CN102719864A - Method for preparing cerium-containing zinc coating - Google Patents

Method for preparing cerium-containing zinc coating Download PDF

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Publication number
CN102719864A
CN102719864A CN2012102163860A CN201210216386A CN102719864A CN 102719864 A CN102719864 A CN 102719864A CN 2012102163860 A CN2012102163860 A CN 2012102163860A CN 201210216386 A CN201210216386 A CN 201210216386A CN 102719864 A CN102719864 A CN 102719864A
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cerium
plating
concentration
coating
sulfate
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CN2012102163860A
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CN102719864B (en
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李谋成
邬明钰
王士栋
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University of Shanghai for Science and Technology
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University of Shanghai for Science and Technology
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Abstract

The invention discloses a method for preparing cerium-containing zinc coating. The method comprises the following main steps: (1) sulfate plating solution for ions to be plated is prepared, wherein the concentration of zinc sulfate is 50-300g/L, and the concentration of cerium sulfate is 0.2-4g/L; sodium citrate serving as rare earth complexing agent, with the concentration of 5-60g/L is added, and sodium hypophosphite with the concentration of 5-60g/L is added; dilute sulfuric acid is adopted to adjust the pH value of the plating solution to be 1-4; the temperature of the plating solution is controlled to be 15-60 DEG C; (2) the direct current electrodeposition method is adopted for plating; in a plating bath containing the plating solution, carbon steel used as the plated material is used as the cathode, a platinum sheet is adopted as the anode, direct current is introduced to the plating bath, the current density is 0.6-4 A/cm<2>, and the plating time is 1-6 min; and finally, the concentration of cerium in the prepared coating is 0.05-0.3 wt%. Aiming at the sulfate system of the DC (direct current) electrodeposition zinc coating, the sodium citrate and the sodium hypophosphite as the substances are adopted for promoting the deposition of cerium, so that the cathodic polarization behavior of cerium in deposition can be improved, the zinc coating containing trace cerium is finally obtained, and the corrosion resistance of the coating is obviously improved.

Description

A kind of preparation method who contains the cerium zinc coating
Technical field
The present invention relates to a kind of in hydrosulphate solution dc electrodeposition preparation contain the method for cerium zinc coating, particularly a kind of preparation method who contains the cerium zinc coating belongs to Surface Engineering and surface anticorrosive processing technology field.
Background technology
Corrosion of Metallic Materials such as iron and steel not only cause scrapping of material and equipment, and cause huge indirect losses such as suspending operation or slashing production, material loss, environmental pollution, have hindered development and national economy.The surface treatment of material is to solve one of most economical effective means of material corrosion and protection.Electroplating technology is because processing unit is simple, processing ease, and advantage such as with low cost becomes one of the most frequently used process for treating surface.
At present; The technological development of electro-galvanizing gets comparatively ripe, and zinc coating is on iron and steel, to use protective coating the most widely, and it belongs to anodic coating; Both can in environment, form layer protecting film; Directly avoid steel substrate to contact with corrosive medium, the method for sacrificial anode capable of using plays the electro-chemical protection effect to matrix again, reaches the purpose that prevents steel corrosion.Because the deterioration of environment and the raising of application requiring in order to satisfy actual production needs, must improve the corrosion resisting property of zinc coating.
REE is called as " industrial VITAMINs " because of its particular structure has excellent characteristic.Last century the nineties, rare earth begins to be used to the chemical conversion treatment of zinc coating, not only can strengthen the solidity to corrosion of steel plate zinc coating, and can also avoid traditional hexavalent chromium chemistry to handle the environmental problem that is caused.Cerium salt is very popular because of factors such as price, performances in the rare earth.In tart electro-galvanizing solution, add rare earth cerium salt, adopt the method for dc electrodeposition, obtain to contain the zinc coating of cerium, make the rare earth modified more convenient and swift of zinc coating, and the existence of micro-cerium there has been tangible improvement to the corrosion resisting property of zinc coating.
People's reported first such as Lokhande from the aqueous solution the direct result of study of galvanic deposit La and Sm film, the influence to the deposition potential of La of different ligands and matrix has been discussed.In acidic medium, selected for use oxalic acid, EDTA and Trisodium Citrate to make part.Polarization curve when adopting potentiostatic method (copper, brass, stainless steel, titanium, ITO) having measured the lanthanum galvanic deposit on different matrix.Experimental result shows that in the electrolytic solution that does not add part, the hydrogen evolution current potential of (except that ITO) is about-1.0V (SCE relatively) on the matrix, and E ° of La 3+=-2.52V can't come out so lanthanum is separated out the interference La that receives hydrogen evolution in galvanic deposit.After adding part in the plating bath, on copper, brass, the stainless steel cathode-0.7~-0.8V (SCE relatively) just begins to have the reduction current of La, and the hydrogen evolution current potential is about-1.2V, thereby can get rid of the interference of hydrogen evolution, makes La +Can go out La from aqueous solution electrodeposition.
Last century the nineties, domestic people such as Li Shijia begin in common galvanizing solution, to add rare earth compound, introduce zinc coating to trace rare-earth, the sedimentation state and the coating performance of research rare earth.Subsequently, be representative with the cerium, in the Repone K plating bath, add the cerium salt of 0.1~0.2 g/L, tested the content of cerium in coating, studied cerium to the corrosion proof influence of zinc coating.The result shows: in the zinc-plated electrolytic solution of bright Repone K of reality, along with the increase of cerium salt concn in the plating bath, the content of cerium is also increasing in the coating.The existence of cerium can improve the solidity to corrosion of zinc coating, at utmost about 35% of raising effectively.When cerium content was between 10ppm-20ppm in the coating, coating had higher corrosion stability, and when surpassing this value, the coating corrosion stability descends on the contrary.
People such as Chu Dewei have studied the alkaline zincate system and have electroplated in the Zn system, adopt suitable cerium salt complexing agent and electroplating additive, have confirmed to electroplate the processing condition of Zn-Ce alloy.Adopt the XRD analysis method to infer the existence of Ce in the coating.Ce in plating bath 2(SO 4) 3Content when being 1g/L, compared Zn-Ce alloy layer and the solidity to corrosion of pure Zn coating in NaCl solution, find that the solidity to corrosion of Zn-Ce alloy layer is more than 3 times of the pure zinc coating of same thickness.
At present, relevant rare earth be introduced in the zinc coating research and document introduction also seldom, the application in the zinc-plated system of hydrosulphate does not have and relates to.The problem that mainly faces is the deposition potential that the equilibrium potential of rare earth is defeated by zinc and hydrogen far away, makes the preparation of rare earth in zinc coating comparatively difficult; Complexing agent is also incomplete same to the sedimentation of rare earth in the different solutions, need carry out research further.
Summary of the invention
Defective to prior art exists the purpose of this invention is to provide a kind of preparation method who contains the cerium zinc coating, be a kind of in hydrosulphate solution the dc electrodeposition preparation contain the method for cerium zinc coating.
For achieving the above object, the present invention adopts following technical scheme:
The present invention is a kind of preparation method who contains the cerium zinc coating, it is characterized in that having following preparation process and processing condition:
A. prepare by plating ionic sulfate liquor, wherein the sulfuric acid zinc concentration is 50 ~ 300g/L, and the concentration of cerous sulfate is 0.2 ~ 4g/L;
B. in above-mentioned sulfate liquor, add the rare-earth enveloping agent Trisodium Citrate, concentration is 5 ~ 60g/L; Add inferior sodium phosphate again, concentration is 5 ~ 60g/L; The pH value that adopts dilute sulphuric acid to regulate plating bath is 1 ~ 4; The temperature of plating bath is controlled to be 15 ~ 60 ℃;
C. adopt the method for dc electrodeposition to electroplate; In filling the plating tank of above-mentioned plating bath, to be negative electrode, with the platinized platinum anode by plating material carbon steel, feed galvanic current, current density is 0.6 ~ 4A/cm2, electroplating time is 1 ~ 6min; The content of the coating middle-weight rare earths cerium that finally makes is 0.05 ~ 0.3wt%.
Compared with prior art, characteristics of the present invention are following:
(1) adopt the hydrosulphate system, do not add other conducting salt, current efficiency is high, and plating solution maintenance is easy; (2) add the complexing agent Trisodium Citrate in the plating bath, formed complex cation, changed the cathodic polarization behavior of cerium, make separating out of cerium become possibility with cerium; (3) add inferior sodium phosphate in the plating bath, provide electronegativity stronger phosphoric, the corrosion resisting property that the deposition (4) of promotion cerium contains the cerium zinc coating obtains very significantly improving.
Description of drawings
Fig. 1 is the scanning shape appearance figure that contains the cerium zinc coating;
Fig. 2 is the EDS spectrogram that contains cerium zinc coating surface microcell.
Embodiment
After specific embodiment of the present invention being described at present.
Embodiment 1
Preparation process and step in the present embodiment are following:
A. at first prepare by plating ionic sulfate liquor, the crystalline sulfuric acid zinc of 60g and the cerous sulfate of 2g are dissolved in the plating bath that is mixed with 1L in the zero(ppm) water.
B. add the inferior sodium phosphate of Trisodium Citrate and the 20g of 20g then, dissolve fully; Adding dilute sulphuric acid adjusting pH value is 2, and bath temperature is controlled to be 55 ℃.
C. adopt the direct current electrode position method to carry out galvanic deposit; In filling the plating tank of above-mentioned sulfate bath, to be negative electrode, with the platinized platinum anode by the plating material plate, feed 0.6A/cm 2Galvanic current, electroplate 2min; The Ce content that final AES records in the coating is 0.1wt%.
Embodiment 2
Preparation process and step in the present embodiment are following:
A. at first prepare by plating ionic sulfate liquor, the crystalline sulfuric acid zinc of 100g and the cerous sulfate of 2g are dissolved in the plating bath that is mixed with 1L in the zero(ppm) water.
B. add the inferior sodium phosphate of Trisodium Citrate and the 20g of 20g then, dissolve fully; Adding dilute sulphuric acid adjusting pH value is 2, and bath temperature is controlled to be 55 ℃.
C. adopt the direct current electrode position method to carry out galvanic deposit; In filling the plating tank of above-mentioned sulfate bath, to be negative electrode, with the platinized platinum anode by the plating material plate, feed 1A/cm 2Galvanic current, electroplate 2min; The Ce content that final AES records in the coating is 0.065wt%.
Embodiment 3
Preparation process and step in the present embodiment are following:
A. at first prepare by plating ionic sulfate liquor, the crystalline sulfuric acid zinc of 350g and the cerous sulfate of 2g are dissolved in the plating bath that is mixed with 1L in the zero(ppm) water.
B. add the inferior sodium phosphate of Trisodium Citrate and the 30g of 30g then, dissolve fully; Adding dilute sulphuric acid adjusting pH value is 2, and bath temperature is controlled to be 25 ℃.
C. adopt the direct current electrode position method to carry out galvanic deposit; In filling the plating tank of above-mentioned sulfate bath, to be negative electrode, with the platinized platinum anode by the plating material plate, feed 2A/cm 2Galvanic current, electroplate 2min; The Ce content that final AES records in the coating is 0.05wt%.

Claims (1)

1. preparation method who contains the cerium zinc coating is characterized in that having following steps:
A. prepare by plating ionic sulfate liquor, wherein the sulfuric acid zinc concentration is 50 ~ 300g/L, and the concentration of cerous sulfate is 0.2 ~ 4g/L;
B. in above-mentioned sulfate liquor, add the rare-earth enveloping agent Trisodium Citrate, concentration is 5 ~ 60g/L; Add inferior sodium phosphate again, concentration is 5 ~ 60g/L; The pH value that adopts dilute sulphuric acid to regulate plating bath is 1 ~ 4; The temperature of plating bath is controlled to be 15 ~ 60 ℃;
C. adopt the method for dc electrodeposition to electroplate; In filling the plating tank of above-mentioned plating bath, to be negative electrode, with the platinized platinum anode by plating material carbon steel, feed galvanic current, current density is 0.6 ~ 4A/cm 2, electroplating time is 1 ~ 6min; The content of the coating middle-weight rare earths cerium that finally makes is 0.05 ~ 0.3wt%.
CN201210216386.0A 2012-06-28 2012-06-28 Method for preparing cerium-containing zinc coating Expired - Fee Related CN102719864B (en)

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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103540966A (en) * 2013-10-29 2014-01-29 常熟市伟达电镀有限责任公司 Anti-abrasive electroplating solution
CN104805477A (en) * 2015-04-02 2015-07-29 上海应用技术学院 Zinc plating liquid used for forming thick zinc coating as well as preparation method and application
CN104988551B (en) * 2013-09-03 2017-07-07 天津大学 Application of the lemon acid doping Cerium conversion film in AA2219 corrosive protection of aluminium alloy
CN107268031A (en) * 2016-03-31 2017-10-20 蔚山大学产学合作部 The electrochemistry recovery method of heavy rare earth metalloid
CN110760862A (en) * 2019-11-26 2020-02-07 江东电子材料有限公司 Production process of smooth-surface roughened electrolytic copper foil

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CN1322857A (en) * 2001-04-26 2001-11-21 上海交通大学 Anticorrosive wear-resistant gradient film
CN101476099A (en) * 2009-01-22 2009-07-08 华南理工大学 Method for steel product batch hot dip galvanizing
CN101565843A (en) * 2009-05-26 2009-10-28 上海大学 Method for preparing zinc-magnesium alloy coating

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Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104988551B (en) * 2013-09-03 2017-07-07 天津大学 Application of the lemon acid doping Cerium conversion film in AA2219 corrosive protection of aluminium alloy
CN103540966A (en) * 2013-10-29 2014-01-29 常熟市伟达电镀有限责任公司 Anti-abrasive electroplating solution
CN104805477A (en) * 2015-04-02 2015-07-29 上海应用技术学院 Zinc plating liquid used for forming thick zinc coating as well as preparation method and application
CN107268031A (en) * 2016-03-31 2017-10-20 蔚山大学产学合作部 The electrochemistry recovery method of heavy rare earth metalloid
CN107268031B (en) * 2016-03-31 2019-06-07 蔚山大学产学合作部 The electrochemistry recovery method of heavy rare earth metalloid
CN110760862A (en) * 2019-11-26 2020-02-07 江东电子材料有限公司 Production process of smooth-surface roughened electrolytic copper foil

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