CN100415942C - Production of nanometer crystal zinc plating - Google Patents
Production of nanometer crystal zinc plating Download PDFInfo
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- CN100415942C CN100415942C CNB2006100232841A CN200610023284A CN100415942C CN 100415942 C CN100415942 C CN 100415942C CN B2006100232841 A CNB2006100232841 A CN B2006100232841A CN 200610023284 A CN200610023284 A CN 200610023284A CN 100415942 C CN100415942 C CN 100415942C
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Abstract
The present invention relates to a preparing method of nanometer crystal zinc plating for pulse electrodeposition, which belongs to the technical field of a pulsed plating technology. The method of the present invention has the preparing process and the steps that (1), firstly, acidic zinc sulphate electroplating solution is prepared; the concentration of the acidic zinc sulphate electroplating solution is from 300 to 700 g/L; diluted sulfuric acid is adopted for adjustment to make a pH value is from 1 to 4; (2), a mixing organic additive of thiourea and benzalacetone is added; the concentration of the thiourea is from 0.5 to 3 g/L; the concentration of the concentration is from 0.1 to 2 g/L; the temperature of the electroplating solution is from 15 to 50 DEG C; (3), a pulsed electroplating method is adopted for carrying out pulse electrodeposition; in an electroplating tank with the zinc sulphate solution, an electroplated material steel plate is used as a cathode, and an insoluble electrode is used as an anode; pulse current is switched on; the density peak value of the pulse current is from 0.1 to 5 A/cm<2>; total electroplating time is from 1 to 15 minutes; finally, nanometer crystal zinc plating of which the particle diameter is smaller than 100 nm can be obtained.
Description
Technical field
The present invention relates to a kind of preparation method of pulse electrodeposition nanometer crystal zinc plating, belong to pulse plating Technology field.
Background technology
Zinc-plated is one of etch-proof effective ways of ferrous materials, and galvanized steel is very extensive in the application in fields such as automobile, building, household electrical appliances, chemical industry, traffic and national defence.In recent years, along with improving constantly of fast development of national economy and living standards of the people, each industrial sector increases day by day to the demand of galvanized steel, and especially the increase in demand to steel plate galvanized is faster.Zinc coating is behind nanometer, and the performance of aspects such as its machinery, physics, electricity, chemistry all is significantly improved, and this makes nanotechnology obtain fast-developing in recent years and extensively payes attention to.Compare with product coating, nanocrystalline coating has performances such as higher hardness, wear resistance, ductility, solidity to corrosion and processibility.Therefore the nanometer of zinc coating is one of effective technical way that improves its over-all properties.
People such as Youssef (Influence of additives and pulse electrodeposition parameters onproduction of nanocrystalline zinc from zinc chloride electrolytes, K.M.S.Youssef, Deng .Journal of the Electrochemical Society, .2004, Vol.151 (2) C103-C111) in the chloride galvanizing system, adds thiocarbamide and polyacrylamide mixed additive, prepare the zinc coating of grain-size at 50nm.Analogy is respected and is virtuously waited the people (it is virtuous etc. that the structural research of nanometer bright nanocrystalline zinc deposit, analogy are respected, SCI, 1999.20 (1): 107-110) also prepared the nanometer zinc coating by adjusting additive in Repone K bright galvanization liquid.These studies show that organic additive can effectively increase the overpotential and the nucleation rate of the cathodic deposition of zinc, thereby cause forming nanocrystalline zinc layer.
People such as H.Yan (A model for nanolaminated growth patterns in Zn and Zn-CoElectrodeposits, H..Yan, Deng .Journal of the Electrochemical Society, 1996, Vol.143 (5): 1577-1583) and in the Chinese patent (application number 200310107939.X) once report adopt the dc electrodeposition technology, in sulfate liquor, prepared nanometer wafer stack zinc coating, the nanometer but the grain-size of these coating all is unrealized on the three dimension scale.
People such as Saber (Pulse current electrodeposition of nanocrystalline zinc.Kh.Saber etc., Materials.Science and Engineering.A.2003 341:174-181) adopts impulse electrodeposition technology to obtain nanometer crystal zinc plating in chloride plate liquid.Compare with direct current, the pulse electrodeposition method can adopt higher pulse peak current density, improves the overpotential and the nucleation rate of the cathodic deposition of zinc, thereby generates nanometer crystal zinc plating.
At present, in the hydrosulphate system, still be difficult to prepare the zinc coating of grain-size less than 100 nanometers.
Summary of the invention
The purpose of this invention is to provide a kind of method for preparing nanometer crystal zinc plating, and adopt suitable processing parameter, enable to prepare the zinc coating of grain-size less than 100nm.
The invention provides a kind of preparation method of nanometer crystal zinc plating, it is characterized in that having following preparation process and step:
A. at first prepare acid zinc sulfate plating bath, the concentration of zinc sulfate plating bath is 300～700g/L; And adopt dilute sulphuric acid to regulate, making its pH value is 1～4;
B. adding is mixed with organic additive then, promptly adds the mixed additive of thiocarbamide and benzylideneacetone, and the concentration of thiocarbamide is 0.5～3g/L, and the concentration of benzylideneacetone is 0.1～2g/L; The temperature of plating bath is 15～50 ℃;
C. adopt pulse plating method to carry out pulse electrodeposition; In filling the plating tank of above-mentioned solution of zinc sulfate, to be negative electrode, with the insoluble electrode anode by the plating carbon steel, feed pulsed current; Pulse current density peak value (Jp) is 0.1～5A/cm
2, conduction time scope (T
On) be 1～8ms, power-off time scope (T
Off) be 4～15ms, total electroplating time is 1～15 minute; Finally can obtain the nanometer crystal zinc plating of particle diameter less than 100nm.
Characteristics of the present invention are: (1) adopts the hydrosulphate system, does not add other conducting salts, the plating bath easy care; (2) utilize thiocarbamide and benzylideneacetone to be mixed with the synergy of organic additive, can increase the overpotential and the nucleation rate of the cathodic deposition of zinc effectively, make to be easy to generate nanometer crystal zinc plating; (3) the parameter area broad of pulsed current signal, the fluctuation of signal is less to the influence of coating in the preparation process.
Embodiment
After now its body of embodiments of the invention being described in.
Embodiment 1
Preparation process and step in the present embodiment are as follows:
A. at first prepare acid zinc sulfate plating bath, adopt zinc sulfate (ZnSO
47H
2O) be dissolved in the distilled water, being mixed with concentration is the zinc sulfate plating bath of 350g/L, and being adjusted to the pH value with dilute sulphuric acid again is 1;
B. add thiocarbamide (H then
2NCSNH
2) and benzylideneacetone (C
6H
5CH=CHCOCH
3) form be mixed with organic additive; The concentration of thiocarbamide is 1g/L, and the concentration of benzylideneacetone is 0.5g/L; The temperature of plating bath is 25 ℃;
C. adopt pulse plating method to carry out pulse electrodeposition; In filling the plating tank of above-mentioned solution of zinc sulfate, to be negative electrode, with Ti/IrO by the plating carbon steel
2Coated electrode is an anode, feeds pulsed current; Pulse current density peak value (Jp) is 2A/cm
2, conduction time (T
On) be 4ms, power-off time (T
Off) be 8ms, total electroplating time is 5min; Finally can obtain the nanometer crystal zinc plating that median size is 70nm.
The zinc coating of experiment gained is tested with X-ray diffraction analysis instrument field emission Electronic Speculum, and the zinc grain-size in the discovery nanometer crystal zinc plating is in 57～79nm scope.
Claims (1)
1. the preparation method of a nanometer crystal zinc plating is characterized in that having following preparation process and step:
A. at first prepare acid zinc sulfate plating bath, the concentration of zinc sulfate plating bath is 300～700g/L; And adopt dilute sulphuric acid to regulate, making its pH value is 1～4;
B. adding is mixed with organic additive then, promptly adds the mixed additive of thiocarbamide and benzylideneacetone, and the concentration of thiocarbamide is 0.5～3g/L, and the concentration of benzylideneacetone is 0.1～2g/L; The temperature of plating bath is 15～50 ℃;
C. adopt pulse plating method to carry out pulse electrodeposition; In filling the plating tank of above-mentioned solution of zinc sulfate, to be negative electrode, with the insoluble electrode anode by the plating carbon steel, feed pulsed current; Pulse current density peak value (Jp) is 0.1～5A/cm
2, conduction time scope (T
On) be 1～8ms, power-off time scope (T
Off) be 4～15ms, total electroplating time is 1～15 minute; Finally can obtain the nanometer crystal zinc plating of particle diameter less than 100nm.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2006100232841A CN100415942C (en) | 2006-01-12 | 2006-01-12 | Production of nanometer crystal zinc plating |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2006100232841A CN100415942C (en) | 2006-01-12 | 2006-01-12 | Production of nanometer crystal zinc plating |
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|---|---|
| CN1818145A CN1818145A (en) | 2006-08-16 |
| CN100415942C true CN100415942C (en) | 2008-09-03 |
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| CNB2006100232841A Expired - Fee Related CN100415942C (en) | 2006-01-12 | 2006-01-12 | Production of nanometer crystal zinc plating |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111270276A (en) * | 2020-03-28 | 2020-06-12 | 武汉钢铁有限公司 | Flash galvanizing plating solution and preparation method thereof and flash galvanizing method |
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| US9005420B2 (en) * | 2007-12-20 | 2015-04-14 | Integran Technologies Inc. | Variable property electrodepositing of metallic structures |
| CN103436928A (en) * | 2013-09-16 | 2013-12-11 | 江苏法尔胜技术开发中心有限公司 | Method for galvanizing steel wire through bidirectional pulse power supply |
| CN104725079B (en) * | 2015-03-12 | 2017-06-20 | 东北大学 | A kind of method for forming smooth compacted zone on carbon containing refractory surface |
| CN106086967A (en) * | 2016-06-18 | 2016-11-09 | 安徽昊博健身器材有限公司 | A kind of method for anticorrosion treatment of outdoor use body-building apparatus steel part |
| CN109119604A (en) * | 2018-07-12 | 2019-01-01 | 暨南大学 | A kind of secondary zinc base battery nanometer Zn@C negative electrode material and preparation method thereof |
| CN110085429B (en) * | 2019-04-17 | 2021-07-02 | 桂林理工大学 | Method for pulse deposition of nano tin dots on medium-high voltage anode aluminum foil for aluminum electrolytic capacitor |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111270276A (en) * | 2020-03-28 | 2020-06-12 | 武汉钢铁有限公司 | Flash galvanizing plating solution and preparation method thereof and flash galvanizing method |
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