CN103741126A - Preparation method of surface self-stratifying composite coating of magnesium alloy - Google Patents
Preparation method of surface self-stratifying composite coating of magnesium alloy Download PDFInfo
- Publication number
- CN103741126A CN103741126A CN201310705732.6A CN201310705732A CN103741126A CN 103741126 A CN103741126 A CN 103741126A CN 201310705732 A CN201310705732 A CN 201310705732A CN 103741126 A CN103741126 A CN 103741126A
- Authority
- CN
- China
- Prior art keywords
- preparation
- tio
- ceo
- colloidal sol
- hours
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Images
Landscapes
- Chemically Coating (AREA)
- Chemical Treatment Of Metals (AREA)
Abstract
The invention discloses a preparation method of a surface self-stratifying CeO2/TiO2 composite coating of a magnesium alloy, and aims to solve the problems of complex preparation process, poor coating effect and poor adhesion property in the prior art. The preparation method provided by the invention comprises: firstly, a step of preprocessing a magnesium alloy sample; a step of preparing a CeO2 sol; a step of preparing a TiO2 sol; a step of preparing a CeO2/TiO2 sol; and a step of spreading the CeO2/TiO2 composite coating. The preparation method provided by the invention realizes that a multi-coating system can be formed on the magnesium alloy AZ31B through once spreading; the CeO2/TiO2 composite coating is formed into a film once; the interlayer interface is eliminated and the problem of poor adhesion property of the thin film is solved; besides, the preparation method provided by the invention is available in raw materials, low in cost, and free of any toxic substance; the whole preparation process is green and environment-friendly; and the preparation method is simple in process and suitable for industrial production.
Description
Technical field
The present invention relates to prepared by a kind of Mg alloy surface gel method from hierarchical composite coating and preparation method thereof.
Background technology
Magnesium alloy has that quality is light, specific tenacity is high, hardness is high, good capability of electromagnetic shielding, machinability and thermoforming performance, good heat conductivility, the good features such as biocompatibility, it is the desirable matrix of Development of New Generation hitech materials, therefore, magnesium alloy has important using value and wide application prospect in fields such as automobile, electronics, aerospace, defence and military, bio-medicals, is called as 21 century " green engineering material ".Along with the development of the process for processing technology of magnesium and constantly perfect, magnesium alloy materials oneself through becoming the third-largest structural metallic engineering material after iron and steel, aluminium alloy, in worldwide, obtain swift and violent development.
At present, for the surface treatment method that improves corrosion resistance of magnesium alloy energy, mainly contain: chemical conversion embrane method (comprises chromic salt, stannate.Phosphoric acid salt etc.), anonizing, electrochemical plating, organic coating method etc.In chromate conversion coating, hexavalent chromium has severe toxicity, causes environmental pollution; Stannate, phosphate conversion film sample pretreatment process complexity, have pollution to water and soil; Anodic oxidation equipment requirements is high, and power consumption is large; Electrochemical plating are poisonous, and difficult treatment, aforesaid method is owing to there being problems in preparation technology, such as the bad control of processing parameter, apply inhomogeneous etc., cause existing between coating and coating a plurality of interfaces, and there are a large amount of defects, the rate of permeation of erosion is very high, has reduced the anticorrosion ability of protective coating.
In sum, existing method ubiquity applies the problems such as weak effect, complex process, process costs height.
Summary of the invention
In order to solve above-mentioned problems of the prior art, the present invention proposes prepared by a kind of Mg alloy surface gel method from hierarchical composite coating, this coating has been eliminated interface between layers, improves the non-corrosibility of coating.
Technical solution of the present invention comprises:
A kind of Mg alloy surface is from layering CeO
2/ TiO
2the preparation method of compound coating, comprises the following steps:
A, first magnesium alloy sample is carried out to pre-treatment;
B, cerous nitrate is dissolved for some time in ethanol according to 5% concentration, add pyroxylin (e) cement, stir, standing aging, obtain CeO
2colloidal sol;
C, by butyl (tetra) titanate and methyl ethyl diketone in molar ratio for 1:2 stirs chelating, add etoh solvent, obtain TiO
2colloidal sol;
D, CeO
2/ TiO
2the preparation of colloidal sol: the CeO that step b is prepared
2the TiO that colloidal sol and step c prepare
2colloidal sol is 1:1 mix and blend by volume, aging 24 hours, obtains CeO
2/ TiO
2colloidal sol;
E, by CeO
2/ TiO
2colloidal sol mixes according to 5:1 volume ratio with trolamine and applies at Mg alloy surface, is dried, curing obtaining from layering CeO
2/ TiO
2compound coating.
In described step b, dissolve 1～3 hour, add 3～8mL pyroxylin (e) cement, stir 1～3 hour, standing aging 24 hours.
In described step c, stir chelating 2 hours.
In described step b, dissolve 2 hours, add 5mL pyroxylin (e) cement, stir 2 hours.
The useful technique effect that the present invention brings:
The present invention proposes a kind of Mg alloy surface from layering CeO
2/ TiO
2the preparation method of compound coating, compared with prior art, this preparation method has realized on magnesium alloy AZ31B and has once applied and just can form multi-coating system, CeO
2/ TiO
2compound coating one-pass film-forming, eliminates interface layer, has solved the poor problem of adhesive force;
Rete that the present invention prepares is fine and close, smooth, even thickness, good with basal body binding force, has stronger erosion resistance,
Raw material of the present invention is easy to get, with low cost, do not use any toxic substance, whole preparation process environmental protection, and technique is simple, is suitable for suitability for industrialized production.
Accompanying drawing explanation
Below in conjunction with accompanying drawing, the present invention is done to further clear, complete explanation:
Fig. 1 is preparation technology's schema of the present invention.
Embodiment
Below in conjunction with embodiment, the present invention is done to further clear, complete explanation:
The selected raw material of the present invention, except special instruction, all can be bought and be obtained by commercial channel.
Embodiment 1:
The present invention, by reference to the accompanying drawings 1, a kind of Mg alloy surface is from layering CeO
2/ TiO
2the preparation method of compound coating, comprises the following steps:
Step 1, magnesium alloy sample is carried out to pre-treatment:
Magnesium alloy AZ31B, after cut mechanically, is to minute surface with 200#, 1200# sand papering to surface, selects NaOH to carry out oil removal treatment, after 5%HF acid-wash activation, dry after cleaning 3 times with distilled water standby;
Step 2, CeO
2the preparation of colloidal sol:
By cerous nitrate (Ce (NO
3)
3) concentration according to 5% dissolves to stir after one hour and add 3mL pyroxylin (e) cement in ethanol, stirs after 3 hours standing aging 24 hours, obtains CeO
2colloidal sol;
Step 3, TiO
2the preparation of colloidal sol:
By butyl (tetra) titanate and methyl ethyl diketone, in molar ratio for 1:2 stirs chelating 2 hours, adding ethanol is that solvent obtains TiO
2colloidal sol;
Step 4, CeO
2/ TiO
2the preparation of colloidal sol:
By the CeO of step 2 preparation
2the TiO of colloidal sol and step 3 preparation
2colloidal sol is pressed 1:1 volume ratio mix and blend, aging 24 hours, obtains CeO
2/ TiO
2colloidal sol;
Step 5, the CeO preparing in step 4
2/ TiO
2colloidal sol mixes according to 5:1 volume ratio with trolamine, again the pretreated magnesium alloy AZ31B of step 1 substrate was processed for 5 seconds in 0.01% plant acid solution, after cleaning, drying in colloidal sol dipping, with the speed of 10cm/h, lift, and rapid airing, obtains pre-treatment film;
Step 6, CeO
2/ TiO
2preparation from hierarchical composite coating:
The pre-treatment film of preparation in step 5 be take to temperature rise rate as 3 ℃/min, 400 ℃ of sintering 1 hour, obtain CeO
2/ TiO
2from hierarchical composite coating.
Embodiment 2:
Difference from Example 1 is: in step 2, by cerous nitrate (Ce (NO
3)
3) concentration according to 5% dissolves to stir after 3 hours and add 8mL pyroxylin (e) cement in ethanol, stirs after 1 hour standing aging 24 hours, obtains CeO
2colloidal sol.After filming, take temperature rise rate as 3 ℃/min, 400 ℃ of sintering 1 hour, obtain CeO
2coating.
Embodiment 3:
Difference from Example 1 is: by butyl (tetra) titanate and methyl ethyl diketone, in molar ratio for 1:2 stirs chelating 2 hours, adding ethanol is that solvent obtains TiO
2colloidal sol.After filming, take temperature rise rate as 3 ℃/min, 400 ℃ of sintering 1 hour, obtain TiO
2coating.
The CeO that table 1 prepares for the embodiment of the present invention 3
2/ TiO
2ceO in hierarchical composite coating and prior art
2coating, TiO
2the corrosion resistance nature comparison of coating:
Table 1
Claims (4)
1. a Mg alloy surface is from layering CeO
2/ TiO
2the preparation method of compound coating, is characterized in that comprising the following steps:
A, first magnesium alloy sample is carried out to pre-treatment;
B, cerous nitrate is dissolved for some time in ethanol according to 5% concentration, add pyroxylin (e) cement, stir, standing aging, obtain CeO
2colloidal sol;
C, by butyl (tetra) titanate and methyl ethyl diketone in molar ratio for 1:2 stirs chelating, add etoh solvent, obtain TiO
2colloidal sol;
D, CeO
2/ TiO
2the preparation of colloidal sol: the CeO that step b is prepared
2the TiO that colloidal sol and step c prepare
2colloidal sol is 1:1 mix and blend by volume, aging 24 hours, obtains CeO
2/ TiO
2colloidal sol;
E, by CeO
2/ TiO
2colloidal sol mixes according to 5:1 volume ratio with trolamine and applies at Mg alloy surface, is dried, curing obtaining from layering CeO
2/ TiO
2compound coating.
2. preparation method according to claim 1, is characterized in that: in described step b, dissolve 1～3 hour, add 3～8mL pyroxylin (e) cement, stir 1～3 hour, standing aging 24 hours.
3. preparation method according to claim 1, is characterized in that: in described step c, stir chelating 2 hours.
4. preparation method according to claim 2, is characterized in that: in described step b, dissolve 2 hours, add 5mL pyroxylin (e) cement, stir 2 hours.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310705732.6A CN103741126B (en) | 2013-12-20 | 2013-12-20 | A kind of preparation method of Mg alloy surface self demixing compound coating |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310705732.6A CN103741126B (en) | 2013-12-20 | 2013-12-20 | A kind of preparation method of Mg alloy surface self demixing compound coating |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103741126A true CN103741126A (en) | 2014-04-23 |
| CN103741126B CN103741126B (en) | 2016-04-20 |
Family
ID=50498189
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310705732.6A Expired - Fee Related CN103741126B (en) | 2013-12-20 | 2013-12-20 | A kind of preparation method of Mg alloy surface self demixing compound coating |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103741126B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112522673A (en) * | 2021-02-18 | 2021-03-19 | 中南大学湘雅医院 | Biomedical magnesium alloy surface rare earth composite film and preparation method thereof |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB0509606D0 (en) * | 2005-05-11 | 2005-06-15 | Univ Sheffield Hallam | Sol-gel derived coating |
| CN1669934A (en) * | 2005-03-04 | 2005-09-21 | 河北工业大学 | Tourmaline/titanium dioxide composite collosol containing rare earth and its preparation method and uses |
| CN1900360A (en) * | 2006-07-14 | 2007-01-24 | 西南大学 | Process for preparing magnesium alloy surface function gradient film |
| CN201567375U (en) * | 2009-12-28 | 2010-09-01 | 重庆理工大学 | Corrosion-Proof coating on surface of magnesium alloy |
| CN202278782U (en) * | 2011-11-07 | 2012-06-20 | 山东科技大学 | Corrosion-resistant composite coating on surface of magnesium alloy |
| CN102718411A (en) * | 2012-06-12 | 2012-10-10 | 华南理工大学 | Natural super-hydrophilic porous TiO2/SiO2 composite thin film and preparation method thereof |
-
2013
- 2013-12-20 CN CN201310705732.6A patent/CN103741126B/en not_active Expired - Fee Related
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1669934A (en) * | 2005-03-04 | 2005-09-21 | 河北工业大学 | Tourmaline/titanium dioxide composite collosol containing rare earth and its preparation method and uses |
| GB0509606D0 (en) * | 2005-05-11 | 2005-06-15 | Univ Sheffield Hallam | Sol-gel derived coating |
| GB2425976A (en) * | 2005-05-11 | 2006-11-15 | Univ Sheffield Hallam | Sol-gel derived coating |
| CN1900360A (en) * | 2006-07-14 | 2007-01-24 | 西南大学 | Process for preparing magnesium alloy surface function gradient film |
| CN201567375U (en) * | 2009-12-28 | 2010-09-01 | 重庆理工大学 | Corrosion-Proof coating on surface of magnesium alloy |
| CN202278782U (en) * | 2011-11-07 | 2012-06-20 | 山东科技大学 | Corrosion-resistant composite coating on surface of magnesium alloy |
| CN102718411A (en) * | 2012-06-12 | 2012-10-10 | 华南理工大学 | Natural super-hydrophilic porous TiO2/SiO2 composite thin film and preparation method thereof |
Non-Patent Citations (2)
| Title |
|---|
| F.E.GHODSI ET AL.: "Study of time effect on the optical properties of spin-coated CeO2-TiO2 thin films", 《SOLAR ENERGY MATERIALS & SOLAR CELLS》 * |
| J.M.FAN ET AL.: "Composite cerium oxide/titanium oxide thin films for corrosion protection of AZ91D magnesium alloy via sol-gel process", 《MATERIALS AND CORROSION》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112522673A (en) * | 2021-02-18 | 2021-03-19 | 中南大学湘雅医院 | Biomedical magnesium alloy surface rare earth composite film and preparation method thereof |
| CN112522673B (en) * | 2021-02-18 | 2021-04-27 | 中南大学湘雅医院 | Biomedical magnesium alloy surface rare earth composite film and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103741126B (en) | 2016-04-20 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Becker | Chromate-free chemical conversion coatings for aluminum alloys | |
| CN103695871B (en) | The rust inhibition anion intercalation hydrotalcite film that a kind of Mg alloy surface hydrothermal deposition legal system is standby | |
| CN101629287B (en) | Magnesium alloy surface treatment process | |
| CN105132900A (en) | Anticorrosion treatment process for converting/electro-statically spraying environment-friendly zirconium titanate on surfaces of aluminum alloys | |
| CN103276386A (en) | Chromium-free environment-friendly passivator for brass cartridge case of cartridge and preparation method | |
| CN102383123A (en) | Anti-corrosion material applicable to surface of aeronautical aluminum alloy and application of anti-corrosion material | |
| Tian et al. | Corrosion inhibition property and promotion of green basil leaves extract materials on Ti-Zr conversion composite coatings | |
| CN103087627B (en) | A kind of metal aluminum alloy silane surface treatment agent and preparation method thereof | |
| CN103102724B (en) | A kind of containing acrylic acid Metal surface silane treatment agent and preparation method thereof | |
| CN103088327A (en) | Metal surface silane treatment agent containing water-soluble phenolic resin and preparation method thereof | |
| CN103741126B (en) | A kind of preparation method of Mg alloy surface self demixing compound coating | |
| CN106009794A (en) | Comprehensive anti-corrosion coating with alloy co-doping, Dacromet and sealing layer | |
| CN103184447B (en) | Aluminum and aluminum alloy surface self-repairing and corrosion-resisting conversion coating and preparation method thereof | |
| CN107400883A (en) | Silane/zirconium composite treating agent and preparation method thereof before galvanized sheet application | |
| CN103103514B (en) | Spraying type ferric solid-acid comprehensive treatment agent and preparation method before spheroidal graphite casting application | |
| Crespo et al. | Electrochemical behaviour of ceramic yttria stabilized zirconia on carbon steel synthesized via sol–gel process | |
| Hao et al. | Characteristics of Ce–Mn film on 6061 alloys and its improved performance | |
| CN102728530A (en) | Method for enhancing anti-corrosion and wear-resisting properties of phosphate film | |
| CN103088328A (en) | Silane finishing agent at surface of galvanized steel sheet and preparation method thereof | |
| CN104761943A (en) | Magnesium alloy corrosion-resistant coating and application thereof | |
| CN105887006B (en) | Capital construction metalwork alloy permeation and Dacroment composite anti-corrosive coating | |
| CN106521596B (en) | A kind of anode surface micro arc plasma body prepares the solution and preparation method of anti-marine microorganism film | |
| CN102127731B (en) | Method for preparing porous metal substrate with high temperature oxidation resistance | |
| CN106011740B (en) | A kind of alloy permeation and Dacroment composite anti-corrosive coating production | |
| CN104109472A (en) | Corrosion resistant aluminum alloy surface treatment agent |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20160420 Termination date: 20171220 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |