CN106399994A - Schiff base complex-phosphate conversion liquid for magnesium alloy surface treatment and utilization method of Schiff base complex-phosphate conversion liquid - Google Patents
Schiff base complex-phosphate conversion liquid for magnesium alloy surface treatment and utilization method of Schiff base complex-phosphate conversion liquid Download PDFInfo
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- CN106399994A CN106399994A CN201611215848.1A CN201611215848A CN106399994A CN 106399994 A CN106399994 A CN 106399994A CN 201611215848 A CN201611215848 A CN 201611215848A CN 106399994 A CN106399994 A CN 106399994A
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
- C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
- C23C22/34—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing fluorides or complex fluorides
- C23C22/36—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing fluorides or complex fluorides containing also phosphates
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Abstract
The invention discloses a Schiff base complex-phosphate conversion liquid for magnesium alloy surface treatment. The conversion liquid is characterized in that sodium dihydrogen phosphate serves as a main film forming agent matched with auxiliary agents such as sodium citrate and sodium fluoride, a polyaspartic acid Schiff base complex excellent in effect of chelation with metal ions is added and loaded on nano mesoporous carbon, dispersity in a system is improved, uniformity in attachment is realized, abrasion resistance of films can be remarkably improved, and mechanical protection of alloy surfaces is promoted. The conversion liquid is capable of quickly forming films on the alloy surfaces and quickly chelating with the metal ions to form long-acting stable protective film layers, and defects of poor mechanical performance and short protection period of traditional phosphoric acid film layers are overcome effectively. The film layers are high in compatibility, environment friendly and low in toxicity, corrosion and scale inhibition is realized, smoothness of the alloy surfaces can be kept, and magnesium alloy surface performances can be improved remarkably.
Description
Technical field
The present invention relates to technical field of magnesium alloy surface treatment, more particularly, to a kind of Schiff for Mg alloy surface process
Alkali coordination compound-phosphate conversion solution and its using method.
Background technology
Magnesium alloy is the metal material of a kind of lightweight, high intensity, and the product weight of equality strength even can compare plastic cement
Also light, the ability of its load that withstands shocks is bigger than aluminium alloy, simultaneously magnesium alloy also have good processability, rapid heat dissipation, antidetonation,
The advantages of anti electromagnetic wave, recoverable, is widely used in fields such as Aero-Space, 3C Product, sports equipments, especially closely
Over year, 3C Product gradually develops to compact direction so that high performance magnesium alloy is more favored by manufacturer.
Although magnesium alloy possesses above-mentioned advantage, because magnesium and its alloy activity are high, its oxide-film is loose porous,
Lead to that material surface corrosion resistance is poor, environmental suitability is poor, limits the use of magnesium alloy.In order to improve these shortcomings, work
Frequently with surface protection technique, magnesium alloy is surface-treated in industry application, wherein chemical conversion treatment be the most quick, effectively,
A kind of economic processing mode, not only can improve alloy corrosion ability, go back the further protective treatment of alloy surface and lay
Good basis.The chemical pretreatment solution that at present magnesium alloy is commonly used mainly have chromate, permanganate, phosphate, permanganate-
The technique of the solution systems such as phosphate, wherein chromate conversion coating is the most ripe, but Cr VI is high carcinogen, at present
Prohibit the use of, although the more environmental protection to a certain extent of the treatment fluid of other class, the conversion film being formed all exists corrosion-resistant
The problems such as property is poor, film layer is also easy to produce crackle is it is difficult to meet engineering demand.In order to improve chemical composition coating presence these lack
Fall into, researchers pass through to add the microstructure that nanoparticle can significantly improve conversion film in conversional solution, such as《Nanometer is hard
The impact of matter relative chemical conversion film microstructure》The result of study of one literary composition shows a nanometer Al2O3, Nano-meter SiO_22Interpolation can have
The raising conversion film crystal grain quantity of effect, improves the consistency of conversion film, obtains higher corrosion resistance, but improves nano-powder and exist
Dispersibility in conversional solution is still more formidable problem, technological operation is required very high, application is limited.
Content of the invention
The present invention, in order to make up the defect of prior art, provides a kind of cooperation of the Schiff's base for Mg alloy surface process
Thing-phosphate conversion solution and its using method, in order to improve the performance of traditional phosphate conversion film.
The present invention is achieved by the following technical solutions：
A kind of schiff bases complex-phosphate conversion solution for Mg alloy surface process, this conversional solution is by following weight portion
Preparation of raw material forms：Poly-aspartate 1-2, sodium citrate 3-5, sodium dihydrogen phosphate 40-50, sodium fluoride 1-2, adjacent hydroxyl aromatic aldehyde
2-3, potassium hydroxide 2-5, dehydrated alcohol 60-80, Polyvinylpyrrolidone 1-2, mesoporous nano carbon 0.5-0.8, deionized water are fitted
Amount, appropriate glacial acetic acid.
Described conversional solution is prepared by following steps：
（1）Sodium dihydrogen phosphate is mixed with a small amount of deionized water, stirring makes it be completely dissolved, and resulting solution is standby；
（2）Sodium citrate is mixed with a small amount of deionized water, stirring makes it be completely dissolved, and resulting solution is standby；
（3）Sodium fluoride is mixed with a small amount of deionized water, stirring makes it be completely dissolved, and resulting solution is standby；
（4）Adjacent hydroxyl aromatic aldehyde is mixed with 30-50 weight portion dehydrated alcohol, stir to its be completely dissolved after standby；
（5）Step will be put into after poly-aspartate, potassium hydroxide mixed grinding 4-5min（4）In system, in 50-60 DEG C of water-bath bar
Stirring reaction 40-60min under part, reaction terminates rear mixed solution sucking filtration, and filtrate, through recrystallization, obtains schiff bases complex, by it
Standby after vacuum drying；
（6）The dehydrated alcohol of Polyvinylpyrrolidone, surplus is put in reaction vessel, opens agitating device, rotating speed is controlled to
300-500 rev/min, it is subsequently added mesoporous nano carbon, after dispersed with stirring 1-2h, add step（5）The Schiff's base cooperation of preparation
Thing, adds the deionized water of 10-15 weight portion, stops stirring, system is entered after mixing 20-30min after continuing with 30-40min
Row sucking filtration is processed, standby after gained screening is vacuum dried；Filtrate is standby；
（7）By step（1）、（2）、（3）、（6）Deionized water is added to adjust to phosphoric acid in system after the material mix homogeneously of preparation
Dihydro na concn is 20-25g/L, then is 3.5-4 with glacial acetic acid regulation system pH value, obtains final product described conversional solution.
A kind of using method of described schiff bases complex-phosphate conversion solution for Mg alloy surface process, bag
Include following steps：
（1）Mg alloy surface is dried after the steps such as oil removing, water rinsing, acid attack, water rinsing, alkali activation, water rinsing naturally
Standby；
（2）Pretreated magnesium alloy is soaked in schiff bases complex-phosphate conversion solution that temperature is 40-50 DEG C and reacts
Take out after 10-15min, then rinse workpiece with water, naturally dry.
The present invention selects sodium dihydrogen phosphate as main film former, assistant with auxiliary agents such as sodium citrate, sodium fluoride, be also added into
Metal ion has the poly-aspartate schiff bases complex of good chelate effect, and is carried on mesoporous nano carbon, carries
Its dispersibility in system high, realizes the purpose of uniformly attachment, can also significantly improve the abrasion resistance of film layer simultaneously, improves
Mechanical protection to alloy surface.The present invention preparation conversional solution can in alloy surface fast filming, and faster sequestration metal from
Son forms long-acting stable protection film layer, effectively improves traditional phosphoric acid film film layer bad mechanical property, the property of protection cycle is short
Can, the film layer compatibility simultaneously is good, be environment-friendly and low-toxicity, corrosion-mitigation scale-inhibition, can keep the fineness of alloy surface, significantly improve magnesium alloy table
Face performance.
Specific embodiment
A kind of schiff bases complex phosphate conversion solution for Mg alloy surface process, this conversional solution is by following weight portion
Preparation of raw material form：Poly-aspartate 1, sodium citrate 3, sodium dihydrogen phosphate 40, sodium fluoride 1, adjacent hydroxyl aromatic aldehyde 2, hydrogen-oxygen
Change potassium 2, dehydrated alcohol 60, Polyvinylpyrrolidone 1, mesoporous nano carbon 0.5, appropriate deionized water, appropriate glacial acetic acid.
This conversional solution is prepared by following steps：
（1）Sodium dihydrogen phosphate is mixed with a small amount of deionized water, stirring makes it be completely dissolved, and resulting solution is standby；
（2）Sodium citrate is mixed with a small amount of deionized water, stirring makes it be completely dissolved, and resulting solution is standby；
（3）Sodium fluoride is mixed with a small amount of deionized water, stirring makes it be completely dissolved, and resulting solution is standby；
（4）Adjacent hydroxyl aromatic aldehyde is mixed with 30 weight portion dehydrated alcohol, stir to its be completely dissolved after standby；
（5）Step will be put into after poly-aspartate, potassium hydroxide mixed grinding 4min（4）In system, under 50 DEG C of water bath condition
Stirring reaction 60min, reaction terminates rear mixed solution sucking filtration, and filtrate through recrystallization, obtains schiff bases complex, is vacuum dried
Standby afterwards；
（6）The dehydrated alcohol of Polyvinylpyrrolidone, surplus is put in reaction vessel, opens agitating device, rotating speed is controlled to
300 revs/min, it is subsequently added mesoporous nano carbon, after dispersed with stirring 1h, add step（5）The schiff bases complex of preparation, continues
Add the deionized water of 10 weight portions after processing 30min, stop stirring after mixing 20min, system carries out sucking filtration process, gained is filtered
Standby after thing is vacuum dried, filtrate is standby；
（7）By step（1）、（2）、（3）、（6）Deionized water is added to adjust to phosphoric acid in system after the material mix homogeneously of preparation
Dihydro na concn is 20g/L, then is 3.5 with glacial acetic acid regulation system pH value, obtains final product described conversional solution.
The using method of this conversional solution comprises the following steps：
（1）Mg alloy surface is dried after the steps such as oil removing, water rinsing, acid attack, water rinsing, alkali activation, water rinsing naturally
Standby；
（2）Pretreated magnesium alloy sample is soaked in after reaction 15min in 40 DEG C of schiff bases complex phosphate conversion solutions
Take out, then rinse workpiece with water, naturally dry.
Performance test is carried out to the conversion film on magnesium alloy sample surface, test result is：
Pattern:Macroscopic view is blackish green, film forming uniform ground, and microcosmic result is solid netted result, has slight crackle, thickness 5.4 μ
m.
Corrosion resistance：By undressed magnesium alloy substrate and sample salt spray test and damp heat test respectively, result is as follows：
| Project | Salt spray test | Damp heat test |
| Matrix | General corrosion after 8h, produces a large amount of erosions | Surface discolouration, a large amount of bubbles of appearance after 24h |
| Sample | After 65h, corrosion pit in surface | Surface light discolouration after 220h, a small amount of bubble |
Claims (3)
1. a kind of schiff bases complex-phosphate conversion solution for Mg alloy surface process it is characterised in that this conversional solution by
The preparation of raw material of following weight portion forms：Poly-aspartate 1-2, sodium citrate 3-5, sodium dihydrogen phosphate 40-50, sodium fluoride 1-2,
Adjacent hydroxyl aromatic aldehyde 2-3, potassium hydroxide 2-5, dehydrated alcohol 60-80, Polyvinylpyrrolidone 1-2, mesoporous nano carbon 0.5-
0.8th, appropriate deionized water, appropriate glacial acetic acid.
2. a kind of schiff bases complex-phosphate conversion solution for Mg alloy surface process as claimed in claim 1, it is special
Levy and be, described conversional solution is prepared by following steps：
（1）Sodium dihydrogen phosphate is mixed with a small amount of deionized water, stirring makes it be completely dissolved, and resulting solution is standby；
（2）Sodium citrate is mixed with a small amount of deionized water, stirring makes it be completely dissolved, and resulting solution is standby；
（3）Sodium fluoride is mixed with a small amount of deionized water, stirring makes it be completely dissolved, and resulting solution is standby；
（4）Adjacent hydroxyl aromatic aldehyde is mixed with 30-50 weight portion dehydrated alcohol, stir to its be completely dissolved after standby；
（5）Step will be put into after poly-aspartate, potassium hydroxide mixed grinding 4-5min（4）In system, in 50-60 DEG C of water-bath bar
Stirring reaction 40-60min under part, reaction terminates rear mixed solution sucking filtration, and filtrate, through recrystallization, obtains schiff bases complex, by it
Standby after vacuum drying；
（6）The dehydrated alcohol of Polyvinylpyrrolidone, surplus is put in reaction vessel, opens agitating device, rotating speed is controlled to
300-500 rev/min, it is subsequently added mesoporous nano carbon, after dispersed with stirring 1-2h, add step（5）The Schiff's base cooperation of preparation
Thing, adds the deionized water of 10-15 weight portion, stops stirring, system is entered after mixing 20-30min after continuing with 30-40min
Row sucking filtration is processed, standby after gained screening is vacuum dried；Filtrate is standby；
（7）By step（1）、（2）、（3）、（6）Deionized water is added to adjust to phosphoric acid in system after the material mix homogeneously of preparation
Dihydro na concn is 20-25g/L, then is 3.5-4 with glacial acetic acid regulation system pH value, obtains final product described conversional solution.
3. a kind of schiff bases complex-phosphate conversion solution for Mg alloy surface process as claimed in claim 1 or 2
Using method is it is characterised in that comprise the following steps：
（1）Mg alloy surface is dried after the steps such as oil removing, water rinsing, acid attack, water rinsing, alkali activation, water rinsing naturally
Standby；
（2）Pretreated magnesium alloy is soaked in schiff bases complex-phosphate conversion solution that temperature is 40-50 DEG C and reacts
Take out after 10-15min, then rinse workpiece with water, naturally dry.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201611215848.1A CN106399994A (en) | 2016-12-26 | 2016-12-26 | Schiff base complex-phosphate conversion liquid for magnesium alloy surface treatment and utilization method of Schiff base complex-phosphate conversion liquid |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201611215848.1A CN106399994A (en) | 2016-12-26 | 2016-12-26 | Schiff base complex-phosphate conversion liquid for magnesium alloy surface treatment and utilization method of Schiff base complex-phosphate conversion liquid |
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| CN106399994A true CN106399994A (en) | 2017-02-15 |
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| CN201611215848.1A Pending CN106399994A (en) | 2016-12-26 | 2016-12-26 | Schiff base complex-phosphate conversion liquid for magnesium alloy surface treatment and utilization method of Schiff base complex-phosphate conversion liquid |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107513648A (en) * | 2017-09-23 | 2017-12-26 | 新沂市中诺新材料科技有限公司 | A kind of heat resistant type aluminium alloy processing technology |
| CN108373536A (en) * | 2018-05-22 | 2018-08-07 | 河北工业大学 | A kind of synthetic method and application with schiff base structure modified polyaspartic acid |
| CN108486634A (en) * | 2018-04-20 | 2018-09-04 | 黄智慧 | A kind of preparation method of corrosion resistant type Mg alloy surface ceramic membrane materials |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101498026A (en) * | 2009-01-22 | 2009-08-05 | 重庆大学 | Electrolytic solution for magnesium alloy anodicoxidation treatment and method for surface treatment of magnesium alloy |
| CN101949010A (en) * | 2010-09-25 | 2011-01-19 | 郑州大学 | Surface pretreatment solution and pretreatment method used for bonding magnesium alloys |
| CN104342683A (en) * | 2013-07-25 | 2015-02-11 | 无锡市石塘湾工业园区开发建设有限公司 | Magnesium alloy work-piece surface anti-corrosion conversion film treatment process |
-
2016
- 2016-12-26 CN CN201611215848.1A patent/CN106399994A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101498026A (en) * | 2009-01-22 | 2009-08-05 | 重庆大学 | Electrolytic solution for magnesium alloy anodicoxidation treatment and method for surface treatment of magnesium alloy |
| CN101949010A (en) * | 2010-09-25 | 2011-01-19 | 郑州大学 | Surface pretreatment solution and pretreatment method used for bonding magnesium alloys |
| CN104342683A (en) * | 2013-07-25 | 2015-02-11 | 无锡市石塘湾工业园区开发建设有限公司 | Magnesium alloy work-piece surface anti-corrosion conversion film treatment process |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107513648A (en) * | 2017-09-23 | 2017-12-26 | 新沂市中诺新材料科技有限公司 | A kind of heat resistant type aluminium alloy processing technology |
| CN108486634A (en) * | 2018-04-20 | 2018-09-04 | 黄智慧 | A kind of preparation method of corrosion resistant type Mg alloy surface ceramic membrane materials |
| CN108373536A (en) * | 2018-05-22 | 2018-08-07 | 河北工业大学 | A kind of synthetic method and application with schiff base structure modified polyaspartic acid |
| CN108373536B (en) * | 2018-05-22 | 2020-04-14 | 河北工业大学 | Synthesis method and application of modified polyaspartic acid with Schiff base structure |
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Application publication date: 20170215 |