CN111349953B - Environment-friendly carrier-free water-based sulfate zinc plating additive - Google Patents
Environment-friendly carrier-free water-based sulfate zinc plating additive Download PDFInfo
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- CN111349953B CN111349953B CN201911053580.XA CN201911053580A CN111349953B CN 111349953 B CN111349953 B CN 111349953B CN 201911053580 A CN201911053580 A CN 201911053580A CN 111349953 B CN111349953 B CN 111349953B
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D3/00—Electroplating: Baths therefor
- C25D3/02—Electroplating: Baths therefor from solutions
- C25D3/22—Electroplating: Baths therefor from solutions of zinc
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D7/00—Electroplating characterised by the article coated
- C25D7/06—Wires; Strips; Foils
- C25D7/0614—Strips or foils
Abstract
The invention discloses an environment-friendly carrier-free water-based sulfate zinc-plating additive, which comprises the following raw materials in percentage by weight: the additive comprises 1-5% of water-soluble aromatic aldehyde organic compound, 5-20% of water-soluble organic compound containing conjugated ketene structure, 1-5% of nicotinic acid, 2-10% of sodium benzoate, 5-20% of sodium polycarboxylate polarization agent, 5-10% of methanol and the balance of water. The invention adopts water-soluble organic compounds as additive components, avoids the defect caused by solubilizing oil-soluble organic matters by nonionic or anionic surfactants, and reduces the COD discharge amount of working solution foam and waste water. The additive of the invention has the characteristics of good conductivity, fast light emission, high current efficiency and good brightness of the traditional sulfate galvanizing, and also has the characteristics of white and bright plating layer without yellowing, good dispersibility, good deep galvanizing performance, low foam, small brittleness of thick galvanizing and no graying after long-term storage.
Description
Technical Field
The invention relates to the technical field of metal corrosion protection and surface, in particular to an environment-friendly carrier-free water-based sulfate zinc plating additive.
Background
Sulfate galvanizing can be traced back to 30 years of the last century in China at the earliest time, and is mainly used for plating iron wires in Shanghai facilities at that time, and the early sulfate galvanizing mainly uses gum arabic, natural peach gum, gelatin, dextrin and the like as brightening agents. In recent years, the Wuhan Sail electroplating technology company Limited develops the additive of 'sulphur Zinc-30' and 'sulphur Zinc-75', which completely ends the history of mainly using natural products as brightening agents, and the brightening agents are changed into main brightening agents made of raw materials such as aromatic sulfonate, aromatic aldehyde ketone and the like, so that mirror surface bright coatings are successfully obtained, and the substances are also commonly used in chloride galvanizing brightening agents.
It cannot be denied, however, that such additives also have serious disadvantages. Especially, the main brightener used by the method is aromatic sulfonate, aromatic aldehyde ketone and other raw materials, has strong pungent smell, is harmful to the skin and eyes of operators, and pollutes water sources and soil; furthermore, the raw materials are all oil-soluble organic compounds, and before the use, the raw materials are fully emulsified by 10-15 times of nonionic or anionic surfactant. Considering the addition and use of newly-prepared galvanizing bath solution and the subsequent supplement addition in the production process, the bath solution contains a large amount of surface active substances with abundant foam, so that the electro-galvanizing layer has large brittleness due to a large amount of surface active substances, the bonding force between the electro-galvanizing layer and a workpiece substrate is poor, and finally the corrosion resistance of a zinc plating layer to the workpiece is reduced; secondly, in the cleaning process of the plating layer, because the surface of the plating layer has too much foam, a large amount of water is needed, and the plating layer is difficult to clean, and the subsequent procedures of light emission, passivation and the like are influenced. Finally, when the zinc-plating bath is treated, a large amount of waste water which is rich in foam and difficult to treat is generated, the COD discharge amount is extremely high, and a water source and soil are seriously polluted.
Disclosure of Invention
The invention provides an environment-friendly carrier-free water-based sulfate galvanizing additive, which aims to solve the problems in the background technology.
The invention provides an environment-friendly carrier-free water-based sulfate zinc-plating additive, which comprises the following raw materials in percentage by weight: the additive comprises 1-5% of water-soluble aromatic aldehyde organic compound, 5-20% of water-soluble organic compound containing conjugated ketene structure, 1-5% of nicotinic acid, 2-10% of sodium benzoate, 5-20% of sodium polycarboxylate polarization agent, 5-10% of methanol and the balance of water.
Preferably, the water-soluble aromatic aldehyde organic compound in the additive is one or a mixture of more of sodium o-chlorobenzaldehyde sulfonate, 2, 4-dihydroxybenzaldehyde and sodium p-methoxybenzaldehyde sulfonate.
Preferably, the water-soluble organic compound containing the conjugated ketene structure in the additive is one or a mixture of more of 3-butene-2-ketone-4 sodium phenolate, sodium benzalacetone sulfonate, 1, 2-naphthoquinone-4-sodium sulfonate, 3,5,2 ' -trihydroxy diphenyl propenone and 3,5,2 ' -trihydroxy-4 ' -sulfo diphenyl propenone sodium salt.
The invention also provides a preparation method of the environment-friendly carrier-free water-based sulfate zinc-plating additive, which comprises the following specific steps:
s1, placing a water-soluble aromatic aldehyde ketone organic compound, a water-soluble organic compound containing a conjugated ketene structure, sodium benzoate and a sodium polycarboxylate polarization agent in a reaction vessel according to mass percentage, and dissolving the compounds in a proper amount of water;
s2, after S1 is finished, heating the temperature in the reaction vessel to 70-80 ℃, adding nicotinic acid and stirring until the nicotinic acid is completely dissolved;
s3, after the above materials are completely dissolved, cooling the temperature in the reaction vessel to room temperature, then adding methanol into the reaction vessel again, and finally quantifying the water to 100 percent.
Preferably, the additive is added into the sulfate galvanizing plating solution in an amount of 5-20 g/L.
Compared with the prior art, the invention has the beneficial effects that: the invention adopts water-soluble organic compounds as additive components, avoids the defect caused by solubilizing oil-soluble organic matters by nonionic or anionic surfactants, and reduces the COD discharge amount of working solution foam and waste water. The additive disclosed by the invention has the characteristics of good conductivity, high light-emitting speed, high current efficiency and good brightness of the traditional sulfate galvanizing, has the characteristics of white bright coating, no yellowing, good dispersibility, good deep galvanizing performance, low foam, small brittleness of galvanized thick coating and no graying after long-term storage, can obtain a bright coating with fine crystallization, good ductility and corrosion resistance, and is a safe, efficient and environment-friendly additive.
Drawings
FIG. 1 is a polarization diagram of the present invention.
In the figure: curve 1: a base liquid; curve 2: base liquid + example one additive 20 g/L.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The preparation process of the zinc plating solution is as follows:
1. the measured zinc sulphate is dissolved by warm water with total volume of 2/3
2. Dissolving boric acid in 80 deg.C hot water, stirring, adding into the above solution
3. Adding zinc powder 1g/L, stirring, standing for 2 hr for precipitation, and filtering
4. Supplementing water level, adding said additive into bath liquid according to a certain dosage
Specifically, when electroplating is performed:
hall cell test: a brass sheet 6X 10cm thick 2mm polished to a mirror surface by a cloth wheel was used as a cathode test piece. The Hull cell was placed in a constant temperature water bath (30-50 ℃ C.) and the test was carried out with the electrolytic zinc plate as the anode and at a constant current density. The pretreatment process of the plating piece comprises the following steps: alkaline degreasing → hot water rinsing → tap water rinsing → acid pickling activation → tap water rinsing → sulfate galvanizing → tap water rinsing → blow drying → performance test.
The steel strip electroplating process comprises the following steps: steel strip paying-off → heating and preheating → acid washing before plating → rinsing → 1# electroplating → 2# electroplating → 3# electroplating → 4# electroplating → plating solution recovery → soap solution cleaning → high-temperature drying → galvanized steel strip taking-up → finished product inspection → packaging and warehousing
Performance testing was performed with reference to the following method:
the dispersion performance of the plating solution is tested by adopting a JB/T7704.4 near-far cathode method, and the K value is 3;
the current efficiency of the plating solution is tested by adopting a copper coulometer method of JB/T7704.3, and the electrochemical equivalent of zinc is 1.220 g/(A.h) in the invention;
the main technical requirements and performance tests of the steel strip are in accordance with the regulations of the industrial standard YB/T024-92 steel strip for armored cables of the department of metallurgical industry; wherein the content of the first and second substances,
directly measuring the thickness of the plating layer by adopting an HHC-02 type magnetic resistance plating layer thickness meter;
the zinc layer weight of the galvanized steel strip was indirectly measured according to the regulations of GB1839 (where the total area of the coupons is coupon width x coupon length).
Example 1
The invention provides a preparation method of an environment-friendly carrier-free water-based sulfate zinc-plating additive, which comprises the following raw materials in percentage by weight: the additive contains 5% of sodium o-chlorobenzaldehyde sulfonate, 5% of 3,5, 2' -trihydroxy diphenyl propenone, 5% of nicotinic acid, 2% of sodium benzoate, 20% of sodium polycarboxylate polarization agent, 10% of methanol and the balance of water.
The invention also provides a preparation method of the environment-friendly carrier-free water-based sulfate zinc-plating additive, which comprises the following specific steps:
s1, placing the o-chlorobenzaldehyde sodium sulfonate, the 3,5, 2' -trihydroxy diphenyl propenone, the sodium benzoate and the polycarboxylate sodium salt polarization agent in a reaction vessel according to mass percentage, and dissolving the polarization agent by using a proper amount of water;
s2, after S1 is finished, heating the temperature in the reaction vessel to 70-80 ℃, adding nicotinic acid and stirring until the nicotinic acid is completely dissolved;
s3, after the above materials are completely dissolved, cooling the temperature in the reaction vessel to room temperature, then adding methanol into the reaction vessel again, and finally quantifying the water to 100 percent.
The electroplating process conditions are as follows: current density: 1A/dm2, temperature: electroplating 40 min at 25 ℃ and pH value of 5.0; through testing, the dispersing capacity of the plating solution is as follows: 52.06% (K — 3), current efficiency: 97.6 percent; according to electrochemical test results, the dispersion performance of the plating solution is equivalent to the current efficiency potassium salt zinc plating level.
The cathodic polarization curve of the bath was measured by potentiostat using model CHI 1200C. T is 25 ℃, and the scanning speed is 7 mv/s; the polarization curve is shown in figure 1. As can be seen from FIG. 1, after the additive is added, the precipitation potential of zinc ions is obviously shifted negatively, and the polarizability is obviously increased.
Example 2
The invention provides a preparation method of an environment-friendly carrier-free water-based sulfate zinc-plating additive, which comprises the following raw materials in percentage by weight: the additive contains 3% of 2, 4-dihydroxy benzaldehyde, 10% of 3-butene-2-ketone-4 sodium phenolate, 3% of nicotinic acid, 6% of sodium benzoate, 10% of a sodium polycarboxylate polarization agent, 8% of methanol and the balance of water.
The invention also provides a preparation method of the environment-friendly carrier-free water-based sulfate zinc-plating additive, which comprises the following specific steps:
s1, placing a water-soluble aromatic aldehyde ketone organic compound, a water-soluble organic compound containing a conjugated ketene structure, sodium benzoate and a sodium polycarboxylate polarization agent in a reaction vessel according to mass percentage, and dissolving the compounds in a proper amount of water;
s2, after S1 is finished, heating the temperature in the reaction vessel to 70-80 ℃, adding nicotinic acid and stirring until the nicotinic acid is completely dissolved;
s3, after the above materials are completely dissolved, cooling the temperature in the reaction vessel to room temperature, then adding methanol into the reaction vessel again, and finally quantifying the water to 100 percent.
The additive is added into the sulfate galvanizing plating solution by 10 g/L.
Example 3
The invention provides a preparation method of an environment-friendly carrier-free water-based sulfate zinc-plating additive, which comprises the following raw materials in percentage by weight: the additive contains 1% of sodium p-methoxybenzaldehyde sulfonate, 20% of 3,5,4 '-trihydroxy-2' -sulfodiphenyl propenone sodium salt, 1% of nicotinic acid, 10% of sodium benzoate, 5% of polycarboxylate sodium salt polarization agent, 5% of methanol and the balance of water.
The invention also provides a preparation method of the environment-friendly carrier-free water-based sulfate zinc-plating additive, which comprises the following specific steps:
s1, placing p-methoxybenzaldehyde sodium sulfonate, 3,5,4 '-trihydroxy-2' -sulfodiphenyl propenone sodium salt, sodium benzoate and polycarboxylic acid sodium salt polarization agent in a reaction vessel according to mass percentage, and dissolving the polarization agent in a proper amount of water;
s2, after S1 is finished, heating the temperature in the reaction vessel to 70-80 ℃, adding nicotinic acid and stirring until the nicotinic acid is completely dissolved;
s3, after the above materials are completely dissolved, cooling the temperature in the reaction vessel to room temperature, then adding methanol into the reaction vessel again, and finally quantifying the water to 100 percent.
The additive is added into the sulfate galvanizing plating solution in an amount of 5 g/L.
The electroplating process conditions are as follows: current density: 1A/dm2, temperature: electroplating 30 min at 35 ℃ and pH value of 4.5;
through testing, the dispersing capacity of the plating solution is as follows: 54.50% (K ═ 3), current efficiency: 98.7 percent.
Performance test result of environment-friendly type carrier-free water-based sulfate zinc-plating additive electroplated steel strip
The above description is only for the preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art should be considered to be within the technical scope of the present invention, and the technical solutions and the inventive concepts thereof according to the present invention should be equivalent or changed within the scope of the present invention.
Claims (3)
1. The environment-friendly carrier-free water-based sulfate zinc-plating additive is characterized by comprising the following raw materials in percentage by weight: the additive comprises 1-5% of a water-soluble aromatic aldehyde organic compound, 5-20% of a water-soluble organic compound containing a conjugated ketene structure, 1-5% of nicotinic acid, 2-10% of sodium benzoate, 5-20% of a sodium polycarboxylate polarization agent, 5-10% of methanol and the balance of water; wherein:
the water-soluble aromatic aldehyde organic compound in the additive is one or a mixture of more of sodium o-chlorobenzaldehyde sulfonate, 2, 4-dihydroxybenzaldehyde and sodium p-methoxybenzaldehyde sulfonate;
the water-soluble organic compound containing the conjugated ketene structure in the additive is 3-butylene-2-ketone-4 sodium phenolate, sodium benzalacetone sulfonate, 1, 2-naphthoquinone-4-sodium sulfonate,
2. The preparation method of the environment-friendly type non-carrier water-based sulfate zinc-plating additive as claimed in claim 1, is characterized by comprising the following steps:
s1, placing a water-soluble aromatic aldehyde ketone organic compound, a water-soluble organic compound containing a conjugated ketene structure, sodium benzoate and a sodium polycarboxylate polarization agent in a reaction vessel according to mass percentage, and dissolving the compounds in a proper amount of water;
s2, after S1 is finished, heating the temperature in the reaction vessel to 70-80 ℃, adding nicotinic acid and stirring until the nicotinic acid is completely dissolved;
s3, after the above materials are completely dissolved, cooling the temperature in the reaction vessel to room temperature, then adding methanol into the reaction vessel again, and finally quantifying the water to 100 percent.
3. The preparation method according to claim 2, wherein the additive is added in the sulfate galvanizing plating solution in an amount of 5 to 20 g/L.
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| US4098656A (en) * | 1976-03-11 | 1978-07-04 | Oxy Metal Industries Corporation | Bright palladium electroplating baths |
| JPH06101087A (en) * | 1992-09-22 | 1994-04-12 | Showa Denko Kk | Brightener for acidic galvanization bath and acidic galvanization bath using this brightener |
| US5951841A (en) * | 1994-12-23 | 1999-09-14 | Basf Aktiengesellschaft | Electroplating baths salts of aromatic hydroxy compounds and their use as brighteners |
| CN102618896A (en) * | 2011-11-14 | 2012-08-01 | 天津市聚兴电镀有限公司 | Potassium chloride-type galvanizing plating solution and its preparation method |
| CN104032336A (en) * | 2013-03-07 | 2014-09-10 | 纳米及先进材料研发院有限公司 | Non-vacuum method for producing light absorbing material applied in solar battery |
| CN104514019A (en) * | 2013-09-27 | 2015-04-15 | 无锡华冶钢铁有限公司 | Cyanide-free silvering electroplating solution and electroplating method |
| CN104878418A (en) * | 2015-06-29 | 2015-09-02 | 广州超邦化工有限公司 | High-stability cyanide-free alkaline galvanization solution |
| CN109576743A (en) * | 2019-01-26 | 2019-04-05 | 宁波市鄞州艾博化工科技有限公司 | Novel acid zinc-plating additive |
-
2019
- 2019-10-31 CN CN201911053580.XA patent/CN111349953B/en active Active
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4098656A (en) * | 1976-03-11 | 1978-07-04 | Oxy Metal Industries Corporation | Bright palladium electroplating baths |
| JPH06101087A (en) * | 1992-09-22 | 1994-04-12 | Showa Denko Kk | Brightener for acidic galvanization bath and acidic galvanization bath using this brightener |
| US5951841A (en) * | 1994-12-23 | 1999-09-14 | Basf Aktiengesellschaft | Electroplating baths salts of aromatic hydroxy compounds and their use as brighteners |
| CN102618896A (en) * | 2011-11-14 | 2012-08-01 | 天津市聚兴电镀有限公司 | Potassium chloride-type galvanizing plating solution and its preparation method |
| CN104032336A (en) * | 2013-03-07 | 2014-09-10 | 纳米及先进材料研发院有限公司 | Non-vacuum method for producing light absorbing material applied in solar battery |
| CN104514019A (en) * | 2013-09-27 | 2015-04-15 | 无锡华冶钢铁有限公司 | Cyanide-free silvering electroplating solution and electroplating method |
| CN104878418A (en) * | 2015-06-29 | 2015-09-02 | 广州超邦化工有限公司 | High-stability cyanide-free alkaline galvanization solution |
| CN109576743A (en) * | 2019-01-26 | 2019-04-05 | 宁波市鄞州艾博化工科技有限公司 | Novel acid zinc-plating additive |
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