CN112030152B - Chromium-free passivation method for surface of galvanized layer - Google Patents
Chromium-free passivation method for surface of galvanized layer Download PDFInfo
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- 238000002161 passivation Methods 0.000 title claims abstract description 88
- 238000000034 method Methods 0.000 title claims abstract description 49
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 63
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 54
- 239000007788 liquid Substances 0.000 claims abstract description 44
- 229920000642 polymer Polymers 0.000 claims abstract description 40
- 239000011248 coating agent Substances 0.000 claims abstract description 34
- 238000000576 coating method Methods 0.000 claims abstract description 34
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims abstract description 33
- 229910000077 silane Inorganic materials 0.000 claims abstract description 33
- 238000006243 chemical reaction Methods 0.000 claims abstract description 28
- 239000011203 carbon fibre reinforced carbon Substances 0.000 claims abstract description 22
- 239000006087 Silane Coupling Agent Substances 0.000 claims abstract description 20
- 239000002131 composite material Substances 0.000 claims abstract description 17
- 238000005260 corrosion Methods 0.000 claims abstract description 14
- 230000007797 corrosion Effects 0.000 claims abstract description 14
- IMQLKJBTEOYOSI-GPIVLXJGSA-N Inositol-hexakisphosphate Chemical compound OP(O)(=O)O[C@H]1[C@H](OP(O)(O)=O)[C@@H](OP(O)(O)=O)[C@H](OP(O)(O)=O)[C@H](OP(O)(O)=O)[C@@H]1OP(O)(O)=O IMQLKJBTEOYOSI-GPIVLXJGSA-N 0.000 claims abstract description 12
- IMQLKJBTEOYOSI-UHFFFAOYSA-N Phytic acid Natural products OP(O)(=O)OC1C(OP(O)(O)=O)C(OP(O)(O)=O)C(OP(O)(O)=O)C(OP(O)(O)=O)C1OP(O)(O)=O IMQLKJBTEOYOSI-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000012298 atmosphere Substances 0.000 claims abstract description 12
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 12
- MEFBJEMVZONFCJ-UHFFFAOYSA-N molybdate Chemical compound [O-][Mo]([O-])(=O)=O MEFBJEMVZONFCJ-UHFFFAOYSA-N 0.000 claims abstract description 12
- 229940068041 phytic acid Drugs 0.000 claims abstract description 12
- 235000002949 phytic acid Nutrition 0.000 claims abstract description 12
- 239000000467 phytic acid Substances 0.000 claims abstract description 12
- 238000003756 stirring Methods 0.000 claims abstract description 12
- 239000006185 dispersion Substances 0.000 claims abstract description 11
- 239000000178 monomer Substances 0.000 claims abstract description 10
- 238000012644 addition polymerization Methods 0.000 claims abstract description 6
- 238000002156 mixing Methods 0.000 claims abstract description 6
- 230000035484 reaction time Effects 0.000 claims description 15
- 230000000694 effects Effects 0.000 claims description 10
- 239000001257 hydrogen Substances 0.000 claims description 6
- 229910052739 hydrogen Inorganic materials 0.000 claims description 6
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 6
- 230000005764 inhibitory process Effects 0.000 claims description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 5
- 239000001301 oxygen Substances 0.000 claims description 5
- 229910052760 oxygen Inorganic materials 0.000 claims description 5
- 150000004756 silanes Chemical class 0.000 claims description 5
- CBOIHMRHGLHBPB-UHFFFAOYSA-N hydroxymethyl Chemical compound O[CH2] CBOIHMRHGLHBPB-UHFFFAOYSA-N 0.000 claims description 4
- 125000003545 alkoxy group Chemical group 0.000 claims description 3
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 2
- 125000000217 alkyl group Chemical group 0.000 claims description 2
- 229910052799 carbon Inorganic materials 0.000 claims description 2
- 229910002091 carbon monoxide Inorganic materials 0.000 claims description 2
- -1 methoxy, ethoxy Chemical group 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- 125000002572 propoxy group Chemical group [*]OC([H])([H])C(C([H])([H])[H])([H])[H] 0.000 claims description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 abstract description 3
- 230000007935 neutral effect Effects 0.000 abstract description 3
- 238000007747 plating Methods 0.000 abstract description 3
- 238000002360 preparation method Methods 0.000 abstract description 3
- 150000003839 salts Chemical class 0.000 abstract description 3
- 239000011701 zinc Substances 0.000 abstract description 3
- 229910052725 zinc Inorganic materials 0.000 abstract description 3
- 239000010410 layer Substances 0.000 description 82
- 239000000243 solution Substances 0.000 description 39
- 230000000052 comparative effect Effects 0.000 description 9
- 229910052751 metal Inorganic materials 0.000 description 9
- 239000002184 metal Substances 0.000 description 9
- 230000009471 action Effects 0.000 description 3
- FWDBOZPQNFPOLF-UHFFFAOYSA-N ethenyl(triethoxy)silane Chemical group CCO[Si](OCC)(OCC)C=C FWDBOZPQNFPOLF-UHFFFAOYSA-N 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 239000007769 metal material Substances 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- CREMABGTGYGIQB-UHFFFAOYSA-N carbon carbon Chemical compound C.C CREMABGTGYGIQB-UHFFFAOYSA-N 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000005886 esterification reaction Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000011241 protective layer Substances 0.000 description 2
- 239000002344 surface layer Substances 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229910002808 Si–O–Si Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- JOPOVCBBYLSVDA-UHFFFAOYSA-N chromium(6+) Chemical compound [Cr+6] JOPOVCBBYLSVDA-UHFFFAOYSA-N 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 238000005536 corrosion prevention Methods 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 150000002431 hydrogen Chemical group 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 125000001165 hydrophobic group Chemical group 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000012044 organic layer Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000010998 test method Methods 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
- C23C22/40—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 molybdates, tungstates or vanadates
-
- 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
- C23C22/48—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 not containing phosphates, hexavalent chromium compounds, fluorides or complex fluorides, molybdates, tungstates, vanadates or oxalates
- C23C22/53—Treatment of zinc or alloys based thereon
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- 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)
- Other Surface Treatments For Metallic Materials (AREA)
Abstract
The invention discloses a chromium-free passivation method for the surface of a galvanized layer, which comprises the following steps: (1) mixing phytic acid, molybdate and a silane coupling agent with an active group containing a carbon-carbon double bond, and uniformly stirring to obtain a solution A; preparing a polymer liquid of which the monomer at least contains two carbon-carbon double bonds and one hydroxyl, wherein the polymer is generated by addition polymerization reaction of one carbon-carbon double bond, and the polymer is a liquid B; preparing a graphene oxide dispersion liquid which is a liquid C; (2) sequentially placing the galvanized coating piece into A, B, C liquid for reaction to obtain the galvanized coating piece with a silane film-polymer-graphene oxide composite passivation layer on the surface; (3) and placing the plated piece in a reducing atmosphere for reaction to obtain the galvanized layer plated piece with the silane film-polymer-graphene composite passivation layer on the surface. The preparation process is simple and economical, the corrosion resistance time of the neutral salt fog of the prepared zinc coating plating piece compounded with the passivation layer is about 700h, the adhesion is first grade, and the electrode potential can reach + 1.4V.
Description
Technical Field
The invention relates to the technical field of metal corrosion prevention, in particular to a chromium-free passivation method for the surface of a galvanized layer.
Background
Because the metal material has strong activity, the common galvanized coating piece is easily oxidized by oxidizing gas or liquid in the environment during the use process, so researchers can compound a protective layer on the metal surface. The protective layer has a cathode protection method of a sacrificial anode, such as plating a layer of metal material with better activity; the other protection method is to compound a passivation layer with poorer activity, such as an oxide layer, an organic-inorganic composite layer and the like, wherein hexavalent chromium or trivalent chromium is most commonly used to oxidize the surface of the coating layer into a compact protective film, but the chromium element used in the method causes environmental pollution, so that the chromium-free passivation method is the development trend in the future. For example, CN201810669324.2 discloses a silane/graphene oxide composite passivation solution and a preparation method and application thereof, in which a metal material is immersed in a mixed solution of a silane coupling agent and graphene oxide to obtain a passivation layer, so as to realize passivation by organic and inorganic composite, but this method is performed by one-time immersion, both hydroxyl groups after silane hydrolysis and hydroxyl groups on the surface of graphene oxide may interact with metal, the material on the surface of the passivation layer is uncertain, and if the organic layer is scratched, the passivation solution is easily damaged, and the impermeability and wear resistance of graphene oxide cannot be fully exerted; meanwhile, the pH value of the passivation solution can reach 2, and the metal surface is etched due to too strong acidity, so that the finally formed passivation layer is not firm and uniform enough. Therefore, the development of a method for preparing a passivation layer with uniformity, compactness, strong bonding force and excellent wear resistance on the surface of a zinc coating is an urgent need.
Disclosure of Invention
The present invention is directed to a chromium-free passivation method for the surface of a galvanized layer to solve the above-mentioned problems of the background art.
In order to solve the technical problems, the invention provides the following technical scheme: a chromium-free passivation method for the surface of a galvanized layer comprises the following steps:
(1) mixing and uniformly stirring phytic acid, molybdate and a silane coupling agent of which an active group contains a carbon-carbon double bond, wherein the concentration of the phytic acid is 10-50mL/L, the concentration of the molybdate is 0.1-1.5g/L, and the concentration of the silane coupling agent is 10-80mL/L, and the solution is solution A; preparing a polymer liquid of which the monomer at least contains two carbon-carbon double bonds and one hydroxyl, wherein the polymer is generated by addition polymerization reaction of one carbon-carbon double bond, and the polymer is a liquid B; preparing a graphene oxide dispersion liquid with the concentration of 0.05-1 wt%, wherein the graphene oxide dispersion liquid is a liquid C;
(2) putting the galvanized coating piece into the solution A to react to form a silane film with a corrosion inhibition effect; then placing the plated part in the solution B to react to obtain an unsaturated polymer modified silane film; finally, the plated part is placed in the solution C to react to obtain a galvanized layer plated part with a silane film-polymer-graphene oxide composite passivation layer on the surface;
firstly, a galvanized coating piece reacts with a solution A containing a silane coupling agent, on one hand, silane molecules are combined with a metal surface layer after being hydrolyzed by alkoxy groups of the silane molecules, meanwhile, the silane molecules form a three-dimensional reticular passive film through Si-O-Si bonding, and phytic acid and molybdate with a corrosion inhibition effect are wrapped inside the silane molecules; however, the net structure among silane molecules cannot bear the long-term action of the corrosive liquid, so on the other hand, unsaturated double bonds contained in active groups in the silane coupling agent can react with carbon-carbon double bonds of polymers in the liquid B to form carbon-carbon single bonds, and the carbon-carbon single bonds are connected with the polymers in a covalent bond mode to form a stable structure, and a polymer layer can effectively fill up gaps of a silane film and increase the compactness and the hydrophobicity of the silane film; and finally, the exposed hydroxyl on the surface of the polymer can be subjected to dehydration esterification reaction with graphene oxide containing a large number of carboxyl groups on the surface, the graphene oxide with a stable six-membered ring structure is compounded on the surface of the passivation layer, and the finally prepared composite passivation layer can remarkably improve the wear resistance and the compactness.
(3) And placing the plated piece in a reducing atmosphere for reaction to obtain the galvanized layer plated piece with the silane film-polymer-graphene composite passivation layer on the surface.
On one hand, the step can solve the problem that the conventional passivation layer is not conductive or poor in conductivity, the passivation layer with the surface layer being graphene can be obtained by performing reducing atmosphere treatment on the passivation layer according to actual needs, the graphene layer also has the wear resistance and compactness of graphene oxide, and the hydrophobicity of the graphene layer can be improved after reduction; on the other hand, because the uniform and compact silane film layer and the polymer layer are arranged between the graphene layer and the metal surface to play an insulating role, the problem that the metal layer is etched due to the fact that the graphene is directly contacted with the metal to form a primary battery is avoided.
Further, the alkoxy group of the silane coupling agent can be one or a combination of methoxy, ethoxy and propoxy.
Further, the monomers of the polymer liquid contain at least one hydroxyl group, and the rest groups are all hydrogen groups or alkyl groups with the carbon content of 1-10.
Except that the polymer monomer at least contains one hydroxyl group which needs to be reacted, the rest groups are hydrophobic groups, so that the problem of corrosive liquid permeation after the graphene or graphene oxide layer is damaged can be avoided, and the polymer monomer can continuously play an isolation role.
Further, the oxygen content of the graphene oxide is 25 at% or more.
Furthermore, the number of layers of the graphene oxide is 3-10, and the transverse dimension is 1-4 μm.
Further, the reaction temperature of the galvanized coating piece in the solution A is 35-50 ℃, and the reaction time is 1-5 min.
Further, the reaction temperature of the galvanized coating in the solution B is 70-90 ℃, and the reaction time is 30-60 min.
Further, the reaction temperature of the galvanized coating piece in the solution C is 50-80 ℃, and the reaction time is 3-10 min.
Further, the stirring speed is 300-.
Further, the reducing atmosphere is hydrogen, carbon monoxide or a mixture of the two.
Compared with the prior art, the invention has the following beneficial effects:
(1) according to the invention, the silane film layer and the polymer layer are connected in a manner of mutual reaction between carbon-carbon double bonds, and the polymer layer can effectively fill the gap of the silane film layer, so that the uniformity and compactness of the passivation layer are improved; and then the polymer layer is combined with the graphene oxide layer through esterification reaction, so that the problem of poor stability of the passivation layer in the prior art is solved.
(2) According to the invention, the graphene oxide is compounded on the outer surface of the organic passivation layer, so that the problem of poor binding force between the graphene oxide and the metal substrate is solved, and the corrosion resistance, compactness and structural stability of the graphene oxide can be effectively reflected on the outermost layer.
(3) The graphene oxide layer can be reduced according to actual use requirements, so that the conductivity and the hydrophobic property of the passivation layer are improved.
(4) The silane coupling agent, the graphene oxide and other materials used in the invention have wide sources and low prices, and the preparation process is simple and time-saving, thereby having wide application prospects.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example one
The invention provides a chromium-free passivation method for the surface of a galvanized layer, which comprises the following steps:
(1) mixing and uniformly stirring phytic acid, molybdate and a silane coupling agent of which an active group contains a carbon-carbon double bond, wherein the concentration of the phytic acid is 10mL/L, the concentration of the molybdate is 0.1g/L, and the concentration of the silane coupling agent is 10mL/L, and the solution is solution A; preparing a polymer liquid of which the monomer at least contains two carbon-carbon double bonds and one hydroxyl, wherein the polymer is generated by addition polymerization reaction of one carbon-carbon double bond, and the polymer is a liquid B; preparing a graphene oxide dispersion liquid with the concentration of 0.05 wt%, wherein the graphene oxide dispersion liquid is a liquid C;
(2) putting the galvanized coating piece into the solution A to react to form a silane film with a corrosion inhibition effect; then placing the plated part in the solution B to react to obtain an unsaturated polymer modified silane film; finally, the plated part is placed in the solution C to react to obtain a galvanized layer plated part with a silane film-polymer-graphene oxide composite passivation layer on the surface;
(3) and placing the plated piece in a reducing atmosphere for reaction to obtain the galvanized layer plated piece with the silane film-polymer-graphene composite passivation layer on the surface.
Wherein the silane coupling agent is vinyltriethoxysilane; the polymer liquid is- [ -CH2-C(CH2OH)(CHCH2)-]n-; the oxygen content of the graphene oxide is 50 at%; the number of layers of the graphene oxide is 3, and the transverse size of the graphene oxide is 1 mu m; the reaction temperature of the galvanized coating piece in the solution A is 35 ℃, and the reaction time is 1 min; the reaction temperature of the galvanized coating piece in the solution B is 70 ℃, and the reaction time is 30 min; the reaction temperature of the galvanized coating piece in the solution C is 50 ℃, and the reaction time is 3 min; the stirring speed is 300r/min, and the time is 10 min; the reducing atmosphere is hydrogen.
Example two
The invention provides a chromium-free passivation method for the surface of a galvanized layer, which comprises the following steps:
(1) mixing and uniformly stirring phytic acid, molybdate and a silane coupling agent of which an active group contains a carbon-carbon double bond, wherein the concentration of the phytic acid is 50mL/L, the concentration of the molybdate is 1.5g/L, and the concentration of the silane coupling agent is 80mL/L, and the solution is solution A; preparing a polymer liquid of which the monomer at least contains two carbon-carbon double bonds and one hydroxyl, wherein the polymer is generated by addition polymerization reaction of one carbon-carbon double bond, and the polymer is a liquid B; preparing a graphene oxide dispersion liquid with the concentration of 1 wt%, wherein the graphene oxide dispersion liquid is a liquid C;
(2) putting the galvanized coating piece into the solution A to react to form a silane film with a corrosion inhibition effect; then placing the plated part in the solution B to react to obtain an unsaturated polymer modified silane film; finally, the plated part is placed in the solution C to react to obtain a galvanized layer plated part with a silane film-polymer-graphene oxide composite passivation layer on the surface;
(3) and placing the plated piece in a reducing atmosphere for reaction to obtain the galvanized layer plated piece with the silane film-polymer-graphene composite passivation layer on the surface.
Wherein the silane coupling agent is vinyltriethoxysilane; the polymer liquid is- [ -CH2-C(CH2OH)(CHCH2)-]n-; the oxygen content of the graphene oxide is 50 at%; the number of layers of the graphene oxide is 10, and the transverse dimension of the graphene oxide is 4 micrometers; the reaction temperature of the galvanized coating piece in the solution A is 50 ℃, and the reaction time is 5 min; the reaction temperature of the galvanized coating piece in the solution B is 90 ℃, and the reaction time is 60 min; the reaction temperature of the galvanized coating piece in the solution C is 80 ℃, and the reaction time is 10 min; the stirring speed is 2500r/min, and the time is 40 min; the reducing atmosphere is hydrogen.
EXAMPLE III
The invention provides a chromium-free passivation method for the surface of a galvanized layer, which comprises the following steps:
(1) mixing and uniformly stirring phytic acid, molybdate and a silane coupling agent of which an active group contains a carbon-carbon double bond, wherein the concentration of the phytic acid is 30mL/L, the concentration of the molybdate is 1g/L, and the concentration of the silane coupling agent is 50mL/L, and the solution is solution A; preparing a polymer liquid of which the monomer at least contains two carbon-carbon double bonds and one hydroxyl, wherein the polymer is generated by addition polymerization reaction of one carbon-carbon double bond, and the polymer is a liquid B; preparing a graphene oxide dispersion liquid with the concentration of 0.6 wt%, wherein the graphene oxide dispersion liquid is a liquid C;
(2) putting the galvanized coating piece into the solution A to react to form a silane film with a corrosion inhibition effect; then placing the plated part in the solution B to react to obtain an unsaturated polymer modified silane film; finally, the plated part is placed in the solution C to react to obtain a galvanized layer plated part with a silane film-polymer-graphene oxide composite passivation layer on the surface;
(3) and placing the plated piece in a reducing atmosphere for reaction to obtain the galvanized layer plated piece with the silane film-polymer-graphene composite passivation layer on the surface.
Wherein the silane coupling agent is vinyltriethoxysilane; the polymer liquid is- [ -CH2-C(CH2OH)(CHCH2)-]n-; the oxygen content of the graphene oxide is 50 at%; the number of layers of the graphene oxide is 5, and the transverse dimension of the graphene oxide is 3 micrometers; the reaction temperature of the galvanized coating piece in the solution A is 40 ℃, and the reaction time is 2 min; the reaction temperature of the galvanized coating piece in the solution B is 85 ℃, and the reaction time is 50 min; the reaction temperature of the galvanized coating piece in the solution C is 60 ℃, and the reaction time is 7 min; the stirring speed is 1000r/min, and the stirring time is 25 min; the reducing atmosphere is hydrogen.
In order to detect the advantages and disadvantages of the passivation method of each embodiment, the invention respectively tests the electrode potential, the corrosion resistance and the adhesive force of the passivation layer of the galvanized coating piece with the silane film-polymer-graphene composite passivation layer on each surface. The electrode potential is the electromotive force of a galvanic cell assembled by each galvanized coating with a passivation layer and a standard hydrogen electrode under the standard state (the solution concentration is 1mol/L, the gas is 100kPa, and the temperature is 298.15K), and the measured electromotive force is the electrode potential of each galvanized coating. The corrosion resistance is judged by a neutral salt spray experiment, and the test method comprises the steps of placing a sample in a test box with the temperature of 35 ℃ and the humidity of 95%, spraying a sodium chloride solution with the concentration of 45g/L onto the sample to be tested, and observing the surface corrosion state of the sample. In the adhesion experiment, vertical lines are engraved on the passivation layer every 1mm, and the adhesion of the passivation layer is judged according to the expansion condition of the nicks.
Through comparative experiments on the three groups of examples, it can be obtained that each group of examples can prepare a passivation layer with excellent performance, and specific data are shown in table 1. It can be seen that the corrosion resistance time of the neutral salt fog of the zinc coating plating piece compounded with the passivation layer prepared by the invention is about 700h, the adhesion force is first grade, the electrode potential can reach +1.4V, and the passivation layer performance of the third embodiment is the best.
TABLE 1
| Electrode potential (V) | Corrosion resistant time (h) | Adhesion force | |
| Example one | +1.0 | 683 | First stage |
| Example two | +1.3 | 751 | First stage |
| EXAMPLE III | +1.4 | 733 | First stage |
| Comparative example 1 | -0.99 | 125 | Second stage |
| Comparative example 2 | -0.56 | 489 | Second stage |
| Comparative example 3 | +1.1 | 631 | Second stage |
| Comparative example 4 | -0.61 | 502 | First stage |
Comparative example 1: the difference from the third embodiment is that the galvanized coating piece has no coating, and various tests are directly carried out on the galvanized coating piece. The zinc-plated part without the passivation layer shows stronger metallicity and is extremely easy to corrode, the electrode potential can be greatly improved under the protection effect of the passivation layer, and the electron losing capability is effectively reduced.
Comparative example 2: the difference from the third embodiment is that A, B, C liquid is directly mixed to be used as the passivation liquid, and the galvanized piece is directly dipped to obtain the passivation layer. Due to the random arrangement of the organic passivation layer (silane film and polymer layer) and the inorganic passivation layer (graphene layer), on one hand, the purity of graphene on the surface of the passivation layer is low, the potential of an electrode is greatly reduced, on the other hand, the wear resistance of the organic passivation layer on the outer surface of a plated part is also reduced, and the adhesive force is reduced.
Comparative example 3: the difference from the third example is that in the absence of the liquid B, the silane film is directly compounded with the graphene layer. Due to the lack of the polymer coating to fill the network voids of the silane film, voids are left behind after the graphene layer is composited, and the compactness and adhesion of the passivation layer may be reduced.
Comparative example 4: the difference from the third example is that graphene oxide is replaced by graphite oxide having a particle size of about 10 μm, which has about 30 layers. Because the graphite oxide has larger size, more pores are generated during deposition on the organic passivation layer, the impermeability to corrosive liquid is reduced, and the electrode potential and the corrosion resistant time are reduced.
It is noted that, herein, relational terms such as first and second, and the like may be used solely to distinguish one entity or action from another entity or action without necessarily requiring or implying any actual such relationship or order between such entities or actions. Also, the terms "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such process, method, article, or apparatus.
Finally, it should be noted that: although the present invention has been described in detail with reference to the foregoing embodiments, it will be apparent to those skilled in the art that changes may be made in the embodiments and/or equivalents thereof without departing from the spirit and scope of the invention. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. A chromium-free passivation method for the surface of a galvanized layer, which is characterized by comprising the following steps:
(1) mixing and uniformly stirring phytic acid, molybdate and a silane coupling agent of which an active group contains a carbon-carbon double bond, wherein the concentration of the phytic acid is 10-50mL/L, the concentration of the molybdate is 0.1-1.5g/L, and the concentration of the silane coupling agent is 10-80mL/L, and the solution is solution A; carrying out addition polymerization on a monomer containing carbon-carbon double bonds to prepare polymer liquid containing at least two carbon-carbon double bonds and one hydroxyl, wherein the polymer liquid is liquid B, and the polymer is- [ -CH2-C (CH2OH) (CHCH2) - ] n-; preparing a graphene oxide dispersion liquid with the concentration of 0.05-1 wt%, wherein the graphene oxide dispersion liquid is a liquid C;
(2) putting the galvanized coating piece into the solution A to react to form a silane film with a corrosion inhibition effect; then placing the plated part in the solution B to react to obtain an unsaturated polymer modified silane film; finally, the plated part is placed in the solution C to react to obtain a galvanized layer plated part with a silane film-polymer-graphene oxide composite passivation layer on the surface;
(3) and placing the plated piece in a reducing atmosphere for reaction to obtain the galvanized layer plated piece with the silane film-polymer-graphene composite passivation layer on the surface.
2. The method of claim 1, wherein the passivation is performed by a chromium-free passivation method for a galvanized layer surface, wherein the passivation method comprises the following steps: the alkoxy group of the silane coupling agent is one or a combination of methoxy, ethoxy and propoxy.
3. The method of claim 1, wherein the passivation is performed by a chromium-free passivation method for a galvanized layer surface, wherein the passivation method comprises the following steps: the monomers of the polymer liquid contain at least one hydroxyl group, and the rest groups are all hydrogen groups or alkyl groups with the carbon content of 1-10.
4. The method of claim 1, wherein the passivation is performed by a chromium-free passivation method for a galvanized layer surface, wherein the passivation method comprises the following steps: the oxygen content of the graphene oxide is more than 25 at%.
5. The method of claim 1, wherein the passivation is performed by a chromium-free passivation method for a galvanized layer surface, wherein the passivation method comprises the following steps: the number of layers of the graphene oxide is 3-10, and the transverse dimension of the graphene oxide is 1-4 mu m.
6. The method of claim 1, wherein the passivation is performed by a chromium-free passivation method for a galvanized layer surface, wherein the passivation method comprises the following steps: the reaction temperature of the galvanized coating piece in the solution A is 35-50 ℃, and the reaction time is 1-5 min.
7. The method of claim 1, wherein the passivation is performed by a chromium-free passivation method for a galvanized layer surface, wherein the passivation method comprises the following steps: the reaction temperature of the galvanized coating piece in the solution B is 70-90 ℃, and the reaction time is 30-60 min.
8. The method of claim 1, wherein the passivation is performed by a chromium-free passivation method for a galvanized layer surface, wherein the passivation method comprises the following steps: the reaction temperature of the galvanized coating piece in the solution C is 50-80 ℃, and the reaction time is 3-10 min.
9. The method of claim 1, wherein the passivation is performed by a chromium-free passivation method for a galvanized layer surface, wherein the passivation method comprises the following steps: the stirring speed is 300-2500r/min, and the time is 10-40 min.
10. The method of claim 1, wherein the passivation is performed by a chromium-free passivation method for a galvanized layer surface, wherein the passivation method comprises the following steps: the reducing atmosphere is hydrogen, carbon monoxide or a mixture of the two.
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