CN112251088B - Double-fluorine treatment liquid, preparation method and magnesium alloy building template surface treatment method - Google Patents
Double-fluorine treatment liquid, preparation method and magnesium alloy building template surface treatment method Download PDFInfo
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- 229910000861 Mg alloy Inorganic materials 0.000 claims description 66
- 239000011737 fluorine Substances 0.000 claims description 57
- 229910052731 fluorine Inorganic materials 0.000 claims description 57
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 57
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims description 46
- 238000005260 corrosion Methods 0.000 claims description 30
- 239000008367 deionised water Substances 0.000 claims description 30
- 229910021641 deionized water Inorganic materials 0.000 claims description 30
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical group F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims description 28
- 230000007797 corrosion Effects 0.000 claims description 27
- 238000000034 method Methods 0.000 claims description 27
- 239000000839 emulsion Substances 0.000 claims description 25
- 238000003756 stirring Methods 0.000 claims description 24
- 239000003112 inhibitor Substances 0.000 claims description 22
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims description 21
- -1 polytetrafluoroethylene Polymers 0.000 claims description 19
- 229920000642 polymer Polymers 0.000 claims description 18
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 17
- 238000001035 drying Methods 0.000 claims description 15
- 239000003822 epoxy resin Substances 0.000 claims description 14
- 239000007788 liquid Substances 0.000 claims description 14
- 229920000647 polyepoxide Polymers 0.000 claims description 14
- 229920005989 resin Polymers 0.000 claims description 14
- 239000011347 resin Substances 0.000 claims description 14
- 229910001506 inorganic fluoride Inorganic materials 0.000 claims description 13
- 238000004381 surface treatment Methods 0.000 claims description 13
- 239000002131 composite material Substances 0.000 claims description 12
- ALTWGIIQPLQAAM-UHFFFAOYSA-N metavanadate Chemical compound [O-][V](=O)=O ALTWGIIQPLQAAM-UHFFFAOYSA-N 0.000 claims description 9
- CMZUMMUJMWNLFH-UHFFFAOYSA-N sodium metavanadate Chemical compound [Na+].[O-][V](=O)=O CMZUMMUJMWNLFH-UHFFFAOYSA-N 0.000 claims description 8
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 claims description 8
- PAJMKGZZBBTTOY-UHFFFAOYSA-N 2-[[2-hydroxy-1-(3-hydroxyoctyl)-2,3,3a,4,9,9a-hexahydro-1h-cyclopenta[g]naphthalen-5-yl]oxy]acetic acid Chemical group C1=CC=C(OCC(O)=O)C2=C1CC1C(CCC(O)CCCCC)C(O)CC1C2 PAJMKGZZBBTTOY-UHFFFAOYSA-N 0.000 claims description 7
- 229920001780 ECTFE Polymers 0.000 claims description 6
- 239000002033 PVDF binder Substances 0.000 claims description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 6
- 239000012530 fluid Substances 0.000 claims description 6
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 6
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 6
- 229920002620 polyvinyl fluoride Polymers 0.000 claims description 6
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 6
- 230000001502 supplementing effect Effects 0.000 claims description 6
- 230000007704 transition Effects 0.000 claims description 6
- UUEWCQRISZBELL-UHFFFAOYSA-N 3-trimethoxysilylpropane-1-thiol Chemical compound CO[Si](OC)(OC)CCCS UUEWCQRISZBELL-UHFFFAOYSA-N 0.000 claims description 5
- 238000004132 cross linking Methods 0.000 claims description 5
- 238000004140 cleaning Methods 0.000 claims description 4
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 claims description 3
- XDLMVUHYZWKMMD-UHFFFAOYSA-N 3-trimethoxysilylpropyl 2-methylprop-2-enoate Chemical group CO[Si](OC)(OC)CCCOC(=O)C(C)=C XDLMVUHYZWKMMD-UHFFFAOYSA-N 0.000 claims description 3
- UNTBPXHCXVWYOI-UHFFFAOYSA-O azanium;oxido(dioxo)vanadium Chemical compound [NH4+].[O-][V](=O)=O UNTBPXHCXVWYOI-UHFFFAOYSA-O 0.000 claims description 3
- 229920000840 ethylene tetrafluoroethylene copolymer Polymers 0.000 claims description 3
- 239000012535 impurity Substances 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 229920002493 poly(chlorotrifluoroethylene) Polymers 0.000 claims description 3
- 239000005023 polychlorotrifluoroethylene (PCTFE) polymer Substances 0.000 claims description 3
- 239000000377 silicon dioxide Substances 0.000 claims description 3
- 235000012239 silicon dioxide Nutrition 0.000 claims description 3
- KKCBUQHMOMHUOY-UHFFFAOYSA-N sodium oxide Chemical compound [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 claims description 3
- 229910001948 sodium oxide Inorganic materials 0.000 claims description 3
- 239000010410 layer Substances 0.000 description 58
- 239000004567 concrete Substances 0.000 description 15
- 238000005406 washing Methods 0.000 description 14
- 238000005238 degreasing Methods 0.000 description 13
- 230000008569 process Effects 0.000 description 12
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 9
- 239000002245 particle Substances 0.000 description 8
- 239000000126 substance Substances 0.000 description 8
- 239000000758 substrate Substances 0.000 description 7
- 229910000838 Al alloy Inorganic materials 0.000 description 6
- 101001108245 Cavia porcellus Neuronal pentraxin-2 Proteins 0.000 description 6
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 6
- 239000002253 acid Substances 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 5
- 238000010276 construction Methods 0.000 description 5
- 230000007935 neutral effect Effects 0.000 description 5
- 238000002360 preparation method Methods 0.000 description 5
- 239000010959 steel Substances 0.000 description 5
- 238000002474 experimental method Methods 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 230000001681 protective effect Effects 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- 239000007921 spray Substances 0.000 description 4
- 229910000831 Steel Inorganic materials 0.000 description 3
- 238000007605 air drying Methods 0.000 description 3
- 239000003513 alkali Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000011780 sodium chloride Substances 0.000 description 3
- 229910000851 Alloy steel Inorganic materials 0.000 description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 2
- 229910019142 PO4 Inorganic materials 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000007822 coupling agent Substances 0.000 description 2
- 125000001153 fluoro group Chemical group F* 0.000 description 2
- 238000009415 formwork Methods 0.000 description 2
- VMUWIFNDNXXSQA-UHFFFAOYSA-N hypofluorite Chemical compound F[O-] VMUWIFNDNXXSQA-UHFFFAOYSA-N 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- 229910052749 magnesium Inorganic materials 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000005543 nano-size silicon particle Substances 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 2
- 239000010452 phosphate Substances 0.000 description 2
- 239000002344 surface layer Substances 0.000 description 2
- 239000002351 wastewater Substances 0.000 description 2
- 239000002023 wood Substances 0.000 description 2
- IRPGOXJVTQTAAN-UHFFFAOYSA-N 2,2,3,3,3-pentafluoropropanal Chemical compound FC(F)(F)C(F)(F)C=O IRPGOXJVTQTAAN-UHFFFAOYSA-N 0.000 description 1
- KLZUFWVZNOTSEM-UHFFFAOYSA-K Aluminum fluoride Inorganic materials F[Al](F)F KLZUFWVZNOTSEM-UHFFFAOYSA-K 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- 229910000640 Fe alloy Inorganic materials 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 238000004873 anchoring Methods 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 239000004568 cement Substances 0.000 description 1
- ZCDOYSPFYFSLEW-UHFFFAOYSA-N chromate(2-) Chemical compound [O-][Cr]([O-])(=O)=O ZCDOYSPFYFSLEW-UHFFFAOYSA-N 0.000 description 1
- JOPOVCBBYLSVDA-UHFFFAOYSA-N chromium(6+) Chemical compound [Cr+6] JOPOVCBBYLSVDA-UHFFFAOYSA-N 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000004512 die casting Methods 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 229920006351 engineering plastic Polymers 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000003628 erosive effect Effects 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- ORUIBWPALBXDOA-UHFFFAOYSA-L magnesium fluoride Chemical compound [F-].[F-].[Mg+2] ORUIBWPALBXDOA-UHFFFAOYSA-L 0.000 description 1
- 229910001635 magnesium fluoride Inorganic materials 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 239000011150 reinforced concrete Substances 0.000 description 1
- 230000008439 repair process Effects 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000012876 topography Methods 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D127/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Coating compositions based on derivatives of such polymers
- C09D127/02—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Coating compositions based on derivatives of such polymers not modified by chemical after-treatment
- C09D127/12—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Coating compositions based on derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
- B05D7/14—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials to metal, e.g. car bodies
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
- B05D7/24—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials for applying particular liquids or other fluent materials
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/08—Anti-corrosive paints
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/16—Antifouling paints; Underwater paints
- C09D5/1687—Use of special additives
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
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- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Wood Science & Technology (AREA)
- Materials Engineering (AREA)
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- Other Surface Treatments For Metallic Materials (AREA)
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Abstract
The invention discloses a difluoride treatment liquid, a preparation method and a magnesium alloy building template surface treatment method; the difluoride treatment liquid comprises the following components in percentage by weight: 20 to 30 percent of inorganic fluoride, 20 to 40 percent of organic fluorine-containing emulsion, 15 to 20 percent of nano silica sol, 0.3 to 0.5 percent of corrosion inhibitor component, 0.8 to 2 percent of silane coupling agent and 20 to 43.9 percent of deionized water. After soaking in the bifluoride treatment solution and drying, a bifluoride composite film layer system with a self-repairing function, which is composed of an inorganic fluoride layer, a transition layer and an organic fluoride layer, can be formed on the surface of the magnesium alloy, the film layer can effectively guarantee the surface hardness, scratch resistance and hydrophobicity of the magnesium alloy template, reduce the friction damage of concrete aggregate to the template and the corrosion damage from external erosion media, prevent the chemical reaction and physical adsorption of cement and the template, and ensure the construction quality and demolding effect of the building wall surface.
Description
Technical Field
The invention belongs to the technical field of concrete engineering construction templates, and particularly relates to a difluoride treatment liquid, a preparation method and a magnesium alloy building template surface treatment method.
Background
The building forming of the reinforced concrete structure is mainly realized by means of a building template. The cost of the building template accounts for almost 20-30% of the total construction cost. The use of the building templates is directly related to the quality and benefit of the whole project. The traditional building templates are all made of wood templates or steel templates, wherein the wood templates are not fireproof, easy to decay and not durable, and the steel templates are relatively heavy, difficult to use on site, high in manufacturing cost and easy to rust.
The generation of the novel aluminum template breaks the contribution of the traditional template and the development is very rapid. However, because the aluminum alloy is neutral metal, the aluminum alloy is easy to corrode in an alkaline concrete environment, so that the problems of potholes, pitted surfaces and the like on the surface of the concrete are caused, and the technical requirements of the fair-faced concrete and the facing fair-faced concrete on the template are difficult to effectively meet by the process technology. In addition, the weight of a single aluminum alloy template is still as much as 30 kilograms, and field operation is still a difficult problem. Therefore, it is imperative to seek more excellent building templates.
Recently, chinese patent application nos. 201510869825.1 and 201910780290.9 disclose magnesium alloy forms in an attempt to replace aluminum alloy forms. The density of the magnesium alloy is only 2/3 of aluminum alloy, and the specific strength and specific rigidity of steel is 1/4 of steel and iron alloy which are both superior to steel and aluminum alloy and far higher than engineering plastics; the magnesium alloy has strong shock absorption performance, reduces the impact of concrete pouring and reduces the construction noise; the casting performance is good, the automatic production capacity and the service life of the die are high, and the die casting process can be favorably adopted for automatic production; the magnesium alloy has stable size, does not cause great change due to the change of the environmental temperature and the time, and can prevent the difficult problem of template splicing caused by deformation. More importantly, the concrete has excellent alkali resistance and can effectively resist the corrosion of concrete. Therefore, in the field of concrete construction formwork engineering, the magnesium alloy is a high-quality light formwork material which cannot be compared with the above materials.
Unfortunately, although the magnesium alloy can effectively resist the alkali corrosion of concrete in work, the surface of the magnesium alloy is soft and easy to adhere water molecules, so that the magnesium alloy is easy to scratch and damage by concrete aggregate, and the problems that the concrete is easy to scratch and damage the surface of a template, adheres to the template, is difficult to fall off and is difficult to clean are difficult to solve. Meanwhile, the template is in a non-alkaline environment in the process of storage and transportation at ordinary times and is easy to be corroded and damaged by atmosphere and water vapor.
Therefore, the surface of the magnesium alloy template still needs to be subjected to scientific and reasonable surface treatment. The surface treatment technology disclosed in the prior art mainly has the following problems:
(1) the problems of the improvement of the surface hardness of the template, the scratch resistance and the hydrophobicity are not considered;
(2) uses the surface treatment technology of phosphorization, spraying and other toxic and harmful substances to be forbidden;
(3) the technical requirements of the fair-faced concrete and the facing fair-faced concrete on the template are difficult to meet.
Based on this, it is urgently needed to develop a surface treatment method suitable for the magnesium alloy building template.
Disclosure of Invention
The invention aims to provide a difluoride treatment liquid, a preparation method and a magnesium alloy building template surface treatment method, so as to solve the technical problems.
In order to achieve the purpose, the invention adopts the following technical scheme:
the difluoride treatment liquid comprises the following components in percentage by weight: 20 to 30 percent of inorganic fluoride, 20 to 40 percent of organic fluorine-containing emulsion, 15 to 20 percent of nano silica sol, 0.3 to 0.5 percent of corrosion inhibitor component, 0.8 to 2 percent of silane coupling agent and 20 to 43.9 percent of deionized water.
The invention further improves the following steps: the inorganic fluoride is one or more of hydrofluoric acid, fluosilicic acid, fluotitanic acid, hypofluoric acid, hydrofluoride, fluosilicate, fluotitanate and hypofluorite.
The invention further improves the following steps: the organic fluorine-containing emulsion is an emulsion formed by blending fluorine-containing water-based resin and water-based epoxy resin, and the weight ratio of the fluorine-containing water-based resin to the water-based epoxy resin is 8:1-5: 1; the organic fluorine-containing emulsion has a self-crosslinking characteristic and a self-layering characteristic;
the fluorine-containing water-based resin is one or more of polytetrafluoroethylene, polyvinylidene fluoride, polyvinyl fluoride, polychlorotrifluoroethylene, ethylene-tetrafluoroethylene copolymer, ethylene-chlorotrifluoroethylene copolymer, polytetrafluoroethylene modified polymer, polyvinylidene fluoride modified polymer, polyvinyl fluoride modified polymer, polychlorotrifluoroethylene modified polymer, ethylene-tetrafluoroethylene copolymer modified polymer and ethylene-chlorotrifluoroethylene copolymer modified polymer.
The waterborne epoxy resin is a conventional waterborne epoxy resin sold in the market.
The invention further improves the following steps: the grain diameter of the nano silica sol is controlled to be 50nm-800nm, wherein the grain diameter is controlled according to the mass percentage; the content of silicon dioxide in the silica sol is controlled to be 30-50%, the content of sodium oxide impurities is less than 0.2%, and the balance is water.
The invention further improves the following steps: the corrosion inhibitor component is one or more of metavanadate or metavanadate.
The invention further improves the following steps: the metavanadate is potassium metavanadate, sodium metavanadate or ammonium metavanadate.
The invention further improves the following steps: the silane coupling agent is one or more of gamma- (2, 3-epoxypropoxy) propyl trimethoxy silane, gamma-aminopropyl triethoxy silane, gamma-methacryloxypropyl and gamma-mercaptopropyl trimethoxy silane.
A preparation method of a difluoride treatment liquid comprises the following steps:
firstly, adding a part of deionized water into a container, then adding inorganic fluoride, uniformly stirring, then adding a corrosion inhibitor component, uniformly stirring, and then adding a silane coupling agent and a nano silica sol; adding the organic fluorine-containing emulsion at normal temperature while stirring, finally supplementing the residual deionized water, and uniformly stirring to obtain the difluoride treatment solution.
A surface treatment method of a magnesium alloy building template comprises the following steps:
immersing a magnesium alloy building template with a clean surface into a difluoride treatment solution, controlling the working temperature of the treatment solution to be 25-60 ℃, and treating for 10-60 min to prepare an initial film layer on the surface of the magnesium alloy building template; then cleaning, airing and drying at 60-80 ℃ to obtain the magnesium alloy building template after surface treatment.
The invention further improves the following steps: after drying, a layer of double-fluorine composite film layer system with self-repairing function, which is composed of an inorganic fluorine layer, a transition layer and an organic fluorine layer, is formed on the surface of the magnesium alloy building template.
The invention further improves the following steps: the surface of the magnesium alloy building template is cleaned through pretreatment; the pretreatment comprises the following steps: degreasing the magnesium alloy building template by adopting an alkaline degreasing method, and then washing and cleaning the magnesium alloy building template by using deionized water to clean the surface of the magnesium alloy building template;
after being immersed in the difluoride treatment solution for treatment, the magnesium alloy building template is washed by deionized water to remove the difluoride treatment solution residue on the surface of the magnesium alloy building template, and then is naturally dried;
the drying time after air drying is 30-60 minutes.
The invention further improves the following steps: the degreasing treatment is to degrease the template by adopting an alkaline degreasing method, and the magnesium alloy surface alkaline degreasing solution known by the technical personnel in the field is adopted, the temperature is generally controlled to be 60-70 ℃, and the time is 2-6 minutes; the method aims to effectively remove oil stains on the surface of the template, obtain a clean surface and establish a good surface state for subsequent treatment.
The invention further improves the following steps: after being immersed, the glass is washed and cleaned by deionized water; the water washing process comprises two processes of hot water washing and warm water washing, wherein the two processes can be executed for multiple times, the hot water washing temperature is controlled to be slightly lower than the alkali washing degreasing temperature, specifically 50-60 ℃, and then the warm water washing temperature is 30-40 ℃, so that the degreasing liquid residue on the surface of the template is effectively removed, and the template is prevented from bringing residual liquid into the next process.
The invention further improves the following steps: the air-drying process is natural air-drying, the time is controlled to be 20-30 minutes, and the main purpose is to promote the automatic layering process and the moisture volatilization process of the organic fluororesin and the epoxy resin.
The invention further improves the following steps: the drying process can be carried out in an oven or a drying tunnel, the temperature is controlled to be 60-80 ℃, the drying time is controlled to be 30-60 minutes, and the main purposes are to promote the water volatilization, the automatic layering of the film layer and the self-crosslinking process of the film layer.
Compared with the prior art, the invention has the following beneficial effects:
(1) because the phosphorus-free and chromium-free conversion film-forming liquid on the surface of the magnesium alloy template does not contain chromate and phosphate, the pollution of the production process and products to the environment is greatly reduced. Although the discharged wastewater contains fluoride, the pollution degree of the fluoride is relatively light compared with hexavalent chromium and phosphate, and the fluoride-containing wastewater is relatively easy to dispose.
(2) When the magnesium alloy template after pretreatment is immersed in the bifluoride conversion solution, hydrofluoric acid can preferentially react with the magnesium alloy substrate to generate inorganic magnesium fluoride and aluminum fluoride film layers, silica sol particles and corrosion inhibitor molecules can be embedded in the defects or cavities of the fluoride film layers in the process, when the fluoride film layer generated by the reaction of the fluoride and the magnesium reaches a certain thickness, the action of fluorine ions on the magnesium template substrate is weakened, at the moment, the organic fluorine resin starts to play a role and is gradually adsorbed on the inorganic fluoride film layer, particularly preferentially adsorbed on the fluoride surface with the characteristic of micro cracks, the resin molecules penetrate into the cracks to perform a mechanical anchoring effect on the film layer, and the nano silicon sol particles and the corrosion inhibitor molecules are also coated in the film forming process of the organic fluoride, so that the effects of improving physical filling and corrosion-retarding repair are achieved. And when the dipping time reaches the specified time, taking out the magnesium alloy membrane plate, washing with pure water to effectively remove residual liquid, then airing in the air, and then transferring into an oven for drying and curing. In the airing and drying process, because the obvious surface tension difference exists between the fluororesin and the epoxy resin, the organic fluorine emulsion can generate the automatic layering phenomenon, the surface layer is rich in the fluororesin with low surface tension, and the bottom layer is mainly composed of the epoxy resin with high surface tension. Finally, a double-layer film structure with obviously different functions, namely a fluorine-containing film layer and an epoxy film layer, is spontaneously formed, and the two layers are firmly combined through chemical bond reaction. Thus, a novel double-fluorine composite film layer system with self-repairing function, which is composed of an inorganic fluorine layer, a transition layer and an organic fluorine layer, is formed on the surface of the magnesium alloy template (as shown in figure 1). The fluorine-containing substance has good lubricity, and the fluorine atoms of the fluorine-containing substance have larger electronegativity, so that the fluorine atoms are easy to bond and react with the epoxy resin, and the bonding performance between the upper fluorine resin layer and the lower epoxy resin layer is improved, so that the surface layer of the template has the excellent performances of weather resistance, hydrophobicity, oleophobicity, stain resistance and the like of the fluorine resin. The surface transition layer of the template is an upper and lower epoxy resin layer with excellent adhesive force, is connected with the fluorine resin layer upwards and is connected with the inorganic fluoride layer downwards. The inorganic fluoride layer is an in-situ growth film layer of the magnesium alloy template substrate, and is very firmly combined with the magnesium alloy template substrate and compact in film layer. The nano silicon sol particles dispersed in the film layer can effectively improve the hardness and scratch resistance of the film layer on the surface of the template, the corrosion inhibitor molecules improve the corrosion resistance of the magnesium alloy template substrate, and the self-repairing function of the magnesium alloy template substrate is exerted when aggressive media penetrate into the film layer and the vicinity of the substrate. The addition of the silane coupling agent improves the crosslinking degree of the film, ensures the uniform dispersion of the corrosion inhibitor molecules and the nano silica sol, and promotes the film to have good compactness and corrosion resistance.
Generally, the novel difluoride chemical treatment method can form a stable difluoride three-layer composite protective film layer system on the surface of a magnesium alloy template, the method is green and environment-friendly, and has no pollution, the surface hardness and scratch resistance of the magnesium alloy template treated by the method are obviously improved (the hardness can reach more than 4H, and the dry friction coefficient can reach 0.04), the surface hydrophobicity of the template is greatly improved (the contact angle can reach more than 110 degrees), and meanwhile, a neutral salt spray resistance experiment can reach more than 800 hours, so that the friction damage caused by concrete aggregate to the template and the corrosion damage from an external erosion medium can be effectively reduced, the chemical reaction and physical adsorption of cement and the template are prevented, and the construction quality and the demolding effect of a building wall surface are ensured.
Drawings
The accompanying drawings, which are incorporated in and constitute a part of this application, illustrate embodiments of the invention and, together with the description, serve to explain the invention and not to limit the invention. In the drawings:
FIG. 1 is a schematic view of a dual-fluorine three-layer composite protective film system designed and prepared on the surface of a magnesium alloy template according to the present invention.
Fig. 2 is a microscopic topography of the dual-fluorine three-layer composite protective film layer on the surface of the magnesium alloy template in embodiment 2 of the present invention.
Fig. 3 is a contact angle diagram of the dual-fluorine three-layer composite protective film layer on the surface of the magnesium alloy template in example 2 of the present invention.
Detailed Description
The present invention will be described in detail below with reference to the embodiments with reference to the attached drawings. It should be noted that the embodiments and features of the embodiments in the present application may be combined with each other without conflict.
The following detailed description is exemplary in nature and is intended to provide further details of the invention. Unless otherwise defined, all technical terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this application belongs. The terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of exemplary embodiments according to the invention.
The invention provides a difluoride treatment fluid which comprises the following components in percentage by weight: 20 to 30 percent of inorganic fluoride, 20 to 40 percent of organic fluorine-containing emulsion, 15 to 20 percent of nano silica sol, 0.3 to 0.5 percent of corrosion inhibitor component, 0.8 to 2 percent of silane coupling agent and 20 to 43.9 percent of deionized water.
The inorganic fluoride is one or more of hydrofluoric acid, fluosilicic acid, fluotitanic acid, hypofluoric acid, hydrofluoride, fluosilicate, fluotitanate and hypofluorite.
The organic fluorine-containing emulsion is an emulsion formed by blending fluorine-containing water-based resin and water-based epoxy resin, and the weight ratio of the fluorine-containing water-based resin to the water-based epoxy resin is 8:1-5: 1; the organic fluorine-containing emulsion has a self-crosslinking characteristic and a self-layering characteristic;
the fluorine-containing water-based resin is one or more of polytetrafluoroethylene, polyvinylidene fluoride, polyvinyl fluoride, polychlorotrifluoroethylene, ethylene-tetrafluoroethylene copolymer, ethylene-chlorotrifluoroethylene copolymer, polytetrafluoroethylene modified polymer, polyvinylidene fluoride modified polymer, polyvinyl fluoride modified polymer, polychlorotrifluoroethylene modified polymer, ethylene-tetrafluoroethylene copolymer modified polymer and ethylene-chlorotrifluoroethylene copolymer modified polymer.
The grain diameter of the nano silica sol is controlled to be 50nm-800nm, wherein the grain diameter is controlled according to the mass percentage; the content of silicon dioxide in the silica sol is controlled to be 30-50%, the content of sodium oxide impurities is less than 0.2%, and the balance is water.
The corrosion inhibitor component is one or more of metavanadate or metavanadate.
The metavanadate is potassium metavanadate, sodium metavanadate or ammonium metavanadate.
The silane coupling agent is one or more of gamma- (2, 3-epoxypropoxy) propyl trimethoxy silane, gamma-aminopropyl triethoxy silane, gamma-methacryloxypropyl and gamma-mercaptopropyl trimethoxy silane.
The invention also provides a preparation method of the difluoride treating fluid, which comprises the following steps:
firstly, adding a part of deionized water into a container, then adding inorganic fluoride, uniformly stirring, then adding a corrosion inhibitor component, uniformly stirring, and then adding a silane coupling agent and a nano silica sol; adding the organic fluorine-containing emulsion at normal temperature while stirring, finally supplementing the residual deionized water, and uniformly stirring to obtain the difluoride treatment solution.
The invention also provides a magnesium alloy building template surface treatment method, which comprises the following steps:
immersing a magnesium alloy building template with a clean surface into a difluoride treatment solution, controlling the working temperature of the treatment solution to be 25-60 ℃, and treating for 10-60 min to prepare an initial film layer on the surface of the magnesium alloy building template; then cleaning, airing and drying at 60-80 ℃ to obtain the magnesium alloy building template after surface treatment.
After drying, a layer of double-fluorine composite film layer system with self-repairing function, which is composed of three layers of an inorganic fluorine layer 2, a transition layer 3 and an organic fluorine layer 4, is formed on the surface of the magnesium alloy building template 1.
Example 1:
a difluoride treatment fluid comprising, in weight percent: 22% of hydrofluoric acid, 30% of organic fluorine-containing emulsion, 16% of 100-phase 200 nm-particle-size nano silica sol, 0.3% of sodium metavanadate corrosion inhibitor component, 1% of gamma- (2, 3-epoxypropoxy) propyl trimethoxy silane coupling agent and 30.7% of deionized water.
Preparing the difluoride treatment solution according to the composition proportion, firstly adding 24% of deionized water into a container, then adding 22% of hydrofluoric acid, uniformly stirring, then adding 0.3% of sodium metavanadate corrosion inhibitor component, uniformly stirring, then adding 1% of- (2, 3-epoxypropoxy) propyl trimethoxy silane coupling agent, synchronously adding 16% of 100-plus-200 nm-particle-size nano silica sol, stirring at normal temperature while adding 30% of self-made organic fluorine-containing emulsion, supplementing the rest 6.7% of deionized water, and stirring for 4 hours to obtain the difluoride treatment solution.
The magnesium alloy template is AM50 series, and the magnesium alloy template is degreased by alkaline degreasing solution on the surface of magnesium alloy, which is well known by the technicians in the field, wherein the degreasing temperature is 60 ℃ and the time is 5 minutes; carrying out two times of deionized water washing; slowly immersing the template into a difluoride treatment solution for difluoride chemical treatment, wherein the temperature of the treatment solution is 45 ℃, and the treatment time is 40 min; carrying out secondary deionized water washing for 2 times; naturally airing for 30 minutes, and continuously drying for 40 minutes in an oven at 80 ℃ to form a double-fluorine composite film layer system (shown in figure 1) with a self-repairing function, which is formed by three layers of an inorganic fluoride layer 2, a transition layer 3 and an organic fluoride layer 4, on the magnesium alloy building template 1. Nanometer sol particles 5 and slow-release molecules 6 are distributed in a layer system of the double-fluorine composite film.
Through an electrochemical tafel curve test in a 3.5% NaCl solution, the self-corrosion current density of the AM50 magnesium alloy template treated by the film layer is improved by more than 2 orders of magnitude relative to that of a blank magnesium alloy template, the non-grid neutral salt spray experiment time can reach 620 hours without damage, the contact angle is 92 degrees, the hardness is 4H, the dry friction coefficient is 0.04, and the impact resistance is more than 50 kg.cm.
Example 2:
a difluoride treatment fluid comprising, in weight percent: 25 percent of hydrofluoric acid, 20 percent of organic fluorine-containing emulsion, 20 percent of 100-phase 200nm nanometer silica sol, 0.5 percent of potassium metavanadate corrosion inhibitor component, 2 percent of gamma- (2, 3-epoxypropoxy) propyl trimethoxy silane coupling agent and 32.5 percent of deionized water. Preparing the difluoride treatment solution according to the composition proportion, firstly adding 20% of deionized water into a container, then adding 25% of hydrofluoric acid, uniformly stirring, then adding 0.5% of potassium metavanadate corrosion inhibitor component, uniformly stirring, then adding 2% of- (2, 3-epoxypropoxy) propyl trimethoxy silane coupling agent, synchronously adding 20% of 100-doped 200 nm-particle-size nano silica sol, stirring at normal temperature while adding 20% of self-made organic fluorine-containing emulsion, supplementing the rest 12.5% of deionized water, and stirring for 5 hours to obtain the difluoride treatment solution.
The magnesium alloy template is AM50 series, and the magnesium alloy template is degreased by alkaline degreasing solution on the surface of magnesium alloy, which is well known by the technicians in the field, wherein the degreasing temperature is 60 ℃ and the time is 5 minutes; carrying out two times of deionized water washing; slowly immersing the template into a difluoride treatment solution to carry out difluoride chemical treatment, wherein the temperature of the treatment solution is 40 ℃, and the treatment time is 40 min; carrying out secondary deionized water washing for 2 times; naturally airing for 20 minutes, and continuously drying in an oven at 80 ℃ for 40 minutes to obtain the difluoride composite film, wherein the microstructure of the difluoride composite film is shown in figure 2.
Through an electrochemical tafel curve test in a 3.5% NaCl solution, the self-corrosion current density of the AM50 magnesium alloy template treated by the film layer is improved by nearly 3 orders of magnitude relative to that of a blank magnesium alloy template, the non-grid neutral salt spray experiment time can reach 800 hours without damage, the contact angle is 110 degrees (shown in figure 3), the hardness is greater than 4H, the dry friction coefficient is 0.05, and the impact resistance is greater than 50 kg.cm.
Example 3:
a difluoride treatment fluid comprising, in weight percent: 20% of hydrofluoric acid, 35% of organic fluorine-containing emulsion, 15% of 100-one nano-silica sol with the particle size of 200nm, 0.4% of potassium metavanadate corrosion inhibitor component, 1.5% of gamma-mercaptopropyl trimethoxysilane coupling agent and 28.1% of deionized water.
Preparing the difluoride treatment liquid according to the composition proportion, firstly adding 20% of deionized water into a container, then adding 20% of hydrofluoric acid, uniformly stirring, then adding 0.4% of potassium metavanadate corrosion inhibitor component, uniformly stirring, then adding 1.5% of gamma-mercaptopropyltrimethoxysilane coupling agent, synchronously adding 15% of 100-doped 200nm nano-silica sol, stirring at normal temperature while adding 35% of self-made organic fluorine-containing emulsion, supplementing the rest 8.1% of deionized water, and stirring for 4 hours to obtain the needed difluoride treatment liquid. The magnesium alloy template is AM50 series, and the magnesium alloy template is degreased by alkaline degreasing solution on the surface of magnesium alloy, which is well known by the technicians in the field, wherein the degreasing temperature is 70 ℃ and the time is 3 minutes; carrying out two times of deionized water washing; slowly immersing the template into a difluoride treatment solution for difluoride chemical treatment, wherein the temperature of the treatment solution is 50 ℃, and the treatment time is 30 min; carrying out secondary deionized water washing for 2 times; naturally airing for 10 minutes, and continuously drying for 40 minutes in an oven at 80 ℃ to obtain the difluoride film layer.
Through an electrochemical tafel curve test in a 3.5% NaCl solution, the self-corrosion current density of the AM50 magnesium alloy template treated by the film layer is improved by 2 orders of magnitude relative to that of a blank magnesium alloy template, the non-grid neutral salt spray experiment time can reach 520 hours without being damaged, the contact angle is 88 degrees, the hardness is greater than 4H, the dry friction coefficient is 0.05, and the impact resistance is greater than 50 kg.cm.
Example 4:
the difference between this example and example 1 is that a difluoride treatment solution comprises the following components (by weight percent): 30 percent of hydrofluoric acid, 28.8 percent of organic fluorine-containing emulsion, 20 percent of nano silica sol with the particle size of 100 and 200nm, 0.4 percent of sodium metavanadate corrosion inhibitor component, 0.8 percent of gamma- (2, 3-epoxypropoxy) propyl trimethoxy silane coupling agent and 20 percent of deionized water.
Example 5:
the difference between this example and example 1 is that a difluoride treatment solution comprises the following components (by weight percent): 20 percent of hydrofluoric acid, 20 percent of organic fluorine-containing emulsion, 15 percent of nano silica sol with the particle size of 100 and 200nm, 0.3 percent of sodium metavanadate corrosion inhibitor component, 0.8 percent of gamma- (2, 3-epoxypropoxy) propyl trimethoxy silane coupling agent and 43.9 percent of deionized water.
Example 6:
the difference between this example and example 1 is that a difluoride treatment solution comprises the following components (by weight percent): 20 percent of hydrofluoric acid, 40 percent of organic fluorine-containing emulsion, 15 percent of nano silica sol with the particle size of 100-200nm, 0.5 percent of sodium metavanadate corrosion inhibitor component, 1.5 percent of gamma- (2, 3-epoxypropoxy) propyl trimethoxy silane coupling agent and 23 percent of deionized water.
It will be appreciated by those skilled in the art that the invention may be embodied in other specific forms without departing from the spirit or essential characteristics thereof. The embodiments disclosed above are therefore to be considered in all respects as illustrative and not restrictive. All changes which come within the scope of or equivalence to the invention are intended to be embraced therein.
Claims (4)
1. The difluoride treatment liquid is characterized by comprising the following components in percentage by weight: 20 to 30 percent of inorganic fluoride, 20 to 40 percent of organic fluorine-containing emulsion, 15 to 20 percent of nano silica sol, 0.3 to 0.5 percent of corrosion inhibitor component, 0.8 to 2 percent of silane coupling agent and 20 to 43.9 percent of deionized water;
the inorganic fluoride is hydrofluoric acid;
the organic fluorine-containing emulsion is an emulsion formed by blending fluorine-containing water-based resin and water-based epoxy resin, and the weight ratio of the fluorine-containing water-based resin to the water-based epoxy resin is 8:1-5: 1; the organic fluorine-containing emulsion has a self-crosslinking characteristic and a self-layering characteristic;
the fluorine-containing water-based resin is one or more of polytetrafluoroethylene, polyvinylidene fluoride, polyvinyl fluoride, polychlorotrifluoroethylene, ethylene-tetrafluoroethylene copolymer, ethylene-chlorotrifluoroethylene copolymer, polytetrafluoroethylene modified polymer, polyvinylidene fluoride modified polymer, polyvinyl fluoride modified polymer, polychlorotrifluoroethylene modified polymer, ethylene-tetrafluoroethylene copolymer modified polymer and ethylene-chlorotrifluoroethylene copolymer modified polymer;
the grain diameter of the nano silica sol is controlled to be 50nm-800nm, wherein the grain diameter is controlled according to the mass percentage; the content of silicon dioxide in the silica sol is controlled to be 30-50%, the content of sodium oxide impurities is less than 0.2%, and the balance is water;
the corrosion inhibitor component is one or more of metavanadate or metavanadate;
the metavanadate is potassium metavanadate, sodium metavanadate or ammonium metavanadate;
the silane coupling agent is one or more of gamma- (2, 3-epoxypropoxy) propyl trimethoxy silane, gamma-aminopropyl triethoxy silane, gamma-methacryloxypropyl and gamma-mercaptopropyl trimethoxy silane.
2. The method of preparing a difluoride treatment fluid of claim 1 comprising the steps of:
firstly, adding a part of deionized water into a container, then adding inorganic fluoride, uniformly stirring, then adding a corrosion inhibitor component, uniformly stirring, and then adding a silane coupling agent and a nano silica sol; adding the organic fluorine-containing emulsion at normal temperature while stirring, finally supplementing the residual deionized water, and uniformly stirring to obtain the difluoride treatment solution.
3. The surface treatment method of the magnesium alloy building template is characterized by comprising the following steps of:
immersing a magnesium alloy building template with a clean surface into the difluoride treatment liquid of claim 1, controlling the working temperature of the treatment liquid to be 25-60 ℃, and treating for 10-60 min to prepare an initial film layer on the surface of the magnesium alloy building template; then cleaning, airing and drying at 60-80 ℃ to obtain the magnesium alloy building template after surface treatment.
4. The method for treating the surface of the magnesium alloy building template according to claim 3, wherein a self-repairing double-fluorine composite film layer system consisting of an inorganic fluorine layer, a transition layer and an organic fluorine layer is formed on the surface of the magnesium alloy building template after drying.
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