CN114921776A - Chromium-free and fluorine-free film passivator for aluminum material and preparation and use method thereof - Google Patents
Chromium-free and fluorine-free film passivator for aluminum material and preparation and use method thereof Download PDFInfo
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- CN114921776A CN114921776A CN202110743160.5A CN202110743160A CN114921776A CN 114921776 A CN114921776 A CN 114921776A CN 202110743160 A CN202110743160 A CN 202110743160A CN 114921776 A CN114921776 A CN 114921776A
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- Prior art keywords
- free
- chromium
- fluorine
- aluminum material
- passivator
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Links
- 229910052782 aluminium Inorganic materials 0.000 title claims abstract description 82
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 title claims abstract description 81
- 239000000463 material Substances 0.000 title claims abstract description 50
- 238000000034 method Methods 0.000 title claims abstract description 17
- 238000002360 preparation method Methods 0.000 title abstract description 16
- 229910019142 PO4 Inorganic materials 0.000 claims abstract description 32
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 32
- 239000010452 phosphate Substances 0.000 claims abstract description 32
- 239000002738 chelating agent Substances 0.000 claims abstract description 31
- 238000005260 corrosion Methods 0.000 claims abstract description 30
- 230000007797 corrosion Effects 0.000 claims abstract description 30
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims abstract description 27
- 239000003112 inhibitor Substances 0.000 claims abstract description 24
- 230000000149 penetrating effect Effects 0.000 claims abstract description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 15
- 238000005507 spraying Methods 0.000 claims abstract description 14
- 239000011248 coating agent Substances 0.000 claims abstract description 11
- 238000000576 coating method Methods 0.000 claims abstract description 11
- -1 phosphate ester Chemical class 0.000 claims abstract description 9
- 239000002994 raw material Substances 0.000 claims abstract description 7
- 238000003756 stirring Methods 0.000 claims description 18
- 239000000843 powder Substances 0.000 claims description 17
- YDONNITUKPKTIG-UHFFFAOYSA-N [Nitrilotris(methylene)]trisphosphonic acid Chemical compound OP(O)(=O)CN(CP(O)(O)=O)CP(O)(O)=O YDONNITUKPKTIG-UHFFFAOYSA-N 0.000 claims description 13
- 239000007788 liquid Substances 0.000 claims description 12
- 238000005406 washing Methods 0.000 claims description 12
- PQHYOGIRXOKOEJ-UHFFFAOYSA-N 2-(1,2-dicarboxyethylamino)butanedioic acid Chemical compound OC(=O)CC(C(O)=O)NC(C(O)=O)CC(O)=O PQHYOGIRXOKOEJ-UHFFFAOYSA-N 0.000 claims description 9
- PCOCFIOYWNCGBM-UHFFFAOYSA-N 4-[(2-methylpropan-2-yl)oxy]-4-oxobutanoic acid Chemical compound CC(C)(C)OC(=O)CCC(O)=O PCOCFIOYWNCGBM-UHFFFAOYSA-N 0.000 claims description 9
- JBJMZCVEBLDYCA-UHFFFAOYSA-N didodecyl butanedioate Chemical compound CCCCCCCCCCCCOC(=O)CCC(=O)OCCCCCCCCCCCC JBJMZCVEBLDYCA-UHFFFAOYSA-N 0.000 claims description 9
- 239000002253 acid Substances 0.000 claims description 8
- 239000010985 leather Substances 0.000 claims description 8
- 239000002736 nonionic surfactant Substances 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 7
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 6
- DVSDDICSXBCMQJ-UHFFFAOYSA-N diethyl 2-acetylbutanedioate Chemical compound CCOC(=O)CC(C(C)=O)C(=O)OCC DVSDDICSXBCMQJ-UHFFFAOYSA-N 0.000 claims description 6
- 239000000428 dust Substances 0.000 claims description 6
- 239000011159 matrix material Substances 0.000 claims description 6
- 238000002791 soaking Methods 0.000 claims description 6
- YAXXOCZAXKLLCV-UHFFFAOYSA-N 3-dodecyloxolane-2,5-dione Chemical compound CCCCCCCCCCCCC1CC(=O)OC1=O YAXXOCZAXKLLCV-UHFFFAOYSA-N 0.000 claims description 5
- WVLBCYQITXONBZ-UHFFFAOYSA-N trimethyl phosphate Chemical compound COP(=O)(OC)OC WVLBCYQITXONBZ-UHFFFAOYSA-N 0.000 claims description 5
- CQCXMYUCNSJSKG-UHFFFAOYSA-N 1-dimethoxyphosphorylethene Chemical compound COP(=O)(OC)C=C CQCXMYUCNSJSKG-UHFFFAOYSA-N 0.000 claims description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 4
- ZJFCVUTYZHUNSW-UHFFFAOYSA-N 3-octadecyloxolane-2,5-dione Chemical compound CCCCCCCCCCCCCCCCCCC1CC(=O)OC1=O ZJFCVUTYZHUNSW-UHFFFAOYSA-N 0.000 claims description 3
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 claims description 3
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 3
- IOVCWXUNBOPUCH-UHFFFAOYSA-M Nitrite anion Chemical compound [O-]N=O IOVCWXUNBOPUCH-UHFFFAOYSA-M 0.000 claims description 3
- SUHOOTKUPISOBE-UHFFFAOYSA-N O-phosphoethanolamine Chemical compound NCCOP(O)(O)=O SUHOOTKUPISOBE-UHFFFAOYSA-N 0.000 claims description 3
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 claims description 3
- FVHDFHJJJGWAFT-UHFFFAOYSA-N [Na].[Na].[Na].[Na].OC(=O)CC(C(O)=O)NC(C(O)=O)CC(O)=O Chemical compound [Na].[Na].[Na].[Na].OC(=O)CC(C(O)=O)NC(C(O)=O)CC(O)=O FVHDFHJJJGWAFT-UHFFFAOYSA-N 0.000 claims description 3
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 3
- 239000003945 anionic surfactant Substances 0.000 claims description 3
- OBXSGRKNCOCTTM-UHFFFAOYSA-N benzyl diethyl phosphate Chemical compound CCOP(=O)(OCC)OCC1=CC=CC=C1 OBXSGRKNCOCTTM-UHFFFAOYSA-N 0.000 claims description 3
- 239000003093 cationic surfactant Substances 0.000 claims description 3
- HAKMAMKAFTZXOZ-UHFFFAOYSA-N dioctoxyphosphorylbenzene Chemical compound CCCCCCCCOP(=O)(OCCCCCCCC)C1=CC=CC=C1 HAKMAMKAFTZXOZ-UHFFFAOYSA-N 0.000 claims description 3
- 229940079886 disodium lauryl sulfosuccinate Drugs 0.000 claims description 3
- KHIQYZGEUSTKSB-UHFFFAOYSA-L disodium;4-dodecoxy-4-oxo-3-sulfobutanoate Chemical compound [Na+].[Na+].CCCCCCCCCCCCOC(=O)C(S(O)(=O)=O)CC([O-])=O.CCCCCCCCCCCCOC(=O)C(S(O)(=O)=O)CC([O-])=O KHIQYZGEUSTKSB-UHFFFAOYSA-L 0.000 claims description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 3
- MEFBJEMVZONFCJ-UHFFFAOYSA-N molybdate Chemical compound [O-][Mo]([O-])(=O)=O MEFBJEMVZONFCJ-UHFFFAOYSA-N 0.000 claims description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 3
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 3
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 claims description 3
- PBYZMCDFOULPGH-UHFFFAOYSA-N tungstate Chemical compound [O-][W]([O-])(=O)=O PBYZMCDFOULPGH-UHFFFAOYSA-N 0.000 claims description 3
- LSGOVYNHVSXFFJ-UHFFFAOYSA-N vanadate(3-) Chemical compound [O-][V]([O-])([O-])=O LSGOVYNHVSXFFJ-UHFFFAOYSA-N 0.000 claims description 3
- 239000002888 zwitterionic surfactant Substances 0.000 claims description 3
- DREPONDJUKIQLX-UHFFFAOYSA-N 1-[ethenyl(ethoxy)phosphoryl]oxyethane Chemical compound CCOP(=O)(C=C)OCC DREPONDJUKIQLX-UHFFFAOYSA-N 0.000 claims 1
- 238000002161 passivation Methods 0.000 abstract description 12
- 239000000853 adhesive Substances 0.000 abstract description 10
- 230000001070 adhesive effect Effects 0.000 abstract description 10
- 239000008233 hard water Substances 0.000 abstract description 6
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- 238000012360 testing method Methods 0.000 description 8
- 239000004327 boric acid Substances 0.000 description 6
- 125000005619 boric acid group Chemical group 0.000 description 5
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 4
- 229910052731 fluorine Inorganic materials 0.000 description 4
- 239000011737 fluorine Substances 0.000 description 4
- FDGBQHCDMSYZRC-UHFFFAOYSA-N 2-hydroxy-2-oxo-1,3,2$l^{5}-dioxaphosphinan-4-amine Chemical group NC1CCOP(O)(=O)O1 FDGBQHCDMSYZRC-UHFFFAOYSA-N 0.000 description 3
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 3
- 239000003153 chemical reaction reagent Substances 0.000 description 3
- 229910052804 chromium Inorganic materials 0.000 description 3
- 239000011651 chromium Substances 0.000 description 3
- VONWDASPFIQPDY-UHFFFAOYSA-N dimethyl methylphosphonate Chemical compound COP(C)(=O)OC VONWDASPFIQPDY-UHFFFAOYSA-N 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- UTCWESKNHLBRDD-UHFFFAOYSA-N 3-chloro-2,2,3,3-tetrafluoropropanoyl chloride Chemical compound FC(F)(Cl)C(F)(F)C(Cl)=O UTCWESKNHLBRDD-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 229940058182 aminoethylphosphinic acid Drugs 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- KKUKTXOBAWVSHC-UHFFFAOYSA-N Dimethylphosphate Chemical compound COP(O)(=O)OC KKUKTXOBAWVSHC-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 1
- 238000005536 corrosion prevention Methods 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 125000004177 diethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000004993 emission spectroscopy Methods 0.000 description 1
- VWCFCFOIUSKKSC-UHFFFAOYSA-N ethane-1,2-diamine;2-hydroxy-1,3,2$l^{5}-dioxaphosphepane 2-oxide Chemical group NCCN.OP1(=O)OCCCCO1 VWCFCFOIUSKKSC-UHFFFAOYSA-N 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002357 osmotic agent Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 230000000979 retarding effect Effects 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 229940080258 tetrasodium iminodisuccinate Drugs 0.000 description 1
- GYBINGQBXROMRS-UHFFFAOYSA-J tetrasodium;2-(1,2-dicarboxylatoethylamino)butanedioate Chemical compound [Na+].[Na+].[Na+].[Na+].[O-]C(=O)CC(C([O-])=O)NC(C([O-])=O)CC([O-])=O GYBINGQBXROMRS-UHFFFAOYSA-J 0.000 description 1
Classifications
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- General Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Chemical Treatment Of Metals (AREA)
Abstract
The invention discloses a chromium-free and fluorine-free film passivator for an aluminum material, which comprises the following raw materials in parts by weight: 5-15 parts of phosphate, 0.5-1.2 parts of chelating agent, 0-0.1 part of penetrating agent, 0.8-2 parts of corrosion inhibitor and the balance of water. The chromium-free and fluorine-free film passivating agent for the aluminum material can ensure that a spraying coating has good adhesive force on the surface of the aluminum material and is not influenced by the quality of hard water, and the chromium-free and fluorine-free passivation is realized by adding phosphate ester, a chelating agent, a penetrating agent and a corrosion inhibitor into a film forming agent and combining a special process, so that the production and preparation process is safer, green and environment-friendly.
Description
Technical Field
The invention relates to a chromium-free and fluorine-free film passivator for an aluminum material and a preparation and use method thereof, which are mainly applied to the field of passivation and corrosion prevention of aluminum materials.
Background
In order to promote the passivation of the surface of the aluminum material and reduce the corrosion of the aluminum material caused by the external environment, the surface of the aluminum material needs to be treated, a layer of passivating agent is applied, the adhesion between the aluminum material and a powder spraying coating in the later period cannot be influenced, and the hard water resistance and the impact resistance of the spraying coating are higher. The existing passivator can be used for a chromium-free process, but fluorine still exists, so that the existing passivator cannot be completely green, safe and environment-friendly.
Disclosure of Invention
In order to improve the passivation efficiency of the surface of the aluminum material and avoid the use of chromium and fluorine, the first aspect of the invention provides a chromium-free and fluorine-free film passivator for the aluminum material, which comprises the following preparation raw materials in parts by weight: 5-15 parts of phosphate, 0.5-1.2 parts of chelating agent, 0-0.1 part of penetrating agent, 0.8-2 parts of corrosion inhibitor and the balance of water.
As a preferred embodiment, the molecular structure of the phosphate ester is
Wherein R is selected from one or a combination of a plurality of methyl, phenyl, ethyl and propyl.
As a preferred embodiment, the phosphate is selected from one or more of diethyl benzylphosphate, dioctyl phenylphosphonate, dimethyl vinylphosphonate, diethyl methyl alkylphosphonate, and dimethyl methylphosphonate.
As a preferred embodiment, the chelating agent is selected from one or more of aminotrimethylene phosphonic acid, iminodisuccinic acid, aminotrimethylene phosphonic acid pentasodium, aminoethyl phosphinic acid, 2-aminoethyl phosphoric acid, ethylene diamine tetramethylene phosphoric acid and iminodisuccinic acid tetrasodium.
As a preferred embodiment, the penetrating agent is selected from one or more of cationic surfactant, anionic surfactant, nonionic surfactant, and zwitterionic surfactant.
As a preferred embodiment, the nonionic surfactant is selected from one or more of disodium lauryl sulfosuccinate, dilauryl succinate, diethyl acetyl succinate, dodecyl succinic anhydride, octadecyl succinic anhydride, and mono-tert-butyl succinate.
As a preferred embodiment, the corrosion inhibitor is selected from one or more of borate, molybdate, tungstate, vanadate, nitrite, orthophosphate and silicate.
As a preferred embodiment, the weight ratio of the phosphate ester to the chelating agent is 1: (0.1-0.16).
The second aspect of the invention provides a preparation method of a chromium-free and fluorine-free film passivator for an aluminum material, which comprises the following steps:
(1) adding the chelating agent into a stirrer and stirring for 30-60min at the rotating speed of 5000-;
(2) slowly adding a penetrating agent and a corrosion inhibitor, and continuously stirring for 1-1.5 h;
(3) adding phosphate, and stirring for 1-2 h.
The third aspect of the invention provides a use method of a chromium-free and fluorine-free film passivator for an aluminum material, which comprises the following steps:
(1) carrying out oil removal, dust removal, acid washing and water washing treatment on the aluminum matrix;
(2) adding the prepared chromium-free fluorine-free leather film passivator into a liquid tank;
(3) and (3) putting the aluminum plate into a passivating agent tank liquid, soaking for 0.5-1min, taking out, drying and spraying powder within 72 h.
Compared with the prior art, the invention has the following beneficial effects:
(1) the chromium-free and fluorine-free coating passivator for the aluminum material can ensure that a sprayed coating has good adhesive force on the surface of the aluminum material and is not influenced by the quality of hard water.
(2) According to the chromium-free and fluorine-free aluminum product leather film passivator, phosphate, a chelating agent, a penetrating agent and a corrosion inhibitor are added into a film forming agent, and a special process combination is adopted, so that the chromium-free and fluorine-free passivation is realized, and the production and preparation process is safer, green and environment-friendly.
(3) The chromium-free and fluorine-free film passivator for the aluminum material can enable the aluminum material to have better corrosion resistance, prolong the corrosion resistance time and have excellent impact resistance.
Detailed Description
In order to improve the passivation efficiency of the surface of the aluminum material and avoid the use of chromium and fluorine, the first aspect of the invention provides a chromium-free and fluorine-free film passivator for the aluminum material, which comprises the following preparation raw materials in parts by weight: 5-15 parts of phosphate, 0.5-1.2 parts of chelating agent, 0-0.1 part of penetrating agent, 0.8-2 parts of corrosion inhibitor and the balance of water.
As a preferred embodiment, the molecular structure of the phosphate ester is
Wherein R is selected from one or a combination of a plurality of methyl, phenyl, ethyl and propyl.
As a preferred embodiment, the phosphate ester is selected from one or more of diethyl benzylphosphate, dioctyl phenylphosphonate, dimethyl vinylphosphonate, diethyl methyl alkylphosphonate, and dimethyl methylphosphonate.
In a preferred embodiment, the phosphate is dimethyl methylphosphonate.
As a preferred embodiment, the chelating agent is selected from one or more of aminotrimethylene phosphonic acid, iminodisuccinic acid, aminotrimethylene phosphonic acid pentasodium, aminoethyl phosphinic acid, 2-aminoethyl phosphoric acid, ethylene diamine tetramethylene phosphoric acid and iminodisuccinic acid tetrasodium.
As a preferred embodiment, the chelating agent is aminotrimethylene phosphonic acid and iminodisuccinic acid.
As a preferred embodiment, the weight ratio of aminotrimethylene phosphonic acid and iminodisuccinic acid is 1: (0.5-1).
As a preferred embodiment, the penetrating agent is selected from one or more of a cationic surfactant, an anionic surfactant, a nonionic surfactant and a zwitterionic surfactant.
As a preferred embodiment, the osmotic agent is a nonionic surfactant.
As a preferred embodiment, the nonionic surfactant is selected from one or more of disodium lauryl sulfosuccinate, dilauryl succinate, diethyl acetyl succinate, dodecyl succinic anhydride, octadecyl succinic anhydride, and mono-tert-butyl succinate.
As a preferred embodiment, the nonionic surfactant is dilauryl succinate and diethyl and mono-tert-butyl succinate.
As a preferred embodiment, the weight ratio of dilauryl succinate to diethyl acetyl succinate to mono-tert-butyl succinate is 1: (1-2): (0.2-0.5).
In the experimental process, the applicant finds that the adhesive force of the passivating agent can be improved and the falling of powder on the surface of the aluminum material can be reduced by adding a small amount of penetrating agent. The possible reasons for guessing are: the penetrant can be directionally arranged on the surface of the aluminum plate, so that the surface tension of the aluminum plate is obviously reduced, and the spraying powder with small particle size is easier to attach on the surface of the aluminum plate. However, the applicant has further found that the use of a penetrant with a high foaming capacity may instead cause a reduction in the adhesion of the spray powder to the aluminium sheet, presumably due to: the penetrant generates bubbles on the surface of the aluminum plate, and the introduction of air causes gaps between the aluminum plate and the passivator to cause the decrease of adhesive force, thereby influencing the spraying effect of the powder.
As a preferred embodiment, the corrosion inhibitor is selected from one or more of borate, molybdate, tungstate, vanadate, nitrite, orthophosphate and silicate.
As a preferred embodiment, the corrosion inhibitor is boric acid.
As a preferred embodiment, the particle size of the boric acid is 200-500 meshes.
As a preferred embodiment, the weight ratio of the phosphate ester to the chelating agent is 1: (0.1-0.16).
The applicant finds that the phosphate ester is methyl dimethyl phosphate, the chelating agent is aminotrimethylene phosphate and iminodisuccinic acid, and the prepared passivating agent is applied to an aluminum plate, so that the corrosion resistance is greatly improved, and the aluminum plate has excellent adhesion. The possible reasons for guessing are: phosphate can be bonded with the aluminum plate, one hydroxyl on the phosphate is combined with hydrogen, and H is generated by combining the hydroxyl with the hydrogen in the drying process 2 O is removed, and the rest hydroxyl groups on the phosphate are combined with the later powder spraying powder, so that the aluminum plate and the powder spraying powder are combined together through chemical bonds, and the acting force is firmer. And in the experimental process, the applicant finds that the chelating agent aminotrimethylene phosphate and iminodisuccinic acid are added into the system, and the weight ratio of the dimethyl methyl phosphate to the chelating agent is 1: (0.1-0.16) can further increase the passivation efficiency of the aluminum plate, retarding the corrosion of the aluminum plate, presumably due to: methyl radicalThe action of dimethyl phosphate and aminotrimethylene phosphate increases the stability of the complex, the length of the bridge connection between the appropriate chelating groups increases the passivation efficiency, and outside the preferred weight ratio range, it may lead to excessive steric hindrance between the substituents and reduced passivation performance.
The second aspect of the invention provides a preparation method of a chromium-free and fluorine-free film passivator for an aluminum material, which comprises the following steps:
(1) adding the chelating agent into a stirrer and stirring for 30-60min at the rotating speed of 5000-;
(2) slowly adding a penetrating agent and a corrosion inhibitor, and continuously stirring for 1-1.5 h;
(3) adding phosphate, and stirring for 1-2 h.
In the preparation process of the aluminum material chromium-free fluorine-free film passivator, the adding speed of the penetrating agent and the corrosion inhibitor is slow, so that more bubbles are avoided, the surface of an aluminum material is passivated unevenly if the bubbles appear, the formation of the film on the surface of the aluminum material is hindered by the bubbles, the surface of the aluminum material is subjected to pitting corrosion, and the service performance of the aluminum material is influenced.
The third aspect of the invention provides a use method of a chromium-free and fluorine-free film passivator for an aluminum material, which comprises the following steps:
(1) carrying out oil removal, dust removal, acid washing and water washing treatment on the aluminum matrix;
(2) adding the prepared chromium-free fluorine-free leather film passivator into a liquid tank;
(3) and (3) putting the aluminum plate into the passivating agent bath solution, soaking for 0.5-1min, taking out, drying and spraying powder within 72 h.
The present invention will be specifically described below by way of examples. It should be noted that the following examples are only for illustrating the present invention and should not be construed as limiting the scope of the present invention, and that the insubstantial modifications and adaptations of the present invention by those skilled in the art based on the above disclosure are still within the scope of the present invention.
In addition, the starting materials used are all commercially available, unless otherwise specified.
Example 1
The chromium-free fluorine-free film passivator for the aluminum material comprises the following preparation raw materials in parts by weight: 5 parts of phosphate, 0.8 part of chelating agent, 0.05 part of penetrating agent, 1 part of corrosion inhibitor and the balance of water.
The phosphate is dimethyl methyl phosphate.
The chelating agent is amino trimethylene phosphonic acid and imino disuccinic acid, and the weight ratio of the chelating agent to the amino trimethylene phosphonic acid is 1: 0.7.
the penetrant is dilauryl succinate, diethyl acetyl succinate and mono-tert-butyl succinate, and the weight ratio of the dilauryl succinate to the diethyl acetyl succinate to the mono-tert-butyl succinate is 1: 1.5: 0.4.
the corrosion inhibitor is boric acid with the grain diameter of 200 meshes, is purchased from Meclin reagent company and has the model number of B887055.
A preparation method of a chromium-free and fluorine-free aluminum coating passivator comprises the following steps:
(1) adding the chelating agent into a stirrer, and stirring at a rotating speed of 5000r/min for 40 min;
(2) slowly adding a penetrating agent and a corrosion inhibitor, and continuously stirring for 1 h;
(3) adding phosphate, and stirring for 1.5 h.
The use method of the chromium-free and fluorine-free film passivator for the aluminum material comprises the following steps:
(1) carrying out oil removal, dust removal, acid washing and water washing treatment on the aluminum matrix;
(2) adding the prepared chromium-free fluorine-free leather film passivator into a liquid tank;
(3) and (3) putting the aluminum plate into the passivating agent bath solution, soaking for 1min, taking out, drying, and standing for 70h for powder spraying.
Example 2
The chromium-free and fluorine-free film passivator for the aluminum material comprises the following raw materials in parts by weight: 10 parts of phosphate, 1 part of chelating agent, 0 part of penetrating agent, 0.8 part of corrosion inhibitor and the balance of water.
The phosphate is dimethyl methyl phosphate.
The chelating agent is amino trimethylene phosphonic acid and imino disuccinic acid, and the weight ratio of the chelating agent to the amino trimethylene phosphonic acid is 1: (0.5-1).
The corrosion inhibitor is boric acid with the grain diameter of 200 meshes, is purchased from Michelin reagent company and has the model of B887055.
A preparation method of a chromium-free and fluorine-free film passivator for an aluminum material comprises the following steps:
(1) adding the chelating agent into a stirrer, and stirring at the rotating speed of 7000r/min for 30 min;
(2) slowly adding a penetrating agent and a corrosion inhibitor, and continuously stirring for 1.5 h;
(3) adding phosphate, and stirring for 2 h.
The use method of the chromium-free and fluorine-free film passivator for the aluminum material comprises the following steps:
(1) carrying out oil removal, dust removal, acid washing and water washing treatment on the aluminum matrix;
(2) adding the prepared chromium-free fluorine-free leather film passivator into a liquid tank;
(3) and (3) placing the aluminum plate into a passivating agent tank liquid, soaking for 50s, taking out, drying, and standing for 72h for powder spraying.
Example 3
The chromium-free and fluorine-free film passivator for the aluminum material comprises the following raw materials in parts by weight: 12 parts of phosphate, 1.2 parts of chelating agent, 0.1 part of penetrating agent, 1.5 parts of corrosion inhibitor and the balance of water.
The phosphate is dimethyl vinyl phosphonate.
The chelating agent is ethylenediamine tetramethylene phosphate and tetrasodium iminodisuccinate, and the weight ratio is 1: 0.75.
the penetrant is dilauryl succinate, dodecyl succinic anhydride and mono-tert-butyl succinate, and the weight ratio of the dilauryl succinate to the dodecyl succinic anhydride to the mono-tert-butyl succinate is 1: 1.5: 0.3.
the corrosion inhibitor is boric acid with the grain diameter of 500 meshes, is purchased from Meclin reagent company and has the model number of B887054.
A preparation method of a chromium-free and fluorine-free aluminum coating passivator comprises the following steps:
(1) adding the chelating agent into a stirrer, and stirring at a rotating speed of 5000r/min for 40 min;
(2) slowly adding a penetrating agent and a corrosion inhibitor, and continuously stirring for 1 h;
(3) adding phosphate, and stirring for 1 h.
The use method of the chromium-free and fluorine-free film passivator for the aluminum material comprises the following steps:
(1) carrying out oil removal, dust removal, acid washing and water washing treatment on the aluminum matrix;
(2) adding the prepared chromium-free fluorine-free leather film passivator into a liquid tank;
(3) and (3) putting the aluminum plate into a passivating agent tank liquid, soaking for 1min, taking out, drying, and standing for 72h for powder spraying.
Example 4
The specific steps of the aluminum material chromium-free fluorine-free film passivator and the preparation and use methods are the same as example 1, and the difference is that the chelating agent is amino trimethylene phosphonic acid, and the weight part is 0.4 part.
Example 5
The specific steps of the aluminum material chromium-free fluorine-free leather film passivator and the preparation and use method are the same as example 1, and the difference is that the corrosion inhibitor is boric acid, and the weight part is 0.5 part.
Performance testing
1. Hard water adhesion resistance test: and replacing the water in the passivation liquid tank with hard water with the hardness of 800 from deionized water, and testing the influence on the adhesive force of the aluminum material.
2. Acid-resistant adhesion test: and (3) adding a 0.025% hydrochloric acid solution into a passivation liquid tank, and testing the influence on the adhesion force of the aluminum material.
3. Testing of the influence of the standing time on the adhesion: and (5) placing the passivated aluminum material for a period of time, and observing the influence of the placing for 72 hours on the adhesive force of the aluminum material.
4. And (3) passivation effect testing: the aluminum panels were treated with the passivates of examples 1-5 and the painted appearance of the aluminum panels was observed.
The adhesive force after the plate hitting is used as the judgment basis. The adhesive force performance index is judged to be represented by 0-5, the larger the value is, the stronger the adhesive force is, the examples are subjected to the above test, and the results are shown in table 1.
The adhesion ratings are given as follows:
TABLE 1
| Hard water adhesion resistance | Acid-resistant adhesion | After standing for 72h, the adhesive force | |
| Example 1 | Grade 5 | Grade 5 | Grade 5 |
| Example 2 | Grade 5 | Grade 5 | Grade 5 |
| Example 3 | Grade 5 | Grade 5 | Grade 5 |
| Example 4 | Grade 5 | Grade 4 | Grade 4 |
| Example 5 | Grade 5 | Grade 4 | 4 stage |
The glow discharge-emission spectroscopy results before the powder coating was not applied showed the presence of elements of P, Zr, O, Al on the substrate surface, and no chromium and fluorine.
The performance tests after powder spraying of example 1 were tested according to the national standards and the results are shown in table 2.
TABLE 2
Claims (10)
1. The chromium-free fluorine-free film passivator for the aluminum material is characterized by comprising the following raw materials in parts by weight: 5-15 parts of phosphate, 0.5-1.2 parts of chelating agent, 0-0.1 part of penetrating agent, 0.8-2 parts of corrosion inhibitor and the balance of water.
2. The chromium-free and fluorine-free aluminum coating passivator according to claim 1, wherein the molecular structure of the phosphate ester is
Wherein R is selected from one or a combination of a plurality of methyl, phenyl, ethyl and propyl.
3. The aluminum material chromium-free fluorine-free film passivator according to claim 1, wherein the phosphate is selected from one or a combination of diethyl benzyl phosphate, dioctyl phenyl phosphonate, dimethyl vinyl phosphonate, diethyl vinyl phosphate, diethyl alkyl methyl alkyl phosphonate and dimethyl methyl phosphate.
4. The aluminum material chromium-free fluorine-free film passivator according to claim 1, wherein the chelating agent is selected from one or a combination of several of aminotrimethylene phosphonic acid, iminodisuccinic acid, aminotrimethylene phosphonic acid pentasodium, aminoethyl hypophosphorous acid, 2-aminoethyl phosphoric acid, ethylene diamine tetramethylene phosphoric acid, and iminodisuccinic acid tetrasodium.
5. The aluminum chromium-free and fluorine-free coating passivator according to claim 1, wherein the penetrating agent is one or a combination of cationic surfactant, anionic surfactant, nonionic surfactant and zwitterionic surfactant.
6. The aluminum material chromium-free fluorine-free film passivator according to claim 5, wherein the non-ionic surfactant is selected from one or more of disodium lauryl sulfosuccinate, dilauryl succinate, diethyl acetyl succinate, dodecyl succinic anhydride, octadecyl succinic anhydride, mono-tert-butyl succinate.
7. The aluminum material chromium-free fluorine-free film passivator according to claim 1, wherein the corrosion inhibitor is selected from one or a combination of borate, molybdate, tungstate, vanadate, nitrite, orthophosphate and silicate.
8. The aluminum material chromium-free fluorine-free coating passivator as claimed in claim 1, wherein the weight ratio of the phosphate to the chelating agent is 1: (0.1-0.16).
9. A method for preparing the chromium-free and fluorine-free aluminum material film passivator according to any one of claims 1 to 8, which is characterized by comprising the following steps:
(1) adding the chelating agent into a stirrer and stirring for 30-60min at the rotating speed of 5000-1000 r/min;
(2) slowly adding a penetrating agent and a corrosion inhibitor, and continuously stirring for 1-1.5 h;
(3) adding phosphate, and stirring for 1-2 hr.
10. The use method of the aluminum material chromium-free fluorine-free film passivator according to any one of claims 1-8, characterized by comprising the following steps:
(1) carrying out oil removal, dust removal, acid washing and water washing treatment on the aluminum matrix;
(2) adding the prepared chromium-free fluorine-free leather film passivator into a liquid tank;
(3) and (3) putting the aluminum plate into a passivating agent tank liquid, soaking for 0.5-1min, taking out, drying and spraying powder within 72 h.
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|---|---|---|---|---|
| US5294265A (en) * | 1992-04-02 | 1994-03-15 | Ppg Industries, Inc. | Non-chrome passivation for metal substrates |
| JP2001167645A (en) * | 1999-12-07 | 2001-06-22 | Showa Electric Wire & Cable Co Ltd | Anti-corrosive cable, and method and apparatus of fabricating the same |
| CN1312739A (en) * | 1998-06-22 | 2001-09-12 | 亨凯尔公司 | Method for treating solid, especially alluminmium surfaces |
| CN103154317A (en) * | 2010-10-05 | 2013-06-12 | 巴斯夫欧洲公司 | Method for passivating a metallic surface |
| CN108193208A (en) * | 2018-01-24 | 2018-06-22 | 合肥铭佑高温技术有限公司 | A kind of high-temperature service corrosion inhibiter and preparation method thereof |
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2021
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5294265A (en) * | 1992-04-02 | 1994-03-15 | Ppg Industries, Inc. | Non-chrome passivation for metal substrates |
| CN1312739A (en) * | 1998-06-22 | 2001-09-12 | 亨凯尔公司 | Method for treating solid, especially alluminmium surfaces |
| JP2001167645A (en) * | 1999-12-07 | 2001-06-22 | Showa Electric Wire & Cable Co Ltd | Anti-corrosive cable, and method and apparatus of fabricating the same |
| CN103154317A (en) * | 2010-10-05 | 2013-06-12 | 巴斯夫欧洲公司 | Method for passivating a metallic surface |
| CN108193208A (en) * | 2018-01-24 | 2018-06-22 | 合肥铭佑高温技术有限公司 | A kind of high-temperature service corrosion inhibiter and preparation method thereof |
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