CN102776500A - 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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- CN102776500A CN102776500A CN2012102404621A CN201210240462A CN102776500A CN 102776500 A CN102776500 A CN 102776500A CN 2012102404621 A CN2012102404621 A CN 2012102404621A CN 201210240462 A CN201210240462 A CN 201210240462A CN 102776500 A CN102776500 A CN 102776500A
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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 present invention relates to chemical conversion processing method and the aluminum or aluminum alloy on the surface of aluminum or aluminum alloy with the epithelium that forms through this surface chemistry conversion processing; In more detail, relating to use does not contain sexavalent chrome and contains chromic treatment solution the chemical conversion processing method on the aluminum or aluminum alloy surface that chemical conversion handles and the aluminum or aluminum alloy with the epithelium that forms through this surface chemistry conversion processing are carried out in the surface of aluminum or aluminum alloy.
Background technology
As the chemical conversion processing method on aluminum or aluminum alloy surface, sexavalent chrome classes such as conventional base-chromate process, chromate process, phosphoric acid-chromate process, zn phosphate method, non-chromate chemical conversion facture (tannic acid method), other various non-chromium classes.
When the chromate process through the sexavalent chrome class or phosphoric acid-chromate process carry out chemical conversion and handle the surface of aluminum or aluminum alloy, though obtain the adaptation of excellent erosion resistance and the excellence of filming, owing to use hexavalent chromate, the generation environmental problem.When zn phosphate method through the non-chromate method or tannic acid method are carried out chemical conversion and are handled the surface of aluminum or aluminum alloy, though do not have environmental problem, the adaptation of filming is excellent, has the problem of erosion resistance than chromate process difference.
As not producing environmental problem, the chemical conversion on the also improved aluminum or aluminum alloy of erosion resistance surface is handled, 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) provides a kind of use to contain chromic treatment solution the surface of aluminum or aluminum alloy has been handled; Obtained to contain chromic chromate process or phosphoric acid-chromate process is handled identical effect, with the pollution abatement problem with employing.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 40～50 ℃ the treatment solution that contains 3 valency chromium and chemical conversion in 1～5 minute is implemented on the surface of the aluminum or aluminum alloy that comprises aluminum or aluminum alloy handled, form erosion resistance and the excellent epithelium of the adaptation of filming.
But trivalent chromium still can pollute environment, still need further develop containing chromic treatment solution, to alleviate the pollution that trivalent chromium causes.
Summary of the invention
Deficiency to prior art; One of the object of the invention is to provide a kind of trivalent chromium content method that low treatment solution is handled the surface of aluminum or aluminum alloy; Can obtain and compare when chromic chromate process or phosphoric acid-chromate process are handled, can obtain the chemical conversion processing method on the aluminum or aluminum alloy surface of above on an equal basis erosion resistance effect through containing.
The inventor furthers investigate in order to address the above problem, and the result finds, adds Ce through containing in the chromic treatment solution of providing at patent documentation 1 (application number 200780001138.1)
3+With silane and adjust other components contents.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 40～50 ℃ treatment solution implements chemical conversion in 1～5 minute to the surface of aluminum or aluminum alloy and handles and form epithelium.
In addition, the chemical conversion processing method on aluminum or aluminum alloy of the present invention surface is characterized in that, anodize is carried out on the surface of aluminum or aluminum alloy, then carries out sealing of hole and handles, and 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 40～50 ℃ treatment solution implements chemical conversion in 1～5 minute to the surface of aluminum or aluminum alloy and handles and form epithelium.
In the chemical conversion processing method and aluminum or aluminum alloy on aluminum or aluminum alloy of the present invention surface, (chromium nitrate concentration is with Cr (NO though use trivalent chromium content is low
3)
3Count 0.5-1g/L) treatment solution chemical conversion carried out on the surface of aluminum or aluminum alloy handled, but can reach equal above erosion resistance with carrying out through chromyl chromate process or phosphoric acid-chromate process comparing when chemical conversion is handled.
As carry out the aluminum or aluminum alloy that chemical conversion is handled through surface chemistry transformation processing method of the present invention, be included in actual all aluminium and the duraluminum that uses in the various technical fields.
Before handling, preferably pre-treatment is carried out on the surface of aluminum or aluminum alloy through surface chemistry transformation processing method of the present invention.Pre-treatment for example can be implemented any one of mechanical means, solvent method, alkaline process, acid wash.
The treatment solution that uses in the surface chemistry transformation processing method of the present invention contains chromium nitrate as necessary composition.The concentration conversion of the chromium nitrate in the treatment solution is Cr (NO
3)
3100% be preferably 0.5-1g/L, more preferably about 0.7g/L.The concentration of the chromium nitrate in the treatment solution is with Cr (NO
3)
3Meter is during less than 0.5g/L, and the erosion resistance on the aluminum or aluminum alloy surface after chemical conversion is handled has inadequate trend.
The treatment solution that uses in the surface chemistry transformation processing method of the present invention contains Ce3+ as necessary composition.The concentration of Ce3+ in the treatment solution is preferably 0.08-0.15g/L, more preferably about 0.1g/L.The concentration of Ce3+ in the treatment solution is during less than 0.08g/L or greater than 0.15g/L, and the erosion resistance on the aluminum or aluminum alloy surface after chemical conversion is handled has inadequate trend.The preferred cerous nitrate that adopts is originated as it.
The treatment solution that uses in the surface chemistry transformation processing method of the present invention contains silane as necessary composition.The concentration of the silane in the treatment solution is preferably 3-6ml/L, more preferably about 4.5ml/L.The concentration of the silane in the treatment solution is during less than 3ml/L or greater than 6ml/L, and the erosion resistance on the aluminum or aluminum alloy surface after chemical conversion is handled has inadequate trend.Preferred silane is BTSE.
The treatment solution that uses in the surface chemistry transformation processing method of the present invention contains ammonium vanadate as necessary composition.The concentration conversion of the ammonium vanadate in the treatment solution is NH
4VO
3100% be preferably 2-3g/L, more preferably about 2.5g/L.The concentration of the ammonium vanadate in the treatment solution is with NH
4VO
3Meter is during less than 2g/L or greater than 3g/L, and the erosion resistance on the aluminum or aluminum alloy surface after chemical conversion is handled has inadequate trend.
The treatment solution that uses in the surface chemistry transformation processing method of the present invention contains potassium fluotitanate as necessary composition.The concentration conversion of the potassium fluotitanate in the treatment solution is K
2TiF
6100% be preferably 4-5g/L, more preferably about 4.5g/L.The concentration of the potassium fluotitanate in the treatment solution is with K
2TiF
6Meter is during less than 4g/L, and the erosion resistance on the aluminum or aluminum alloy surface after chemical conversion is handled has inadequate trend.In addition, the concentration of the potassium fluotitanate in the treatment solution is with K
2TiF
6When meter surpassed 5g/L, the erosion resistance on the aluminum or aluminum alloy surface after chemical conversion is handled also had inadequate trend.
The treatment solution that uses in the surface chemistry transformation processing method of the present invention contains lithium fluoride as necessary composition.The concentration conversion of the lithium fluoride in the treatment solution be LiF100% be preferably 1-2g/L, more preferably about 1.5g/L.During less than 1g/L, the erosion resistance on the aluminum or aluminum alloy surface after chemical conversion is handled has inadequate trend to the concentration of the lithium fluoride in the treatment solution in LiF.In addition, during above 2g/L, the erosion resistance on the aluminum or aluminum alloy surface after chemical conversion is handled also has inadequate trend to the concentration of the lithium fluoride in the treatment solution in LiF.
The treatment solution that uses in the surface chemistry transformation processing method of the present invention contains nitric acid as necessary composition.The concentration conversion of the nitric acid in the 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 the treatment solution is with HNO
3Meter is during less than 0.5mL/L, and the erosion resistance on the aluminum or aluminum alloy surface after chemical conversion is handled has inadequate trend.In addition, the concentration of the nitric acid in the treatment solution is with HNO
3When meter surpasses 1.8mL/L, even increase the raising of the erosion resistance of also finding to match with it.
Because the treatment solution that uses in the surface chemistry transformation processing method of the present invention has above-mentioned composition, its pH is a slightly acidic.
In the surface chemistry transformation processing method of the present invention, the liquid temperature of treatment solution is maintained at 40～50 ℃ implements.When the liquid temperature is lower than 40 ℃ or liquid temperature when surpassing 50 ℃, the erosion resistance on the aluminum or aluminum alloy surface after chemical conversion is handled has inadequate trend.
In the surface chemistry transformation processing method of the present invention, the chemical conversion processing time is 1～5 minute.Chemical conversion is handled the time during less than 1 minute, and the erosion resistance on the aluminum or aluminum alloy surface after chemical conversion is handled has inadequate trend.In addition, the chemical conversion processing time is when surpassing 5 minutes, even prolong the raising of the erosion resistance of also finding to match with it.
After carrying out the chemical conversion processing under these conditions, wash and the pure water washing, carry out drying then.Usually about room temperature～90 ℃, implemented 10～120 minutes for drying.
Excellent corrosion resistance with aluminum or aluminum alloy goods of the epithelium that forms through surface chemistry transformation processing method of the present invention is compared when handling through chromate process or phosphoric acid-chromate process and can be reached equal above erosion resistance effect.
Embodiment
For ease of understanding the present invention, it is following that the present invention enumerates embodiment.Those skilled in the art should understand, and said embodiment helps to understand the present invention, should not be regarded as concrete restriction of the present invention.
Embodiment 1～3 and Comparative Examples 1～7
With LY12 aluminum alloy plate materials electrochemical deoiling, the tap water flushing, acetone and deionized water ultrasonic cleaning dry up.In each embodiment 1～3 and Comparative Examples 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 the table 1
3+, silane, ammonium vanadate, potassium fluotitanate, lithium fluoride and nitric acid 45 ℃ treatment solution in dipping 3 minutes, implement the tap water washing under the room temperature in 30 seconds then, then implement the pure water washing under the room temperature in 30 seconds.Implement 20 minutes dryings at 80 ℃ at last.
Then, implement corrosion resistance test, measure grade through salt water resistance spray testing method according to JIS Z 2371.Can know by the data shown in the table 1; Among 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, and is relative therewith, under the situation of the comparative example 1～7 of from the treatment solution of the present invention's use, removing any one composition; The erosion resistance grade of 96 hours salt spray testings is 1.5～5.5.
Table 1
Embodiment 1～3 and Comparative Examples 8-13
With LY12 aluminum alloy plate materials electrochemical deoiling, the tap water flushing, acetone and deionized water ultrasonic cleaning dry up.In each embodiment 1～3 and Comparative Examples 8-13, respectively with Cr (NO
3)
3, Ce
3+, silane, NH
4VO
3, K
2TiF
6, LiF and HNO
3Meter contained in 45 ℃ the treatment solution of chromium nitrate, Ce3+, silane, ammonium vanadate, potassium fluotitanate, lithium fluoride and nitric acid dipping 3 minutes with the concentration shown in the table 1, implement the tap water washing under the room temperature in 30 seconds then, then implemented the pure water washing under the room temperature in 30 seconds.Implement 20 minutes dryings at 80 ℃ at last.Wherein the treatment solution composition among the Comparative Examples 8-13 comes from the embodiment of patent documentation 1 (application number 2007800011381).
Then, implement corrosion resistance test, measure grade through salt water resistance spray testing method according to JIS Z 2371.Data by table 2 can find out, the present invention use the chromium treatment solution of low levels handle aluminum or aluminum alloy obtained with patent documentation 1 (application number 200780001138.1) in high-load chromium treatment solution handle the erosion resistance of aluminum or aluminum alloy.
Table 2
Applicant's statement; The present invention explains detailed process equipment of the present invention and technical process through the foregoing description; But the present invention is not limited to above-mentioned detailed process equipment and technical process, does not mean that promptly the present invention must rely on above-mentioned detailed process equipment and technical process could be implemented.The person of ordinary skill in the field should understand, and to any improvement of the present invention, to the interpolation of the equivalence replacement of each raw material of product of the present invention and ancillary component, the selection of concrete mode etc., all drops within protection scope of the present invention and the open scope.
Claims (10)
1. the chemical conversion processing method on an aluminum or aluminum alloy 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
2TiF6 counts 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 40～50 ℃ treatment solution implements chemical conversion in 1～5 minute to the surface of aluminum or aluminum alloy and handles and form epithelium.
2. method according to claim 1 is characterized in that, preferred chromium nitrate concentration is with Cr (NO
3)
3Count 0.7g/L.
3. method according to claim 1 is characterized in that, preferred Ce
3+Concentration is 0.1g/L.
4. method according to claim 1 is characterized in that, preferred silane concentration is 4.5ml/L.
5. method according to claim 1 is characterized in that, preferred ammonium vanadate concentration is with NH
4VO
3Count 2.5g/L.
6. method according to claim 1 is characterized in that, preferred potassium fluotitanate concentration is with K
2TiF
6Count 4.5g/L.
7. method according to claim 1 is characterized in that the preferred fluorinated lithium concentration is counted 1.5g/L with LiF.
8. method according to claim 1 is characterized in that, preferred concentration of nitric acid is with HNO
3Count 1mL/L.
9. method according to claim 1 is characterized in that, preferred Ce
3+Derive from cerous nitrate.
10. method according to claim 1 is characterized in that, preferred silane is BTSE.
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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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| Publication Number | Publication Date |
|---|---|
| CN102776500A true CN102776500A (en) | 2012-11-14 |
| CN102776500B CN102776500B (en) | 2014-07-16 |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103866311A (en) * | 2014-03-06 | 2014-06-18 | 武汉材料保护研究所 | Method for preparing chemical conversion film on aluminum alloy surface on basis of molybdate |
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 |
-
2012
- 2012-07-11 CN CN201210240462.1A patent/CN102776500B/en not_active Expired - Fee Related
Patent 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 |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103866311A (en) * | 2014-03-06 | 2014-06-18 | 武汉材料保护研究所 | Method for preparing chemical conversion film on aluminum alloy surface on basis of molybdate |
| 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 |
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