CN1528954A - Nano Multi-layer zinc film electroplating preparation method - Google Patents
Nano Multi-layer zinc film electroplating preparation method Download PDFInfo
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- CN1528954A CN1528954A CNA200310107939XA CN200310107939A CN1528954A CN 1528954 A CN1528954 A CN 1528954A CN A200310107939X A CNA200310107939X A CN A200310107939XA CN 200310107939 A CN200310107939 A CN 200310107939A CN 1528954 A CN1528954 A CN 1528954A
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Abstract
The invention is a electric plating method for nano multi-layer zinc film, it uses electric plating zinc liquid system with high stability, the electric plating liquid is made up of main salt zinc sulfate 50-200g/L, conducting salt natrium sulfate 50-150g/L, buffer agen 10-30g/L and water. The pH value of liquid is controlled between 4.5-5.5, at first, the zinc sulfate, natrium sulfate and buffer agent are dissolved in the water respectively, then uses dilute sulfuric acid or sodium hydroxide to adjust the buffer liquid to preset acidity, then the main salt and conducting salt are blended, and adjusts the acidity to preset value, it uses the pure zinc board as positive electrode, the piece is uses as the negative electrode, controls the current density of negative electrode, the nano multi-layer zinc plating layer can be acquired under normal temperature, the single layer thickness is between 10 and 100 nano. The plating liquid of the invention is mild, the stability is high, easy to be controlled.
Description
Technical field:
The present invention relates to a kind of electroplating preparation method of nanometer multilayer zinc film; can there be any additives work at ambient temperature; can access the laminar nano zinc coating, be mainly used in the anticorrosive protection of metallic element, belong to material protection and technical field of chemical engineering.
Background technology:
For many years, zinc coating is one of main surfacecti proteon means of common iron, and wherein automobile steel, particularly steel plate mostly adopt zinc-plated resist technology anticorrosive.The corrosion of steel not only causes the huge waste of material, the energy, and bring the pollution of environment and the generation of various disastrous accident traffic accidents, therefore, pursue higher resistance to corrosion is the target that the material protection personnel make great efforts always, various zincincation technology are fully paid attention to, electro-galvanizing is not only arranged, also have pot galvanize; Pure zinc coating is not only arranged, also have various zn alloy coatings, also have multiple zinc-plated aftertreatment technology to be used to guarantee that the zinc coating corrosion resistance satisfies the service requirements that improves constantly in addition.
Nano material since its structure dimension in nanometer scale, sub-dimensional effect of amount of substance and interfacial effect etc. produce material impact to material property, tend to produce many unusual unique phenomenons, give the function of nano material uniqueness.To the research of nano material corrosion behavior, up to the eighties of last century late nineteen eighties just attract much attention (J Electrochem Soc, 1998:2162-2170).When most of nano material increases resistance to corrosion decline because of specific surface area, find that also the part nano material has excellent corrosion resistance.Wherein, the nanometer electro-galvanized layer that obtains under the certain condition be exactly erosion resistance because of nanometer be improved a kind of, so the zinc coating nanometer is considered to one of important technology approach that the surface of steel plate zinc coating is carried out the characteristic trait improvement.H.Yan (J.Electrochem.Soc., 1996, Vol.143 No.5:1577-1583) adopts simple sulfate zinc plating system to obtain the nanometer zinc coating, and finds that alloying can further increase the coating resistance to corrosion.But, his resulting nano-deposit is the composite Nano multilayer film of zinc and zinc oxide, show that electroplating not merely is metal electrodeposition, especially complicated and difficult is, electrodeposition process is accompanied by the very fast variation of plating bath acidity, need often to adjust and stablize, otherwise just can depart from the sedimentary suitable working range of nanometer film with maintenance acidity.In any case such working conditions also is difficult to the requirement of competent Iron And Steel Industry scale operation, so, applying of this technology influenced.
Virtuous grade (SCI, 1999,20 (1): 107～110) adopt Repone K bright galvanization solution system, also obtain the nanometer electro-galvanized layer by the method for adjusting brightener are respected in analogy.Its principle is similar to common bright galvanization, just stronger to the intervention dynamics of grain growing, thereby make crystal particle scale be reduced to nanoscale, therefore, resulting nanometer zinc coating fragility is big, and poor ductility, physical strength are also relatively poor, textural defect has lost the value of nanometer modification apparently higher than common zinc coating.
Summary of the invention:
The objective of the invention is to deficiency, propose a kind of electroplating preparation method of nanometer multilayer zinc film, reduce the running maintenance difficulty of plating bath, stable even, careful nanometer zinc coating, the erosion resistance of raising coating of obtaining at the prior art existence.
For realizing such purpose, in the method for the present invention, adopted a kind of high stability electro-galvanizing solution system, electroplate liquid is made of main salt zinc sulfate 50～200g/L, conducting salt sodium sulfate 50～150g/L, buffer reagent and water, adopt 5～10% dilute sulphuric acids or sodium hydroxide that plating bath acidity pH value is controlled between 4.5～5.5, be preferably in 4.7～5.3.Wherein buffer reagent can be stablized plating bath acidity in electroplating process, adopts acetic acid, sodium-acetate, propionic acid, Sodium Propionate, butyric acid, Sodium propanecarboxylate, Succinic Acid etc., and content is between 10～30g/L.
During the preparation electroplate liquid, at first main salt zinc sulfate, conducting salt sodium sulfate and buffer reagent are dissolved in the water respectively, adjust buffer agent solution to the acidity of setting with dilute sulphuric acid or sodium hydroxide again, then main salt and supporting electrolyte are mixed under stirring condition, adjust acidity once more to set(ting)value.During plating, make anode with pure zine plate, workpiece to be plated is made negative electrode, and the control cathode current density is 0.5～10Adm
-2, electroplating time is 10～30 minutes, and working temperature is 15～40 ℃, and the best is 25～30 ℃, and promptly electrodepositable obtains the nanometer multilayer zinc coating.
Zinc sulfate is the main salt in the electroplate liquid, its content between 50～200g/L, the thickness in monolayer of the concentration affects nano-coating of main salt; Under the similarity condition, main salt concentration is high more, and thickness in monolayer is big more, and what measure no matter concentration take greater than 200g/L, all is difficult to the stable nanometer individual layer that obtains; The low nano-deposit thickness that helps controlling though concentration becomes,, too low meeting significantly descends current efficiency, is difficult to realize high workload efficient.
Sodium sulfate is conducting salt, and in order to improve the electric conductivity of solution, content is 50～100g/L.
Buffer reagent plays the effect of stablizing bath pH value in electroplating process, and it should be able to make bath pH value stability between 4.5～5.5 increase.Select the reference conditions of buffer reagent that two aspects are arranged, at first surge capability is the strongest in above-mentioned acidity interval, and secondly contained ion and zine ion complex ability are lower, to reduce the interference of buffer reagent to electrodeposition process as far as possible.As propionic acid, Sodium Propionate, butyric acid, Sodium propanecarboxylate, acetic acid, sodium-acetate, Succinic Acid etc., one kind of can being competent at, content is between 10～30g/L.
According to the kind of buffer reagent, select to adopt dilute sulphuric acid or diluted sodium hydroxide solution to adjust plating bath to suitable work acidity interval.
Dissolving the back respectively by above-mentioned each component can at room temperature use easily according to the electroplate liquid that suitable order mixing is constituted, the temperature range of works better is between 15～40 ℃, be preferably 25～30 ℃, temperature is lower than 10 ℃ of easy crystallizations of metal-salt and separates out then coating roughen of temperature drift.
Above-mentioned plating bath need be worked under agitation condition, as magnetic force rotation stirrings, liquid-flow stirring etc. all can, the effect of stirring can influence the apparent pattern of coating, intensive stirs the upper limit that can make electroplating current density and improves, raising current efficiency.
The matrix that carries out galvanic deposit under above-mentioned plating condition can be steel such as steel plate, steel wire, also can be other any steel construction piece, perhaps other not with the metal of plating bath generation chemical reaction.
Before carrying out galvanic deposit, matrix is carried out conventional pre-treatment and can improve binding force of cladding material.
Owing to do not contain compositions such as the strong chlorion of corrodibility, ammonium ion, so this plating bath is lower to the corrodibility of electroplating device, performance is gentle.
The nanometer zinc coating that above-mentioned galvanic deposit obtains, the subsequent disposal that can carry out as conventional zinc coating.
In the galvanic deposit system of the present invention, owing to do not contain the expendable organic additive, compare with bright galvanization, Composition Control becomes easily, and can prolong the pitch time that plating bath needs regularly to purify, thereby production cost is reduced, and reduces treatment cost of waste liquor simultaneously.
Nanometer galvanizing technique of the present invention can obtain the laminar nano zinc coating on metallic matrix, thickness in monolayer can appropriate regulation between 10 to 100 nanometers, increases with main salt concentration.Coating is careful, and outward appearance presents the silvery white slightly metalluster of dull gray.
The high power electron microscope observation can find that coating is uniform single nanometer multilayer zinc film.
Salt-fog test result shows that the nanometer zinc coating of the inventive method preparation is compared with routine is zinc-plated, and resistance to corrosion significantly improves.
Nanometer galvanized method plating bath temperature of the present invention and, corrodibility is low, stability is high, works under the condition without any other additive, need not frequently to adjust plating bath, just can obtain the nano-multilayer film of even compact.The coating resistance to corrosion significantly strengthens, and the plating condition is controlled easily, and production cost and treatment cost of waste liquor are reduced.
Embodiment:
Further specify the excellent properties of technical scheme of the present invention and coating of the present invention embodiment below by specific embodiment.
Embodiment 1
Plating bath is formed: zinc sulfate 50/L, and sodium sulfate 50g/L, sodium-acetate 10g/L, at first adjusting sodium acetate soln pH value with 5% dilute sulphuric acid is 4.5, adds the solution of other component then respectively, mix, 20 ℃ of plating bath working temperatures, the magnetic force rotation is stirred.
The cold-rolling mild steel plate of negative electrode: 10cm * 10cm, thickness are 1mm, through alkali cleaning and cleanup acid treatment.
Anode: pure zine plate 20cm * 20cm
Plating condition: cathode current density 0.5Adm
-2, 15 minutes time.
Plating is after distilled water flushing, and seasoning.
Effect: the coating outward appearance presents silvery white gloss, and is careful smooth, observes the microscopic appearance of coating under the emission Electronic Speculum on the scene, and can see and arrange laminate structure closely, about 40 nanometers of thickness in monolayer, thickness is approaching.Nanometer steel plate galvanized and common steel plate galvanized are contrasted, carry out neutral salt spray test according to national standard, the result shows that nano-deposit salt fog resistance corrosive power is enhanced about more than once.
Embodiment 2.
Plating bath is formed: zinc sulfate 124g/L, and sodium sulfate 75g/L, sodium-acetate 20g/L takes the identical method with embodiment 1, and adjusting pH value is 5.0,25 ℃ of plating bath working temperatures, magnetic force rotation stirring.
The cold-rolling mild steel plate of negative electrode: 10cm * 10cm, thickness are 1mm, through alkali cleaning and cleanup acid treatment.
Anode: pure zine plate 20cm * 20cm
Plating condition: current density 1Adm
-2, 30 minutes time.
Plating is after distilled water flushing, and seasoning.
Effect: coating is apparent similar to embodiment 1, and test detects and shows that coating also is nano-multilayer film, and corrosion resistance significantly is better than conventional zinc-plated.
Embodiment 3:
Plating bath is formed: zinc sulfate 200g/L, and sodium sulfate 150g/L, sodium-acetate 30g/L, method adjustment pH value is 5.3 similarly to Example 1,20 ℃ of plating bath working temperatures, the magnetic force rotation is stirred.
The copper coin of negative electrode: 10cm * 10cm, thickness are 0.2mm, wash processing through chemical rightenning.
Anode: pure zine plate 20cm * 20cm
Plating condition: current density 10Adm
-2, 30 minutes time.
Plating is after distilled water flushing, and seasoning.
Effect: coating is apparent substantially the same manner as Example 1, and an X-ray analysis and an emission electron microscopy observation result show, the thickness in monolayer of nano-multilayer film is significantly greater than example 1, about 70 nanometers, and salt-fog test shows the good resistance corrosive power.
Claims (4)
1. the electroplating preparation method of a nanometer multilayer zinc film, it is characterized in that electroplate liquid is by main salt zinc sulfate 50～200g/L, conducting salt sodium sulfate 50～150g/L, buffer reagent 10～30g/L and water constitute, adopt dilute sulphuric acid or sodium hydroxide that plating bath acidity pH value is controlled between 4.5～5.5, at first with main salt zinc sulfate, conducting salt sodium sulfate and buffer reagent are dissolved in the water respectively, adjust buffer agent solution to the acidity of setting with dilute sulphuric acid or sodium hydroxide again, then main salt and supporting electrolyte are mixed under stirring condition, adjust acidity once more to set(ting)value, make anode with pure zine plate during plating, workpiece to be plated is made negative electrode, and the control cathode current density is 0.5～10Adm
-2, electroplating time is 10～60 minutes, and working temperature is 15～40 ℃, and promptly electrodepositable obtains the nanometer multilayer zinc coating, and thickness in monolayer is between 10 to 100 nanometers.
2, the electroplating preparation method of nanometer multilayer zinc film as claimed in claim 1, the pH value that it is characterized in that described electroplate liquid is 4.7～5.3.
3, the electroplating preparation method of nanometer multilayer zinc film as claimed in claim 1 is characterized in that described buffer reagent adopts acetic acid, sodium-acetate, propionic acid, Sodium Propionate, butyric acid, Sodium propanecarboxylate or Succinic Acid.
4, the electroplating preparation method of nanometer multilayer zinc film as claimed in claim 1 is characterized in that described working temperature is 25～30 ℃.
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| CN 200310107939 CN1255578C (en) | 2003-10-16 | 2003-10-16 | Nano Multi-layer zinc film electroplating preparation method |
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| CN1255578C CN1255578C (en) | 2006-05-10 |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100415942C (en) * | 2006-01-12 | 2008-09-03 | 上海大学 | Production of nanometer crystal zinc plating |
| CN105908224A (en) * | 2016-06-18 | 2016-08-31 | 安徽昊博健身器材有限公司 | Surface treatment method for steel piece |
| CN111005042A (en) * | 2018-10-05 | 2020-04-14 | 爱富意喜制链株式会社 | Plated component |
-
2003
- 2003-10-16 CN CN 200310107939 patent/CN1255578C/en not_active Expired - Fee Related
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100415942C (en) * | 2006-01-12 | 2008-09-03 | 上海大学 | Production of nanometer crystal zinc plating |
| CN105908224A (en) * | 2016-06-18 | 2016-08-31 | 安徽昊博健身器材有限公司 | Surface treatment method for steel piece |
| CN111005042A (en) * | 2018-10-05 | 2020-04-14 | 爱富意喜制链株式会社 | Plated component |
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| Publication number | Publication date |
|---|---|
| CN1255578C (en) | 2006-05-10 |
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