CN101008098A - Two-step electrochemical method for preparing aluminum base composite material surface protection coating - Google Patents
Two-step electrochemical method for preparing aluminum base composite material surface protection coating Download PDFInfo
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- CN101008098A CN101008098A CN 200610147647 CN200610147647A CN101008098A CN 101008098 A CN101008098 A CN 101008098A CN 200610147647 CN200610147647 CN 200610147647 CN 200610147647 A CN200610147647 A CN 200610147647A CN 101008098 A CN101008098 A CN 101008098A
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Abstract
The invention discloses a method for preparing surface protective coating for composite material, belonging to material engineering technology field. The method comprises following steps: (1) pretreating surface of composite material: polishing, oil removing and acid activating, getting pretreated surface; (2) oxidating anode of composite material: taking mixture of hydric sulphate, oxalic acid, boracic acid and glycerin as anode oxidating liquid, anodizing the TiB2 particle intensified aluminium- base composite material and forming an aluminum oxide membrane; (3) polarizing with constant current cathode and depositing rare earth compound; getting one homogenous rare earth compound membrane on surface of material by making use of cathodic electrochemical reaction in rare earth salt mixing solution. The invention employs two- step electrochemistry method to treat the surface of composite material and gets compact protective membrane with a certain thickness on the surface of composite material, which increases anti- corrosion property, and the process is simple.
Description
Technical field
What the present invention relates to is a kind of preparation method of surface coating, specifically, is the method that a kind of two-step electrochemical prepares aluminum base composite material surface protection coating, belongs to field of material engineering technology.
Background technology
In-situ self-generated TiB
2In the particle enhanced aluminum-based composite material, the introducing of enhanced granule has improved the mechanical property of this material greatly, and it is all had broad application prospects in various fields.But TiB
2Enhanced granule exists and to cause the corrosion resistance of matrix material more much lower than matrix alloy, seriously limit this material at some etching condition than the use in the severe rugged environment.This mainly is because TiB
2Particle has electroconductibility, and the galvanic couple reaction very easily takes place in corrosive atmosphere for it and base aluminum, thereby has quickened the corrosion of aluminum substrate.Improve the corrosion resistance of this matrix material, particularly improve the solidity to corrosion of material surface, it is particularly important to better meet the practical application in industry demand for this matrix material.
Relevant raising anticorrosive coating on surface of aluminium base composite material preparation technology's report mainly is at SiC particle reinforced composite materials, and the processing method multimode is imitated, and aluminium alloy, anode oxidation method more to be seen.
Find by prior art documents, people such as He Chunlin write articles " the corrosion proof electrochemical impedance research of SiCp/2024Al matrix material anode oxide film " at " Acta Metallurgica Sinica " 2001:37 (8): 869-872, the sulfuric acid electrolyte that this article proposes to adopt has carried out anodic oxidation to the SiCp/2024Al matrix material, carrying out sealing of hole with potassium bichromate solution handles, improved the corrosion resistance nature of matrix material to a certain extent, but test is found the existence of enhanced granule and has been limited the integrity and the homogeneity of oxidation filming, the dichromate hole sealing solution of Cai Yonging contains a large amount of hexavalent chromiums simultaneously, its toxicity is big, environment is caused great pollution, the serious harm HUMAN HEALTH.
Summary of the invention
The present invention is directed to the deficiency that exists in the above-mentioned technology, provide a kind of two-step electrochemical to prepare the method for aluminum base composite material surface protection coating, make it remedy the discontinuous deficiency of single anodic oxidation matrix material film forming on the one hand, adopt on the other hand at rare earths salt cathodic deposition rare earth compound, replace deleterious chromic salt hole-sealing technology, thereby improved the corrosion resistance of composite material surface greatly, be more suitable in industrial applying.
The present invention implements by the following technical programs, the present invention adopts mixed acid anodic oxidation electrolytic solution, prepares pellumina at composite material surface, again with pellumina as negative electrode, in the rare-earth salts mixing solutions, carry out the continuous current cathodic polarization, rare earth compound is deposited at material surface.Effectively improve in-situ self-generated TiB by the two-step electrochemical surface treatment
2Particle enhanced aluminum-based composite material surface corrosion resistance nature.
Concrete steps of the present invention are as follows:
(1) matrix material is carried out surface preparation: adopt polishing, oil removing and acidic activated, obtain pretreating surface;
(2) matrix material anodic oxidation: adopt sulfuric acid, oxalic acid, boric acid and glycerol mixing solutions as anodizing solution, to original position TiB
2Particle enhanced aluminum-based composite material carries out anodizing, generates one deck pellumina on its surface;
(3) continuous current cathodic polarization deposition of rare-earth compound: utilize the electrochemical cathode reaction in the rare-earth salts mixing solutions, obtain layer of even rare earth compound film at material surface.
In the described step (1), finishing method is: successively through #180, #320, #600, #1000 sand papering polishing, mechanical polishing again.
In the described step (1), the used degreasing fluid of oil removing is an acetone soln.
In the described step (1), acidic activated being specially: activate 10-20s in immersion nitric acid and the hydrofluoric acid mixing solutions, nitric acid and hydrofluoric acid volume ratio are 3: 1.
In the described step (2), anodizing solution adopts the deionized water preparation, and the shared quality percentage composition of each composition is as follows: 15.0-20.0% sulfuric acid, 1.0-2.0% oxalic acid, 0.03-0.05% boric acid and 0.03-0.05% glycerol.
In the described step (2), the anode oxidation process parameter is: current density is 1.0-1.5A/dm
2, oxidizing temperature is 15 ℃, oxidization time is 0.5-1h.
In the described step (3), the rare-earth salts mixing solutions composition that adopts in the cathodic polarization: cerous chlorate or cerous sulfate concentration range are 1.5-2.5 * 10
-3Mol/L, the glycerol concentration range is 0.3-0.5ml/L.
In the described step (3), cathodic deposition is: as negative electrode, stereotype is as anode with oxide film, current density 1.0-2.0mA/dm
2, 25 ℃ of treatment temps, the treatment time is 0.5-1.5h.
The present invention has substantive distinguishing features and marked improvement, adopts the two-step electrochemical method, promptly first anodic oxidation, the preparation technology of back cathodic polarization: prepare pellumina by first anodic oxidation at composite material surface, eliminate conductive particle TiB
2And the possibility of galvanic couple reaction takes place between the base aluminum, utilize the bipolarity and the TiB of anode oxide film
2Particulate electroconductibility adopts cathodic deposition polarize oxide film and TiB in rare earths salt
2Particle is by oxide film porous layer and the TiB of the electrochemical reaction in the solution at negative electrode
2Deposition layer of even rare earth compound film on the particle surface.The present invention remedied the deficiency of matrix material anode oxide film poor continuity, eliminated the harm that traditional chromic acid salt hole-sealing technology brings environment and human body.Adopt this technology TiB in position
2The protective coating of particle enhanced aluminum-based composite material surface preparation carries out electro-chemical test in NaCl solution, corrosion electric current density is compared with untreated material, and 2-3 the order of magnitude descended.This shows that supercoat has good corrosion resistance.This technological operation is easy, suitability is strong.
Embodiment
Below embodiments of the invention are elaborated: present embodiment is being to implement under the prerequisite with the technical solution of the present invention, provided detailed embodiment and concrete operating process, but protection scope of the present invention is not limited to following embodiment.
Embodiment 1
1) matrix material through #180, #320, #600, #1000 sand papering polishing, carries out mechanical polishing successively again.After the acetone soln oil removing, immerse activation 10s in nitric acid and the hydrofluoric acid mixing solutions (volume ratio 3: 1);
2) adopting concentration is that 15.0% sulfuric acid, 1.5% oxalic acid, 0.05% boric acid and 0.05% glycerol mixed solution are as electrolytic solution, at 1.5A/dm
2, matrix material is carried out the 0.5h anodic oxidation under 15 ℃, generate the pellumina of thickness 12-15 μ m;
3) with oxide film as negative electrode, stereotype is as anode, carries out cathodic polarization and handles.Rare earths salt composition: cerous chlorate concentration 1.5 * 10
-3Mol/L, glycerol concentration 0.3ml/L, current density 1.0mA/dm
2, 25 ℃ of treatment temps, 0.5 hour treatment time.
Carry out electrochemical test in 3.5wt.%NaCl solution, the result shows: surface treated sample is compared with untreated sample, and corrosion resistance obviously improves, and corrosion electric current density is from 10
-5A/cm
2The order of magnitude is reduced to 10
-7A/cm
2The order of magnitude, the corrosion current of the oxide film of this corrosion electric current density and chromic salt sealing of hole has been in the same order of magnitude.
Embodiment 2
1) matrix material through #180, #320, #600, #1000 sand papering polishing, carries out mechanical polishing successively again.After the acetone soln oil removing, immerse activation 20s in nitric acid and the hydrofluoric acid mixing solutions (volume ratio 3: 1);
2) adopting concentration is that 18.0% sulfuric acid, 2.0% oxalic acid, 0.04% boric acid and 0.03% glycerol mixed solution are as electrolytic solution, at 1.5A/dm
2, matrix material is carried out the 1h anodic oxidation under 15 ℃, generate the pellumina of thickness 20-25 μ m;
3) with oxide film as negative electrode, stereotype is as anode, carries out cathodic polarization and handles.Rare salts solution composition of going up: cerous chlorate concentration 2.5 * 10
-3Mol/L, glycerol concentration 0.5ml/L, current density 1.5mA/dm
2, 25 ℃ of treatment temps, 1 hour treatment time.
Carry out electrochemical test in 3.5wt.%NaCl solution, the result shows: surface treated sample is compared with untreated sample, and corrosion resistance obviously improves, and corrosion electric current density is from 10
-5A/cm
2The order of magnitude is reduced to 10
-8A/cm
2The order of magnitude.
Embodiment 3
1) matrix material through #180, #320, #600, #1000 sand papering polishing, carries out mechanical polishing successively again.After the acetone soln oil removing, immerse activation 15s in nitric acid and the hydrofluoric acid mixing solutions (volume ratio 3: 1);
2) adopting concentration is that 20.0% sulfuric acid, 1.0% oxalic acid, 0.03% boric acid and 0.04% glycerol mixed solution are as electrolytic solution, at 1.0A/dm
2, matrix material is carried out the 1h anodic oxidation under 15 ℃, generate the pellumina of thickness 20-25 μ m;
3) with oxide film as negative electrode, stereotype is as anode, carries out cathodic polarization and handles.Rare earths salt composition: cerous sulfate concentration 2.5 * 10
-3Mol/L, glycerol concentration 0.5ml/L, current density 2.0mA/dm
2, 25 ℃ of treatment temps, 1.5 hours treatment times.
Carry out electrochemical test in 3.5wt.%NaCl solution, the result shows: surface treated sample is compared with untreated sample, and corrosion resistance obviously improves, and corrosion electric current density is from 10
-5A/cm
2The order of magnitude is reduced to 10
-8A/cm
2The order of magnitude.
Embodiment 4
1) matrix material through #180, #320, #600, #1000 sand papering polishing, carries out mechanical polishing successively again.After the acetone soln oil removing, immerse activation 15s in nitric acid and the hydrofluoric acid mixing solutions (volume ratio 3: 1);
2) adopting concentration is that 20.0% sulfuric acid, 1.0% oxalic acid, 0.03% boric acid and 0.04% glycerol mixed solution are as electrolytic solution, at 1.2A/dm
2, matrix material is carried out the 0.75h anodic oxidation under 15 ℃, generate the pellumina of thickness 18-22 μ m;
3) with oxide film as negative electrode, stereotype is as anode, carries out cathodic polarization and handles.Rare earths salt composition: cerous sulfate concentration 2.0 * 10
-3Mol/L, interior three determining alcohol 0.4ml/L, current density 2.0mA/dm
2, 25 ℃ of treatment temps, 1 hour treatment time.
Carry out electrochemical test in 3.5wt.%NaCl solution, the result shows: surface treated sample is compared with untreated sample, and corrosion resistance obviously improves, and corrosion electric current density is from 10
-5A/cm
2The order of magnitude, electricity is reduced to 10
-8A/cm
2The order of magnitude.
Claims (8)
1. a two-step electrochemical prepares the method for aluminum base composite material surface protection coating, it is characterized in that concrete steps are as follows:
(1) matrix material is carried out surface preparation: adopt polishing, oil removing and acidic activated, obtain pretreating surface;
(2) matrix material anodic oxidation: adopt sulfuric acid, oxalic acid, boric acid and glycerol mixing solutions as anodizing solution, to original position TiB
2Particle enhanced aluminum-based composite material carries out anodizing, generates one deck pellumina on its surface;
(3) continuous current cathodic polarization deposition of rare-earth compound: utilize the electrochemical cathode reaction in the rare-earth salts mixing solutions, obtain layer of even rare earth compound film at material surface.
2. two-step electrochemical according to claim 1 prepares the method for aluminum base composite material surface protection coating, it is characterized in that, in the described step (1), finishing method is: successively through #180, #320, #600, #1000 sand papering polishing, mechanical polishing again.
3. two-step electrochemical according to claim 1 prepares the method for aluminum base composite material surface protection coating, it is characterized in that, in the described step (1), the used degreasing fluid of oil removing is an acetone soln.
4. two-step electrochemical according to claim 1 prepares the method for aluminum base composite material surface protection coating, it is characterized in that, in the described step (1), acidic activated being specially: activate 10-20s in immersion nitric acid and the hydrofluoric acid mixing solutions, nitric acid and hydrofluoric acid volume ratio are 3: 1.
5. two-step electrochemical according to claim 1 prepares the method for aluminum base composite material surface protection coating, it is characterized in that, in the described step (2), anodizing solution adopts the deionized water preparation, and the shared quality percentage composition of each composition is as follows: 15.0-20.0% sulfuric acid, 1.0-2.0% oxalic acid, 0.03-0.05% boric acid and 0.03-0.05% glycerol.
6. two-step electrochemical according to claim 1 prepares the method for aluminum base composite material surface protection coating, it is characterized in that, in the described step (2), the anode oxidation process parameter is: current density is 1.0-1.5A/dm
2, oxidizing temperature is 15 ℃, oxidization time is 0.5-1h.
7. two-step electrochemical according to claim 1 prepares the method for aluminum base composite material surface protection coating, it is characterized in that, in the described step (3), rare-earth salts mixing solutions composition: cerous chlorate or cerous sulfate concentration range are 1.5-2.5 * 10
-3Mol/L, the glycerol concentration range is 0.3-0.5ml/L.
8. two-step electrochemical according to claim 1 prepares the method for aluminum base composite material surface protection coating, it is characterized in that, in the described step (3), cathodic deposition is: as negative electrode, stereotype is as anode with oxide film, current density 1.0-2.0mA/dm
2, 25 ℃ of treatment temps, the treatment time is 0.5-1.5h.
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101220495B (en) * | 2007-09-28 | 2010-09-15 | 四川航空液压机械厂 | Method for processing multiple anodization surface of light metal products |
| CN102808207A (en) * | 2012-09-05 | 2012-12-05 | 天津大学 | Preparation method for aluminum anode oxidized films |
| CN103290452A (en) * | 2013-04-08 | 2013-09-11 | 西安建筑科技大学 | Preparation method for corrosion-resistant nano-array alumina/ceria composite membrane |
| CN104372394A (en) * | 2014-07-03 | 2015-02-25 | 西安工业大学 | Preparation method for oxide ceramic layer |
| CN104797726A (en) * | 2012-10-17 | 2015-07-22 | 法国肯联铝业 | Vacuum chamber elements made of aluminium alloy |
| CN104611671B (en) * | 2015-01-08 | 2017-08-08 | 广西大学 | A kind of intermediate layer for stopping elements diffusion and preparation method thereof |
| CN108517550A (en) * | 2018-06-13 | 2018-09-11 | 沈阳富创精密设备有限公司 | A kind of addition rare earth element sulfuric acid-oxalic acid anodizing aluminium film preparation method |
| CN111364081A (en) * | 2020-04-02 | 2020-07-03 | 南京理工大学 | Preparation method of porous alumina template with gradient change of aperture and thickness |
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2006
- 2006-12-21 CN CNB2006101476472A patent/CN100564608C/en not_active Expired - Fee Related
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101220495B (en) * | 2007-09-28 | 2010-09-15 | 四川航空液压机械厂 | Method for processing multiple anodization surface of light metal products |
| CN102808207A (en) * | 2012-09-05 | 2012-12-05 | 天津大学 | Preparation method for aluminum anode oxidized films |
| CN104797726A (en) * | 2012-10-17 | 2015-07-22 | 法国肯联铝业 | Vacuum chamber elements made of aluminium alloy |
| CN104797726B (en) * | 2012-10-17 | 2017-10-24 | 伊苏瓦尔肯联铝业 | The vacuum chamber element being made up of aluminium alloy |
| TWI615480B (en) * | 2012-10-17 | 2018-02-21 | 伊蘇瓦爾肯聯鋁業 | Vacuum chambers elements made of aluminum alloy |
| CN103290452A (en) * | 2013-04-08 | 2013-09-11 | 西安建筑科技大学 | Preparation method for corrosion-resistant nano-array alumina/ceria composite membrane |
| CN103290452B (en) * | 2013-04-08 | 2015-08-19 | 西安建筑科技大学 | A kind of preparation method of corrosion proof nano-array alumina/ceria composite membrane |
| CN104372394A (en) * | 2014-07-03 | 2015-02-25 | 西安工业大学 | Preparation method for oxide ceramic layer |
| CN104611671B (en) * | 2015-01-08 | 2017-08-08 | 广西大学 | A kind of intermediate layer for stopping elements diffusion and preparation method thereof |
| CN108517550A (en) * | 2018-06-13 | 2018-09-11 | 沈阳富创精密设备有限公司 | A kind of addition rare earth element sulfuric acid-oxalic acid anodizing aluminium film preparation method |
| CN111364081A (en) * | 2020-04-02 | 2020-07-03 | 南京理工大学 | Preparation method of porous alumina template with gradient change of aperture and thickness |
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