterized in that that it contains arabinose as a monosaccharide. 30. Bath according to claim 20, characterized in that it contains mannose as the monosaccharide. 31. Bath according to claim 20, characterized in that geke η r; ζ does not prove that it contains er3c rose as a conosaccharide. 32. Bath according to claim 20, characterized in that it contains glyceraldehyde "." As the monosaccharide. -26- 609848 / 088S 33. Bath according to claim 20, characterized gekenrzeicb. net, there *? it contains kai to se as OliiXcsaccharide. 54. Bath according to claim 20, characterized r. e t that it is cellobiose as oligosaccharide er.thiiö » 35. Bath according to claim 20, characterized ge ke r. r- ζ does not show that it contains gentiohiosa as oligosaccharide. 36. A bath according to claim 20, characterized Eke g η η ζ e i net, that it contains as polysaccharide lactose. 37. Bath according to claim 20, characterized. net that it contains starch as a polysaccharide. 38. Bath according to claim 20, characterized net that it contains cellulose as a polysaccharide. , .-, - <<E [>; PL ING. H. BOHR 609848/0885 /