CN101356300B - Method for chemical conversion treatment of the surface of aluminum material and aluminum material - Google Patents

Method for chemical conversion treatment of the surface of aluminum material and aluminum material Download PDF

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CN101356300B
CN101356300B CN2007800011381A CN200780001138A CN101356300B CN 101356300 B CN101356300 B CN 101356300B CN 2007800011381 A CN2007800011381 A CN 2007800011381A CN 200780001138 A CN200780001138 A CN 200780001138A CN 101356300 B CN101356300 B CN 101356300B
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aluminium
chemical conversion
treatment solution
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CN101356300A (en
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铃木光夫
小野武
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Mitsui Mining and Smelting Co Ltd
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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
    • C23C22/40—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 molybdates, tungstates or vanadates
    • C23C22/44—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 molybdates, tungstates or vanadates containing also fluorides or complex fluorides
    • 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
    • C23C2222/00—Aspects relating to chemical surface treatment of metallic material by reaction of the surface with a reactive medium
    • C23C2222/10—Use of solutions containing trivalent chromium but free of hexavalent chromium

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  • Chemical & Material Sciences (AREA)
  • General Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Chemical Treatment Of Metals (AREA)

Abstract

Disclosed is a method for chemical conversion treatment of the surface of an aluminum material comprising aluminum or an aluminum alloy. The method comprises performing a chemical conversion treatment of the surface of the aluminum material with a treatment solution for 1 to 5 minutes to form a coating film having excellent corrosion resistance and coating film adhesion property, wherein the treatment solution contains a trivalent chromium, and has a chromium nitrate content of 3 to 12 g/L in terms of Cr(NO3)3, a ammonium vanadate content of 0.5 to 7 g/L in terms of NH4VO3, a potassium fluorotitanate content of 0.5 to 3 g/L in terms of K2TiF6, a lithium fluoride content of 0.5 to 3 g/L in terms of LiF, a nitric acid content of 0.5 to 1.8 mL/L in terms of HNO3, and a liquid temperature of 40 to 50 C. Also disclosed is an aluminum material having a coating film formed by the method.

Description

The chemical conversion processing method of aluminium material surface and aluminium
Technical field
The chemical conversion on surface that the present invention relates to comprise the aluminium (hereinafter aluminium and aluminium alloy being referred to as aluminium) of aluminum or aluminum alloy is handled (changing into processings) method and is had aluminium by the epithelium of this surface chemistry conversion processing formation, in more detail, relating to use does not contain sexavalent chrome and contains chromic treatment solution the chemical conversion processing method of the aluminium material surface that chemical conversion handles and the aluminium with the epithelium that forms by this surface chemistry conversion processing are carried out in the surface of aluminium.
Background technology
Chemical conversion processing method as aluminium material surface, 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 (for example with reference to non-patent literature 1, patent documentation 1～6).
When the chromate process by the sexavalent chrome class or phosphoric acid-chromate process carry out chemical conversion and handle the surface of aluminium, though obtain excellent erosion resistance and the adaptation of the excellence of filming, owing to use hexavalent chromate, the generation environmental problem.When zinc phosphate method by the non-chromate method or tannic acid method are carried out chemical conversion and are handled the surface of aluminium, though there be the problem of erosion resistance than chromate process difference in the adaptation excellence that does not have environmental problem, films.
As not producing environmental problem, the erosion resistance also chemical conversion of improved aluminium material surface is handled, and has proposed to use and has contained the surface chemistry transformation processing method of chromic various treatment solutions (for example with reference to patent documentation 7～10.), further develop containing chromic treatment solution.
Non-patent literature 1:(society) sufacing association compiles, and " sufacing brief guide ", Nikkan Kogyo Shimbun, in February, 1998, p.691
Patent documentation 1: Japanese kokai publication hei 7-90614 communique
Patent documentation 2: Japanese kokai publication hei 10-237667 communique
Patent documentation 3: Japanese kokai publication hei 11-131254 communique
Patent documentation 4: TOHKEMY 2000-34577 communique
Patent documentation 5: TOHKEMY 2002-249886 communique
Patent documentation 6: TOHKEMY 2002-275649 communique
Patent documentation 7: TOHKEMY 2002-332575 communique
Patent documentation 8: TOHKEMY 2002-332581 communique
Patent documentation 9: TOHKEMY 2003-213446 communique
Patent documentation 10: TOHKEMY 2005-281852 communique
Summary of the invention
The objective of the invention is to, though providing use to contain chromic treatment solution handles the surface of aluminium, but with compare when chromic chromate process or phosphoric acid-chromate process are handled by containing, can reach the chemical conversion processing method of aluminium material surface of equal above effect and aluminium with the epithelium that forms by this surface chemistry conversion processing.
The inventor furthers investigate in order to address the above problem, found that, carry out the chemical conversion of specified time handles by the surface of carrying out the aluminium of sealing of hole processing after using the treatment solution that contains chromium nitrate, ammonium vanadate, potassium fluotitanate, lithium fluoride and nitric acid with particular concentration to carry out anodic oxidation treatment to the surface of aluminium or to the surface under the specific temperature, the aluminium goods of the adaptation two aspect excellences that can obtain erosion resistance and film, thus the present invention finished.
That is, the chemical conversion processing method of aluminium material surface of the present invention is characterized in that, uses 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 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 aluminium and handles and form epithelium.
In addition, the chemical conversion processing method of aluminium material surface of the present invention is characterized in that, anodic oxidation treatment is carried out on the surface of aluminium, then carries out sealing of hole and handles, and then, uses 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 3Counting 0.5～1.8mL/L, liquid temperature and be 40～50 ℃ treatment solution implements chemical conversion in 1～5 minute and handles and form epithelium.
Further, aluminium of the present invention is characterized in that, has by using 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 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 aluminium and handles the epithelium that forms.
In addition, aluminium of the present invention is characterized in that, has by the surface to aluminium to carry out anodic oxidation treatment, then carries out sealing of hole and handles, and then, uses 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 3Counting 0.5～1.8mL/L, liquid temperature and be 40～50 ℃ treatment solution implements chemical conversion in 1～5 minute and handles the epithelium that forms.
In the chemical conversion processing method and aluminium of aluminium material surface of the present invention, contain chromic treatment solution though use does not contain sexavalent chrome the chemical conversion processing is carried out on the surface of aluminium, with the effect of being undertaken by chromyl chromate process or phosphoric acid-chromate process comparing when chemical conversion is handled more than reaching on an equal basis.
Description of drawings
Fig. 1 has implemented the photo of the state after the anti-corrosion test of the test film that the chemical conversion of embodiment 1 handles for expression.
Fig. 2 has implemented the photo of the state after the anti-corrosion test of the test film that the chemical conversion of embodiment 2 handles for expression.
Fig. 3 has implemented the photo of the state after the anti-corrosion test of the test film that the chemical conversion of comparative example 1 handles for expression.
Fig. 4 has implemented the photo of the state after the anti-corrosion test of the test film that the chemical conversion of comparative example 2 handles for expression.
Fig. 5 has implemented the photo of the state after the anti-corrosion test of the test film that the chemical conversion of comparative example 3 handles for expression.
Fig. 6 has implemented the photo of the state after the anti-corrosion test of the test film that the chemical conversion of comparative example 4 handles for expression.
Fig. 7 has implemented the photo of the state after the anti-corrosion test of the test film that the chemical conversion of comparative example 5 handles for expression.
Fig. 8 has implemented the photo of the state after the anti-corrosion test of the test film that the chemical conversion of comparative example 6 handles for expression.
Fig. 9 has implemented the photo of the state after the anti-corrosion test of the test film that the chemical conversion of comparative example 7 handles for expression.
Embodiment
As carry out the aluminium that chemical conversion is handled by surface chemistry transformation processing method of the present invention, be included in actual all aluminium and the aluminium alloy that uses in the various technical fields, for example, the AC1A that stipulates among the JIS H5202, AC1B, AC2A, AC2B, AC3A, AC4A, AAC4B, AC4C, AC4CH, AC4D, AC5A, AC7A, AC8A, AC8B, AC8C, AC9A, aluminum alloy castinges such as AC9B, the ADC1 of regulation among the JIS H 5302, ADC3, ADC5, ADC6, ADC10, ADC10Z, ADC12, ADC12Z, aluminium alloy die castings such as ADC14, the alloy of stipulating among JIS H4000 numbering 2017,2219,3003,3104,4032,5005,5154,6101,6061,7075,8021 wrought materials such as aluminium alloy such as grade (Zhan Shencai).In addition, as the form of the aluminium goods that carry out the surface chemistry conversion processing among the present invention, can enumerate die casting product, sand casting product, die casting, wrought materials etc.
Before handling, preferably pre-treatment is carried out on the surface of aluminium by 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.For example, can wash then and implement by being that the temperature of 5g/L is a dipping 1 minute in 40 ℃ the aqueous solution in the concentration of ア Network タ Application 70 (メ Application テ Star Network ス society system, acid ammonium fluoride).
In the surface chemistry transformation processing method of the present invention, carry out anodic oxidation treatment by the surface to aluminium, then carry out sealing of hole and handle, implement surface chemistry conversion processing of the present invention then, erosion resistance further improves.It is known in this technical field that anodic oxidation treatment that adopts among the present invention and sealing of hole are handled, and among the present invention, can directly utilize known anodic oxidation treatment technology and sealing of hole treatment technology.For example, be that 1～5mol/L, boric acid concentration are to be 0.5～5A/dm with current density in the treatment solution of 0.1～0.3mol/L at sulfuric acid concentration 2, bathe temperature and be 20～30 ℃ and carry out 10～30 minutes anodic oxidation treatment, be to be that 85 ℃ of dippings carried out sealing of hole in 2～10 minutes and handle to bathe temperature in the treatment solution of 1～5g/L in nickelous acetate concentration then.
The treatment solution that uses in the surface chemistry transformation processing method of the present invention contains chromium nitrate as necessary composition.Chromium nitrate can obtain with the form of 9 water salt, anhydrous salt or the 40 quality % aqueous solution, can use any one goods among the present invention.The concentration conversion of the chromium nitrate in the treatment solution is Cr (NO 3) 3100% be preferably 3～12g/L, more preferably about 4～10g/L.Therefore, when using chromium nitrate 9 water salt, the concentration of chromium nitrate 9 water salt is preferably about 4.2～20.1g/L.The concentration of the chromium nitrate in the treatment solution is with Cr (NO 3) 3Meter is during less than 3g/L, and the erosion resistance of the aluminium material surface after chemical conversion is handled has inadequate trend.In addition, the concentration of the chromium nitrate in the treatment solution is with Cr (NO 3) 3When meter surpasses 12g/L, even increase the raising of also finding the erosion resistance that matches with it.
The treatment solution that uses in the surface chemistry transformation processing method of the present invention contains ammonium vanadate as necessary composition.Ammonium vanadate is commercially available with the purity of 98 quality %, 99 quality %, can use any one goods among the present invention.The concentration conversion of the ammonium vanadate in the treatment solution is NH 4VO 3100% be preferably 0.5～7g/L, more preferably about 1.5～5g/L.The concentration of the ammonium vanadate in the treatment solution is with NH 4VO 3Meter is during less than 0.5g/L, and the erosion resistance of the aluminium material surface after chemical conversion is handled has inadequate trend.In addition, the concentration of the ammonium vanadate in the treatment solution is with NH 4VO 3When meter surpasses 7g/L, even increase the raising of also finding the erosion resistance that matches with it.
The treatment solution that uses in the surface chemistry transformation processing method of the present invention contains potassium fluotitanate as necessary composition.Potassium fluotitanate is commercially available with 98 quality % or above purity, can use any one goods among the present invention.The concentration conversion of the potassium fluotitanate in the treatment solution is K 2TiF 6100% be preferably 0.5～3g/L, more preferably about 0.7～2.5g/L.The concentration of the potassium fluotitanate in the treatment solution is with K 2TiF 6Meter is during less than 0.5g/L, and the erosion resistance of the aluminium material 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 surpasses 3g/L, even increase the raising of also finding the erosion resistance that matches with it.
The treatment solution that uses in the surface chemistry transformation processing method of the present invention contains lithium fluoride as necessary composition.Lithium fluoride is commercially available with the purity of 99 quality %, can use any one commercially available product among the present invention.The concentration conversion of the lithium fluoride in the treatment solution be LiF100% be preferably 0.5～3g/L, more preferably about 0.7～2.5g/L.During less than 0.5g/L, the erosion resistance of the aluminium material surface after chemical conversion is handled has inadequate trend to the concentration of the lithium fluoride in the treatment solution in LiF.In addition, the concentration of the lithium fluoride in the treatment solution is in LiF during above 3g/L, even increase the raising of also finding the erosion resistance that matches with it.
The treatment solution that uses in the surface chemistry transformation processing method of the present invention contains nitric acid as necessary composition.Nitric acid is commercially available with the aqueous solution of 50 capacity %, 62 capacity %, 67.5 capacity % etc., can use any one goods among the present invention.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 of the aluminium material 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 also finding the erosion resistance that matches 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 of the aluminium material 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 of the aluminium material 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 also finding the erosion resistance that matches 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.
Have the erosion resistance of aluminium goods of the epithelium that forms by surface chemistry transformation processing method of the present invention and the adaptation two aspect excellences of filming, compare when handling and to reach equal above effect by chromate process or phosphoric acid-chromate process.
Embodiment
Hereinafter the present invention is carried out specific description based on embodiment and comparative example.
Embodiment 1～2 and comparative example 1～7
Flooded 1 minute in the aqueous solution of the ア Network タ of the concentration 5g/L of 40 ℃ of liquid temperature Application 70 (メ Application テ Star Network ス society system) using the ADC-12 alloy to carry out a large amount of test films that the die casting casting obtains, the tap water of implementing then under the room temperature washed 30 seconds, then implemented the pure water washing under the room temperature in 30 seconds.
In each embodiment and comparative example, use the test film of 2 above-mentioned pre-treatments of process, dipping is 3 minutes in the treatment solution that contains 45 ℃ of chromium nitrate-9 water salt, 40 quality % chromium sulphates (III), 99 quality % ammonium vanadate, 98 quality % potassium fluotitanates, 99 quality % lithium fluoride, 62 capacity % nitric acid and 95 capacity % vitriolic with the amount shown in the table 1, 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.Being noted that embodiment 1 and embodiment 2 are illustrated under the same treatment condition implements each result of twice.
For concentration that must composition among the present invention shown in the table 1, because the molecular weight of chromium nitrate-9 water salt is 400, Cr (NO 3) 3Molecular weight be 238, the amount 10g/L of chromium nitrate-9 water salt is with Cr (NO 3) 3The concentration of meter is 5.95g/L{10 * (238/400) }, the amount 3g/L of 99 quality % ammonium vanadate is with NH 4VO 3The concentration of meter is 2.97g/L, and the amount 1g/L of 98 quality % potassium fluotitanates is with K 2TiF 6The concentration of meter is 0.98g/L, and 99 quality % lithium fluoride concentration 2g/L are 1.89g/L in the concentration of LiF, and the amount 2mL/L of 62 capacity % nitric acid is with HNO 3The concentration of meter is 1.24mL/L.
Then, implement corrosion resistance test, measure grade (レ イ テ イ Application グ Na Application バ one) by salt water resistance spray testing method according to JIS Z 2371.For embodiment 1 and 2 brine spray times of embodiment is 96 hours, for 1～5 brine spray time of comparative example be 24 hours, be 48 hours for comparative example 6 and 7 brine spray times of comparative example.Their result is as shown in table 1.In addition, the photo of each test film behind these corrosion resistance tests is shown in Fig. 1～9.
Figure S2007800011381D00071
By the data shown in the table 1 as can be known, among the embodiment 1 and embodiment 2 of chemical conversion processing method of the present invention, the erosion resistance grade of 96 hours salt spray testings is more than 9.9, relative therewith, under the situation of the comparative example 1～5 of from the treatment solution of the present invention's use, removing any one composition, the erosion resistance grade of 24 hours salt spray testings is 0.5～7.5, change at the chromium nitrate of the treatment solution that the present invention is used under the situation of comparative example 6 of chromium sulphate, the erosion resistance grade of 48 hours salt spray testings is 6.0, nitric acid at the treatment solution that the present invention is used is changed under the situation of vitriolic comparative example 7, and the erosion resistance grade of 48 hours salt spray testings is 7.5.And, when in the treatment solution that the present invention uses, further adding phosphoric acid, in the processing of aluminum die cast, not only do not find the raising of erosion resistance, and in this chemical conversion is handled, produce precipitation, be difficult to treatment solution is managed.
Embodiment 3～25 and comparative example 8～19
Flooded 1 minute in as ア Network タ Application 70 (the メ Application テ Star Network ス society system) aqueous solution of 5g/L in 40 ℃ of liquid temperature, concentration using the ADC-12 alloy to carry out a large amount of test films that die casting casting obtains, 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.
In each embodiment 3～25 and comparative example 8～19, use the test film of 2 or 3 the above-mentioned pre-treatments of process, respectively with Cr (NO 3) 3, NH 4VO 3, K 2TiF 6, LiF and HNO 3Meter contained in 45 ℃ the treatment solution of chromium nitrate, ammonium vanadate, potassium fluotitanate, lithium fluoride and nitric acid dipping 3 minutes with the concentration shown in table 2 and the table 3, 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.
Then, implemented corrosion resistance test with 96 hours brine spray time, measure grade by salt water resistance spray testing method according to JIS Z 2371.And, the measured value scope of following differentiation grade, when 2 or 3 test films all belong to same group in each embodiment and the comparative example, the symbol of this group shown in table 2 and table 3, when striding two groups between the symbol of these two groups additional "～", shown in table 2 and table 3.
◎: grade 10～9.5,
Zero: grade 9.4～9.0,
△: grade 8.9～8.4,
*: grade is below 8.3.
Figure S2007800011381D00091
Figure S2007800011381D00101
Embodiment 26～27
Flooded 1 minute in as ア Network タ Application 70 (the メ Application テ Star Network ス society system) aqueous solution of 5g/L in 40 ℃ of liquid temperature, concentration using the ADC-12 alloy to carry out a large amount of test films that die casting casting obtains, 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.
Use 95 capacity % sulfuric acid, use 99.5 quality % boric acid, use 99 quality % Nickel diacetate tetrahydrates as sulfuric acid as nickelous acetate as boric acid, to through the test film of above-mentioned pre-treatment in the treatment solution of sulfuric acid concentration 2mol/L, boric acid concentration 0.2mol/L with current density 2A/dm 2, bathe 25 ℃ of anodic oxidation treatment of carrying out 20 minutes of temperature, then in the treatment solution of nickelous acetate concentration 2g/L, carried out sealing of hole in 5 minutes and handle to bathe 85 ℃ of dippings of temperature.
In each embodiment 26 and embodiment 27, use the test film of 6 above-mentioned pre-treatments of process and further implemented the test film that anodic oxidation treatment and sealing of hole are handled as mentioned above, under the condition identical, implement the surface chemistry conversion processing with embodiment 1.
Then,, respectively 2 test films are implemented the corrosion resistance test of 96 hours brine spray time, 120 hours or 240 hours, measured grade by salt water resistance spray testing method according to JIS Z 2371.The mean value of the grade of two test films is as shown in table 4.
[table 4]
Table 4
Figure S2007800011381D00111
By the data shown in the table 4 as can be known, by the surface of aluminium being carried out anodic oxidation treatment, then carry out sealing of hole and handle, implement surface chemistry conversion processing of the present invention then, erosion resistance is further improved.

Claims (5)

1. the chemical conversion processing method of aluminium material surface is characterized in that, uses 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 and count 0.5～3g/L and concentration of nitric acid with HNO with LiF 3Counting 0.5～1.8mL/L and liquid temperature and be 40～50 ℃ treatment solution implements chemical conversion in 1～5 minute to the surface of the aluminium that comprises aluminum or aluminum alloy and handles and form epithelium.
2. the chemical conversion processing method of aluminium material surface is characterized in that, anodic oxidation treatment is carried out on the surface of the aluminium that comprises aluminum or aluminum alloy, then carries out sealing of hole and handles, and then, uses 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 and count 0.5～3g/L and concentration of nitric acid with HNO with LiF 3Counting 0.5～1.8mL/L and liquid temperature and be 40～50 ℃ treatment solution implements chemical conversion in 1～5 minute and handles and form epithelium.
3. aluminium is characterized in that, has by using 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 and count 0.5～3g/L and concentration of nitric acid with HNO with LiF 3Counting 0.5～1.8mL/L and liquid temperature and be 40～50 ℃ treatment solution implements chemical conversion in 1～5 minute to the surface of the aluminium that comprises aluminum or aluminum alloy and handles the epithelium that forms.
4. aluminium is characterized in that, has by the surface to the aluminium that comprises aluminum or aluminum alloy to carry out anodic oxidation treatment, then carries out sealing of hole and handles, and then, uses 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 and count 0.5～3g/L and concentration of nitric acid with HNO with LiF 3Counting 0.5～1.8mL/L and liquid temperature is the epithelium of 40～50 ℃ treatment solution enforcement chemical conversion in 1～5 minute processing formation.
5. claim 3 or 4 described aluminiums, wherein, aluminium is aluminium alloy die casting goods.
CN2007800011381A 2006-01-10 2007-01-09 Method for chemical conversion treatment of the surface of aluminum material and aluminum material Expired - Fee Related CN101356300B (en)

Applications Claiming Priority (5)

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JP2006003058 2006-01-10
JP003058/2006 2006-01-10
JP265778/2006 2006-09-28
JP2006265778 2006-09-28
PCT/JP2007/050077 WO2007080849A1 (en) 2006-01-10 2007-01-09 Method for chemical conversion treatment of the surface of aluminum material and aluminum material

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