CN116836572B - Composite acid-resistant concrete protective coating material and preparation method and application thereof - Google Patents
Composite acid-resistant concrete protective coating material and preparation method and application thereof Download PDFInfo
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- CN116836572B CN116836572B CN202310456415.9A CN202310456415A CN116836572B CN 116836572 B CN116836572 B CN 116836572B CN 202310456415 A CN202310456415 A CN 202310456415A CN 116836572 B CN116836572 B CN 116836572B
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- 239000004567 concrete Substances 0.000 title claims abstract description 91
- 239000000463 material Substances 0.000 title claims abstract description 87
- 239000002253 acid Substances 0.000 title claims abstract description 63
- 239000002131 composite material Substances 0.000 title claims abstract description 38
- 239000011253 protective coating Substances 0.000 title claims abstract description 32
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 238000000576 coating method Methods 0.000 claims abstract description 85
- 239000011248 coating agent Substances 0.000 claims abstract description 77
- 239000000843 powder Substances 0.000 claims abstract description 68
- 229920002037 poly(vinyl butyral) polymer Polymers 0.000 claims abstract description 43
- 239000006184 cosolvent Substances 0.000 claims abstract description 28
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 claims abstract description 26
- 238000002156 mixing Methods 0.000 claims abstract description 16
- 229910004298 SiO 2 Inorganic materials 0.000 claims abstract description 14
- 238000000034 method Methods 0.000 claims abstract description 13
- 229910052882 wollastonite Inorganic materials 0.000 claims abstract description 11
- 239000010456 wollastonite Substances 0.000 claims abstract description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 36
- 238000003756 stirring Methods 0.000 claims description 35
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 33
- 229920000620 organic polymer Polymers 0.000 claims description 29
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 24
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 claims description 22
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 14
- 239000000758 substrate Substances 0.000 claims description 14
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 11
- 239000002994 raw material Substances 0.000 claims description 10
- 239000000126 substance Substances 0.000 claims description 10
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 9
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 9
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 7
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 7
- 238000001035 drying Methods 0.000 claims description 7
- 229910052710 silicon Inorganic materials 0.000 claims description 7
- 239000010703 silicon Substances 0.000 claims description 7
- 229910000831 Steel Inorganic materials 0.000 claims description 6
- 238000004140 cleaning Methods 0.000 claims description 6
- 238000007790 scraping Methods 0.000 claims description 6
- 238000007789 sealing Methods 0.000 claims description 6
- 239000010959 steel Substances 0.000 claims description 6
- 239000012530 fluid Substances 0.000 claims description 5
- 238000012423 maintenance Methods 0.000 claims description 5
- 239000011148 porous material Substances 0.000 claims description 5
- 238000000498 ball milling Methods 0.000 claims description 4
- 230000007547 defect Effects 0.000 claims description 4
- 239000006185 dispersion Substances 0.000 claims description 4
- 239000000839 emulsion Substances 0.000 claims description 4
- UEZVMMHDMIWARA-UHFFFAOYSA-N Metaphosphoric acid Chemical compound OP(=O)=O UEZVMMHDMIWARA-UHFFFAOYSA-N 0.000 claims description 3
- 230000001680 brushing effect Effects 0.000 claims description 3
- 235000006408 oxalic acid Nutrition 0.000 claims description 3
- 239000004568 cement Substances 0.000 abstract description 11
- 238000005260 corrosion Methods 0.000 abstract description 7
- 230000007797 corrosion Effects 0.000 abstract description 6
- 230000008569 process Effects 0.000 abstract description 6
- 239000011812 mixed powder Substances 0.000 abstract description 5
- 230000005284 excitation Effects 0.000 abstract description 3
- 230000032683 aging Effects 0.000 abstract 1
- 238000012360 testing method Methods 0.000 description 36
- 239000000243 solution Substances 0.000 description 23
- 239000003973 paint Substances 0.000 description 12
- 239000011159 matrix material Substances 0.000 description 11
- 239000011259 mixed solution Substances 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 8
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 6
- 239000006255 coating slurry Substances 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 238000010422 painting Methods 0.000 description 6
- 239000010881 fly ash Substances 0.000 description 5
- 230000035699 permeability Effects 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- 230000002378 acidificating effect Effects 0.000 description 4
- 238000002474 experimental method Methods 0.000 description 4
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 3
- 239000000853 adhesive Substances 0.000 description 3
- 230000001070 adhesive effect Effects 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 238000003763 carbonization Methods 0.000 description 3
- 238000005336 cracking Methods 0.000 description 3
- 230000001804 emulsifying effect Effects 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 239000004570 mortar (masonry) Substances 0.000 description 3
- 239000004814 polyurethane Substances 0.000 description 3
- 229920002635 polyurethane Polymers 0.000 description 3
- 229910000077 silane Inorganic materials 0.000 description 3
- 238000007655 standard test method Methods 0.000 description 3
- 239000002344 surface layer Substances 0.000 description 3
- 238000010998 test method Methods 0.000 description 3
- 238000005303 weighing Methods 0.000 description 3
- 229910001294 Reinforcing steel Inorganic materials 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 239000001569 carbon dioxide Substances 0.000 description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- 239000011247 coating layer Substances 0.000 description 2
- 238000010276 construction Methods 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 238000006731 degradation reaction Methods 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical compound [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000003822 epoxy resin Substances 0.000 description 2
- 229920000876 geopolymer Polymers 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- 239000010410 layer Substances 0.000 description 2
- 230000007774 longterm Effects 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 229920000647 polyepoxide Polymers 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 230000008961 swelling Effects 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 230000005587 bubbling Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000011161 development Methods 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
- 238000005187 foaming Methods 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- -1 halogen ions Chemical class 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 230000009545 invasion Effects 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000010907 mechanical stirring Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002897 polymer film coating Substances 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 230000008439 repair process Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
- C04B41/45—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements
- C04B41/52—Multiple coating or impregnating multiple coating or impregnating with the same composition or with compositions only differing in the concentration of the constituents, is classified as single coating or impregnation
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
- C04B41/009—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone characterised by the material treated
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
- C04B41/60—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone of only artificial stone
- C04B41/61—Coating or impregnation
- C04B41/70—Coating or impregnation for obtaining at least two superposed coatings having different compositions
-
- 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
- C09D1/00—Coating compositions, e.g. paints, varnishes or lacquers, based on inorganic substances
-
- 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
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
- C09D7/61—Additives non-macromolecular inorganic
-
- 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
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/65—Additives macromolecular
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Ceramic Engineering (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Structural Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- Wood Science & Technology (AREA)
- Inorganic Chemistry (AREA)
- Paints Or Removers (AREA)
- Aftertreatments Of Artificial And Natural Stones (AREA)
Abstract
The invention discloses a composite acid-resistant cement concrete protective coating material, and a preparation method and application thereof. The method comprises the steps of adding mixed powder of metakaolin, wollastonite powder, nano SiO 2 and the like into an organic solution of a mixed cosolvent of polyvinyl butyral (PVB), and obtaining a coating material through weak acid excitation, mixing, homogenizing and dispersing. The coating material can be directly coated on the surface of the concrete after the primer treatment, and has the characteristics of difficult aging, good durability, good interface bonding performance, acid corrosion resistance and low cost because the main component of the coating material is inorganic matter, and the use process is simple and efficient.
Description
Technical Field
The invention belongs to the field of cement concrete protection and repair, and in particular relates to a composite acid-resistant concrete protection coating material obtained by mixing metakaolin, wollastonite powder, nano SiO 2 and the like to obtain powder components, adding the powder components into an organic solution of a polyvinyl butyral (PVB) mixed cosolvent, adding weak acid for excitation and then homogenizing and dispersing, and a preparation method thereof.
Background
Concrete is widely used as civil engineering material in industrial and civil buildings, and the cement concrete material is alkaline and has a PH value of over 10. In weak acid gas-liquid service environment, the corrosion is likely to suffer from physical and chemical erosion such as halogen ions, sewage, carbon dioxide, sulfate and the like, and due to the porous structure, the corrosion is often transferred from the surface to the inside, so that the performance of the concrete structure is degraded, the internal reinforcing steel bars are corroded, the whole service life is reduced, and therefore, effective measures must be taken on the surface layer of the matrix to prevent harmful ions from invading the inside of the concrete. Surface coating technology has become an economically viable method of improving the durability of the overall system. The surface coating forms a protective barrier between the concrete surface layer and the external environment, thereby effectively blocking harmful ion invasion and preventing or delaying the degradation of the concrete structure.
Most of the surface coatings at present are organic coatings, mainly acrylic resin, epoxy resin, polyurethane and silane/siloxane, and the coating can form a continuous polymer film coating on the surface layer of concrete, and has strong hydrophobic property. The organic paint has wide application, and the paint is recommended in JT/T695-2007 standard of concrete bridge structure surface coating anti-corrosion technical condition, etc. The organic coating has good sealing performance, has good isolation effect on gas, water, ions and the like, and can effectively improve the durability of the concrete. Research shows that the organic paint can obviously reduce the water absorption rate and chloride ion diffusion coefficient of concrete, obviously reduce the carbonization of concrete, and the carbonization resistance of the acrylate paint, the epoxy resin paint and the polyurethane paint is sequentially enhanced. After the polyurethane-based paint and the epoxy-based paint are subjected to dry-wet and hot-cold circulation for 5 months, the paint has no water seepage phenomenon, the change of the permeability is negligible, and the organic paint is also suitable for concrete engineering in low-temperature areas. The organic paint has wide application and good effect, but has insufficient weather resistance, is easy to age, and can obviously reduce the action effect under high temperature and ultraviolet irradiation to generate cracks or flaking.
The inorganic coating mainly comprises a cement-based permeable crystallization type waterproof coating, a silane coating, a geopolymer coating, a silicate coating and the like, has the advantages of wide raw material sources, low cost and the like, but the inorganic coating material also has some disadvantages, such as inferior toughness as an organic polymer coating, easy cracking and possibly poor matrix combination; the permeable crystallization type waterproof paint is easy to fall off under the acidic condition, the crystal has poor corrosion resistance and lower bonding strength with concrete; most of the geopolymer coatings need to be cured at high temperature, and construction is difficult in wet and cold environments; the silane coating and the siloxane coating have poor carbonization resistance, can not effectively reduce the diffusion rate of carbon dioxide, have poor concrete treatment effects on higher and lower porosity, have excessive pores on the surface of the concrete, are difficult to fully impregnate, can not effectively reduce the water absorption rate of the concrete, and the like.
Therefore, aiming at the urgent requirement of long-term durability protection of concrete in a special weak acidic service environment, in view of the limitation of crack resistance toughness of the traditional inorganic coating and weather resistance and environmental protection of the organic coating, the development of inorganic-based composite surface coating materials has important significance.
Disclosure of Invention
Aiming at the problems that in the prior art, the concrete organic coating is insufficient in weather resistance and easy to age, the inorganic coating is insufficient in toughness, the usability under acidic conditions is insufficient, the construction is inconvenient, the requirement of long-term durability protection of the concrete in a weak acidic environment is difficult to meet, and the like, the invention provides a concrete composite acid-resistant coating material, a preparation method and application thereof, and the material can fully combine the performance advantages of the organic coating and the inorganic coating to prepare a composite coating material meeting the performance requirement; the preparation method has no special requirements on equipment, is beneficial to industrial production and has good application effect.
In order to achieve the technical aim, the invention provides a composite acid-resistant concrete protective coating material, which comprises raw materials of mixed powder material, weak acid, organic polymer and cosolvent, wherein the mass ratio of the weak acid to the powder material is 5:1-1:5, the mass ratio of the powder material to the organic polymer is 1:0.05-1:0.25, and the mass ratio of the organic polymer to the cosolvent is 5:1-1:15;
the powder material is formed by mixing the following powder substances in percentage by mass: 20-100% of metakaolin, 0-40% of wollastonite powder and 0-40% of nano SiO 2;
the weak acid comprises at least one of phosphoric acid, metaphosphoric acid, oxalic acid, acetic acid and carbonic acid;
the cosolvent comprises at least one of methanol, ethanol, propanol, n-butanol and isobutanol.
The invention has the preferable technical scheme that: the organic polymer is polyvinyl butyral, and a cosolvent is adopted to disperse the polyvinyl butyral to form a uniform solution; when the cosolvent comprises two substances of methanol or ethanol or propanol and n-butanol or isobutanol, the mass ratio of the methanol or ethanol or propanol to the n-butanol or isobutanol is 10:1-1:5.
The invention has the preferable technical scheme that: the powder material is formed by mixing the following powder substances in percentage by mass: 60-100% of metakaolin, 0-20% of wollastonite powder and 0-20% of nano SiO 2.
The invention has the preferable technical scheme that: the mass ratio of the weak acid to the powder material is 2:1-1:3.
The invention has the preferable technical scheme that: the mass ratio of the organic polymer to the cosolvent is 1:5-1:10.
The invention has the preferable technical scheme that: the mass ratio of the methanol or the ethanol or the propanol to the n-butanol or the isobutanol in the cosolvent is 5:1-1:1.
The invention also provides a preparation method of the composite acid-resistant concrete protective coating material, which is prepared from the raw materials for preparing the composite acid-resistant concrete protective coating material, and comprises the following specific steps:
(1) Preparing powder materials, uniformly mixing the powder materials in a co-ball milling mode, so that the specific surface area of the powder is more than or equal to 10000m 3/kg;
(2) Dispersing an organic polymer in a dispersion emulsion homogenizer by adopting a cosolvent to form a uniform solution;
(3) Adding the powder material with the specific surface area more than or equal to 10000m 3/kg in the step (1) into the organic polymer solution in the step (2), uniformly mixing and stirring under the condition of stirring speed of 0-2000 r/min, then adding the weak acid excitant, continuously uniformly stirring under the condition of stirring speed of 500-3000 r/min, and preparing the fluid composite acid-resistant concrete protective coating material, wherein the overall stirring time is 1-1 h.
The invention has the preferable technical scheme that: the specific surface area of the split bodies in the powder material in the step (1) is more than or equal to 20000m 3/kg.
The invention has the preferable technical scheme that: in the step (3), the powder material is added into the organic polymer solution, the stirring speed is 200-1000 r/min, the stirring speed is 1000-2000 r/min after the weak acid excitant is added, and the stirring is uniform to form the fluid composite acid-resistant concrete protective coating material, and the stirring time is 1-30 min.
The invention provides an application of the composite acid-resistant concrete protective coating material prepared by the preparation method of the composite acid-resistant concrete protective coating material, which comprises the following specific steps:
(1) Cleaning and drying the surface of a concrete substrate, uniformly brushing at least two layers of inorganic silicon primer, sealing surface pores and defects, and airing for later use;
(2) And uniformly coating the composite acid-resistant concrete protective coating material on the surface of the concrete matrix treated by the primer, controlling the thickness of the coating to be 3-10 mm, then scraping the surface with a steel rule, enabling the surface of the coating to be smooth and flat, covering with a film after finishing, and then carrying out natural standing maintenance at the temperature of not lower than 20 ℃.
The invention uses weak acid to excite chemical reactivity of inorganic components, bulk density filling is carried out among different particle sizes, and simultaneously uses the properties of organic polymer homogeneously dispersed particles and the characteristic of rapid film formation, so that the prepared composite coating has high performance and acid resistance. The weak acid excitant is used for exciting the chemical reactivity of inorganic components, and does not damage the structure of concrete. The organic polymer is polyvinyl butyral (PVB) and is used for improving the film forming property of the coating material, increasing the toughness of the coating and avoiding the problem that the inorganic coating is easy to crack. The cosolvent package is used for assisting in dissolving the organic polymer and uniformly dispersing the powder component.
In the invention, the powder materials are uniformly mixed by adopting a co-ball milling mode, so that the specific surface area of the powder is more than or equal to 10000m < 3 >/kg; the organic polymer mixed solution is prepared by mixing the organic polymer mixed solution with the solvent according to the above-described proportion, and uniformly dispersing the organic polymer in the mixed solution by using a dispersing and emulsifying homogenizer. The liquid-solid mixing method adopts a two-stage mechanical stirring method, so that the raw materials can be uniformly stirred. The coating material provided by the invention can be uniformly coated on the surface of the concrete material treated by the primer. The concrete substrate is required to be cleaned and dried on the surface, then inorganic silicon primer is uniformly coated for two times, surface pores and defects are closed, and then the concrete substrate is dried for standby.
Compared with the prior art, the technical scheme of the invention has the beneficial technical effects that:
(1) The invention utilizes the organic solution of the mixed cosolvent of polyvinyl butyral (PVB), and adds the mixed powder of metakaolin, wollastonite powder, nano SiO 2 and the like, and the coating material is obtained through weak acid excitation, mixing, homogenizing and dispersing. The water-insoluble PVB resin polymer material is uniformly dispersed in the phosphoric acid-based inorganic material, so that the acid-base resistance, the flexibility and the flexibility of the PVB film-forming material are fully utilized, and the prepared composite acid-resistant coating material has the advantages of strong weather resistance, good impermeability and waterproofness, strong interface bonding performance, low cost and the like.
(2) The cement concrete matrix is alkaline, is extremely easy to be corroded and damaged in weak acid or acid service environment, and leads to degradation of structural performance and corrosion of internal reinforcing steel bars, so that the overall service life is reduced.
(3) The preparation method of the composite coating can be used for referencing the existing technology, has no special requirements on equipment, is simple to operate, has low cost and is beneficial to industrial production.
Drawings
FIG. 1 is a photograph of a concrete test piece A in example 1;
FIGS. 2 and 3 are photographs of concrete test pieces in comparative test 1;
FIG. 4 is a photograph of a concrete sample B in example 2;
FIG. 5 is a photograph of a concrete sample C in example 3;
FIG. 6 is a photograph of a concrete test piece in comparative experiment 2.
Detailed Description
The invention is further described below with reference to the drawings and examples. The following technical solutions presented in the drawings are specific to embodiments of the present invention and are not intended to limit the scope of the claimed invention. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
The raw materials of the composite acid-resistant concrete protective coating material comprise mixed powder materials, weak acid, organic polymer and cosolvent, wherein the organic polymer is polyvinyl butyral, the polyvinyl butyral is dispersed by the cosolvent to form a uniform solution, and the weak acid comprises at least one of phosphoric acid, metaphosphoric acid, oxalic acid, acetic acid and carbonic acid; the mass ratio of the weak acid to the powder material is 5:1-1:5, and the preferable mass ratio is 2:1-1:3; the mass ratio of the organic polymer to the cosolvent is 5:1-1:15, and the preferable mass ratio is 1:5-1:10; the mass ratio of the powder material to the organic polymer is 1:0.05-1:0.25; the powder material is formed by mixing the following powder substances in percentage by mass: 20-100% of metakaolin, 0-40% of wollastonite powder and 0-40% of nano SiO 2; the preferable scheme is as follows: 60-100% of metakaolin, 0-20% of wollastonite powder and 0-20% of nano SiO 2.
The cosolvent comprises at least one of methanol, ethanol, propanol, n-butanol and isobutanol. When the cosolvent comprises two substances of methanol or ethanol or propanol and n-butanol or isobutanol at the same time, the mass ratio of the methanol or ethanol or propanol to the n-butanol or isobutanol is 10:1-1:5, and the preferred mass ratio is 5:1-1:1.
The preparation method of the composite acid-resistant concrete protective coating material in the embodiment comprises the following specific steps:
(1) Preparing powder materials, uniformly mixing the powder materials by adopting a co-ball milling mode, so that the specific surface area of the powder is more than or equal to 10000m 3/kg, preferably the specific surface area is more than or equal to 20000m 3/kg
(2) Dispersing an organic polymer in a dispersion emulsion homogenizer by adopting a cosolvent to form a uniform solution;
(3) Adding the powder material with the specific surface area more than or equal to 10000m 3/kg in the step (1) into the organic polymer solution in the step (2), uniformly mixing and stirring under the condition of stirring speed of 0-2000 r/min (preferably stirring speed of 200-1000 r/min), then adding the weak acid excitant, continuously uniformly stirring under the condition of stirring speed of 500-3000 r/min (preferably 1000-2000 r/min), and preparing the fluid composite acid-resistant concrete protective coating material, wherein the overall stirring time is 1-1 h (preferably 1-30 min).
The application of the composite acid-resistant concrete protective coating material in the following examples comprises the following specific steps:
(1) Cleaning and drying the surface of a concrete substrate, uniformly brushing at least two layers of inorganic silicon primer, sealing surface pores and defects, and airing for later use;
(2) And uniformly coating the composite acid-resistant concrete protective coating material on the surface of the concrete matrix treated by the primer, controlling the thickness of the coating to be 3-10 mm, then scraping the surface with a steel rule, enabling the surface of the coating to be smooth and flat, covering with a film after finishing, and then carrying out natural standing maintenance at the temperature of not lower than 20 ℃.
The invention will be further described with reference to the following specific examples, but the scope of the invention is not limited thereto.
Example 1: the test materials included commercially available Metakaolin (MK), H 3PO4 solutions, polyvinyl butyral (PVB), and the like, see the following table:
| Sequence number | Variety of species | Mass ratio | Remarks |
| 1 | Metakaolin (MK) | 1.0 | White powder, specific surface area 25000m 3/kg |
| 2 | Phosphoric acid (H 3PO4) solution | 1.0 | Purity is more than or equal to 85 percent |
| 3 | Polyvinyl butyral (PVB) | 0.19 | White powder |
| 4 | Ethanol | 1.52 | Analytical grade |
Selecting a cement concrete substrate, requiring surface cleaning and drying, pre-painting inorganic silicon primer on the surface, painting for two times, requiring completely and uniformly sealing the concrete surface, and then airing for later use.
Weighing PVB powder and ethanol solution according to the mass ratio of 1:8, and using an FJ200-SH digital display dispersion emulsion homogenizer with adjustable rotating speed to uniformly disperse the PVB powder in ethanol to prepare PVB mixed solution. 10g of metakaolin is weighed and added into 17.1g of PVB mixed solution at a constant speed, a constant-speed cantilever type electric stirrer is adopted, the stirring speed is 500-800 r/min, 10g of H 3PO4 solution is dripped in 1min, the stirring speed is adjusted to 1000-1500 r/min, and stirring is continued until the uniform-flow state composite acid-resistant concrete protective coating material slurry is obtained, and the whole stirring process is 5-10 min.
And (3) horizontally placing the surface-treated concrete test piece, uniformly coating the surface with coating slurry, scraping a collecting surface with a steel rule, controlling the thickness of the coating to be about 5mm, and carrying out natural standing maintenance after the coating surface is required to be smooth and flat, so as to prepare the concrete test piece A (shown in figure 1).
Testing the pull-off strength of the coating and the matrix by using a portable adhesive force tester according to ASTM-D4541-2009"Standard Test Method for Pull-Off Strength of Coatings Using Portable Adhesion Testers",; the relative permeability coefficient of the coating itself was tested according to the relevant specifications for the mortar impermeability test in SL/T352-2022, hydraulic concrete test procedure, the test results of the coating are shown in FIG. 1 and Table 1:
Table 1 shows the results of the application test of the coating material prepared in example 1
The inventors of the present application conducted comparative experiment 1 with respect to example 1, and prepared the test raw material of the coating layer of comparative experiment 1 and the stirring process of the coating layer were the same as in example 1. The difference is that the surface of the cement concrete substrate is not pre-painted with primer, and the surface is directly painted with coating slurry. In the coating process, the coating cannot be well adhered to the substrate, a swelling and foaming phenomenon is generated (shown in fig. 2), and the coating is easy to slip off from the substrate (shown in fig. 3), because the coating is weak acid, the cement concrete is alkaline, and the coating and the cement concrete are chemically reacted. The test results are shown in Table 2 below:
table 2 shows the results of the application test of the coating material prepared in comparative test 1
| Sequence number | Test index | Test results |
| 1 | Appearance of | Swelling, bubbling, cracking of the coating, corrosion of the substrate by acid |
| 2 | Interfacial bonding force with a substrate | Failure to bond well |
| 3 | Acid resistance | / |
| 4 | Crack resistance | Cracking and drying, and then falling off from the base |
| 5 | Coefficient of relative permeability | / |
Example 2
The test materials included commercially available Metakaolin (MK), wollastonite powder, H 3PO4 solution, polyvinyl butyral (PVB), and the like, as shown in the following table:
Selecting a cement concrete substrate, requiring surface cleaning and drying, pre-painting inorganic silicon primer on the surface, painting the surface twice, ensuring that the surface of the concrete is completely and uniformly sealed, and then airing the concrete for later use. Weighing PVB powder and cosolvent solution (ethanol and n-butanol in a ratio of 2:1) according to a mass ratio of 1:9, and uniformly dispersing the PVB powder in the cosolvent by using a digital display dispersing emulsifying homogenizer with adjustable rotating speed to prepare PVB mixed solution. 9.0g of metakaolin and 10g of wollastonite powder are weighed and mixed, then the mixture is added into 19.0g of PVB mixed solution at a constant speed, a constant-speed cantilever type electric stirrer is adopted, the stirring speed is 500-800 r/min, 10g of H 3PO4 solution is dripped in 1min, the stirring speed is adjusted to 1000-1500 r/min, and stirring is continued until uniform-flow-state coating slurry is obtained, and the whole stirring process is 10-15 min.
And (3) horizontally placing the surface-treated concrete test piece, uniformly coating the surface with coating slurry, scraping the surface with a steel rule, controlling the thickness of the coating to be about 3mm, and preparing the concrete test piece B (shown in figure 4) by standing and curing the coated surface in a room after the coating is covered by a film.
Testing the pull-off strength of the coating and the matrix by using a portable adhesive force tester according to ASTM-D4541-2009"Standard Test Method for Pull-Off Strength of Coatings Using Portable Adhesion Testers",; the relative permeability coefficient of the coating itself was tested according to the relevant specifications for the mortar impermeability test in SL/T352-2022, hydraulic concrete test procedure, the test results of the coating are shown in FIG. 4 and Table 3:
Table 3 shows the results of the application test of the coating material prepared in example 2
Example 3
The test raw materials include commercial Metakaolin (MK), nano SiO 2, fly ash, H 3PO4 solution, polyvinyl butyral (PVB) and the like, and the following table is provided:
| Sequence number | Variety of species | Mass ratio | Remarks |
| 1 | Metakaolin (MK) | 0.9 | White powder |
| 2 | Nano SiO 2 | 0.5 | White powder |
| 3 | Fly ash | 0.5 | Gray powder |
| 4 | Phosphoric acid (H 3PO4) solution | 1.2 | Purity is more than or equal to 85 percent |
| 5 | Polyvinyl butyral (PVB) | 0.2 | White powder |
| 6 | Ethanol | 1.8 | Analytical grade |
Selecting a cement concrete substrate, requiring surface cleaning and drying, pre-painting inorganic silicon primer on the surface, painting for two times, requiring completely and uniformly sealing the concrete surface, and then airing for later use.
Weighing PVB powder and ethanol solution according to the mass ratio of 1:9, and using a digital display dispersing emulsifying homogenizer, wherein the rotating speed is adjustable, so that the PVB powder is uniformly dispersed in the ethanol to prepare PVB mixed solution. 9.0g of metakaolin, 5g of nano SiO 2 and 5g of fly ash are weighed, mixed and ground by a ball mill, and the specific surface area after grinding is 19000m 3/kg; adding the mixed powder into 20.0g of PVB mixed solution at a constant speed, adopting a constant-speed cantilever type electric stirrer, dripping 12.0g of H 3PO4 solution within 1min, adjusting the stirring speed to 1000-1500 r/min, and continuously stirring until uniform-flow-state coating slurry is obtained, wherein the whole stirring process is 15-20 min.
And (3) horizontally placing the surface-treated concrete test piece, uniformly coating the surface with coating slurry, scraping a collecting surface with a steel rule, controlling the thickness of the coating to be about 5mm, and carrying out natural standing maintenance after the coating surface is required to be smooth and flat and the film is covered to prepare the concrete test piece C (shown in figure 5).
Testing the pull-off strength of the coating and the matrix by using a portable adhesive force tester according to ASTM-D4541-2009"Standard Test Method for Pull-Off Strength of Coatings Using Portable Adhesion Testers",; the relative permeability coefficient of the coating itself was tested according to the relevant specifications for the mortar impermeability test in SL/T352-2022, hydraulic concrete test procedure, the test results of the coating are shown in FIG. 5 and Table 4:
Table 4 shows the results of the application test of the coating material prepared in example 3
Comparative test 2, comparative example 3, the test raw materials included commercial Metakaolin (MK), nano SiO 2, fly ash, H 3PO4 solution, without polyvinyl butyral (PVB), see table below:
| Sequence number | Variety of species | Mass ratio | Remarks |
| 1 | Metakaolin (MK) | 0.9 | White powder |
| 2 | Nano SiO 2 | 0.5 | White powder |
| 3 | Fly ash | 0.5 | Gray powder |
| 4 | Phosphoric acid (H 3PO4) solution | 1.2 | Purity is more than or equal to 85 percent |
The test reduced the process of preparing and using PVB mixed solutions, with the remainder being essentially the same as in example 3. The test results of the coatings are shown in fig. 6 and table 5:
Table 5 shows the results of the application test of the coating material prepared in comparative experiment 2
The result shows that the polyvinyl butyral (PVB) component is not adopted, the coating has larger shrinkage deformation, the thickness is controlled to be 3mm, and when the coating is coated on the surface of a concrete matrix, the coating has large brittleness after being coated on the surface of the concrete matrix, and the coating is easy to crack to cause poor adhesion with the matrix and water permeation.
The foregoing description of certain embodiments of the invention has been presented only to provide a particular and detailed description of the invention, but is not to be construed as limiting the scope of the invention. It should be noted that it will be apparent to those skilled in the art that several variations and modifications can be made without departing from the spirit of the invention, which are all within the scope of the invention. Accordingly, the scope of the invention should be assessed as that of the appended claims.
Claims (9)
1. A composite acid-resistant concrete protective coating material is characterized in that: the raw materials of the protective coating material comprise powder materials, weak acid, organic polymers and a cosolvent, wherein the mass ratio of the weak acid to the powder materials is 5:1-1:5, the mass ratio of the powder materials to the organic polymers is 1:0.05-1:0.25, and the mass ratio of the organic polymers to the cosolvent is 5:1-1:15;
The powder material is formed by mixing the following powder substances in percentage by mass: 20% -100% of metakaolin, 0% -40% of wollastonite powder and 0% -40% of nano SiO 2;
The weak acid comprises at least one of phosphoric acid, metaphosphoric acid, oxalic acid and acetic acid;
The cosolvent comprises at least one of methanol, ethanol, propanol, n-butanol and isobutanol;
The organic polymer is polyvinyl butyral, and a cosolvent is adopted to disperse the polyvinyl butyral to form a uniform solution; when the cosolvent comprises methanol or ethanol or propanol and n-butanol or isobutanol, the mass ratio of the methanol or ethanol or propanol to the n-butanol or isobutanol is 10:1-1:5.
2. The composite acid-resistant concrete protective coating material according to claim 1, wherein the powder material is formed by mixing the following powder substances in percentage by mass: 60-100% of metakaolin, 0-20% of wollastonite powder and 0-20% of nano SiO 2.
3. The composite acid resistant concrete protective coating material of claim 1, wherein: the mass ratio of the weak acid to the powder material is 2:1-1:3.
4. The composite acid resistant concrete protective coating material of claim 1, wherein: the mass ratio of the organic polymer to the cosolvent is 1:5-1:10.
5. The composite acid resistant concrete protective coating material of claim 1, wherein: the mass ratio of the methanol or the ethanol or the propanol to the n-butanol or the isobutanol in the cosolvent is 5:1-1:1.
6. A preparation method of a composite acid-resistant concrete protective coating material, which is characterized by adopting the preparation raw materials of the composite acid-resistant concrete protective coating material as claimed in any one of claims 1 to 5, and comprises the following specific steps:
(1) Preparing powder materials, uniformly mixing the powder materials in a co-ball milling mode, so that the specific surface area of the powder is more than or equal to 10000m 3/kg;
(2) Dispersing an organic polymer in a dispersion emulsion homogenizer by adopting a cosolvent to form a uniform solution;
(3) Adding the powder material with the specific surface area more than or equal to 10000m 3/kg in the step (1) into the organic polymer solution in the step (2), uniformly mixing and stirring under the condition of stirring speed of 0-2000 r/min, then adding weak acid, and continuously and uniformly stirring under the condition of stirring speed of 500-3000 r/min to prepare the fluid composite acid-resistant concrete protective coating material, wherein the overall stirring time is 1 min-1 h.
7. The method for preparing the composite acid-resistant concrete protective coating material according to claim 6, which is characterized in that: the specific surface area of the powder in the powder material in the step (1) is more than or equal to 20000m 3/kg.
8. The method for preparing the composite acid-resistant concrete protective coating material according to claim 6, which is characterized in that: in the step (3), the powder material is added into the organic polymer solution, the stirring speed is 200-1000 r/min, the stirring speed is 1000-2000 r/min after weak acid is added, and the powder material is uniformly stirred to form the fluid composite acid-resistant concrete protective coating material, and the stirring time is 1-30 min.
9. Use of a composite acid resistant concrete protective coating material prepared according to the method of preparation of a composite acid resistant concrete protective coating material according to any one of claims 6 to 8, characterized by the specific steps of:
(1) Cleaning and drying the surface of a concrete substrate, uniformly brushing at least two layers of inorganic silicon primer, sealing surface pores and defects, and airing for later use;
(2) And uniformly coating the composite acid-resistant concrete protective coating material on the surface of a concrete substrate treated by the primer, controlling the thickness of the coating to be 3-10 mm, then scraping a finishing surface by using a steel rule, enabling the surface of the coating to be smooth and flat, covering the finished coating by using a film, and then carrying out natural standing maintenance in an environment of not lower than 20 ℃.
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