CN102471911A - Process for the electrolytic copper plating of zinc diecasting having a reduced tendency to blister formation - Google Patents

Process for the electrolytic copper plating of zinc diecasting having a reduced tendency to blister formation Download PDF

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Publication number
CN102471911A
CN102471911A CN2010800366963A CN201080036696A CN102471911A CN 102471911 A CN102471911 A CN 102471911A CN 2010800366963 A CN2010800366963 A CN 2010800366963A CN 201080036696 A CN201080036696 A CN 201080036696A CN 102471911 A CN102471911 A CN 102471911A
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Prior art keywords
plating
copper layer
copper
electrolytic solution
electrolyte
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CN102471911B (en
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F·加斯纳
F·施特劳宾格
K·赖斯米勒
G·维尔特
S·诺伊豪斯
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Umicore Galvanotechnik GmbH
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Umicore Galvanotechnik GmbH
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    • CCHEMISTRY; METALLURGY
    • C25ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25DPROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D3/00Electroplating: Baths therefor
    • C25D3/02Electroplating: Baths therefor from solutions
    • C25D3/38Electroplating: Baths therefor from solutions of copper
    • CCHEMISTRY; METALLURGY
    • C25ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25DPROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D5/00Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
    • C25D5/10Electroplating with more than one layer of the same or of different metals
    • CCHEMISTRY; METALLURGY
    • C25ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25DPROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D5/00Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
    • C25D5/48After-treatment of electroplated surfaces
    • C25D5/50After-treatment of electroplated surfaces by heat-treatment
    • CCHEMISTRY; METALLURGY
    • C25ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25DPROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D5/00Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
    • C25D5/627Electroplating characterised by the visual appearance of the layers, e.g. colour, brightness or mat appearance

Abstract

In the electroplating of zinc diecastings with a copper layer, the electrolyte penetrates into the pores of the zinc diecasting. When the temperature is increased later, this leads to vaporization of the electrolyte liquid in the pores and to blistering or flaking of the copper layer. It is proposed that plating be carried out in two steps. In the first step, only a thin copper layer of less than 1 micrometer is applied and the plated parts are then treated at a temperature which leads to vaporization of the electrolyte liquid. The thin copper layer is still sufficiently porous for the vapour to be able to escape. Only the solid constituents of the electrolyte remain. The copper layer is then thickened to a final thickness of from about 20 to 30 micrometers. In this plating step, electrolyte liquid no longer penetrates into the pores of the zinc diecasting. The parts which are coated in this way display no blistering or flaking of the copper layer after storage at a temperature of 150 DEG C.

Description

Foaming with reduction forms the electrolytic copper plating process of the zine pressure casting of tendency
The foaming that the present invention relates to have reduction forms the electrolytic copper plating process of the zine pressure casting of (blister formation) tendency.
Deposited copper is fully known (reference 4) as far as those skilled in the art on zinc products or zine pressure casting.
According to prior art (reference 1,2,3), the first step in the copper facing of zine pressure casting is by alkaline cyanide electrolytic solution deposited copper.Subsequently, common deposition is from bright copper layers or the nickel or the bronze layer of acid electrolyte.
Special difficulty is the tissue of the base material of formation when injection-molded in the electro-galvanizing die casting.Casting be coarse crystallization and be penetrated in the inner hole.Only thin skin is fine and close in imporous.Forming in injection-molded process through the quick cooling of melt on the casting die wall should skin.Only this outside casting cortex can be electroplated according to prior art.But this black skin is very responsive, in preprocessing process, is corroded by oil removing and pickling sometimes and destroys, and makes the hole of base material come out sometimes.Plating bath itself also can destroy this black skin.
The coating of good bond can not be applied on the ruined surface again.In addition, because pretreatment baths or the ruined black skin of electrolyte cross are penetrated in the hole of base material, therefore usually bubble.In heat treatment process subsequently, liquid evaporation that has infiltrated and the outside coating that promotes to apply are to form blister or elevated regions.Under disadvantageous situation, the copper layer peels off.
Other shortcoming of method described in the prior is to use highly toxic electrolytic solution.From the reason of labour hygiene and environment, substituting electrolyte composition is therefore seemingly desirable.
The object of the present invention is to provide a kind of zine pressure casting process for electrolytically plating copper, can avoid the above-mentioned shortcoming of prior art thus greatly.
Method through comprising following process steps realizes this purpose:
A) by the first bronze medal layer of the copper electrolyte deposit thickness that contains pyrophosphate salt less than 1 micron,
B) flushing and under the temperature that improves dry these parts and
C) in containing the copper electrolyte of pyrophosphate salt, the first bronze medal layer is thickened 10 to 20 microns.
According to the present invention, at first on the black skin of zine pressure casting by the thin copper layer of the copper electrolyte deposit thickness that contains pyrophosphate salt less than 1 micron.In this first plating step or even in preprocessing process through oil removing and pickling, this black skin is destroyed usually.As a result, electrolytic solution can be penetrated in preprocessing process or in the plating process in the open now porous microstructure of zine pressure casting.Therefore this method it is highly important that the copper layer that in the first plating step, applies still has the enough porositys of the carrier fluid of electrolytic solution, the carrier fluid of this electrolytic solution evaporates overflowing in heat treatment process subsequently.Therefore this layer should not be thicker than 1 micron, and thickness is preferably 0.1 to 0.5 micron, is in particular 0.2 to 0.3 micron.
After the first plating step, be dried time enough, for example 10 to 60 minutes with the flushing of this parts and through under 100 to 180 ℃, preferred 120 to 160 ℃ and preferred about 140 ℃ especially temperature, storing.In this thermal treatment, be penetrated into the carrier fluid evaporation of the electrolytic solution in the porous zinc.Because of its low thickness, the copper layer that exists as the result of the first plating step remains porous, and for the steam in forming, is not impermeable, and the steam that forms when making heating can be overflowed.Only the solids component of electrolytic solution (salt) remains in the hole, and these can further not disturb.The existence of remaining electrolyte salt can be studied through for example SEM and/or EDX and confirm.
Wash preferred water and carry out, and be fully known those skilled in the art.
After plating and exsiccant zine pressure casting have cooled off, if suitable then proceed plating in identical containing in the pyrophosphate method of electro-plating liquid, up to having deposited about 5 to 50 microns, preferred 10 to 30 microns, preferred especially 10 to 20 microns copper.The thin copper layer that when the second plating step begins, has existed has prevented that obviously liquid electrolyte is penetrated in the porous zinc-base bottom material.The parts of plating bear about 30 minutes of storage under 150 ℃ and do not have and bubble to form or even peel off in this way.
The copper layer of first substep in a) can be through the electrochemical method deposition.Electrolytic deposition (reference 4) here is possible.Second copper coating can deposit on reductibility ground, or preferably through the electrolytic process deposition.In electrolytic process, mainly can mention three kinds of different plating methods:
1. be used for the wheel plating (drum plating) of bulk materials and mass-produced parts:
In this plating method, use the low relatively working current density (order of magnitude: 0.05-0.5A/dm 2)
2. the rack plating that is used for individual component:
In this plating method, use the medium working current density (order of magnitude: 0.2-5A/dm 2)
3. the high speed plating that in continuous device, is used for band or wire rod:
In this plating part, use the very high working current density (order of magnitude: 5-100A/dm 2)
Preceding two kinds of plating methods (wheel plating and rack plating) are important often as far as copper facing, depend on different electrolytic solution types, and wheel plating (low current density) or rack plating (medium current density) are possible.
As stated, process step a) and c) in the copper layer be applied on the zine pressure casting advantageously carry out through electrolytic process.Here no matter, treat that importantly sedimentary metal remains in the solution consistently in this process, be in continuous processing or discrete method, to electroplate.In order to ensure this point, electrolytic solution of the present invention contains pyrophosphate salt as complexing agent.
The amount that is present in the pyrophosphate ions in the electrolytic solution can be provided with the specific aim mode by those skilled in the art.It is subject to the following fact: the concentration in the electrolytic solution should be higher than minimum so that can realize above-mentioned effect with enough degree.On the other hand, the amount of pyrophosphate salt to be used is arranged by economic factors.In this case, can mention EP1146148 and the relevant information that wherein provides.The amount of pyrophosphate salt to be used is preferably the 50-400 grams per liter in this electrolytic solution.Especially preferably use the amount of 100-350 grams per liter electrolytic solution, preferred very especially about 200 grams per liter electrolytic solution.If pyrophosphate salt is not introduced with the form of the salt component of treating metal refining, it can be with basic metal diphosphate or earth alkali metal diphosphate or with H 2P 2O 7Use with the form of basic metal or alkaline earth metal carbonate/supercarbonate combination.Preferably use K for this reason 2P 2O 7
In used electrolytic solution, treat that sedimentary copper exists in solution with its ionic species.They are preferably introduced with the water-soluble salt form, and said water-soluble salt preferably is selected from pyrophosphate salt, carbonate, subcarbonate (hydroxycarbonate), supercarbonate, sulphite, vitriol, phosphoric acid salt, nitrite, nitrate salt, halogenide, oxyhydroxide, oxide compound-oxyhydroxide, oxide compound and combination thereof.Particularly preferably be very much wherein to have the embodiment that the ionic salt form uses copper, said salt is selected from pyrophosphate salt, carbonate, subcarbonate, oxide compound-oxyhydroxide, oxyhydroxide and supercarbonate.How to measure the color to the gained layer in which kind of the salt introducing electrolytic solution is conclusive, and can require to be provided with according to the human consumer.The ionic concn of copper can be set at 5 to 100 grams per liter electrolytic solution, preferred 10 to 50 grams per liter electrolytic solution.The gained ionic concn is preferably 15 to 30 grams per liter electrolytic solution especially.The preferred especially copper that uses every liter of about 15-20 gram of electrolytic solution, and copper is incorporated in the electrolytic solution with pyrophosphate salt, carbonate or basic carbonate salt form.
The pH of electrolytic solution is for electroplating desired 6 to 13.Be preferably 6-12, preferred especially 6-10.Most preferably use the pH of about 7.9-8.1.
Except treating sedimentary metal and be used as the pyrophosphate salt of complexing agent that this electrolytic solution can contain other organic additive that serves as brightener, wetting agent or stablizer.Electrolytic solution of the present invention also need not to use cationic surfactant.Only when the outward appearance of treating settled layer must satisfy particular requirement, just preferably add further brightener and wetting agent.Preferred one or more compounds that are selected from monocarboxylic acid and dicarboxylicacid, alkansulfonic acid, trimethyl-glycine and aromatic nitro compound that add.These compounds serve as the bath stabilizing agent of electrolytic solution.Especially preferably use carboxylic acid, alkansulfonic acid, particularly methylsulfonic acid or nitrophenyl triazole or its mixture.Mentioned suitable alkansulfonic acid among the EP1001054.Possible carboxylic acid is for example Hydrocerol A, oxalic acid, glyconic acid or the like (Jordan, Manfred, Die galvanische Abscheidung von Zinn und Zinnlegierungen, 1993, the 156 pages of Saulgau).Trimethyl-glycine to be used is preferably from WO2004/005528 or from Jordan, those of Manfred (Die galvanische Abscheidung von Zinn und Zinnlegierungen, 1993, the 156 pages of Saulgau).Particularly preferably be those disclosed among the EP636713.In this respect, very especially preferably use 1-(3-sulfopropyl) pyridine
Figure BDA0000136686240000041
trimethyl-glycine or 1-(3-sulfopropyl)-2-vinyl pyridine
Figure BDA0000136686240000042
trimethyl-glycine.
Electrolytic solution of the present invention be characterised in that its do not contain be categorized as poisonous (T) or very the poison (T +) Hazardous substances.It does not contain prussiate, do not contain thiourea derivative and does not contain thiol derivative.
Can be based on those skilled in the art's general knowledge and carry out the deposition of copper layer under the temperature of selecting.Be preferably 20 to 60 ℃, electrolytic bath remains in this TR in electrolytic process.More preferably 30-50 ℃.Most preferably under about 40 ℃ temperature, deposit.
Can in the known electrochemical cell of those skilled in the art, carry out step a) and c) in copper deposition (reference 1).When using nontoxic electrolytic solution, can use various anodes.Can use the combination of solubility or insoluble anode or solubility and insoluble anode.
As soluble anode, the preferred anode of forming by the material that is selected from electrolytic copper, phosphorated copper and copper alloy that uses.As insoluble anode, the preferred use by being selected from platinized titanium, graphite, iridium-transition metal mixed oxide and special carbon material (anode that " diamond-like carbon " or material DLC) are formed or the combination of these anodic.Especially preferably use by iridium-ruthenium mixed oxide the mixing oxide anode that iridium-ruthenium-titanium mixed oxide or iridium-tantalum mixed oxide is formed.Other insoluble anode is found in Cobley, people such as A.J., (The use of insoluble Anodes in Acid Sulphate Copper Electrodeposition Solutions, Trans IMF, 2001,79 (3), the 113rd and 114 page).
If the use insoluble anode when the base material (it represents negative electrode) of copper layer to be supplied is separated through ion-exchange membrane with the mode that forms cathode space and anode chamber with insoluble anode, obtains the particularly preferred embodiment of this method.In the case, only cathode space is filled by nontoxic electrolytic solution.Only contain electrolyte salt, for example the aqueous solution of potassium pyrophosphate, salt of wormwood, Pottasium Hydroxide, saleratus or its mixture preferably is present in the anode chamber.As ion-exchange membrane, can use cationic or the anionic exchange membrane.Preferred used thickness is 50 to 200 microns a Nafion film.
Thereby the thermal treatment between method of the present invention and particularly two the plating steps makes the carrier fluid of used electrolytic solution to be removed to make it can in parts heat-processed subsequently, not cause the degree of bubbling and forming or peeling off.On the contrary; If do not having by the electrolytic solution that for example contains pyrophosphate salt the copper layer to be put on zinc under the heat treated situation of step b) of the present invention; Then be penetrated into liquid in the porous substrate material and will be no longer can in the process of subsequently heating application member, overflow, and because the vp that produces and in coating, cause bubbling and form or peel off.This is that prior art institute is unforeseeable.
Reference
(1)Praktische?Galvanotechnik
Eugen G.Leuze Verlag, Saulgau, the 6th edition, 2005.
(2)Technologie?der?Galvanotechnik
Gaida,Aβmann
Eugen?G.Leuze?Verlag,Saulgau,2nd?edition,2008.
(3)Galvanotechnik
Nasser?Kanani
Carl?Hanser?Verlag,Munich,2nd?edition,2009.
(4)Kupferschichten
Nasser?Kanani
Eugen?G.Leuze?Verlag,Saulgau,1st?edition,2000.
Embodiment
Use has the electrolytic solution of following composition and uses copper plating zine pressure casting:
The potassium pyrophosphate of 300 grams per liters
The cupric pyrophosphate of 30 grams per liters
Water complements to 1 liter
With methylsulfonic acid with pH regulator to 8.
At 40 ℃ and 0.5A/dm 2Current density under in tube plating zine pressure casting 3 minutes.With this parts flushing, store 30 minutes down at 150 ℃ subsequently, after the cooling, further plating is 2 hours in identical bath.
The inspection foaming forms 30 minutes under 150 ℃ temperature in drying oven, does not have parts in coating, to show foaming.

Claims (3)

1. the foaming that the copper electroplating method that is used for zine pressure casting, this method have reduction forms tendency, it is characterized in that following steps:
A) by the first bronze medal layer of the copper electrolyte deposit thickness that contains pyrophosphate salt less than 1 micron,
B) flushing and under the temperature that improves dry these parts and
C) in containing the copper electrolyte of pyrophosphate salt, the first bronze medal layer is thickened 10 to 20 microns.
2. the method for claim 1 is characterized in that, in step a), first bronze medal is deposited to 0.1 to 0.5 micron thickness.
3. the method for claim 1 is characterized in that, in step b), these parts are 100 to 180 ℃ of times that store 10 to 60 minutes down.
CN201080036696.3A 2009-09-11 2010-08-12 Process for the electrolytic copper plating of zinc diecasting having a reduced tendency to blister formation Active CN102471911B (en)

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DE102009041250.6 2009-09-11
DE102009041250A DE102009041250B4 (en) 2009-09-11 2009-09-11 Process for the electrolytic copper plating of zinc die casting with reduced tendency to blister
PCT/EP2010/004942 WO2011029507A1 (en) 2009-09-11 2010-08-12 Process for the electrolytic copper plating of zinc diecasting having a reduced tendency to blister formation

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EP (1) EP2475808A1 (en)
JP (1) JP2013504685A (en)
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DE (1) DE102009041250B4 (en)
WO (1) WO2011029507A1 (en)

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EP2475808A1 (en) 2012-07-18
DE102009041250B4 (en) 2011-09-01
WO2011029507A1 (en) 2011-03-17
CN102471911B (en) 2014-10-15
US20120217166A1 (en) 2012-08-30
JP2013504685A (en) 2013-02-07
DE102009041250A1 (en) 2011-05-12
KR20120079065A (en) 2012-07-11

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