CN104040033A - Electrolyte and its use for the deposition of black ruthenium coatings and coatings obtained in this way - Google Patents
Electrolyte and its use for the deposition of black ruthenium coatings and coatings obtained in this way Download PDFInfo
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- CN104040033A CN104040033A CN201280029704.0A CN201280029704A CN104040033A CN 104040033 A CN104040033 A CN 104040033A CN 201280029704 A CN201280029704 A CN 201280029704A CN 104040033 A CN104040033 A CN 104040033A
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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
- C25D3/50—Electroplating: Baths therefor from solutions of platinum group metals
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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
- C25D3/50—Electroplating: Baths therefor from solutions of platinum group metals
- C25D3/52—Electroplating: Baths therefor from solutions of platinum group metals characterised by the organic bath constituents used
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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
- C25D7/00—Electroplating characterised by the article coated
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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
- C25D7/00—Electroplating characterised by the article coated
- C25D7/005—Jewels; Clockworks; Coins
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D17/00—Constructional parts, or assemblies thereof, of cells for electrolytic coating
- C25D17/10—Electrodes, e.g. composition, counter electrode
Abstract
The invention relates to a ruthenium electrolyte which is suitable for the deposition of decorative and industrial layers having a particular blackness. The invention further relates to the use of the electrolyte of the invention in a process for the deposition of decorative and industrial layers of ruthenium having a particular blackness (black ruthenium) on jewelry, decorative goods, consumer goods and industrial articles. The invention therefore likewise relates to corresponding layers and the articles coated in this way. The electrolyte is characterized in that it operates in the weakly acidic to alkaline pH range.
Description
The present invention relates to a kind of ruthenium electrolytic solution that deposition has the ornamental of specific blackness and industrialness layer that is suitable for.The invention further relates to and use in one approach this used for electrolyte of the present invention to there is the ornamental of specific blackness and industrialness ruthenium layer (" black ruthenium ") in deposition on jewelry, ornamental commodity, the consumer's goods and industrial article.Therefore the present invention relates to corresponding layer and equally by the article of coating in this way.
The consumer's goods and industrial article, jewelry and ornamental commodity are upgraded for corrosion prevention and/or optics with thin oxidation-stabilized metal level coating.Even if must to be mechanicalness stable and also should not show corrosion or wear phenomenon in long-term use for these layers.The mode of producing the empirical tests of this class layer is electro-plating method, by these electro-plating methods, can obtain many metals and alloy layer with high quality form.The example of knowing from daily life is bronze and layer of brass, the chromium coating on vehicle component, zinc-plated instrument or the gold plate on watchband in door handle or knob By Electrolysis formula deposition.
Concrete challenge in field of electroplating is to produce metal level oxidation-stabilized and that mechanicalness is strong, and these metal levels have black color and not only can decorate and jewelry industry is interesting but also can be used for industrial application (for example, at sun power sciemtifec and technical sphere).Only there are several metals to be available for producing these oxidation-stabilized black layers.Except ruthenium, rhodium and nickel are suitable.Because high raw materials cost, the use of Noble Metal Rhodium is limited to jewelry industry.Due to nickel be contactant containing nickel metal layer, cheap nickel and the use of nickel-containing alloys are only possible and will observe strict rules under exception, especially in jewelry and consumer lines industry.For described all Application Areass, using ruthenium is a kind of attractive replacement scheme.
For produce the electrolytic solution of black ruthenium layer at electro-plating method, be known in the art.The ruthenium (US 6117301, US 3576724, JP 63259095, WO 2001/011113, DE 19741990, US 4375392, JP 2054792, EP 1975282) of the ruthenium that the bath (baths) that those use the most widely comprises the form in the complex compound with thionamic acid or conduct time amino chlorine (nitridochloro) or inferior amino bromine (nitridobromo) complex compound.The pH of these baths is often in acid range.
DE1959907 has described and in a kind of plating bath, has used double-core ruthenium complex [Ru
2nCl
xbr
8- x(H
2o)
2]
3-.In one embodiment, used inferior amino chloro-complex [Ru
2nCl
8(H
2o)
2]
3-.JP56119791 relates to a kind of containing from the ruthenium of 1g/l to 20g/l and is selected from the ruthenium electrolytic solution of the compound of group or the derivative of mentioned these compounds together with one or more, this group is comprised of the following: dicarboxylic acid and tricarboxylic acid, Phenylsulfonic acid, containing N aromatics and amino acid, and additionally used therein from the sulfocompound of 0.01g/l to 10g/l as melanism additive.
In order to make jewelry and the upgrading of ornamental commodity, black layer must not only have outstanding mechanical adhesion intensity and also will have flawless optical quality.They must produce and have very dark blackness as requested with the form of light or dumb light.This is at industrial trade, especially applicable equally in the application of sun power science and technology.For making the black layer of consumer's goods upgrading also must meet the harsh requirement with regard to mechanical stability.Especially, even through the long-term time, they also must wear and tear without any black under frequent use.
In the prior art the described ruthenium that meets these requirements bathe and processing requirement use toxicology on problematic compound (as sulfocompound) as melanism additive or comprise other transition metal so that desired mechanical adhesion intensity to be provided, this makes in deposition process, to be difficult to this bath to be safeguarded.In addition, acid bath only allows to deposit on the metal with relative inertness characteristic.
According to US 4082625, the ruthenium settling of light color can also obtain in alkaline range.US 350049 has described a kind of method for deposit ruthenium within the scope of the pH of 9-10.By complex anion (EDTA, NTA, CDTA), ruthenium is remained in the solution within the scope of this pH.Obtained the stable still ruthenium settling of light color.
In US 4297178, described, in the nonacid bath of water-based, also used the inferior amino chloro-complex of ruthenium for galvanic deposit ruthenium.It contains oxalic acid or oxalate negatively charged ion extraly.Problematic is whether the settling of producing by this way has suitable blackness.
Consider the prior art of quoting at this, an object of the present invention is to provide a kind of stable electrolytic solution and its purposes, can on these metals, produce lasting as far as possible and black as far as possible ruthenium settling thus.In addition also just should likely in strong acidic environment, on unsettled article, deposit.
These objects and the other object that can draw from prior art in a kind of obvious mode can realize by a kind of electrolytic solution with the characteristic properties of claim 1.In claim 2-9, pointed out the favourable embodiment of this electrolytic solution of the present invention.Electrolytic solution of the present invention purposes has in the method for the invention been described in claim 10-19.These settled layers are followed claim 20-24.Claim 25 is for the article of coating by this way.
Provide a kind of used for electrolyte with from >=5 to 12 pH to have the ornamental of specific blackness and industrialness ruthenium layer in deposition, this electrolytic solution has following component:
A) press ruthenium metal and calculate, concentration is the ruthenium from the dissolving of 0.2 grams per liter to 20 grams per liter (g/l);
B) concentration is one or more negatively charged ion of dicarboxylic acid, tricarboxylic acid or the tetracarboxylic acid of 0.05 mol/L-2 mol/L;
C) one or more thia rings;
D) one or more cats products, the especially tensio-active agent based on quaternary ammonium salt,
Though this cause extremely effectively and simple so but advantageously realize these stated objects.This electrolytic solution provides very durable and extremely black ruthenium settling on electroconductibility, especially metallicity article.Only when using strongly-acid electrolytic solution, likely on electroconductibility, particularly metallicity article, deposit black ruthenium coating so far.Therefore, in the situation that need the underlying metal of coating for fear of the erosion to base material, before applying, these must be equipped with the middle layer (gold, palladium or palladium/nickel, etc.) of erosion resistance.Yet ionogen of the present invention makes it also likely to work in a kind of medium, in this medium, can electroplate by die case zinc, brass or the bronze base material forming without intermediate deposit.
Can use ruthenium with the form of water-soluble cpds known to those skilled in the art, preferably as thering is chemical formula [Ru
2n(H
2o)
2x
8]
3-double-core anionic time amino halide complex, wherein X is a kind of halide-ions.Particularly preferably be chloro complex compound [Ru
2n(H
2o)
2cl
8]
3-.The amount of the complex compound in electrolytic solution of the present invention can preferably be selected, and makes the concentration of calculating ruthenium by ruthenium metal after this compound dissolves completely in the scope from 0.5 grams per liter electrolytic solution to 10 grams per liter electrolytic solution.The electrolytic solution completing particularly preferably contains from 1 gram to 8 grams ruthenium/rise electrolytic solution, very particularly preferably ruthenium/the rise electrolytic solution from 3 grams to 8 grams.Give preferably to have only ruthenium deposits from electrolytic solution of the present invention.In this case, this electrolytic solution does not further contain the transition metal ion except ruthenium.
This electrolytic solution contains the specific organic compound with one or more hydroxy-acid groups.Especially, these are dicarboxylic acid, tricarboxylic acid or tetracarboxylic acid.These are that fully know and passable to those skilled in the art, and for example, at works, (the 22nd edition, S.Hirzel-Verlag, finds in p.324ff) for Beyer-Walter, Lehrbuch der Organischen Chemie.In this context, particularly preferably be the acid that is selected from lower group, this group is comprised of the following: oxalic acid, citric acid, tartrate, succsinic acid, toxilic acid, pentanedioic acid, hexanodioic acid, propanedioic acid, oxysuccinic acid.These acid are present in the electrolytic solution under pH to be set naturally with its anionic form.
By these carboxylic acids referred in this with 0.05 mole every liter-2 mol/L, preferably 0.1 mol/L-1 mol/L and very particularly preferably the concentration of 0.2 mol/L-0.5 mol/L add in electrolytic solution.This is specially adapted to the use of oxalic acid, supposes at this electrolytic solution mesoxalic acid and also serves as conductive salt.
At this, same specific sulphur compound existing in these electrolytic solution is discussed.Specifically exist one or more sulphur compounds that contain at least one sulphur atom (thia ring) at heterocyclic system (Beyer-Walter, Lehrbuch der Organischen Chemie, the 22nd edition, S.Hirzel-Verlag, p.703ff).These can be optionally contain at least one sulphur atom and/or heteroatoms (as nitrogen) that at least one is other, aromatic series or saturated five or six-ring based on carbon or corresponding condensed ring system wholly or in part.These thia rings to be used preferably sufficiently soluble in water can be in this electrolytic solution effectively to utilize in suitable temperature range.Preferred compound is to be selected from those of lower group, this group is comprised of the following: 3-(2-[4-morpholinodithio base-2-sulfydryl) propanesulfonic acid sodium salt, asccharin sodium salt, asccharin-N-propyl sulfonic acid sodium salt, 6-methyl-3,4-dihydro-1,2,3-Evil thiazine-4-ketone 2,2-dioxide, benzothiazole, 2-mercaptobenzothiazole, thiazole, isothiazole and their derivative.Be not bound by the theory in this proposition, suppose that thia ring contributes to the degree of depth melanism when deposit ruthenium.In this electrolytic solution, with from 0.001 mol/L to 4 mol/L, preferably from the concentration of 0.002 mol/L to 1 mol/L, and very particularly preferably to use this thia ring from the concentration of 0.004 mol/L to 0.01 mol/L.
The same surfactant that has one or more cats product types in this electrolytic solution.Especially, such possible tensio-active agent is quaternary ammonium salt.These be to those skilled in the art fully know (Beyer-Walter, Lehrbuch der Organischen Chemie, the 22nd edition, S.Hirzel-Verlag, p.251ff).Give to be preferably selected from the ammonium salt of lower group, this group is comprised of the following: octyl group trimethylammonium bromide, octyl group trimethyl ammonium chloride, DTAB, decyl trimethyl ammonium chloride, Trimethyllaurylammonium bromide, Dodecyl trimethyl ammonium chloride, Tetradecyl Trimethyl Ammonium Bromide, tetradecyl trimethyl ammonium chloride, cetyl trimethylammonium bromide, palmityl trimethyl ammonium chloride, ethyl dimethyl hexadecyl brometo de amonio, ethyl dimethyl cetyl chloride ammonium, benzyl dimethyl decyl ammonium chloride, benzyl dimethyl lauryl ammonium chloride, benzyl dimethyl tetradecyl ammonium chloride, with benzyl dimethyl cetyl chloride ammonium.
By these cats products of paying attention at this, with 0.1 mM/l-20 mM/ls, preferably 0.5 mM/l-10 mM/ls and very particularly preferably use this electrolytic solution from the concentration of 1 mM/l to 5 mM/ls, and these cats products are also conclusive to the settled layer of darker black.
The pH of this electrolytic solution preferably in slightly acidic only in alkaline scope.Preferably this pH is set as to a value in from 5 to 12 scope.In use, the pH of this electrolytic solution is more preferably in from 6 to 9, particularly preferably from 7 to 8 scope.Especially preferably set approximately 7.5 pH.By adding buffer substance, this pH is remained unchanged.These art personnel to this area be fully know (chemistry and physics handbook, CRC press, the 66th edition, D-144ff).Preferred buffering system is the damping fluid of borate, phosphoric acid salt and carbonate.Compound for the production of these buffering systems can be selected from lower group, and this group is comprised of the following: boric acid, potassium primary phosphate, dipotassium hydrogen phosphate, saleratus and carbonic acid dipotassium.With 0.08 mol/L-1.15 mol/L, preferably 0.15 mol/L-0.65 mol/L and very particularly preferably the concentration of 0.2 mol/L-0.4 mol/L (based on negatively charged ion) use this buffering system.
Naturally, the other additive that is conducive to deposition can be added in the electrolytic solution of paying attention at this.These art personnel to this area are group (the Praktische Galvanotechnik that give preferably to select free conductive salt, further melanism additive, brightening agent composition that fully know, the 5th edition, Eugen G.Leuze Verlag, Bad Saulgau, p.39ff) those.
The present invention provides the purposes of electrolytic solution of the present invention equally.In use, those skilled in the art is immersed in this electrolytic solution as negative electrode this being needed to the electroconductibility of coating, especially metallicity article, and makes generation current flow between this anode and negative electrode.In the same favourable embodiment that the use of this electrolytic solution of the present invention has preferably been described for electrolytic solution more than those, carry out.The flow of this electric current should be enough to cause and on this electroconductibility, particularly metallicity article, within one acceptable period, deposits black ruthenium coating.One of skill in the art will appreciate that for this strength of electric field that must arrange.0.1A/dm is preferably set
2-10A/dm
2current density.This current density is particularly preferably from 0.2A/dm
2to 5A/dm
2, and very particularly preferably from 0.5A/dm
2to 2A/dm
2.
In deposition process, the temperature of this electrolytic solution can suitably be arranged by those skilled in the art.Need advantageously 10 ℃-80 ℃ of the temperature ranges that arrange.Give preferably Temperature Setting from 50 ℃ to 75 ℃ and particularly preferably 60 ℃ to 70 ℃.For this discussed electrolytic solution, maybe advantageously in deposition process, stir.
As anode, the embodiment that equally likely selects those skilled in the art can consider for this purpose.Give preferably to use the anode of being made by the material that is selected from lower group, this group is comprised of the following: platinized titanium, graphite, iridium-transition metal mixed oxide and extraordinary carbon material (" diamond-like carbon ", DLC), or their combination.Have been found that the insoluble anode of being made by platinized titanium or iridium-transition metal mixed oxide is favourable.Particularly preferably be and use the anode of being made by platinized titanium.
The present invention provides the black ruthenium layer that can obtain by method of the present invention equally.These layers have from 0.1 μ m to 3 μ m, preferably from 0.2 μ m to 1.5 μ m and very particularly preferably from the thickness of 0.3 μ m to 1.3 μ m.The sulphur content that layer of the present invention has the external region (inwardly observing from visible surface) of its approximately 1.1 (± 0.2) μ m be from by weight 3% to by weight 6%, preferably from by weight 3.1% to by weight 5% and particularly preferably from by weight 3.2% to by weight 4.5%.This sulphur content is particularly preferably approximately by weight 4%.In same external region, this ruthenium layer also have from by weight 1% to by weight 2%, preferably from by weight 1.1% to by weight 1.8% and very particularly preferably from by weight 1.15% to 1.5% carbon content by weight.This value is particularly preferably approximately by weight 1.2%.In same external region, this ruthenium layer have from by weight 15% to by weight 20%, preferably from by weight 16% to by weight 19% and particularly preferably from by weight 17% to 18.5% oxygen level by weight.In this this oxygen level, be particularly preferably approximately by weight 18%.Concentration for the sulphur in this layer under consideration seems particularly advantageously to have the gradient that concentration increases from outside to inside.Therefore, often measure directly at this lip-deep sulphur concentration of approximately 2% by weight and can in the direction to inner, rise to by weight 5%.These values have been passed through GDOES method (glow discharge optical emission spectroscopy method at this; R.Kenneth Marcus, Jose Broekaert: the glow discharge plasma in analyzing spectrography, power press, ISBN0-471-60699-5; With Thomas Nelis, Richard Payling: glow discharge optical emission spectroscopy method practical guide, RSC, ISBN 0-85404-521-X) determine.
The present invention further provides the special article having according to layer of the present invention, as ornamental commodity, the consumer's goods and industrial article.Giving particularly preferred article is, thus they in the situation that because their basic metal characteristic can not deposit accordingly in acid range.
Consider the above, in electroconductibility according to the present invention, particularly depositing black ruthenium coating on metallicity article can be by carrying out as the mode of following instance:
For electrolyzing applies black ruthenium layer, jewelry piece, ornamental commodity, the consumer's goods or industrial article (being all called as base material) are immersed in electrolytic solution of the present invention and form negative electrode.Will be by for example platinized titanium (product information: from Umicore electroplating technology limited-liability company
) anode made immerses in this electrolytic solution equally.Between this anode and this negative electrode, apply suitable current flow subsequently.In order to obtain the homogeneous layer firmly adhering to, should not surpass 10 amperes of/square decimeter [A/dm
2] maximum current density.Surpass this value, may deposit proportional unbodied ruthenium.Consequently, these layers may be inhomogeneous and have under mechanical stress black wearing and tearing.Selected current density is also by the type decided of plating process.In barrel plating technique, preferred current density is from 0.1A/dm
2to 1A/dm
2scope in.In rack plating technique, from 0.5A/dm
2to 5A/dm
2current density cause the flawless black ruthenium layer of optics.
Described by ruthenium electrolytic solution provided by the invention, a kind of, for for example deposit the technique of ornamental layer pitch black and optional light on jewelry and ornamental commodity, be especially most suitable.This technique is equally by the invention provides.This electrolytic solution can be optimized in barrel plating and rack plating technique.Electrolytic solution described here make it likely to produce on suitable material tight especially and pitch black (L is up to 50) ruthenium settling (see Fig. 1, Fig. 1 show comparison example and according to the result of example 1 of the present invention).In addition, when using this electrolytic solution, likely in slightly acidic, to alkaline range, work, this scope allows black ruthenium coating to be deposited on underlying metal first and this metal need not be equipped with a upper precious metal middle layer in advance.Neither be apparent according to known prior art this point.
Five kinds of samples have been checked.The production of sample can be taked following instance.
Table 1:
* according to JP2001049485, * * is according to 1975282
These methods (electrolytic solution is according to the present invention) in alkaline range of can clearly finding out provide relatively good L* value.By adding a kind of cats product, as wetting agent, promote further melanism.
Use one according to the reference colour survey meter of CIE-L*a*b* system, on these resulting layers, to measure color value.
Also by GDOES(glow discharge optical emission spectroscopy method) detected these layer.In argon plasma, these samples " splash " spread all on generally smooth plane and excite to send specific radiation.In an optical spectrometer, detect this radiation.By Multi-Nominal Matrix, calibrate the calculating of carrying out concentration and the degree of depth.
Example:
General method:
Sheet brass is immersed in a kind of electrolytic solution with component described below.
Comparison example-according to the formula of US4297178:
The Ru of 6.2g/l, as [Ru
2n(H
2o) Cl
8]
3-
The oxalic acid of 80g/l
By potassium hydroxide, pH is arranged to 7.5
pH：7.5（70℃）
Working temperature: 70 ℃
Current density: 1A/dm
2
L*=68.6
Embodiment according to the present invention 1(type i):
The Ru of 6.2g/l, as [Ru
2n(H
2o) Cl
8]
3-
The oxalic acid of 80g/l
The potassium primary phosphate of 20g/l
Asccharin-N-propyl sulfonic acid sodium salt of 2g/l
The quaternary ammonium salt of 600mg/l
pH：7.5（70℃）
Working temperature: 70 ℃
Current density: 1A/dm
2
L*=55.5
Embodiment according to the present invention 2(Type II):
The Ru of 3g/l, as [Ru
2n(H
2o)X
8]
3-, X=halide-ions
The oxalic acid of 40g/l
The potassium primary phosphate of 20g/l
The 3-of 1g/l (2-[4-morpholinodithio base-2-sulfydryl) propanesulfonic acid sodium salt
The quaternary ammonium salt of 400mg/l
pH：8（75℃）
Working temperature: 75 ℃
Current density: 1A/dm
2
L*=52.3
The example 3(type-iii of sulfur heterocyclic ring not):
The Ru of 3g/l, as [Ru
2n(H
2o)X
8]
3-, X=halide-ions
The oxalic acid of 60g/l
The potassium primary phosphate of 40g/l
The quaternary ammonium salt of 300mg/l
pH：6（75℃）
Working temperature: 75 ℃
Current density: 1A/dm
2
L*=69.2
Claims (25)
1. there is from >=5 to 12 pH for depositing an electrolytic solution with the ornamental of specific blackness and industrialness ruthenium layer,
It is characterized in that,
This ionogen has following component:
A) press ruthenium metal and calculate, concentration is the ruthenium from the dissolving of 0.2 grams per liter to 20 grams per liter (g/l);
B) concentration is one or more negatively charged ion from dicarboxylic acid, tricarboxylic acid or the tetracarboxylic acid of 0.05 mol/L-2 mol/L;
C) one or more thia rings;
D) one or more cats products.
2. electrolytic solution as claimed in claim 1,
It is characterized in that
Ruthenium is as having chemical formula [Ru
2n(H
2o)
2x
8]
3-double-core anionic ruthenium time amino halide complex and exist, wherein X is a kind of halide-ions.
3. the electrolytic solution as described in claim 1 and/or 2,
It is characterized in that
After this compound dissolves completely, the concentration of ruthenium is in the scope from 2 grams per liter to 8 grams per liter electrolytic solution.
4. as the electrolytic solution as described in one or more in aforementioned claim,
It is characterized in that
This ionogen is not containing other transition metal ion.
5. as the electrolytic solution as described in one or more in aforementioned claim,
It is characterized in that
This carboxylic acid is selected from lower group, and this group is comprised of the following: oxalic acid, citric acid, tartrate, succsinic acid, toxilic acid, pentanedioic acid, hexanodioic acid, propanedioic acid, oxysuccinic acid.
6. as the electrolytic solution as described in one or more in aforementioned claim,
It is characterized in that
This thia ring is selected from lower group, this group is comprised of the following: 3-(2-[4-morpholinodithio base-2-sulfydryl) propanesulfonic acid sodium salt, asccharin sodium salt, asccharin N-propyl sulfonic acid sodium salt, 6-methyl-3,4-dihydro-1,2,3-Evil thiazine-4-ketone 2,2-dioxide, benzothiazole, 2-mercaptobenzothiazole, thiazole, isothiazole and their derivative.
7. as the electrolytic solution as described in one or more in aforementioned claim,
It is characterized in that
This tensio-active agent is selected from lower group, this group is comprised of the following: octyl group trimethylammonium bromide, octyl group trimethyl ammonium chloride, DTAB, decyl trimethyl ammonium chloride, Trimethyllaurylammonium bromide, Dodecyl trimethyl ammonium chloride, Tetradecyl Trimethyl Ammonium Bromide, tetradecyl trimethyl ammonium chloride, cetyl trimethylammonium bromide, palmityl trimethyl ammonium chloride, ethyl dimethyl hexadecyl brometo de amonio, ethyl dimethyl cetyl chloride ammonium, benzyl dimethyl decyl ammonium chloride, benzyl dimethyl lauryl ammonium chloride, benzyl dimethyl tetradecyl ammonium chloride, with benzyl dimethyl cetyl chloride ammonium, and their mixture.
8. as the electrolytic solution as described in one or more in aforementioned claim,
It is characterized in that
The pH of this electrolytic solution is in the scope of 7-8.
9. as the electrolytic solution as described in one or more in aforementioned claim,
It is characterized in that
This electrolytic solution comprises a kind of buffering system, the group that this buffering system selects the damping fluid of free borate, phosphoric acid salt and carbonate to form.
10. the electrolytic solution purposes in following methods, the method is for by immersing this electrolytic solution using the article for the treatment of coating as negative electrode and establishing current flow and deposit black ruthenium coating between this anode and this negative electrode on this electroconductibility, especially metallicity article
It is characterized in that
Select as in one or more aforementioned claim described in electrolytic solution.
11. purposes as claimed in claim 10,
It is characterized in that
Ruthenium is as having chemical formula [Ru
2n(H
2o)
2x
8]
3-double-core anionic ruthenium time amino halide complex and exist, wherein X is a kind of halide-ions.
12. purposes as described in claim 10 and/or 11,
It is characterized in that
After this compound dissolves completely, the concentration of ruthenium is in the scope from 2 grams per liter electrolytic solution to 8 grams per liter electrolytic solution.
13. as the purposes as described in one or more in claim 10-12,
It is characterized in that
This ionogen is not containing other transition metal ion.
14. as the purposes as described in one or more in claim 10-13,
It is characterized in that
This carboxylic acid is selected from lower group, and this group is comprised of the following: oxalic acid, citric acid, tartrate, succsinic acid, toxilic acid, pentanedioic acid, hexanodioic acid, propanedioic acid, oxysuccinic acid.
15. as the purposes as described in one or more in claim 10-14,
It is characterized in that
This thia ring is selected from lower group, this group is comprised of the following: 3-(2-[4-morpholinodithio base-2-sulfydryl) propanesulfonic acid sodium salt, asccharin sodium salt, asccharin N-propyl sulfonic acid sodium salt, 6-methyl-3,4-dihydro-1,2,3-Evil thiazine-4-ketone 2,2-dioxide, benzothiazole, 2-mercaptobenzothiazole, thiazole, isothiazole and their derivative.
16. as the purposes as described in one or more in claim 10-15,
It is characterized in that
This tensio-active agent is selected from lower group, this group is comprised of the following: octyl group trimethylammonium bromide, octyl group trimethyl ammonium chloride, DTAB, decyl trimethyl ammonium chloride, Trimethyllaurylammonium bromide, Dodecyl trimethyl ammonium chloride, Tetradecyl Trimethyl Ammonium Bromide, tetradecyl trimethyl ammonium chloride, cetyl trimethylammonium bromide, palmityl trimethyl ammonium chloride, ethyl dimethyl hexadecyl brometo de amonio, ethyl dimethyl cetyl chloride ammonium, benzyl dimethyl decyl ammonium chloride, benzyl dimethyl lauryl ammonium chloride, benzyl dimethyl tetradecyl ammonium chloride, with benzyl dimethyl cetyl chloride ammonium, and their mixture.
17. as the purposes as described in one or more in claim 10-16,
It is characterized in that
Set current density is 0.1A/dm
2-10A/dm
2.
18. as the purposes as described in one or more in claim 10-17,
It is characterized in that
Set temperature is 10 ℃-80 ℃.
19. as the purposes as described in one or more in claim 10-18,
It is characterized in that
The insoluble anode that use is made by the material that is selected from lower group and the combination of these anodes, this group is comprised of the following: platinized titanium, graphite, iridium-transition metal mixed oxide and extraordinary carbon material.
20. 1 kinds can be as described in one or more in claim 10-19 and the black ruthenium layer obtaining.
21. ruthenium layers as described in claim 20,
It is characterized in that
The thickness that it has is from 0.1 μ m to 3 μ m.
22. ruthenium layers as described in claim 20,
It is characterized in that
The sulphur content that this layer has in the external region of 1 μ m is from by weight 3% to by weight 6%.
23. ruthenium layers as described in claim 20,
It is characterized in that
The carbon content that this layer has in the external region of this 1 μ m is from by weight 1% to by weight 2%.
24. ruthenium layers described in claim 21,
It is characterized in that
The oxygen level that this layer has in the external region of this 1 μ m is from by weight 15% to by weight 20%.
25. 1 kinds have as the article of the ruthenium layer as described in one or more in claim 20-24.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE102011105207.4A DE102011105207B4 (en) | 2011-06-17 | 2011-06-17 | Electrolyte and its use for the deposition of black ruthenium coatings and coatings and articles obtained therefrom |
| DE102011105207.4 | 2011-06-17 | ||
| PCT/EP2012/060924 WO2012171856A2 (en) | 2011-06-17 | 2012-06-08 | Electrolyte and its use for the deposition of black ruthenium coatings and coatings obtained in this way |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104040033A true CN104040033A (en) | 2014-09-10 |
| CN104040033B CN104040033B (en) | 2017-12-19 |
Family
ID=46210286
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201280029704.0A Active CN104040033B (en) | 2011-06-17 | 2012-06-08 | Electrolyte and its coating for depositing the purposes of black ruthenium coating and obtaining in this way |
Country Status (8)
| Country | Link |
|---|---|
| US (1) | US20140131209A1 (en) |
| EP (1) | EP2723922B1 (en) |
| JP (1) | JP2014519555A (en) |
| KR (1) | KR20140033424A (en) |
| CN (1) | CN104040033B (en) |
| DE (1) | DE102011105207B4 (en) |
| ES (1) | ES2754262T3 (en) |
| WO (1) | WO2012171856A2 (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105018908A (en) * | 2015-03-23 | 2015-11-04 | 深圳市贝加电子材料有限公司 | Chemical ruthenium plating solution for circuit board surface treatment and circuit board surface treatment method |
| CN108350592A (en) * | 2015-10-21 | 2018-07-31 | 优美科电镀技术有限公司 | Additive for silver palladium alloy electrolyte |
| CN110965088A (en) * | 2019-08-27 | 2020-04-07 | 周大福珠宝金行（深圳）有限公司 | Ancient restoring process of gold and ancient restoring gold |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20210018498A (en) | 2018-07-06 | 2021-02-17 | 멀린 솔라 테크놀로지스 인코포레이티드 | Method for blackening metal articles |
| DE102019109188B4 (en) | 2019-04-08 | 2022-08-11 | Umicore Galvanotechnik Gmbh | Use of an electrolyte for the deposition of anthracite/black rhodium/ruthenium alloy layers |
| DE102020131371A1 (en) | 2020-11-26 | 2022-06-02 | Umicore Galvanotechnik Gmbh | Ruthenium alloy layer and their layer combinations |
| US11558010B2 (en) | 2021-02-22 | 2023-01-17 | Merlin Solar Technologies, Inc. | Method for blackening an electrical conduit |
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Also Published As
| Publication number | Publication date |
|---|---|
| US20140131209A1 (en) | 2014-05-15 |
| DE102011105207B4 (en) | 2015-09-10 |
| CN104040033B (en) | 2017-12-19 |
| WO2012171856A3 (en) | 2014-03-27 |
| KR20140033424A (en) | 2014-03-18 |
| EP2723922A2 (en) | 2014-04-30 |
| ES2754262T3 (en) | 2020-04-16 |
| DE102011105207A1 (en) | 2012-12-20 |
| EP2723922B1 (en) | 2019-08-28 |
| WO2012171856A2 (en) | 2012-12-20 |
| JP2014519555A (en) | 2014-08-14 |
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