CN101302635B - Steel member acidic electroplating additive for copper pre-plating and pre-plating process - Google Patents
Steel member acidic electroplating additive for copper pre-plating and pre-plating process Download PDFInfo
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- CN101302635B CN101302635B CN2008100258889A CN200810025888A CN101302635B CN 101302635 B CN101302635 B CN 101302635B CN 2008100258889 A CN2008100258889 A CN 2008100258889A CN 200810025888 A CN200810025888 A CN 200810025888A CN 101302635 B CN101302635 B CN 101302635B
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Abstract
The invention relates to a copper plating process pre-plating addition agent, comprising a key light agent and an auxiliary light agent, wherein the key light agent comprises (1) a nonionic surfactant, (2) a sulfur and nitrogen containing organic compound, (3) an alcohol compound, (4) an aldehyde compound, (5) a ketone compound, (6) dyes, (7) a metallic salt and (8) water; the auxiliary light agent comprises (1) a nonionic surfactant, (2) an aldehyde compound, (3) dyes, (4) chloride, (5) a metallic salt, (6) water and (7) an inorganic acid. Preplating is a process which directly carries out copper plating in an acidic solution, thereby overcoming the disadvantage that copper plating can not be directly carried out in a steel acidic solution and realizing direct copper preplating on a steel part; moreover, the copper plating process pre-plating addition agent solves the bonding force between a copper plating layer and an iron matrix and realizes the aims of environment protection and lower cost.
Description
Technical field:
The present invention relates to the electroplating additive and the steel part electro-coppering pre-plating process of preplating in the steel part copper-plating technique, belong to the copper facing field of steel part.
Background technology:
For the acid copper-plating technology of steel part, before carrying out copper facing work,, need carry out pre-plating process in order to solve the defective of binding force of cladding material in the acidic bath.Applied pre-plating process has cyanide copper plating process, nickel plating technology and alkaline non-cyanide copper-plating technique on the Electroplating Production at present.Cyanide copper plating process is low because of cost, quality good, processing ease is used by wide model.But owing to contain the prussiate of severe toxicity, use this method to cause great influence to human and environment in the employed additive, country has now prohibited use.Nickel preplating technology costs an arm and a leg because of metallic nickel, and the cost height adopts this technology can't compare with other copper-plating technique on cost, and the user has only and just will consider use where necessary.The alkaline non-cyanide copper-plating technique is with fastest developing speed and be expected to replace the plating new technology of hypertoxic prussiate over past ten years, and its typical type has: citric acid-tartrate copper facing, EDTA copper facing, copper plating with ethylene glycol as complexing agent (patent publication No. CN85103672), non-cyanide alkali biuret copper plating (patent publication No. CN1183485) and organophosphate copper facing etc.The electroplating solution majority of alkaline copper plating technology adds that by a kind of main complex compound multiple auxiliary complex and other additives form, because employed complex compound differs far away to the complex ability of cupric ion and prussiate to the complex ability of cupric ion, steady potential as the cyanide electroplating cathodic polarization is about-1.5V, and above-mentioned cyanide-free copper electroplating have only-0.8～-1.0V, therefore, when adopting this method to carry out preplating, because the copper-plated galvanic deposit of alkaline non-cyanide mainly is to generate stable complex ion by cupric ion and multicomponent complex reaction, when steel part is gone into the groove plating, because the discharge potential of copper complex ion raises, cathodic polarization increases and the careful copper coating of acquisition crystallization, but, the basic solution of multicomponent complex again simultaneously easily and the iron-based precursor reactant cause the very easily passivation and influence bonding force of iron-based surface, thereby the insufficient problem of bonding force of copper plate and iron-based body does not solve as yet at all.In addition, even the present best cyanide-free copper electroplating technology-organophosphate electroplating technology of performance all is to belong to this type of technology as the E-Brite Ultra Cu cyanide-free alkaline copper plating of EPI U.S. ElectroChem and United States Patent (USP) 4251282,4469569 disclosed cyanide-free copper electroplating technologies etc.Though the organophosphate cyanide-free copper electroplating technology of this type of import can directly be electroplated on steel substrate, obtain good combination power comparatively copper coating, but the plating bath cost costliness of such technology, the product price of import reaches 25～30 yuan every liter, is 5～7 times of cyanide electroplating cost.In sum, based on electroplating cost and electroplating quality factor, the alkaline non-cyanide copper-plating technique still fails to be accepted by users so far, is difficult to apply.
For the technology that the existing electroplating additive that is alkaline multicomponent complex both at home and abroad carries out preplating, iron and steel non-cyanide pre-plating copper direct copper-plated additive and pre-plating process under the tart condition do not appear in the newspapers so far as yet.
Summary of the invention:
The invention reside in provides a kind of additive and pre-plating process that carries out the copper facing preplating of steel part in acidic solution, solving in the iron and steel acidic solution can't direct copper-plated defective, directly pre-copper facing on steel part solves the bonding force and the realization environmental protection of copper plate and iron-based body and reduces cost and is purpose.
The copper facing preplating additive of realizing the object of the invention comprises the key light agent and helps two parts of photo etching:
The key light agent comprises: (1) nonionic surface active agent, (2) sulfur-bearing, nitrogen organic compound, (3) alcohol compound, (4) aldehyde compound, (5) ketone compounds, (6) dyestuff, (7) metal-salt, (8) water.Wherein:
(1) nonionic surface active agent comprises and a kind ofly is selected from high fatty alcohol Soxylat A 25-7, fatty alcohol-polyoxyethylene ether, alkylphenol polyoxyethylene, polyoxyethylene glycol, polypropylene glycol, polyethers etc. to three kinds.The effect of nonionic surface active agent is to improve effectively cathodic polarization, the discharge reduction of resistanceization cupric ion.
(2) sulfur-bearing, nitrogen organic compound comprise and a kind ofly are selected from benzotriazole, 2-mercaptobenzoimidazole, thiocarbamide, thiosinamine, ethylene thiourea, sodium polydithio-dipropyl sulfonate, thiazolidine thioketones, methionine(Met) etc. to three kinds.Sulfur-bearing, the effect of nitrogen organic compound are to generate surface compound with cupric ion effectively, the discharge reduction of resistanceization cupric ion.
(3) alcohol compound comprises that one or both are selected from ethanol, methyl alcohol, glycerol etc.The effect of alcohol compound is to improve the distribution capability of tensio-active agent in the cathodic area.
(4) aldehyde compound comprises and a kind ofly is selected from Vanillin, piperonal, o-chlorobenzaldehyde, formaldehyde etc. to two kinds.The effect of aldehyde compound is to adjust the velocity of discharge of high and low current density district cupric ion by from discharge reduction on negative electrode.
(5) ketone compounds comprise a kind of or two kinds be selected from benzylideneacetone, Ben Yajiaji ketone, acetone etc.The effect of ketone compounds is discharge reduction on negative electrode, adjusts the velocity of discharge of cupric ion.
(6) dyestuff comprise a kind of to three kinds be selected from that the strong green B of taking, methylene blue, methyl violet, methyne are green, tropeolin-D, phenolphthalein etc.The effect of dyestuff is to improve the leveling ability of coating.
(7) metal-salt comprises and a kind ofly is selected from copper sulfate, zinc sulfate, titanium sulfate, cerous sulfate etc. to three kinds.The effect of metal-salt is to make coating crystallization refinement.
By using the key light agent, can improve cathodic polarization, effectively suppress the discharge reduction of cupric ion, make copper layer crystallization refinement, good with matrix bond.
Help photo etching to comprise: (1) nonionic surface active agent, (2) aldehyde compound, (3) dyestuff, (4) muriate, (5) metal-salt, (6) water, (7) mineral acid.Wherein:
(1) nonionic surface active agent comprises and a kind ofly is selected from high fatty alcohol Soxylat A 25-7, fatty alcohol-polyoxyethylene ether, alkylphenol polyoxyethylene, polyoxyethylene glycol, polypropylene glycol, polyethers etc. to three kinds; The effect of nonionic surface active agent is to improve cathodic polarization, the discharge reduction of resistanceization cupric ion.
(2) aldehyde compound comprises and a kind ofly is selected from Vanillin, piperonal, o-chlorobenzaldehyde, formaldehyde etc. to two kinds.The effect of aldehyde compound be to regulate high current density with in, the velocity of discharge of low current density district cupric ion.
(3) dyestuff comprise a kind of to two kinds be selected from that the strong green B of taking, methylene blue, methyl violet, methyne are green, tropeolin-D, phenolphthalein etc.The effect of dyestuff is to improve cathodic polarization, increases the performance of filling and leading up of copper coating.
(4) muriate comprises that one or both are selected from hydrochloric acid, zinc chloride, cupric chloride, nickelous chloride etc.The electric current that muriatic effect is to increase high Current Zone makes coating crystallization refinement with density range.
(5) metal-salt comprises that one or both are selected from copper sulfate, zinc sulfate, titanium sulfate, cerous sulfate etc.The effect of metal-salt is to generate complex ion with dyestuff, makes copper coating crystallization refinement.
(6) mineral acid comprises that concentrated hydrochloric acid, vitriolic are a kind of.The mineral acid effect is to increase the conductive capability of plating bath.
Pre-plating process prescription and working conditions
The prescription (represent unit by every liter of composition weight: grams per liter calculates) of pre-plating bath:
Cupric sulfate pentahydrate 5～25, sulfuric acid 20～90,
Key light agent 20～30 helps photo etching 20～25,
Water is surplus.
The pre-plating process standard:
| Composition and technological specification | Scope |
| Temperature (℃) | 20～40 |
| Cathode current density (A/dm 2) | 0.5～1.5 |
| Cathodic deposition speed (1A/dm 2The time) (μ/min) | 0.2～0.25 |
| Anode | Phosphor-copper and graphite |
| Cathode area: annode area | 1∶1.5～2 |
| Negative electrode moves | Need |
| Filter | Continuously or intermittently |
Key light agent and help the consumption of photo etching:
During key light agent 400～450 gram/kilo-amperes
When helping photo etching 350～400 gram/kilo-amperes
Adopt the plating flow process of the steel part of the direct strike copper plating technique of acidity of the present invention to be:
(1) part to be plated is carried out electrochemical deoiling, rust cleaning operation;
(2) part washing to be plated, washing again after the alkaline electrolysis oil removing;
(3) weak sulfuric acid activation;
(4) washing;
(5) acid directly pre-copper facing;
(6) washing;
(7) acid bright copper plating is to finished product.
Adopt the pre-copper plating additive of acidity of the present invention, its acid direct copper-plated solution is a kind of single salts solution, owing to producing the intensive resistance, nonionic surface active agent selective adsorption on negative electrode of additive turns usefulness into, the aldehydes of additive and ketone compounds produce the depolarize adjusting of appropriateness in the negative electrode selective reduction simultaneously, simultaneously, the sulfur-bearing of additive, nitrogen compound generates surface complex at negative electrode electrostatic double layer and cupric ion generation coordination reaction, comprehensive action by additive, cathodic polarization increases when making galvanic deposit, the acquisition light thereby the discharge potential of cupric ion raises, crystallization is careful, the coating good with matrix bond.
Adopt additive of the present invention, can finish and directly carry out pre-copper-plated technology in acidic solution, itself and existing cyanide-free alkaline copper plating and cyanide copper plating have bigger beneficial effect, specifically are compared as follows shown in the table:
Specific embodiment:
One, the prescription of additive
1, the prescription of key light agent: specialize as of the present invention, contained raw material weight beyond every liter of solution of key light agent of additive dewaters (unit: restrain) can be as follows:
(1) prescription 1
Fatty alcohol-polyoxyethylene ether 1.0, benzotriazole 0.2, ethanol 10.0, formaldehyde 10.0, Ben Yajiaji ketone 0.2, strong green B0.1, the copper sulfate 2.0 taken.
(2) prescription 2
Alkylphenol polyoxyethylene 1.5,2-mercaptobenzoimidazole 0.1, methyl alcohol 10.0, Vanillin 0.2, acetone 2.0, methyl violet 0.05, zinc sulfate 3.0.
(3) prescription 3
Polyoxyethylene glycol 1.5, thiosinamine 2.0, glycerol 3.5, piperonal 0.1, methyne are green 0.05, tropeolin-D 0.05, titanium sulfate 1.0.
(4) prescription 4
Polypropylene glycol 2.0, ethylene thiourea 1.5, methionine(Met) 2.5, ethanol 8.0, o-chlorobenzaldehyde 0.2, phenolphthalein 0.1, copper sulfate 5.0, zinc sulfate 3.0.
(5) prescription 5
Polyethers 1.0, thiazolidine thioketones 0.2, glycerol 5.0, formaldehyde 20.0, benzylideneacetone 1.5, methyl violet 0.1, cerous sulfate 1.0.
(6) prescription 6
Fatty alcohol-polyoxyethylene ether 1.5, polypropylene glycol 1.5, ethylene thiourea 2.0, methionine(Met) 2.5, ethanol 8.5, methyl alcohol 2.0, o-chlorobenzaldehyde 0.1, phenolphthalein 0.05, copper sulfate 5.0, zinc sulfate 3.0.
(7) prescription 7
Fatty alcohol-polyoxyethylene ether 1.0, thiazolidine thioketones 0.05, benzotriazole 0.1, ethanol 20.0, formaldehyde 15.0, Ben Yajiaji ketone 0.2, acetone 0.8, strongly take that green B 0.1, methyne are green 0.2, tropeolin-D 0.05, copper sulfate 5.0.
(8) prescription 8
Polypropylene glycol 2.0, polyethers 0.5, ethylene thiourea 1.5, sodium polydithio-dipropyl sulfonate 0.1, ethanol 10.0, Vanillin 0.2, piperonal 0.1, acetone 2.0, tropeolin-D 0.05, phenolphthalein 0.05, zinc sulfate 3.0.
(9) prescription 9
Alkylphenol polyoxyethylene 1.0, polyoxyethylene glycol 1.0, polypropylene glycol 1.0, thiosinamine 1.0, ethylene thiourea 1.0, sodium polydithio-dipropyl sulfonate 0.1, ethanol 8.0, glycerol 2.5, piperonal 0.1, formaldehyde 5.0, Ben Yajiaji ketone 0.1, acetone 1.0, methylene blue 0.03, methyl violet 0.05, methyne are green 0.03, copper sulfate 3.0, zinc sulfate 1.5, titanium sulfate 1.0.
(10) prescription 10:
Fatty alcohol-polyoxyethylene ether 0.2～1.0; Polyoxyethylene glycol 0.5～5.0;
Thiocarbamide 0.2～2.0; Thiazolidine thioketones 0.01～0.1;
Ethylene thiourea 0.05～0.5; 2-mercaptobenzoimidazole 0.01～0.1;
Methionine(Met) 0.1～1.0; Sodium polydithio-dipropyl sulfonate 0.2～1.0;
Benzotriazole 0.1～0.5; Ethanol 5～30;
Formaldehyde 5～50; Acetone 0.5～2;
Strong by green B 0.01～0.05; Copper sulfate 0.5～3.0.
Being embodied as of prescription 10:
Prescription 10-1:
Fatty alcohol-polyoxyethylene ether 0.2; Polyoxyethylene glycol 0.5;
Thiocarbamide 0.2; Thiazolidine thioketones 0.01;
Ethylene thiourea 0.05; 2-mercaptobenzoimidazole 0.01;
Methionine(Met) 0.1; Sodium polydithio-dipropyl sulfonate 0.2;
Benzotriazole 0.1; Ethanol 5;
Formaldehyde 5; Acetone 0.5;
Strong by green B 0.01; Copper sulfate 0.5.
Prescription 10-2:
Fatty alcohol-polyoxyethylene ether 1.0; Polyoxyethylene glycol 5.0;
Thiocarbamide 2.0; Thiazolidine thioketones 0.1;
Ethylene thiourea 0.5; 2-mercaptobenzoimidazole 0.1;
Methionine(Met) 1.0; Sodium polydithio-dipropyl sulfonate 1.0;
Benzotriazole 0.5; Ethanol 30;
Formaldehyde 50; Acetone 2;
Strong by green B 0.05; Copper sulfate 3.0.
Prescription 10-3:
Fatty alcohol-polyoxyethylene ether 0.8; Polyoxyethylene glycol 2.5;
Thiocarbamide 1.0; Thiazolidine thioketones 0.04;
Ethylene thiourea 0.3; 2-mercaptobenzoimidazole 0.06;
Methionine(Met) 0.6; Sodium polydithio-dipropyl sulfonate 0.5;
Benzotriazole 0.4; Ethanol 25;
Formaldehyde 35; Acetone 0.9;
Strong by green B 0.03; Copper sulfate 2.5.
Prescription 10-4
Fatty alcohol-polyoxyethylene ether 0.7; Polyoxyethylene glycol 2.0;
Thiocarbamide 1.1; Thiazolidine thioketones 0.03;
Ethylene thiourea 0.25; 2-mercaptobenzoimidazole 0.05;
Methionine(Met) 0.5; Sodium polydithio-dipropyl sulfonate 0.7;
Benzotriazole 0.2; Ethanol 20;
Formaldehyde 25; Acetone 0.7;
Strong by green B 0.02; Copper sulfate 2.0.
(11) prescription 11:
Fatty alcohol-polyoxyethylene ether 0.2～0.5; Polyoxyethylene glycol 0.5～5.0;
Thiocarbamide 0.2～2.0; Ethylene thiourea 0.1～0.8;
2-mercaptobenzoimidazole 0.01～0.1; Methionine(Met) 0.05～1.5;
Sodium polydithio-dipropyl sulfonate 0.2～1.5; Benzotriazole 0.1～0.5;
Methyl alcohol 10～40; Formaldehyde 5～50;
Ben Yajiaji ketone 0.2～0.8; Strong by green B 0.01～0.05;
Methylene blue 0.01～0.05; Copper sulfate 0.5～3.0
Being embodied as of prescription 11:
Prescription 11-1:
Fatty alcohol-polyoxyethylene ether 0.2; Polyoxyethylene glycol 0.5;
Thiocarbamide 0.2; Ethylene thiourea 0.1;
2-mercaptobenzoimidazole 0.01; Methionine(Met) 0.05;
Sodium polydithio-dipropyl sulfonate 0.2; Benzotriazole 0.1;
Methyl alcohol 10; Formaldehyde 5;
Ben Yajiaji ketone 0.2; Strong by green B 0.01;
Methylene blue 0.01; Copper sulfate 0.5
Prescription 11-2
Fatty alcohol-polyoxyethylene ether 0.5; Polyoxyethylene glycol 5.0;
Thiocarbamide 2.0; Ethylene thiourea 0.8;
2-mercaptobenzoimidazole 0.1; Methionine(Met) 1.5;
Sodium polydithio-dipropyl sulfonate 1.5; Benzotriazole 0.5;
Methyl alcohol 40; Formaldehyde 50;
Ben Yajiaji ketone 0.8; Strong by green B 0.05;
Methylene blue 0.05; Copper sulfate 3.0.
Prescription 11-3
Fatty alcohol-polyoxyethylene ether 0.3; Polyoxyethylene glycol 2.0;
Thiocarbamide 0.9; Ethylene thiourea 0.6;
2-mercaptobenzoimidazole 0.06; Methionine(Met) 0.9;
Sodium polydithio-dipropyl sulfonate 1.2; Benzotriazole 0.33;
Methyl alcohol 30; Formaldehyde 35;
Ben Yajiaji ketone 0.6; Strong by green B 0.03;
Methylene blue 0.03; Copper sulfate 2.5.
Prescription 11-4
Fatty alcohol-polyoxyethylene ether 0.4; Polyoxyethylene glycol 3.5;
Thiocarbamide 1.2; Ethylene thiourea 0.5;
2-mercaptobenzoimidazole 0.04; Methionine(Met) 1.2;
Sodium polydithio-dipropyl sulfonate 0.7; Benzotriazole 0.27;
Methyl alcohol 20; Formaldehyde 45;
Ben Yajiaji ketone 0.4; Strong by green B 0.04;
Methylene blue 0.04; Copper sulfate 2.0
Prescription 12
Fatty alcohol-polyoxyethylene ether 0.1～0.5; Polyoxyethylene glycol 0.5～5.0;
Thiocarbamide 0.3～3.0; Thiazolidine thioketones 0.05～0.5;
2-mercaptobenzoimidazole 0.01～0.1; Methionine(Met) 0.05～1.5;
Sodium polydithio-dipropyl sulfonate 0.2～2.0; Ethanol 5～30;
Formaldehyde 5～50; Acetone 0.5～2;
Methylene blue 0.01～0.05; Methyl violet 0.01～0.05;
Copper sulfate 0.5～3.0
The concrete mode of prescription 12 is:
Prescription 12-1
Fatty alcohol-polyoxyethylene ether 0.1; Polyoxyethylene glycol 0.5;
Thiocarbamide 0.3; Thiazolidine thioketones 0.05;
2-mercaptobenzoimidazole 0.01; Methionine(Met) 0.05;
Sodium polydithio-dipropyl sulfonate 0.2; Ethanol 5;
Formaldehyde 5; Acetone 0.5;
Methylene blue 0.01; Methyl violet 0.01
Copper sulfate 0.5
Prescription 12-2
Fatty alcohol-polyoxyethylene ether 0.5; Polyoxyethylene glycol 5.0;
Thiocarbamide 3.0; Thiazolidine thioketones 0.5;
2-mercaptobenzoimidazole 0.1; Methionine(Met) 1.5;
Sodium polydithio-dipropyl sulfonate 2.0; Ethanol 30;
Formaldehyde 50; Acetone 2;
Methylene blue 0.05; Methyl violet 0.05
Copper sulfate 3.0
Prescription 12-3
Fatty alcohol-polyoxyethylene ether 0.3; Polyoxyethylene glycol 2.5;
Thiocarbamide 2.3; Thiazolidine thioketones 0.35;
2-mercaptobenzoimidazole 0.06; Methionine(Met) 0.85;
Sodium polydithio-dipropyl sulfonate 1.2; Ethanol 20;
Formaldehyde 30; Acetone 1.5;
Methylene blue 0.02; Methyl violet 0.03
Copper sulfate 2.5
Prescription 12-4
Fatty alcohol-polyoxyethylene ether 0.2; Polyoxyethylene glycol 3.5;
Thiocarbamide 2.3; Thiazolidine thioketones 0.3;
2-mercaptobenzoimidazole 0.05; Methionine(Met) 1.25;
Sodium polydithio-dipropyl sulfonate 0.7; Ethanol 10;
Formaldehyde 20; Acetone 1.2;
Methylene blue 0.03; Methyl violet 0.04
Copper sulfate 2.0
2, help the prescription of photo etching: specialize as of the present invention, additive help every liter of solution of photo etching dewater beyond contained raw material weight (unit: gram) can be as follows:
(1) prescription 1
Fatty alcohol-polyoxyethylene ether 0.2, Vanillin 0.02, methylene blue 0.1,36% concentrated hydrochloric acid 5.0, copper sulfate 3.0.
(2) prescription 2
Alkylphenol polyoxyethylene 0.8, formaldehyde 2.0, methyl violet 0.1,36% concentrated hydrochloric acid 8.0, zinc sulfate 5.0.
(3) prescription 3
Polyoxyethylene glycol 0.8, piperonal 0.5, methyne are green 0.1, tropeolin-D 0.03, cupric chloride 1.5, titanium sulfate 2.0,36% concentrated hydrochloric acid 10.0.
(4) prescription 4
Polypropylene glycol 1.5, o-chlorobenzaldehyde 0.3, methylene blue 0.1, zinc chloride 3.0, zinc sulfate 5.0, titanium sulfate 3.0.
(5) prescription 5
Polyethers 1.0, o-chlorobenzaldehyde 0.2, formaldehyde 8.0, phenolphthalein 0.1, nickelous chloride 2.5, cerous sulfate 1.0.
(6) prescription 6
Fatty alcohol-polyoxyethylene ether 1.0, alkylphenol polyoxyethylene 0.2, Vanillin 0.1, methylene blue 0.1, methyl violet 0.15, concentrated hydrochloric acid 8.5, copper sulfate 3.0, zinc sulfate 5.0.
(7) prescription 7
Fatty alcohol-polyoxyethylene ether 0.1, polypropylene glycol 1.0, o-chlorobenzaldehyde 0.2, formaldehyde 1.0, methylene blue 0.1, zinc chloride 2.0, zinc sulfate 3.0, titanium sulfate 2.0.
(8) prescription 8
Polyoxyethylene glycol 0.6, alkylphenol polyoxyethylene 0.8, piperonal 0.5, methyne are green 0.1, tropeolin-D 0.03, cupric chloride 2.5, formaldehyde 1.0, titanium sulfate 2.0
(9) prescription 9:
Fatty alcohol-polyoxyethylene ether 1.0, polyoxyethylene glycol 0.6, polypropylene glycol 0.5, o-chlorobenzaldehyde 0.5, formaldehyde 0.5, tropeolin-D 0.02, phenolphthalein 0.1, cupric chloride 1.5, zinc chloride 2.0, copper sulfate 3.0, sulfuric acid 2.0.
(10) prescription 10
Fatty alcohol-polyoxyethylene ether 0.06～0.55; Alkylphenol polyoxyethylene 0.05～0.5;
Formaldehyde 10～50; Tropeolin-D 0.005～0.02;
Tin protochloride 0.1～1.0 zinc sulfate 0.5～2.0;
36% concentrated hydrochloric acid 3～5
The concrete prescription of prescription 10 is:
Prescription 10-1:
Fatty alcohol-polyoxyethylene ether 0.06; Alkylphenol polyoxyethylene 0.05;
Formaldehyde 10; Tropeolin-D 0.005;
Tin protochloride 0.1 zinc sulfate 0.5;
36% concentrated hydrochloric acid 3
Prescription 10-2
Fatty alcohol-polyoxyethylene ether 0.55; Alkylphenol polyoxyethylene 0.5;
Formaldehyde 50; Tropeolin-D 0.02;
Tin protochloride 1.0 zinc sulfate 2.0;
36% concentrated hydrochloric acid 5
Prescription 10-3
Fatty alcohol-polyoxyethylene ether 0.36; Alkylphenol polyoxyethylene 0.35;
Formaldehyde 35; Tropeolin-D 0.015;
Tin protochloride 0.7 zinc sulfate 1.5;
36% concentrated hydrochloric acid 4
Prescription 10-4
Fatty alcohol-polyoxyethylene ether 0.26; Alkylphenol polyoxyethylene 0.25;
Formaldehyde 21; Tropeolin-D 0.009;
Tin protochloride 0.5 zinc sulfate 0.9;
36% concentrated hydrochloric acid 3.5
(10) prescription 11:
Fatty alcohol-polyoxyethylene ether 0.08～1.3; Formaldehyde 5～20;
Tropeolin-D 0.005～0.02; Nickelous chloride 0.1～2.0;
Zinc sulfate 0.5～5.0; % concentrated hydrochloric acid 3～5
The concrete prescription of prescription 11 is:
Prescription 11-1:
Fatty alcohol-polyoxyethylene ether 0.08; Formaldehyde 5;
Tropeolin-D 0.005; Nickelous chloride 0.1;
Zinc sulfate 0.5; 36% concentrated hydrochloric acid 3
Prescription 11-2
Fatty alcohol-polyoxyethylene ether 1.3; Formaldehyde 20;
Tropeolin-D 0.02; Nickelous chloride 2.0;
Zinc sulfate 5.0; 36% concentrated hydrochloric acid 5
Prescription 11-3
Fatty alcohol-polyoxyethylene ether 0.59; Formaldehyde 15;
Tropeolin-D 0.015; Nickelous chloride 1.1;
Zinc sulfate 3.5; 36% concentrated hydrochloric acid 4
Prescription 11-4
Fatty alcohol-polyoxyethylene ether 1.1; Formaldehyde 18;
Tropeolin-D 0.018; Nickelous chloride 1.5;
Zinc sulfate 4.5; 36% concentrated hydrochloric acid 4.3
(11) prescription 12:
Fatty alcohol-polyoxyethylene ether 0.21～1.05; Formaldehyde 10～30;
Tropeolin-D 0.005～0.02; Zinc sulfate 0.5～2.0;
36% concentrated hydrochloric acid 3～6
The concrete prescription of prescription 12 is:
Prescription 12-1:
Fatty alcohol-polyoxyethylene ether 0.21; Formaldehyde 10;
Tropeolin-D 0.005; Zinc sulfate 0.5;
36% concentrated hydrochloric acid 3
Prescription 12-2
Fatty alcohol-polyoxyethylene ether 1.05; Formaldehyde 30;
Tropeolin-D 0.02; Zinc sulfate 2.0;
36% concentrated hydrochloric acid 6
Prescription 12-3
Fatty alcohol-polyoxyethylene ether 0.61; Formaldehyde 20;
Tropeolin-D 0.015; Zinc sulfate 1.2;
36% concentrated hydrochloric acid 4.5
Prescription 12-4
Fatty alcohol-polyoxyethylene ether 0.9; Formaldehyde 25;
Tropeolin-D 0.018; Zinc sulfate 1.7;
36% concentrated hydrochloric acid 5
Two, electroplating technology process
Adopt the plating flow process of the steel part of the direct strike copper plating technique of acidity of the present invention to be:
(1) part to be plated is carried out electrochemical deoiling, rust cleaning operation;
(2) part washing to be plated, washing again after the alkaline electrolysis oil removing;
(3) weak sulfuric acid activation is to part to be plated;
(4) washing;
(5) acid directly pre-copper facing;
(6) washing;
(7) acid bright copper plating is to finished product.
Wherein pre-electric electroplating technology prescription and working conditions: adopt the thick cold-rolling mild steel plate of 5 * 5cm 0.2mm to electroplate.
1, pre-electroplating technology (1)
Get in the above-mentioned additive key light agent prescription 1 in the prescription to the prescription 12-4 each prescription and help prescription 1 in the photo etching prescription to each prescription sampling respectively of prescription 12-4, according to key light agent prescription 1 with help photo etching prescription 1, key light agent prescription 2 and help photo etching prescription 2, key light agent prescription 3 and help photo etching prescription 3, until key light agent prescription 12-4 with help photo etching prescription 12-4 corresponding, totally 21 prescriptions are by electroplating in advance as following table:
| Composition and technological specification | Scope |
| Cupric sulfate pentahydrate (g/L) | 5 |
| Sulfuric acid (g/L) | 20 |
| Additive A (key light agent) (g/L) | 20 |
| Additive B (helping photo etching) (g/L) | 20 |
| Temperature (℃) | 20-25 |
| Cathode current density (A/dm 2) | 0.5 |
| Cathodic deposition speed (1A/dm 2The time) (μ/min) | 0.2～0.25 |
| Anode | Phosphor-copper |
| Cathode area: annode area | 1∶1.5 |
| Negative electrode moves | Need |
| Filter | Intermittently |
2, pre-electroplating technology (2)
Get in the above-mentioned additive key light agent prescription 1 in the prescription to the prescription 12-4 each prescription and help prescription 1 in the photo etching prescription to each prescription sampling respectively of prescription 12-4, according to key light agent prescription 1 with help photo etching prescription 1, key light agent prescription 2 and help photo etching prescription 2, key light agent prescription 3 and help photo etching prescription 3, until key light agent prescription 12-4 with help photo etching prescription 12-4 corresponding, totally 21 prescriptions are by electroplating in advance as following table:
| Composition and technological specification | Scope |
| Cupric sulfate pentahydrate (g/L) | 25 |
| Sulfuric acid (g/L) | 90 |
| Additive A (key light agent) (g/L) | 30 |
| Additive B (helping photo etching) (g/L) | 25 |
| Temperature (℃) | 38-40 |
| Cathode current density (A/dm 2) | 1.5 |
| Cathodic deposition speed (1A/dm 2The time) (μ/min) | 0.25 |
| Anode | Graphite |
| Cathode area: annode area | 1∶～2 |
| Negative electrode moves | Need |
| Filter | Continuously |
3, pre-electroplating technology (3)
Get in the above-mentioned additive key light agent prescription 1 in the prescription to the prescription 12-4 each prescription and help prescription 1 in the photo etching prescription to each prescription sampling respectively of prescription 12-4, according to key light agent prescription 1 with help photo etching prescription 1, key light agent prescription 2 and help photo etching prescription 2, key light agent prescription 3 and help photo etching prescription 3, until key light agent prescription 12-4 with help photo etching prescription 12-4 corresponding, totally 21 prescriptions are by electroplating in advance as following table:
| Composition and technological specification | Scope |
| Cupric sulfate pentahydrate (g/L) | 18 |
| Sulfuric acid (g/L) | 75 |
| Additive A (key light agent) (g/L) | 25 |
| Additive B (helping photo etching) (g/L) | 20 |
| Temperature (℃) | 30～35 |
| Cathode current density (A/dm 2) | 1.0 |
| Cathodic deposition speed (1A/dm 2The time) (μ/min) | 0.25 |
| Anode | Graphite |
| Cathode area: annode area | 1∶1.5 |
| Negative electrode moves | Need |
| Filter | Intermittently |
Part after the directly pre-copper facing of acidity is carried out acid bright copper plating again, can obtain the copper coating of light fully behind the acid copper-plating, obtain the 1-63 test specimen.
Three, coating experiment
1. binding force of cladding material test
In the experimental technique formula range, electroplate with the thick cold-rolling mild steel plate of 5 * 5cm 0.2mm.With the 1-63 test specimen by " GB235-82 reverse bend test of metal method " alternating bending to fracture and copper-plated test piece is heated to 300 ± 25 ℃ after immediately at two kinds of experimental methods of room temperature water chilling, coating is non-foaming, does not peel in conjunction with well.
2. coating ferroxyl test
Current density is 0.5A/dm in pre-plating process (1) formula range
25 * 5cm mild steel plate test specimen, clean up after the plating and dry up filter paper with 1 * 1cm, the dipping Tripotassium iron hexacyanide 10 grams per liters, sodium-chlor 20 grams per liter experimental liquids are close in the test piece, calculate every square centimeter of Bluepoint number after 20 minutes.Through weighted mean, specific as follows:
As seen, adopt plating piece of the present invention to have hole hardly, close the symbol requirement.
3. cathode efficiency test
Press 4 test specimens of the prescription 10 of pre-plating process (1),, adopt copper voltameter method to measure different D through weighted mean
KThe direct copper-plated cathode efficiency of following acidity.
4. covering power test
At 4 prescriptions of pre-plating process (1) prescription 10, cut-off directly is 2; 4; 6mm, the iron pipe of hole depth 50mm one end blind hole was electroplated 5 minutes.
Adopt additive of the present invention, can be under acid solution, directly workpiece to be plated is carried out the pre-plating process of direct copper plating, coating and iron-based body adhesion are good, copper coating when the copper coating of preplating again can be with acid bright copper plating fully in conjunction with in, thereby really solve the problem of the adhesion between iron-based body and the copper coating. In addition, the plating bath cost, only need 4～5 yuan/liter, compare with existing cyanide-free alkaline copper plating, only be its 1/4th to sixth, and, but the waste water Direct precipitation is processed, and the metal complex waste water of cyanide-free alkaline copper plating want after the contact break reaction could precipitate and separate, cost is also than height of the present invention. Utilize the complete low toxicity of electroplate liquid of the present invention, the environmental protection that is highly advantageous to is the clearer production technology of national encourage growth. Solution composition is simple, processing ease, and stable performance, cathode efficiency 80～97% can be used for a long time.
Claims (1)
1. a copper-plating technique preplating additive is characterized in that comprising the key light agent and helps two parts of photo etching, and wherein each component is following three kinds of situations by weight in every liter of key light agent aqueous solution:
(1)
Fatty alcohol-polyoxyethylene ether 0.2～1.0 gram, polyoxyethylene glycol 0.5～5.0 gram,
Thiocarbamide 0.2～2.0 gram, thiazolidine thioketones 0.01～0.1 gram,
Ethylene thiourea 0.05～0.5 gram, 2-mercaptobenzoimidazole 0.01～0.1 gram,
Methionine(Met) 0.1～1.0 gram, sodium polydithio-dipropyl sulfonate 0.2～1.0 gram,
Benzotriazole 0.1～0.5 gram, ethanol 5～30 grams,
Formaldehyde 5～50 grams, acetone 0.5～2 gram,
Strong green B 0.01～0.05 gram, copper sulfate 0.5～3.0 gram taken
Water is surplus;
(2)
Fatty alcohol-polyoxyethylene ether 0.2～0.5 gram, polyoxyethylene glycol 0.5～5.0 gram,
Thiocarbamide 0.2～2.0 gram, ethylene thiourea 0.1～0.8 gram,
2-mercaptobenzoimidazole 0.01～0.1 gram, methionine(Met) 0.05～1.5 gram,
Sodium polydithio-dipropyl sulfonate 0.2～1.5 gram, benzotriazole 0.1～0.5 gram,
Methyl alcohol 10～40 grams, formaldehyde 5～50 grams,
Ben Yajiaji ketone 0.2～0.8 gram, strong by green B 0.01～0.05 gram,
Methylene blue 0.01～0.05 gram, copper sulfate 0.5～3.0 gram;
Water is surplus;
(3)
Fatty alcohol-polyoxyethylene ether 0.1～0.5 gram, polyoxyethylene glycol 0.5～5.0 gram,
Thiocarbamide 0.3～3.0 gram, thiazolidine thioketones 0.05～0.5 gram,
2-mercaptobenzoimidazole 0.01～0.1 gram, methionine(Met) 0.05～1.5 gram,
Sodium polydithio-dipropyl sulfonate 0.2～2.0 gram, ethanol 5～30 grams,
Formaldehyde 5～50 grams, acetone 0.5～2 gram,
Methylene blue 0.01～0.05 gram, methyl violet 0.01～0.05 gram,
Copper sulfate 0.5～3.0 gram;
Water is surplus;
Help in the photo etching aqueous solution each component to be following three kinds of situations by weight at every liter:
(1)
Fatty alcohol-polyoxyethylene ether 0.06～0.55 gram, alkylphenol polyoxyethylene 0.05～0.5 gram,
Formaldehyde 10～50 grams, tropeolin-D 0.005～0.02 gram,
Tin protochloride 0.1～1.0 gram, zinc sulfate 0.5～2.0 gram,
36% concentrated hydrochloric acid, 3～5 grams;
Water is surplus;
(2)
Fatty alcohol-polyoxyethylene ether 0.06～0.55 gram, alkylphenol polyoxyethylene 0.05～0.5 gram,
Formaldehyde 10～50 grams, tropeolin-D 0.005～0.02 gram,
Tin protochloride 0.1～1.0 gram, zinc sulfate 0.5～2.0 gram,
36% concentrated hydrochloric acid, 3～5 grams;
Water is surplus;
(3)
Fatty alcohol-polyoxyethylene ether 0.06～0.55 gram, alkylphenol polyoxyethylene 0.05～0.5 gram,
Formaldehyde 10～50 grams, tropeolin-D 0.005～0.02 gram,
Tin protochloride 0.1～1.0 gram, zinc sulfate 0.5～2.0 gram,
36% concentrated hydrochloric acid, 3～5 grams;
Water is surplus.
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| Application Number | Priority Date | Filing Date | Title |
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| CN2008100258889A CN101302635B (en) | 2008-01-18 | 2008-01-18 | Steel member acidic electroplating additive for copper pre-plating and pre-plating process |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2008100258889A CN101302635B (en) | 2008-01-18 | 2008-01-18 | Steel member acidic electroplating additive for copper pre-plating and pre-plating process |
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| CN101302635B true CN101302635B (en) | 2010-12-08 |
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