CN104040033B - Electrolyte and its coating for depositing the purposes of black ruthenium coating and obtaining in this way - Google Patents
Electrolyte and its coating for depositing the purposes of black ruthenium coating and obtaining in this way Download PDFInfo
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- CN104040033B CN104040033B CN201280029704.0A CN201280029704A CN104040033B CN 104040033 B CN104040033 B CN 104040033B CN 201280029704 A CN201280029704 A CN 201280029704A CN 104040033 B CN104040033 B CN 104040033B
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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
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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
- C25D17/00—Constructional parts, or assemblies thereof, of cells for electrolytic coating
- C25D17/10—Electrodes, e.g. composition, counter electrode
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Abstract
The present invention relates to a kind of dicoration for being suitable for deposition with specific blackness and the ruthenium electrolyte of industrialness layer.The invention further relates to be used for dicoration and industrialness layer of ruthenium of the deposition with specific blackness on jewelry, ornamental commodity, the consumer goods and the article of industry using the electrolyte of the present invention in one approach（" black ruthenium "）.Therefore the present invention also relates to corresponding layer and the article by coating in this way.The electrolyte is characterised by its pH operated within range in faintly acid to alkalescence.
Description
The present invention relates to a kind of dicoration for being suitable for deposition with specific blackness and the ruthenium electrolyte of industrialness layer.This hair
It is bright further in one approach using the present invention the electrolyte be used for jewelry, ornamental commodity, the consumer goods and
Dicoration and industrialness layer of ruthenium of the deposition with specific blackness on industrial article（" black ruthenium "）.Therefore the present invention also relates to corresponding
Layer and the article by coating in this way.
The consumer goods and industrial article, jewelry and ornamental commodity are used to corrode with thin oxidation-stabilized metal level coating
Protection and/or optics upgrading.These layers must be both mechanical stability and even if should not also show in long-term use
Corrosion or wear phenomenon.The mode for producing the empirical tests of this kind of layer is electro-plating method, can be with high-quality by these electro-plating methods
Amount form obtains many metals and alloy-layer.Well known example is that electrolytic deposits on door handle or knob from daily life
Bronze and layer of brass, the chrome plating on vehicle component, zinc-plated instrument or the gold plate on watchband.
Specific challenge in field of electroplating is the oxidation-stabilized and strong mechanicalness metal level of production, and these metal levels have
Black color and not only can be interesting but also can be used for commercial Application in decoration and jewellery sector（Such as in solar energy science and technology
Field）.Only several metals are available for producing these oxidation-stabilized black layer.In addition to ruthenium, rhodium and nickel are suitable.Cause
For high cost of material, the use of Noble Metal Rhodium is limited to jewellery sector.It is contactant due to nickel and containing nickel metal layer,
The use of cheap nickel and nickel-containing alloys is only possible in exceptional cases and to observe strict regulation, especially in pearl
Precious and consumer lines industry.The use of ruthenium is a kind of attractive alternative solution for described all application fields.
Electrolyte for producing black ruthenium layer in electro-plating method is known in the art.Those are most widely used
Bath（baths）Ruthenium comprising the form in the complex compound with sulfamic acid is used as time amino chlorine
（nitridochloro）Or secondary amino bromine（nitridobromo）The ruthenium of complex compound（US 6117301、US 3576724、JP
63259095、WO 2001/011113、DE 19741990、US 4375392、JP 2054792、EP 1975282）.These baths
PH often in acid range.
DE1959907 describes uses dinuclear ruthenium complex [Ru in a kind of electroplating bath2NClxBr8-x(H2O)2]3-.One
In individual embodiment, secondary amino chloro-complex [Ru has been used2NCl8(H2O)2]3-.JP56119791 be related to it is a kind of contain from 1g/l to
The compound or the ruthenium of the derivative of these mentioned compounds that 20g/l ruthenium is selected from the group together with one or more are electrolysed
Liquid, the group are made up of the following：Dicarboxylic acids and tricarboxylic acids, benzene sulfonic acid, aromatic compound containing N and amino acid, and at it
In additionally used sulfur-containing compound from 0.01g/l to 10g/l as melanism additive.
In order that jewelry and the upgrading of ornamental commodity, black layer must not only will also be with outstanding mechanical cohesive strength
Flawless optical quality.They allow for producing and with very deep in the form of bright or dumb light as requested
Blackness.This in industrial trade, especially solar energy science and technology application in it is equally applicable.For making the black layer of consumer goods upgrading also
The rigors must being fulfilled for for mechanical stability.Especially, even in frequently using it is lower by the long-term time they
Also must be worn without any black.
The ruthenium for meeting these requirements bath and technological requirement described in the prior art uses problematic in toxicology
Compound（Such as sulfur-containing compound）As melanism additive or comprising other transition metal to provide required mechanical adhesion
Intensity, this to be difficult to safeguard the bath in deposition process.In addition, acid bath is only allowed in relative inertness characteristic
Deposited on metal.
According to US 4082625, light ruthenium deposit can also obtain in alkaline range.US 350049 describes use
A kind of method of ruthenium is deposited in the range of the pH in 9-10.Pass through complex anion（EDTA、NTA、CDTA）Ruthenium is maintained at this
In solution in the range of kind pH.Obtain the ruthenium deposit of stable still light color.
Described in US 4297178, the secondary amino chloro-complex that ruthenium is also used in water-based nonacid bath is used for electricity
Deposit ruthenium.It extraly contains oxalic acid or oxalic acid salt anionic.It is problematic to be whether the deposit produced by this way has
There is suitable blackness.
In view of prior art cited herein, it is an object of the invention to come provide a kind of electrolyte of stabilization and
Its purposes, it is possible thereby to produce as lasting as possible and as black as possible ruthenium deposit on these metals.In addition,
It should just be possible to be deposited on article unstable in strong acidic environment.
These purposes and the other purpose that can be drawn with a kind of obvious way from prior art can be by one
The electrolyte of characteristic properties of the kind with claim 1 is realized.The electrolyte of the present invention is indicated in claim 2-9
Advantageous embodiment.The purposes of the electrolyte of the present invention in the method for the invention is described in claim 10-19.These
Sedimentary follows claim 20-24.Article of the claim 25 for coating by this way.
There is provided a kind of electrolyte of the pH with from >=5 to 12 be used for deposit dicoration and industrialness with specific blackness
Layer of ruthenium, the electrolyte have following components：
a）Calculated by ruthenium metal, concentration is from 0.2 g/l to 20 g/l（g/l）Dissolving ruthenium;
b）Concentration is the dicarboxylic acids of the mol/L of 0.05 mol/L -2, the one or more of tricarboxylic acids or tetrabasic carboxylic acid it is cloudy from
Son;
c）One or more thia rings;
d）One or more cationic surfactants, the surfactant of quaternary ammonium salt is based especially on,
Though this causes extremely effective and simple such but is advantageous to realize these purposes stated.The electrolyte exists
Electric conductivity, very durable and extremely black ruthenium deposit is especially provided on metallicity article.So far only when using highly acid
It is possible to deposit black ruthenium coating in electric conductivity, particularly on metallicity article during electrolyte.Therefore, the basis gold of coating is being needed
In order to avoid the erosion to base material in the case of category, the intermediate layer that these must be equipped with corrosion resistance before being coated（Gold,
Palladium or palladium/nickel, etc.）.However, the electrolyte of the present invention is allowed to it is also possible to being worked in a kind of medium, in this medium
The base material being made up of die case zinc, brass or bronze can be electroplated without intermediate deposit.
Ruthenium can be used in the form of water soluble compound known to those skilled in the art, preferably as with chemistry
Formula [Ru2N(H2O)2X8]3-Double-core anionic time amino halide complex, wherein X is a kind of halide ion.Give especially excellent
Choosing is chloro complex compound [Ru2N(H2O)2Cl8]3-.The amount of complex compound in the electrolyte of the present invention can preferably select, and make
Calculate the concentration of ruthenium from 0.5 g/l of electrolyte to 10 g/l of electrolyte by ruthenium metal after the compound is completely dissolved
In the range of.The electrolyte of completion particularly preferably contains from 1 gram to 8 grams ruthenium/liter electrolyte, very particularly preferably from 3 grams to 8 grams
Ruthenium/liter electrolyte.Give preferably have only ruthenium from the present invention electrolyte in deposit.In this case, the electrolyte
Not further containing the transition metal ions in addition to ruthenium.
The electrolyte contains the specific organic compound with one or more hydroxy-acid groups.Especially, these are dicarboxyls
Acid, tricarboxylic acids or tetrabasic carboxylic acid.These are fully well known to those skilled in the art and can be with for example, in works
（Beyer-Walter, Lehrbuch der Organischen Chemie, the 22nd edition, S.Hirzel-Verlag, p.324ff）
In find.In this context, the acid being particularly preferably selected from the group is given, the group is made up of the following：Oxalic acid, lemon
Acid, tartaric acid, butanedioic acid, maleic acid, glutaric acid, adipic acid, malonic acid, malic acid.These acid are natural with its anionic form
Ground is present in the electrolyte under pH to be set.
Will referred in this these carboxylic acids with 0.05 mole every liter -2 mol/Ls, preferably the mol/L of 0.1 mol/L -1,
And very particularly preferably the concentration of the mol/L of 0.2 mol/L -0.5 is added in electrolyte.This is especially suitable for oxalic acid
Use, it is assumed that act also as conductive salt in the electrolyte mesoxalic acid.
The specific sulphur compound equally existed in this discusses these electrolyte.One or more specifically be present to exist
Heterocyclic system contains at least one sulphur atom（Thia ring）Sulphur compound（Beyer-Walter,Lehrbuch der
Organischen Chemie, the 22nd edition, S.Hirzel-Verlag, p.703ff）.These can optionally be containing at least one
Individual sulphur atom and/or at least one other hetero atom（Such as nitrogen）, aromatic series or complete or partial saturation based on carbon
Five or hexatomic ring or corresponding fused ring system.These thia rings to be used are preferably sufficiently soluble in water with can be
Effectively utilized within the scope of suitable temperature in the electrolyte.Preferable compound is those being selected from the group, and the group is by following
Items composition：3- (2-[4-morpholinodithio base -2- sulfydryls) propane sulfonic acid sodium salt, saccharin sodium salt, saccharin-N- propyl sulfonic acids sodium salt, 6- first
Base -3,4- dihydro -1,2,3- Evil thiazine -4- ketone 2,2- dioxide, benzothiazole, 2-mercaptobenzothiazole, thiazole, different thiophene
Azoles and their derivative.It is not bound by the theory herein proposed, it is assumed that thia ring contributes to the depth when depositing ruthenium black
Change.In the electrolyte, with from 0.001 mol/L to 4 mol/Ls, preferably from the dense of 0.002 mol/L to 1 mol/L
Degree, and very particularly preferably to use the thia ring from 0.004 mol/L to the concentration of 0.01 mol/L.
The surface reactive material of one or more cationic surfactant types is equally existed in the electrolyte.Especially
It, such possible surfactant is quaternary ammonium salt.These are fully well known to those skilled in the art
（Beyer-Walter, Lehrbuch der Organischen Chemie, the 22nd edition, S.Hirzel-Verlag,
p.251ff）.The ammonium salt being preferably selected from the group is given, the group is made up of the following：Octyl trimethyl ammonium bromide, octyl group
Trimethyl ammonium chloride, DTAB, decyl trimethyl ammonium chloride, DTAB, dodecyl
Trimethyl ammonium chloride, TTAB, tetradecyl trimethyl ammonium chloride, cetyl trimethylammonium bromide,
Hexadecyltrimethylammonium chloride, ethyl dimethyl hexadecyl base ammonium bromide, ethyl dimethyl hexadecyl ammonium chloride, benzyl
Dimethyl decyl ammonium chloride, benzyl dimethyl lauryl ammonium chloride, benzyl dimethyl tetradecyl ammonium chloride and benzene first
Base dimethyl hexadecyl ammonium chloride.
By these cationic surfactants paid attention to herein with 0.1 mM/l -20 mM/ls, preferably
0.5 mM/l -10 mM/ls and very particularly preferably the concentration from 1 mM/l to 5 mM/ls in the electricity
Used in solution liquid, and these cationic surfactants are also conclusive to the sedimentary of deeper black.
The pH of the electrolyte is preferably in the scope of only faintly acid to alkalescence.It is preferred that the pH is set as from 5 to 12
In the range of one value.In use, the pH of the electrolyte more preferably from 6 to 9, particularly preferably from 7 to 8 scope
It is interior.The particularly preferably pH of setting about 7.5.The pH is set to keep constant by adding buffer substance.These art personnel to this area
It is fully well known（Handbook of Chemistry and Physics, CRC publishing houses, the 66th edition, D-144ff）.Preferable buffer system be borate,
The buffer solution of phosphate and carbonate.Compound for producing these buffer systems can be selected from the group, and the group is by following
Item composition：Boric acid, potassium dihydrogen phosphate, dipotassium hydrogen phosphate, saleratus and dipotassium carbonate.Rubbed with 0.08 mol/L -1.15
You/liter, the preferably mol/L of 0.15 mol/L -0.65 and the very particularly preferably concentration of the mol/L of 0.2 mol/L -0.4
（Based on anion）Use the buffer system.
Naturally, the other additive that can be beneficial to deposition is added in the electrolyte paid attention at this.This
The art personnel to this area are that fully well known give preferably is selected from by conductive salt, further melanism additive, light a bit
The group of bright dose of composition（Praktische Galvanotechnik, the 5th edition, Eugen G.Leuze Verlag, Bad
Saulgau, p.39ff）Those.
Present invention likewise provides the purposes of the electrolyte of the present invention.In use, those skilled in the art will be this
Need the electric conductivity of coating, especially metallicity article is immersed in the electrolyte as negative electrode, and made in the anode and the moon
Current flow is produced between pole.The use of the electrolyte of the present invention has been described above same preferably more than those for electrolyte
Carried out in sample advantageous embodiment.The flow of the electric current should be enough to cause in the electric conductivity, be particularly on metallicity article
The black ruthenium coating of deposition in one acceptable time.Those skilled in the art will be appreciated that the electric-field strength that must be provided with for this
Degree.It is preferably provided with 0.1A/dm2-10A/dm2Current density.The current density is particularly preferably from 0.2A/dm2To 5A/dm2, simultaneously
And very particularly preferably from 0.5A/dm2To 2A/dm2。
The temperature of the electrolyte can suitably be set by those skilled in the art in deposition process.Have to be placed
Advantageously 10 DEG C -80 DEG C of temperature range.Give and be preferably set in temperature from 50 DEG C to 75 DEG C and particularly preferred 60
DEG C to 70 DEG C.Maybe advantageously it is stirred for the electrolyte discussed in deposition process.
As anode, it is also possible to select the embodiment that those skilled in the art can consider for this purpose.Give excellent
Choosing is to use anode, group made of the material being selected from the group to be made up of the following：Platinized titanium, graphite, iridium-transition gold
Belong to mixed oxide and special carbon material（" diamond-like-carbon ", DLC）, or combinations thereof.It has been found that by platinized titanium
Or insoluble anode made of iridium-transition metal mixed oxides is favourable.Give and particularly preferably use by platinized titanium
Manufactured anode.
Present invention likewise provides the black ruthenium layer that can be obtained by the method for the present invention.These layers have from 0.1 μm to 3
μm, preferred from 0.2 μm to the 1.5 μm and very particularly preferably thickness from 0.3 μm to 1.3 μm.The present invention layer at it about
The perimeter of 1.1 (± 0.2) μm（From inwardly being carried out from visible surface）In the sulfur content that has 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
Meter 4.5%.The sulfur content is particularly preferably about by weight 4%.In same perimeter, the layer of ruthenium also has 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
The carbon content of 1.15% to by weight 1.5%.The value is particularly preferably about by weight 1.2%., should in same perimeter
Layer of ruthenium has from by weight 15% to by weight 20%, preferably from by weight 16% to by weight 19% and especially excellent
Select the oxygen content from by weight 17% to by weight 18.5%.The oxygen content is particularly preferably about by weight 18% herein.It is right
The concentration of sulphur in this layer under consideration seems particularly advantageously there is the increased gradient of concentration from outside to inside.Cause
This, often measure directly by weight about 2% sulphur concentration on a surface can be risen on direction internally by
Weight meter 5%.These values pass through GDOES methods herein（Glow Discharge Optical Emission spectroscopic methodology；R.Kenneth Marcus,
Jose Broekaert：Glow discharge plasma in spectroscopic methodology is analyzed, power publishing house, ISBN0-471-60699-5；
With Thomas Nelis, Richard Payling：Glow Discharge Optical Emission spectroscopic methodology practical guide, RSC,
ISBN 0-85404-521-X）It is determined that.
The present invention further provides the special article with the layer according to the present invention, such as ornamental commodity, the consumer goods and work
Industry article.Giving particularly preferred article is, in their case because their alkali metal characteristic is in acid range
It is interior to be deposited accordingly.
Consider described above, black ruthenium coating is particularly deposited on metallicity article can lead to according to the electric conductivity of the present invention
The mode such as following instance is crossed to carry out：
In order to which electrolytic applies black ruthenium layer, by jewelry block, ornamental commodity, the consumer goods or industrial article（All it is referred to as
Base material）Immerse in the electrolyte of the present invention and form negative electrode.Will be by such as platinized titanium（Product information：Electroplated from Umicore
Technical concern Co., Ltd）Manufactured anode is equally immersed in the electrolyte.Then in the anode and this
Apply suitable current flow between negative electrode.In order to obtain the conforming layer of firm attachment, 10 amperes/square decimeter are not to be exceeded
[A/dm2] maximum current density.More than this value, proportional unbodied ruthenium may be deposited.As a result, these layers can
It can be uneven and there is black abrasion under mechanical stress.Selected current density is also determined by the type of plating process
It is fixed.In barrel plating technique, preferable current density is from 0.1A/dm2To 1A/dm2In the range of.In rack plating process, from
0.5A/dm2To 5A/dm2Current density cause the flawless black ruthenium layer of optics.
Described ruthenium electrolyte provided by the present invention, it is used to for example deposit on jewelry and ornamental commodity in one kind
It is especially most suitable in the technique of ornamental pitch black and optional bright layer.This technique is equally carried by the present invention
For.The electrolyte can be optimized in barrel plating and rack plating process.Electrolyte described here is made it possible to appropriate
Produced on material especially close and pitch black（L is up to 50）Ruthenium deposit（See that Fig. 1, Fig. 1 show comparison example and according to this hair
The result of bright example 1）.In addition, being possible to work in faintly acid to alkaline range when using the electrolyte, the scope is first
Allow black ruthenium coating to be deposited on underlying metal and this metal need not be pre-equipped with a upper noble metal intermediate layer.According to
The prior art this point known is nor obvious.
Examine five kinds of samples.The production of sample can take following instance.
Table 1：
* according to JP2001049485, * * are according to 1975282
It should be apparent that these methods in alkaline range（Electrolyte is according to the present invention）Provide relatively good L*
Value.It is used as wetting agent by adding a kind of cationic surfactant to promote further melanism.
Using measuring color value on a layer according to the reference colour measuring instrument of CIE-L*a*b* systems obtained by these.
Also pass through GDOES（Glow Discharge Optical Emission spectroscopic methodology）It has detected these layers.These are tried in argon plasma
Sample " splash " spreads all on generally flat plane and excited to send specific radiation.In an optical spectrometer
Middle detection radiation.The calculating to concentration and depth is carried out by Multi-Nominal Matrix calibration.
Example：
Conventional method：
One brass sheet is immersed in a kind of electrolyte with component described below.
Comparison example-according to US4297178 formula：
6.2g/l Ru, as [Ru2N(H2O)Cl8]3-
80g/l oxalic acid
PH is arranged to 7.5 by potassium hydroxide
pH：7.5（70℃）
Operating temperature：70℃
Current density：1A/dm2
L*=68.6
Embodiment according to the present invention 1（Type I）：
6.2g/l Ru, as [Ru2N(H2O)Cl8]3-
80g/l oxalic acid
20g/l potassium dihydrogen phosphate
2g/l saccharin-N- propyl sulfonic acid sodium salts
600mg/l quaternary ammonium salt
pH：7.5（70℃）
Operating temperature：70℃
Current density：1A/dm2
L*=55.5
Embodiment according to the present invention 2（Type II）：
3g/l Ru, as [Ru2N(H2O)X8]3-, X=halide ion
40g/l oxalic acid
20g/l potassium dihydrogen phosphate
1g/l 3- (2-[4-morpholinodithio base -2- sulfydryls) propane sulfonic acid sodium salt
400mg/l quaternary ammonium salt
pH：8（75℃）
Operating temperature：75℃
Current density：1A/dm2
L*=52.3
The not example 3 of sulfur heterocyclic ring（Type-iii）：
3g/l Ru, as [Ru2N(H2O)X8]3-, X=halide ion
60g/l oxalic acid
40g/l potassium dihydrogen phosphate
300mg/l quaternary ammonium salt
pH：6（75℃）
Operating temperature：75℃
Current density：1A/dm2
L*=69.2
Claims (25)
1. a kind of be used to deposit dicoration and industrialness with specific blackness on conductive objects with the pH from >=5 to 12
The electrolyte of layer of ruthenium,
Characterized in that,
The electrolyte has following components：
A) calculated by ruthenium metal, concentration is the ruthenium from the dissolving of 0.2 g/l to 20 g/l (g/l)；
B) concentration is one or more anion from the dicarboxylic acids of the mol/L of 0.05 mol/L -2, tricarboxylic acids or tetrabasic carboxylic acid；
C) one or more thia rings；
D) one or more cationic surfactants.
2. electrolyte as claimed in claim 1,
It is characterized in that
Ruthenium is as with chemical formula [Ru2N(H2O)2X8]3-Double-core anionic ruthenium time amino halide complex and exist, its
Middle X is a kind of halide ion.
3. electrolyte as claimed in claim 2,
It is characterized in that
The concentration of ruthenium is from 2 g/l to 8 g/l after the double-core anionic ruthenium time amino halide complex is completely dissolved
In the range of electrolyte.
4. electrolyte as claimed any one in claims 1 to 3,
It is characterized in that
The electrolyte is free of other transition metal ions.
5. electrolyte as claimed any one in claims 1 to 3,
It is characterized in that
The carboxylic acid is selected from the group, and the group is made up of the following：Oxalic acid, citric acid, tartaric acid, butanedioic acid, maleic acid, penta 2
Acid, adipic acid, malonic acid, malic acid.
6. electrolyte as claimed any one in claims 1 to 3,
It is characterized in that
The thia ring is selected from the group, and the group is made up of the following：3- (2-[4-morpholinodithio base -2- sulfydryls) propane sulfonic acid sodium salt, sugar
Smart sodium salt, saccharin N- propyl sulfonic acids sodium salt, 6- methyl -3,4- dihydro -1,2,3- Evil thiazine -4- ketone 2,2- dioxide, benzo
Thiazole, 2-mercaptobenzothiazole, thiazole, isothiazole.
7. electrolyte as claimed any one in claims 1 to 3,
It is characterized in that
The surfactant is selected from the group, and the group is made up of the following：Octyl trimethyl ammonium bromide, octyl trimethyl chlorination
Ammonium, DTAB, decyl trimethyl ammonium chloride, DTAB, trimethyl chlorination
Ammonium, TTAB, tetradecyl trimethyl ammonium chloride, cetyl trimethylammonium bromide, cetyl three
Ammonio methacrylate, ethyl dimethyl hexadecyl base ammonium bromide, ethyl dimethyl hexadecyl ammonium chloride, benzyl dimethyl decyl
Ammonium chloride, benzyl dimethyl lauryl ammonium chloride, benzyl dimethyl tetradecyl ammonium chloride and benzyl dimethyl ten
Six alkyl ammomium chlorides and their mixture.
8. electrolyte as claimed any one in claims 1 to 3,
It is characterized in that
The pH of the electrolyte is in the range of 7-8.
9. electrolyte as claimed any one in claims 1 to 3,
It is characterized in that
The electrolyte includes a kind of buffer system, and the buffer system is selected from the buffer solution group by borate, phosphate and carbonate
Into group.
10. a kind of purposes of electrolyte in following methods, this method is used to immerse by regarding the article for treating coating as negative electrode
In the electrolyte and establish current flow between the anode and the negative electrode and black ruthenium coating deposited on the conductive objects,
It is characterized in that
Select the electrolyte as described in any one of claim 1 to 9.
11. purposes as claimed in claim 10,
It is characterized in that
Ruthenium is as with chemical formula [Ru2N(H2O)2X8]3-Double-core anionic ruthenium time amino halide complex and exist, its
Middle X is a kind of halide ion.
12. purposes as claimed in claim 11,
It is characterized in that
The concentration of ruthenium is from 2 g/l of electrolyte to 8 after double-core anionic ruthenium time amino halide complex is completely dissolved
In the range of g/l electrolyte.
13. such as the purposes any one of claim 10-12,
It is characterized in that
The electrolyte is free of other transition metal ions.
14. such as the purposes any one of claim 10-12,
It is characterized in that
The carboxylic acid is selected from the group, and the group is made up of the following：Oxalic acid, citric acid, tartaric acid, butanedioic acid, maleic acid, penta 2
Acid, adipic acid, malonic acid, malic acid.
15. such as the purposes any one of claim 10-12,
It is characterized in that
The thia ring is selected from the group, and the group is made up of the following：3- (2-[4-morpholinodithio base -2- sulfydryls) propane sulfonic acid sodium salt, sugar
Smart sodium salt, saccharin N- propyl sulfonic acids sodium salt, 6- methyl -3,4- dihydro -1,2,3- Evil thiazine -4- ketone 2,2- dioxide, benzo
Thiazole, 2-mercaptobenzothiazole, thiazole, isothiazole.
16. such as the purposes any one of claim 10-12,
It is characterized in that
The surfactant is selected from the group, and the group is made up of the following：Octyl trimethyl ammonium bromide, octyl trimethyl chlorination
Ammonium, DTAB, decyl trimethyl ammonium chloride, DTAB, trimethyl chlorination
Ammonium, TTAB, tetradecyl trimethyl ammonium chloride, cetyl trimethylammonium bromide, cetyl three
Ammonio methacrylate, ethyl dimethyl hexadecyl base ammonium bromide, ethyl dimethyl hexadecyl ammonium chloride, benzyl dimethyl decyl
Ammonium chloride, benzyl dimethyl lauryl ammonium chloride, benzyl dimethyl tetradecyl ammonium chloride and benzyl dimethyl ten
Six alkyl ammomium chlorides and their mixture.
17. such as the purposes any one of claim 10-12,
It is characterized in that
Set current density is 0.1A/dm2-10A/dm2。
18. such as the purposes any one of claim 10-12,
It is characterized in that
Set temperature is 10 DEG C -80 DEG C.
19. such as the purposes any one of claim 10-12,
It is characterized in that
The combination of insoluble anode and these anodes made of the material by being selected from the group is used, the group is by the following group
Into：Platinized titanium, graphite, iridium-transition metal mixed oxides and special carbon material.
A kind of 20. black ruthenium layer on conductive objects that can be obtained as any one of claim 10-19.
21. layer of ruthenium as described in claim 20,
It is characterized in that
The thickness that it has is from 0.1 μm to 3 μm.
22. layer of ruthenium as described in claim 20,
It is characterized in that
The sulfur content that this layer has in 1 μm of perimeter is from by weight 3% to by weight 6%.
23. layer of ruthenium as described in claim 20,
It is characterized in that
The carbon content that this layer has in 1 μm of the perimeter is from by weight 1% to by weight 2%.
24. the layer of ruthenium as described in claim 21,
It is characterized in that
The oxygen content that this layer has in 1 μm of the perimeter is from by weight 15% to by weight 20%.
A kind of 25. conductive objects with the layer of ruthenium as any one of in claim 20-24.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE102011105207.4 | 2011-06-17 | ||
| 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 |
| 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 CN104040033A (en) | 2014-09-10 |
| CN104040033B true CN104040033B (en) | 2017-12-19 |
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| Application Number | Title | Priority Date | Filing Date |
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| 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) |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| 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 |
| PL3159435T3 (en) * | 2015-10-21 | 2018-10-31 | Umicore Galvanotechnik Gmbh | Additive for silver palladium alloy electrolytes |
| 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 |
| 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 |
| 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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2011
- 2011-06-17 DE DE102011105207.4A patent/DE102011105207B4/en active Active
-
2012
- 2012-06-08 US US14/126,769 patent/US20140131209A1/en not_active Abandoned
- 2012-06-08 JP JP2014515143A patent/JP2014519555A/en active Pending
- 2012-06-08 EP EP12726136.0A patent/EP2723922B1/en active Active
- 2012-06-08 ES ES12726136T patent/ES2754262T3/en active Active
- 2012-06-08 KR KR1020137033450A patent/KR20140033424A/en not_active Application Discontinuation
- 2012-06-08 WO PCT/EP2012/060924 patent/WO2012171856A2/en active Application Filing
- 2012-06-08 CN CN201280029704.0A patent/CN104040033B/en active Active
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Also Published As
| Publication number | Publication date |
|---|---|
| JP2014519555A (en) | 2014-08-14 |
| DE102011105207B4 (en) | 2015-09-10 |
| WO2012171856A3 (en) | 2014-03-27 |
| EP2723922B1 (en) | 2019-08-28 |
| ES2754262T3 (en) | 2020-04-16 |
| KR20140033424A (en) | 2014-03-18 |
| DE102011105207A1 (en) | 2012-12-20 |
| EP2723922A2 (en) | 2014-04-30 |
| US20140131209A1 (en) | 2014-05-15 |
| CN104040033A (en) | 2014-09-10 |
| WO2012171856A2 (en) | 2012-12-20 |
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