CN103741126B - A kind of preparation method of Mg alloy surface self demixing compound coating - Google Patents
A kind of preparation method of Mg alloy surface self demixing compound coating Download PDFInfo
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- CN103741126B CN103741126B CN201310705732.6A CN201310705732A CN103741126B CN 103741126 B CN103741126 B CN 103741126B CN 201310705732 A CN201310705732 A CN 201310705732A CN 103741126 B CN103741126 B CN 103741126B
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- tio
- preparation
- ceo
- colloidal sol
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Abstract
The invention discloses a kind of Mg alloy surface self demixing CeO
2/ TiO
2the preparation method of compound coating, which solves complicated process of preparation in prior art, coating result is poor, adhesion property is poor problem.Preparation method of the present invention comprises the following steps: first carry out pretreated step to magnesium alloy sample; CeO
2sol preparation step; TiO
2sol preparation step; CeO
2/ TiO
2the preparation process of colloidal sol: CeO
2/ TiO
2compound coating coating step.Preparation method of the present invention to achieve on magnesium alloy AZ31B once coating just can form multi-coating system, CeO
2/ TiO
2compound coating one-pass film-forming, eliminates interface layer, solves the problem of adhesive force difference; 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.
Description
Technical field
The present invention relates to self demixing compound coating prepared by a kind of Mg alloy surface gel method 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, the features such as good heat conductivility, good biocompatibility, it is the desired 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, mainly contain for the surface treatment method improving corrosion resistance of magnesium alloy energy: 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 are complicated, have pollution to water and soil; Anodic oxidation equipment requirements is high, and power consumption is large; Electrochemical plating are poisonous, and difficult treatment, owing to there are problems in preparation technology in aforesaid method, the bad control of such as processing parameter, apply uneven etc., cause between coating and coating, there is multiple interface, and there is a large amount of defect, the rate of permeation of erosion is very high, reduces 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 self demixing compound coating prepared by a kind of Mg alloy surface gel method, this coating eliminates interface between layers, improves the non-corrosibility of coating.
Technical solution of the present invention comprises:
A kind of Mg alloy surface self demixing CeO
2/ TiO
2the preparation method of compound coating, comprises the following steps:
A, first pre-treatment is carried out to magnesium alloy sample;
B, by cerous nitrate according to 5% concentration dissolve for some time in ethanol, add pyroxylin (e) cement, stir, leave standstill 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 and trolamine mix according to 5:1 volume ratio and carry out applying at Mg alloy surface, dry, solidify and obtain self demixing CeO
2/ TiO
2compound coating.
Dissolve 1 ~ 3 hour in described step b, add 3 ~ 8mL pyroxylin (e) cement, stir 1 ~ 3 hour, leave standstill aging 24 hours.
Chelating is stirred 2 hours in described step c.
Dissolve 2 hours in described step b, add 5mL pyroxylin (e) cement, stir 2 hours.
The Advantageous Effects that the present invention brings:
The present invention proposes a kind of Mg alloy surface self demixing CeO
2/ TiO
2the preparation method of compound coating, compared with prior art, this preparation method to achieve on magnesium alloy AZ31B once coating just can form multi-coating system, CeO
2/ TiO
2compound coating one-pass film-forming, eliminates interface layer, solves the problem of adhesive force difference;
The rete that the present invention prepares is fine and close, smooth, thickness even, 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, explanation clear, complete is further done to the present invention:
Fig. 1 is preparation technology's schema of the present invention.
Embodiment
Below in conjunction with embodiment, explanation clear, complete is further done to the present invention:
Raw material selected by the present invention, unless otherwise indicated, all buys by commercial channel and obtains.
Embodiment 1:
The present invention, by reference to the accompanying drawings 1, a kind of Mg alloy surface self demixing CeO
2/ TiO
2the preparation method of compound coating, comprises the following steps:
Step 1, pre-treatment is carried out to magnesium alloy sample:
By magnesium alloy AZ31B after cut mechanically, extremely with 200#, 1200# sand papering in minute surface, select NaOH to carry out oil removal treatment, after 5%HF acid-wash activation, dry for subsequent use after cleaning 3 times with distilled water in surface;
Step 2, CeO
2the preparation of colloidal sol:
By cerous nitrate (Ce (NO
3)
3) concentration according to 5% dissolves stirring in ethanol and add 3mL pyroxylin (e) cement after one hour, stir after 3 hours and leave standstill aging 24 hours, obtain 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:
CeO prepared by step 2
2tiO prepared by colloidal sol and step 3
21:1 volume ratio mix and blend pressed by colloidal sol, aging 24 hours, obtains CeO
2/ TiO
2colloidal sol;
Step 5, the CeO prepared in step 4
2/ TiO
2colloidal sol mixes according to 5:1 volume ratio with trolamine, again pretreated for step 1 magnesium alloy AZ31B substrate was processed for 5 seconds in the plant acid solution of 0.01%, flood in colloidal sol after cleaning, drying, lift with the speed of 10cm/h, and rapid airing, obtain pre-treatment film;
Step 6, CeO
2/ TiO
2the preparation of self demixing compound coating:
Be 3 DEG C/min by the pre-treatment film of preparation in step 5 with temperature rise rate, 400 DEG C of sintering 1 hour, obtain CeO
2/ TiO
2self demixing compound coating.
Embodiment 2:
Difference from Example 1 is: in step 2, by cerous nitrate (Ce (NO
3)
3) concentration according to 5% dissolves stirring in ethanol and add 8mL pyroxylin (e) cement after 3 hours, stir after 1 hour and leave standstill aging 24 hours, obtain CeO
2colloidal sol.Be 3 DEG C/min with temperature rise rate after film, 400 DEG C 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.Be 3 DEG C/min with temperature rise rate after film, 400 DEG C 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 self demixing compound coating and prior art
2coating, TiO
2the corrosion resistance nature of coating compares:
Table 1
Claims (4)
1. a Mg alloy surface self demixing CeO
2/ TiO
2the preparation method of compound coating, is characterized in that comprising the following steps:
A, first pre-treatment is carried out to magnesium alloy sample;
B, by cerous nitrate according to 5% concentration dissolve for some time in ethanol, add pyroxylin (e) cement, stir, leave standstill 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 and trolamine mix according to 5:1 volume ratio and carry out applying at Mg alloy surface, dry, solidify and obtain self demixing CeO
2/ TiO
2compound coating.
2. preparation method according to claim 1, is characterized in that: dissolve 1 ~ 3 hour in described step b, add 3 ~ 8mL pyroxylin (e) cement, stir 1 ~ 3 hour, leaves standstill aging 24 hours.
3. preparation method according to claim 1, is characterized in that: stir chelating in described step c 2 hours.
4. preparation method according to claim 2, is characterized in that: dissolve 2 hours in described step b, 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)
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|---|---|---|---|
| CN201310705732.6A CN103741126B (en) | 2013-12-20 | 2013-12-20 | A kind of preparation method of Mg alloy surface self demixing compound coating |
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| Publication Number | Publication Date |
|---|---|
| CN103741126A CN103741126A (en) | 2014-04-23 |
| CN103741126B true CN103741126B (en) | 2016-04-20 |
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| 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 |
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 (6)
| 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 |
| 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 |
|---|
| Composite cerium oxide/titanium oxide thin films for corrosion protection of AZ91D magnesium alloy via sol-gel process;J.M.Fan et al.;《Materials and Corrosion》;20091231;第60卷(第6期);2.Experimental及图1 * |
| Study of time effect on the optical properties of spin-coated CeO2-TiO2 thin films;F.E.Ghodsi et al.;《Solar Energy Materials & Solar Cells》;20011231;第68卷;2.Experimental及图1 * |
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| CN103741126A (en) | 2014-04-23 |
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