Summary of the invention
For above-mentioned technical problem, an object of the present invention is to provide a kind of low foam carrier brightening agent that contains the non-ionic type organic silicon surfactant;
Another object of the present invention is to provide a kind of softening agent by the composite gained of above-mentioned low foam carrier brightening agent;
Another object of the present invention is to provide a kind of brightening agent by the composite gained of above-mentioned low foam carrier brightening agent;
Another object of the present invention is to provide a kind of by above-mentioned softening agent and the composite Additives in Potassium Chloride Zinc Plating Bath obtained of brightening agent;
Another object of the present invention is to provide a kind of technique of utilizing above-mentioned Additives in Potassium Chloride Zinc Plating Bath to carry out Potassium Chloride Zinc Plating.
The technical solution adopted in the present invention is as follows:
A kind of low foam carrier brightening agent, calculate by mass percentage, contains 90~95% nonionic surface active agent and 5~10% non-ionic type organic silicon surfactant.
Preferably, shown in the structural formula as I of described non-ionic type organic silicon surfactant:
Wherein, R=O (C
2H
4O)
a(C
3H
6O)
b(C
2H
4O)
cCH
3, a=16, b=10, c=15; N=7~9.
Preferably, described nonionic surface active agent can be at least a in polyoxyethylene octylphenol ether (EO 50~100), Dodecyl Polyoxyethylene Ether (EO 50~100), isomerous tridecanol polyoxyethylene ether (EO 50~100).
A kind of softening agent, measure by mass percentage, contains following component: low foam carrier brightening agent 10~15%, and Sodium Benzoate 6~15%, solubility promoter 5~10%, surplus is water; Described solubility promoter is at least a in methyl alcohol, ethanol, ethylene glycol ethyl ether, Virahol.
A kind of brightening agent, measure by mass percentage, contains following component: main brightener 3-6%, and low foam carrier brightening agent 5~10%, solubility promoter 5~10%, surplus is water; Described solubility promoter is at least a in methyl alcohol, ethanol, ethylene glycol ethyl ether, Virahol.
Preferably, described main brightener is at least a in the reactant of o-chlorobenzaldehyde, BENZALACETONE, o-chlorobenzaldehyde and BENZALACETONE, and wherein, the chemical formula of the reactant of described o-chlorobenzaldehyde and BENZALACETONE is as shown in II:
A kind of Additives in Potassium Chloride Zinc Plating Bath, comprise above-mentioned softening agent and brightening agent.
A kind of potassium chloride zinc plating process, is characterized in that, in electroplate liquid used, contains above-mentioned Additives in Potassium Chloride Zinc Plating Bath.
Preferably, the electroplating technical conditions of described Potassium Chloride Zinc Plating is: temperature is 10~50 ℃, pH4.8~5.6, and the rack plating current density is 0.5~4 ampere/square decimeter, barrel plating strength of current is 100~200 amperes/every barrel.
Preferably, in electroplating process, electroplate liquid adopts pressurized air to stir and continuous filtration, per hour electroplate liquid is filtered 1~4 time.
Beneficial effect of the present invention is:
(1) use the low bubble of plating solution of Potassium Chloride Zinc Plating softening agent of the present invention and brightening agent, can stir with pressurized air, allow current density large, Huo Shi groove test current can be brought up to 2A from 1A, the full sheet light of Huo Shi groove test piece, in production, the permission current density can be from 0.5-2A/dm
2Bring up to 0.5-4A/dm
2, sedimentation velocity is fast, at Dk=3A/dm
2The time, average deposition speed reaches 55 μ/h;
(2) by pneumatic blending, can be the main harmful impurity F e in plating solution
2+Be oxidized to Fe
3+, and remove by the continuous filtration of tank liquor;
(3) the depletion of additive amount is low, compares with the first-generation, s-generation potassium chloride zinc plating process, and the depletion of additive amount can reduce 30-50%;
(4) zinc coating organism folder is attached few; zinc coating coordinates the trivalent chromium bright blue passivation with protective material; solidity to corrosion (neutral salt spray test) >=96 hour; coordinate the trivalent chromium colorful passivation with protective material; solidity to corrosion (neutral salt spray test) >=160 hour, surpass cyanide zinc plating wastewater and without the solidity to corrosion of cyanogen alkali zinc trivalent chromium passivation.
Embodiment
The present invention is further illustrated below in conjunction with embodiment, but be not limited to this.If no special instructions, " % " used in following examples all refers to mass percent.
Use the low bubble of plating solution of Potassium Chloride Zinc Plating softening agent of the present invention and brightening agent, can stir with pressurized air, allow current density large, Huo Shi groove test current can be brought up to 2A from 1A, the full sheet light of Huo Shi groove test piece, in production, the permission current density can be from 0.5-2A/dm
2Bring up to 0.5-4A/dm
2, sedimentation velocity is fast, at Dk=3A/dm
2The time, average deposition speed reaches 55 μ/h.Use softening agent of the present invention and brightening agent to carry out electroplate liquid formulation and the processing condition of potassium chloride zinc plating process as shown in table 1.Certainly, in those skilled in the art's understanding scope, softening agent of the present invention and brightening agent also can be used for other potassium chloride zinc plating process.
The electroplate liquid formulation of table 1 potassium chloride zinc plating process and processing condition
Softening agent forms: low foam carrier brightening agent 10~15%, Sodium Benzoate 6~15%, solubility promoter 5~10%, and surplus is water;
Brightening agent forms: main brightener 3~6%, low foam carrier brightening agent 5~10%, solubility promoter 5~10%, surplus are water;
Wherein, above-mentioned low foam carrier brightening agent is comprised of nonionic surface active agent and non-ionic type organic silicon surfactant, described nonionic surface active agent is polyoxyethylene octylphenol ether (EO 50~100), Dodecyl Polyoxyethylene Ether (EO 50~100), at least a in isomerous tridecanol polyoxyethylene ether (EO 50~100); Shown in the structural formula as I of described non-ionic type organic silicon surfactant:
Wherein, R=O (C
2H
4O)
a(C
3H
6O)
b(C
2H
4O)
cCH
3, a=16, b=10, c=15; N=7~9.
Described main brightener is at least a in the reactant of o-chlorobenzaldehyde, BENZALACETONE, o-chlorobenzaldehyde and BENZALACETONE, and wherein, the chemical formula of the reactant of described o-chlorobenzaldehyde and BENZALACETONE is as shown in II:
Described solubility promoter is at least a in methyl alcohol, ethanol, ethylene glycol ethyl ether, Virahol.
The concrete operation step that the electroplate liquid of use table 1 carries out potassium chloride zinc plating process is:
Galvanizing process flow:
Zinc-plated part reaches the standard grade → and electrochemical deoiling → ultrasonic wave oil removing → catholyte oil removing, scale removal → washing * 2 → acid deoiling → washing * 2 → anode electrolysis oil removing → washing * 2 → acid activation → washing * 2 → Potassium Chloride Zinc Plating → washing * 2 → ultrasonic wave water washing → rare nitric acid bright dipping → washing * 2 → SF-571 trivalent chromium coloured silk blunt (or the SF-572 trivalent chromium bright blue is blunt) → washing * 2 → pure water wash → hot water wash (50 ℃) → blowing → oven dry → lower extension.
Embodiment 1
Electroplate liquid formulation and the processing condition of potassium chloride zinc plating process are as shown in table 2:
Table 2
Softening agent forms: and 10% low foam carrier brightening agent (comprise 0.5% non-ionic type organic silicon surfactant, 9.5% isomerous tridecanol polyoxyethylene ether, EO=100), 6% Sodium Benzoate, 5% methyl alcohol, surplus is water;
Brightening agent forms: 3% o-chlorobenzaldehyde, 5.3% low foam carrier brightening agent (comprise 0.3% non-ionic type organic silicon surfactant, 5% isomerous tridecanol polyoxyethylene ether, EO=50), 5% methyl alcohol, surplus is water;
Wherein, the structural formula of above-mentioned non-ionic type organic silicon surfactant is:
R=O(C
2H
4O)
a(C
3H
6O)
b(C
2H
4O)
cCH
3,a=16,b=10,c=15;n=7。
Adopt Potassium Chloride Zinc Plating electroplate liquid formulation and the processing condition of embodiment 1 to carry out the test of Huo Shi groove, plating solution does not carry out the pressurized air stirring, and the full sheet crow of Huo Shi groove test piece light is gloomy, and plating solution adopts pressurized air to stir, the full sheet light of Huo Shi groove test piece.
Embodiment 2
Electroplate liquid formulation and the processing condition of potassium chloride zinc plating process are as shown in table 3:
Table 3
Softening agent forms: 10.8% low foam carrier brightening agent (comprising 0.8% non-ionic type organic silicon surfactant, 10% isomerous tridecanol polyoxyethylene ether EO=100), and 7% Sodium Benzoate, 6% ethanol, surplus is water;
Brightening agent forms: 4% BENZALACETONE, 6.4% low foam carrier brightening agent (comprising 0.4% non-ionic type organic silicon surfactant, 6% isomerous tridecanol polyoxyethylene ether EO=50), and 6% ethanol, surplus is water;
Wherein, the structural formula of above-mentioned non-ionic type organic silicon surfactant is:
R=O(C
2H
4O)
a(C
3H
6O)
b(C
2H
4O)
cCH
3,a=16,b=10,c=15;n=8。
Adopt Potassium Chloride Zinc Plating electroplate liquid formulation and the processing condition of embodiment 2 to carry out the test of Huo Shi groove, plating solution does not carry out the pressurized air stirring, and the full sheet crow of Huo Shi groove test piece light is gloomy, and plating solution adopts pressurized air to stir, the full sheet light of Huo Shi groove test piece.
Embodiment 3
Electroplate liquid formulation and the processing condition of potassium chloride zinc plating process are as shown in table 4:
Table 4
Softening agent forms: 10% low foam carrier brightening agent (comprising 0.7% non-ionic type organic silicon surfactant, 9.3% polyoxyethylene octylphenol ether EO=100), and 8% Sodium Benzoate, 8% ethylene glycol ethyl ether, surplus is water;
Brightening agent forms: 5% o-chlorobenzaldehyde and BENZALACETONE reactant, 10% low foam carrier brightening agent (comprising 0.5% non-ionic type organic silicon surfactant, 9.5% Dodecyl Polyoxyethylene Ether EO=50), 7% ethylene glycol ethyl ether, surplus are water;
Wherein, the structural formula of o-chlorobenzaldehyde and BENZALACETONE reactant is:
The structural formula of non-ionic type organic silicon surfactant is:
R=O(C
2H
4O)
a(C
3H
6O)
b(C
2H
4O)
cCH
3,a=16,b=10,c=15;n=9。
Adopt Potassium Chloride Zinc Plating electroplate liquid formulation and the processing condition of embodiment 3 to carry out the test of Huo Shi groove, plating solution does not carry out the pressurized air stirring, and the full sheet crow of Huo Shi groove test piece light is gloomy, and plating solution adopts pressurized air to stir, the full sheet light of Huo Shi groove test piece.
Embodiment 4
Electroplate liquid formulation and the processing condition of potassium chloride zinc plating process are as shown in table 5:
Table 5
Softening agent forms: 12.6% low foam carrier brightening agent (comprising 1% non-ionic type organic silicon surfactant, 11.6% polyoxyethylene octylphenol ether EO=100), and 10% Sodium Benzoate, 8% Virahol, surplus is water;
Brightening agent forms: 4% o-chlorobenzaldehyde, 2% BENZALACETONE, 10% low foam carrier brightening agent (comprising 0.3% non-ionic type organic silicon surfactant, 9.7% polyoxyethylene octylphenol ether EO=50), and 8% Virahol, surplus is water;
Wherein, the structural formula of non-ionic type organic silicon surfactant is:
R=O(C
2H
4O)
a(C
3H
6O)
b(C
2H
4O)
cCH
3,n=9,a=16,b=10,c=15。
Adopt Potassium Chloride Zinc Plating electroplate liquid formulation and the processing condition of embodiment 4 to carry out the test of Huo Shi groove, plating solution does not carry out the pressurized air stirring, and the full sheet crow of Huo Shi groove test piece light is gloomy, and plating solution adopts pressurized air to stir, the full sheet light of Huo Shi groove test piece.
Implement 5
Electroplate liquid formulation and the processing condition of potassium chloride zinc plating process are as shown in table 6
Table 6
Softening agent forms: 15% low foam carrier brightening agent (comprising 1% non-ionic type organic silicon surfactant, 14% Dodecyl Polyoxyethylene Ether EO=100), and 15% Sodium Benzoate, 10% ethylene glycol ethyl ether, surplus is water;
Brightening agent forms: 6% BENZALACETONE, and 8% low foam carrier brightening agent (comprising 0.4% non-ionic type organic silicon surfactant, 7.6% Dodecyl Polyoxyethylene Ether EO=50), 10% ethylene glycol ethyl ether, surplus is water;
Wherein, the structural formula of non-ionic type organic silicon surfactant is:
R=O(C
2H
4O)
a(C
3H
6O)
b(C
2H
4O)
cCH
3,a=16,b=10,c=15;n=8。
Adopt Potassium Chloride Zinc Plating electroplate liquid formulation and the processing condition of embodiment 5 to carry out the test of Huo Shi groove, plating solution does not carry out the pressurized air stirring, and the full sheet crow of Huo Shi groove test piece light is gloomy, and plating solution adopts pressurized air to stir, the full sheet light of Huo Shi groove test piece.
The performance test of the embodiment of the present invention 1~5 electroplate liquid used:
1. current efficiency: adopt weighting method, current density 1A/dm
2, current efficiency is greater than 97.86%.
2. sedimentation velocity: at Dk=3A/dm
2, average deposition speed is 55 μ m/h.
3. solution dispersibility: the test of Huo Shi groove, electric current 1A, by 8 method test results: 39.09%.
4. covering power: testing method is the endoporus method, and its inwall all has coating.
The embodiment of the present invention 1~5 gained coating performance test:
1, binding force of cladding material test
(1) pliability test:
(100 * 50mm) through pre-treatment, adopts the zinc-plated 8-10 μ of the zincincation m of embodiment 1~5, and the test piece alternating bending of coating, to fracture, is split and located without the dezincify layer, and coating does not separate with matrix to test two light A3 steel plates that employing thickness is 1mm.
(2) thermal shock test:
It is workpiece that the stamping forming loudspeaker of soft steel are adopted in experiment, and zinc-plated 8-10 μ m after pre-treatment was placed on the workpiece of coating in the baking oven of 200 ℃ insulation 1 hour, after taking-up, dropped into immediately in cold water, and coating does not bubble and peels.
2, the solidity to corrosion of zinc coating
(1) the stamping forming loudspeaker of experiment employing soft steel are workpiece, after pre-treatment, zinc-plated 8-10 μ m, through rare nitric acid bright dipping, adopt the three SF-571 trivalent chromium colour passivator passivation that inspire confidence in company, add sealing, timeliness is carried out neutral salt spray test after 48 hours, through 160 hours, its surface white rust<5% is qualified.
(2) experiment workpiece and zincincation be with (1), zinc-platedly by rare nitric acid, shares the same light, and adopts the three SF-572 trivalent chromium bright blue passivator passivation that inspire confidence in company to add sealing, timeliness is carried out neutral salt spray test after 48 hours, through 96 hours, its surface white rust<5% is qualified.