DE1621109A1 - Metal product of high flexibility or pliability and corrosion resistance and method of manufacturing the same - Google Patents

Description

PATENT ADVOCATE

DR.-ING H FlNCK. ·

DIPL-IN G. H BÖHM
DIPL.-ING. 3. STAEGER 2 ?. AP

MDMC-HEN 5
MOLLERSTR. 31

M 21 222
Case 627

Description of the patent application.

the Pinna M&T? Chemicals Ine., New Χοϋτ, ΙΙ.Υ., V.St.A.

concerning

"Uetallprodulct high flexibility or suppleness and corrosion resistance as well as process for the production same "

Priorities: May 2, 1966 - V.St.A.

The invention relates to a new method for electroplating or electroplating. She concerns in particular a new process for the separation of stains Electroplating or for galvanic nickel deposition, which is particularly characterized by its high flexibility or suppleness and protective effect as well as its Ability to form a very corrosion-resistant product old chrome plated or plated, distinguishes T *

109816/1700

As is well known to those skilled in the art, products plated with chrome can be deposited by depositing a characterized by their flexibility or suppleness and smoothing or leveling ability first cladding or a first coat of semi-gloss dots that is characterized by its flexibility or suppleness and smoothing or leveling ability, a second plating or a second Plating of bright nickel and a final chrome plating or a final chrome coating on one metal or base metal manufactured ο Although see system can make it possible to obtain a product characterized by better corrosion resistance, it proved under extreme conditions as not sharing satisfaction ”. For example, it has been found that this system predicts too quickly when it is high. Stresses, strains, stresses or loads is subject to «Typical rvreiee can this can be observed in the vicinity of bolt bores or screw holes. When the bolt or the screw is tightened or tightened tensions can be generated and / or cracks or fissures, which allow attack by corrosive agents with a resulting impairment or deterioration of the cladding or the coating, in the cladding or in the coating to form.

It is an object of the invention to provide a new fuck plating

- 5 -109816/1700 __ — _.

BATH

-S-

or a new nickel plating, which respectively which is characterized by its or its ability to maintain maximum flexibility or suppleness and Corrosion resistance distinguishes itself to be provided ο Furthermore the invention is directed to a new chrome plating or a mmen chrome plating, which or which is characterized by its or its corrosion resistance, in particular under conditions of high tension, elongation or stress or deformation or respectively Deformation, excellent. Other goals will emerge from the description below. .

According to certain characteristics, that includes processes according to the sensitivity for the production of a nickel plating or a Nickel coating, which is characterized by its or its ability to receive a chrome plating or a chrome coating to a high degree characterized by flexibility or suppleness, the electroplating or galvanic coating of a Base metal or base metal with a first Layer of sulphurous, flexible or supple semi-gloss nickel plating or sulfur-free, flexible or supple semi-gloss nickel coating, the deposition of an r-wide layer of a metal of the type of copper, silver and gold with a thickness of 0.1 to 1.25 yea said semi-gloss nickel plating or on said semi-gloss nickel coating and electroplating or galvanic coating of said second layer with a bright nickel plating or a bright

109 816/1700 -4- '

BATH

1 R 7 1 1 O 9

Third layer nickel coating. ^IO ^ ^M

. The base metal or base metal which can be plated or coated by the method according to the invention can be Elsen including iron alloys such as steel, copper, nickel, brass, bronze, zinc or an alloy of any of these metals, etc., be. The excellent results according to the invention are particularly noticeable when the base metal or base metal is steel. It is a special feature of the method according to the invention that it allows the production of plated or coated products with excellent and unexpected properties if the material on which the flatting or the coating is deposited is an injection molding or shell casting based on zinc or zinc (zipc -base die-casting) is.

According to certain characteristics, the first stage of the invention Process the precipitation of a hereinafter referred to as "copper base plating" or "copper base plating" ("base copper plate") designated copper deposition on the Base metal or base metal include. In the case of injection molded or shell castings based on zinc or zinc base, this can be essential; in the case of other base metals, for example steel, this can be optional. The deposition of the desired Copper base plating or copper base plating the injection molding or shell molding on a zinc basis zinc or zinc can be deposited by the deposition of copper

109816/1700

can be made from a cyanide / copper plating bath " ! Typically, such a bath can have the -iLusainmentioned in the following fact : i, where all values are expressed in g / l Riad", so far nothing else is indicated.

Tabel I. Preferred minimum maximum 52 45 60 18th 15th 22nd

Duration share

Cu *

Free KCN (or NaCN)

• added as copper cyanide (CuCN)

The deposition dor Kupfergrundplattiorung or Kupferbasisplattierung can by electroplating or galvanic coating during B to 12 minutes, for example 10 minutes, at 60 to 70 ⁰ C, for example 65 ° C, and a cathodic current density of 3 to 6 A / dm, beispielaweiee 4.5 A / dm. The bath is preferably agitated or stirred, for example by stirring or moving with air or by means of a cathode rocker or rocker u, deposit.

The base metal or acisBietall, typically either a) an injection molding or shell casting based on zinc or zinc baaia with the above-described copper base plating or copper base plating or b. ' the steel base metal or steel base metal,

10 9 816/1 700 " ^BAÖ

soft if necessary a copper base plating or respectively Copper base plating can then be further treated according to the method according to the invention. Preferably confused. including on the base metal or base metal of the injection molding or shell casting on a zinc basis or zinc base old of the copper base plating or white copper plating, respectively, an additional layer of a sulfur-free, flexible or cutting semi-gloss nickel plating or a sulfur-free, flexible or supple, semi-glossy nickel plating is deposited. the Semi-gloss nickel plating or the semi-gloss nickel coating can typically catfish through galvanic deposition a bath of the Watts-type, a sulphamate bath, a chloride-free one Sulfamate bath, etc. or by other means including the decomposition of nickel carbonyl with resulting nickel deposition or by still other means of producing nickel-plated, plated or coated (nickel-clad) base metal or base metal are deposited.

A typical Watts bath useful in practicing the invention may contain the following ingredients in aqueous solution, all values except for pH a being expressed in g / l ο

- 7 -109816/1700

Table II

Components minimum maximum Preferred Nickel sulfates 200 500 300 Nickel chloride 30th 80 45 Boric acid 35 55 45 Semi-gloss builderaueata 0.2 3 0.75 electrometric
PH value 3 5 4.0

A typical one useful in practicing the invention Sulphamate-type bath may contain the following components:

Table III 3 maximum Preferred Components minimum 600 375 Nickel sulfamate 330 60 45 Nickel chloride 15th 55 45 Boric acid 35 3 0.75 Halbglansbilfinerzusats 0 5 4.0 electrometric
PH value

A typical one useful in practicing the invention Fluoborate-type bath: may contain the following components:

8th -

BATH ORIGINAL

109816/1700

Table IV 2 lüaxlaum 1621109 minimum »Liner of the Erfir 400 Components 250 60 Preferred Nickel fluorate OK 30th 300 Nickel chloride 15th 3 20th Boric acid Semi-gloss additive 0.2 4th 20th electrometric
PH value 0.75 in at the Durehfühi 3.0 usually usable tyois

Sulfate-type chloride-free bath may contain the following ingredients contain:

Components .

Nickel sulfate Boric acid

Semi-gloss additive

olektrometrisscher PH value

Table V maximum Preferred minimum 500 400 300 55 * 5 35 3 0.75 tz 0.2 5 4.0 3

A sulfamate-type bath that does not contain chloride can be used when performing the chloride-free bath contain:.

suitable typical following ingredients

BATH ORIGINAL

10981671700

TabsUe VI

Components minimum maximum Preferred Nickel sulfamate 300 400 350 Boric acid 35 ! 55 45 Semi-gloss builder susatβ 0.2 3 0.75 e lectromet ri scher
PH value 3 5 4.0

It is clear that the above baths have constituents outside the specified preferred minima and maxima may contain decreasing amounts “the most satisfactory and most economical operation can normally be achieved, however, when the Components are present in the baths in the specified quantities.

Halbg? Anabildnarzusätze, which when performing this first stage of the method according to the invention (using the Baths of Tables II to VI) can be used include typically coumarin, butynediol, chloral aydrate, etc. The preferred semi-brightener additive is coumarin at one concentration from 0.2 to J g / l, for example 0.75 ß / 1

The galvanic coating of the first sulfur-free, flexible or supple, smooth nickel plating or of the erate sulfur-free, flexible or supple, semi-glossy nickel plating can be obtained from the semi-gloss plating sheets of Tables II to VI by using a power current density of 1 to 10 A / dm, for example 5 A / dm to 60 ⁰ C, for example 55 ⁰ C, while

1Q981-6 / 1700

OK to 50 minutes, every 25 minutes. During this time, it may be possible to deposit a semi-glossy niche on the base metal or base metal with a ■ typical thickness of · ϊ5 to 40 iu, for example 25 in ».

The Halbglanznickelplattierung or the semi-bright nickel coating may be substantially ochwefelfrei, that is less than about 0 _r G04% sulfur, typischerweiee 0.002 to 0.004% sulfur and tianchmal only 0.001 to 0.0015% sulfur, "Dje flexibility or suppleness of Halbglanzplat ~ orientation or of the semi-gloss coating can be such that T / 2R can have a value of about 0.4 when measured by Chrysler's well-known standard micrometer test or the well-known standard micrometer test.

According to the method according to the invention, on the first sulfur-free flexible or supple semi-gloss nickel plating or on the first sulfur-free flexible or supple semi-gloss nickel coating a second layer of a metal like copper, silver or gold are electrodeposited. Preferably the second layer is copper.

The deposition of the second layer 5 can typically be carried out using an acidic copper plating bath, a pyrophosphate / copper plating bath, a carbon / copper plating bath, etc.

109816/1 700

A typical acidic copper plating bath can be used have the composition given in de: c following Table VIx;

Table YII (Saturation)
80
20th Preferred Components minimum 240
75
15th CuSO ₄ . 5 H ₂ O
sulfuric acid
Add 180
70
■ ■ ■. ■ Ί0

The additive is preferably in the acidic copper plating bath & in Rochelle salt or Kiu.iur <] na jrium tartrate, phenol sulfonic acid, etc. Preferred additives are llochelle salt or KaliXimn & triiiKtart.-cate in an amount of 10 to 20 g / 1 "for example 15 g / Bas electroplating or electroplating from an acidic copper plating bath can take place at / + C to 50 ° C, for example 45 ° C, for 0.5 to 2 minutes ₅ , for example 0.5 meow, with vigorous stirring or

It is carried out with air at a cathode-torrent density of 1 to 5 A / dm, for example 3 A / dm ¹ ".

The one deposited as the second layer after the process according to the invention Kupfer3cjaicht can also consist of a pyrophosphate / copper Flapping bath. Typi ^ chei-wise such a thing can Bath the composition given in the following Table VXII have?! :

~ 12 -

mQlH

109816/1700

part VIII

Components Minimum Maximum Preferred

Cu 20 30 25

P ₂ O ₇ " ⁴ 140 210 175

The galvanic deposition of copper from a pyrophosphate / £ upfer ° -Sad can with a Sümper & im-S ⁵ of 40 to 60 ⁰ G, for example 50 ⁰ C, for 0.5 to 2 minutes, for example 0.5 minute, with vigorous stirring or moving with air at a cathode tetrom density of 1 to 4 A / dm, for example 3 A / dm «

You second layer of copper metal can also consist of one Cyanide / copper bath of the composition given in Table IX below are galvanically deposited:

Tabel TZ Components Minimum Maximum Preferred

Cu ♦ 45 60 52

Free KCIi _{i5 22} ^

(or HaCH)

* added as copper cyanide

The additive is preferably used in a copper plating bath wetting agents, etc · Electroplating as galvanic * Covering from a cyanide / copper flattiorung bath can take place at 60 to

- 15 -

10 9 8 16/17 00 bad original

7O ⁰ C, for example 65 ⁰ C, for 0.5 to 2 minutes, for example 0.5 minutes, with stirring or agitation at a cathode current density of 1 to 6 A / dm, for example, 5 A / dm, are performed.

If the one on the first bright nickel plating, respectively the second deposited on the first semi-bright nickel coating If the layer is silver, it can be deposited from a bath of the composition given in Table X below:

Table X

Components Minimum Maximum Preferred

Silver 30 45 38

Free KGN

(or NaCN) 70 110 90

Electroplating 1 »ezlehimgswelse gal ^ aüaisshe deposition from the Sllberplattierußgsbad the X table KSSM at ZO to i? Ü ^o C, for example 22 ⁰ C ₁ during 0.5 to 2 minutes", for example O ₉ 5 minute under vigorous stirring or agitation with XiUft can be carried out with a cathode current of 0.5 to 2 A / dm, for example 1 A / dm

If the one on the first semi-bright nickel plating, respectively the second deposited on the first semi-gloss nickel coating Layer of gold is can ele from a bath as shown in the table below XX specified composition are deposited.

109816/1700

1621109 maximum Preferred 12th 8th 15th 12th

Table XI

Bast parts minimum

Au * 2

Free KCM η *

(or NaCN)

* added as potassium gold anide

. The additive in the Croldplating bath is preferably potassium carbonate, potassium phosphate, potassium ferroeyanide, etc. The preferred additive is potassium ferroeyanide in an amount of 1 to M g / l, for example 4 g / l. Bas electroplating or electrodeposition on the gold plating bath is at 60 ° to? 0 ° 0, for example, 60 ⁰ C, for 0.5 to 2 minutes, for example 0.5 minute with moderate stirring besiehuiigswaise moving, as by an electric stirrer or a cathode swing or «rocker is achieved, can be carried out at a cathode current density of 1 to 3 A / dm, for example Ί A / dm

Bas deposition of the metal on the type of copper, silver be "relationship as gold according to the procedure set forth above allows to achieve a layer of a Elekt2? Oplattierung or a galvanic coating with ailner thickness of about 0.1 to 1.25 _t li example" about O

According to the method according to the invention k <? Jm on the second Layer of copper, silver or gold a third layer, namely a ulanznickelplattiermxg respectively a

BAD ORlGiNA 15

109816/1700

Glansnickel Übersug, be deposited. The galvanic Ahacheiden γόη Gla & snlekel can be made from plating baths with a content on kickel sulfate, a chloride, for example nickel chloride, a buffering agent, for example boric acid, and a network » medium. Such baths include the Watts bath and the bath with a high concentration of chlorides. Other baths can use a combination of τ © η nickel fluorate with nickel sulfate and Nickel chloride or with combinations τοη nickel sulfamate and nickel chloride. Typical * baths of the Watta type and strong 'chlorine-containing baths' are given in the following Tables ZII and XIII specified.

Tabel XII 200 maximum Preferred 30th 400 300 Baths of Wadding Tyim 30th 75 60 Beatand parts Upa 38 ° C 50 40 Nickel sulfate 65 ° C 50 ° C Nickel chloride mechanically Boric acid and / or air temperature or pumping the Stir respectively 2.5 Solution, etc. Move 4.5 3.5 PH value

- 16 -

10 9 816/1700; _SAD

Strong Table XIII
Chloride-containing baths maximum Preferred Stirring or mechanical and / or
Move air or pumps
the solution 2.5 4 _f 5 3.5 Components 225 PH value Nickel chloride 150 150 85 Nickel sulfate 40 50 40 Boric acid 30th 65 ⁰ C 55 ° C temperature 38 ° C

Primary nickel brighteners in an amount of 0.002 to 0.2 g / l, for example 0.05 g / l, and secondary glass formers in an amount of 1 to 30 g / l, for example 5 g / l, can also be used in the electroplating baths of Tables XII and XIII. l, and secondary auxiliary glossing agents in an amount of 0.5 to 3 g / l, for example 1 g / l, be present. Typical primary brighteners include acetylenic compounds, such as butynediol, or pyridinium compounds, such as quaternized pyridine derivatives. Typical secondary brighteners include, for example sulfur / oxygen compounds _fr as saccharine, Na ^ or riumbenzolsulfonat benzolsulfonsaures sodium, uav.O typical secondary auxiliary brighteners include sodium allylsulfonate or sodium allylsuifonsaures.

The deposition of the third layer, namely, the Glanznickelplattlerung or of Glejaraickelüberzugee can at 40 to 60 ° 0, for example 50 ⁰ C and at a pH of

10981S / 1700 ___ _. * ^1? *

'te ORIGINAL

2.5 to 4.5, such as 5.5, for 8 to 14 minutes, for example 10 minutes, are performed to achieve a GlanznickeIplattierung or © ines bright nickel coating having a thickness of 7 to 12 P _t, γλ telapielsweise 10 to allow·

The base metal or Baeiastdtall with these 5 plating or overlay layers can be useful, though oine surface plated or coated with ulanznickel is desirable. Other decorative bright nickel surfaces can also be used including those brushed as atlas or satin surfaces or very glossy surfaces Surfaces (satin or brushed finishes) are used become 'be it that they are produced by mechanical or other means.

However, it is a new and most unexpected aspect of the composite deposit obtained in this way (with a first layer of sulfur-free, flexible or semi-glossy nickel, a second layer of Zupfer, silver or gold and a third layer von Gtl & nzni @ kelplattierung or (shiny nickel cover) that they are particularly tied together by their willingness to accept an ear orbital plating or a chrome coating, which means the achievement of a chrome-plated O @ § '"i8hungsw @ isa coated Pl & ttienang or a chromium plated b £ @ zi & bung w @ ls @ coated stieammengesetzten coating with a high degree isn @ rvrartet ύοά flexibility beziehungswei-

BATH

108816/1700

its suppleness ^! equips, shows Jane i '«

Chrome can be on the bright nickel plating or rather the glossy coating by the method according to the invention Precipitation from a chrome plating bath of In the following Table XIV specified composition are deposited.

Table 3EV ilaicimum Prefer Components minimum 400
4.0 250
2.5 CrO ₃
so. " ² .250
2.5

Sulphate can be provided in the form of sodium sulphate or sulfuric acid. Other components can also be present in the mentioned chrome bath, for example those "which prick the bath self-regulatingly or quickly,! Typical for such other components in the bath are in the form ύοώ. Strontium ions provided for strontium sulfate or in the form of potassium silicofluoride or potassium fluorosilicate 7or seen ions of formula " ²

The Flat animals or overcoats with chromium according to the, invention can at temperatures of 45 to 55 ° C ", for example, 5O ⁰ C _9, ten for example, 5 for minutes · for 2 to 4 minutes, with a Kathodenstromdlchte of 12 bl: j 20 A / dm, at therapy 14 A / dm, carried out yrerden «O? j]> le. _t ; histically, this can make it possible to achieve an OhrompAattierraig beziahiMigureise

109816/1700 ^e ^ o

gee with a thickness of 0.1 to % O si, for example 0.25 M, allow »

Εε is an unexpected feature of the chromium-plated or coated shielding compounds, which according to the invention Processes are generated that they are characterized by their unevaluated high corrosion resistance · It is a tesoader's salient feature of the new product according to the invention, that it is against the united or common Effect of tension, strain or stress and corrosive atmosphere exceptionally resistant or consistently 1st. It can lieIfr.rlalFweiae noted that when an after the "rfiridungsgfera" procedure manufactured with chrome plated or plated Product severe corrosion conditions, for example in the Corrodkote test or in the Corrodkote test (ASTM tasfe mumber B380-61T), subject to * this new product in surprisingly little or none over a period of 20 hours Corrosion showed if typical chrome plated respectively exaggerated depositions of the stand dos. «" eohnik show a high Degree of corrosion at the end of the 20-hour test respectively of the 20-hour attempt

But Ea let a imerwaxtst superior Merkmml this new product that it atäsidigk this high degree of Korrosionsb @ at "tightening, tendons or claiming: ince maintains · For example, if e £ n steel, with composite? Plating and / or ÄUSitmmengs esetztem Übex »a ^ g Cflatai steel composite)

09816 / 17OO

an arc of, for example, 90 to * lt? Q ° is bent (or if an injection-molded or shell casting on a zinc basis or Zijakbasie is bent around an * arc of, for example, 20 to 25 °), the following can be used:? estg; aste?, li5 Been _T that the Piättiermig or respectively the extremely elno retains sufficient flexibility or suppleness, so that their

or its corrosion resistance is essentially the same is like that of the non-bent specimen after 20 hours. On the other hand shows one by a plating process of the prior art similarly tensioned, stretched or stressed cladding Taosiohungqweisu a through a plating process of the prior art similarly tensioned, stretched, respectively stressed composite coating; a high degree of Corrosion at the end of the 20-hour test or the 20- - »hourly attempt.

If the base or Baal metal, like steel or an injection molding or shell casting on a zinc basis or zinc basis> a strong tension, strain or stress will imtonrorfen, as it is typically in the area immediately around a bolt hole respectively a screw hole is observed (that is, when the said area by attaching a nut and a bolt or a screw, which is screwed tight or be tightened to the base metal or base metal is tensioned) it is surprisingly found that the implementation of the method according to the invention the corrosion in

. - 21 "»

109816/1700 from

': ■ - 21 - ■ - ■'.

this deformed, warped or deformed area reduced to a minimum or substantially a If a steel-based or steel-based part with a hole according to the inventive method, plated or coated and with a similar XeIl on a steel base or steel base, which is produced according to typical processes of the prior art (i.e. semi-bright nickel and subsequently bright nickel and chrome) plated respectively was overdone »is compared, it is found that if a bolt or screw is inserted through the hole and screwed in such a way, respectively is tightened, that a significant deformation, versieung or deformation is generated in the normal way that product produced by the method according to the invention, the stresses generated and the corrosion during a period of time which is substantially greater than in the case of by the method state-of-the-art manufactured objects ,, resists ·

. The invention is explained in more detail with reference to the following examples, which are not to be interpreted as a base, all ropes being parts by weight, unless otherwise stated.

In these examples, the plating or coating was, unless specifically stated otherwise, on a base metal plate or base metal plate 1010 alloy steel with a thickness of about 1.5 mm and dimensions of 10 cm χ 15 cm carried out «

In all cases, unless otherwise stated,

1098167 1700

BATH

On the cleaned or cleaned steel base metal or steel base metal, a semi-gloss nickel plating or a semi-gloss nickel coating by deposition from a plating bath containing 45 g / l coal chloride, 300 g / l nickel sulfate, 45 g / l boric acid and 0.75 g / 1 coumarin, the pH being Value was held at about 4.0. Di · Operating the Halbglansbades was 55 ⁰ C * The Kathodenatromdlchte was 5 A / dm and the bath was agitated with air or moved. Plating, said to be coating, was carried out for 25 minutes to result in a deposition of 25 M half-glued noggles.

Whenever there is talk of a "nick!" of 0.05 g / 1 »saccharin as a secondary glass former in an amount of 1 g / l and butenediol monosulfate as a secondary auxiliary glazing agent in an amount of 1 g / l. The bath was set to an electrometric pH of 5 , 5 and a temperature of 50 ⁰ C kept. When plating or coating for 10 minutes, the bright nickel coating was obtained in a thickness of 10 η.

When decorative chromium plating was used, it was obtained by depositing from a bath containing 250 g / l chromic acid and 2.5 g / l sulfate (Ls sulfuric acid provided). Deposition over a period of 3 minutes at a cathode current density of 14 A / dm ² allowed one to be achieved

- 25 -109816/17 00

Decoration chrome plating or «a decoration chrome coating with a thickness of 0.25» ·

In the following Examples, a content of 38 g / l silver and 90 g / l free Kalitimoyanld (KCN) was treated with silver from a Silberplattierungsbad old plated or coated Bas plating or coating, 0.5 minute at a Kathodenstromdlchte of Λ A / dm while achieving a silver deposit of 0.25'ju. carried out.

In the following examples, gold was plated or fibersogenic with gold from a gold plating bath containing 6 g / l gold as gold yanal salt and 12 g / l potassium cyanide. Um * flattening or plating was carried out for 0.5 minute at a cathode current density of 1 i / dsr to achieve a gold deposit of 0.25 ρ.

In the following examples, copper was poured from a copper plating bath containing 240 g / l CuSO ₄ . 5 H ₂ O, 75 g / l sulfuric acid and 15 g / l Rochelle salts or Kaliumnatriumtartraten at 45 ⁰ C for 0.5 Hinute with vigorous stirring or agitation with air and at a Katho & enetromdichte of 3 k / äm while achieving a plating or a coating with a thickness of 0.25 ρ plated or coated "

In Example 6, the injection molding or shell casting used was a Zinkgrundlag® or zinc base

- 24 -109816/1700

BATH

■ - 24 -

Plate with a thickness of 1 * 5 and dimensions tob 10 cm χ 15 cm. This was cleaned or cleaned and provided with a copper base plating or copper base plating from a Blektroplattiextuigabad old with a content of 52 g / l copper and 18 g / l free cjjranide (added as potassium aoyanide). The electroplating or galvanic plating with this copper base plating or copper base plating was carried out for 10 minutes at 65 ° C. and a cathode current density of 5 A / am to achieve a copper plating with a thickness of 12 ρ.

example 1 In the EoatroXl b # ei © hungewei «e comparative example, the

reference-white standard «tahlbaeIs-

metal plate old of a bellows-polished nickel plating respectively a half-gloss nickel plating, then old a glossy nickel plate tion or a ßlanznlokel coating and then old a chrome plating or a chrome coating as specified above "

Example 2

In this example, which shows the implementation of a preferred embodiment of the method according to the invention, the standard steel base metal plate or standard steel base metal plate was coated with a semi-gloss nickel plating £ iehungsw @ i @ e 'a half-bent nickel cover, then old one

108 816 / 1700- bad original

copper plating or a copper coating, then with a glossy nickel plating or a glossy nickel coating and then with a chrome plating respectively iinoE. Chrome plating as indicated above - provided.

Example g

In this example, which shows the implementation of the invention The standard steel base metal plate or standard steel base metal plate with a Semi-bright nickel plating or one. Semi-gloss nickel plating, then with a silver plating respectively a silver print, then with a bright nickel plating or a shiny nickel coating and then with a chrome plating or a chrome plating as above indicated provided.

Example 4-

In this example, which shows the implementation of the invention Process represents Mixde the standard steel base metal plate or standard steel basal metal plate with a Semi-gloss nickel plating or a semi-gloss nickel coating, then with a gold plating or a Gold plating, then with a glossy nickel plating or, respectively, a bright nickel plating and then with a chrome plating or a chrome plating as indicated above Mistake.

10S816 / 1 700 ^BAD

Example ^

In this control or comparison example the standard steel base metal plate or standard steel base metal plate first with a gold plating or a gold plating, then with a shiny nickel plating or respectively a shiny nickel coating and then provided with a chrome plating or a Chroidibtfrsiig.

Example 6

In this control or previous example, was the standard steel base metal plate or standard steel base metal plate first with a copper plating respectively a copper plating and then provided with a chrome plating or a chrome plating.

Example 7

In this example, which shows the implementation of the erfindungsgeraäßdii Procedure illustrated using the standard injection molding method Standard casting 3tüak on zinc basis respectively Zinc base first with a copper base plating respectively a Eupfor base plate, then with a Semi-gloss nickel plating or a semi-gloss nickel coating, then with a second layer of copper, then with a bright nickel plating or a bright nickel plating and then with a chronicle explanation respectively provided with a chrome coating.

109816/1700 ς— - - 27 -

• ORIGINAL BATHROOM ·

Each of the Stahlgrsi & daietaXlpiatten or steel base stable panels or injection-molded or cast-shell plates based on tin or zinc For example, the oT> was given in more detail on Corrodkote- ~ 3fcan £ ardprüfung or d®m specified in more detail above Subjected to the Gorrodkote Standard Test. The steel plates were bent around an arc of 120 ° and inserted into an direction or a mounting frame (jug) installed or assembled the injection-molded or shell-molded plates zinc-based or zinc-based were bent around an arc of 20 ° and placed in a jig or «built into Stontagegestell © or assembled. She was testing by holding each plate in her Clamping device besie & weise of your mounting frame during Carried out 20 hours under conditions and after the test the following results were found:

Table XV Orundmetall- by way of example Basiame tallkorroeion example Yes 1 Neia 2 Hein 5 no Yes 5 - Yes 6th no ■ 7

- 28 -

109816/1700 ^ _0RraW At

Examination of the samples at the end of the 20-hour test indicated that in the bent area in the control and comparative examples 1, 5 and 6 there was substantial corrosion of the base metal or base metal, as is evident from many brown ones (in the case of steel) Rust strips or "strokes, which completely covered this area" showed. In the case of Examples 2, 3, 4 and 7, the bent areas were completely free of base metal or base metal corrosion. .

So it is from the above Table XV, in which the results of Corrodkote ^ test or the Corrodkote-Ver * · Suches are summarized, clear _v that the novel process to achieve a chrome plated or coated product, which is high due to its corrosion resistance if the flatting or the coating. In the above table, for example, a comparison of Examples 1 and 2 shows that the interposition or insertion of the copper layer with a thickness of 0.4 does (between the semi-bright nickel plating or the Semi-bright nickel plating and bright nickel plating or bright nickel plating) allows the achievement of a chromium-plated or coated composite plating or a chromium-plated or coated composite coating, which has a significantly greater corrosion resistance than that of the control or comparative tests *

109816/1700 ^

• -

By looking at the examples 3 and M && ζΰ particular by comparing the same troll with the Kon besieh ^ Bgswelse Comparative Example 1) shows that di © use also v © a silver or gold as the second layer achieving excellent results allowed "Ik? In all of these systems, the method according to the invention enables a significantly better product to be achieved.

A comparison between Example 4 (test example) and Example 5 (control or comparative example) clearly shows that the presence of the semi-gloss nickel layer in the new combination according to the invention contributes to the corrosion resistance of the product in an outstanding or excellent way o The comparative example 6 clearly illustrates that the presence of both the semi-bright nickel layer and the glossy nickel layer contributes significantly to the corrosion resistance of the product. Example 7 'soft £ ie Diarchfährung of he f indungsgemaSen procedure Aawenduftg to © in injection molding or'S'chalengußs ^ Ueck on Zickg; rus: illustrates .dl.age b © © zi himgsweis © zinc-based plays the violin on, ds. ß know the excellent results a © will also be obtained »

Various modifications of the invention are possible

Claims 10 9016/1700

Claims (1)

Patent claim® 1o) Metal product of high flexibility or suppleness and corrosion resistance with a base metal or base metal with a sulfur-free, flexible or plating or a s © Sw @ f®lfr @len flexible relational • as smooth Hal ^ glsiissiickelüberzug first layer and a Glanssii © & ®lpl & ttierung or a Glanznickelü ^ üraig AXN ^ ©! TARER layer, characterized in that 8wi @@ li @ ä ä®r H & lbglans & lckelplattierung like or @ m IalbglanimioktliifeorKug and the Glansnickelplattierung b @ ^ i @ huügsweis (S dem Glansniekelübarsug copper, silver ₆ of which copper is preferred, in a Thick® of 0.1 Ms 1.25 yes «preferably 0.2 $ » width S @ M9s 2o) Metallp ^ odisltt Ziach Mspradh "1, characterized gekennseichnet that on the Glansnlckalplattierung or the gloss nlokelübersug e ± m Ghromplattierung or a Chromüb @ rsug as sueätsllche layer. 3 '} Process for the production of the metal product according to claim 1 or 2 by electroplating or galvanic overlaying a base metal or base metal old a metal-free, flexible or solid nickel-plated nickel plating, catfish of a free, flexible, respectively. ugly supple - 51 - 109816/1700 ORiGIiSIAL BATHROOM Semi-gloss nickel coating as the first layer and a bright nickel plating or a bright nickel coating as a further layer, characterized in that one on the semi-bright nickel plating or on the semi-bright nickel plating copper, silver or gold, of which copper is preferred, in a bead from 0.1 to 1.25 µ, preferably 0.25 µ, deposited as the second layer and only then apply the glossy nickel plating or the glossy nickel coating as a third layer * 4.) The method according to claim 3, characterized in that aan used as base metal or base metal steel 3 ') A method according to claim 3, characterized in that aan ala Grocdnetall or Basiaaetall "in ZinkepritzguBstück or Zinkschalengußetuck ait a Kopfergrundplattierung or Kupferbasisplattierung, preferably one of 7» 5 to 15 u, used. 6o) Method according to claim 3 to 5 »characterized in that one the semi-gloss nickel plating or the Semi-gloss nickel oil coating in a thickness of 15 to 40 Ii separates. 7 °) Method according to claim 3 to 6, characterized in that dcS the second metal layer is deposited in G, 5 to 2 minutes. BAD 09816/1700 8 ») Method according to claims 5 to 7 _9, characterized in that the bright nickel plating or the bright coating is deposited in a thickness of 7 ^ is 12 u . 9 ») Method according to claim 3 to 8“ characterized in that an ear plating or a chrome borisug, preferably one or one with a thickness of 0.1 to 1.0 yu, as a fourth layer is applied to the bright nickel plating or the bright nickel plating as a third layer Electroplating or electroplating applies. 10.) Method according to claim 3 to 5 or 7 to 9 »characterized in that that the semi-gloss nickel plating or the semi-gloss nickel plating in a thickness of 7 «5 to 15 ρ separates. PATENT LAWYERS UR.-IHÖ H HNCtt DIM.- IN ». H.! OHR DtPL-IMA LtTAMBt ^BATH 109816/1700