CN114921776B - Aluminum chromium-free fluoride-free film passivating agent and preparation and use methods thereof - Google Patents
Aluminum chromium-free fluoride-free film passivating agent and preparation and use methods thereof Download PDFInfo
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- CN114921776B CN114921776B CN202110743160.5A CN202110743160A CN114921776B CN 114921776 B CN114921776 B CN 114921776B CN 202110743160 A CN202110743160 A CN 202110743160A CN 114921776 B CN114921776 B CN 114921776B
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- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 title claims abstract description 77
- 229910052782 aluminium Inorganic materials 0.000 title claims abstract description 77
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- 238000000034 method Methods 0.000 title claims abstract description 15
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 77
- 238000005260 corrosion Methods 0.000 claims abstract description 33
- 230000007797 corrosion Effects 0.000 claims abstract description 33
- 229910019142 PO4 Inorganic materials 0.000 claims abstract description 32
- 239000010452 phosphate Substances 0.000 claims abstract description 32
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims abstract description 32
- 239000002738 chelating agent Substances 0.000 claims abstract description 30
- 239000003112 inhibitor Substances 0.000 claims abstract description 28
- 230000000149 penetrating effect Effects 0.000 claims abstract description 24
- 238000005507 spraying Methods 0.000 claims abstract description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000002994 raw material Substances 0.000 claims abstract description 8
- 238000004519 manufacturing process Methods 0.000 claims abstract description 3
- 239000011248 coating agent Substances 0.000 claims description 23
- 238000000576 coating method Methods 0.000 claims description 23
- 238000003756 stirring Methods 0.000 claims description 18
- 239000000843 powder Substances 0.000 claims description 14
- 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 11
- 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
- WVLBCYQITXONBZ-UHFFFAOYSA-N trimethyl phosphate Chemical compound COP(=O)(OC)OC WVLBCYQITXONBZ-UHFFFAOYSA-N 0.000 claims description 9
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 8
- 239000002736 nonionic surfactant Substances 0.000 claims description 8
- 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 7
- JBJMZCVEBLDYCA-UHFFFAOYSA-N didodecyl butanedioate Chemical group CCCCCCCCCCCCOC(=O)CCC(=O)OCCCCCCCCCCCC JBJMZCVEBLDYCA-UHFFFAOYSA-N 0.000 claims description 7
- 238000001035 drying Methods 0.000 claims description 7
- 239000007788 liquid Substances 0.000 claims description 6
- 238000005554 pickling Methods 0.000 claims description 6
- 238000002791 soaking Methods 0.000 claims description 6
- 239000000758 substrate Substances 0.000 claims description 6
- 238000005406 washing Methods 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 5
- CQCXMYUCNSJSKG-UHFFFAOYSA-N 1-dimethoxyphosphorylethene Chemical compound COP(=O)(OC)C=C CQCXMYUCNSJSKG-UHFFFAOYSA-N 0.000 claims description 4
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 4
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 claims description 4
- NYYLZXREFNYPKB-UHFFFAOYSA-N 1-[ethoxy(methyl)phosphoryl]oxyethane Chemical compound CCOP(C)(=O)OCC NYYLZXREFNYPKB-UHFFFAOYSA-N 0.000 claims 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 claims description 3
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 3
- SUHOOTKUPISOBE-UHFFFAOYSA-N O-phosphoethanolamine Chemical compound NCCOP(O)(O)=O SUHOOTKUPISOBE-UHFFFAOYSA-N 0.000 claims description 3
- 229940058182 aminoethylphosphinic acid Drugs 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
- 150000001642 boronic acid derivatives Chemical class 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
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 3
- 150000002826 nitrites Chemical class 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
- 150000004760 silicates Chemical class 0.000 claims description 3
- 229940080258 tetrasodium iminodisuccinate Drugs 0.000 claims description 3
- 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 claims description 3
- LSGOVYNHVSXFFJ-UHFFFAOYSA-N vanadate(3-) Chemical class [O-][V]([O-])([O-])=O LSGOVYNHVSXFFJ-UHFFFAOYSA-N 0.000 claims description 3
- 238000002161 passivation Methods 0.000 abstract description 13
- 239000000853 adhesive Substances 0.000 abstract description 8
- 230000001070 adhesive effect Effects 0.000 abstract description 8
- 239000008233 hard water Substances 0.000 abstract description 6
- 239000000463 material Substances 0.000 description 18
- 230000000694 effects Effects 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- 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
- YAXXOCZAXKLLCV-UHFFFAOYSA-N 3-dodecyloxolane-2,5-dione Chemical compound CCCCCCCCCCCCC1CC(=O)OC1=O YAXXOCZAXKLLCV-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
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- XTOQOJJNGPEPMM-UHFFFAOYSA-N o-(2-oxo-1,3,2$l^{5}-dioxaphosphinan-2-yl)hydroxylamine Chemical group NOP1(=O)OCCCO1 XTOQOJJNGPEPMM-UHFFFAOYSA-N 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- DREPONDJUKIQLX-UHFFFAOYSA-N 1-[ethenyl(ethoxy)phosphoryl]oxyethane Chemical compound CCOP(=O)(C=C)OCC DREPONDJUKIQLX-UHFFFAOYSA-N 0.000 description 2
- MJJJJEUEZVGFLW-UHFFFAOYSA-N 2-dodecyl-2-sulfobutanedioic acid Chemical compound CCCCCCCCCCCCC(S(O)(=O)=O)(C(O)=O)CC(O)=O MJJJJEUEZVGFLW-UHFFFAOYSA-N 0.000 description 2
- ZJFCVUTYZHUNSW-UHFFFAOYSA-N 3-octadecyloxolane-2,5-dione Chemical compound CCCCCCCCCCCCCCCCCCC1CC(=O)OC1=O ZJFCVUTYZHUNSW-UHFFFAOYSA-N 0.000 description 2
- QXNVGIXVLWOKEQ-UHFFFAOYSA-N Disodium Chemical compound [Na][Na] QXNVGIXVLWOKEQ-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 239000003945 anionic surfactant Substances 0.000 description 2
- 239000003093 cationic surfactant Substances 0.000 description 2
- 239000012467 final product Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 239000002888 zwitterionic surfactant Substances 0.000 description 2
- FDGBQHCDMSYZRC-UHFFFAOYSA-N 2-hydroxy-2-oxo-1,3,2$l^{5}-dioxaphosphinan-4-amine Chemical compound NC1CCOP(O)(=O)O1 FDGBQHCDMSYZRC-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 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 description 1
- 239000004411 aluminium Substances 0.000 description 1
- 230000009286 beneficial effect 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
- VONWDASPFIQPDY-UHFFFAOYSA-N dimethyl methylphosphonate Chemical group COP(C)(=O)OC VONWDASPFIQPDY-UHFFFAOYSA-N 0.000 description 1
- 238000000295 emission spectrum Methods 0.000 description 1
- WEIQRLLXVVSKIL-UHFFFAOYSA-N ethyl 2,2-diethyl-3-oxobutanoate Chemical compound CCOC(=O)C(CC)(CC)C(C)=O WEIQRLLXVVSKIL-UHFFFAOYSA-N 0.000 description 1
- 125000003916 ethylene diamine group Chemical group 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229940098458 powder spray Drugs 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 125000001424 substituent group Chemical group 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 an aluminum chromium-free fluoride-free film passivating agent, 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. The aluminum chromium-free fluoride-free film passivating agent can enable a spray coating to have good adhesive force on the surface of the aluminum, is not influenced by the quality of hard water, achieves chromium-free fluoride-free passivation through a special process combination by adding phosphate, chelating agent, penetrating agent and corrosion inhibitor into a film forming agent, and is safer, more environment-friendly and environment-friendly in production and preparation process.
Description
Technical Field
The invention relates to an aluminum chromium-free fluoride-free film passivating agent 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 passivation of the surface of the aluminum material and reduce corrosion of the external environment to the aluminum material, the surface of the aluminum material needs to be treated, a layer of passivating agent is applied, and the adhesive force of the aluminum material and the powder spraying coating in the later period is not influenced, so that the hard water resistance and the impact resistance of the spraying coating are stronger. The existing passivating agent can achieve a chromium-free process, but fluorine still exists, and the complete green, safe and environment-friendly effect cannot be achieved.
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 an aluminum material chromium-free fluoride-free film passivating agent, which is prepared from 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.
As a preferred embodiment, the molecular structure of the phosphate isWherein 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 a combination of more of diethyl benzyl phosphate, dioctyl phenyl phosphonate, dimethyl vinyl phosphonate, diethyl vinyl phosphate, diethyl methyl phosphonate and methyl dimethyl phosphate.
As a preferred embodiment, the chelating agent is selected from one or a combination of several of aminotrimethylene phosphonic acid, iminodisuccinic acid, pentasodium aminotrimethylene phosphonic acid, aminoethylphosphinic acid, 2-aminoethylphosphoric acid, ethylenediamine tetramethylene phosphoric acid, tetrasodium iminodisuccinate.
As a preferred embodiment, the penetrating agent is selected from one or a combination of several of cationic surfactants, anionic surfactants, nonionic surfactants, and zwitterionic surfactants.
As a preferred embodiment, the nonionic surfactant is selected from one or a combination of several of lauryl sulfosuccinic acid monoester disodium, dilauryl succinate, diethyl acetylsuccinate, dodecyl succinic anhydride, octadecyl succinic anhydride, and mono-tert-butyl succinate.
As a preferred embodiment, the corrosion inhibitor is selected from one or a combination of a plurality of borates, molybdates, tungstates, vanadates, nitrites, orthophosphates and silicates.
As a preferred embodiment, the weight ratio of the phosphate to the chelating agent is 1: (0.1-0.16).
The second aspect of the invention provides a preparation method of an aluminum chromium-free fluoride-free coating passivating agent, which comprises the following steps:
(1) Adding the chelating agent into a stirrer, and stirring at a rotation speed of 5000-1000r/min for 30-60min;
(2) Slowly adding the penetrating agent and the corrosion inhibitor, and continuously stirring for 1-1.5h;
(3) Adding phosphate, and stirring for 1-2 h.
The third aspect of the invention provides a use method of an aluminum chromium-free fluoride-free coating passivating agent, which comprises the following steps:
(1) Deoiling, dedusting, pickling and washing the aluminum substrate;
(2) Adding the prepared chromium-free fluoride-free coating passivating agent into a liquid tank;
(3) And (3) putting the aluminum plate into a passivating agent tank liquor, soaking for 0.5-1min, taking out and drying, and spraying powder within 72 h.
Compared with the prior art, the invention has the following beneficial effects:
(1) The aluminum chromium-free fluoride-free film passivating agent can enable a spray coating to have good adhesive force on the surface of the aluminum, and is not influenced by the quality of hard water.
(2) According to the aluminum chromium-free fluorine-free film passivating agent, phosphate, chelating agent, penetrating agent and corrosion inhibitor are added into the film forming agent, and the chromium-free fluorine-free passivation is achieved through a special process combination, so that the production and preparation process is safer, green and environment-friendly.
(3) The aluminum chromium-free fluoride-free coating passivating agent can enable the aluminum 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 an aluminum material chromium-free fluoride-free film passivating agent, which is prepared from 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.
As a preferred embodiment, the molecular structure of the phosphate isWherein 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 a combination of more of diethyl benzyl phosphate, dioctyl phenyl phosphonate, dimethyl vinyl phosphonate, diethyl vinyl phosphate, diethyl methyl phosphonate and methyl dimethyl phosphate.
As a preferred embodiment, the phosphate is dimethyl methylphosphonate.
As a preferred embodiment, the chelating agent is selected from one or a combination of several of aminotrimethylene phosphonic acid, iminodisuccinic acid, pentasodium aminotrimethylene phosphonic acid, aminoethylphosphinic acid, 2-aminoethylphosphoric acid, ethylenediamine tetramethylene phosphoric acid, tetrasodium iminodisuccinate.
As a preferred embodiment, the chelating agents are aminotrimethylene phosphonic acid and iminodisuccinic acid.
As a preferred embodiment, the weight ratio of the aminotrimethylene phosphonic acid to the iminodisuccinic acid is 1: (0.5-1).
As a preferred embodiment, the penetrating agent is selected from one or a combination of several of cationic surfactants, anionic surfactants, nonionic surfactants, and zwitterionic surfactants.
As a preferred embodiment, the penetrant is a nonionic surfactant.
As a preferred embodiment, the nonionic surfactant is selected from one or a combination of several of lauryl sulfosuccinic acid monoester disodium, dilauryl succinate, diethyl acetylsuccinate, dodecyl succinic anhydride, octadecyl succinic anhydride, and mono-tert-butyl succinate.
As a preferred embodiment, the nonionic surfactants are dilauryl succinate and diethyl acetoacetate and mono-t-butyl succinate.
As a preferred embodiment, the weight ratio of dilauryl succinate to diethyl acetylsuccinate to mono-tert-butylsuccinate is 1: (1-2): (0.2-0.5).
The applicant finds that the adhesive force of the passivating agent can be improved and the falling-off of the aluminum surface powder body can be reduced by adding a small amount of penetrating agent in the experimental process. The possible reasons for the guess are: the penetrating agent can be arranged on the surface of the aluminum plate in an oriented way, 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 further found that the use of penetrants with a high foaming capacity would instead result in a reduced adhesion of the powder spray to the aluminium sheet, presumably for the following reasons: the penetrating agent generates bubbles on the surface of the aluminum plate, and air is introduced to enable gaps to appear between the aluminum plate and the passivating agent, so that adhesive force is reduced, and further the spraying effect of the powder is affected.
As a preferred embodiment, the corrosion inhibitor is selected from one or a combination of a plurality of borates, molybdates, tungstates, vanadates, nitrites, orthophosphates and silicates.
As a preferred embodiment, the corrosion inhibitor is boric acid.
As a preferred embodiment, the boric acid has a particle size of 200-500 mesh.
As a preferred embodiment, the weight ratio of the phosphate to the chelating agent is 1: (0.1-0.16).
The applicant finds that the phosphate is methyl dimethyl phosphate, the chelating agent is amino trimethylene phosphate and imino disuccinic acid, and the prepared passivating agent is applied to an aluminum plate, so that the corrosion resistance is greatly improved, and the passivating agent has excellent adhesive force with the aluminum plate. The possible reasons for the guess are: the phosphate can be bonded with the aluminum plate, one hydroxyl group on the phosphate is combined with hydrogen, and H generated by the combination of the hydroxyl group and the hydrogen in the drying process 2 O is removed, and the rest hydroxyl groups on the phosphate are combined with the powder sprayed later, so that the aluminum plate and the powder sprayed are combined together through chemical bonds, and the acting force is firmer. And the applicant found during the experiment that the chelating agents of aminotrimethylene phosphate and iminodisuccinic acid were added to the system, the weight ratio of methyl dimethyl phosphate to chelating agent was 1: (0.1-0.16) can further increase the passivation efficiency of the aluminum plate, delay the corrosion of the aluminum plate, and the possible reasons are suspected to be: the effect of methyl dimethyl phosphate and amino trimethylene phosphate increases the stability of the complex, the length of bridge connection between suitable chelating groups increases passivation efficiency, and the fact that the ratio of methyl dimethyl phosphate to amino trimethylene phosphate is not within the preferred weight ratio may lead to excessive steric hindrance between substituents, which may instead reduce the corresponding passivation performance.
The second aspect of the invention provides a preparation method of an aluminum chromium-free fluoride-free coating passivating agent, which comprises the following steps:
(1) Adding the chelating agent into a stirrer, and stirring at a rotation speed of 5000-1000r/min for 30-60min;
(2) Slowly adding the penetrating agent and the corrosion inhibitor, and continuously stirring for 1-1.5h;
(3) Adding phosphate, and stirring for 1-2 h.
In the preparation process of the chromium-free fluorine-free coating passivating agent for the aluminum material, the adding speed of the penetrating agent and the corrosion inhibitor is slower, so that more bubbles are avoided, if the bubbles possibly cause uneven passivation when the surface of the aluminum material is passivated, the bubbles prevent the film forming on the surface of the aluminum material, the pitting phenomenon on the surface of the aluminum material possibly occurs, and the service performance of the aluminum material is affected.
The third aspect of the invention provides a use method of an aluminum chromium-free fluoride-free coating passivating agent, which comprises the following steps:
(1) Deoiling, dedusting, pickling and washing the aluminum substrate;
(2) Adding the prepared chromium-free fluoride-free coating passivating agent into a liquid tank;
(3) And (3) putting the aluminum plate into a passivating agent tank liquor, soaking for 0.5-1min, taking out and drying, and spraying powder within 72 h.
The present invention will be specifically described below by way of examples. It is noted herein that the following examples are given solely for the purpose of further illustration and are not to be construed as limitations on the scope of the invention, as will be apparent to those skilled in the art in light of the foregoing disclosure.
In addition, the raw materials used are commercially available unless otherwise indicated.
Example 1
The aluminum chromium-free fluoride-free film passivating agent 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 methyl dimethyl phosphate.
The chelating agent is amino trimethylene phosphonic acid and iminodisuccinic acid, and the weight ratio is 1:0.7.
the penetrating agent is dilauryl succinate, diethyl acetylsuccinate and mono-tert-butyl succinate, and the weight ratio is 1:1.5:0.4.
the corrosion inhibitor is boric acid, the grain diameter is 200 meshes, and the corrosion inhibitor is purchased from Milin reagent company, and the model is B887055.
The preparation method of the aluminum chromium-free fluoride-free film passivating agent comprises the following steps:
(1) Adding the chelating agent into a stirrer, and stirring for 40min at a rotation speed of 5000 r/min;
(2) Slowly adding the penetrating agent and the corrosion inhibitor, and continuously stirring for 1h;
(3) Adding phosphate, and stirring for 1.5 h.
The application method of the aluminum chromium-free fluoride-free coating passivating agent comprises the following steps:
(1) Deoiling, dedusting, pickling and washing the aluminum substrate;
(2) Adding the prepared chromium-free fluoride-free coating passivating agent into a liquid tank;
(3) And (3) putting the aluminum plate into a passivating agent tank liquor, soaking for 1min, taking out, drying, and standing for 70h for powder spraying.
Example 2
The aluminum chromium-free fluoride-free film passivating agent comprises the following preparation 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 methyl dimethyl phosphate.
The chelating agent is amino trimethylene phosphonic acid and iminodisuccinic acid, and the weight ratio is 1: (0.5-1).
The corrosion inhibitor is boric acid, the grain diameter is 200 meshes, and the corrosion inhibitor is purchased from Milin reagent company, and the model is B887055.
The preparation method of the aluminum chromium-free fluoride-free film passivating agent comprises the following steps:
(1) Adding the chelating agent into a stirrer, and stirring at a rotating speed of 7000r/min for 30min;
(2) Slowly adding the penetrating agent and the corrosion inhibitor, and continuously stirring for 1.5h;
(3) Adding phosphate, and stirring for 2h to obtain the final product.
The application method of the aluminum chromium-free fluoride-free coating passivating agent comprises the following steps:
(1) Deoiling, dedusting, pickling and washing the aluminum substrate;
(2) Adding the prepared chromium-free fluoride-free coating passivating agent into a liquid tank;
(3) And (3) putting the aluminum plate into a passivating agent tank solution, soaking for 50s, taking out, drying, and standing for 72h for powder spraying.
Example 3
The aluminum chromium-free fluoride-free film passivating agent comprises the following preparation 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 phosphoric acid and iminodisuccinic acid tetrasodium, and the weight ratio is 1:0.75.
the penetrating agent is dilauryl succinate, dodecyl succinic anhydride and mono-tert-butyl succinate, and the weight ratio is 1:1.5:0.3.
the corrosion inhibitor is boric acid, the particle size is 500 meshes, and the corrosion inhibitor is purchased from Milin reagent company, and the model is B887054.
The preparation method of the aluminum chromium-free fluoride-free film passivating agent comprises the following steps:
(1) Adding the chelating agent into a stirrer, and stirring for 40min at a rotation speed of 5000 r/min;
(2) Slowly adding the penetrating agent and the corrosion inhibitor, and continuously stirring for 1h;
(3) Adding phosphate, and stirring for 1h to obtain the final product.
The application method of the aluminum chromium-free fluoride-free coating passivating agent comprises the following steps:
(1) Deoiling, dedusting, pickling and washing the aluminum substrate;
(2) Adding the prepared chromium-free fluoride-free coating passivating agent into a liquid tank;
(3) And (3) putting the aluminum plate into a passivating agent tank liquor, soaking for 1min, taking out, drying, and standing for 72h for powder spraying.
Example 4
The specific steps of the aluminum chromium-free fluoride-free film passivating agent and the preparation and use method are the same as those of the example 1, and the chelating agent is amino trimethylene phosphonic acid, and the weight part of the chelating agent is 0.4 part.
Example 5
The specific steps of the aluminum chromium-free fluoride-free film passivating agent and the preparation and use method are the same as those of the example 1, and the difference is that the corrosion inhibitor is boric acid and the weight part of the corrosion inhibitor is 0.5 part.
Performance testing
1. Hard water resistance adhesion test: the effect on the adhesion of the aluminum material was tested by replacing the water in the passivation tank with hard water having a hardness of 800 by deionized water.
2. Acid resistance adhesion test: a0.025% hydrochloric acid solution was added to the passivation tank to test the effect on the adhesion of the aluminum material.
3. Test of the effect of the time of placement on adhesion: and placing the passivated aluminum material for a period of time, and observing the influence of the placement for 72 hours on the adhesive force of the aluminum material.
4. Passivation effect test: the aluminum panels were treated with the passivating agents of examples 1-5 and observed for appearance after spraying.
The adhesive force after the board is printed is used as a judgment basis. The adhesion performance index was determined to be 0 to 5, and the greater the number, the stronger the adhesion, and the results of the above-described test were shown in table 1.
The adhesion rating is illustrated below:
TABLE 1
| Hard water resistance | Acid adhesion resistance | Adhesion after 72h of standing | |
| 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 | Grade 4 |
The glow discharge-emission spectrum results before the powder coating was not applied showed the presence of elements of P, zr, O, al on the surface of the base layer, free of chromium and fluorine.
The performance test of example 1 after powder spraying was tested according to national standards, and the results are shown in table 2.
TABLE 2
Claims (7)
1. The aluminum chromium-free fluoride-free coating passivating agent is characterized by comprising 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.
The penetrating agent is a nonionic surfactant; the nonionic surfactant is dilauryl succinate, diethyl acetylsuccinate and mono-tert-butyl succinate, and the weight ratio is 1: (1-2): (0.2-0.5);
the weight ratio of the phosphate to the chelating agent is 1: (0.1-0.16).
2. The aluminum chromium-free fluorine-free coating passivating agent according to claim 1, wherein the molecular structure of the phosphate isWherein R is selected from one or a combination of a plurality of methyl, phenyl, ethyl and propyl.
3. The aluminum chromium-free and fluorine-free coating passivating agent according to claim 1, wherein the phosphate is selected from one or a combination of a plurality of benzyl diethyl phosphate, dioctyl phenyl phosphonate, dimethyl vinyl phosphonate, diethyl methyl phosphonate and methyl dimethyl phosphate.
4. The aluminum chromium-free fluorine-free coating passivating agent according to claim 1, wherein the chelating agent is selected from one or a combination of several of amino trimethylene phosphonic acid, iminodisuccinic acid, pentasodium amino trimethylene phosphonic acid, aminoethylphosphinic acid, 2-aminoethylphosphoric acid, ethylenediamine tetramethylene phosphoric acid, and tetrasodium iminodisuccinate.
5. The aluminum chromium-free fluorine-free coating passivating agent according to claim 1, wherein the corrosion inhibitor is selected from one or a combination of a plurality of borates, molybdates, tungstates, vanadates, nitrites, orthophosphates and silicates.
6. A method for producing the aluminum chromium-free fluorine-free film passivating agent according to any one of claims 1 to 5, characterized by comprising the steps of:
(1) Adding the chelating agent into a stirrer, and stirring at a rotation speed of 5000-1000r/min for 30-60min;
(2) Slowly adding the penetrating agent and the corrosion inhibitor, and continuously stirring for 1-1.5h;
(3) Adding phosphate, and stirring for 1-2 h.
7. A method of using the aluminum chromium-free fluorine-free film passivating agent of any one of claims 1-5, comprising the steps of:
(1) Deoiling, dedusting, pickling and washing the aluminum substrate;
(2) Adding the prepared chromium-free fluoride-free coating passivating agent into a liquid tank;
(3) And (3) putting the aluminum plate into a passivating agent tank liquor, soaking for 0.5-1min, taking out and drying, and spraying powder within 72 h.
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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 |
| 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 |
-
2021
- 2021-07-01 CN CN202110743160.5A patent/CN114921776B/en active Active
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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