CN115787010A - Black ruthenium plating solution and application thereof in preparation of pseudo-classic gold or platinum and other ornaments - Google Patents
Black ruthenium plating solution and application thereof in preparation of pseudo-classic gold or platinum and other ornaments Download PDFInfo
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Abstract
The invention relates to the field of ornament preparation processes, in particular to a black ruthenium plating solution and application thereof in preparation of ancient gold or platinum and other ornaments. The black ruthenium plating solution contains: a) With [ Ru (bpy) 2 ] a [Ru(en) 3 ] b [Ru 2 N(H 2 O) 2 X 3 ] c A ruthenium complex present in the form; wherein X is a halogen anion, and the concentration of Ru is 0.02M-0.1M; b) Salts of halogen anions at a concentration of 0.001M to 1M; c) A sulfur-containing compound present as a blackening agent; and d) a sacrificial oxidant; wherein the pH value of the black ruthenium plating solution is less than or equal to 3.
Description
Technical Field
The invention relates to the field of ornament preparation processes, in particular to a black ruthenium plating solution and application thereof in preparation of ancient gold or platinum and other ornaments.
Background
The prior art generally considers that gold and western platinum are not easy to age generally and have low antiquity similarity, and the main reasons are that the gold and western platinum are stable in chemical property and not easy to oxidize, and the traditional vulcanization antiquing is not friendly to the environment. In addition, the natural oxidation of gold and west platinum generally presents reddish brown spots, does not present uniform and stable black lines, has insufficient aesthetic feeling and cannot be produced in a standardized way.
Ruthenium is a platinum group noble metal in light gray color, and is often used for functional and decorative plating because of its excellent corrosion and wear resistance. The 'black ruthenium' is commonly called 'black gold' because of the function of adding a blackening agent in the plating solution, the ruthenium plating film can emit black, but the traditional black ruthenium plating has the problems of insufficient color, poor plating uniformity and poor mechanical property because of unstable blackening agent. And the traditional black ruthenium plating does not have research on the ancient and antique effects.
The chinese patent application published as 2006-02-08 and publication No. CN1729884a discloses a process method for producing different color effects after color separation and electroplating on the surface of a metal material, but the method has low automation degree and has no description on the aspects of polishing and distressing after electro-black ruthenium.
The Chinese patent application with publication number CN101675185A, published as 2008/03/05/2008, discloses a phosphonic acid derivative black ruthenium plating solution formula which is relatively conventional and has an unsatisfactory color plating effect.
In summary, the existing antique finishing technology, such as silver antique finishing, generally adopts a sulfur boiling mode, is not environment-friendly, has gray color, has irregular color of a film layer, does not have thick feeling, is like a semi-finished product, and has poor antique finishing process. In addition, the existing antique technology does not have research on the aspects of 24K gold, platinum and 18K gold. The products of gold and western platinum are generally reddish brown spots due to natural oxidation, cannot present uniform and stable black lines, have poor aesthetic feeling and cannot be produced in a standardized way. The existing black ruthenium plating solution has the problems of insufficient color, poor plating uniformity and poor mechanical property due to the instability of a blackening agent. And the traditional black ruthenium plating does not have research on the ancient and antique effect.
Disclosure of Invention
The invention relates to a black ruthenium plating solution, which contains: a) With [ Ru (bpy) 2 ] a [Ru(en) 3 ] b [Ru 2 N(H 2 O) 2 X 3 ] c A ruthenium complex present in the form; wherein X is a halogen anion, and the concentration of Ru is 0.02M-0.1M; b) A salt of a halogen anion at a concentration of 0.001M to 1M; c) A sulfur-containing compound present as a blackening agent; and d) a sacrificial oxidant;
wherein the pH value of the black ruthenium plating solution is less than or equal to 3.
The method also provides a preparation method of the black ruthenium plating solution, which comprises the following steps:
i) Heating a ruthenium compound, and a complexing agent, an auxiliary complexing agent and a sulfamic acid substance which are excessive relative to the ruthenium compound under an acidic condition to form a ruthenium complex;
wherein the complexing agent comprises ethylenediamine and/or salts thereof, and pyridine derivative salts; the auxiliary coordination agent is one or more of ammonium citrate, nitrite and sulfite;
ii) maintaining acidic and heated conditions, and adding to i) a salt of a halide anion, a blackening agent and a sacrificial oxidizing agent.
The invention also provides a preparation method of the retro precious metals (particularly retro gold and retro platinum), which comprises the step of performing antiquing treatment by adopting the black ruthenium plating solution.
The invention also provides a pseudo-classic noble metal (in particular pseudo-classic gold and pseudo-classic platinum) and an ornament containing the pseudo-classic noble metal.
Compared with the prior art, the invention provides the black ruthenium plating solution for the antique effect process of jewelry. The process based on the black ruthenium plating solution solves the problems of poor binding force and grey color of the black ruthenium plating film and noble metals, particularly gold and platinum. The process preferentially applies a magnetorheological polishing technology, and the black ruthenium coating is made into the antique effect on the surfaces of gold and platinum. The effect ensures that the whole color of the product is slightly dark, black is left in partial positions, the structure of the black-left part is stable, the color is thick, lines are clear, the product is rich in layering sense and age sense, and the product presents unique vintage charm. The process product basically does not influence the color and weight of the product, and the noble metal waste generated in the production process is purified and recovered, so that no hazardous waste is generated, and the process is environment-friendly.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, and it is obvious that the drawings in the following description are some embodiments of the present invention, and other drawings can be obtained by those skilled in the art without creative efforts.
FIG. 1 is a photograph of an ornament made in accordance with one embodiment of the present invention.
FIG. 2 is a photograph of an ornament made in accordance with one embodiment of the present invention; a adopts a comparative example black ruthenium liquid medicine which is gray; b is the black ruthenium liquid medicine provided by the invention, and the color is dark black.
FIG. 3 shows the results of the adhesion detection of the plating layer; a is a comparative example black ruthenium liquid medicine film-coating experimental sheet, and B is the black ruthenium liquid medicine film-coating experimental sheet provided by the invention.
FIG. 4 is a graph showing the results of a bending test; a is a comparative example black ruthenium liquid medicine film-coating experimental sheet, and B is the black ruthenium liquid medicine film-coating experimental sheet provided by the invention.
Detailed Description
Reference will now be made in detail to embodiments of the invention, one or more examples of which are described below. Each example is provided by way of explanation, not limitation, of the invention. Indeed, it will be apparent to those skilled in the art that various modifications and variations can be made in the present invention without departing from the scope or spirit of the invention. For instance, features illustrated or described as part of one embodiment, can be used on another embodiment to yield a still further embodiment.
Unless otherwise defined, all terms (including technical and scientific terms) used in disclosing the invention are to be interpreted as commonly understood by one of ordinary skill in the art to which this invention belongs. The following definitions serve to better understand the teachings of the present invention by way of further guidance. The terminology used in the description of the invention herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention.
The term "and/or", "and/or" as used herein is intended to be inclusive of any one of the two or more items listed in association, and also to include any and all combinations of the items listed in association, including any two or more of the items listed in association, any more of the items listed in association, or all combinations of the items listed in association. It should be noted that when at least three items are connected by at least two conjunctive combinations selected from "and/or", "or/and", "and/or", it should be understood that, in the present application, the technical solutions definitely include the technical solutions all connected by "logic and", and also the technical solutions all connected by "logic or". For example, "A and/or B" includes A, B and A + B. For another example, the embodiments of "a, and/or, B, and/or, C, and/or, D" include any of A, B, C, D (i.e., all connected by "logical or"), any and all combinations of A, B, C, D, i.e., any two or any three of A, B, C, D, and any and all four combinations of A, B, C, D (i.e., all connected by "logical and").
As used herein, the terms "comprising," "including," and "comprising" are synonymous, inclusive or open-ended, and do not exclude additional, unrecited members, elements, or method steps.
The recitation of numerical ranges by endpoints herein includes all numbers and fractions subsumed within that range, as well as the recited endpoints.
The present invention relates to concentration values, which include fluctuations within a certain range. For example, it may fluctuate within a corresponding accuracy range. For example, 2%, may be allowed to fluctuate within ± 0.1%. For values that are larger or do not require more fine control, the meaning is also allowed to include greater fluctuations. For example, 100mM, may allow fluctuations within the range of. + -. 1%, + -2%, + -5%, etc. The molecular weight is referred to, allowing the meaning to include fluctuations of ± 10%.
In the present invention, the terms "plurality", and the like mean, unless otherwise specified, 2 or more in number.
In the present invention, the technical features described in the open type include a closed technical solution composed of the listed features, and also include an open technical solution including the listed features.
In the present invention, "preferably", "better" and "preferable" are only embodiments or examples with better description, and it should be understood that the scope of the present invention is not limited by them. In the present invention, "optionally", "optional" and "optional" refer to the presence or absence, i.e., to any one selected from the two juxtapositions "present" or "absent". If multiple optional parts appear in one technical scheme, if no special description exists, and no contradiction or mutual constraint relation exists, each optional part is independent.
All documents referred to herein are incorporated by reference into this application as if each were individually incorporated by reference. The citation referred to herein is incorporated by reference in its entirety for all purposes unless otherwise in conflict with the present disclosure's objectives and/or technical solutions. Where a citation is referred to herein, the definition of a reference in the document, including features, terms, nouns, phrases, etc., that is relevant, is also incorporated by reference. In the present invention, when the citation is referred to, the cited examples and preferred embodiments of the related art features are also incorporated by reference into the present application, but the present invention is not limited to the embodiments. It should be understood that where the citation conflicts with the description herein, the application will control or be adapted in accordance with the description herein.
The invention relates to a black ruthenium plating solution, which contains: a) With [ Ru (bpy) 2 ] a [Ru(en) 3 ] b [Ru 2 N(H 2 O) 2 X 3 ] c A ruthenium complex present in the form; wherein X is a halogen anion, and the concentration of Ru is 0.02M-0.1M; b) Salts of halogen anions at a concentration of 0.001M to 1M; c) A sulfur-containing compound present as a blackening agent; and d) a sacrificial oxidant;
wherein the pH value of the black ruthenium plating solution is less than or equal to 3.
bpy is a pyridine group and en is an ethylenediamine group.
a. b and c are positive integers not equal to 0.
The pH of the black ruthenium plating solution is preferably 0.5 to 2.5.
a) The concentration of the component (Ru) may be 0.05M or 0.07M.
b) The concentration of the halogen anion may be 0.005M, 0.01M, 0.05M, 0.1M, or 0.5M.
The solvent of the black ruthenium plating solution can be double distilled water, deionized water or ultrapure water.
In some embodiments, the cation of the salt of the halide anion is an ammonium ion.
When the cation is an ammonium ion (such as ammonium chloride, ammonium bromide, ammonium iodide, etc.), these components can be used as a brightener at the same time, so that no additional brightener can be added.
In some embodiments, the sacrificial oxidizing agent is one or more of ascorbic acid, hydroxylamine sulfate, sodium hexametaphosphate, or trisodium phosphate.
The amount of the sacrificial oxidizing agent to be added may be 0.01M to 5M, for example, 0.05M, 0.1M, 0.5M, 1M or 3M.
In some embodiments, the sulfur-containing compound comprises one or more of thiomalic acid, thioglycolic acid, β -mercaptopropionic acid, thiourea, ammonium thiocyanate, thiourea derivatives.
The amount of the blackening agent to be added may be 0.01M to 10M, for example, 0.05M, 0.1M, 0.5M, 1M, 3M, 5M, or 7M.
In some embodiments, the black ruthenium plating solution comprises a brightener. The brightener can be used as an auxiliary color former to improve the smoothness and flexibility of the black ruthenium coating.
The amount of the brightener may be 0.01M to 10M, for example, 0.05M, 0.1M, 0.5M, 1M, 3M, 5M, or 7M.
Further, the brightening agent is selected from one or more of methyl amine iodide, sodium xylene sulfonate, ammonium chloride, magnesium sulfate and ammonium bromide.
In some embodiments, the concentration of the black ruthenium plating solution is 2 ° Be to 25 ° Be, for example, 5 ° Be, 10 ° Be, 15 ° Be, and 20 ° Be.
In some embodiments, the halide anion is Cl - 、Br - 、I - At least one of (1).
In some embodiments, the Black ruthenium plating solution has a color number of Black 6C.
According to still another aspect of the present invention, there is also provided a method for preparing the black ruthenium plating solution as described above, comprising:
i) Heating a ruthenium compound, and a complexing agent, an auxiliary complexing agent and a sulfamic acid substance which are excessive relative to the ruthenium compound under an acidic condition to form a ruthenium complex;
wherein the complexing agent comprises ethylenediamine and/or salts thereof, and pyridine derivative salts; the auxiliary coordination agent is one or more of ammonium citrate, nitrite and sulfite;
ii) maintaining acidic and heating conditions, and adding to i) a salt of a halide anion, a blackening agent and a sacrificial oxidizing agent.
In some embodiments, the ruthenium compound comprises one or more of ruthenium trichloride, ruthenium sulfate, ruthenium nitrosylsulfate, and ruthenium sulfamate.
In some embodiments, the heating is at a temperature of 60 ℃ to 80 ℃, e.g., 65 ℃,70 ℃, 75 ℃.
According to still another aspect of the present invention, there is also provided a method for preparing antique precious metals, comprising the step of performing a seasoning treatment using the black ruthenium plating solution as described above.
Methods for the preparation of retro noble metals may be known to those skilled in the art, for example as previously disclosed in CN110965088A, CN113774435a by the applicant.
In some embodiments, the method of making comprises:
1) Holding the noble metal by a mold, and electroplating by using the black ruthenium plating solution;
2) Removing black from the black-plated noble metal holding die, and polishing;
3) And (4) carrying out acid treatment on the polished noble metal, and then carrying out mold clamping and grinding again.
In some embodiments, the plating process conditions are: the temperature of the electroplating solution is 30-70 ℃, and the cathode current density is 0.3A/dm 2 ～10.0A/dm 2 The electroplating time is 3-30 minutes.
The workpiece is preferably swung at 10-60 revolutions per minute during the electroplating process.
In some embodiments, the acid used for the acid treatment is one or more of sulfuric acid (preferably 98% sulfuric acid), hydrochloric acid and nitric acid, and the acid treatment temperature is 80-130 ℃; the time is 5 to 20s.
In some embodiments, the mold-holding black removing is to leave a black line on the concave line and the seam, and rub off black parts with No. 800-1200 abrasive paper in the rest places. Further preferably, the polishing treatment is performed on the convex part of the product in a polishing machine by using a polishing agent and a magnetic polishing material, and the polishing time is preferably 5min to 60min, such as 10min, 20min, 30min, 40min and 50min. The polishing machine can be one or more of a magnetic needle polishing machine, a ball polishing machine or a magnetorheological polishing machine.
In some embodiments, the polishing comprises magnetic polishing, preferably magnetorheological polishing, more preferably 3-axis magnetorheological polishing.
In some embodiments, the magnetorheological finishing conditions comprise: the magnetic field intensity is 60 to 85 percent, the rotating speed of the main shaft is 50 to 120r/min, and the polishing time is 15 to 30min.
In some embodiments, the polishing agent is one or more of ethyl acetate, butyl acetate, ethylene glycol, alumina, silica.
In some embodiments, the magnetic polishing material is one or more of a magnetic needle, a magnetic bead, magnetic sand, atomized iron powder, carbonyl iron powder.
In some embodiments, the method further comprises the step of recovering and purifying the precious metal waste.
The precious metal recovery and purification usually comprises the steps of target material adsorption (the target material usually comprises one or more of cellulose ethylene dihydrazide, sulfhydryl polyethylene glycol silicon and methyl mercaptan polystyrene), desorption, precipitation reduction and precious metal smelting, and then the precious metal is recycled in a production line.
In some embodiments, the noble metal is gold and/or platinum.
The gold can be 24K gold, 18K gold, etc.
The invention also relates to the antique noble metal prepared by the method.
According to a further aspect of the invention, it also relates to an ornament containing a retro noble metal as described above.
In the present invention, the term "ornament" refers to any decorative article, typically jewelry, home furnishings, and the like. Preferably jewelry, such as ornaments worn on the head, such as hairpin, earrings and the like; the ornament worn on the broad-toe body, such as a necklace, a brooch, a bracelet, a ring, a foot ring and the like; but also can be valuable pens, watches, cutters, nameplates and the like.
The article may also comprise other decorative materials, typically platinum, gold, silver, precious stones, for example.
The ornament can contain one or more retro precious metals, such as retro gold and retro platinum.
Gemstones as defined herein are broad and include natural mineral crystals such as diamonds, crystals, emeralds, rubies, sapphires, and chrysophytes (alexandrite, cat's eye) boulders, and the like; also a few are natural monomineral aggregates, such as ono, opal. There are also a few organic materials, such as amber, pearl, coral, coal essence, which are also included in the broad term gem.
Embodiments of the present invention will be described in detail with reference to examples. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention. The experimental procedures for the conditions not specified in the following examples, preferably with reference to the guidelines given in the present invention, may also be performed according to the experimental manual or the conventional conditions in the art, and may also be performed according to other experimental procedures known in the art, or according to the conditions suggested by the manufacturer.
In the following specific examples, the measurement parameters relating to the components of the raw materials, if not specified otherwise, may be subject to slight deviations within the accuracy of the weighing. Temperature and time parameters are involved to allow for acceptable deviation due to instrument test accuracy or operational accuracy.
EXAMPLE 1 preparation of Black ruthenium plating solution
1. Ruthenium trichloride or ruthenium sulfate is selected as a ruthenium source of the plating solution, 0.05mol of ruthenium compound (ruthenium mass fraction is 30% -60%) is dissolved in 1L of ultrapure water to obtain a solution A, and the concentration of ruthenium is detected to be about 0.02mol/L.
2. Adding 1mol of ethylenediamine, 0.03mol of 2,2' -bipyridine, 0.01mol of arylamino sulfonic acid and 0.015mol of sodium nitrite into the solution A, refluxing for 5h, and performing post-treatment such as precipitation, filtration and curing reaction to obtain a series of compounds containing a structural formula [ Ru (bpy) 2 ] a [Ru(en) 3 ] b [Ru 2 N(H 2 O) 2 Cl 3 ] c The ruthenium mixed complex B has special stability due to the formation of a cyclic chelate structure.
3. When preparing the plating solution, the complex B was diluted with ultrapure water to a concentration of 0.05mol/L in terms of Ru. Sulfuric acid, sulfate or sulfamate is added into the plating solution, the concentration is about 1mol/L, and the solution is stirred for 1h at 70 ℃, so that the stability of the ruthenium plating solution is improved.
4. And a halogen anion compound is added to improve the deposition speed of ruthenium, and a ruthenium coating without cracks can be generated at a proper concentration, so that the brightness and the mechanical strength of the ruthenium coating are improved. A suitable halide anion is Cl - And Br - One or more kinds may be used. When the plating solution is prepared, ammonium chloride and ammonium bromide are added, the concentration of the ammonium chloride and the ammonium bromide is about 0.5mol/L, and the solution is stirred for 2 hours at the temperature of 70 ℃ to obtain the plating solution C.
5. Adding beta-mercaptopropionic acid, thiourea derivatives and other mercapto compounds into the plating solution C at a concentration of 0.01-10 mol/L, wherein the mercapto compounds and the complex B can play a role in blackening. And 3mol/L of hydroxylamine sulfate and sodium hexametaphosphate are added to improve the oxidation resistance of the plating solution C and stabilize the blackness of the ruthenium plating film. Adding the additive, stirring for 3h at 70 ℃, and adjusting the pH to be less than 3 to obtain the final product plating solution D.
6. During electroplating, the plating solution D is kept at the temperature of 60-70 ℃ with strong mechanical stirring. Suitable current densities are from 5 to 10ASD. Too high or too low can affect the blackness and the bonding force of the coating film. In addition, the concentration of the solution needs to be paid extra attention when the plating solution works, 2-25 DEG Be is more appropriate generally, and the excessively high concentration of the solution can cause poor coating quality and increase the consumption of medicines.
EXAMPLE 2 preparation of Black ruthenium plating solution
1. Ruthenium trichloride or ruthenium sulfate is selected as a ruthenium source of the plating solution, 0.05mol of ruthenium compound (ruthenium mass fraction is 30% -60%) is dissolved in 1L of ultrapure water to obtain a solution A, and the concentration of ruthenium is detected to be about 0.05mol/L.
2. Adding 0.05mol of ethylenediamine, 0.06mol of 2,2' -bipyridine, 0.005mol of arylamino sulfonic acid and 0.03mol of sodium nitrite into the solution A, refluxing for 4h, and performing post-treatment such as precipitation, filtration and curing reaction to obtain a series of compounds containing a structural formula [ Ru (bpy) 2 ] a [Ru(en) 3 ] b [Ru 2 N(H 2 O) 2 Cl 3 ] c The ruthenium mixed complex B has special stability due to the formation of a cyclic chelate structure.
3. When preparing the plating solution, the complex B was diluted with ultrapure water to a concentration of 0.02mol/L as Ru. Sulfuric acid, sulfate or sulfamate is added into the plating solution, the concentration is about 0.05mol/L, and the solution is stirred for 1 hour at 70 ℃, so that the stability of the ruthenium plating solution is improved.
4. And a halogen anion compound is added to improve the deposition speed of ruthenium, and a ruthenium coating without cracks can be generated at a proper concentration, so that the brightness and the mechanical strength of the ruthenium coating are improved. A suitable halide anion is Cl - . When the plating solution is prepared, ammonium chloride is added, the concentration is about 0.01mol/L, and the solution is stirred for 2 hours at the temperature of 70 ℃ to obtain plating solution C.
5. And (3) adding a mercapto compound such as 0.1mol/L beta-mercaptopropionic acid and thiourea derivatives into the plating solution C, wherein the mercapto compound and the complex B can play a role in blackening. And 5mol/L of hydroxylamine sulfate and sodium hexametaphosphate are added to improve the oxidation resistance of the plating solution C and stabilize the blackness of the ruthenium plating film. Adding the additive, stirring for 3h at 70 ℃, and adjusting the pH to be less than 3 to obtain the final product plating solution D.
6. During electroplating, the plating solution D is kept at the temperature of 60-70 ℃ with strong mechanical stirring. Suitable current densities are from 5 to 10ASD. Too high or too low will affect the blackness and adhesion of the coating. In addition, the concentration of the solution needs to be paid extra attention when the plating solution works, 2-25 DEG Be is more appropriate generally, and the excessively high concentration of the solution can cause poor coating quality and increase the consumption of medicines.
EXAMPLE 3 preparation of Black ruthenium plating solution
1. Ruthenium trichloride or ruthenium sulfate is selected as a ruthenium source of the plating solution, 0.05mol of ruthenium compound (ruthenium mass fraction is 30% -60%) is dissolved in 1L of ultrapure water to obtain a solution A, and the concentration of ruthenium is detected to be about 0.1mol/L.
2. Adding 2mol of ethylenediamine, 0.02mol of 2,2' -bipyridine, 0.02mol of aryl sulfamic acid and 0.01mol of sodium nitrite into the solution A, refluxing for 7 hours, and performing post-treatment such as precipitation, filtration, curing reaction and the like to obtain a series of compounds containing a structural formula [ Ru (bpy) 2 ] a [Ru(en) 3 ] b [Ru 2 N(H 2 O) 2 Cl 3 ] c The ruthenium mixed complex B has special stability due to the formation of a cyclic chelate structure.
3. When preparing the plating solution, the complex B was diluted with ultrapure water to a concentration of 0.1mol/L in terms of Ru. Sulfuric acid, sulfate or sulfamate is added into the plating solution, the concentration is about 2mol/L, and the solution is stirred for 1h at 70 ℃, so that the stability of the ruthenium plating solution is improved.
4. And a halogen anion compound is added to improve the deposition speed of ruthenium, and a ruthenium coating without cracks can be generated at a proper concentration, so that the brightness and the mechanical strength of the ruthenium coating are improved. A suitable halide anion is Br - . Ammonium bromide is added when preparing the plating solution, and the concentrationAbout 1mol/L, and stirring at the temperature of 70 ℃ for 2 hours to obtain plating solution C.
5. And (3) adding 10mol/L beta-mercaptopropionic acid, thiourea derivatives and other compounds containing sulfydryl into the plating solution C, wherein the sulfydryl compound and the complex B can play a role in blackening. And adding 0.01mol/L hydroxylamine sulfate and sodium hexametaphosphate to improve the oxidation resistance of the plating solution C and stabilize the blackness of the ruthenium plating film. Adding the additive, stirring for 3h at 70 ℃, and adjusting the pH to be less than 3 to obtain the final product plating solution D.
6. During electroplating, the plating solution D is kept at the temperature of 60-70 ℃ with strong mechanical stirring. Suitable current densities are from 5 to 10ASD. Too high or too low can affect the blackness and the bonding force of the coating film. In addition, the concentration of the solution needs to be paid extra attention when the plating solution works, 2-25 DEG Be is more appropriate generally, and the excessively high concentration of the solution can cause poor coating quality and increase the consumption of medicines.
Example 4 Black ruthenium plating solution and its application in antique jewelry
The general steps for preparing the antique jewelry can refer to Chinese patent applications CN110965088A and CN113774435A, the general description of which is as follows:
step one, carrying out die holding on gold and west platinum blanks;
step two, preparing ultra-deep black ruthenium plating solution (see examples 1 to 3);
step three, carrying out ultra-deep black ruthenium electroplating on gold and western platinum after die holding;
performing surface treatment such as mold-holding black removal, magnetic polishing and the like on the black-plated gold and the platinum;
step five, performing acid treatment, mold holding, embedding assembly and polishing on the gold and the platinum after surface treatment to obtain a product;
and step six, recovering the waste precious metals generated in the process, and recycling the waste precious metals for production after purification treatment.
The detail improvement is as follows:
the conditions for ultra-deep black ruthenium plating can generally include: the temperature of the electroplating solution is 30-70 ℃, the pH value of the electroplating solution is 0.5-2.5, the cathode current density is 0.3-10.0A/dm < 2 >, the electroplating time is 3-30 minutes, and the workpiece swings at 10-60 revolutions per minute.
The black part is removed by using 800-1200 # abrasive paper in the step of die holding and polishing, and the convex part of the product is polished by using a polishing agent and a magnetic polishing material in a polishing machine for 5-60 min; the polishing machine is one or more of a magnetic needle polishing machine, a ball polishing machine or a magneto-rheological polishing machine.
An exemplary picture of the product produced is shown in figure 1.
Examples of the experiments
Tests were conducted using the black ruthenium plating solution of example 1, when it relates to jewelry preparation, prepared using the method of example 4. The comparative example was produced by germany (graceful kol) using an externally purchased black ruthenium plating solution, and the publication date of the corresponding patent to the product was 09/10/2014, and the granted publication number was CN104040033B. Except that the black ruthenium plating solution is different and the plating parameters are different (the plating parameters of the comparative example adopt the recommended parameters of the commercial products), the other parameters are consistent.
1. Blackness detection
And (3) performing blackness detection on the black ruthenium coating by using a color spectrum spectrophotometer DS-700D. The color measurement principle is as follows: the reflectivity is measured by projecting the object with ultraviolet and LED light sources to obtain three parameters of L (black-white), a (green-red) and b (blue-yellow). The smaller the L (black-white) number, the darker the L (black-white) number, the smaller the a (green-red) number, the greener the L (green-red) number, and the smaller the b (blue-yellow) number, the bluer the L (black-white) number.
Experimental procedure
The equipment is turned on first, the instrument is placed on a calibration base for white calibration, and then the instrument is aligned with air for black calibration. And after the calibration is finished, the equipment is switched to a proper caliber, and a corresponding mode is selected according to the caliber. And placing the electroplated black ruthenium sample at the bottom of the color measuring instrument, and starting clicking to measure.
The ornaments prepared from different groups are shown in figure 2. The results of the measurements are shown in Table 1.
TABLE 1
In table 1, the L value of the self-contained black ruthenium liquid medicine is 35.34 which is smaller than the L value of the purchased black ruthenium liquid medicine, i.e., the self-contained black ruthenium liquid medicine is coated more black, and the self-contained black ruthenium liquid medicine can be obviously coated with a darker and darker color by the visual method of fig. 2.
2. Binding force detection
First cladding layer adhesive force detection
Experimental procedure
The experimental piece is used for electroplating the black ruthenium coating, and the process parameters are as follows: the current density is 5ASD, the temperature is 65 ℃, and the electroplating time is 5min. After electroplating, the test piece is fixed on a clamp, 3M gummed paper is pasted on the surface of an electroplated layer, an eraser is used for rubbing back and forth on the surface of the electroplated layer to enable the electroplated layer to be completely attached, and then the electroplated layer is quickly torn in a 45-degree direction.
The results of the experiment are shown in FIG. 3. As can be seen from FIG. 3, the self-determined black ruthenium solution coating film has no phenomena of fading, peeling and bubbling, and the purchased black ruthenium solution coating film has obvious phenomena of coating film peeling and fading through visual observation.
Bend experiment
Experimental procedure
Electroplating the experimental piece with a black ruthenium coating, wherein the electroplating process comprises the following steps: the current density is 5ASD, the temperature is 65 ℃, and the electroplating time is 5min. After electroplating, the test piece was fixed on a jig and bent at 90 ℃, and then the bent surface was observed with a 10-fold microscope.
As can be seen from fig. 4, the independent black ruthenium solution coating film has no phenomena of discoloration, peeling and bubbling, and the purchased black ruthenium solution coating film has obvious phenomena of coating film peeling and discoloration on the curved surface, which are observed by a visual method.
In conclusion, the blackness and the binding force of the black ruthenium plating solution provided by the invention are obviously superior to those of the products sold in the market.
The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. Therefore, the protection scope of the present patent should be subject to the appended claims, and the description and drawings can be used to explain the contents of the claims.
Claims (23)
1. A black ruthenium plating solution comprising: a) With [ Ru (bpy) 2 ] a [Ru(en) 3 ] b [Ru 2 N(H 2 O) 2 X 3 ] c A ruthenium complex present in the form; wherein X is a halogen anion, and the concentration of Ru is 0.02M-0.1M; b) Salts of halogen anions at a concentration of 0.001M to 1M; c) A sulfur-containing compound present as a blackening agent; and d) a sacrificial oxidant;
wherein the pH value of the black ruthenium plating solution is less than or equal to 3.
2. The black ruthenium plating solution according to claim 1, wherein the cation of the salt of the halide anion is an ammonium ion.
3. The black ruthenium plating bath according to claim 1 wherein the sacrificial oxidant is one or more of ascorbic acid, hydroxylamine sulfate, sodium hexametaphosphate, or trisodium phosphate.
4. The black ruthenium plating bath according to claim 1, wherein the sulfur containing compounds comprise one or more of thiomalic acid, thioglycolic acid, β -mercaptopropionic acid, thiourea, ammonium thiocyanate, thiourea derivatives.
5. The black ruthenium plating bath according to any one of claims 1 to 4 comprising a brightener selected from one or more of methyl amine iodide, sodium xylene sulfonate, ammonium chloride, magnesium sulfate, and ammonium bromide.
6. The black ruthenium plating solution according to any one of claims 1 to 4, having a concentration of 2 ° Be to 25 ° Be.
7. The black ruthenium plating solution according to any one of claims 1 to 4, wherein the halide anion is Cl - 、Br - 、I - At least one of (1).
8. The Black ruthenium plating solution according to any one of claims 1 to 4, having a color number of Black 6C.
9. The method for preparing a black ruthenium plating solution according to any one of claims 1 to 8 comprising:
i) Heating a ruthenium compound, and a complexing agent, an auxiliary complexing agent and a sulfamic acid substance which are excessive relative to the ruthenium compound under an acidic condition to form a ruthenium complex;
wherein the complexing agent comprises ethylenediamine and/or salts thereof, and pyridine derivative salts; the auxiliary coordination agent is one or more of ammonium citrate, nitrite and sulfite;
ii) maintaining acidic and heated conditions, and adding to i) a salt of a halide anion, a blackening agent and a sacrificial oxidizing agent.
10. The production method according to claim 9, wherein the ruthenium compound includes one or more of ruthenium trichloride, ruthenium sulfate, ruthenium nitrososulfate, and ruthenium sulfamate.
11. The method according to claim 9, wherein the heating temperature is 60 ℃ to 80 ℃.
12. A method for producing antique noble metals, comprising the step of conducting a weathering treatment with the black ruthenium plating solution according to any one of claims 1 to 8.
13. The method of manufacturing of claim 12, comprising:
1) Holding the noble metal by a mold, and electroplating by using the black ruthenium plating solution;
2) Removing black from the black-plated noble metal holding die, and polishing;
3) And (4) carrying out acid treatment on the polished noble metal, and then carrying out mold clamping and grinding again.
14. The production method according to claim 13, wherein the plating treatment is performed under conditions of:the temperature of the electroplating solution is 30-70 ℃, and the cathode current density is 0.3A/dm 2 ～10.0A/dm 2 The electroplating time is 3-30 minutes.
15. The preparation method according to claim 13, wherein the acid used in the acid treatment is one or more of sulfuric acid, hydrochloric acid and nitric acid, and the acid treatment temperature is 80-130 ℃; the time is 5 to 20s.
16. The method for preparing the Chinese herbal medicine composition for treating the chronic pelvic inflammatory disease of the patient as claimed in claim 13, wherein the pattern blackening is carried out by leaving a black line on the concave line and the seam, and rubbing off the black part with No. 800-1200 sandpaper on the rest part.
17. The production method according to claim 13, wherein the polishing is magnetic polishing.
18. The method of claim 17, wherein the polishing is magnetorheological polishing.
19. The method of claim 18, wherein the magnetorheological finishing conditions comprise: the magnetic field intensity is 60 to 85 percent, the rotating speed of the main shaft is 50 to 120r/min, and the polishing time is 15 to 30min.
20. The method of claim 13, further comprising the step of recovering and purifying precious metal scrap.
21. The production method according to any one of claims 12 to 20, wherein the noble metal is gold and/or platinum.
22. A retro noble metal produced by the method of any one of claims 12 to 21.
23. An ornamental article comprising the antique noble metal of claim 22.
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| CN202211540845.0A CN115787010A (en) | 2022-12-02 | 2022-12-02 | Black ruthenium plating solution and application thereof in preparation of pseudo-classic gold or platinum and other ornaments |
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| CN202211540845.0A CN115787010A (en) | 2022-12-02 | 2022-12-02 | Black ruthenium plating solution and application thereof in preparation of pseudo-classic gold or platinum and other ornaments |
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