EP0575244B1 - Procédé de traitement de substrats à base d'aluminium en vue de leur anodisation, bain mis en oeuvre dans ce procédé et concentré pour préparer le bain - Google Patents
Procédé de traitement de substrats à base d'aluminium en vue de leur anodisation, bain mis en oeuvre dans ce procédé et concentré pour préparer le bain Download PDFInfo
- Publication number
- EP0575244B1 EP0575244B1 EP93401533A EP93401533A EP0575244B1 EP 0575244 B1 EP0575244 B1 EP 0575244B1 EP 93401533 A EP93401533 A EP 93401533A EP 93401533 A EP93401533 A EP 93401533A EP 0575244 B1 EP0575244 B1 EP 0575244B1
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- EP
- European Patent Office
- Prior art keywords
- bath
- acid
- acids
- concentration
- group
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 title claims abstract description 38
- 229910052782 aluminium Inorganic materials 0.000 title claims abstract description 38
- 238000000034 method Methods 0.000 title claims abstract description 17
- 239000012141 concentrate Substances 0.000 title claims description 7
- 238000002048 anodisation reaction Methods 0.000 title claims description 6
- 239000000758 substrate Substances 0.000 title abstract description 14
- 239000004411 aluminium Substances 0.000 title abstract description 5
- 239000002253 acid Substances 0.000 claims abstract description 41
- 235000011007 phosphoric acid Nutrition 0.000 claims abstract description 11
- 150000003016 phosphoric acids Chemical class 0.000 claims abstract description 7
- 235000011149 sulphuric acid Nutrition 0.000 claims abstract 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 18
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 12
- 150000007513 acids Chemical class 0.000 claims description 11
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 9
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 8
- 150000001875 compounds Chemical class 0.000 claims description 7
- 238000004519 manufacturing process Methods 0.000 claims description 7
- 229910017604 nitric acid Inorganic materials 0.000 claims description 7
- 150000003863 ammonium salts Chemical class 0.000 claims description 6
- 239000002904 solvent Substances 0.000 claims description 6
- 229910003638 H2SiF6 Inorganic materials 0.000 claims description 5
- 229910045601 alloy Inorganic materials 0.000 claims description 5
- 239000000956 alloy Substances 0.000 claims description 5
- 125000000129 anionic group Chemical group 0.000 claims description 5
- 239000013065 commercial product Substances 0.000 claims description 5
- ZEFWRWWINDLIIV-UHFFFAOYSA-N tetrafluorosilane;dihydrofluoride Chemical compound F.F.F[Si](F)(F)F ZEFWRWWINDLIIV-UHFFFAOYSA-N 0.000 claims description 5
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 4
- 125000002091 cationic group Chemical group 0.000 claims description 4
- 238000010790 dilution Methods 0.000 claims description 3
- 239000012895 dilution Substances 0.000 claims description 3
- 229910003708 H2TiF6 Inorganic materials 0.000 claims 4
- 229910003899 H2ZrF6 Inorganic materials 0.000 claims 4
- 159000000011 group IA salts Chemical class 0.000 claims 4
- 238000003486 chemical etching Methods 0.000 claims 2
- 239000003795 chemical substances by application Substances 0.000 claims 2
- 238000007254 oxidation reaction Methods 0.000 abstract description 16
- 230000003647 oxidation Effects 0.000 abstract description 13
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 abstract description 2
- 229910052710 silicon Inorganic materials 0.000 abstract description 2
- 239000010703 silicon Substances 0.000 abstract description 2
- 238000004381 surface treatment Methods 0.000 abstract description 2
- 150000003608 titanium Chemical class 0.000 abstract description 2
- 229910052726 zirconium Inorganic materials 0.000 abstract description 2
- 238000005554 pickling Methods 0.000 description 35
- 238000002474 experimental method Methods 0.000 description 14
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 12
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 5
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 5
- 238000005238 degreasing Methods 0.000 description 5
- 238000004061 bleaching Methods 0.000 description 4
- 230000000295 complement effect Effects 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- RGHNJXZEOKUKBD-SQOUGZDYSA-M D-gluconate Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C([O-])=O RGHNJXZEOKUKBD-SQOUGZDYSA-M 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- 150000001447 alkali salts Chemical class 0.000 description 3
- 238000007743 anodising Methods 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 239000008139 complexing agent Substances 0.000 description 3
- 229940050410 gluconate Drugs 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 238000001556 precipitation Methods 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 230000008030 elimination Effects 0.000 description 2
- 238000003379 elimination reaction Methods 0.000 description 2
- 239000010410 layer Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 150000002823 nitrates Chemical class 0.000 description 2
- 239000002736 nonionic surfactant Substances 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000010802 sludge Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 230000001629 suppression Effects 0.000 description 2
- 229910000553 6063 aluminium alloy Inorganic materials 0.000 description 1
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 1
- 229910017090 AlO 2 Inorganic materials 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- FBPFZTCFMRRESA-FSIIMWSLSA-N D-Glucitol Natural products OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-N 0.000 description 1
- FBPFZTCFMRRESA-JGWLITMVSA-N D-glucitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-JGWLITMVSA-N 0.000 description 1
- 229910004039 HBF4 Inorganic materials 0.000 description 1
- 229910004713 HPF6 Inorganic materials 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 229910020491 K2TiF6 Inorganic materials 0.000 description 1
- 229910020148 K2ZrF6 Inorganic materials 0.000 description 1
- 229910017855 NH 4 F Inorganic materials 0.000 description 1
- 229910017665 NH4HF2 Inorganic materials 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 244000085553 Triticum polonicum Species 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 238000003915 air pollution Methods 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical group [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 1
- 150000004645 aluminates Chemical class 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- ANBBXQWFNXMHLD-UHFFFAOYSA-N aluminum;sodium;oxygen(2-) Chemical compound [O-2].[O-2].[Na+].[Al+3] ANBBXQWFNXMHLD-UHFFFAOYSA-N 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- LDDQLRUQCUTJBB-UHFFFAOYSA-N ammonium fluoride Chemical compound [NH4+].[F-] LDDQLRUQCUTJBB-UHFFFAOYSA-N 0.000 description 1
- 239000003093 cationic surfactant Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000001186 cumulative effect Effects 0.000 description 1
- RXCBCUJUGULOGC-UHFFFAOYSA-H dipotassium;tetrafluorotitanium;difluoride Chemical compound [F-].[F-].[F-].[F-].[F-].[F-].[K+].[K+].[Ti+4] RXCBCUJUGULOGC-UHFFFAOYSA-H 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 150000002334 glycols Chemical class 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- 239000003456 ion exchange resin Substances 0.000 description 1
- 229920003303 ion-exchange polymer Polymers 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- LNOPIUAQISRISI-UHFFFAOYSA-N n'-hydroxy-2-propan-2-ylsulfonylethanimidamide Chemical compound CC(C)S(=O)(=O)CC(N)=NO LNOPIUAQISRISI-UHFFFAOYSA-N 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 235000021317 phosphate Nutrition 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- KWYUFKZDYYNOTN-UHFFFAOYSA-M potassium hydroxide Substances [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 1
- 125000001453 quaternary ammonium group Chemical group 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 238000005204 segregation Methods 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 229910001388 sodium aluminate Inorganic materials 0.000 description 1
- PNGLEYLFMHGIQO-UHFFFAOYSA-M sodium;3-(n-ethyl-3-methoxyanilino)-2-hydroxypropane-1-sulfonate;dihydrate Chemical compound O.O.[Na+].[O-]S(=O)(=O)CC(O)CN(CC)C1=CC=CC(OC)=C1 PNGLEYLFMHGIQO-UHFFFAOYSA-M 0.000 description 1
- 239000000600 sorbitol Substances 0.000 description 1
- 238000009987 spinning Methods 0.000 description 1
- 150000003871 sulfonates Chemical class 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 230000004580 weight loss Effects 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
- C25D11/02—Anodisation
- C25D11/04—Anodisation of aluminium or alloys based thereon
- C25D11/16—Pretreatment, e.g. desmutting
Definitions
- the subject of the invention is a method of treatment aluminum-based substrates for anodizing.
- It also relates to a bath used in this process as well as a concentrate for the preparation of the bath.
- Substrates i.e. parts and profiles based on aluminum, in other words aluminum or one of its alloys, are used in industry and in particular in architectural application, in particular for the manufacture of frames.
- above parts and profiles can be painted or be electrolytic anodizing treatment of aluminum in an acid medium.
- the parts and profiles are protected by an artificially formed Al 2 O 3 oxide layer; according to the desired degree of protection which is a function of the use of the parts inside or outside, the alumina layer can be more or less thick; its thickness is generally between 2 and 30 micrometers.
- the steps preceding the anodic oxidation include the so-called satin-finishing step producing a pickling which consists in removing the surface layer from the substrates; in practice, the treated parts or sections are pickled to a thickness of approximately 30 microns, which corresponds to a weight loss of approximately 90 g / m 2 .
- complexing agents are added to the above-mentioned baths such as gluconate.
- the invention therefore aims to provide a method and a bath of the kind in question which do not exhibit the disadvantages inherent in the prior art and thanks to which it is possible to impart excellent mattness treated substrates.
- the Applicant Company has had the merit of find that, unexpectedly and surprisingly, it became possible to obtain substrates with a excellent mattness and appearance without risk of exploitation and while reducing the amount of alkaline releases (soda and aluminate) as well as the pickling thickness from then on that a bath is used for the satin-finishing step acid comprising at least one fluorinated derivative of titanium and / or zirconium and / or silicon as well as at least one acid from the group comprising nitric, sulfuric and phosphoric.
- the subject of the invention is the use, for the satin-finishing step, in a treatment process for the anodizing of parts and profiles of aluminum or one of its alloys used in application architectural, in particular for the manufacture of frames, of an acid bath comprising at least one of the compounds of the group comprising the fluometallic acids H 2 TiF 6 , H 2 ZrF 6 and H 2 SiF 6 as well as their alkali salts or d ammonium at a concentration of at least 1 g / l and at least one of the acids of the group comprising nitric acid, sulfuric acid and phosphoric acid at a concentration of between 0.5 and 100 ml per liter of bath, expressed as concentrated commercial acid and advantageously non-ionic, anionic, cationic surfactants and third-party solvents.
- the satin-finishing step using the acid bath is followed by a complementary light satin-finishing step using an alkaline bath, the conditions of this satin-finishing being such that it leads to pickling of '' not more than 40 g / m 2 of aluminum.
- the bath according to the invention for the treatment is characterized by the fact that it comprises at least one of the compounds from the group comprising the fluometallic acids H 2 TiF 6 , H 2 ZrF 6 and H 2 SiF 6 as well as their alkali or ammonium salts at a concentration of at least 1 g / l and at least one of the acids from the group consisting of sulfuric and phosphoric acids at a concentration of between 0.5 and 100 ml per liter of bath, expressed as concentrated commercial acid and advantageously nonionic surfactants , anionic, cationic and third-party solvents.
- the concentrate according to the invention which is capable of providing by dilution with water the bath according to the invention defined above, is characterized in that it contains at least one of the compounds of the group comprising fluometallic acids H 2 TiF 6 , H 2 ZrF 6 and H 2 SiF 6 as well as their alkali or ammonium salts at a concentration of commercial product of between 50 and 99.5% and at least one acid from the group consisting of sulfuric and phosphoric acids at a concentration of commercial product of 0.5 to 50%.
- Sulfuric and phosphoric acids have the advantage of being present on the anodic oxidation lines in the acid degreasing (H 3 PO 4 ), bleaching (HNO 3 ) and anodic oxidation (H 2 SO 4 ) baths. ; they can also be regenerated from these baths by already known methods (ion exchange resins for example); they can also be used directly in the acid pickling bath if their pollution rate allows, which is the case in the context of the present invention.
- the above concentrate can be diluted in water to a concentration between 1 per thousand and 10% for constitute the ready-to-use bath.
- the above concentrations as well as the duration and the temperature of the satin-finishing step are adjusted so as to obtain a pickling rate of at least 5 g / m 2 of the substrate.
- the surfactants in question may be chosen from the group comprising alkylphenols, polyalkoxylated alcohols and amines, alkyl-, alkylaryl- and arylsulfates, sulfonates, phosphates and quaternary ammoniums.
- Third party solvents can for example be glycols.
- the temperature of the satin-finishing bath is understood between 15 ° C and 80 ° C and, preferably, between 20 and 60 ° C.
- the time during which the action of the bath is maintained is between 1 minute and 1 hour .
- the processing time in industry will preferably not exceed about thirty minutes.
- a complementary light alkaline pickling carried out according to a process in itself known and such that it leads to pickling of at most 40 g / m 2 aluminum;
- Such an additive which is based on gluconate can be that marketed by the Applicant Company under the PROGAL G 313 TA brand.
- the alkaline pickling bath thus formed is put for a period of 2 to 20 minutes on the parts coming out of the acid pickling bath.
- Aluminum profiles are treated as follows: Step 1 Aqueous sodium degreasing in an aqueous solution at 100 g / l of IPRO 77 AP marketed by the Applicant Company, 2nd step Cold rinse with running water, Stage 3 Pickling (satin) acid (see the 8 comparative experiments whose characteristics result from Table I), Step 4 Cold rinse with running water, Step 5 Alkaline pickling (satin finishing) with a bath having the characteristics indicated below, Step 6 Cold rinse with running water, Step 7 Nitric bleaching in a 180 g / l bath of concentrated nitric acid in water, Step 8 Cold rinse with running water, Step 9 Anodic sulfuric oxidation in a bath with 180 g / l of concentrated sulfuric acid (temperature 18 ° C), Step 10 Cold rinse with running water, Step 11 Rinsing in demineralized water, Step 12 Clogging with hot demineralized water (98 ° C).
- the temperature of the acid pickling bath is 30 ° C.
- the treatment time is chosen to have a pickling of approximately 25 g / m 2 .
- Step 5 uses a permanent satin-finishing bath, the characteristics of which are: free soda about 100 g / l aluminum about 140 g / l temperature 60 ° C.
- the treatment time in this bath and when the acid pickling baths are those called b1 to b6, is that necessary to have a pickling rate of approximately 25 g / m 2 .
- step 3 the baths b1 and b9 to b14 defined in Table III are used.
- Baths b1 and b9 to b14 are used at 30 ° C and for the time necessary to cause the treated parts to lose weight in the order of 25 g / m 2 . These baths are used respectively to carry out experiments 1 and 9 to 14, the results of which are collated in Table IV. Exp. No.
- Series 6063 aluminum profiles are treated by proceeding as in Example 1, but by varying in step 3 the concentration of potassium fluorotitanate K 2 TiF 6 as well as the temperature and by examining the influence of these variations on the pickling speed of aluminum parts.
- the time required to obtain a pickling rate of approximately 24 g / m 2 was determined for each of the K 2 TiF 6 concentrations and for each of the temperatures chosen, the 98% sulfuric acid concentration being 3 ml / l .
- the processing time is then understood between six minutes and about thirty minutes, time easily manageable on a production line.
- the acid pickling bath (step 3) used is constituted by the bath bl described in Example 1. Sa working temperature is 30 ° C and soaking time is 15 minutes.
- the dullness measured according to the same method at the end of step 12, is 5, that is to say clearly improved compared to the dullness measured in the same conditions according to experiment 8 of example 1 and which industrially located at 12-15.
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Engineering & Computer Science (AREA)
- Cleaning And De-Greasing Of Metallic Materials By Chemical Methods (AREA)
- ing And Chemical Polishing (AREA)
- Manufacture And Refinement Of Metals (AREA)
- Chemical Treatment Of Metals (AREA)
- Printing Plates And Materials Therefor (AREA)
- Materials For Photolithography (AREA)
- Detergent Compositions (AREA)
Description
- une étape de dégraissage généralement en milieu alcalin pour éliminer les souillures organiques, étant toutefois noté que des dégraissages faisant intervenir l'acide phosphorique sont parfois utilisés,
- une étape de rinçage à l'eau courante froide,
- une étape de traitement chimique de surface ou satinage pour gommer les défauts de surface des pièces et pour conférer à l'aluminium un aspect généralement non brillant,
- une ou plusieurs étapes de rinçage en eau froide,
- une étape de blanchiment acide généralement à l'aide d'acide nitrique,
- une ou plusieurs étapes de rinçage en eau froide,
- l'oxydation anodique proprement dite, souvent réalisée dans le cas des applications architecturales à l'aide d'une solution à base d'acide sulfurique,
- une ou plusieurs étapes de rinçage d'abord en eau courante puis en eau déminéralisée,
- une étape dite de colmatage servant à fermer les pores créés par l'oxydation anodique.
- la suppression des traits de filage liés au passage des profilés dans des filières plus ou moins âgées,
- la suppression des zones de ségrégation cristalline, notamment dans le cas de profilés creux,
- un aspect uniforme mat et reproductible en fin de traitement.
- jusqu'à 25% en poids d'acide chlorhydrique ou nitrique et
- de 1 à 25% en poids d'un acide minéral fluoré ou d'un de ses sels choisi de préférence dans le groupe constitué par HF, H2SiF6, HPF6, HBF4, K2ZrF6, K2TiF6, NH4F, NH4HF2.
Etape 1 | Dégraissage sodique aqueux dans une solution aqueuse à 100 g/l d'IPRO 77 AP commercialisé par la Société Demanderesse, |
Etape 2 | Rinçage froid à l'eau courante, |
Etape 3 | Décapage (satinage) acide (voir les 8 expériences comparatives dont les caractéristiques résultent du Tableau I), |
Etape 4 | Rinçage froid à l'eau courante, |
Etape 5 | Décapage (satinage) alcalin avec un bain ayant les caractéristiques indiquées plus loin, |
Etape 6 | Rinçage froid à l'eau courante, |
Etape 7 | Blanchiment nitrique dans un bain à 180 g/l d'acide nitrique concentré dans l'eau, |
Etape 8 | Rinçage froid à l'eau courante, |
Etape 9 | Oxydation anodique sulfurique dans un bain à 180 g/l d'acide sulfurique concentré (température 18°C), |
Etape 10 | Rinçage froid à l'eau courante, |
Etape 11 | Rinçage dans de l'eau déminéralisée, |
Etape 12 | Colmatage à l'eau déminéralisée chaude (98°C). |
Bain N° | Composition chimique des bains de décapage | |
Produit fluoré | Acide complémentaire | |
b1 | H2TiF6 à 60% : 40 g/l | H2SO4 à 98% = 3 ml |
b2 | H2ZrF6 à 45% : 68 g/l | " |
b3 | H2SiF6 à 34% : 63 g/l | " |
b4 | HF à 50% : 35,5 g/l | " |
b5 | HPF6 à 60% : 36 g/l | " |
b6 | HBF4 à 50% : 26 g/l | " |
b7 et b8 | Eau pure | - |
soude libre | environ 100 g/l |
aluminium | environ 140 g/l |
température | 60°C. |
- ainsi dans l'expérience mettant en oeuvre le bain b7, on maintient l'action du bain alcalin de l'étape 5 pendant un temps suffisant pour obtenir un décapage d'environ 50 g/m2, comparable au cumul des décapages acide et alcalin des expériences 1 à 6, et
- dans l'expérience mettant en oeuvre le bain b8, on procède selon la pratique actuelle sur les lignes d'oxydation anodique de l'aluminium, à savoir un satinage alcalin classique d'environ 18 à 20 minutes qui se traduit par un décapage d'environ 80 à 90 g/m2 d'aluminium.
Exp. No. | Taux de décapage acide | Taux de satinage alcalin | Taux de décapage global | Brillance après étape 8 | Observation |
1 | 24 g/m2 | 16 g/m2 | 40 g/m2 | 18 | Aspect correct de l'aluminium |
2 | 30 g/m2 | 17 g/m2 | 47 g/m2 | 28 | Formation d'un dépôt noirâtre après présatinage qui s'élimine dans l'étape alcaline |
3 | 19 g/m2 | 23 g/m2 | 42 g/m2 | 36 | Aspect correct de l'aluminium |
4 | 26 g/m2 | 20 g/m2 | 46 g/m2 | 68 | Aspect correct de l'aluminium |
5 | 22 g/m2 | 21 g/m2 | 43 g/m2 | 56 | Formation d'un dépôt noirâtre après présatinage qui s'élimine dans l'étape alcaline |
6 | 20 g/m2 | 21 g/m2 | 41 g/m2 | 30 | Aspect correct de l'aluminium |
7 | - | 51 g/m2 | 59 g/m2 | 53 | Référence à taux de décapage comparable |
8 | - | 86 g/m2 | 86 g/m2 | 40 | Référence pratique actuelle |
Bain N° | Composition chimique des bains de décapage | |
Produit fluoré | Acide complémentaire | |
b1 | H2TiF6 à 60%=25 ml/l | H2SO4 à 98% = 5,4 g/l |
b9 | " | HCl à 35% =11,5 g/l |
b10 | " | HNO3 à 60% =11,5 g/l |
b11 | " | H3PO4 à 75% = 7,2 g/l |
b12 | " | acide oxalique = 7,1 g/l |
b13 | " | acide sulfamique = 10,7 g/l |
b14 | " | acide citrique =10,5 g/l |
Exp. No. | Taux de décapage acide | Taux de satinage alcalin | Taux de décapage global | Brillance après étape 8 | Observation |
1 | 24 g/m2 | 16 g/m2 | 40 g/m2 | 18 | |
9 | 27 g/m2 | 23 g/m2 | 50 g/m2 | 24 | Aspect piqué de la surface de l'aluminium |
10 | 17 g/m2 | 27 g/m2 | 44 g/m2 | 12 | |
11 | 22 g/m2 | 26 g/m2 | 48 g/m2 | 26 | |
12 | 30 g/m2 | 27 g/m2 | 57 g/m2 | 47 | |
13 | 25 g/m2 | 26 g/m2 | 51 g/m2 | 58 | |
14 | 25 g/m2 | 25 g/m2 | 50 g/m2 | 51 |
K2TiF6 | Température | Temps nécessaire pour avoir un taux de décapage d'environ 24 g/m2 |
0,9 g/l | 30°C | 400 minutes |
60°C | 66 minutes | |
80°C | 26 minutes | |
22 g/l | 20°C | 29 minutes |
30°C | 15 minutes | |
40°C | 8 minutes | |
60°C | 3 minutes | |
80°C | 1 minute | |
57 g/l | 20°C | 18 minutes |
30°C | 6 minutes | |
60°C | 1 minute | |
88 g/l | 20°C | 6 minutes |
30°C | 1 minute |
Claims (4)
- Utilisation, pour l'étape de satinage, dans un procédé de traitement pour l'anodisation de pièces et profilés en aluminium ou en l'un de ses alliages mis en oeuvre en application architecturale, en particulier pour la fabrication des huisseries, d'un bain acide comprenant au moins l'un des composés du groupe comprenant les acides fluométalliques H2TiF6, H2ZrF6 et H2SiF6 ainsi que leurs sels alcalins ou d'ammonium à une concentration d'au moins 1 g/l et au moins l'un des acides du groupe comprenant l'acide nitrique, l'acide sulfurique et l'acide phosphorique à une concentration comprise entre 0,5 et 100 ml par litre de bain, exprimée en acide concentré du commerce et avantageusement des agents tensio-actifs non ioniques, anioniques, cationiques et des tiers solvants.
- Bain de satinage acide pour le traitement, en vue de leur anodisation, de pièces et profilés en aluminium ou en l'un de ses alliages mis en oeuvre en application architecturale, en particulier pour la fabrication des huisseries, caractérisé par le fait qu'il comprend au moins l'un des composés du groupe comprenant les acides fluométalliques H2TiF6, H2ZrF6 et H2SiF6 ainsi que leurs sels alcalins ou d'ammonium à une concentration d'au moins 1 g/l et au moins l'un des acides du groupe constitué par les acides sulfurique et phosphorique à une concentration comprise entre 0,5 et 100 ml par litre de bain, exprimée en acide concentré du commerce et avantageusement des agents tensio-actifs non ioniques, anioniques, cationiques et des tiers solvants.
- Concentré propre à fournir par dilution avec de l'eau le bain selon la revendication 2, caractérisé par le fait qu'il contient au moins l'un des composés du groupe comprenant les acides fluométalliques H2TiF6, H2ZrF6 et H2SiF6 ainsi que leurs sels alcalins ou d'ammonium à une concentration en produit commercial comprise entre 50 et 99,5% et au moins un acide du groupe constitué par les acides sulfurique et phosphorique à une concentration en produit commercial de 0,5 à 50%.
- Concentré propre à fournir, par dilution avec de l'eau et l'un des acides sulfurique et phosphorique, le bain selon la revendication 2, caractérisé par le fait qu'il contient au moins l'un des composés du groupe comprenant les acides fluométalliques H2TiF6, H2ZrF6 et H2SiF6 ainsi que leurs sels alcalins ou d'ammonium à une concentration en produit commercial comprise entre 50 et 99,5%.
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
FR9207352 | 1992-06-17 | ||
FR929207352A FR2692599B1 (fr) | 1992-06-17 | 1992-06-17 | Procédé de traitement de substrats à base d'aluminium en vue de leur anodisation, bain mis en Óoeuvre dans ce procédé et concentré pour préparer le bain. |
Publications (2)
Publication Number | Publication Date |
---|---|
EP0575244A1 EP0575244A1 (fr) | 1993-12-22 |
EP0575244B1 true EP0575244B1 (fr) | 1999-05-06 |
Family
ID=9430843
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP93401533A Expired - Lifetime EP0575244B1 (fr) | 1992-06-17 | 1993-06-15 | Procédé de traitement de substrats à base d'aluminium en vue de leur anodisation, bain mis en oeuvre dans ce procédé et concentré pour préparer le bain |
Country Status (8)
Country | Link |
---|---|
US (1) | US5460694A (fr) |
EP (1) | EP0575244B1 (fr) |
JP (1) | JPH06184791A (fr) |
AT (1) | ATE179766T1 (fr) |
CA (2) | CA2098690A1 (fr) |
DE (1) | DE69324729T2 (fr) |
ES (1) | ES2130236T3 (fr) |
FR (1) | FR2692599B1 (fr) |
Cited By (1)
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US12104272B2 (en) | 2023-02-14 | 2024-10-01 | Prc-Desoto International, Inc. | Treated substrates |
Families Citing this family (21)
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KR0183826B1 (ko) * | 1996-03-04 | 1999-05-01 | 김광호 | 연마공정 후처리용 세정 용액 및 그를 이용하는 세정 방법 |
US6043206A (en) | 1996-10-19 | 2000-03-28 | Samsung Electronics Co., Ltd. | Solutions for cleaning integrated circuit substrates |
US5932023A (en) * | 1997-02-25 | 1999-08-03 | Ward; Glen Douglas | Method of washing a vehicle using a two-part washing composition |
US7910218B2 (en) | 2003-10-22 | 2011-03-22 | Applied Materials, Inc. | Cleaning and refurbishing chamber components having metal coatings |
US7618769B2 (en) * | 2004-06-07 | 2009-11-17 | Applied Materials, Inc. | Textured chamber surface |
US7670436B2 (en) | 2004-11-03 | 2010-03-02 | Applied Materials, Inc. | Support ring assembly |
US8617672B2 (en) | 2005-07-13 | 2013-12-31 | Applied Materials, Inc. | Localized surface annealing of components for substrate processing chambers |
US7762114B2 (en) | 2005-09-09 | 2010-07-27 | Applied Materials, Inc. | Flow-formed chamber component having a textured surface |
US9127362B2 (en) | 2005-10-31 | 2015-09-08 | Applied Materials, Inc. | Process kit and target for substrate processing chamber |
US8790499B2 (en) | 2005-11-25 | 2014-07-29 | Applied Materials, Inc. | Process kit components for titanium sputtering chamber |
US7981262B2 (en) | 2007-01-29 | 2011-07-19 | Applied Materials, Inc. | Process kit for substrate processing chamber |
US7942969B2 (en) | 2007-05-30 | 2011-05-17 | Applied Materials, Inc. | Substrate cleaning chamber and components |
US8097093B2 (en) * | 2007-09-28 | 2012-01-17 | Ppg Industries Ohio, Inc | Methods for treating a ferrous metal substrate |
US9428410B2 (en) | 2007-09-28 | 2016-08-30 | Ppg Industries Ohio, Inc. | Methods for treating a ferrous metal substrate |
KR101475173B1 (ko) * | 2011-06-24 | 2014-12-19 | 애플 인크. | 양극산화처리된 부품의 미용적 결함 저감 |
TWI444508B (zh) * | 2012-05-07 | 2014-07-11 | Catcher Technology Co Ltd | 具止滑皮革質感表面之金屬工件製造方法 |
DE102012015579A1 (de) * | 2012-08-08 | 2014-02-13 | Premium Aerotec Gmbh | Oberflächenschutzverfahren für Bauteile aus Aluminium bzw. Aluminiumlegierungen mit einem Nachweis einer unzulässigen Überhitzung |
US9273399B2 (en) | 2013-03-15 | 2016-03-01 | Ppg Industries Ohio, Inc. | Pretreatment compositions and methods for coating a battery electrode |
US9101954B2 (en) | 2013-09-17 | 2015-08-11 | Applied Materials, Inc. | Geometries and patterns for surface texturing to increase deposition retention |
US10435806B2 (en) | 2015-10-12 | 2019-10-08 | Prc-Desoto International, Inc. | Methods for electrolytically depositing pretreatment compositions |
EP3498890A1 (fr) * | 2017-12-12 | 2019-06-19 | Hydro Aluminium Rolled Products GmbH | Procédé de décapage pour profilés, bandes laminées et tôles d'alliages d'aluminium |
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Publication number | Priority date | Publication date | Assignee | Title |
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US3943039A (en) * | 1974-10-08 | 1976-03-09 | Kaiser Aluminum & Chemical Corporation | Anodizing pretreatment for nickel plating |
US4076779A (en) * | 1975-08-01 | 1978-02-28 | Wallace-Murray Corporation | Method of restoring the fluid permeability of a used, ceramic fluid-release mold |
US4148670A (en) * | 1976-04-05 | 1979-04-10 | Amchem Products, Inc. | Coating solution for metal surface |
FR2417537A1 (fr) * | 1978-02-21 | 1979-09-14 | Parker Ste Continentale | Composition a base d'hafnium pour inhiber la corrosion des metaux |
GB2127354B (en) * | 1982-09-23 | 1985-12-04 | James Michael Kape | Process and composition for preparing aluminum alloy surfaces for anodizing |
US4719038A (en) * | 1983-12-27 | 1988-01-12 | Nippon Paint Co., Ltd. | Corrosion resistant, coated metal laminate, its preparation and coating materials |
US4502925A (en) * | 1984-06-11 | 1985-03-05 | American Hoechst Corporation | Process for aluminum surface preparation |
FR2598402B1 (fr) * | 1986-05-07 | 1990-06-01 | Rhone Poulenc Chimie | Procede de nettoyage de surfaces filtrantes |
AU574609B2 (en) * | 1986-05-12 | 1988-07-07 | Nippon Steel Corporation | Chromate treatment of metal coated steel sheet |
US5030323A (en) * | 1987-06-01 | 1991-07-09 | Henkel Corporation | Surface conditioner for formed metal surfaces |
US4992116A (en) * | 1989-04-21 | 1991-02-12 | Henkel Corporation | Method and composition for coating aluminum |
US5139586A (en) * | 1991-02-11 | 1992-08-18 | Coral International, Inc. | Coating composition and method for the treatment of formed metal surfaces |
US5227016A (en) * | 1992-02-25 | 1993-07-13 | Henkel Corporation | Process and composition for desmutting surfaces of aluminum and its alloys |
-
1992
- 1992-06-17 FR FR929207352A patent/FR2692599B1/fr not_active Expired - Fee Related
-
1993
- 1993-06-15 DE DE69324729T patent/DE69324729T2/de not_active Expired - Fee Related
- 1993-06-15 EP EP93401533A patent/EP0575244B1/fr not_active Expired - Lifetime
- 1993-06-15 ES ES93401533T patent/ES2130236T3/es not_active Expired - Lifetime
- 1993-06-15 AT AT93401533T patent/ATE179766T1/de not_active IP Right Cessation
- 1993-06-17 JP JP5146523A patent/JPH06184791A/ja active Pending
- 1993-06-17 CA CA002098690A patent/CA2098690A1/fr not_active Abandoned
- 1993-06-17 US US08/077,611 patent/US5460694A/en not_active Expired - Fee Related
- 1993-06-17 CA CA002098689A patent/CA2098689A1/fr not_active Abandoned
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US12104272B2 (en) | 2023-02-14 | 2024-10-01 | Prc-Desoto International, Inc. | Treated substrates |
Also Published As
Publication number | Publication date |
---|---|
EP0575244A1 (fr) | 1993-12-22 |
FR2692599A1 (fr) | 1993-12-24 |
DE69324729D1 (de) | 1999-06-10 |
CA2098689A1 (fr) | 1993-12-18 |
US5460694A (en) | 1995-10-24 |
JPH06184791A (ja) | 1994-07-05 |
ATE179766T1 (de) | 1999-05-15 |
ES2130236T3 (es) | 1999-07-01 |
CA2098690A1 (fr) | 1993-12-18 |
FR2692599B1 (fr) | 1994-09-16 |
DE69324729T2 (de) | 1999-12-02 |
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