CN101445929B - Aluminum alloy material with excellent surface stability and method for manufacturing the same - Google Patents
Aluminum alloy material with excellent surface stability and method for manufacturing the same Download PDFInfo
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- CN101445929B CN101445929B CN2008101787502A CN200810178750A CN101445929B CN 101445929 B CN101445929 B CN 101445929B CN 2008101787502 A CN2008101787502 A CN 2008101787502A CN 200810178750 A CN200810178750 A CN 200810178750A CN 101445929 B CN101445929 B CN 101445929B
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- aluminum alloy
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- aluminium
- press oil
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- 229910000838 Al alloy Inorganic materials 0.000 title claims abstract description 123
- 239000000956 alloy Substances 0.000 title claims abstract description 95
- 238000000034 method Methods 0.000 title abstract description 14
- 238000004519 manufacturing process Methods 0.000 title abstract description 6
- 150000002148 esters Chemical class 0.000 claims abstract description 38
- 229910019142 PO4 Inorganic materials 0.000 claims abstract description 23
- 239000010452 phosphate Substances 0.000 claims abstract description 22
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims abstract description 20
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000000203 mixture Substances 0.000 claims description 39
- 239000000243 solution Substances 0.000 claims description 31
- NBIIXXVUZAFLBC-UHFFFAOYSA-L Phosphate ion(2-) Chemical class OP([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-L 0.000 claims description 29
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 29
- 239000012267 brine Substances 0.000 claims description 26
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 claims description 26
- 238000002360 preparation method Methods 0.000 claims description 19
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 14
- 229910052698 phosphorus Inorganic materials 0.000 claims description 13
- 239000011574 phosphorus Substances 0.000 claims description 13
- 239000011248 coating agent Substances 0.000 claims description 10
- 238000000576 coating method Methods 0.000 claims description 10
- -1 hypophosphite monohydrate hydrogen salt Chemical class 0.000 claims description 10
- 125000004429 atom Chemical group 0.000 claims description 9
- 229910052739 hydrogen Inorganic materials 0.000 claims description 9
- 239000001257 hydrogen Substances 0.000 claims description 9
- 238000012546 transfer Methods 0.000 claims description 5
- 238000006243 chemical reaction Methods 0.000 abstract description 48
- 238000005238 degreasing Methods 0.000 abstract description 25
- 230000000694 effects Effects 0.000 abstract description 16
- 229910052782 aluminium Inorganic materials 0.000 abstract description 15
- 239000000463 material Substances 0.000 abstract description 15
- 238000011282 treatment Methods 0.000 abstract description 7
- 229910045601 alloy Inorganic materials 0.000 abstract description 5
- 239000000126 substance Substances 0.000 abstract description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 4
- 230000036571 hydration Effects 0.000 abstract 2
- 238000006703 hydration reaction Methods 0.000 abstract 2
- 239000007864 aqueous solution Substances 0.000 description 27
- 239000011777 magnesium Substances 0.000 description 22
- 235000021317 phosphate Nutrition 0.000 description 20
- 238000012360 testing method Methods 0.000 description 16
- 230000000052 comparative effect Effects 0.000 description 14
- 239000004411 aluminium Substances 0.000 description 12
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 12
- 238000012545 processing Methods 0.000 description 12
- 239000002904 solvent Substances 0.000 description 10
- RGPUVZXXZFNFBF-UHFFFAOYSA-K diphosphonooxyalumanyl dihydrogen phosphate Chemical compound [Al+3].OP(O)([O-])=O.OP(O)([O-])=O.OP(O)([O-])=O RGPUVZXXZFNFBF-UHFFFAOYSA-K 0.000 description 9
- 239000003153 chemical reaction reagent Substances 0.000 description 8
- 150000003839 salts Chemical class 0.000 description 8
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 6
- NBIIXXVUZAFLBC-UHFFFAOYSA-M dihydrogenphosphate Chemical compound OP(O)([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-M 0.000 description 6
- 229910052749 magnesium Inorganic materials 0.000 description 6
- 238000002203 pretreatment Methods 0.000 description 6
- 230000008859 change Effects 0.000 description 5
- 238000001125 extrusion Methods 0.000 description 5
- 238000007598 dipping method Methods 0.000 description 4
- 239000003973 paint Substances 0.000 description 4
- 238000005096 rolling process Methods 0.000 description 4
- LVGKNOAMLMIIKO-UHFFFAOYSA-N Elaidinsaeure-aethylester Natural products CCCCCCCCC=CCCCCCCCC(=O)OCC LVGKNOAMLMIIKO-UHFFFAOYSA-N 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- LVGKNOAMLMIIKO-QXMHVHEDSA-N ethyl oleate Chemical compound CCCCCCCC\C=C/CCCCCCCC(=O)OCC LVGKNOAMLMIIKO-QXMHVHEDSA-N 0.000 description 3
- 229940093471 ethyl oleate Drugs 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 238000010129 solution processing Methods 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- KVCWSJZUKMSPLM-UHFFFAOYSA-N O.O[PH2]=O Chemical compound O.O[PH2]=O KVCWSJZUKMSPLM-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 238000000026 X-ray photoelectron spectrum Methods 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 238000003483 aging Methods 0.000 description 2
- 150000001398 aluminium Chemical class 0.000 description 2
- ILRRQNADMUWWFW-UHFFFAOYSA-K aluminium phosphate Chemical compound O1[Al]2OP1(=O)O2 ILRRQNADMUWWFW-UHFFFAOYSA-K 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 230000003628 erosive effect Effects 0.000 description 2
- 239000012530 fluid Substances 0.000 description 2
- 239000010410 layer Substances 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 2
- 239000007921 spray Substances 0.000 description 2
- 238000003466 welding Methods 0.000 description 2
- QMMJWQMCMRUYTG-UHFFFAOYSA-N 1,2,4,5-tetrachloro-3-(trifluoromethyl)benzene Chemical compound FC(F)(F)C1=C(Cl)C(Cl)=CC(Cl)=C1Cl QMMJWQMCMRUYTG-UHFFFAOYSA-N 0.000 description 1
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- HVUMOYIDDBPOLL-XWVZOOPGSA-N Sorbitan monostearate Chemical compound CCCCCCCCCCCCCCCCCC(=O)OC[C@@H](O)[C@H]1OC[C@H](O)[C@H]1O HVUMOYIDDBPOLL-XWVZOOPGSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 238000005275 alloying Methods 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
- 238000000137 annealing Methods 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052681 coesite Inorganic materials 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 239000002826 coolant Substances 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 238000010422 painting Methods 0.000 description 1
- 230000002688 persistence Effects 0.000 description 1
- XNGIFLGASWRNHJ-UHFFFAOYSA-L phthalate(2-) Chemical compound [O-]C(=O)C1=CC=CC=C1C([O-])=O XNGIFLGASWRNHJ-UHFFFAOYSA-L 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 230000000284 resting effect Effects 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 238000007669 thermal treatment Methods 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
- 239000002912 waste gas Substances 0.000 description 1
- LRXTYHSAJDENHV-UHFFFAOYSA-H zinc phosphate Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O LRXTYHSAJDENHV-UHFFFAOYSA-H 0.000 description 1
- 229910000165 zinc phosphate Inorganic materials 0.000 description 1
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Classifications
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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
- C23C22/07—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 phosphates
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C21/00—Alloys based on aluminium
- C22C21/02—Alloys based on aluminium with silicon as the next major constituent
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C21/00—Alloys based on aluminium
- C22C21/06—Alloys based on aluminium with magnesium as the next major constituent
-
- 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
- C23C22/78—Pretreatment of the material to be coated
-
- 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
- C23C22/82—After-treatment
-
- 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
- C23C26/00—Coating not provided for in groups C23C2/00 - C23C24/00
-
- 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
- C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
Abstract
The aim of the present invention is to provide an aluminum alloy material with excellent surface stability and a method for manufacturing the same. The material not only maintain the effect of a profiling oil containing ester component until degreasing of a chemical conversion treatment, but also maintain excellent water wattability of the chemical conversion treatment. In the invention, ester-containing profiling oil is coated on the surface of a material having Mg alumium alloy of hydration phosphate or hydration hydrophosphate containing phosphor concentration more than 2.0 atom %.
Description
Technical field
Aluminum alloy materials that the present invention relates to have superior surface performance and preparation method thereof, the described aluminum alloy materials that has superior surface performance is applicable to automobile, is particularly useful for car panel; Until degreasing that chemical transformation is handled the time, not only can keep the effect of the press oil (press oil) that contains the ester composition, and the good wettability can keep chemical transformation and handle the time.Aluminum alloy materials of the present invention is meant the aluminium alloy that adopts various preparation method's preparations such as pressure rolling plate, pressure rolling paper tinsel, extruded section, forged material, cast material.
Background technology
As everyone knows, various all the time aluminum alloy materials (following also aluminium is called Al), the member or the parts that just are being widely used as conveyors such as automobile, boats and ships, aircraft or vehicle, machine, electrical equipment, buildings, formation thing, opticinstrument, implements according to each characteristic of every kind of alloy are used.
In recent years, at the global environment problem that discharging waste gas is brought, require to improve the mileage number (Japanese: Ran Charges) that per unit fuel travels by the lightweight of car body.Therefore, 1/3 and the application of aluminum in car body with excellent energy absorption that replaces the ferrous materials that in the past used, proportion to be about iron increases.
When aluminium alloy is used as car panel, the erosion resistance after formability, weldability, connectivity, the chemical transformation property handled, the covering with paint, attractive in appearance etc. there is requirement.The method that adopts aluminium alloy to prepare car panel has, 1) moulding (cuts out certain size, extrusion forming is a definite shape then), 2) engage (welding and/or engage), 3) chemical transformation handles (carrying out degreasing → carry out surface adjustments → zinc phosphate processing by colloid phthalate processing etc. by sanitising agent), 4) covering with paint (carrying out linging → lay-off undercoat → be coated with surface layer) by electrophoretic painting, with the situation that in the past adopted steel plate be essentially identical.
On the other hand,, make to the time that enters the car body manufacturing step by above-mentioned car panel, the trend that prolonged than is in the past arranged from aluminium alloy plate itself along with carry out the modular of trolley part.
The modularization of so-called trolley part is meant in automobile factory, and each parts of directly being installed on car body after the inferior assembling of parts company (sub assembly), are being installed on the method for car body.Its main purpose is the difficult operation of automobile factory is oversimplified, and enhances productivity.Also have the production stage of shortening, reduce half-finished effect.Though increased the burden of parts companies, have the effect of the whole cost that reduces motor corporation and parts company, on the result, help to reduce the cost of automobile.
Automobile was to be main flow to press manufactory on the lenient side to the mode of directly receiving of automobile factory with the carrying approach of aluminium alloy plate in the past.But, if modular propelling will have to via parts company, then from the manufacturing of aluminium alloy plate body to the time that enters above-mentioned manufacturing step, in any case will be all than prolong in the past.Therefore, the surface protection angle from aluminium alloy plate need cover processing with oil.
But, in this case, the surface property that certainly exists aluminium alloy plate through the time change, especially to chemical transformation handle property, covering with paint property is brought dysgenic problem.What wherein known is, along with through the time change, the degreasing deterioration when chemical transformation is handled, chemical transformation is handled tunicle and is difficult to adhere to, and on the result erosion resistance is brought influence.
Therefore, improve chemical transformation at the magnesium by removing the aluminium alloy containing magnesium surface (following also magnesium is called Mg) and handle aspects such as property, making great efforts (with reference to patent documentation 1～5) always.But, only by removing Mg, can not obtain surface property through the time with low uncertainty, the aluminum alloy materials that has superior surface performance.
In addition, in order to obtain the aluminium alloy plate of excellence aspect the especially wettability after degreasing and connectivity, proposed to adjust the Mg amount of surperficial tunicle of aluminium alloy plate and OH amount, adjusted the automotive body panels aluminium alloy plate (with reference to patent documentation 6) of coating slushing oil in back 14 days on the surface.But, only protect the surface by adjust in back 14 days coating slushing oil on the surface, can not obtain surface property through the time with low uncertainty, the aluminium alloy plate that has superior surface performance.
In addition, for obtain surface property through the time aluminium alloy plate with low uncertainty.Proposed to comprise contain Mg be 2～10 weight % aluminium alloy plate the metallic aluminium matrix and at the phosphate coating of the aluminium that forms on this matrix and the pellumina that on this phosphate coating, forms with further be coated with the automobile body-used aluminium alloy plate (with reference to patent documentation 7) of slushing oil thereon.In addition, to prevent that the damaged and raising pull and stretch processibility in the aluminium alloy carrying from being purpose, the scheme (with reference to non-patent literature 1) with moulding oil (press oil) the aluminium coating alloy surface that contains the ester composition has been proposed.
[patent documentation 1] Japanese kokai publication hei 06-256980 communique (in full)
[patent documentation 2] Japanese kokai publication hei 06-256881 communique (in full)
[patent documentation 3] Japanese kokai publication hei 06-220564 communique (in full)
[patent documentation 4] Japanese kokai publication hei 04-214835 communique (in full)
[patent documentation 5] Japanese kokai publication hei 02-115385 communique (in full)
[patent documentation 6] TOHKEMY 2006-200007 communique (in full)
[patent documentation 7] No. 2744697 communique of Japanese Patent (in full)
[non-patent literature 1] Tanaka, holt, field, storehouse work " the モ デ Le acidulants degreasing self-criticism of ア system ミ ニ ウ system surface ", light metal association the 111st time phase in autumn conference lecture summary collection, 167,2006 years, p.p.331～332.
Summary of the invention
In the embodiment of above-mentioned patent documentation 7, compare evaluation as benchmark with placing the material in a week after the specimen preparation.But, aforesaid aluminum alloy surface characteristic through the time change from the variable quantity maximum to the week after the specimen preparation, variation afterwards is less.Therefore, according to the evaluation result shown in the above-mentioned patent documentation 7, can not guarantee the stability of purpose surface property.In addition,,, increased the pull and stretch processibility of alloy, the problem of the degreasing when also exist reducing chemical transformation and handling (, reduce surface stability) though the ester composition in the press oil works as oiliness improver as disclosed in the above-mentioned non-patent literature 1.
Especially in the purposes that automobile is used etc., the water-wet stability the when chemical transformation of aluminum alloy materials is handled, covering with paint property, engage persistence, welding stability etc. requirement is arranged.Especially require a kind of aluminum alloy materials that has superior surface performance, described aluminum alloy materials from the shipment of makers' factory, carry out extrusion molding etc., during carrying out the degreasing that chemical transformation handles again, not only can keep the effect of press oil, and the good wettability can keep chemical transformation and handle the time.
The objective of the invention is to solve above-mentioned problem, provide a kind of have superior surface performance contain aluminum alloy materials of Mg and preparation method thereof, described material is when the degreasing of handling until chemical transformation, not only can keep the effect of the press oil that contains the ester composition, and the good wettability can keep chemical transformation and handle the time.
For achieving the above object, according to the described invention in the 1st aspect of the present invention, it can obtain a kind of aluminum alloy materials that has superior surface performance, wherein, contain on the surface that contains the Mg aluminum alloy materials that phosphorus concentration is hydrated phosphate more than the 2.0 atom % or hypophosphite monohydrate hydrogen salt on the surface, owing to be coated with the press oil that contains the ester composition, thereby when degreasing that chemical transformation is handled, not only can keep the effect of the press oil that contains the ester composition, and the good wettability can keep chemical transformation and handle the time.
According to the described invention in the 2nd aspect, comprise aluminum alloy materials is transferred to step that the biphosphate salt brine solution of less than 4 handles and the step that is coated with the press oil that contains the ester composition on the aluminum alloy materials of handling with the above-mentioned dihydrogen phosphate aqueous solution with pH.Thus, can prepare the aluminum alloy materials that has superior surface performance, described material not only can be kept the effect of the press oil that contains the ester composition until degreasing that chemical transformation is handled the time, and the good wettability can keep chemical transformation and handle the time.
, wherein, use to transfer to pH 2.5 or more by adding phosphoric acid and the biphosphate salt brine solution processing of less than 4 as the described invention in the 2nd aspect according to the described invention in the 3rd aspect.Thus, not only can prepare the aluminum alloy materials that has superior surface performance, described material both can have been kept the effect of the press oil that contains the ester composition, the good wettability in the time of can keeping the chemical transformation processing again when the degreasing of handling until chemical transformation; And can be when handling aluminum alloy materials with hydrophosphate, in above-mentioned biphosphate salt brine solution, do not produce and result from the muddiness (=transparent) of non-solvent components, suppress the generation that pipe arrangement stops up, reduce the frequency of maintaining.
As mentioned above, according to the described invention in the 1st aspect of the present invention, it can obtain a kind of aluminum alloy materials that has superior surface performance, wherein, contain on the surface that contains the Mg aluminum alloy materials that phosphorus concentration is hydrated phosphate more than the 2.0 atom % or hypophosphite monohydrate hydrogen salt on the surface, owing to be coated with the press oil that contains the ester composition, thereby before the degreasing that chemical transformation is handled, not only can keep the effect of the press oil that contains the ester composition, and the good wettability can keep chemical transformation and handle the time.
In addition, the described invention in the 2nd aspect according to the present invention, comprise aluminum alloy materials is transferred to step that the biphosphate salt brine solution of less than 4 handles and the step that is coated with the press oil that contains the ester composition on the aluminum alloy materials of handling with the above-mentioned dihydrogen phosphate aqueous solution with pH, therefore can prepare the aluminum alloy materials that has superior surface performance, described material is when the degreasing of handling until chemical transformation, not only can keep the effect of the press oil that contains the ester composition, and the good wettability can keep chemical transformation and handle the time.
In addition, the described invention in the 3rd aspect is as the described invention in the 2nd aspect according to the present invention, wherein, with transferring to pH 2.5 or more by adding phosphoric acid and the biphosphate salt brine solution processing of less than 4, therefore not only can prepare the aluminum alloy materials that has superior surface performance, described material both can have been kept the effect of the press oil that contains the ester composition, the good wettability in the time of can keeping the chemical transformation processing again when the degreasing of handling until chemical transformation; And can be when handling aluminum alloy materials with hydrophosphate, in above-mentioned biphosphate salt brine solution, do not produce and result from the muddiness (=transparent) of non-solvent components, suppress the generation that pipe arrangement stops up, reduce the frequency of maintaining.
Description of drawings
Fig. 1 is the synoptic diagram for the surface texture of investigating the aluminum alloy materials after hydrophosphate processing of the present invention and press oil are coated with.
Embodiment
Below for the present invention, in illustrated embodiment, further describe.
(structure of the aluminum alloy materials that has superior surface performance that the present invention relates to)
The aluminum alloy materials that has superior surface performance that the present invention relates to wherein, contains on the surface that contains the Mg aluminum alloy materials that phosphorus concentration is hydrated phosphate more than the 2.0 atom % or hypophosphite monohydrate hydrogen salt on the surface, is coated with the press oil that contains the ester composition.Thus, can obtain a kind of aluminum alloy materials that has superior surface performance, described material not only can kept the effect of the press oil that contains the ester composition before the degreasing that chemical transformation is handled, and the good wettability can keep chemical transformation and handle the time.
Below describe the reason of reaching said structure in detail.
The inventor be conceived to aluminum alloy materials in recent years from the shipment of makers' factory, carry out extrusion molding etc., prolong on this aspect until the full time that carries out the degreasing that chemical transformation handles again.That is, be conceived to surface protection equal angles, must prolong this point of time that covers with oil from aluminum alloy materials.In addition, because aluminum alloy materials also carries out extrusion molding etc. before chemical transformation is handled, so the oil that requires formability to improve.Even use both oil of requirement that satisfies this surface protection and formability to be coated with; can the aluminum alloy materials that have superior surface performance of the good wettability in the time of fully carried out the degreasing when chemical transformation is handled and can keep chemical transformation handling have carried out lucubrate to this.The result, found first, if scrutinize finish materials, the condition of aluminum alloy materials, contain on the surface that contains the Mg aluminum alloy materials that phosphorus concentration is hydrated phosphate more than the 2.0 atom % or hypophosphite monohydrate hydrogen salt on the surface, coating contains the press oil of ester composition, then can realize above-mentioned purpose.
Can realize above-mentioned purpose by this structure, infer that wherein the proterties of aluminum alloy surface as shown in Figure 1 may play bigger effect.Promptly think, in Fig. 1, the biphosphate salt brine solution that is transferred to less than 4 with pH (for example, aluminium dihydrogen phosphate aqueous solution) to containing the Mg aluminum alloy materials (here, abbreviate aluminium alloy as aluminium alloy, to for example exist on its surface, the aluminium alloy of Mg-Ox be called aluminum alloy materials) surface when carrying out surface treatment, surface at this aluminum alloy materials forms the hypophosphite monohydrate salt deposit, between this hydrated phosphate or hypophosphite monohydrate hydrogen salt layer and aluminum alloy materials, have that (O-) the firm chemical bond of Xing Chenging on the other hand, has the OH base residual at the offside of aluminum alloy materials by oxygen, can become the composition of preserving moisture, hinder the ester composition absorption in the press oil.
According to this method, when the degreasing of handling until chemical transformation, on the surface of aluminum alloy materials, hydrated phosphate does not combine with the press oil that contains the ester composition, and the stable press oil that keeps specified amount, thereby can keep the effect of press oil.In addition and since the press oil that contains the ester composition not with the hypophosphite monohydrate salt binding, thereby when degreasing, can remove the good wettability when keeping chemical transformation and handling fully.According to the above, think and to realize the aluminum alloy materials that has superior surface performance.
The present invention below is described in detail in detail.
(Al alloy)
Purposes according to the Al alloy material, though the Al alloy that the present invention adopts can use by various preparation methods' preparations such as pressure rolling plate, pressure rolling paper tinsel, extruded section, forged material, cast material, various Al alloys that stipulate or that be similar to JIS among AA, the JIS, containing Mg is prerequisite.In this case, preferred Mg content is more than the 0.25 weight %.Thereby the less Al alloy of Mg content is not suitable for the problem that the present invention will solve.
The upper limit of Mg content is not particularly limited, but considers the various characteristics balance when using with parts as structure, preferably is no more than 5.5 quality %.
Enumerate concrete example as under the situation that is used for automobile, preferred 0.2% endurance is the above high-strength aluminum alloy material of 100Mpa.As the aluminium alloy that satisfies this specific character, normally in this structure unit purposes widespread use, 5000 be, 6000 be, 7000 the alloy of the higher widespread use of endurance such as be, preferably use as required through modified aluminium alloy.From the age hardening energy of excellence or the angle that the alloying element amount is less, chip reclaims property or the formability aspect is also excellent, preferred 6000 line aluminium alloys.
(hydrated phosphate)
Dihydrogen phosphate of the present invention is meant and contains biphosphate (H in the salt
2PO
4) the general name of salt.Described dihydrogen phosphate is preferably selected from the salt of metal at least a among Al, K, Ca, Mn, the Li.More preferably Al.
Must form the oxide film thereon of aluminium at aluminum alloy material surface, hydrated phosphate of the present invention exists or is dispersed on the oxide film thereon of described aluminium or in the oxide film thereon.Therefore, contain hydrated phosphate at aluminum alloy material surface, this condition of surface that particularly just is meant described in the present invention.
(hydrated phosphate is to the attachment means of aluminum alloy material surface)
These hydrated phosphates adhere to aluminum alloy material surface, can handle (the following hydrophosphate that also is generically and collectively referred to as is handled) by the aqueous solution of phosphoric acid dihydric salt and carry out in the preparation process of aluminum alloy materials or beyond the preparation process.In the preparation process of aluminum alloy materials, for example can be with water coolant after the thermal treatment of solution processing or annealing etc. or the rinse water in the cleaning step, handle (below be generically and collectively referred to as dihydrogen phosphate handle) as the aqueous solution that contains these dihydrogen phosphates (making its dissolving).
The temperature of biphosphate salt brine solution can be a room temperature, also can heat etc.In addition, the treatment time is not particularly limited, and can suitably select according to other treatment condition such as concentration of aqueous solution or temperature or to the adhesion amount of the hope of aluminum alloy material surface.For example, employing is as the aluminium dihydrogen phosphate { Al (H of reagent
2PO
4)
3, when its concentration of aqueous solution is 1～10g/L (" L " is meant the meaning of " liter ") here, aluminum alloy materials can be flooded in these aqueous solution 1～10 second or sprays.In addition, when concentration of aqueous solution was 1g/L, pH was 3.4; During 10g/L, pH is 2.4.The pH of biphosphate salt brine solution can be transferred to less than 4 in the present invention.
In addition, in the biphosphate salt brine solution, add phosphoric acid and be more than 2.5 with pH regulator and the solution of less than 4 is handled aluminum alloy materials by adopting, not only can prepare the aluminum alloy materials good wettability, that have superior surface performance in the time of to keep the chemical transformation processing, and can be when handling aluminum alloy materials with hydrophosphate, in above-mentioned phosphate dihydrogen salt solution, do not produce and result from the muddiness (=transparent) of non-solvent components, thereby suppress the generation that pipe arrangement stops up, reduce the frequency of maintaining.
When aluminum alloy material surface adheres to,, there is no need to remove the oxide film thereon or the magnesium of the aluminium that has formed in aluminum alloy surface fully at hydrated phosphate by following the pre-treatments such as cleaning of etching method.But in the preparation process of above-mentioned aluminum alloy materials, for example according to other purposes of step, after by pre-treatment the oxide film thereon of the aluminium of aluminum alloy material surface or magnesium being removed, the surface that hydrated phosphate is attached to aluminum alloy materials is to allow certainly.In this case, owing on aluminum alloy material surface, can form the oxide film thereon of aluminium rapidly, so hydrated phosphate of the present invention exists or is dispersed on the oxide film thereon of this aluminium or in the oxide film thereon.
(coating contains the method for the press oil of ester composition on the aluminum alloy materials of handling with the biphosphate salt brine solution)
Then, to being coated with the method for the press oil that contains the ester composition on the aluminum alloy materials after handling, describe through above-mentioned biphosphate salt brine solution.For example, can only above-mentioned aluminum alloy materials be immersed in and contain with in the press oil of ethyl oleate as the ester composition.Method or condition that coating contains the press oil of ester composition are not particularly limited, and can extensively adopt the method or the condition of common coating press oil.The ester composition also is not limited to ethyl oleate, also can utilize various ester compositions such as butyl stearate or anhydrosorbitol monostearate.
(about surface stability)
Secondly, the surface stability for the aluminum alloy materials that has been coated with the above-mentioned press oil that contains the ester composition describes.Aluminum alloy materials after will the be coated with above-mentioned press oil that contains the ester composition, indoor placement adopted common alkaline defatting agent to carry out degreasing after 6 months under 15～35 ℃, in the environment of 50～90%RH, reached 100% during evaluation water-wet area occupation ratio.This shows; at aluminum alloy materials from the shipment of makers' factory during until degreasing that chemical transformation is handled; even be coated with the press oil that contains the ester composition of the surface protection of satisfying aluminum alloy materials and extrusion molding and so on for a long time, also can provide good wettability in the time of can keeping chemical transformation and handle, through the time with low uncertainty, the aluminum alloy materials that has superior surface performance and preparation method thereof.
Embodiment
Embodiments of the invention below are described.Adopt the cold-rolled aluminum alloy sheet (thickness of slab 1mm) of 6,000 6022 specifications that are, the test piece of long 70mm * wide 150mm.The aluminium alloy plate of this 6022 specifications contains Mg:0.55%, Si:0.95%, and 0.2% endurance is 230MPa.
When carrying out pre-treatment before phosphatizing, after flooding 1～10 second in 60～90 ℃ commercially available weakly alkaline degreasing fluid or spraying, flooded 1～10 second in 50～90 ℃ 1～20 quality % nitric acid or sulfuric acid or spray, water cleans then.
Adopt above-mentioned pre-treatment condition, can remove the oxide film thereon or the magnesium of the aluminium that the test piece surface formed.But, owing on the test piece surface, can form the oxide film thereon of aluminium rapidly,, exist or be dispersed on this alumina tunicle or in the oxide film thereon so handle and attached to the hydrated phosphate on test piece surface by hydrophosphate.
For having carried out aluminium alloy test piece this pre-treatment or that do not carry out pre-treatment, adopt aluminium dihydrogen phosphate { Al (H as reagent
2PO
4)
3The concentration of aqueous solution of preparation dipping test piece respectively is the aqueous solution of 1g/L, 10g/L.With them as embodiment 1～4 (with reference to following table 1).The pH of the aqueous solution of this moment is respectively 3.4,2.4,3.4 and 2.4.In addition, adopt mentioned reagent, to concentration is in the aqueous solution of 0.1g/L to 0.4g/L, adds the phosphoric acid (reagent of 85% purity of producing with the pure medicine of light) of the described amount of table 1 with respect to each aqueous solution of every 1L, and preparation pH transfers to 2.5 to 3.8 biphosphate salt brine solution.With them as embodiment 5～8.
In addition, in order to compare, having prepared the test piece, the concentration of aqueous solution that do not flood test piece in the aqueous solution that has adopted mentioned reagent respectively is the solution of 0.1g/L.With they as a comparative example 1～4 (with reference to following table 2).The pH equal 6.4 of the aqueous solution of comparative example 2,4.Adopt mentioned reagent, for concentration is the aqueous solution of 0.1g/L and the aqueous solution of 0.4g/L, add the phosphoric acid (reagent of 85% purity of producing with the pure medicine of light) of the described amount of table 2 with respect to each aqueous solution of every 1L, preparation pH all transfers to 2.0 biphosphate salt brine solution.With they as a comparative example 5 and 6.In embodiment 1～8, comparative example 2 and comparative example 4～6, the dipping time of each test piece is 10 seconds.
In addition, the surface of the embodiment 1～8 after above-mentioned specified hydrophosphate processing finished and the test piece of comparative example 1～6 adopts x-ray photoelectron spectrum analysis method to analyze.Measuring method and condition are as follows.Here, the most surperficial to removing, begin from the surface to analyze about the phosphorus concentration on surface to the composition of the depth direction of dark 200nm, phosphorus concentration (atom %) maximum of analytical value is defined as the phosphorus concentration (atom %) on substrate top layer.Because the most surperficial state can not obtain accurate values because of pollution.
(measuring method and condition)
Device: the system QuanteraSXM of Physical electronics, inc. automatically scanning x-ray photoelectron light-dividing device
X-ray source: monochromatization AlKa
X-ray power: 43.7W
X-ray beam diameter: 200 μ m
Photoelectron output angle: 45 °
Ar+ splash speed: with the about 4.6nm/ branch of SiO2 conversion
The measuring method of surface phosphorus concentration is not limited in x-ray photoelectron spectrum analysis method (XPS), also adopts XPS for example fluorescent X-ray or high frequency light emitting discharge light-emitting area in addition to analyze analytical procedures such as (GDS).
Its result is, the surperficial phosphorus concentration of embodiment is shown in above-mentioned table 1, about embodiment 1,2,3,4,5,6,7 and 8, be respectively 2.1～3.3,2.4～4.4,2.2～3.6,2.4～4.5,3.2～3.8,2.8～3.3,3.2～4.0 and 2.0～2.6.In addition, the surperficial phosphorus concentration of comparative example about comparative example 1,2,3,4,5 and 6, is respectively 0.8～1.2,1.1～1.6,0.6～1.2,1.3～1.6,0.9～1.6 and 1.1～1.9 shown in above-mentioned table 2.
In addition, by the muddy state of the treatment solution after the hydrophosphate processing end of visual observation afore mentioned rules, judge having or not of non-solvent components.Its result is, adopting the biphosphate salt brine solution that does not add phosphoric acid to carry out having confirmed the muddiness that causes because of non-solvent components in the treatment solution of embodiment 1～4 that hydrophosphate handles and comparative example 2 and 4.This non-solvent components is meant the composition that is mixed with crystallinity and noncrystalline aluminum phosphate (AlPO4).On the other hand, carried out not seeing muddiness (transparent) in the treatment solution of embodiment 5～8 that hydrophosphate handles and comparative example 5 and 6 at the biphosphate salt brine solution that employing is added with phosphoric acid because of non-solvent components causes.In comparative example 5 and 6, though do not see the muddiness that causes because of non-solvent components, as mentioned below, its crucial water-wet area occupation ratio is much smaller than 90% of benchmark.
Then, with above-mentioned test piece of having handled through the biphosphate salt brine solution (embodiment 1～8, comparative example 2 and 4～6) and the above-mentioned test piece of handling without the biphosphate salt brine solution (embodiment 1～8, comparative example 2 and 4～6), with containing with the press oil dipping of ethyl oleate as the ester composition.
Then, investigate, carried out following test for ageing stability to the surface of the test piece that has been coated with the press oil that contains above-mentioned ester composition.With the test piece that has been coated with the press oil that contains above-mentioned ester composition indoor placement 6 months under 15～35 ℃, in the environment of 50～90%RH.Then, after 6 months for automobile with commercially available weak base degreasing fluid (40 ℃ of temperature) in the water-wet area occupation ratio with respect to test piece area (only one-sided) of dipping 2 minutes the time measure (result is for good, and numerical value is higher).Wettability in the time of thus can the evaluating chemical conversion process (stable chemical transformation is handled property).Its result is, the water-wet area occupation ratio of embodiment 1～8 is all above 90% (with reference to above-mentioned table 1) of benchmark.This shows, the modularization by aforesaid trolley part etc., even in moist environment, place or long-term between resting period, the surface property of aluminum alloy materials also not can through the time change, keep stable.But comparative example 1,2,3,4,5 and 6 water-wet area occupation ratio were respectively for 40%, 55%, 0%, 33%, 38% and 52% (with reference to above-mentioned table 2), much smaller than 90% of benchmark.This shows, the surface property of aluminum alloy materials exist through the time change.
As above-mentioned embodiment 5～8, aluminium dihydrogen phosphate aqueous solution concentration is the lower concentration of 0.1g/L～0.4g/L, be more than 2.5 to the phosphoric acid that wherein adds the afore mentioned rules amount and with pH regulator and the biphosphate salt brine solution of less than 4 in, the solution equilibria of the aqueous solution is destroyed.In addition, the destruction of this solution equilibria increases relevant with the concentration that forms the dihydrogen phosphate (referring to aluminium dihydrogen phosphate) of unbound state (the dissolved state though do not dissociate) important in the reaction of hydrated phosphate or hypophosphite monohydrate hydrogen salt at aluminum alloy material surface here.Although the concentration of aqueous solution of the aluminium dihydrogen phosphate before the interpolation phosphoric acid is low, but the concentration increase of the aluminium dihydrogen phosphate of this unbound state still can work out, and promptly prepares the aluminum alloy materials good wettability, that have superior surface performance in the time of can keeping the chemical transformation processing.In addition, handle aluminum alloy materials by adopting as the biphosphate salt brine solution of embodiment 5～8, in above-mentioned biphosphate salt brine solution, do not have to produce and result from the muddiness of non-solvent components, its detailed mechanism is still indeterminate at present, but infer it is in the aluminium dihydrogen phosphate aqueous solution of the lower concentration before adding phosphoric acid, produced certain interaction by adding phosphoric acid.
As mentioned above, by containing on the surface on the surface that contains the Mg aluminum alloy materials that phosphorus concentration is hydrated phosphate more than the 2.0 atom % or hypophosphite monohydrate hydrogen salt, be coated with the structure of the press oil that contains the ester composition, can obtain a kind of aluminum alloy materials that has superior surface performance, it not only can keep the effect of the press oil that contains the ester composition when degreasing that chemical transformation is handled, and the good wettability can keep chemical transformation and handle the time.
In the present embodiment, as above-mentioned embodiment 1～4, as the biphosphate salt brine solution, though, be not limited in this, for the salt that contains biphosphate in the salt gets final product to have adopted aluminium dihydrogen phosphate to be illustrated as the example of reagent.The aqueous solution pH that contains the salt of biphosphate in this salt is transferred to less than 4, the aluminum alloy materials good wettability, that have superior surface performance in the time of can keeping the chemical transformation processing by handling aluminum alloy materials with this aqueous solution, can preparing.
In addition, as above-mentioned embodiment 5～8, the phosphoric acid of the concentration by adopt adding specified amount and transfer to pH more than 2.5 and the aqueous solution of less than 4 is handled aluminum alloy materials, not only can prepare the good wettability in the time of to keep the chemical transformation processing, the aluminum alloy materials that has superior surface performance, and can be when handling aluminum alloy materials with hydrophosphate, in above-mentioned biphosphate salt brine solution, do not produce and result from the muddiness (=transparent) of non-solvent components, suppress the generation that pipe arrangement stops up, reduce the frequency of maintaining.
Claims (3)
1. an aluminum alloy materials that has superior surface performance is characterized in that, contains on the surface that contains the Mg aluminum alloy materials that phosphorus concentration is hydrated phosphate more than the 2.0 atom % or hypophosphite monohydrate hydrogen salt on the surface, is coated with the press oil that contains the ester composition,
In the described aluminum alloy materials, the content of Mg is more than the 0.25 weight %.
2. the preparation method of an aluminum alloy materials that has superior surface performance is characterized in that, comprising: aluminum alloy materials is transferred to the step that the biphosphate salt brine solution of less than 4 is handled with pH; With to containing through above-mentioned biphosphate salt brine solution surface treated on the aluminum alloy materials that phosphorus concentration is hydrated phosphate more than the 2.0 atom % or hypophosphite monohydrate hydrogen salt, coating contains the step of the press oil of ester composition,
In the described aluminum alloy materials, the content of Mg is more than the 0.25 weight %.
3. the preparation method of the aluminum alloy materials that has superior surface performance according to claim 2 is characterized in that, uses to transfer to pH more than 2.5 by adding phosphoric acid and the biphosphate salt brine solution of less than 4 is handled.
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| WO2019083973A1 (en) * | 2017-10-23 | 2019-05-02 | Novelis Inc. | Reactive quenching solutions and methods of use |
| KR102348576B1 (en) * | 2019-12-17 | 2022-01-06 | 주식회사 포스코 | Steel sheet having excellent yellowing resistance and phosphating property and method for preparing the same |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| EP0557531A1 (en) * | 1991-09-04 | 1993-09-01 | Furukawa Aluminum Co., Ltd. | Aluminum alloy sheet for automotive body and production thereof |
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| JPH05123648A (en) * | 1991-10-31 | 1993-05-21 | Furukawa Alum Co Ltd | Coated aluminum plate excellent in forming workability and its production |
| JPH05148664A (en) * | 1991-11-22 | 1993-06-15 | Sky Alum Co Ltd | Aluminum alloy sheet for forming excellent in galling property |
| DE4433946A1 (en) * | 1994-09-23 | 1996-03-28 | Henkel Kgaa | Phosphating process without rinsing |
| JPH11269595A (en) | 1998-01-22 | 1999-10-05 | Nippon Steel Corp | Automotive magnesium-containing aluminum alloy treated sheet excellent in zinc phosphate treatability and its production |
| JP2003013253A (en) * | 2001-07-04 | 2003-01-15 | Kobe Steel Ltd | Aluminum-alloy structural material superior in adhesiveness to coating and method for evaluating adhesiveness to coating of aluminum-alloy structural material |
| JP2006200007A (en) | 2005-01-21 | 2006-08-03 | Furukawa Sky Kk | Aluminum alloy sheet for automobile body sheet having excellent water wettability after degreasing and adhesive property |
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| EP0557531A1 (en) * | 1991-09-04 | 1993-09-01 | Furukawa Aluminum Co., Ltd. | Aluminum alloy sheet for automotive body and production thereof |
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| JP2010031350A (en) | 2010-02-12 |
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