CN102471911B - 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
CN102471911B
CN102471911B CN201080036696.3A CN201080036696A CN102471911B CN 102471911 B CN102471911 B CN 102471911B CN 201080036696 A CN201080036696 A CN 201080036696A CN 102471911 B CN102471911 B CN 102471911B
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Prior art keywords
plating
copper layer
copper
electrolytic solution
electrolyte
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CN201080036696.3A
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CN102471911A (en
Inventor
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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    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D3/00—Electroplating: Baths therefor
    • C25D3/02—Electroplating: Baths therefor from solutions
    • C25D3/38—Electroplating: Baths therefor from solutions of copper
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
    • C25D5/10—Electroplating with more than one layer of the same or of different metals
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
    • C25D5/48—After-treatment of electroplated surfaces
    • C25D5/50—After-treatment of electroplated surfaces by heat-treatment
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
    • C25D5/627—Electroplating 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

There is the electrolytic copper plating process of the zine pressure casting of the foaming formability of reduction
The present invention relates to the electrolytic copper plating process of the zine pressure casting of foaming formation (blister formation) tendency with reduction.
On zinc products or zine pressure casting, deposited copper is abundant known (reference 4) for those skilled in the art.
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, conventionally deposit bright copper layers or nickel or the bronze layer from acid electrolyte.
In electro-galvanizing die casting, special difficulty is the tissue of the base material of formation when injection-molded.Casting be coarse crystallization and be penetrated in inner hole.Only thin skin is fine and close in imporous.Quick cooling this skin that forms in injection-molded process by melt in casting die wall.Only this outside casting cortex can be electroplated according to prior art.But this black skin is very responsive, in preprocessing process, corroded and destroy by oil removing and pickling sometimes, the hole of base material is come out sometimes.Plating bath itself also can destroy this black skin.
The coating of good bond can not be applied on destroyed surface again.In addition, because pretreatment baths or the destroyed black skin of electrolyte cross are penetrated in the hole of base material, therefore usually bubble.In heat treatment process subsequently, the liquid evaporation having infiltrated the outside coating that promotes to apply are to form blister or elevated regions.In disadvantageous situation, copper layer peels off.
Other shortcoming of method described in the prior is to use highly toxic electrolytic solution.For 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 greatly avoid thus the above-mentioned shortcoming of prior art.
By comprising that the method for following process steps realizes this object:
A) by the first bronze medal layer that is less than 1 micron containing the copper electrolyte deposit thickness of pyrophosphate salt,
B) rinse and be dried these parts at the temperature improving, and
C) containing the first bronze medal layer being thickened to 10 to 20 microns in the copper electrolyte of pyrophosphate salt.
According to the present invention, the thin copper layer that is first less than 1 micron by the copper electrolyte deposit thickness that contains pyrophosphate salt on the black skin of zine pressure casting.In this first plating step or even, in the preprocessing process by oil removing and pickling, this black skin is conventionally destroyed.As a result, electrolytic solution can be penetrated in the now open porous microstructure of zine pressure casting in preprocessing process or in plating process.Therefore the method be it is highly important that, the copper layer applying in the first plating step still has the porosity enough for the carrier fluid of electrolytic solution, and the carrier fluid of this electrolytic solution evaporates to overflow 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, this parts are rinsed and by for example, at 100 to 180 DEG C, preferably 120 to 160 DEG C and particularly preferably store at the temperature of approximately 140 DEG C and be dried time enough, 10 to 60 minutes.In this thermal treatment, be penetrated into the carrier fluid evaporation of the electrolytic solution in porous zinc.Because of its low thickness, the copper layer existing as the result of the first plating step remains porous, and not impermeable for the steam in forming, and the steam forming while making to heat can overflow.Only the solids component of electrolytic solution (salt) remains in hole, and these can further not disturb.The existence of remaining electrolyte salt can be studied to confirm by for example SEM and/or EDX.
Rinse preferred water and carry out, and be fully known to those skilled in the art.
After plating and dry zine pressure casting are cooling, if suitable, proceed plating identical containing in pyrophosphate method of electro-plating liquid, until deposited approximately 5 to 50 microns, preferably 10 to 30 microns, the copper of 10 to 20 microns particularly preferably.The thin copper layer having existed in the time that the second plating step starts has obviously prevented that liquid electrolyte is penetrated in porous zinc-base bottom material.The parts of plating bear the storage approximately 30 minutes at 150 DEG C and form or even peel off without bubbling in this way.
The copper layer of the first sub-step in a) can deposit by electrochemical method.Electrolytic deposition (reference 4) is here possible.The second copper coating can deposit on reductibility ground, or preferably deposits by electrolytic process.In electrolytic process, mainly can mention three kinds of different plating methods:
1. plate (drum plating) for the wheel of bulk materials and mass-produced parts:
In this plating method, use the relatively low working current density (order of magnitude: 0.05-0.5A/dm 2)
2. for the rack plating of indivedual parts:
In this plating method, use the medium working current density (order of magnitude: 0.2-5A/dm 2)
In continuous device for the high speed plating of band or wire rod:
In this plating part, use the very high working current density (order of magnitude: 5-100A/dm 2)
First two plating method (wheel plating and rack plating) is important often for copper facing, depends on different electrolytic solution types, and wheel plating (low current density) or rack plating (medium current density) are possible.
As mentioned above, a) and c) copper layer is applied on zine pressure casting and is advantageously undertaken by electrolytic process at processing step.Here, importantly metal to be deposited remains on consistently in solution in this process, no matter is to electroplate in continuous processing or discrete method.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 electrolytic solution can be arranged in specific aim mode by those skilled in the art.It is limited to the following fact: the concentration in electrolytic solution should be higher than minimum to 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 wherein providing.In this electrolytic solution, the amount of pyrophosphate salt to be used is preferably 50-400 grams per liter.Particularly preferably use the amount of 100-350 grams per liter electrolytic solution, very particularly preferably approximately 200 grams per liter electrolytic solution.If pyrophosphate salt is not introduced with the form of the salt component for the treatment of metal refining, it can be with basic metal diphosphate or alkaline-earth metal diphosphate or with H 2p 2o 7use with the form of basic metal or the combination of alkaline earth metal carbonate/supercarbonate.Preferably use K for this reason 2p 2o 7.
In electrolytic solution used, copper to be deposited exists in solution with its ionic species.They are preferably introduced with water-soluble salt form, and described water-soluble salt is preferably selected from pyrophosphate salt, carbonate, subcarbonate (hydroxycarbonate), supercarbonate, sulphite, vitriol, phosphoric acid salt, nitrite, nitrate, halogenide, oxyhydroxide, oxide compound-oxyhydroxide, oxide compound and combination thereof.Very particularly preferably be wherein to use the embodiment of copper with the salt form with ion, described salt is selected from pyrophosphate salt, carbonate, subcarbonate, oxide compound-oxyhydroxide, oxyhydroxide and supercarbonate.To in which kind of salt introducing electrolytic solution, be conclusive to the color of gained layer how to measure, and can require to arrange according to human consumer.The ionic concn of copper can be set as 5 to 100 grams per liter electrolytic solution, preferred 10 to 50 grams per liter electrolytic solution.Gained ionic concn is particularly preferably 15 to 30 grams per liter electrolytic solution.Particularly preferably use the copper of every liter of about 15-20 of electrolytic solution gram, and copper is incorporated in 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, particularly preferably 6-10.Most preferably use the pH of about 7.9-8.1.
Except metal to be deposited with as the pyrophosphate salt of complexing agent, this electrolytic solution can contain other organic additive that serves as brightener, wetting agent or stablizer.Electrolytic solution of the present invention is also without using cationic surfactant.Only, when in the time that the outward appearance of settled layer must meet particular requirement, just preferably add further brightener and wetting agent.Preferably add one or more compounds that are selected from monocarboxylic acid and dicarboxylic acid, alkansulfonic acid, trimethyl-glycine and aromatic nitro compound.These compounds serve as the bath stabilizing agent of electrolytic solution.Particularly preferably use carboxylic acid, alkansulfonic acid, particularly methylsulfonic acid or nitrophenyl triazole or its mixture.In EP1001054, mention suitable alkansulfonic acid.Possible carboxylic acid is for example citric acid, oxalic acid, glyconic acid etc. (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 in EP636713.In this respect, very particularly preferably use 1-(3-sulfopropyl) pyridine trimethyl-glycine or 1-(3-sulfopropyl)-2-vinyl pyridine trimethyl-glycine.
Electrolytic solution of the present invention is characterised in that it is containing being categorized as poisonous (T) or very malicious (T +) Hazardous substances.It is not containing prussiate, not containing thiourea derivative with not containing thiol derivative.
At the temperature that can select at the general knowledge based on those skilled in the art, carry out the deposition of copper layer.Be preferably 20 to 60 DEG C, in electrolytic process, electrolytic bath remains in this temperature range.More preferably 30-50 DEG C.Most preferably at the temperature of approximately 40 DEG C, deposit.
Can in the known electrochemical cell of those skilled in the art, carry out the copper deposition (reference 1) of step a) and c).In the time 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, preferably use the anode being formed by the material that is selected from electrolytic copper, phosphorous copper and copper alloy.As insoluble anode, preferably use by titanium, graphite, iridium-transition metal mixed oxide and the special carbon material (anode that " diamond-like carbon " or material DLC) form or the combination of these anodes that are selected from platinum plating.Particularly preferably use by iridium-ruthenium mixed oxide the mixing oxide anode of iridium-ruthenium-titanium mixed oxide or iridium-tantalum mixed oxide composition.Other insoluble anode is found in Cobley, the people such as A.J., (The use of insoluble Anodes in Acid Sulphate Copper Electrodeposition Solutions, Trans IMF, the 2001,79 (3), the 113rd and 114 pages).
If use insoluble anode, in the time that the base material (it represents negative electrode) of copper layer to be supplied is separated by ion-exchange membrane to form the mode of cathode space and anode chamber with insoluble anode, obtains the particularly preferred embodiment of the 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, potassium hydroxide, saleratus or its mixture is preferably present in anode chamber.As ion-exchange membrane, can use cationic or anionic exchange membrane.Preferably used thickness is the Nafion film of 50 to 200 microns.
Thereby method of the present invention and the particularly thermal treatment between two plating steps can be removed to the carrier fluid of electrolytic solution used to make it can not cause the degree of bubbling and forming or peeling off in parts heat-processed subsequently.On the contrary, if there is no by for example electrolytic solution containing pyrophosphate salt, copper layer to be put on to zinc in step of the present invention heat treated situation b), the liquid being penetrated in porous substrate material will no longer can be overflowed in the process of heating application member subsequently, and causes in coating due to the vapour pressure producing bubbling forming or peeling 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 copper plating zine pressure casting of following composition:
The potassium pyrophosphate of 300 grams per liters
The cupric pyrophosphate of 30 grams per liters
Water complements to 1 liter
With methylsulfonic acid by pH regulator to 8.
At 40 DEG C and 0.5A/dm 2current density under in cylinder plating zine pressure casting 3 minutes.Subsequently this parts are rinsed, at 150 DEG C, store 30 minutes, cooling after, further plating 2 hours in identical electrolysis bath of liquid.
In drying oven, at the temperature of 150 DEG C, check to bubble to form 30 minutes, do not have parts in coating, to show foaming.

Claims (3)

1. for the electrolytic copper plating process of zine pressure casting, the method has the foaming formability of reduction, it is characterized in that following steps:
A) by the first bronze medal layer that is less than 1 micron containing the copper electrolyte deposit thickness of pyrophosphate salt,
B) rinse and be dried these parts at the temperature of 100-180 DEG C, and
C) containing the first bronze medal layer being thickened to 10 to 20 microns in the copper electrolyte of pyrophosphate salt.
2. the method for claim 1, is characterized in that, in step a), the first bronze medal is deposited to the thickness of 0.1 to 0.5 micron.
3. the method for claim 1, is characterized in that, in step b), these parts store the time of 10 to 60 minutes at 100 to 180 DEG C.
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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CN102471911B true CN102471911B (en) 2014-10-15

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US (1) US20120217166A1 (en)
EP (1) EP2475808A1 (en)
JP (1) JP2013504685A (en)
KR (1) KR20120079065A (en)
CN (1) CN102471911B (en)
DE (1) DE102009041250B4 (en)
WO (1) WO2011029507A1 (en)

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CN101123127A (en) * 2007-09-21 2008-02-13 施义明 A micro silver plating and copper-coated copper multi-strand line and its making method

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CN101123127A (en) * 2007-09-21 2008-02-13 施义明 A micro silver plating and copper-coated copper multi-strand line and its making method

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WO2011029507A1 (en) 2011-03-17
DE102009041250B4 (en) 2011-09-01
EP2475808A1 (en) 2012-07-18
US20120217166A1 (en) 2012-08-30
KR20120079065A (en) 2012-07-11
DE102009041250A1 (en) 2011-05-12
JP2013504685A (en) 2013-02-07
CN102471911A (en) 2012-05-23

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