CN102776500B - Aluminum or aluminum alloy surface chemical conversion treatment method - Google Patents
Aluminum or aluminum alloy surface chemical conversion treatment method Download PDFInfo
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- CN102776500B CN102776500B CN201210240462.1A CN201210240462A CN102776500B CN 102776500 B CN102776500 B CN 102776500B CN 201210240462 A CN201210240462 A CN 201210240462A CN 102776500 B CN102776500 B CN 102776500B
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Abstract
The invention relates to an aluminum or aluminum alloy surface chemical conversion treatment method. The aluminum profile surface chemical conversion treatment method comprises the step of implementing chemical conversion treatment to the surface of the aluminum or aluminum alloy for 1-5min by using 0.5-1g/L Cr(NO3)3, 0.08-0.15g/L Ce<3+>, 3-6ml/L silane, 2-3g/L NH4VO3, 4-5g/L K2TiF6, 1-2g/L LiF, 0.5-1.8ml/L HNO3 and treating fluid with liquid temperature of 40-50 DEG C to form a surface film, wherein the formed surface film has excellent corrosion resistance property.
Description
Technical field
The aluminum or aluminum alloy that the present invention relates to the surperficial chemical conversion processing method of aluminum or aluminum alloy and there is the epithelium forming by this surface chemistry conversion processing, in more detail, relate to use and containing sexavalent chrome, containing chromic treatment solution, the surface of aluminum or aluminum alloy is not carried out the chemical conversion processing method on aluminum or aluminum alloy surface of chemical conversion processing and the aluminum or aluminum alloy with the epithelium forming by this surface chemistry conversion processing.
Background technology
As the chemical conversion processing method on aluminum or aluminum alloy surface, the sexavalent chrome classes such as conventional base-chromate process, chromate process, phosphoric acid-chromate process, zinc phosphate method, non-chromate chemical conversion facture (tannic acid method), other various non-chromium classes.
When the chromate process by sexavalent chrome class or phosphoric acid-chromate process carry out chemical conversion and process the surface of aluminum or aluminum alloy, although the excellent adaptation that obtains excellent erosion resistance and film, owing to using hexavalent chromate, generation environmental problem.When the zinc phosphate method by non-chromate method or tannic acid method are carried out chemical conversion and are processed the surface of aluminum or aluminum alloy, although there is no environmental problem, the adaptation of filming is excellent, has the erosion resistance problem poorer than chromate process.
As not producing environmental problem, the erosion resistance also chemical conversion on improved aluminum or aluminum alloy surface is processed, and has proposed to use the surface chemistry transformation processing method that contains chromic various treatment solutions.For example: patent documentation 1(application number 200780001138.1) provide a kind of use to contain chromic treatment solution the surface of aluminum or aluminum alloy is processed, obtained and contained chromic chromate process with employing or phosphoric acid-chromate process is processed identical effect, with pollution abatement problem.In the chemical conversion processing method on this aluminum or aluminum alloy surface, use chromium nitrate concentration with Cr (NO
3)
3count 3～12g/L, ammonium vanadate concentration with NH
4vO
3count 0.5～7g/L, potassium fluotitanate concentration with K
2tiF
6count 0.5～3g/L, lithium fluoride concentration is counted 0.5～3g/L, concentration of nitric acid with HNO with LiF
3count 0.5～1.8mL/L, liquid temperature and be the treatment solution containing 3 valency chromium of 40～50 ℃ and chemical conversion in 1～5 minute is implemented in the surface of the aluminum or aluminum alloy that comprises aluminum or aluminum alloy process, form erosion resistance and the epithelium of the adaptation excellence of filming.
But trivalent chromium still can, to environment, still need further to develop the pollution causing to alleviate trivalent chromium to containing chromic treatment solution.
Summary of the invention
For the deficiencies in the prior art, the method that one of object of the present invention is to provide treatment solution that a kind of trivalent chromium content is low to process the surface of aluminum or aluminum alloy, can obtain and compare by containing when chromic chromate process or phosphoric acid-chromate process are processed, can obtain the chemical conversion processing method on the aluminum or aluminum alloy surface of equal above erosion resistance effect.
The inventor conducts in-depth research in order to address the above problem, and found that, by patent documentation 1(application number 200780001138.1) provide contain chromic treatment solution in add Ce
3+with silane and adjust the content of other component.Can significantly reduce chromic usage quantity, Cr (NO
3)
3usage quantity be 0.5-1g/L.
That is, the chemical conversion processing method on aluminum or aluminum alloy of the present invention surface, is characterized in that, uses chromium nitrate concentration with Cr (NO
3)
3count 0.5-1g/L, Ce
3+concentration is that 0.08-0.15g/L, silane concentration are that 3-6ml/L, ammonium vanadate concentration are with NH
4vO
3count 2-3g/L, potassium fluotitanate concentration with K
2tiF
6count 4-5g/L, lithium fluoride concentration is counted 1-2g/L, concentration of nitric acid with HNO with LiF
3counting 0.5～1.8mL/L, liquid temperature and be the treatment solution of 40～50 ℃ implements chemical conversion in 1～5 minute to the surface of aluminum or aluminum alloy and processes and form epithelium.
In addition, the chemical conversion processing method on aluminum or aluminum alloy of the present invention surface, is characterized in that, anodic oxidation treatment is carried out in the surface of aluminum or aluminum alloy, then carries out sealing of hole processing, then, uses chromium nitrate concentration with Cr (NO
3)
3count 0.5-1g/L, Ce
3+concentration is that 0.08-0.15g/L, silane concentration are that 3-6ml/L, ammonium vanadate concentration are counted 2-3g/L, potassium fluotitanate concentration with K with NH4VO3
2tiF
6count 4-5g/L, lithium fluoride concentration is counted 1-2g/L, concentration of nitric acid with HNO with LiF
3counting 0.5～1.8mL/L, liquid temperature and be the treatment solution of 40～50 ℃ implements chemical conversion in 1～5 minute to the surface of aluminum or aluminum alloy and processes and form epithelium.
In the chemical conversion processing method and aluminum or aluminum alloy on aluminum or aluminum alloy of the present invention surface, although use trivalent chromium content is low, (chromium nitrate concentration is with Cr (NO
3)
3count 0.5-1g/L) treatment solution chemical conversion processing is carried out in the surface of aluminum or aluminum alloy, but with by chromyl chromate process or phosphoric acid-chromate process, undertaken comparing and can reach equal above erosion resistance when chemical conversion is processed.
As the aluminum or aluminum alloy that carries out chemical conversion processing by surface chemistry transformation processing method of the present invention, be included in the actual all aluminum and its alloys that use in various technical fields.
Before processing by surface chemistry transformation processing method of the present invention, preferably pre-treatment is carried out in the surface of aluminum or aluminum alloy.Pre-treatment for example can be implemented any one of mechanical means, solvent method, alkaline process, acid wash.
The treatment solution using in surface chemistry transformation processing method of the present invention contains chromium nitrate as essential component.The concentration conversion of the chromium nitrate in treatment solution is Cr (NO
3)
3100% is preferably 0.5-1g/L, about 0.7g/L more preferably.The concentration of the chromium nitrate in treatment solution is with Cr (NO
3)
3when meter is less than 0.5g/L, the erosion resistance on the aluminum or aluminum alloy surface after chemical conversion is processed has inadequate trend.
The treatment solution using in surface chemistry transformation processing method of the present invention contains Ce3+ as essential component.The concentration of Ce3+ in treatment solution is preferably 0.08-0.15g/L, about 0.1g/L more preferably.When the concentration of the Ce3+ in treatment solution is less than 0.08g/L or is greater than 0.15g/L, the erosion resistance on the aluminum or aluminum alloy surface after chemical conversion is processed has inadequate trend.Preferably adopt cerous nitrate to originate as it.
The treatment solution using in surface chemistry transformation processing method of the present invention contains silane as essential component.The concentration of the silane in treatment solution is preferably 3-6ml/L, about 4.5ml/L more preferably.When the concentration of the silane in treatment solution is less than 3ml/L or is greater than 6ml/L, the erosion resistance on the aluminum or aluminum alloy surface after chemical conversion is processed has inadequate trend.Preferred silane is BTSE.
The treatment solution using in surface chemistry transformation processing method of the present invention contains ammonium vanadate as essential component.The concentration conversion of the ammonium vanadate in treatment solution is NH
4vO
3100% is preferably 2-3g/L, about 2.5g/L more preferably.The concentration of the ammonium vanadate in treatment solution is with NH
4vO
3when meter is less than 2g/L or is greater than 3g/L, the erosion resistance on the aluminum or aluminum alloy surface after chemical conversion is processed has inadequate trend.
The treatment solution using in surface chemistry transformation processing method of the present invention contains potassium fluotitanate as essential component.The concentration conversion of the potassium fluotitanate in treatment solution is K
2tiF
6100% is preferably 4-5g/L, about 4.5g/L more preferably.The concentration of the potassium fluotitanate in treatment solution is with K
2tiF
6when meter is less than 4g/L, the erosion resistance on the aluminum or aluminum alloy surface after chemical conversion is processed has inadequate trend.In addition, the concentration of the potassium fluotitanate in treatment solution is with K
2tiF
6when meter surpasses 5g/L, the erosion resistance on the aluminum or aluminum alloy surface after chemical conversion is processed also has inadequate trend.
The treatment solution using in surface chemistry transformation processing method of the present invention contains lithium fluoride as essential component.The concentration conversion of the lithium fluoride in treatment solution is that LiF100% is preferably 1-2g/L, about 1.5g/L more preferably.When the concentration of the lithium fluoride in treatment solution is less than 1g/L in LiF, the erosion resistance on the aluminum or aluminum alloy surface after chemical conversion is processed has inadequate trend.In addition, the concentration of the lithium fluoride in treatment solution is in LiF during over 2g/L, and the erosion resistance on the aluminum or aluminum alloy surface after chemical conversion is processed also has inadequate trend.
The treatment solution using in surface chemistry transformation processing method of the present invention contains nitric acid as essential component.The concentration conversion of the nitric acid in treatment solution is HNO
3100% is preferably 0.5～1.8mL/L, 0.7～1.7mL/L more preferably.The concentration of the nitric acid in treatment solution is with HNO
3when meter is less than 0.5mL/L, the erosion resistance on the aluminum or aluminum alloy surface after chemical conversion is processed has inadequate trend.In addition, the concentration of the nitric acid in treatment solution is with HNO
3when meter surpasses 1.8mL/L, even if increase the raising of the erosion resistance that also discovery matches with it.
Because the treatment solution using in surface chemistry transformation processing method of the present invention has above-mentioned composition, its pH is slightly acidic.
In surface chemistry transformation processing method of the present invention, the liquid temperature for the treatment of solution is maintained to 40～50 ℃ and implements.Liquid temperature is during lower than 40 ℃ or when liquid temperature surpasses 50 ℃, and the erosion resistance on the aluminum or aluminum alloy surface after chemical conversion is processed has inadequate trend.
In surface chemistry transformation processing method of the present invention, the chemical conversion processing time is 1～5 minute.The chemical conversion processing time, while being less than 1 minute, the erosion resistance on the aluminum or aluminum alloy surface after chemical conversion is processed had inadequate trend.In addition, the chemical conversion processing time is while surpassing 5 minutes, even if extend the raising of the erosion resistance that also discovery matches with it.
Carry out under these conditions after chemical conversion processing, wash and pure water washing, be then dried.For dry conventionally in room temperature～90 a ℃ left and right implement 10～120 minutes.
The excellent corrosion resistance with the aluminum or aluminum alloy goods of the epithelium forming by surface chemistry transformation processing method of the present invention, compares when processing by chromate process or phosphoric acid-chromate process and can reach equal above erosion resistance effect.
Embodiment
For ease of understanding the present invention, it is as follows that the present invention enumerates embodiment.Those skilled in the art should understand, described embodiment helps to understand the present invention, should not be considered as concrete restriction of the present invention.
Embodiment 1～3 and comparative example 1～7
By LY12 aluminum alloy plate materials electrochemical deoiling, tap water rinses, and acetone and deionized water ultrasonic cleaning, dry up.In each embodiment 1～3 and comparative example 1～7, respectively with Cr (NO
3)
3, Ce
3+, silane, NH
4vO
3, K
2tiF
6, LiF and HNO
3meter contains chromium nitrate, Ce with the concentration shown in table 1
3+, silane, ammonium vanadate, potassium fluotitanate, lithium fluoride and nitric acid the treatment solution of 45 ℃ in flood 3 minutes, then implement the tap water washing under room temperature in 30 seconds, then implement the pure water washing under room temperature in 30 seconds.Finally at 80 ℃, implement to be dried for 20 minutes.
Then,, by implementing corrosion resistance test according to the salt water resistance spray testing method of JIS Z 2371, measure grade.Data are as shown in Table 1 known, in the embodiment 1-3 of chemical conversion processing method of the present invention, the erosion resistance grade of 96 hours salt spray testings is more than 9.9, on the other hand, in the situation that remove the comparative example 1～7 of any one composition the treatment solution using from the present invention, the erosion resistance grade of 96 hours salt spray testings is 1.5～5.5.
Table 1
Embodiment 1～3 and comparative example 8-13
By LY12 aluminum alloy plate materials electrochemical deoiling, tap water rinses, and acetone and deionized water ultrasonic cleaning, dry up.In each embodiment 1～3 and comparative example 8-13, respectively with Cr (NO
3)
3, Ce
3+, silane, NH
4vO
3, K
2tiF
6, LiF and HNO
3in the treatment solution of 45 ℃ that meter contains chromium nitrate, Ce3+, silane, ammonium vanadate, potassium fluotitanate, lithium fluoride and nitric acid with the concentration shown in table 1, flood 3 minutes, then implement the tap water washing under room temperature in 30 seconds, then implement the pure water washing under room temperature in 30 seconds.Finally at 80 ℃, implement to be dried for 20 minutes.Wherein the treatment solution composition in comparative example 8-13 comes from patent documentation 1(application number 2007800011381) embodiment.
Then,, by implementing corrosion resistance test according to the salt water resistance spray testing method of JIS Z 2371, measure grade.Data by table 2 can find out, the present invention uses the chromium treatment solution of low levels to process aluminum or aluminum alloy and obtained and patent documentation 1(application number 200780001138.1) in the chromium treatment solution of high-content process the erosion resistance of aluminum or aluminum alloy.
Table 2
Applicant's statement, the present invention illustrates detailed process equipment and process flow process of the present invention by above-described embodiment, but the present invention is not limited to above-mentioned detailed process equipment and process flow process, do not mean that the present invention must rely on above-mentioned detailed process equipment and process flow process and could implement.Person of ordinary skill in the field should understand, any improvement in the present invention, to the selection of the interpolation of the equivalence replacement of each raw material of product of the present invention and ancillary component, concrete mode etc., within all dropping on protection scope of the present invention and open scope.
Claims (8)
1. the chemical conversion processing method on aluminum or aluminum alloy surface, is characterized in that, uses by chromium nitrate concentration with Cr (NO
3)
3count 0.5-1g/L, cerous nitrate concentration with Ce
3+count 0.08-0.15g/L, BTSE concentration is that 3-6ml/L, ammonium vanadate concentration are with NH
4vO
3count 2-3g/L, potassium fluotitanate concentration with K
2tiF
6count 4-5g/L, lithium fluoride concentration is counted 1-2g/L, concentration of nitric acid with HNO with LiF
3count that 0.5～1.8mL/L forms, liquid temperature is that the treatment solution of 40～50 ℃ is implemented chemical conversion in 1～5 minute to the surface of aluminum or aluminum alloy and processed and form epithelium.
2. method according to claim 1, is characterized in that, chromium nitrate concentration is with Cr (NO
3)
3count 0.7g/L.
3. method according to claim 1, is characterized in that, Ce
3+concentration is 0.1g/L.
4. method according to claim 1, is characterized in that, BTSE concentration is 4.5ml/L.
5. method according to claim 1, is characterized in that, ammonium vanadate concentration is with NH
4vO
3count 2.5g/L.
6. method according to claim 1, is characterized in that, potassium fluotitanate concentration is with K
2tiF
6count 4.5g/L.
7. method according to claim 1, is characterized in that, lithium fluoride concentration is counted 1.5g/L with LiF.
8. method according to claim 1, is characterized in that, concentration of nitric acid is with HNO
3count 1mL/L.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210240462.1A CN102776500B (en) | 2012-07-11 | 2012-07-11 | Aluminum or aluminum alloy surface chemical conversion treatment method |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210240462.1A CN102776500B (en) | 2012-07-11 | 2012-07-11 | Aluminum or aluminum alloy surface chemical conversion treatment method |
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| CN103866311B (en) * | 2014-03-06 | 2016-05-18 | 武汉材料保护研究所 | One is prepared chemical conversion film method based on molybdate in aluminum alloy surface |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101356300B (en) * | 2006-01-10 | 2010-11-03 | 三井金属矿业株式会社 | Method for chemical conversion treatment of the surface of aluminum material and aluminum material |
| CN101717930B (en) * | 2009-12-25 | 2012-02-01 | 华烁科技股份有限公司 | Environment-friendly nano water-based silane treatment agent capable of improving anti-corrosion performance of metal surface |
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2012
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101356300B (en) * | 2006-01-10 | 2010-11-03 | 三井金属矿业株式会社 | Method for chemical conversion treatment of the surface of aluminum material and aluminum material |
| CN101717930B (en) * | 2009-12-25 | 2012-02-01 | 华烁科技股份有限公司 | Environment-friendly nano water-based silane treatment agent capable of improving anti-corrosion performance of metal surface |
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