CN1516754A - Mixture for use as brightening agent in electrodeposit solution of silver gold orone of their alloys - Google Patents
Mixture for use as brightening agent in electrodeposit solution of silver gold orone of their alloys Download PDFInfo
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- CN1516754A CN1516754A CNA028118626A CN02811862A CN1516754A CN 1516754 A CN1516754 A CN 1516754A CN A028118626 A CNA028118626 A CN A028118626A CN 02811862 A CN02811862 A CN 02811862A CN 1516754 A CN1516754 A CN 1516754A
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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
- C25D3/56—Electroplating: Baths therefor from solutions of alloys
- C25D3/64—Electroplating: Baths therefor from solutions of alloys containing more than 50% by weight of silver
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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
- C25D3/46—Electroplating: Baths therefor from solutions of silver
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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
- C25D3/48—Electroplating: Baths therefor from solutions of gold
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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
- C25D3/56—Electroplating: Baths therefor from solutions of alloys
- C25D3/62—Electroplating: Baths therefor from solutions of alloys containing more than 50% by weight of gold
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- Electroplating And Plating Baths Therefor (AREA)
Abstract
The invention concerns a mixture in solid form containing: dithiocarbamoyldithiocarbazate of formula (I): H2N-(C=S)-NH-NH-(C=S)-S<->M<+>, wherein: M<+> represents an alkaline cation or an ammonium and a xanthate of formula (II): R-O-(C=S)-S<->M<+>, wherein R represents a C1-C12 hydrocarbon group, optionally branched or unsaturated, optionally cyclic or aromatic, and M<+> represents an alkaline cation or an ammonium. The invention also concerns a method for making said mixture. The invention further concerns the use of said solid mixture and basic solutions containing said mixture as brightening agent in electrolytic solutions, in particular in cyanide-containing baths, for electrodeposit of silver, gold or one of their alloys.
Description
The present invention relates to a kind of solid mixt, it can be especially as the brightening agent in the electrolytic solution of one of electrolytic deposition silver, gold or its alloy.The present invention also relates to this preparation process of mixture and purposes.
As everyone knows, the purpose of sneaking into brightening agent in electrolytic deposition liquid is metal refining or alloy, the effect of described brightening agent be improve the luminance brightness of sedimentary metal or alloy.
In containing in the cyanogen plating bath of silver, use the metallic compound of antimony, selenium or tellurium usually, or the compound of sulfur-bearing is as brightening agent.
The sulfocompound that can enumerate has thiocarbamide, nitric sulfid, and the product of following formula A and B:
H
2N-(C＝S)-NH-NH-(C＝S)-S-K
+????(A)
And
K
+(S--C＝S)-HN-(C＝S)-NH-NH
2????(B)，
Its purposes is documented in US 3,446,716 or FR 1,475,290 in.
As U.S. Pat 3,446,716 embodiment 1 is disclosed, and the product of formula A is the reaction by thiosemicarbazide and nitric sulfid, obtains under solvent refluxes in as methyl alcohol.
Well-knownly in the current industry be, nitric sulfid is a kind of compound of poison especially, and it is operational hazards and make us very much nauseating not only.And, when incomplete, can in the mixture of brightening agent compound, find the nitric sulfid of trace at least with the reaction of thiosemicarbazide.With the passing of time, this can cause the formation of remaining parasitic sulfide, and it is not wish in the electrolyzer to exist, because they cause the settling dimness, and has low current density, particularly is lower than 0.5A/dm
2Current density.
In addition, top compd A and B also have following shortcoming: the life-span in water is very short, and only reaches 3A/dm at electric current
2The time, even will be in the presence of wetting agent, it just has actual effect as brightening agent.
The present inventor seeks a kind of method described in the document that is different from, so that prepare product A avoiding using under the situation of nitric sulfid, described nitric sulfid is because of its toxic action and to pollute the ability of final product well-known.The present inventor unexpectedly finds, make the reaction of former acid metal salt of excessive basic yellow or xanthogenic acid ammonium and thiosemicarbazide, can make solid-state product mixtures, more specifically, be the mixture of product A and xanthogenic acid ammonium or the former acid metal salt of basic yellow, it has more independent product A and has improved a lot of bright abilities.
In addition, extra test shows, can also use by above-mentioned solid product mixture being dissolved in aqueous composition that water obtains as brightening agent, but also show, same solid product and aqueous composition can be used as deposited gold or gold/silver alloys further, perhaps mainly contain the brightening agent in the electrolytic solution of different-alloy of gold and/or silver.
Thereby a first aspect of the present invention relates to a kind of new solid mixture, as new Industrial products.
Another aspect of the present invention relates to a kind of method for preparing this solid product mixture.
Another aspect of the present invention relates to and comprises the aqueous composition of this mixture in water.
The purposes that relates in one aspect to above-mentioned solid mixture and aqueous composition as brightening agent more of the present invention, and the electrolytic solution that comprises these new brightening agents.
More specifically, according to basic feature, the present invention relates to a kind of solid mixt, especially, it can be used as the brightening agent in the electrolytic deposition liquid of one of silver, gold or its alloy, and this solid mixt comprises:
The dithio carboxamide dithio carbazic acid salt of-following formula
H
2N-(C＝S)-NH-NH-(C＝S)-S-M
+????(I)
In the formula, M
+Represent alkaline kation or ammonium cation; And
The xanthogenate of-following formula
R-O-(C＝S)-S-M
+?????????????????(II)
In the formula, the R representative is optional to be side chain or undersaturated, optional C for ring-type or aromaticity
1-C
12Alkyl, and M
+Represent alkaline kation or ammonium cation.
According to a useful variant of the present invention, in solid mixt of the present invention, xanthogenate (II) is alkyl xanthogenic acid sodium, potassium or ammonium, and wherein, this alkyl R is the saturated alkyl of straight or branched.
Constitute the formula (I) of mixture of the present invention and (II) ratio of compound can change very widely.Yet, the amount of the xanthogenate (II) that is comprised in the mixture of the present invention can advantageously be chosen, and makes the amount of this compound (II) in described mixture can improve contain the bright ability in cyanogen electrolytic deposition liquid of dithio carboxamide dithio carbazic acid salt (I) at silver effectively.
For this reason, preferred mixture of the present invention comprises 0.0003～80%, the more preferably xanthogenate of the formula of 0.0003～40% weight (II), and this xanthogenate is preferably alkyl xanthogenic acid sodium, potassium or ammonium, and wherein this alkyl is the saturated C of straight or branched
1-C
6Alkyl.
Mixture of the present invention as defined above is that the xanthogenate reaction by thiosemicarbazide and excessive formula (II) obtains, and reaction conditions is to have solvent, and preferably heats under 35～100 ℃ temperature.Choice of Solvent should make easy to operate under the solvent refluxing temperature.
Preferred reaction is to carry out under the situation of every mole of thiosemicarbazide and the xanthogenate reaction of at least 1.05 moles formula (II).
According to another essential characteristic of the present invention, the invention still further relates to the method for the above-mentioned solid mixture of preparation.
This method comprises the step that the step that makes thiosemicarbazide and the defined xanthogenate reaction of excessive above-mentioned formula (II) and thiosemicarbazide react, and this is reflected at temperature is to carry out in 35～100 ℃ the solvent; And the step of filtered and recycled solid mixture subsequently.
The list of solvent that can be used for carrying out above-mentioned reaction is longer.It can be to be selected from following all kinds of SOLVENTS or solvent mixture: C
1-C
6Alcohol, particularly as methyl alcohol, ethanol, 1-propyl alcohol, Virahol, butanols, amylalcohol, hexanol; Ether, particularly ether; Triethylamine; Acetonitrile; Dioxane; Water; And their mixture.
At last, after the step of the reaction of thiosemicarbazide and formula (II) xanthogenate, preferably carry out at least one step in the following step: rotation (spinning), filter, with solvent washing (the particularly step of washing) with dehydrated alcohol, and dry, these steps are prior to reclaiming solid step itself.
Thereby, the method according to this invention, preferred thiosemicarbazide and alkyl xanthogenic acid an alkali metal salt or alkyl xanthogenic acid ammonium (as potassium ethyl xanthonate) react in solvent, and described solvent is preferably alcohol, as methyl alcohol, ethanol or 2-propyl alcohol.
Preferred this is reflected under the state that keeps solvent refluxing and carries out, and for alcoholic solvent, generally is to carry out under 40～80 ℃ temperature.
React after heating for some time, during this period of time generally greater than 20 minutes.
With the reaction mixture cool to room temperature, preferably be cooled to 10 ℃ or lower then.This cooling causes xanchromatic solid salt precipitation, and it can pass through isolated by vacuum filtration.Then, preferably wash and the dry solid product that is reclaimed with a spot of alcohol, preferably dry under 35～65 ℃ temperature, so that obtain the xanchromatic solid product.
By analyzing, particularly by the IR spectroscopic analysis, this yellow solid product shows that it comprises two kinds of solid products of mixture I of the present invention and II.
The test of carrying out within the scope of the invention can confirm, when it is added to the electrolytic deposition liquid of silver, particularly silver contain in the cyanogen electrolytic deposition liquid time, this mixture is active especially brightening agent, and uses the resulting luminance brightness of dithio carboxamide dithio carbazic acid salt to have tangible raising more separately.
And other tests show, same mixture be added to the electrolytic deposition gold or based on the electrolytic solution of the various alloys of gold and/or silver in the time, also have significant bright performance.
In addition, find that also mixture of the present invention can be dissolved in the alkaline aqueous solution, the pH of described alkaline aqueous solution is very concrete, is 11～14.Find also that simultaneously this alkaline aqueous composition itself can be used as the electrolytic deposition liquid that the liquid brightening agent directly is used for same type.
Thereby, according to its another essential characteristic, the invention still further relates to a kind of alkaline moisture solution, this aqueous solution is in the presence of alkali, obtain by above-mentioned solid mixture of the present invention is dissolved in the water, described alkali can make this pH value of aqueous solution reach 10～14.
According to the present invention, can use the pH that can make described composition to reach 10～14 any alkali or the mixture of alkali, prepare this mixed water composition.These alkali preferably are selected from: sodium hydroxide, potassium hydroxide, ammonium hydroxide, yellow soda ash, salt of wormwood, volatile salt, and sodium phosphate, potassiumphosphate, ammonium phosphate, triethylamine, and their mixture.
According to its another essential characteristic, the present invention relates to mixture as defined above, and aqueous composition by in the presence of alkali, this mixture dissolving being obtained, as the purposes of brightening agent, wherein said alkali can make the pH value of this aqueous composition reach 10～14 in the electrolytic deposition liquid of one of silver, gold or its alloy.
Verified, solid that these are new or liquid brightening agent are for alkaline electrolyte, and it is particularly advantageous especially containing cyanogen electrolytic solution.
Also find, utilize solid mixture of the present invention or derive from the aqueous composition of this mixture and the brightness effect that obtains, under the situation that the aqueous solution or alcoholic solution with methyl, ethyl, n-propyl or potassium isopropyl xanthate, sodium or ammonium are used in combination, can obtain bigger enhancing, the described aqueous solution or alcoholic solution are as bright toughener.
The alcohol that is preferred for preparing these bright tougheners is selected from methyl alcohol, ethanol or Virahol.
According to its another essential characteristic, the present invention relates to be used for the electrolytic solution of one of electrolytic deposition silver, gold or its alloy, it comprises solid mixture as defined above, or by dissolving the alkaline aqueous solution that contains this mixture that this mixture obtains, as brightening agent, in case of necessity, described brightening agent uses in the presence of the solution that is used as bright toughener as defined above.
Electrolytic solution of the present invention preferably comprises the silver of 0.3～150g/l, the gold of the more preferably silver of 3～150g/l, and/or 0.1～75g/l, and preferably these two kinds of metals are with prussiate, and particularly the form of Jian Xing double cyanide exists.
According to the present invention, the content of solid mixture in this electrolytic solution is generally the solid mixture of 0.05mg/l at least, preferred 0.05～1500mg/l.This concentration also can obtain by means of the aqueous composition as defined above of q.s.
In addition, electrolytic solution of the present invention particularly contains cyanogen electrolytic solution, can comprise electrolytic solution, especially for depositing silver, gold, gold/silver alloys or with silver and/or gold be major metal alloy contain any composition of using always in the cyanogen electrolytic solution.
The free potassuim cyanide that comprises 0.1～200g/l in preferred these electrolytic solution.
Also preferred electrolytic solution of the present invention comprises wetting agent, and the ratio of this wetting agent is generally 0.0001～25g/l.
Preferred institute by wetting agent be selected from: turkey red oil, the 2-sodium naphthalene sulfonate, 1,3, the 6-sodium naphthalene sulfonate, the 2-sodium naphthalene sulfonate, the condensation product of sodium naphthalene sulfonate and formaldehyde, macrogol ester, the dimethoxy Tetraglycol 99, sulfonated fatty amides reaches polyoxyethylene alkyl amine.
At last, also have the electrolytic solution of anthology invention further to comprise at least a following compound that is selected from: the arsenic of dissolved state, antimony, selenium, tellurium, lead, EDTA, and basic salt, basic carbonate, alkaline hydrated oxide, ammonia solution, alkaline phosphate, naphthene sulfonic acid, thiocarbamide, thioacetamide, thiosulphate, alkaline sulfite, alkaline succinate, alkaline tartrate, the alkalescence Citrate trianion, alkaline glucose hydrochlorate, mercaptobenzothiazole, glycerine, ethylene glycol, and basic salt.
Under situation of the present invention, all these products all have advantage commonly known in the art.
Thereby for example Sulfothiorine is to produce extra luminance brightness to the contribution of deposition of silver liquid.
In addition, golden electrolytic solution comprises alkaline phosphate and/or alkaline thiosulphate is more favourable, and these additives are commonly known in the art, and respectively as buffering salt and conduction salt or brightening agent.They also can advantageously comprise the nickel of prussiate form, as alloyed metal.
Similarly, the effect that adds the EDTA of sodium-salt form is some metallic impurity of complexing consumingly, and can avoid the macroscopic irregularity of the metal deposit relevant with metallic pollution.
For example, can also be by means of antimony complex, the complex compound of glycerine form especially so that for electrolytic deposit brings extra hardness quality, makes it can have hardness greater than 160HV (Vickers) under 50g.
In addition, electrolytic solution of the present invention also comprises the various alloyed metals of q.s with the form of solution, traditional mode, makes sedimentary silver of institute and/or golden alloy comprise this metal.Particularly, the alloyed metal that can comprise in the electrolytic solution is selected from palladium, tin, and copper, nickel, cobalt, zinc, cadmium, antimony, indium and germanium, the amount of these metals must be enough, so that utilize the alloy of its sedimentary silver and/or gold to comprise this alloyed metal of 0～40% weight.
Embodiment
Embodiment 1: solid brightening agent mixture synthetic
1.6 in the ethanol that rises, 1 mole thiosemicarbazide and 1.2 moles potassium ethyl xanthonate are reacted.
This mixture was kept at least one hour under reflux state.
Then this mixture is cooled to below 20 ℃.
The crystallization of xanchromatic solid product leaches and drying under 65 ℃ then.Relatively product (I) and formation (II), M are determined in the IR spectroscopic analysis
+Represent potassium cationic.
Embodiment 2: the preparation of blast solution
The solid that a. will derive from embodiment 1 is dissolved in the potassium hydroxide solution with the concentration of 25g/l, and its pH is adjusted to 12.
Obtain No. 1, bright solution.
B. the xanthogenic acid aqueous solutions of potassium for preparing 50g/l is done contrast.This solution is appointed as solution No. 2.
Embodiment 3: the electrolytic solution that designs for depositing silver
Preparation solution (I), it comprises:
The silver of-40g/l, the i.e. KAg of 66g/l (CN)
2,
The potassium cyanide of-80g/l,
The Sulfothiorine of-0.3g/l, and
The naphthene sulfonic acid of-2g/l and the condenses of formaldehyde (this condenses serves as wetting agent).
A) solid that will derive from embodiment 1 is added in the above-mentioned electrolytic solution with 50mg/l.
B) No. 1, the bright solution of embodiment 2 is added in the solution (I) with 2.5ml/l.
C) No. 1+1ml/l of 1ml/l light solution solution is added to for No. 2 in the solution (I).
To derive from a, three kinds of electrolytic solution of b and c are added in the HULL electrolyzer, and this HULL electrolyzer moves 10 minutes under 1A, and speed of rotation is 250rpm.
Under all situations, for 0.01～7A/dm
2Current density, all obtain the settling that becomes clear.
Embodiment 4: the electrolytic solution that designs for depositing silver
Preparation solution, this solution comprises:
The silver of-36g/l, the i.e. KAg of 66g/l (CN)
2,
The potassium cyanide of-150g/l, and
The turkey red oil of-2g/l (this product serves as wetting agent).
Following bright mixture 1,2,3 is added in this solution:
Mixture 1:
-50mg/l derives from the solid mixture of embodiment 1,
The Sulfothiorine of-3g/l, and
The antimony of-0.8g/l glycerine complex form.
Mixture 2:
-50mg/l derives from the solid mixture of embodiment 1,
The rose vitriol of-1g/l, and
The antimony of-0.8g/l alkalescence tartrate complex form.
Mixture 3:
-50mg/l derives from the solid mixture of embodiment 1,
The selenocyanic acid potassium of-3g/l, and
The antimony of-3g/l alkaline glucose hydrochlorate complex form.
Three kinds of electrolytic solution that prepare above are added in the HULL electrolyzer, and this HULL electrolyzer moves 10 minutes under 1A, and speed of rotation is 250rpm.
Under these three kinds of situations, for 0.01～7A/dm
2Current density, equal settlings that can obtain to become clear.
Embodiment 5: the electrolytic solution that designs for depositing silver
Preparation solution, this solution comprises:
The silver of-36g/l, the i.e. KAg of 66g/l (CN)
2,
The potassium cyanide of-100g/l,
-50mg/l derives from the solid mixture of embodiment 1,
The turkey red oil of-2g/l (this product serves as wetting agent),
The Sulfothiorine of-3g/l, and
-2g/l contains the nickel of cyano complex form.
The solution for preparing above is added in the HULL electrolyzer, and this HULL electrolyzer moves 10 minutes under 1A, and speed of rotation is 250rpm.
For 0.001～5A/dm
2Current density, the settling that can obtain to become clear.
This sedimental nickel content is 0.01～3%.
Embodiment 6: the synergistic confirmation of two kinds of compositions of the present invention's solid mixture
In the present embodiment, the effect that derives from the solid mixture that is made of potassium ethyl xanthonate and dithio carboxamide dithio carbazic acid potassium of embodiment 1 is compared with using the effect that each composition obtained separately.
For this reason, the solution of preparation alkaline electrolyte (II), it is composed as follows:
The silver of-36g/l silver potassium double cyanide form,
The potassium cyanide of-150g/l,
-2g/l serves as the turkey red oil of wetting agent.
Be labeled as the electrolytic solution of 6-1 to 6-6 by this alkaline electrolyte (II) preparation, the composition of these electrolytic solution is as shown in the table:
| Composition | ??6-1 | ??6-2 | ??6-3 | ??6-4 | ??6-5 | ??6-6 |
| ??Ag | ??36g/l | ??36g/l | ??36g/l | ??36g/l | ??36g/l | ??36g/l |
| Free KCN | ??150g/1 | ??150g/l | ??150g/l | ??150g/l | ??150g/l | ??150g/l |
| Turkey red oil | ??2g/l | ??2g/l | ??2g/l | ??2g/l | ??2g/l | ??2g/l |
| Ethyl xanthate | ??0 | ??12mg/l | ??38mg/l | ??0 | ??0 | ??5mg/l |
| Dithio carboxamide dithio carbazic acid salt | ??0 | ??0 | ??0 | ??38mg/l | ??0 | ??0mg/l |
| Mixture of the present invention | ??0 | ??0 | ??0 | ??0 | ??38mg/l | ??15mg/l |
These different mixtures are tested at the HULL electrolyzer, and this HULL electrolyzer moves 10 minutes under 1A, and speed of rotation is 250rpm, promptly adopts 7～0.01A/dm
2Current density.
With regard to its luminance brightness, check adopts above-mentioned 6-1 to the settling that the different electrolytes of 6-6 obtains, and provides following result:
-6-1: dim white in saturating yellow outward appearance, at 7～0.01A/dm
2All current densities under
-6-2: An Dan white appearance slightly, at 7～0.01A/dm
2All current densities under
-6-3: dim slightly white in saturating yellow outward appearance, at 7～0.01A/dm
2All current densities under
-6-4: current density is less than 3A/dm
2(3～0.01A/dm
2) time, bright outward appearance; Current density is 7～3.1A/dm
2The time, white appearance
-6-5: current density is less than 7A/dm
2(7～0.01A/dm
2) time, bright outward appearance.These values confirm that in the Hull electrolyzer this Hull electrolyzer moves 10 minutes under 2A, speed of rotation 250rpm, and it makes that can observe in current density is about 12～0.01A/dm
2The settling that obtains down.
-6-6: current density is lower than 7A/dm
2(7 to 0.01A/dm
2) time, bright outward appearance.These values confirm that in the Hull electrolyzer this Hull electrolyzer moves 10 minutes under 2A, speed of rotation 250rpm, and it makes that can observe in current density is about 12～0.01A/dm
2The settling that obtains down.
With regard to one of two kinds of products of the independent mixture that adopts the present invention, reality is proved conclusively in these results' contrast clearly, and mixture of the present invention has produced especially effectively light effect really.
With the comparable result of the result who obtains with electrolytic solution 6-5 is to obtain by replacing solid-state brightening agent mixture with the basic solution of this mixture.
In solution 6-6, the form of basic solution that can solid mixture adds the brightening agent mixture, and the result is the same.
In the result's who should be noted that at electrolytic solution 6-5 and 6-6 the comparison, can as electrolytic solution 6-6,, reduce the amount of solid mixture of the present invention, not damage the quality of brightness effect simultaneously again by means of the extra potassium ethyl xanthonate that adds.
Embodiment 7: the electrolytic solution that is used for deposited gold
Preparation solution, this solution comprises:
-8g/l KAu (CN)
2The gold of form,
The potassium primary phosphate of-40g/l,
The potassium cyanide of-100g/l,
-50mg/l derives from the solid mixture of embodiment 1,
The turkey red oil of-2g/l (this product serves as wetting agent),
The Sulfothiorine of-3g/l, and
-2g/l contains the nickel of cyano complex form.
The deposition of gold thing that this electrolytic solution can obtain to become clear, it can be applicable to decorate.
Claims (21)
1. solid mixture, this mixture can be used as silver, and the brightening agent in the electrolytic solution of the electrodeposition groove of one of gold or its alloy is characterized in that it comprises:
The dithio carboxamide dithio carbazic acid salt of-following formula
H
2N-(C＝S)-NH-NH-(C＝S)-S-M
+????????????(I)
In the formula, M
+Represent alkaline kation or ammonium cation; And
The xanthogenate of-following formula
R-O-(C＝S)-S-M
+????????????????????????(II)
In the formula, the R representative is optional to be side chain or undersaturated, optional C for ring-type or aromaticity
1-C
12Alkyl, and M
+Represent alkaline kation or ammonium cation.
2. according to the mixture of claim 1, it is characterized in that described xanthogenate (II) is an alkyl xanthogenic acid sodium, potassium or ammonium, wherein this alkyl R is the saturated C of straight or branched
1-C
6Alkyl.
3. according to the mixture of one of claim 1 or 2, it is characterized in that the content of described xanthogenate (II) in this mixture can improve the bright ability in the silver-colored galvanic deposition cell that dithio carboxamide dithio carbazic acid salt (I) containing cyanogen effectively.
4. according to the mixture of one of claim 1 to 3, it is characterized in that it comprises 0.0003～80% weight, the xanthogenate of preferred 0.0003～40% weight (II).
5. according to the mixture of one of claim 1 to 4, it is characterized in that it can obtain by thiosemicarbazide and excessive formula (II) xanthogenate reaction, reaction conditions is to have solvent, and heats under 35～100 ℃ temperature.
6. according to the mixture of claim 5, it is characterized in that it is to obtain by the reaction of every mole of thiosemicarbazide with at least 1.05 moles xanthogenate (II).
7. alkaline aqueous composition, it is to obtain by the mixture of one of claim 1 to 6 is dissolved in the water in the presence of the mixture of alkali or alkali, the mixture of described alkali or alkali can make the pH value of this aqueous composition reach 10～14.
8. according to the aqueous composition of claim 7, it is characterized in that described alkali is selected from sodium hydroxide, potassium hydroxide and ammonium hydroxide, yellow soda ash, salt of wormwood and volatile salt, sodium phosphate, potassiumphosphate and ammonium phosphate, triethylamine, and their mixture.
9. the method for the aqueous composition of a solid mixture for preparing one of claim 1 to 6 or claim 7 or 8, it is characterized in that this method comprises the step that makes thiosemicarbazide and excessive xanthogenate reaction according to the defined formula of one of claim 1 to 3 (II), the condition that this reaction takes place is to have solvent, and heats under 35～100 ℃ temperature; Reach step by the filtered and recycled solid mixture.
10. according to the method for claim 9, it is characterized in that described solvent is to be selected from following solvent or solvent mixture: methyl alcohol, ethanol, 1-propyl alcohol, Virahol, butanols, amylalcohol, hexanol, ether, acetonitrile, dioxane, triethylamine, water, and their mixture.
11., it is characterized in that after the step of described thiosemicarbazide and formula (II) xanthogenate reaction, be rotated, filter, with at least one step in solvent washing or the drying according to the method for one of claim 9 or 10.
12. the mixture of one of claim 1 to 6, or the composition of one of claim 7 or 8, or the product that obtains according to the method for one of claim 9 to 11, as the purposes of the brightening agent in the electrolytic solution, described used for electrolyte is in the galvanic deposit of one of silver, gold or its alloy.
13., it is characterized in that described electrolytic solution is alkaline electrolyte according to the purposes of claim 12.
14., it is characterized in that described electrolytic solution is for containing cyanogen electrolytic solution according to the purposes of claim 12 or 13.
15. purposes according to one of claim 12 to 14, it is characterized in that described brightening agent and be used in combination as the solution of bright toughener, this solution is made of the aqueous solution or the alcoholic solution of methyl, ethyl, n-propyl or potassium isopropyl xanthate, sodium or ammonium, and described alcohol is preferably methyl alcohol, ethanol or Virahol.
16. electrolytic solution that is used for one of electrolytic deposition silver, gold or its alloy, it is characterized in that it comprises the mixture of one of claim 1 to 6, or the composition of claim 7 or 8, or according to the product of the method for one of claim 9 to 11 preparation, as brightening agent.
17. according to the electrolytic solution of claim 16, it is characterized in that it comprises the silver of 0.3～150g/l and/or the gold of 0.1～75g/l, preferably these two kinds of metals are the prussiate form, more preferably Jian Xing double cyanide form; At least the solid mixture of one of 0.05mg/l claim 1 to 6, or the solid mixture that obtains according to the method for one of claim 9 to 11; And the wetting agent of 0.0001～25g/l.
18., it is characterized in that it also comprises the free potassuim cyanide of 0.1～200g/l according to the electrolytic solution of claim 16 or 17.
19. electrolytic solution according to one of claim 16 to 18, it is characterized in that it comprises is selected from following wetting agent: turkey red oil, 1,3,6-naphthalene trisulfonic acid sodium, the 2-sodium naphthalene sulfonate, the condenses of sodium naphthalene sulfonate and formaldehyde, macrogol ester, dimethoxy Tetraglycol 99, sulfonated fatty amides, and polyoxyethylene alkylamine.
20., it is characterized in that it further comprises at least a following compound that is selected from: the arsenic of dissolved state, antimony, selenium, tellurium, lead, EDTA according to the electrolytic solution of one of claim 16 to 19, and basic salt, basic carbonate, alkaline hydrated oxide, ammonia solution, alkaline phosphate, naphthene sulfonic acid, thiocarbamide, thioacetamide, thiosulphate, alkaline sulfite, alkaline succinate, alkaline tartrate, the alkalescence Citrate trianion, the alkaline glucose hydrochlorate, mercaptobenzothiazole, glycerine, ethylene glycol, and basic salt.
21. according to the electrolytic solution of one of claim 16 to 20, it is characterized in that it comprises gold and/or silver-colored in main metal, its feature is that also it also comprises at least a following alloyed metal that is selected from: palladium, tin, copper, nickel, cobalt, zinc, cadmium, indium, germanium and antimony, it is enough that the amount of described alloyed metal is wanted, so that comprise containing of 0～40% weight of golden metal in the silver-colored and/or golden alloy of electrolytic deposition.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| FR0107646A FR2825721B1 (en) | 2001-06-12 | 2001-06-12 | MIXTURE FOR USE AS A BRILLIANT IN A BATH OF ELECTROLYTIC DEPOSIT OF SILVER, GOLD OR ONE OF THEIR ALLOYS |
| FR01/07646 | 2001-06-12 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1516754A true CN1516754A (en) | 2004-07-28 |
Family
ID=8864203
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNA028118626A Pending CN1516754A (en) | 2001-06-12 | 2002-06-12 | Mixture for use as brightening agent in electrodeposit solution of silver gold orone of their alloys |
Country Status (4)
| Country | Link |
|---|---|
| EP (1) | EP1397532A1 (en) |
| CN (1) | CN1516754A (en) |
| FR (1) | FR2825721B1 (en) |
| WO (1) | WO2002101119A1 (en) |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102154667A (en) * | 2009-09-25 | 2011-08-17 | 罗门哈斯电子材料有限公司 | Anti-displacement hard gold compositions |
| CN103741180A (en) * | 2014-01-10 | 2014-04-23 | 哈尔滨工业大学 | Cyanide-free bright electrogilding additive and application thereof |
| CN104387305A (en) * | 2014-10-21 | 2015-03-04 | 陕西延长石油矿业有限责任公司 | Preparation method and application of ore dressing collecting agent for multi-metal sulphide ore |
| 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 |
| CN110699713A (en) * | 2019-11-21 | 2020-01-17 | 长春黄金研究院有限公司 | Cyanide-free gold alloy electroforming solution and using method thereof |
| CN111647919A (en) * | 2019-03-04 | 2020-09-11 | 弗劳恩霍夫应用研究促进协会 | Aqueous preparation for producing gold and silver layers |
| WO2021215422A1 (en) * | 2020-04-21 | 2021-10-28 | 日本エレクトロプレイティング・エンジニヤ－ス株式会社 | Cyanide type electrolytic roughening silver plating liquid |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE102007049496A1 (en) * | 2007-09-14 | 2009-03-19 | Extrude Hone Gmbh | Electrolyte for electrochemical machining |
| WO2012001132A1 (en) * | 2010-06-30 | 2012-01-05 | Schauenburg Ruhrkunststoff Gmbh | Tribologically loadable mixed noble metal/metal layers |
| US9631282B2 (en) | 2010-06-30 | 2017-04-25 | Schauenburg Ruhrkunststoff Gmbh | Method for depositing a nickel-metal layer |
| JP7061065B2 (en) | 2015-11-13 | 2022-04-27 | シオン・パワー・コーポレーション | Additives for electrochemical cells |
| EP3168915B1 (en) * | 2015-11-13 | 2019-08-07 | Basf Se | Additives for electrochemical cells |
| WO2018213661A2 (en) | 2017-05-19 | 2018-11-22 | Sion Power Corporation | Passivating agents for electrochemical cells |
| US10868306B2 (en) | 2017-05-19 | 2020-12-15 | Sion Power Corporation | Passivating agents for electrochemical cells |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| NL90899C (en) * | 1953-04-28 | |||
| NL197948A (en) * | 1954-06-26 | |||
| DE1521025B2 (en) * | 1966-01-05 | 1971-04-08 | Fa Dr Ing Max Schlotter. 7340 Geis hngen | GALVANIC CYANIDIC SHINY SILVER BATH |
| ES368263A1 (en) * | 1968-06-27 | 1971-05-01 | Schering Ag | Bright silver electroplating |
-
2001
- 2001-06-12 FR FR0107646A patent/FR2825721B1/en not_active Expired - Fee Related
-
2002
- 2002-06-12 EP EP02745515A patent/EP1397532A1/en not_active Withdrawn
- 2002-06-12 WO PCT/FR2002/002003 patent/WO2002101119A1/en not_active Application Discontinuation
- 2002-06-12 CN CNA028118626A patent/CN1516754A/en active Pending
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102154667A (en) * | 2009-09-25 | 2011-08-17 | 罗门哈斯电子材料有限公司 | Anti-displacement hard gold compositions |
| CN102154667B (en) * | 2009-09-25 | 2015-01-14 | 罗门哈斯电子材料有限公司 | Anti-displacement hard gold compositions |
| CN103741180A (en) * | 2014-01-10 | 2014-04-23 | 哈尔滨工业大学 | Cyanide-free bright electrogilding additive and application thereof |
| CN103741180B (en) * | 2014-01-10 | 2015-11-25 | 哈尔滨工业大学 | Non-cyanide bright electrogilding additive and application thereof |
| CN104387305A (en) * | 2014-10-21 | 2015-03-04 | 陕西延长石油矿业有限责任公司 | Preparation method and application of ore dressing collecting agent for multi-metal sulphide ore |
| 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 |
| CN111647919A (en) * | 2019-03-04 | 2020-09-11 | 弗劳恩霍夫应用研究促进协会 | Aqueous preparation for producing gold and silver layers |
| CN110699713A (en) * | 2019-11-21 | 2020-01-17 | 长春黄金研究院有限公司 | Cyanide-free gold alloy electroforming solution and using method thereof |
| WO2021215422A1 (en) * | 2020-04-21 | 2021-10-28 | 日本エレクトロプレイティング・エンジニヤ－ス株式会社 | Cyanide type electrolytic roughening silver plating liquid |
| JP2021172836A (en) * | 2020-04-21 | 2021-11-01 | 日本エレクトロプレイテイング・エンジニヤース株式会社 | Cyan-based electrolytic roughening silver plating solution |
| JP7213842B2 (en) | 2020-04-21 | 2023-01-27 | Ｅｅｊａ株式会社 | Cyanide electrolytic roughening silver plating solution |
Also Published As
| Publication number | Publication date |
|---|---|
| FR2825721A1 (en) | 2002-12-13 |
| WO2002101119A1 (en) | 2002-12-19 |
| EP1397532A1 (en) | 2004-03-17 |
| FR2825721B1 (en) | 2003-10-03 |
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