CN107419310B - Trivalent chromium plating layer and preparation method thereof - Google Patents
Trivalent chromium plating layer and preparation method thereof Download PDFInfo
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- CN107419310B CN107419310B CN201710899809.6A CN201710899809A CN107419310B CN 107419310 B CN107419310 B CN 107419310B CN 201710899809 A CN201710899809 A CN 201710899809A CN 107419310 B CN107419310 B CN 107419310B
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- trivalent chromium
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- 239000011651 chromium Substances 0.000 title claims abstract description 121
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 title claims abstract description 116
- 229910052804 chromium Inorganic materials 0.000 title claims abstract description 116
- 238000007747 plating Methods 0.000 title claims abstract description 89
- 238000002360 preparation method Methods 0.000 title claims abstract description 27
- 238000009713 electroplating Methods 0.000 claims abstract description 84
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 59
- 239000000463 material Substances 0.000 claims abstract description 57
- 150000003839 salts Chemical class 0.000 claims abstract description 29
- 239000008139 complexing agent Substances 0.000 claims abstract description 28
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 26
- 150000001844 chromium Chemical class 0.000 claims abstract description 23
- 150000001868 cobalt Chemical class 0.000 claims abstract description 23
- 239000000758 substrate Substances 0.000 claims abstract description 22
- 239000006172 buffering agent Substances 0.000 claims abstract description 20
- 238000005282 brightening Methods 0.000 claims abstract description 17
- 239000008367 deionised water Substances 0.000 claims abstract description 15
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 15
- DHMQDGOQFOQNFH-UHFFFAOYSA-N Glycine Chemical compound NCC(O)=O DHMQDGOQFOQNFH-UHFFFAOYSA-N 0.000 claims description 50
- 239000000203 mixture Substances 0.000 claims description 48
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 44
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- -1 2-amino-3- (3-hydroxy-thiopropionyl) -benzenesulfonic acid Chemical group 0.000 claims description 31
- 238000000034 method Methods 0.000 claims description 25
- 239000004471 Glycine Substances 0.000 claims description 23
- XUJNEKJLAYXESH-UHFFFAOYSA-N cysteine Natural products SCC(N)C(O)=O XUJNEKJLAYXESH-UHFFFAOYSA-N 0.000 claims description 23
- 235000018417 cysteine Nutrition 0.000 claims description 23
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- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 19
- BJEPYKJPYRNKOW-UHFFFAOYSA-N alpha-hydroxysuccinic acid Natural products OC(=O)C(O)CC(O)=O BJEPYKJPYRNKOW-UHFFFAOYSA-N 0.000 claims description 19
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 claims description 19
- 229910052921 ammonium sulfate Inorganic materials 0.000 claims description 19
- 235000011130 ammonium sulphate Nutrition 0.000 claims description 19
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims description 19
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- 229910052938 sodium sulfate Inorganic materials 0.000 claims description 19
- 235000011152 sodium sulphate Nutrition 0.000 claims description 19
- 238000000576 coating method Methods 0.000 claims description 18
- 229910000403 monosodium phosphate Inorganic materials 0.000 claims description 18
- 235000019799 monosodium phosphate Nutrition 0.000 claims description 18
- AJPJDKMHJJGVTQ-UHFFFAOYSA-M sodium dihydrogen phosphate Chemical compound [Na+].OP(O)([O-])=O AJPJDKMHJJGVTQ-UHFFFAOYSA-M 0.000 claims description 18
- 239000011248 coating agent Substances 0.000 claims description 17
- GRWVQDDAKZFPFI-UHFFFAOYSA-H chromium(III) sulfate Chemical group [Cr+3].[Cr+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O GRWVQDDAKZFPFI-UHFFFAOYSA-H 0.000 claims description 8
- 239000001257 hydrogen Substances 0.000 claims description 8
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- 239000012811 non-conductive material Substances 0.000 claims description 8
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- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 6
- 239000000919 ceramic Substances 0.000 claims description 6
- 229910017052 cobalt Inorganic materials 0.000 claims description 6
- 239000010941 cobalt Substances 0.000 claims description 6
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 6
- 229940044175 cobalt sulfate Drugs 0.000 claims description 6
- 229910000361 cobalt sulfate Inorganic materials 0.000 claims description 6
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 claims description 6
- 239000002270 dispersing agent Substances 0.000 claims description 6
- 239000011521 glass Substances 0.000 claims description 6
- 239000003381 stabilizer Substances 0.000 claims description 6
- 229910052717 sulfur Inorganic materials 0.000 claims description 6
- 239000011593 sulfur Substances 0.000 claims description 6
- 239000012752 auxiliary agent Substances 0.000 claims description 5
- 229940011182 cobalt acetate Drugs 0.000 claims description 5
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 claims description 5
- 239000004020 conductor Substances 0.000 claims description 5
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 4
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- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 4
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims description 4
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- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 3
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- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims 1
- 239000000243 solution Substances 0.000 description 68
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- 125000000151 cysteine group Chemical group N[C@@H](CS)C(=O)* 0.000 description 1
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- 229910010272 inorganic material Inorganic materials 0.000 description 1
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 1
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- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
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- 239000011591 potassium Substances 0.000 description 1
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- OTYBMLCTZGSZBG-UHFFFAOYSA-L potassium sulfate Chemical compound [K+].[K+].[O-]S([O-])(=O)=O OTYBMLCTZGSZBG-UHFFFAOYSA-L 0.000 description 1
- 229910052939 potassium sulfate Inorganic materials 0.000 description 1
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- KOUKXHPPRFNWPP-UHFFFAOYSA-N pyrazine-2,5-dicarboxylic acid;hydrate Chemical compound O.OC(=O)C1=CN=C(C(O)=O)C=N1 KOUKXHPPRFNWPP-UHFFFAOYSA-N 0.000 description 1
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Classifications
-
- 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
Abstract
The invention relates to the field of trivalent chromium electroplating, in particular to a trivalent chromium plating layer and a preparation method thereof. Preparation method of trivalent chromium plating layerAt least comprising the following steps: immersing a base material into trivalent chromium electroplating solution, and electroplating by taking the base material as a cathode, wherein the electroplating temperature is 20-45 ℃, and the current density is 6A/dm2～25A/dm2Electroplating for 5-30 min; the trivalent chromium plating layer is plated on the base material; the surface of the substrate at least comprises a conductive layer; the trivalent chromium electroplating solution at least comprises the following components: trivalent water-soluble chromium salt: 15-20 parts by weight; cobalt salt: 12-16 parts by weight; conductive salt: 20-35 parts by weight; a complexing agent: 4-6 parts by weight; buffering agent: 7-10 parts by weight; a blackening agent: 0.5 to 1.6 parts by weight; brightening agent: 0.01 to 0.5 part by weight; deionized water: 100 parts by weight.
Description
Technical Field
The invention relates to the field of trivalent chromium electroplating, in particular to a trivalent chromium plating layer and a preparation method thereof.
Background
The black chromium plating belongs to a special plating in functional chromium coatings, and has wide application because of good physical and chemical properties, fascinating appearance and good wear resistance, corrosion resistance and temperature resistance. The main components of the black chromium coating are metal chromium and chromium oxide, the chromium oxide particles are dispersed in the metal chromium medium, and the black chromium coating has strong absorption effect on solar radiation due to the interband transition of the metal chromium and the resonance of the chromium oxide particles. Black chromium plating is often used to prevent diffuse reflection of light on components such as cameras, optical instruments, military weapons, and instrumentation systems; in order to achieve more efficient use of solar energy, people also often perform black chromium electroplating treatment on the surface of the solar absorber.
The traditional electroplating black chromium adopts electroplating solution which takes chromic anhydride as a main component and has high toxicity and high pollution, and is strictly limited by countries all over the world at present. The research on the use of a trivalent chromium system to replace a hexavalent chromium system to electroplate black chromium has important significance. At present, a great deal of work is done on the research of trivalent chromium electroplating solution at home and abroad, wherein the trivalent chromium electroplating solution is used for replacing hexavalent chromium electroplating solution and is gradually popularized and applied in the aspect of decorative chromium plating, but the research on trivalent chromium electroplating black chromium is less, the trivalent chromium electroplating black chromium is basically a chloride system, the problems of poor impurity resistance, serious corrosion of chlorine generated at an anode to a plating bath, difficult maintenance of the electroplating solution and the like exist, and the current black chromium plating layer also has the problems of darker surface, poor brightness, high porosity of the plating layer, poor corrosion resistance, poor binding force between the plating layer and a base material and the like.
Aiming at the technical problems, the research of the invention is mainly based on a sulfate system with better environmental protection and stability, and the invention provides a trivalent chromium plating layer and a preparation method thereof.
Disclosure of Invention
To is coming toIn order to solve the above technical problems, a first aspect of the present invention provides a method for preparing a trivalent chromium plating layer, which at least comprises the following steps: immersing a base material into trivalent chromium electroplating solution, and electroplating by taking the base material as a cathode, wherein the electroplating temperature is 20-45 ℃, and the current density is 6A/dm2～25A/dm2Electroplating for 5-30 min; the trivalent chromium plating layer is plated on the base material; the surface of the substrate at least comprises a conductive layer;
the trivalent chromium electroplating solution at least comprises the following components: trivalent water-soluble chromium salt: 15-20 parts by weight; cobalt salt: 12-16 parts by weight; conductive salt: 20-35 parts by weight; a complexing agent: 4-6 parts by weight; buffering agent: 7-10 parts by weight; a blackening agent: 0.5 to 1.6 parts by weight; brightening agent: 0.01 to 0.5 part by weight; deionized water: 100 parts by weight.
As a preferred technical scheme of the invention, the trivalent water-soluble chromium salt is chromium sulfate; the cobalt salt is selected from one or more of cobalt sulfate, cobalt nitrate and cobalt acetate; the conductive salt is a mixture of sodium sulfate and ammonium sulfate, and the mass ratio of the sodium sulfate to the ammonium sulfate is 1: 0.3 to 1.2.
As a preferred technical solution of the present invention, the complexing agent is a mixture of formic acid, glycine and malic acid, and the mass ratio of formic acid, glycine and malic acid is 1: 0.5-3: 0.2 to 2.
According to a preferable technical scheme of the invention, the buffering agent is a mixture of boric acid and sodium dihydrogen phosphate, and the mass ratio of the boric acid to the sodium dihydrogen phosphate is (2-6): 1.
as a preferable technical scheme of the invention, the blackening agent is selected from one or more of aspartic acid, methionine, cystine, cysteine, arginine, glycine and 2-aminobenzothiazole-7-formic acid.
According to a preferable technical scheme of the invention, the blackening agent is a mixture of cysteine and 2-aminobenzothiazole-7-formic acid, and the mass ratio of the cysteine to the 2-aminobenzothiazole-7-formic acid is 1: 0.1 to 0.5.
In a preferred embodiment of the present invention, the brightener is one or more selected from 2-amino-3- (3-hydroxy-thiopropionyl) -benzenesulfonic acid, thiourea, 3-mercapto-1-propane sulfonic acid sodium salt, 2-methylimidazole, and 2-mercaptobenzimidazole.
In a preferred embodiment of the present invention, the brightener is 2-amino-3- (3-hydroxy-thiopropionyl) -benzenesulfonic acid.
As a preferred technical solution of the present invention, the trivalent chromium electroplating solution further includes an auxiliary agent, and the auxiliary agent is one or more selected from a stabilizer, a dispersant, and a displacement agent.
In order to solve the technical problems, the second aspect of the invention provides a trivalent chromium plating layer prepared by the preparation method of the trivalent chromium plating layer; the composition at least comprises: chromium, cobalt, hydrogen, oxygen, sulfur, phosphorus; the substrate is made of a conductive material or a non-conductive material with a conductive layer on the surface; the conductive layer on the surface of the conductive base material and the conductive layer on the surface of the non-conductive base material are selected from one or more alloys of iron, stainless steel, copper, nickel, silver, gold and conductive ceramics; the base material of the non-conductive material is any one of plastic, ceramic and glass.
The above-described and other features, aspects, and advantages of the present application will become more apparent with reference to the following detailed description.
Has the advantages that:
(1) the preparation method of the trivalent chromium plating layer adopts a sulfate system with better environmental protection and stability and the trivalent chromium with far lower toxicity than hexavalent chromium for electroplating, has no pollution to the environment and is an electroplating method which accords with national clean production.
(2) The trivalent chromium plating layer consists of chromium, cobalt, hydrogen, oxygen, sulfur and phosphorus elements, is dark black in color and uniform in color, has good blackening degree, and is strong in binding force with a base material, compact, low in porosity and very good in corrosion resistance.
Detailed Description
The disclosure may be understood more readily by reference to the following detailed description of preferred embodiments of the invention and the examples included therein. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. In case of conflict, the present specification, including definitions, will control.
The term "prepared from …" as used herein is synonymous with "comprising". The terms "comprises," "comprising," "includes," "including," "has," "having," "contains," "containing," or any other variation thereof, as used herein, are intended to cover a non-exclusive inclusion. For example, a composition, process, method, article, or apparatus that comprises a list of elements is not necessarily limited to only those elements but may include other elements not expressly listed or inherent to such composition, process, method, article, or apparatus.
The conjunction "consisting of …" excludes any unspecified elements, steps or components. If used in a claim, the phrase is intended to claim as closed, meaning that it does not contain materials other than those described, except for the conventional impurities associated therewith. When the phrase "consisting of …" appears in a clause of the subject matter of the claims rather than immediately after the subject matter, it defines only the elements described in the clause; other elements are not excluded from the claims as a whole.
When an amount, concentration, or other value or parameter is expressed as a range, preferred range, or as a range of upper preferable values and lower preferable values, this is to be understood as specifically disclosing all ranges formed from any pair of any upper range limit or preferred value and any lower range limit or preferred value, regardless of whether ranges are separately disclosed. For example, when a range of "1 to 5" is disclosed, the described range should be interpreted to include the ranges "1 to 4", "1 to 3", "1 to 2 and 4 to 5", "1 to 3 and 5", and the like. When a range of values is described herein, unless otherwise stated, the range is intended to include the endpoints thereof and all integers and fractions within the range.
The singular forms "a", "an" and "the" include plural referents unless the context clearly dictates otherwise. "optional" or "any" means that the subsequently described event or events may or may not occur, and that the description includes instances where the event occurs and instances where it does not.
Approximating language, as used herein throughout the specification and claims, is intended to modify a quantity, such that the invention is not limited to the specific quantity, but includes portions that are literally received for modification without substantial change in the basic function to which the invention is related. Accordingly, the use of "about" to modify a numerical value means that the invention is not limited to the precise value. In some instances, the approximating language may correspond to the precision of an instrument for measuring the value. In the present description and claims, range limitations may be combined and/or interchanged, including all sub-ranges contained therein if not otherwise stated.
In addition, the indefinite articles "a" and "an" preceding an element or component of the invention are not intended to limit the number requirement (i.e., the number of occurrences) of the element or component. Thus, "a" or "an" should be read to include one or at least one, and the singular form of an element or component also includes the plural unless the stated number clearly indicates that the singular form is intended.
In order to solve the above technical problems, a first aspect of the present invention provides a method for preparing a trivalent chromium plating layer, comprising at least the following steps: immersing a base material into trivalent chromium electroplating solution, and electroplating by taking the base material as a cathode, wherein the electroplating temperature is 20-45 ℃, and the current density is 6A/dm2～25A/dm2Electroplating for 5-30 min; the trivalent chromium plating layer is plated on the base material; the surface of the substrate at least comprises a conductive layer;
the trivalent chromium electroplating solution at least comprises the following components: trivalent water-soluble chromium salt: 15-20 parts by weight; cobalt salt: 12-16 parts by weight; conductive salt: 20-35 parts by weight; a complexing agent: 4-6 parts by weight; buffering agent: 7-10 parts by weight; a blackening agent: 0.5 to 1.6 parts by weight; brightening agent: 0.01 to 0.5 part by weight; deionized water: 100 parts by weight.
As a preferable technical scheme of the invention, the preparation method of the trivalent chromium plating layer at least comprises the following stepsThe method comprises the following steps: immersing a base material into trivalent chromium electroplating solution, and electroplating by taking the base material as a cathode, wherein the electroplating temperature is 28-36 ℃, and the current density is 14A/dm2～20A/dm2Electroplating time is 10-20 min; the trivalent chromium plating layer is plated on the base material; the surface of the substrate at least comprises a conductive layer;
the trivalent chromium electroplating solution at least comprises the following components: trivalent water-soluble chromium salt: 18 parts by weight; cobalt salt: 13 parts by weight; conductive salt: 27 parts by weight; a complexing agent: 4.8 parts by weight; buffering agent: 8 parts by weight; a blackening agent: 1.2 parts by weight; brightening agent: 0.3 part by weight; deionized water: 100 parts by weight.
As a preferred technical scheme of the invention, the trivalent water-soluble chromium salt is chromium sulfate; the cobalt salt is selected from one or more of cobalt sulfate, cobalt nitrate and cobalt acetate.
As a preferable technical scheme of the invention, the cobalt salt is cobalt acetate.
As a preferable technical scheme, the mass ratio of the trivalent water-soluble chromium salt to the cobalt salt is 1.2-1.5: 1.
conductive salt
Conductivity is one of the important parameters for evaluating the performance of a plating solution. The electroplating solution has good conductivity, namely high conductivity, can reduce the voltage of the electroplating bath, save electric energy and improve the dispersing capacity of the electroplating solution. The conductivity of the trivalent chromium salt electroplating solution is low, and conductive salt is required to be added. The conductive salt has the effects of improving the conductivity of the plating solution, reducing the bath voltage and improving the dispersing ability of the plating solution. The conductive salt is chloride or sulfate of potassium, sodium and ammonium.
As a preferred technical solution of the present invention, the conductive salt is selected from one or more of potassium sulfate, sodium sulfate and ammonium sulfate.
As a preferable technical solution of the present invention, the conductive salt is a mixture of sodium sulfate and ammonium sulfate, and the mass ratio of the sodium sulfate to the ammonium sulfate is 1: 0.3 to 1.2.
As a preferable technical solution of the present invention, the conductive salt is a mixture of sodium sulfate and ammonium sulfate, and the mass ratio of the sodium sulfate to the ammonium sulfate is 1: 0.8.
Cr3+has the ability to form a complex compound in a simple aqueous solution without other complexing agents, Cr3+Usually in a stable d2sp3In the form of complex ion, wherein [ Cr (H)2O)6]3+The complex is octahedral structure, belongs to an inner rail type complex, has larger kinetic inertia, and electrons are difficult to obtain on a cathode to obtain an acceptable chromium coating, so that the cathode for chromium electroplating can greatly separate out hydrogen, and the pH value near the surface of the cathode is increased. When the pH is higher>At 4, [ Cr (H)2O)6]3+Hydroxyl bridging can occur to generate hydroxyl bridged mono-or poly-polymeric compounds, and the poly-complexes are stable, so that chromium is difficult to separate from a polymeric form and reduce at a cathode, and the electrodeposited chromium is difficult to continue; meanwhile, the impurities are mixed in the plating layer, so that the plating layer is loose in crystallization and even falls off and cannot be thickened. Therefore, to achieve electrodeposition of trivalent chromium, a complexing agent must be added to exchange for water molecules to make [ Cr (H)2O)6]3+The conversion to the electrochemically active trivalent chromium complex facilitates electrodeposition of trivalent chromium.
Complexing agent
In the trivalent chromium electroplating solution, a coordination agent is coordinated with chromium ions to form relatively stable coordination ions, so that the trivalent chromium ions are easier to discharge, and the deposition of metallic chromium is promoted. Organic acid is selected as a complexing agent in trivalent chromium electroplating, and the organic acid and Cr are mixed3+The coordination of (A) is relatively stable, and it is convenient for decomplexing and wastewater treatment, and in order to improve the plating effect, binary or multicomponent complexing agents are usually used.
In a preferred embodiment of the present invention, the complexing agent is an organic acid.
In a preferred embodiment of the present invention, the complexing agent is one or more selected from monocarboxylic acids, dicarboxylic acids, hydroxycarboxylic acids, and aminocarboxylic acids.
As the monocarboxylic acid, formic acid, acetic acid, propionic acid, butyric acid and the like can be listed.
As the dicarboxylic acid, oxalic acid, malonic acid, succinic acid, glutaric acid and the like can be exemplified.
As the hydroxycarboxylic acid, glycolic acid, lactic acid, malic acid, tartaric acid, citric acid, gluconic acid, etc. may be mentioned.
As the aminocarboxylic acid, glycine, alanine, aspartic acid, iminodiacetic acid, glutamic acid, nitrilotriacetic acid, ethylenediaminetetraacetic acid, etc. may be mentioned.
In a preferred embodiment of the present invention, the complexing agent is one or more selected from formic acid, acetic acid, propionic acid, butyric acid, oxalic acid, malonic acid, succinic acid, glutaric acid, glycolic acid, lactic acid, malic acid, tartaric acid, citric acid, gluconic acid, glycine, alanine, aspartic acid, iminodiacetic acid, glutamic acid, nitrilotriacetic acid, and ethylenediaminetetraacetic acid.
As a preferred technical solution of the present invention, the complexing agent is a mixture of formic acid, glycine and malic acid, and the mass ratio of formic acid, glycine and malic acid is 1: 0.5-3: 0.2 to 2.
As a preferred technical solution of the present invention, the complexing agent is a mixture of formic acid, glycine and malic acid, and the mass ratio of formic acid, glycine and malic acid is 1: 1.2: 0.7.
buffering agent
The buffer is added to adjust the pH value of the electroplating solution, so that the pH value of the solution is stabilized in a certain range in the electroplating process, and the formation of a chromium plating layer is facilitated.
In a preferred embodiment of the present invention, the buffer is selected from one or more of boric acid, acetate, citrate, phosphate, ammonium salt, and carbonate.
According to a preferable technical scheme of the invention, the buffering agent is a mixture of boric acid and sodium dihydrogen phosphate, and the mass ratio of the boric acid to the sodium dihydrogen phosphate is (2-6): 1.
as a preferred technical solution of the present invention, the buffer is a mixture of boric acid and sodium dihydrogen phosphate, and the mass ratio of boric acid to sodium dihydrogen phosphate is 4.5: 1.
blackening agent
The blackening agent is mainly an organic or inorganic compound containing nitrogen and sulfur, one class of the blackening agent is a sulfur-containing compound, and the compound comprises thiosemicarbazide, thiourea, thioacetic acid, thiocyanide and the like, and the compound has strong cathode adsorbability and can inhibit the reduction of metal ions at a cathode; particularly, in a low current density area, the hydrogen evolution of the area is obviously increased, the generated hydrogen permeates into a plating layer, the phenomena of foaming, scutching, poor binding force and the like of the plating layer are easily caused, other substances are needed for balancing, but the stability is better, and the color of the obtained plating layer is generally yellow and black; the other class of substances is amino acid compounds, such as aspartic acid, cysteine, arginine, glycine and the like, which have good effects, and the obtained coating is generally bluish black in color and has no defects of the former compounds, but has poor compatibility with a plurality of components and is easy to oxidize and decompose.
In a preferred embodiment of the present invention, the blackening agent is an amino acid compound.
As a preferable technical scheme of the invention, the blackening agent is selected from one or more of aspartic acid, methionine, cystine, cysteine, arginine, glycine and 2-aminobenzothiazole-7-formic acid.
According to a preferable technical scheme of the invention, the blackening agent is a mixture of cysteine and 2-aminobenzothiazole-7-formic acid, and the mass ratio of the cysteine to the 2-aminobenzothiazole-7-formic acid is 1: 0.1 to 0.5.
According to a preferable technical scheme of the invention, the blackening agent is a mixture of cysteine and 2-aminobenzothiazole-7-formic acid, and the mass ratio of the cysteine to the 2-aminobenzothiazole-7-formic acid is 1: 0.2.
CAS of the 2-aminobenzothiazole-7-carboxylic acid: 71224-95-8, and a method for preparing the same, comprising at least the steps of:
a. adding 11.3g of 3-aminobenzoic acid and 75mL of chlorobenzene into a 250mL three-necked bottle, stirring, dropwise adding 2.1mL of 98 wt% concentrated sulfuric acid at-5-0 ℃, and continuing to react for 25min after dropwise adding within 30 min. Adding 6.8g of sodium thiocyanate, stirring for reaction for 5min, adding 0.22g of benzyltriethylammonium chloride, and reacting at constant temperature of 100 ℃ for 10 h. And (4) carrying out suction filtration, washing and drying to obtain the N- (3-carboxyl phenyl) thiourea.
b. 8.4g N- (3-carboxyphenyl) thiourea was added to a 250mL three-necked flask and 2.2mL Br was added dropwise2The mixture was added dropwise to 30mL of chlorobenzene in 1 hour, and the reaction was carried out at a constant temperature of 70 ℃ for 4 hours. Cooling, adding 25mL of diethyl ether, filtering, and drying to obtain a solid substance. And adding the solid substance into 70mL ethyl acetate, heating and refluxing for 3h, cooling, performing suction filtration, and drying to obtain the 2-aminobenzothiazole-7-formic acid.
Brightening agent
The brightness of the plating layer can be improved by adding the brightening agent into the electroplating solution. The brightening effect of a brightener is an integrated process, not the result of the action of a brightener. At lower voltages, brighteners can significantly increase cathodic polarization. The addition of the brightener can ensure that the plating solution can obtain a bright plating layer within a proper current density range, and the electrodeposition behavior of trivalent chromium plating cannot be changed after the brightener is added.
In a preferred embodiment of the present invention, the brightener is one or more selected from 2-amino-3- (3-hydroxy-thiopropionyl) -benzenesulfonic acid, thiourea, 3-mercapto-1-propane sulfonic acid sodium salt, 2-methylimidazole, and 2-mercaptobenzimidazole.
In a preferred embodiment of the present invention, the brightener is 2-amino-3- (3-hydroxy-thiopropionyl) -benzenesulfonic acid.
The preparation method of the 2-amino-3- (3-hydroxy-thiopropionyl) -benzenesulfonic acid at least comprises the following steps:
a. adding 50mL of solvent and 0.1mol of aniline into a four-mouth bottle provided with a stirrer, a dropping funnel, a condenser and a thermometer, stirring, controlling the reaction temperature at 50 ℃, and slowly dropwise adding 6mL of 98 wt% concentrated sulfuric acid; after dripping, keeping the temperature at 50 ℃ for 30min, then slowly heating to 168-172 ℃, and keeping the temperature for 7 h; during the reaction period, continuously dropping the solvent, and simultaneously continuously evaporating the solvent to keep the total solvent amount in the reactor basically unchanged; after the reaction is finished, cooling, adjusting the pH of the solution in the bottle to 8-9 by using a 20 wt% sodium carbonate aqueous solution, filtering, removing filter residues, and acidifying the filtrate by using 20 wt% dilute sulfuric acid until the pH is 2; filtering, washing and drying to obtain 2-amino-benzenesulfonic acid; the solvent is a mixture of No. 180 solvent oil and petroleum ether, and the volume ratio of the No. 180 solvent oil to the petroleum ether is 4: 1; the No. 180 solvent oil is purchased from Anginol electronic materials, Inc. of Suzhou;
b. adding 0.2mol of 2-amino-benzenesulfonic acid, 0.8mol of sodium thiocyanate and 260mL of formic acid into a 500mL three-necked bottle provided with a mechanical stirrer and a constant-pressure dropping funnel, stirring, cooling with ice water, slowly dropwise adding 0.4mol of bromine at 0-5 ℃, continuously stirring for 2-3 h, pouring the reaction mixture into 500mL of ice water, stirring for 5min, filtering, mixing a filter cake with 200mL of water, neutralizing the residual acid with a saturated sodium bicarbonate solution, filtering, washing the filter cake with water to be neutral, and performing vacuum drying to obtain a crude product, and recrystallizing the crude product with ethyl acetate to obtain 2-amino-3-sulfo-phenyl isothiocyanate;
c. 0.25mol of aminoacetic acid and 0.2mol of 2-amino-3-sulfo-phenyl isothiocyanate are added into 125mL of ethanol, the mixture is stirred for 2.5 hours at room temperature, the solution gradually becomes turbid, solid is separated out, the solvent is removed by reduced pressure distillation, the obtained solid is washed three times by 15 wt% dilute hydrochloric acid and water, and the crude product is obtained by drying. Recrystallizing in petroleum ether and chloroform, and drying to obtain the 2-amino-3- (3-hydroxy-thiopropionyl) -benzenesulfonic acid.
As a preferred technical solution of the present invention, the trivalent chromium electroplating solution further includes an auxiliary agent, and the auxiliary agent is one or more selected from a stabilizer, a dispersant and a displacement agent.
Stabilizer
The stabilizer belongs to a compound reducing agent, can eliminate an oxidant in the plating solution, and can inhibit Cr in trivalent chromium electroplating6+And generating and stabilizing the plating solution.
As a preferable technical scheme of the invention, the stabilizing agent is selected from one or more of ascorbic acid, bromide, formaldehyde and ferrous sulfate.
Dispersing agent
The dispersant can obviously improve the dispersing capacity and the covering capacity of the plating solution, provides powerful guarantee for obtaining a uniform plating layer, and can adopt nitrogen-containing aromatic organic compounds, such as ammonium benzenesulfonate. Surfactants having dispersing action may also be used, but these are required to be used in combination with suitable additives.
Dislocation agent
The displacement agent can obviously improve the covering capacity of the solution, is generally a mixed solution of organic matters and inorganic matters, and some products use a certain amount of compounds of iron group elements; some surfactants, such as polyethylene glycol, polyoxyethylene lauryl ether, alkylphenol ethoxylates, and polysorbates, are used.
The preparation method of the trivalent chromium electroplating solution at least comprises the following steps:
taking deionized water according to the weight parts, heating to 55 ℃, adding trivalent soluble chromium salt and cobalt salt, and stirring for dissolving; and then sequentially adding conductive salt, a coordination agent, a buffering agent, a blackening agent and a brightening agent, stirring and dissolving, aging the obtained solution at room temperature for 12 hours, and then adjusting the pH of the solution to 2.6-3.8 by using 20 wt% of dilute sulfuric acid and 15 wt% of ammonia water to obtain the trivalent chromium electroplating solution.
As a preferable technical scheme, the preparation method of the trivalent chromium coating comprises a heat treatment step, wherein the heat treatment step is to place the base material plated with the trivalent chromium coating into a vacuum drying box and treat the base material at 220-280 ℃ for 3-5 hours.
In order to solve the technical problems, the second aspect of the invention provides a trivalent chromium plating layer prepared by the preparation method of the trivalent chromium plating layer; the composition at least comprises: chromium, cobalt, hydrogen, oxygen, sulfur, phosphorus; the substrate is made of a conductive material or a non-conductive material with a conductive layer on the surface; the conductive layer on the surface of the base material made of conductive material and the conductive layer on the surface of the base material made of non-conductive material are selected from one or more alloys of iron, stainless steel, copper, nickel, silver, gold and conductive ceramics; the base material of the non-conductive material is any one of plastic, ceramic and glass.
The inventor finds that cobalt salt and chromium salt are used in the preparation of the trivalent chromium plating layer, the surface of the trivalent chromium plating layer obtained by compounding the conductive salt, the coordination agent, the buffering agent, the blackening agent and the brightening agent is uniform and black, the brightness is good, the reflectivity is low, the plating layer has good binding force with the base material, and the obtained plating layer is uniform and compact, low in porosity and good in corrosion resistance. The present inventors surmise the possible reason that the present invention uses a system in which cobalt and chromium are co-deposited, and regulates the deposition rate of cobalt and chromium by coordination of a complexing agent, a blackening agent and a brightener, thereby giving a plating layer having good properties. The blackening agent and the brightening agent used in the invention have good compatibility and reducibility, inhibit the generation of hexavalent chromium and enhance the stability of the electroplating solution. The 2-aminobenzothiazole-7-formic acid and the 2-amino-3- (3-hydroxy-thiopropionyl) -benzenesulfonic acid have strong carboxyl and sulfo acidity, enhance the conductivity and the dispersibility of the solution, ensure that other groups on a benzene ring and metal ions have good coordination by the electron withdrawing property of the 2-aminobenzothiazole-7-formic acid and the 2-amino-3- (3-hydroxy-thiopropionyl) -benzenesulfonic acid, ensure that a plating layer is compact and bright, and possibly form intramolecular hydrogen bonds, are favorable for destroying the hydroxyl bridge function of trivalent chromium ions and hydroxide ions during long-time electroplating, and further enhance the stability of the system.
The present invention will be specifically described below by way of examples. It should be noted that the following examples are only for illustrating the present invention and should not be construed as limiting the scope of the present invention, and that the insubstantial modifications and adaptations of the present invention by those skilled in the art based on the above disclosure are still within the scope of the present invention.
In addition, the starting materials used are all commercially available, unless otherwise specified.
Example 1:
embodiment 1 provides a method for preparing a trivalent chromium plating layer, which at least comprises the following steps: immersing a base material into trivalent chromium electroplating solution, and electroplating by using the base material as a cathode, wherein the electroplating temperature is 20 ℃, and the current density is 6A/dm2Electroplating time is 5 min; the trivalent chromium plating layer is plated on the base material; the above-mentionedThe surface of the substrate at least comprises a conductive layer;
the trivalent chromium electroplating solution at least comprises the following components: trivalent water-soluble chromium salt: 15 parts by weight; cobalt salt: 12 parts by weight; conductive salt: 20 parts by weight; a complexing agent: 4 parts by weight; buffering agent: 7 parts by weight; a blackening agent: 0.5 part by weight; brightening agent: 0.01 part by weight; deionized water: 100 parts by weight.
The trivalent water-soluble chromium salt is chromium sulfate; the cobalt salt is cobalt sulfate; the conductive salt is a mixture of sodium sulfate and ammonium sulfate, and the mass ratio of the sodium sulfate to the ammonium sulfate is 1: 0.3; the complexing agent is a mixture of formic acid, glycine and malic acid, and the mass ratio of the formic acid to the glycine to the malic acid is 1: 0.5: 0.2; the buffering agent is a mixture of boric acid and sodium dihydrogen phosphate, and the mass ratio of the boric acid to the sodium dihydrogen phosphate is 2: 1; the blackening agent is a mixture of cysteine and 2-aminobenzothiazole-7-formic acid, and the mass ratio of the cysteine to the 2-aminobenzothiazole-7-formic acid is 1: 0.1; the brightener is 2-amino-3- (3-hydroxy-thiopropionyl) -benzenesulfonic acid.
The preparation method of the 2-aminobenzothiazole-7-formic acid at least comprises the following steps:
a. adding 11.3g of 3-aminobenzoic acid and 75mL of chlorobenzene into a 250mL three-necked bottle, stirring, dropwise adding 2.1mL of 98 wt% concentrated sulfuric acid at-2 ℃, and continuing to react for 25min after the dropwise addition is finished within 30 min. Adding 6.8g of sodium thiocyanate, stirring for reaction for 5min, adding 0.22g of benzyltriethylammonium chloride, and reacting at constant temperature of 100 ℃ for 10 h. And (4) carrying out suction filtration, washing and drying to obtain the N- (3-carboxyphenyl) thiourea.
b. 8.4g N- (3-carboxyphenyl) thiourea was added to a 250mL three-necked flask and 2.2mL Br was added dropwise2The mixture was added dropwise to 30mL of chlorobenzene in 1 hour, and the reaction was carried out at a constant temperature of 70 ℃ for 4 hours. Cooling, adding 25mL of diethyl ether, filtering, and drying to obtain a solid substance. And adding the solid substance into 70mL ethyl acetate, heating and refluxing for 3h, cooling, performing suction filtration, and drying to obtain the 2-aminobenzothiazole-7-formic acid.
The preparation method of the 2-amino-3- (3-hydroxy-thiopropionyl) -benzenesulfonic acid at least comprises the following steps:
a. adding 50mL of solvent and 0.1mol of aniline into a four-mouth bottle provided with a stirrer, a dropping funnel, a condenser and a thermometer, stirring, controlling the reaction temperature at 50 ℃, and slowly dropwise adding 6mL of 98 wt% concentrated sulfuric acid; after dripping, keeping the temperature at 50 ℃ for 30min, then slowly heating to 170 ℃, and keeping the temperature for 7 h; during the reaction period, continuously dropping the solvent, and simultaneously continuously evaporating the solvent to keep the total solvent amount in the reactor basically unchanged; cooling after the reaction is finished, adjusting the pH of the solution in the bottle to 8 by using 20 wt% of sodium carbonate aqueous solution, filtering, removing filter residues, and acidifying the filtrate by using 20 wt% of dilute sulfuric acid until the pH is 2; filtering, washing and drying to obtain 2-amino-benzenesulfonic acid; the solvent is a mixture of No. 180 solvent oil and petroleum ether, and the volume ratio of the No. 180 solvent oil to the petroleum ether is 4: 1; the No. 180 solvent oil is purchased from Anginol electronic materials, Inc. of Suzhou;
b. adding 0.2mol of 2-amino-benzenesulfonic acid, 0.8mol of sodium thiocyanate and 260mL of formic acid into a 500mL three-necked bottle provided with a mechanical stirrer and a constant-pressure dropping funnel, stirring, cooling with ice water, slowly dropwise adding 0.4mol of bromine at 0 ℃, continuously stirring for 2.5 hours, pouring the reaction mixture into 500mL of ice water, stirring for 5 minutes, filtering, mixing a filter cake with 200mL of water, neutralizing the residual acid with a saturated sodium bicarbonate solution, filtering, washing the filter cake with water to be neutral, and drying in vacuum to obtain a crude product, and recrystallizing the crude product with ethyl acetate to obtain 2-amino-3-sulfo-phenyl isothiocyanate;
c. 0.25mol of aminoacetic acid and 0.2mol of 2-amino-3-sulfo-phenyl isothiocyanate are added into 125mL of ethanol, the mixture is stirred for 2.5 hours at room temperature, the solution gradually becomes turbid, solid is separated out, the solvent is removed by reduced pressure distillation, the obtained solid is washed three times by 15 wt% dilute hydrochloric acid and water, and the crude product is obtained by drying. Recrystallizing in petroleum ether and chloroform, and drying to obtain the 2-amino-3- (3-hydroxy-thiopropionyl) -benzenesulfonic acid.
Example 2:
embodiment 2 provides a method for preparing a trivalent chromium plating layer, which at least comprises the following steps: immersing the substrate in a trivalent chromium electroplating bath containing said substrateElectroplating with cathode at 20 deg.C and current density of 6A/dm2Electroplating time is 5 min; the trivalent chromium plating layer is plated on the base material; the surface of the substrate at least comprises a conductive layer;
the trivalent chromium electroplating solution at least comprises the following components: trivalent water-soluble chromium salt: 20 parts by weight; cobalt salt: 16 parts by weight; conductive salt: 35 parts by weight; a complexing agent: 6 parts by weight; buffering agent: 10 parts by weight; a blackening agent: 1.6 parts by weight; brightening agent: 0.5 part by weight; deionized water: 100 parts by weight.
The trivalent water-soluble chromium salt is chromium sulfate; the cobalt salt is cobalt sulfate; the conductive salt is a mixture of sodium sulfate and ammonium sulfate, and the mass ratio of the sodium sulfate to the ammonium sulfate is 1: 0.3; the complexing agent is a mixture of formic acid, glycine and malic acid, and the mass ratio of the formic acid to the glycine to the malic acid is 1: 0.5: 0.2; the buffering agent is a mixture of boric acid and sodium dihydrogen phosphate, and the mass ratio of the boric acid to the sodium dihydrogen phosphate is 2: 1; the blackening agent is a mixture of cysteine and 2-aminobenzothiazole-7-formic acid, and the mass ratio of the cysteine to the 2-aminobenzothiazole-7-formic acid is 1: 0.1; the brightener is 2-amino-3- (3-hydroxy-thiopropionyl) -benzenesulfonic acid.
The preparation method of the 2-aminobenzothiazole-7-formic acid is the same as that of example 1.
The preparation of 2-amino-3- (3-hydroxy-thiopropionyl) -benzenesulfonic acid was the same as in example 1.
Example 3:
embodiment 3 provides a method for preparing a trivalent chromium plating layer, which at least comprises the following steps: immersing a base material into trivalent chromium electroplating solution, and electroplating by using the base material as a cathode, wherein the electroplating temperature is 20 ℃, and the current density is 6A/dm2Electroplating time is 5 min; the trivalent chromium plating layer is plated on the base material; the surface of the substrate at least comprises a conductive layer;
the trivalent chromium electroplating solution at least comprises the following components: trivalent water-soluble chromium salt: 18 parts by weight; cobalt salt: 13 parts by weight; conductive salt: 27 parts by weight; a complexing agent: 4.8 parts by weight; buffering agent: 8 parts by weight; a blackening agent: 1.2 parts by weight; brightening agent: 0.3 part by weight; deionized water: 100 parts by weight.
The trivalent water-soluble chromium salt is chromium sulfate; the cobalt salt is cobalt sulfate; the conductive salt is a mixture of sodium sulfate and ammonium sulfate, and the mass ratio of the sodium sulfate to the ammonium sulfate is 1: 0.3; the complexing agent is a mixture of formic acid, glycine and malic acid, and the mass ratio of the formic acid to the glycine to the malic acid is 1: 0.5: 0.2; the buffering agent is a mixture of boric acid and sodium dihydrogen phosphate, and the mass ratio of the boric acid to the sodium dihydrogen phosphate is 2: 1; the blackening agent is a mixture of cysteine and 2-aminobenzothiazole-7-formic acid, and the mass ratio of the cysteine to the 2-aminobenzothiazole-7-formic acid is 1: 0.1; the brightener is 2-amino-3- (3-hydroxy-thiopropionyl) -benzenesulfonic acid.
The preparation method of the 2-aminobenzothiazole-7-formic acid is the same as that of example 1.
The preparation of 2-amino-3- (3-hydroxy-thiopropionyl) -benzenesulfonic acid was the same as in example 1.
Example 4:
embodiment 4 provides a method for preparing a trivalent chromium plating layer, which at least comprises the following steps: immersing a base material into trivalent chromium electroplating solution, and electroplating by using the base material as a cathode, wherein the electroplating temperature is 20 ℃, and the current density is 6A/dm2Electroplating time is 5 min; the trivalent chromium plating layer is plated on the base material; the surface of the substrate at least comprises a conductive layer;
the trivalent chromium electroplating solution at least comprises the following components: trivalent water-soluble chromium salt: 18 parts by weight; cobalt salt: 13 parts by weight; conductive salt: 27 parts by weight; a complexing agent: 4.8 parts by weight; buffering agent: 8 parts by weight; a blackening agent: 1.2 parts by weight; brightening agent: 0.3 part by weight; deionized water: 100 parts by weight.
The trivalent water-soluble chromium salt is chromium sulfate; the cobalt salt is cobalt nitrate; the conductive salt is a mixture of sodium sulfate and ammonium sulfate, and the mass ratio of the sodium sulfate to the ammonium sulfate is 1: 1.2; the complexing agent is a mixture of formic acid, glycine and malic acid, and the mass ratio of the formic acid to the glycine to the malic acid is 1: 3: 2; the buffer is a mixture of boric acid and sodium dihydrogen phosphate, and the mass ratio of the boric acid to the sodium dihydrogen phosphate is 6: 1; the blackening agent is a mixture of cysteine and 2-aminobenzothiazole-7-formic acid, and the mass ratio of the cysteine to the 2-aminobenzothiazole-7-formic acid is 1: 0.5; the brightener is 2-amino-3- (3-hydroxy-thiopropionyl) -benzenesulfonic acid.
The preparation method of the 2-aminobenzothiazole-7-formic acid is the same as that of example 1.
The preparation of 2-amino-3- (3-hydroxy-thiopropionyl) -benzenesulfonic acid was the same as in example 1.
Example 5:
embodiment 5 provides a method for preparing a trivalent chromium plating layer, comprising at least the steps of: immersing a base material into trivalent chromium electroplating solution, and electroplating by using the base material as a cathode, wherein the electroplating temperature is 20 ℃, and the current density is 6A/dm2Electroplating time is 5 min; the trivalent chromium plating layer is plated on the base material; the surface of the substrate at least comprises a conductive layer;
the trivalent chromium electroplating solution at least comprises the following components: trivalent water-soluble chromium salt: 18 parts by weight; cobalt salt: 13 parts by weight; conductive salt: 27 parts by weight; a complexing agent: 4.8 parts by weight; buffering agent: 8 parts by weight; a blackening agent: 1.2 parts by weight; brightening agent: 0.3 part by weight; deionized water: 100 parts by weight.
The trivalent water-soluble chromium salt is chromium sulfate; the cobalt salt is cobalt acetate; the conductive salt is a mixture of sodium sulfate and ammonium sulfate, and the mass ratio of the sodium sulfate to the ammonium sulfate is 1: 0.8; the complexing agent is a mixture of formic acid, glycine and malic acid, and the mass ratio of the formic acid to the glycine to the malic acid is 1: 1.2: 0.7; the buffer is a mixture of boric acid and sodium dihydrogen phosphate, and the mass ratio of the boric acid to the sodium dihydrogen phosphate is 4.5: 1; the blackening agent is a mixture of cysteine and 2-aminobenzothiazole-7-formic acid, and the mass ratio of the cysteine to the 2-aminobenzothiazole-7-formic acid is 1: 0.2; the brightener is 2-amino-3- (3-hydroxy-thiopropionyl) -benzenesulfonic acid.
The preparation method of the 2-aminobenzothiazole-7-formic acid is the same as that of example 1.
The preparation of 2-amino-3- (3-hydroxy-thiopropionyl) -benzenesulfonic acid was the same as in example 1.
Example 6:
example 6 the same embodiment as example 5 except that the plating temperature was 45 ℃ and the current density was 25A/dm2The plating time was 30 min.
Example 7:
example 7 the same embodiment as example 5 was conducted except that the plating temperature was 28 ℃ and the current density was 14A/dm2The plating time was 10 min.
Example 8:
example 8 the same embodiment as example 5 except that the plating temperature was 36 ℃ and the current density was 20A/dm2The plating time was 20 min.
Example 9:
the embodiment of example 9 is the same as example 8, except that the trivalent chromium plating solution further includes a dispersant PEG 400.
Comparative example 1:
the embodiment of comparative example 1 is the same as example 9 except that the trivalent chromium plating solution does not include a brightener.
Comparative example 2:
the embodiment of comparative example 2 is the same as example 9 except that the trivalent chromium plating bath does not include a blackening agent.
Comparative example 3:
the embodiment of comparative example 3 is the same as that of example 9 except that the blackening agent is cysteine.
Comparative example 4:
comparative example 4 is the same as example 9 except that the blackening agent is 2-aminobenzothiazole-7-carboxylic acid.
Comparative example 5:
comparative example 5 is the same as example 9 except that the mass of cysteine and 2-aminobenzothiazole-7-carboxylic acid in the blackening agent is 1: 0.6.
performance evaluation:
the trivalent chromium plating solutions described in examples 1 to 9 and comparative examples 1 to 5 were prepared by the following methods:
taking deionized water according to the weight parts, heating to 55 ℃, adding trivalent soluble chromium salt and cobalt salt, and stirring for dissolving; and then sequentially adding conductive salt, a coordination agent, a buffering agent, a blackening agent and a brightening agent, stirring and dissolving, aging the obtained solution at room temperature for 12 hours, and then adjusting the pH to 2.8 by using 20 wt% of dilute sulfuric acid and 15 wt% of ammonia water to obtain the trivalent chromium electroplating solution.
The plating experiment was carried out using a Hull cell, with a trivalent chromium plating bath volume of 250 mL. The cathode is the substrate, the anode is a DSA titanium-based coating anode plate, and the size is 50mm multiplied by 100mm multiplied by 2 mm.
The base material adopted in the experiment is a commercially available H62 brass sheet, the size is 50mm multiplied by 100mm multiplied by 0.2mm, the base material needs to be polished to be bright by 200-mesh and 600-mesh water abrasive paper respectively before electroplating, then the grease on the surface of the base material is removed by using a phosphorus-free degreasing and degreasing cleaning solution (manufactured by Shanghai Yao rock chemical Co., Ltd.), finally, the base material is washed clean by water and dried, and then electroplating can be carried out, and the electroplating process uses compressed air for stirring.
Putting the base material into the electroplating solution described in the embodiment 1-9 and the comparative example 1-5 for electroplating, plating a trivalent chromium plating layer on the surface of the base material, putting the base material plated with the trivalent chromium plating layer into a vacuum drying oven for heat treatment, namely, treating at 260 ℃ for 3.5h, and then testing the performance of the plating layer.
Appearance of the product
And detecting the appearance of the coating by adopting an empirical evaluation method of visual brightness. The grading reference standards for the empirical evaluation of the visual brightness are as follows:
a. the surface of the grade (full bright) plating layer is bright, and the face and the five sense organs can be clearly seen;
b. the surface of the second-level (bright) plating layer is bright, so that five sense organs and the face can be seen, but the picture is weakened;
c. the three-level (semi-bright) plating layer has slight brightness, and five sense organs can only see the outline;
d. the four-level (non-bright) coating surface is basically matt and no facial contour can be seen.
The coating reflectance (%) to light was measured using an ultraviolet-visible spectrophotometer. The solar radiation energy is mainly concentrated in the range of 200-5000 nm, and the light with the wavelength range of 200-900 nm accounts for more than 60% of the total solar radiation energy, so the test wavelength range is 200-900 nm. For opaque materials, the light transmission is negligible and the sum of the reflectance and absorbance is 1. The various colors produced on the object are the result of their selective absorption of different wavelengths in the visible light range. When the object absorbs all visible light waves in equal quantity and the absorption rate reaches more than 90%, the object is black; when the absorption rate reaches more than 96%, the object is dark black.
Binding force
Thermal shock test: and (3) preserving the heat of the electroplated base material for 1h at the temperature of 300 ℃, taking out the electroplated base material, quenching the electroplated base material in ice water, and repeating the steps for 10 times until the coating is not peeled off to be qualified.
Porosity of the material
The porosity is measured by a filter paper pasting method, wherein the trivalent chromium plating layer is made of steel as a substrate and chromium as a plating layer, so the selected test solution is a mixed solution of potassium ferricyanide, ammonium chloride and sodium chloride, and the basic composition of the test solution is as follows: potassium ferricyanide K3Fe(CN)610g/L, ammonium chloride NH430g/L of Cl, 60g/L of sodium chloride NaCl and deionized water as a solvent.
The test method comprises the following steps: the filter paper soaked with the detection solution is tightly attached to the surface of the electroplated substrate, no air bubbles should exist between the filter paper and the surface, the detection solution can be continuously supplemented to keep the filter paper wet, after the filter paper is attached for 10min, the filter paper printed with blue spots is taken off, the filter paper is washed by distilled water and then placed on a clean glass plate, and the number of gaps is calculated after the filter paper is dried.
The calculation method of the porosity comprises the following steps: a glass plate marked with grids (the area of the grids is 1 cm)2) Placing on filter paper printed with pore speckles, counting the number of speckles with color in each square, and calculating the porosity (number of speckles/cm) from plating to substrate2): the porosity is n/S, wherein n refers to the number of pore spots; s is the area of the coating to be measured in cm2(ii) a The measurement was performed 3 times, and the average value was taken as the measurement result.
In calculating porosity, the size of the spot is specified as follows: the diameter of the spot is below lmm, and one spot is calculated according to one pore; the diameter of each spot is within 1-3 mm, and one spot is calculated according to 3 holes; the diameter of the spot is within 3-5 mm, and one spot is calculated according to 10 holes.
Corrosion resistance
The corrosion resistance was examined by a copper accelerated acetate spray test (CASS test). The preparation method of the test solution comprises the following steps: dissolving sodium chloride (NaCl, AR) in deionized water to give a concentration of 50 + -1 g/L, and adding cupric chloride (CuCl)2AR) so that the concentration thereof is 0.26. + -. 0.02 g/L. Adjusting the pH value of the solution to 3.1-3.3 by glacial acetic acid.
Placing the base material to be tested in a salt spray corrosion test box, enabling the base material to be tested to form a 30-degree angle with a vertical line, and setting the spraying temperature of the salt spray box to be 50 ℃ and the saturation temperature to be 55 ℃. Spraying is carried out for 16h continuously. And taking out the substrate after the completion, rinsing the substrate by using deionized water, and then respectively drying the substrate by blowing.
The method for evaluating the corrosion resistance grade comprises the following steps:
covering a transparent organic glass with squares (5mm x 5mm) on the main surface of the sample coating, dividing into several squares, calculating the total number of squares N and the squares η containing one or more corrosion points in these squares: corrosion rate γ (%). eta./N
And sequentially measuring the corrosion rate of six tested samples of each coating, and taking the average value to obtain the corrosion rate of the coating. The corrosion resistance rating results were determined according to the following table. The 0-0.5 means that the corrosion rate is between 0% and 0.5%, including 0.5% but not including 0%.
| Corrosion rate γ (%) | 0 | 0～0.25 | 0.25～0.5 | 0.5～1 | 1～2 | 2～4 | 4～8 | 8～16 | 16～32 | 32～64 | >64 |
| Rating of grade | 10 | 9 | 8 | 7 | 6 | 5 | 4 | 3 | 2 | 1 | 0 |
Table 1 performance characterization test
As can be seen from Table 1, the trivalent chromium plating layer in the invention is dark black, has good brightness, low reflectivity to sunlight, high absorption rate, good bonding force with the substrate, compact plating layer, low porosity and very good anti-corrosion effect.
The foregoing examples are merely illustrative and serve to explain some of the features of the method of the present invention. The appended claims are intended to claim as broad a scope as is contemplated, and the examples presented herein are merely illustrative of selected implementations in accordance with all possible combinations of examples. Accordingly, it is applicants' intention that the appended claims are not to be limited by the choice of examples illustrating features of the invention. Also, where numerical ranges are used in the claims, subranges therein are included, and variations in these ranges are also to be construed as possible being covered by the appended claims.
Claims (6)
1. A preparation method of a trivalent chromium plating layer is characterized by at least comprising the following steps: immersing a base material into trivalent chromium electroplating solution, and electroplating by taking the base material as a cathode, wherein the electroplating temperature is 20-45 ℃, and the current density is 6A/dm2～25A/dm2Electroplating for 5-30 min; the trivalent chromium plating layer is plated on the base material; the surface of the substrate at least comprises a conductive layer;
the trivalent chromium electroplating solution at least comprises the following components: trivalent water-soluble chromium salt: 15-20 parts by weight; cobalt salt: 12-16 parts by weight; conductive salt: 20-35 parts by weight; a complexing agent: 4-6 parts by weight; buffering agent: 7-10 parts by weight; a blackening agent: 0.5 to 1.6 parts by weight; brightening agent: 0.01 to 0.5 part by weight; deionized water: 100 parts by weight;
the blackening agent is a mixture of cysteine and 2-aminobenzothiazole-7-formic acid, and the mass ratio of the cysteine to the 2-aminobenzothiazole-7-formic acid is 1: 0.1 to 0.5;
the brightener is 2-amino-3- (3-hydroxy-thiopropionyl) -benzenesulfonic acid.
2. The method of claim 1, wherein the trivalent water soluble chromium salt is chromium sulfate; the cobalt salt is selected from one or more of cobalt sulfate, cobalt nitrate and cobalt acetate; the conductive salt is a mixture of sodium sulfate and ammonium sulfate, and the mass ratio of the sodium sulfate to the ammonium sulfate is 1: 0.3 to 1.2.
3. The method for preparing a trivalent chromium coating according to claim 1, wherein the complexing agent is a mixture of formic acid, glycine and malic acid, and the mass ratio of formic acid, glycine and fruit acid is 1: 0.5-3: 0.2 to 2.
4. The method for preparing a trivalent chromium coating according to claim 1, wherein the buffering agent is a mixture of boric acid and sodium dihydrogen phosphate, and the mass ratio of the boric acid to the sodium dihydrogen phosphate is 2-6: 1.
5. the method of claim 1, wherein the trivalent chromium plating bath further comprises an auxiliary agent selected from one or more of a stabilizer, a dispersant, and a displacement agent.
6. A trivalent chromium plating layer, characterized by being prepared by the preparation method of any one of claims 1 to 5; the composition at least comprises: chromium, cobalt, hydrogen, oxygen, sulfur, phosphorus; the substrate is made of a conductive material or a non-conductive material with a conductive layer on the surface; the conductive layer on the surface of the base material made of conductive material and the conductive layer on the surface of the base material made of non-conductive material are selected from one or more alloys of iron, stainless steel, copper, nickel, silver, gold and conductive ceramics; the base material of the non-conductive material is any one of plastic, ceramic and glass.
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| EP4023793A1 (en) * | 2021-01-05 | 2022-07-06 | Coventya SAS | Electroplating bath for depositing chromium or chromium alloy from a trivalent chromium bath and process for depositing chromium or chromium alloy |
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| CN111699284B (en) * | 2018-02-09 | 2022-12-30 | 日本制铁株式会社 | Steel sheet for container and method for producing steel sheet for container |
| CN110117782A (en) * | 2019-05-14 | 2019-08-13 | 广州超邦化工有限公司 | A kind of non-cyanide plating cadmium titanium alloy and trivalent chromium passivation coating and preparation method thereof |
| CN111962105A (en) * | 2020-09-11 | 2020-11-20 | 广东涂乐师新材料科技有限公司 | Trivalent black chromium electroplating agent simple to mix and preparation method thereof |
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| CN116770375B (en) * | 2023-06-06 | 2024-01-02 | 中山博美新材料科技有限公司 | Plating solution for black chromium plating layer, and preparation method and application thereof |
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| CN105264122A (en) * | 2013-01-10 | 2016-01-20 | 科文特亚股份有限公司 | Apparatus and method of maintaining trivalent chromium bath plating efficiency |
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| EP4023793A1 (en) * | 2021-01-05 | 2022-07-06 | Coventya SAS | Electroplating bath for depositing chromium or chromium alloy from a trivalent chromium bath and process for depositing chromium or chromium alloy |
| WO2022148691A1 (en) * | 2021-01-05 | 2022-07-14 | Coventya Sas | Electroplating bath for depositing chromium or chromium alloy and process for depositing chromium or chromium alloy |
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Denomination of invention: A trivalent chromium coating and its preparation method Effective date of registration: 20231123 Granted publication date: 20200103 Pledgee: The Bank of Shanghai branch Caohejing Limited by Share Ltd. Pledgor: WINSTAR CHEMICALS (SHANGHAI) Co.,Ltd. Registration number: Y2023980066990 |