CN1114719C - Surface treated aluminium material with good wording sealing and connection and crossion-resisting - Google Patents
Surface treated aluminium material with good wording sealing and connection and crossion-resisting Download PDFInfo
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- CN1114719C CN1114719C CN 96109604 CN96109604A CN1114719C CN 1114719 C CN1114719 C CN 1114719C CN 96109604 CN96109604 CN 96109604 CN 96109604 A CN96109604 A CN 96109604A CN 1114719 C CN1114719 C CN 1114719C
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- airtight property
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- 229910052782 aluminium Inorganic materials 0.000 title claims abstract description 57
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 title claims abstract description 46
- 239000004411 aluminium Substances 0.000 title claims abstract description 44
- 239000000463 material Substances 0.000 title claims abstract description 21
- 238000007789 sealing Methods 0.000 title 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims abstract description 90
- 229910052804 chromium Inorganic materials 0.000 claims abstract description 63
- 239000011651 chromium Substances 0.000 claims abstract description 63
- 238000005260 corrosion Methods 0.000 claims abstract description 29
- 230000007797 corrosion Effects 0.000 claims abstract description 29
- 229910052751 metal Inorganic materials 0.000 claims abstract description 13
- 239000002184 metal Substances 0.000 claims abstract description 13
- 238000012545 processing Methods 0.000 claims description 50
- KRVSOGSZCMJSLX-UHFFFAOYSA-L chromic acid Substances O[Cr](O)(=O)=O KRVSOGSZCMJSLX-UHFFFAOYSA-L 0.000 claims description 22
- AWJWCTOOIBYHON-UHFFFAOYSA-N furo[3,4-b]pyrazine-5,7-dione Chemical compound C1=CN=C2C(=O)OC(=O)C2=N1 AWJWCTOOIBYHON-UHFFFAOYSA-N 0.000 claims description 22
- 239000008151 electrolyte solution Substances 0.000 claims description 19
- 210000000981 epithelium Anatomy 0.000 claims description 19
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 4
- 229910000838 Al alloy Inorganic materials 0.000 abstract description 6
- 239000000956 alloy Substances 0.000 abstract description 2
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 abstract 1
- 229910000423 chromium oxide Inorganic materials 0.000 abstract 1
- 230000009916 joint effect Effects 0.000 abstract 1
- 238000000034 method Methods 0.000 description 21
- 238000000576 coating method Methods 0.000 description 19
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 18
- 239000011248 coating agent Substances 0.000 description 18
- 238000001035 drying Methods 0.000 description 15
- 238000004080 punching Methods 0.000 description 12
- 229920005992 thermoplastic resin Polymers 0.000 description 12
- 150000001398 aluminium Chemical class 0.000 description 11
- 238000005406 washing Methods 0.000 description 10
- ZCDOYSPFYFSLEW-UHFFFAOYSA-N chromate(2-) Chemical compound [O-][Cr]([O-])(=O)=O ZCDOYSPFYFSLEW-UHFFFAOYSA-N 0.000 description 8
- 238000010409 ironing Methods 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 238000005868 electrolysis reaction Methods 0.000 description 6
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical compound [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 description 6
- 229910000831 Steel Inorganic materials 0.000 description 5
- 238000007493 shaping process Methods 0.000 description 5
- 239000010959 steel Substances 0.000 description 5
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 4
- 229910052731 fluorine Inorganic materials 0.000 description 4
- 239000011737 fluorine Substances 0.000 description 4
- 229920005989 resin Polymers 0.000 description 4
- 239000011347 resin Substances 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 239000003513 alkali Substances 0.000 description 3
- 229910001593 boehmite Inorganic materials 0.000 description 3
- 239000003795 chemical substances by application Substances 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
- 150000001875 compounds Chemical class 0.000 description 3
- 229920001577 copolymer Polymers 0.000 description 3
- 238000005238 degreasing Methods 0.000 description 3
- 238000000151 deposition Methods 0.000 description 3
- 230000008021 deposition Effects 0.000 description 3
- 150000005690 diesters Chemical class 0.000 description 3
- WMYWOWFOOVUPFY-UHFFFAOYSA-L dihydroxy(dioxo)chromium;phosphoric acid Chemical compound OP(O)(O)=O.O[Cr](O)(=O)=O WMYWOWFOOVUPFY-UHFFFAOYSA-L 0.000 description 3
- 238000007598 dipping method Methods 0.000 description 3
- 238000011049 filling Methods 0.000 description 3
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 238000000465 moulding Methods 0.000 description 3
- 239000003921 oil Substances 0.000 description 3
- 229920001225 polyester resin Polymers 0.000 description 3
- 239000004645 polyester resin Substances 0.000 description 3
- NROKBHXJSPEDAR-UHFFFAOYSA-M potassium fluoride Chemical compound [F-].[K+] NROKBHXJSPEDAR-UHFFFAOYSA-M 0.000 description 3
- 238000003825 pressing Methods 0.000 description 3
- 235000013024 sodium fluoride Nutrition 0.000 description 3
- 239000011775 sodium fluoride Substances 0.000 description 3
- 238000004381 surface treatment Methods 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 2
- BRAPHPYGGAMVSS-UHFFFAOYSA-I [Si+4].[F-].[Na+].[F-].[F-].[F-].[F-] Chemical compound [Si+4].[F-].[Na+].[F-].[F-].[F-].[F-] BRAPHPYGGAMVSS-UHFFFAOYSA-I 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- LDDQLRUQCUTJBB-UHFFFAOYSA-N ammonium fluoride Chemical compound [NH4+].[F-] LDDQLRUQCUTJBB-UHFFFAOYSA-N 0.000 description 2
- 238000003754 machining Methods 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 239000003973 paint Substances 0.000 description 2
- -1 polyethylene terephthalate Polymers 0.000 description 2
- 229920000139 polyethylene terephthalate Polymers 0.000 description 2
- 239000005020 polyethylene terephthalate Substances 0.000 description 2
- 238000002203 pretreatment Methods 0.000 description 2
- 229920001187 thermosetting polymer Polymers 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- 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 2
- 229910000165 zinc phosphate Inorganic materials 0.000 description 2
- MMINFSMURORWKH-UHFFFAOYSA-N 3,6-dioxabicyclo[6.2.2]dodeca-1(10),8,11-triene-2,7-dione Chemical group O=C1OCCOC(=O)C2=CC=C1C=C2 MMINFSMURORWKH-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N Acrylic acid Chemical class OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 239000004593 Epoxy Substances 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
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- 229910000861 Mg alloy Inorganic materials 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- RPJKYODNJDVOOO-UHFFFAOYSA-N [B].F Chemical compound [B].F RPJKYODNJDVOOO-UHFFFAOYSA-N 0.000 description 1
- ZUGLAKUCQBESPV-UHFFFAOYSA-J [F-].[Na+].[B+3].[F-].[F-].[F-] Chemical compound [F-].[Na+].[B+3].[F-].[F-].[F-] ZUGLAKUCQBESPV-UHFFFAOYSA-J 0.000 description 1
- 239000002390 adhesive tape Substances 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 125000003368 amide group Chemical group 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 238000006701 autoxidation reaction Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- 230000003628 erosive effect Effects 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 238000007429 general method Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 1
- 238000003475 lamination Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000000088 plastic resin Substances 0.000 description 1
- 229920005668 polycarbonate resin Polymers 0.000 description 1
- 239000004431 polycarbonate resin Substances 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920006267 polyester film Polymers 0.000 description 1
- 235000003270 potassium fluoride Nutrition 0.000 description 1
- 239000011698 potassium fluoride Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 231100000241 scar Toxicity 0.000 description 1
- MNTPMEHIQKUBIC-UHFFFAOYSA-N silicon;hydrofluoride Chemical compound F.[Si] MNTPMEHIQKUBIC-UHFFFAOYSA-N 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000003351 stiffener Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 150000003544 thiamines Chemical class 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
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- Chemical Treatment Of Metals (AREA)
Abstract
The present invention relates to a surface treated aluminium material or aluminium alloy material with excellent working tight joint property and corrosion resistance. The present invention is characterized in that at least one side surface of the aluminium material is formed with 3 to 200 mg/m of metal chromium and hydrated chromium oxide film of which the chromium is 3 to 50 mg/m.
Description
Invention field
The present invention relates to a kind of surface treatment of making the band plate-like aluminum or aluminum alloy material of jar usefulness, refer to a kind ofly especially, still have the connecting airtight property with coating or diaphragm-operated excellence at deep Drawn Can or after do dashing the strictness processing of ironing jar etc., and the aluminium sheet of corrosion resistance excellent.
Background technology
The surface preparation of relevant aluminium alloy comprises chromate treating, and phosphoric acid chromate treating, zinc phosphate processing, anodic oxidation treatment, boehmite (boehmite) are handled etc., its be according to automobile with, building materials with purposes such as, jar materials, select respectively in the use.When an occasion of using as jar material, the phosphoric acid chromate treating is a main flow, and in the occasion of the can body and the lid of two-chip type jar, is to use different treatment solutions.These methods all are dipping chromate treating, and it is to use as the Coating Pretreatment of connecting airtight property of coating and corrosion resistance excellent.These flood chromate treating, owing to be not to be processed as prerequisite with the strictness after the application, therefore, can't be applied to the moulding method that cover paint that deep Drawn Can for example or punching press plate jar etc. or diaphragm reshape jar.For this reason, occurred connecting airtight property of coating is flooded the more excellent pre-treatment epithelium of chromate treating, the trial of carrying out with the processing of electrolysis chromic acid facture, for example, 5-179488 discloses as Japanese kokai publication hei, have in vitriolated chromic acid solution, carry out catholyte with low current density, and generate the method for colourless chromic salt epithelium, but this epithelium is owing to there is no metallic chromium layer, therefore there is no sufficient connecting airtight property of processing, diaphragm is peeled off or the disruptive situation and easily produce, and makes it to be applied to aforesaid moulding method.With connecting airtight property of diaphragm-operated be most important factor, suppose promptly to allow to be shaped, as after the processing to connect airtight power abundant inadequately, lack the anti-diaphragm bottom side corrodibility after content-filled again, so that can't the strong content of filling corrodibility.
Summary of the invention
The object of the present invention is to provide the aluminium of a kind of connecting airtight property of processing and corrosion resistance excellent.Along with improving because of surface treatment with coating or connecting airtight property of diaphragm-operated, applicable deep Drawn Can of aluminium of the present invention or dried shaping of dashing the ironing jar, again through imposing surface treatment, and after this kind is shaped processing again under the situation of filling content, aluminium of the present invention has anti-diaphragm bottom side corrodibility.
Technical program of the present invention lies in providing a kind of have excellent connecting airtight property of processing and corrosion proof surface treated aluminum material, it is characterized in that: at least one side surface of aluminium, be formed with 3～200mg/m
2Chromium metal, and chromium is 3～50mg/m
2Chromium hydrous oxide epithelium.
Technical scheme of the present invention is to provide a kind of have excellent connecting airtight property of processing and corrosion proof surface treated aluminum material again, it is characterized in that: it is at least one side surface with aluminium, use contains the electrolytic solution of anhydrous chromic acid 10g/l～200g/l and fluorion 0.2g/l～9.1g/l, is 10～300A/dm at the electrolytic current density of negative electrode
2Under carry out catholyte and handle, form 3～200mg/m
2Chromium metal, and chromium is 3～50mg/m
2Chromium hydrous oxide epithelium.
Technical scheme of the present invention is to provide a kind of have excellent connecting airtight property of processing and corrosion proof surface treated aluminum material again, it is characterized in that: it is at least one side surface with aluminium, use contains the electrolytic solution of anhydrous chromic acid 10g/l～200g/l and fluorion 0.2g/l～9.1g/l, is 30～200A/dm at the electrolytic current density of negative electrode
2Under carry out catholyte and handle, form 3～200mg/m
2Chromium metal, and chromium is 3～50mg/m
2Chromium hydrous oxide epithelium.
Technical program of the present invention also lies in providing a kind of have excellent connecting airtight property of processing and corrosion proof surface treated aluminum material, it is characterized in that: it is at least one side surface with aluminium, use contains anhydrous chromic acid 10g/l～200g/l and fluorion 0.2g/l～9.1g/l and the following electrolytic solution of sulfate ion 2g/l, is 30～200A/dm at the electrolytic current density of negative electrode
2Under carry out catholyte and handle, form 3～200mg/m
2Chromium metal, and chromium is 3～50mg/m
2Chromium hydrous oxide epithelium.
Technical scheme of the present invention more is to provide a kind of have excellent connecting airtight property of processing and corrosion proof surface treated aluminum material, it is characterized in that: it is at least one side surface with aluminium, use contains the electrolytic solution of anhydrous chromic acid 10g/l～200g/l and sulfate ion 0.2～5g/l, is 30～200A/dm at the electrolytic current density of negative electrode
2Under carry out catholyte and handle, form 3～200mg/m
2Chromium metal, and chromium is 3～50mg/m
2Chromium hydrous oxide epithelium.
The surface treated aluminum material of connecting airtight property of processing of the present invention and corrosion resistance excellent, applicable to the strict purposes of processing, can make impossible up to now use aluminium make deep Drawn Can or do towards the ironing jar becomes possibility.
Embodiment
Below, with the present invention is described in detail, the present invention can make after the aluminium application or the connecting airtight property after diaphragm laminated, be increased to applicable deep Drawn Can or do degree towards the pressing can shaping, the shaping that 20～40% the deep Drawn Can that is machined to original gauge or the punching press about thin-walled property to 40～70% are plated jar becomes possibility.
The chemical constitution of aluminium is to be decided by the mechanical property of the shape of jar and materials used, usually, the material that is used for two-chip type DI (DrawnandIronned punching press pressing) jar or DRD (DrawnandRedrawn deep-draw) jar there is no particular restriction, so long as be main composition, can add the aluminium alloy of manganese or magnesium etc. therein and form with aluminium.
Use the DI jar of aluminium, connecting airtight property and no problem, so be that its processing of accepting is to make tank wall thickness be reduced to about 1/3 of original gauge because the DI jar is to make jar by the punching press pressing processing of using soluble oil.After the system jar, clean, drying, in order to give solidity to corrosion to content, jar inner face side be through spraying application.Particularly,, carry out application after the processing in the occasion of DI jar, the processing after the application, be contract inner edge, reel fixingly, and the DI jar can be accepted strict processing hardly.On the other hand, will be through the steel plate or the aluminium alloy plate of application, under the state that does not use soluble oil, give the DRD jar that deep-draw becomes, or, in recent years polyester film sheet is given DTR (Draw-Thin/Redraw attenuation deep-draw) jar the occasion that laminated one-tenth steel plate is made, after coating or diaphragm are coated on metal sheet, need to accept strict deep-draw processing.Again, under the situation of not using soluble oil, the wall thickness thin-walled of DTR jar is changed in 40～70% the punching press ironing processing of original gauge, it is to need further to accept strict processing, and therefore, it is required to have better connecting airtight property of processing.
Secondly, the effect of just relevant with connecting airtight property of processing chromium metal describes now.The surface of aluminium and aluminium alloy be easy to form stable and fine and close oxide scale film, but this oxide scale film and coating or connecting airtight property of diaphragm-operated is not good.After oxide scale film is removed, or on the autoxidation epithelium, as previously mentioned, implement chromate treating, phosphoric acid chromate treating, zinc phosphate processing, anodic oxidation treatment, boehmite processing or the like in alkaline solution.These dipping chromate treating is not to be processed as prerequisite with the strictness after the application, therefore is not suitable for cover paint or diaphragm-operated system can shaping method as deep Drawn Can or punching press ironing jar etc.Again, as will flooding the more excellent pre-treatment epithelium of connecting airtight property of chromate treating coating, method with the generation of electrolysis chromic acid facture, having a kind of is in vitriolated chromic acid solution, carry out catholyte with low current density and generate the method for colourless chromic salt epithelium, this epithelium also is the cause because of no metallic chromium layer, there is no sufficient connecting airtight property of processing, and is not suitable for aforesaid moulding method.Though the effect of relevant chromium metal is not necessarily clear and definite, can infer as follows: aluminium is easy to generate oxide film, by application heating or diaphragm laminated, can easily form oxide film.This oxide film is fragile layer, and no cohesive force can destroy by handling ease ground, and becomes the immediate cause of connecting airtight property deterioration.Therefore, form,, infer that connecting airtight property of coating can improve if when generating the aftertreatment layer that is constituted by chromium metal and chromium hydrous oxide in order to remove oxide film and to prevent.When the oxide thickness of aluminium approaches,, still,, so can cause peeling off of interfacial oxide film because alumite is not good with the cementability of chromium hydrous oxide though can not produce destruction owing to fragile oxide film again.Chromium metal has the effect as the wedding agent of alumite and chromium hydrous oxide, infers that it can prevent the interface peel between oxide film.The effect of the corrosive chromium metal in relevant anti-diaphragm bottom side also is that the processing back is to occupy the status of domination with coating or connecting airtight property of diaphragm-operated, when connecting airtight property is abundant inadequately, can't prevent that the cathode layer behind the filling content from peeling off.As mentioned above, metallic chromium layer has the diffusion of anti-block and as the function of the wedding agent between oxide compound, therefore, even minimum also should have 3mg/m
2There is no the upper limit of the chromium metal that undermines connecting airtight property, by the variation of tone and effect economically, the upper limit is to be defined as 200mg/m
2
Relevant method at aluminium material surface formation chromium metal should be used to contain anhydrous chromic acid 10g/l～200g/l, and the electrolytic solution of fluorion 0.2g/l～9.1g/l is at current density 10～300A/dm
2Under carry out catholyte and handle, in order to make certainization of separating out of chromium metal, be more preferably, at current density 30～200A/dm
2Under make catholyte and handle.Again, even in bath, be added into sulfuric acid till the 2g/l, with 30A/dm
2Therefore and no problem above current density, chromium metal also can electrolytic depositions.Again, replace fluorochemical, use and only add the occasion that vitriolic is bathed, as if the scope that sulfuric acid concentration is defined in 0.2～5g/l, if with 30A/dm
2Above high current density electrolysis, chromium metal meeting electrolytic deposition, therefore, should be as far as possible with high current density electrolysis.
Anhydrous chromic acid is defined in more than the 10g/l, is because if when using than the lower concentration of this concentration, the bath resistance during electrolysis can increase, and causes waste of electric energy.When fluorinion concentration is set as 0.2g/l when following, chromium metal can not separated out, and therefore lower limit is set as this value.Again, when current density at 10A/dm
2When following, chromium metal can not separated out, and 10～25A/dm
2Though chromium metal can be separated out, efficient can reduce terrifically, and therefore, chromium metal can be separated out hardly, again, and the also difficult control of the amount of separating out.Therefore, the current density lower limit is set as 10A/dm
2, be more preferably 30A/dm
2Again, when surpassing 300A/dm
2The time, it is too high that bath voltage can become, and can become waste of electric energy.
Add vitriolic and bathe, in response to addition, for the necessary current density of the electrolytic deposition of chromium metal the tendency that increases is arranged, and the effect of fluorion can weaken, therefore, the upper limit of sulfuric acid addition is made as 5g/l.Again, bathe,, then there is no the current density range that chromium metal is separated out, therefore be defined in this scope if sulfuric acid concentration is not located in the scope of 0.2～5g/l if only add vitriolic.According to these baths,, 30A/dm must be arranged though chromium metal can be separated out
2Above high current density is handled.
Fluorion is to add with the form of metal-salt or acid.For example, can use hydrofluoric acid, boron hydrofluoric acid, silicon hydrofluoric acid, acid potassium fluoride, Potassium monofluoride, Sodium Fluoride, Neutral ammonium fluoride, boron Sodium Fluoride, silicon Sodium Fluoride or the like.
The temperature of treatment solution there is no specific, is preferably 30～60 ℃ scope.If below 30 ℃, owing to have the phenomenon of generating heat, be necessary to cool off because of electrolysis, this is not too economical.Similarly,, be holding temperature, be necessary to heat if more than 60 ℃, also uneconomical.
Preferable chromium metal adhesion amount among the present invention is 3～200mg/m
2, chromium hydrous oxide amount is 3～50mg/m in chromium
2, be necessary to satisfy simultaneously this scope.
The present invention in order to give after the anti-application or the connecting airtight property of the strict processing in diaphragm laminated back and the erosion resistance after the processing, needs to form the aftertreatment epithelium of containing metal chromium on the surface of aluminium.As coating, be to use in the resin of epoxies polyester system, be added with the solvent-borne type thermosetting coating of phenol, amido etc. as stiffening agent.Also can suitably use and utilize acrylic acid series etc. and the water-based type thermosetting coating of Water-borne modification again.These coating, because of being required processibility, coating is formed need be very strict.
The coating process of coating can use coated tool coating continuously on the aluminium of roll coil of strip shape, carries out drying, baking again, and the method for batching, also can aluminium is tabular for coating with what cut off, toasted again.
Using the diaphragm-operated occasion, but the use heat plastic resin, and giving an actual example of thermoplastic resin is vibrin, polycarbonate resin, poly-thiamines resin etc.Vibrin can use various vibrin, it can lift specific examples is polyethylene terephthalate, poly-terephthalic acid fourth diester, poly-phthalein diacid second diester, based on the copolymer polyester resin of ethylene terephthalate unit, or by the vibrin that mixture constituted of those materials.
Above-mentioned vibrin is coated on the method for steel plate, can give an actual example into: on the two sides of steel plate directly with the method for fused vibrin extrusion lamination, after melt extruding, with the diaphragm that not extend or extend orientation of general method with the diaphragm shaping, with heat fuse or be situated between with the laminated method of caking agent or and with the method for these methods etc., no matter be any method, equal method for makings of applicable resin-coated steel sheet of the present invention.
The first embodiment of the present invention below is described.With aluminium (JIS numbers A5052) with alkali degreasing clean the surface cleaned after, in 35 ℃ the electrolytic solution that is constituted with anhydrous chromic acid 30g/l, Sodium Fluoride 2g/l (fluorion 0.90g/l), with 50A/dm
2Current density carry out catholyte, generate chromium metal 10mg/m
2, and chromium is 20mg/m
2The chromium hydrous oxide.In washing, after the drying, with the following method thermoplastic resin that on this aluminium, is covered, at first, this aluminium is calorified 240 ℃, and on the face that becomes jar inner face side, and become on the face of jar exterior side, simultaneously laminated respectively by the polyethylene terephthalate 88 ear % that rubs, it is two (thick: 25 μ m to extending the copolymer polyester resin diaphragm that poly-m-phthalic acid second diester 12 rubs that ear % constituted, planar orientation coefficient: 0.126 (top and bottom are all like this), fusing point: 229 ℃), and be added with the titanium oxide pigments of 15 weight % and be coloured to white have the two (thick: as 20 μ m), directly to be impregnated in the water and to cool off of same composition with above-mentioned resin film to extending the copolymer polyester resin diaphragm.After laminated, give drying, the 50mg/m that on its two sides, is coated with
2Paraffin, implement following processing again.At first, behind the blank that is charged and attacked into diameter 160mm, form the punching press jar of diameter 100mm.Then, by punch process again, form the jar of punching press again of tank diameter 80mm.By with this punching press jar Compound Machining again, in the time of punch process again, implement ironing processing, form the punching press ironing jar of tank diameter 66mm.In this Compound Machining, processing conditions is to become the portion of punch process again of jar upper end and press the interval that adds between the Ministry of worker, be 20mm, punching press punch die shoulder R is 1.5 times of thickness of slab again, again between punching press punch die and the drift every 1.0 times that are thickness of slab, what ironing added the Ministry of worker is 55% of original gauge at interval.No matter be any processing, all do not make water as cooling, lubricant, implement with dry type.For the diaphragm of assessing the flange part that is shaped jar connects airtight portion, the width of can body top with 15mm cut out, measure it with the T-stripping test and connect airtight intensity.Again, in order to assess anti-diaphragm bottom side corrodibility, cut out the test film of 50mm size by can body portion, cut out the cruciform scar that arrives bottom with cutter, after will connecting airtight lid with adhesive tape with the part that assessment has nothing to do, with 37 ℃ of 2 weeks of dipping, assessment is peeled off wide because of the film that corrosion is caused in the corrosion test liquid of 1.5% citric acid and 1.5% salt.
The second embodiment of the present invention below is described.Use the electrolytic solution identical, with 10A/dm with embodiment 1
2Current density carry out catholyte, the generation chromium metal is 3mg/m
2, count 50mg/m with chromium
2The chromium hydrous oxide.In washing, after the drying, the identical thermoplastic resin of lining and embodiment 1 on aluminium carries out the processing identical with embodiment 1, assesses its connecting airtight property and solidity to corrosion.
The third embodiment of the present invention below is described.According to the mode identical, in 40 ℃ of electrolytic solution that anhydrous chromic acid 10g/l, Neutral ammonium fluoride 0.4g/l (is 0.21g/l with the fluorine ionometer) are formed, with 30A/dm with embodiment 1
2Current density carry out catholyte, generate chromium metal 30mg/m
2, chromium is 3mg/m
2The chromium hydrous oxide.Washing, after the drying, the lining thermoplastic resin identical with embodiment on this aluminium carries out the processing identical with embodiment 1, assesses its connecting airtight property and solidity to corrosion.
The fourth embodiment of the present invention below is described.According to the mode identical, in 50 ℃ of electrolytic solution that anhydrous chromic acid 10g/l, Sodium Fluoride 0.4g/l (is 9.1g/l with the fluorine ionometer) are formed, with 300A/dm with embodiment 1
2Current density carry out catholyte, generate chromium metal 30mg/m
2, chromium is 3mg/m
2The chromium hydrous oxide.Washing, after the drying, the identical thermoplastic resin of lining and embodiment 1 on this aluminium carries out the processing identical with embodiment 1, assesses its connecting airtight property and solidity to corrosion.
The fifth embodiment of the present invention below is described.According to the mode identical, in 50 ℃ of electrolytic solution that anhydrous chromic acid 30g/l, sodium silicofluoride 1g/l (is 0.61g/l with the fluorine ionometer), sulfuric acid 0.2g/l are formed, with 30A/dm with embodiment 1
2Current density carry out catholyte, generate chromium metal 5mg/m
2, chromium is 40mg/m
2The chromium hydrous oxide.Washing, after the drying, the lining thermoplastic resin identical with embodiment on this aluminium carries out the processing identical with embodiment 1, assesses its connecting airtight property and solidity to corrosion.
The sixth embodiment of the present invention below is described.According to the mode identical, in 50 ℃ of electrolytic solution that anhydrous chromic acid 100g/l, silicon Sodium Fluoride 1g/l (is 0.61g/l with the fluorine ionometer), sulfuric acid 2g/l are formed, with 100A/dm with embodiment 1
2Current density carry out catholyte, generate chromium metal 10mg/m
2, chromium is 50mg/m
2The chromium hydrous oxide.Washing, after the drying, the lining thermoplastic resin identical with embodiment on this aluminium carries out the processing identical with embodiment 1, assesses its connecting airtight property and solidity to corrosion.
The seventh embodiment of the present invention below is described.According to the mode identical, in 40 ℃ of electrolytic solution that anhydrous chromic acid 100g/l, sulfuric acid 5g/l are formed, with 30A/dm with embodiment 1
2Current density carry out catholyte, generate chromium metal 30mg/m
2, chromium is 45mg/m
2The chromium hydrous oxide.Washing, after the drying, the identical thermoplastic resin of lining and embodiment 1 on this aluminium carries out the processing identical with embodiment 1, assesses its connecting airtight property and solidity to corrosion.
The eighth embodiment of the present invention below is described.According to the mode identical, in 40 ℃ of electrolytic solution that anhydrous chromic acid 30g/l, sulfuric acid 0.2g/l are formed, with 100A/dm with embodiment 1
2Current density make catholyte, generate chromium metal 45mg/m
2, chromium is 35mg/m
2The chromium hydrous oxide.Washing, after the drying, the thermoplastic resin of lining identical with embodiment 1 on this aluminium carries out the processing identical with embodiment 1, assesses its connecting airtight property and solidity to corrosion.
Comparative example 1 of the present invention below is described.Use the electrolytic solution identical, with 5A/dm with embodiment 1
2Current density carry out catholyte, only generating chromium is 20mg/m
2The chromium hydrous oxide.Washing, after the drying, the lining thermoplastic resin identical with embodiment on this aluminium carries out the processing identical with embodiment 1, assesses its connecting airtight property and solidity to corrosion.
Comparative example 2 of the present invention below is described.Will the aluminium identical carry out after alkali degreasing cleans with embodiment 1, carry out application type chromate treating (Japanese Pa Kelai advances ancient corporate system) with 30 ℃ after, carry out 2 minutes drying with 100 ℃ drying ovens, generation chromium is 15mg/m
2The chromic salt epithelium.Then, the lining thermoplastic resin identical with embodiment 1 on this aluminium carries out the processing identical with embodiment 1, assesses its connecting airtight property and solidity to corrosion.
Comparative example 3 of the present invention below is described.Will the aluminium identical carry out using the electrolytic solution that is added with anhydrous chromic acid 20g/l, sulfuric acid 0.4g/l, with 5A/dm after alkali degreasing cleans with embodiment 1
2Current density carry out catholyte, only generate chromium water oxycompound, wherein chromium is 80mg/m
2In washing, after the drying, the identical thermoplastic resin of lining and embodiment 1 on this aluminium carries out the processing identical with embodiment 1 again, assesses its connecting airtight property and solidity to corrosion.(table 1)
| Bathe and form (g/l) | Current density A/dm 2 | Chromium metal amount (mg/m 2) | Chromium hydrous oxide amount (mg/m 2) | The stripping strength (kg/15mm) on jar top | Diaphragm is peeled off wide (mm) | |||
| ?CrO 3 | The F ion | ?H 2SO 4 | ||||||
| Embodiment 1 | ?30 | ?0.90 | ?0 | ?50 | ?10 | ?20 | ?1.2 | ?0.5 |
| Embodiment 2 | ?30 | ?0.90 | ?0 | ?10 | ?3 | ?3 | ?0.6 | ?1.0 |
| Embodiment 3 | ?10 | ?0.21 | ?0 | ?30 | ?30 | ?50 | ?0.8 | ?0.8 |
| Embodiment 4 | ?200 | ?9.1 | ?0 | ?300 | ?200 | ?10 | ?1.4 | ?0.5 |
| Embodiment 5 | ?30 | ?0.61 | ?0.2 | ?30 | ?5 | ?40 | ?0.8 | ?0.8 |
| Embodiment 6 | ?100 | ?0.61 | ?2 | ?100 | ?10 | ?50 | ?0.7 | ?1.0 |
| Embodiment 7 | ?100 | ?0 | ?5 | ?30 | ?3 | ?45 | ?0.6 | ?1.2 |
| Embodiment 8 | ?30 | ?0 | ?0.2 | ?100 | ?45 | ?35 | ?1.0 | ?0.8 |
| Comparative example 1 | ?30 | ?0.90 | ?0 | ?5 | ?0 | ?20 | ?0 | Comprehensively |
| Comparative example 2 | ?- | ?- | ?- | ?- | ?0 | ?15 | ?0 | Comprehensively |
| Comparative example 3 | ?20 | ?0 | ?0.4 | ?5 | ?0 | ?80 | ?0 | Comprehensively |
Claims (5)
1. one kind has excellent connecting airtight property of processing and corrosion proof surface treated aluminum material, it is characterized in that: at least one side surface of aluminium, be formed with 3～200mg/m
2Chromium metal, and chromium is 3～50mg/m
2Chromium hydrous oxide epithelium.
2. one kind has excellent connecting airtight property of processing and corrosion proof surface treated aluminum material, it is characterized in that: it is at least one side surface with aluminium, use contains the electrolytic solution of anhydrous chromic acid 10g/l～200g/l and fluorion 0.2g/l～9.1g/l, is 10～300A/dm at the electrolytic current density of negative electrode
2Under carry out catholyte and handle, form 3～200mg/m
2Chromium metal, and chromium is 3～50mg/m
2Chromium hydrous oxide epithelium.
3. one kind has excellent connecting airtight property of processing and corrosion proof surface treated aluminum material, it is characterized in that: it is at least one side surface with aluminium, use contains the electrolytic solution of anhydrous chromic acid 10g/l～200g/l and fluorion 0.2g/l～9.1g/l, is 30～200A/dm at the electrolytic current density of negative electrode
2Under carry out catholyte and handle, form 3～200mg/m
2Chromium metal, and chromium is 3～50mg/m
2Chromium hydrous oxide epithelium.
4, a kind of have excellent connecting airtight property of processing and a corrosion proof surface treated aluminum material, it is characterized in that: it is at least one side surface with aluminium, use contains anhydrous chromic acid 10g/l～200g/l and fluorion 0.2g/l～9.1g/l and the following electrolytic solution of sulfate ion 2g/l, is 30～200A/dm at the electrolytic current density of negative electrode
2Under carry out catholyte and handle, form 3～200mg/m
2Chromium metal, and chromium is 3～50mg/m
2Chromium hydrous oxide epithelium.
5. one kind has excellent connecting airtight property of processing and corrosion proof surface treated aluminum material, it is characterized in that: it is at least one side surface with aluminium, use contains the electrolytic solution of anhydrous chromic acid 10g/l～200g/l and sulfate ion 0.2～5g/l, is 30～200A/dm at the electrolytic current density of negative electrode
2Under carry out catholyte and handle, form 3～200mg/m
2Chromium metal, and chromium is 3～50mg/m
2Chromium hydrous oxide epithelium.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 96109604 CN1114719C (en) | 1996-08-22 | 1996-08-22 | Surface treated aluminium material with good wording sealing and connection and crossion-resisting |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 96109604 CN1114719C (en) | 1996-08-22 | 1996-08-22 | Surface treated aluminium material with good wording sealing and connection and crossion-resisting |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1174900A CN1174900A (en) | 1998-03-04 |
| CN1114719C true CN1114719C (en) | 2003-07-16 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 96109604 Expired - Fee Related CN1114719C (en) | 1996-08-22 | 1996-08-22 | Surface treated aluminium material with good wording sealing and connection and crossion-resisting |
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| CN (1) | CN1114719C (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| KR101206004B1 (en) * | 2009-02-16 | 2012-11-29 | 닛폰 스틸 앤드 스미킨 스테인레스 스틸 코포레이션 | Cr COATED STAINLESS STEEL HAVING SUPERIOR CORROSION RESISTANCE AFTER PROCESSING |
| JP5335595B2 (en) * | 2009-02-16 | 2013-11-06 | 新日鐵住金ステンレス株式会社 | Chrome-plated stainless steel plate with excellent post-processing corrosion resistance |
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