CN107904628B - It is a kind of based on ultrasonic wave added malic acid-glycine betaine eutectic solvent electrogalvanizing method - Google Patents
It is a kind of based on ultrasonic wave added malic acid-glycine betaine eutectic solvent electrogalvanizing method Download PDFInfo
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- CN107904628B CN107904628B CN201711335164.XA CN201711335164A CN107904628B CN 107904628 B CN107904628 B CN 107904628B CN 201711335164 A CN201711335164 A CN 201711335164A CN 107904628 B CN107904628 B CN 107904628B
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- eutectic solvent
- malic acid
- glycine betaine
- zinc
- ultrasonic wave
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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
- C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
- C25D5/20—Electroplating using ultrasonics, vibrations
Abstract
The invention discloses a kind of based on ultrasonic wave added malic acid-glycine betaine eutectic solvent electrogalvanizing method, belongs to electroplating technology.Malic acid, glycine betaine and distillation water termostat are stirred to get transparent eutectic solvent first by this method, zinc chloride are then added in eutectic solvent again to constant temperature stirs to get the eutectic solvent containing zinc, in this, as electroplate liquid；Using pure zinc as anode, mild steel etc. is used as cathode, is immersed in progress constant current plating in electroplate liquid；In the plating process, apply ultrasonic auxiliary electric plating.The invention, which solves high viscosity eutectic solvent, can not carry out the technical problem of electro-deposition., chloride galvanizing zinc-plated relative to conventional cyanide, the present invention used in eutectic solvent environment-friendly biodegradable, belong to Green Chemistry solvent.
Description
Technical field
The invention belongs to electroplating technologies, and in particular to a kind of electrogalvanizing method based on eutectic solvent.
Background technique
Electrogalvanizing be using electrolysis installation by material by oil removing, pickling, after be put into ingredient be zinc salt solution in, and even
The cathode for connecing electrolysis installation places zine plate on the opposite of material, and the anode for being connected to electrolysis installation powers on, using electric current from
Anode will be in one layer of zinc of deposited on materials to the displacement of cathode.Alkaline zinc plating alkaline galvanizing technology refers to the pH value of plating solution
It is alkalinity.But because of complexing agent difference, and it is zinc-plated and two kinds of zincate galvanizing to be divided into cyanide.Zinc-plated cyanide is a very ancient
Plating.There are mainly three types of ingredients in plating solution: main salt zinc oxide, complexing agent Cymag and conductive salt sodium hydroxide (being commonly called as caustic soda).
It is not no brightener in the cyaniding plating liquor of early stage.With the raising of people's esthetic requirement, and in cyanating solution galvanizing solution
The brightener of bright effect is joined.Cyanide zinc plating wastewater process stabilizing, coating are careful.Solution dispersibility is good.According to Cymag
How much differences of content, and be divided into high cyanogen, middle cyanogen and three kinds of low-cyanide zinc plating.The disadvantage of cyanide zinc plating wastewater is that toxicity is too big, right
Environmental hazard is serious.Potassium chloride (or sodium chloride) zincincation is a kind of completely new non-cyanogen galvanization to grow up the 1980s
Technique.Its main component are as follows: zinc chloride main salt is generally 70-90g/L using content.Potassium chloride makees conductive salt, using content from
140-280g/L etc. can be adjusted arbitrarily according to different demands.Boric acid makees pH value buffer agent, with stablize pH value 4.6-5.6 it
Between.Since this plating solution is to work at room temperature, the solubility of boric acid is not high, and general content control is in 25-30g/L.On
State it is zinc-plated to environment have certain pollution.Eutectic solvent has the type of eutectic solvent very much, and it is heavy to be presently available for electricity
Long-pending has glycine betaine-urea, glycine betaine-ethylene glycol, xylitol-glycine betaine-water etc., but there are also other a large amount of eutectic solvents
Solvability and very weak, the electrochemistry evolution reaction of metal ion since its viscosity coefficient is much larger than aqueous solution, to metal salt
Mostly diffusing step controls.In high viscosity eutectic solvent electrodeposition process, it has been found that cathode is heavy due to metal ion
Long-pending and bubble generation forms one layer on cathode surface and contains bladdery high viscosity liquid, to prevent the heavy of metal ion
Product.
Summary of the invention
In order to overcome the deficiencies of the prior art, the purpose of the present invention is to provide one kind to be based on ultrasonic wave added malic acid-beet
The electrogalvanizing method of alkali eutectic solvent can not carry out the difficulty of electro-deposition to solve high viscosity low conductivity eutectic solvent
Topic.
In order to achieve the above technical purposes, the present invention is achieved by the following technical programs.
The present invention provides a kind of based on malic acid-glycine betaine eutectic solvent electrogalvanizing method, specifically includes as follows
Step:
(1) preparation of the eutectic solvent containing zinc: first, in accordance with molar ratio 1:1:4 weigh malic acid, glycine betaine, distilled water,
Then constant temperature stirs to get transparent eutectic solvent under the conditions of 60 DEG C, then according to malic acid molar ratio 0.05-0.15:
1 weighs zinc chloride, is added to constant temperature in above-mentioned eutectic solvent and stirs to get the eutectic solvent containing zinc, in this, as plating
Liquid.
(2) using pure zine plate as anode, mild steel is immersed in the electroplate liquid that step (1) obtains as cathode and carries out perseverance
Electric current plating, in which: cathode and anode direct range are 1-2cm；In the plating process, it is plated using ultrasonic auxiliary electric.
(3) after the completion of being electroplated, mild steel is taken out into cleaning, drying.
Further, constant current density is 10-20mA/cm in the step (2)2。
Further, temperature of electroplating solution is 50-70 DEG C in the step (2).
Further, electroplating time is 15-30 minutes in the step (2).
The principles of science of the present invention:
When ultrasonic wave added deposition, the cavitation bubble surface of ultrasonic wave can make radially uniform Non-Linear Vibration, it can be to anti-
Answer the secondary uniform spherical wave of liquid radiation.On the surface that bubble is moved to particle, this spherical wave will be in the table of the particle
Cause the micro- whirling motion of reaction solution on face, it can be achieved that homogeneous media mixes, the local concentration for eliminating electrolyte is uneven.Ultrasonic wave electricity
The jet stream of ultrasonic vibration and generation in deposition can make the bubble for being gathered in cathode surface be detached from cathode surface rapidly, and with solution
Flowing be distributed in entire solution, can prevent cathode nearby solution viscosity increase and bubble aggregation lead to not carry out electricity
The problem of deposition.
Compared with prior art, the present invention has following technical effect that
1, the invention, which solves high viscosity eutectic solvent, can not carry out the technical problem of electro-deposition.
2, zinc-plated relative to conventional cyanide, chloride galvanizing, the present invention used in eutectic solvent environment-friendly biodegradable,
Belong to Green Chemistry solvent.
Detailed description of the invention
Fig. 1 is the SEM figure for the electrogalvanizing that embodiment 1 obtains in the present invention；
As shown in Figure 1, about 1-3 μm of the crystallite dimension of electrogalvanizing.
Fig. 2 is the EDS energy spectrum diagram for the electrogalvanizing that embodiment 1 obtains in the present invention；
As shown in Fig. 2, the EDS power spectrum of electrogalvanizing illustrates surface for zinc composition.
Fig. 3 is the XRD diagram for the electrogalvanizing that the embodiment of the present invention 1 obtains；
As shown in figure 3, the XRD diagram of electrogalvanizing, ordinate is intensity, and abscissa is two times of angles, and diffraction maximum is metallic zinc
And iron matrix.
Specific embodiment
Below in conjunction with specific embodiment, the present invention is further illustrated, but the present invention is not limited to following implementations
Example.
Embodiment 1
It weighs 0.1mol malic acid, 0.1mol glycine betaine, 0.4mol distilled water respectively first to be placed in beaker, use
Then preservative film sealed beaker stirs to get transparent eutectic solvent in 60 DEG C of constant temperature.Then the chlorination of 0.01mol is added
Zinc stirs to get eutectic solvent containing zinc in 60 DEG C of constant temperature.
Using pure zine plate as anode, mild steel as cathode, immerse the eutectic solvent containing zinc of heating water bath to 60 DEG C into
Row 15 minutes constant currents plating, wherein cathode and anode direct range are 1cm, current density 10mA/cm2.In electroplating process
In, apply ultrasonic auxiliary electric plating, supersonic frequency: 40KHz, ultrasonic power 150W.
After the completion of plating, mild steel taking-up is cleaned 2 times with distilled water, finally 60 DEG C of drying in an oven.
Embodiment 2
It weighs 0.1mol malic acid, 0.1mol glycine betaine, 0.4mol distilled water respectively first to be placed in beaker, use
Then preservative film sealed beaker stirs to get transparent eutectic solvent in 60 DEG C of constant temperature.Then the chlorination of 0.005mol is added
Zinc stirs to get eutectic solvent containing zinc in 60 DEG C of constant temperature.
Using pure zine plate as anode, mild steel as cathode, immerse the eutectic solvent containing zinc of heating water bath to 50 DEG C into
Row 30 minutes constant currents plating, wherein cathode and anode direct range are 2cm, current density 15mA/cm2；In electroplating process
In, apply ultrasonic auxiliary electric plating, supersonic frequency: 40KHz, ultrasonic power 150W.
After the completion of plating, mild steel taking-up is cleaned 2 times with distilled water, finally 60 DEG C of drying in an oven.
Embodiment 3
It weighs 0.1mol malic acid, 0.1mol glycine betaine, 0.4mol distilled water respectively first to be placed in beaker, use
Then preservative film sealed beaker stirs to get transparent eutectic solvent in 60 DEG C of constant temperature.Then the chlorination of 0.015mol is added
Zinc stirs to get eutectic solvent containing zinc in 60 DEG C of constant temperature；
Using electrolytic zinc as anode, mild steel as cathode, immerse the eutectic solvent containing zinc of heating water bath to 70 DEG C into
Row 15 minutes constant currents plating, wherein cathode and anode direct range are 1cm, current density 20mA/cm2；In electroplating process
In, apply ultrasonic auxiliary electric plating, supersonic frequency: 40KHz, ultrasonic power 100W.
After the completion of plating, mild steel taking-up is cleaned 2 times with distilled water, finally 60 DEG C of drying in an oven.
The foregoing is merely illustrative of the preferred embodiments of the present invention, is not intended to limit the invention, all in essence of the invention
Within mind and principle, any modification, equivalent replacement, improvement and so on be should all be included in the protection scope of the present invention.
Claims (4)
1. a kind of based on ultrasonic wave added malic acid-glycine betaine eutectic solvent electrogalvanizing method, it is characterised in that including as follows
Step:
(1) malic acid, glycine betaine, distilled water, then the preparation of the eutectic solvent containing zinc: are weighed first, in accordance with molar ratio 1:1:4
Constant temperature stirs to get transparent eutectic solvent under the conditions of 60 DEG C, claims then according to 0.05~0.15:1 of malic acid molar ratio
Amount zinc chloride is added to constant temperature in above-mentioned eutectic solvent and stirs to get the eutectic solvent containing zinc, in this, as electroplate liquid；
(2) using pure zine plate as anode, mild steel is immersed in the electroplate liquid that step (1) obtains as cathode and carries out constant current
Plating, in which: cathode and anode direct range are 1-2cm；
In the constant current plating, plated using ultrasonic auxiliary electric；
(3) after the completion of being electroplated, mild steel is taken out into cleaning, drying.
2. as described in claim 1 based on ultrasonic wave added malic acid-glycine betaine eutectic solvent electrogalvanizing method, feature
It is, constant current density is 10~20mA/cm in the step (2)2。
3. as described in claim 1 based on ultrasonic wave added malic acid-glycine betaine eutectic solvent electrogalvanizing method, feature
Be: temperature of electroplating solution is 50~70 DEG C in the step (2).
4. as described in claim 1 based on ultrasonic wave added malic acid-glycine betaine eutectic solvent electrogalvanizing method, feature
Be: electroplating time is 15~30 minutes in the step (2).
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| CN201711335164.XA CN107904628B (en) | 2017-12-14 | 2017-12-14 | It is a kind of based on ultrasonic wave added malic acid-glycine betaine eutectic solvent electrogalvanizing method |
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| CN201711335164.XA CN107904628B (en) | 2017-12-14 | 2017-12-14 | It is a kind of based on ultrasonic wave added malic acid-glycine betaine eutectic solvent electrogalvanizing method |
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| CN107904628A CN107904628A (en) | 2018-04-13 |
| CN107904628B true CN107904628B (en) | 2019-05-07 |
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106283140A (en) * | 2016-10-27 | 2017-01-04 | 安徽工业大学 | A kind of nickel-phosphorus alloy plating method based on glycine betaine urea water eutectic solvent |
| CN106435672A (en) * | 2016-08-26 | 2017-02-22 | 无锡光旭新材料科技有限公司 | Tin, zinc and nickel electroplating method based on choline chloride-malic acid deep-eutectic solvents |
| CN106498461A (en) * | 2016-10-27 | 2017-03-15 | 安徽工业大学 | A kind of nickel-cobalt alloy plating method based on glycine betaine urea water eutectic solvent |
| CN106498452A (en) * | 2016-10-27 | 2017-03-15 | 安徽工业大学 | A kind of electrogalvanizing method based on glycine betaine urea water eutectic solvent |
-
2017
- 2017-12-14 CN CN201711335164.XA patent/CN107904628B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106435672A (en) * | 2016-08-26 | 2017-02-22 | 无锡光旭新材料科技有限公司 | Tin, zinc and nickel electroplating method based on choline chloride-malic acid deep-eutectic solvents |
| CN106283140A (en) * | 2016-10-27 | 2017-01-04 | 安徽工业大学 | A kind of nickel-phosphorus alloy plating method based on glycine betaine urea water eutectic solvent |
| CN106498461A (en) * | 2016-10-27 | 2017-03-15 | 安徽工业大学 | A kind of nickel-cobalt alloy plating method based on glycine betaine urea water eutectic solvent |
| CN106498452A (en) * | 2016-10-27 | 2017-03-15 | 安徽工业大学 | A kind of electrogalvanizing method based on glycine betaine urea water eutectic solvent |
Non-Patent Citations (1)
| Title |
|---|
| Sono-electrodeposition (20 and 850 kHz) of copper in aqueous and deep eutectic solvents;Bruno G. Pollet等;《Electrochimica Acta 》;20090106;第53卷;摘要 |
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