CN113897115B - Protective basalt flake coating capable of improving corrosion resistance of concrete and preparation method thereof - Google Patents

Protective basalt flake coating capable of improving corrosion resistance of concrete and preparation method thereof Download PDF

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CN113897115B
CN113897115B CN202111230259.1A CN202111230259A CN113897115B CN 113897115 B CN113897115 B CN 113897115B CN 202111230259 A CN202111230259 A CN 202111230259A CN 113897115 B CN113897115 B CN 113897115B
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parts
basalt
solvent
coating
component
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CN113897115A (en
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白永平
曹柏青
安英斌
王建伟
李先林
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Zhongke Huakun Beijing Technology Co ltd
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Hualinhai Hainan New Material Technology Co ltd
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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
    • C09D163/00—Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
    • 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
    • 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
    • C09D7/20—Diluents or solvents
    • 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
    • C09D7/62—Additives non-macromolecular inorganic modified by treatment with other compounds
    • 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
    • C09D7/70—Additives characterised by shape, e.g. fibres, flakes or microspheres
    • 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
    • C09D7/80—Processes for incorporating ingredients

Abstract

The invention provides a protective basalt flake coating for improving corrosion resistance of concrete and a preparation method thereof, wherein the coating comprises a component A and a component B, the component A is composed of epoxy resin, basalt flakes, nano-graphite alkyne, a silane coupling agent, an auxiliary agent and a solvent A, and the component B is composed of a curing agent and a solvent B; the weight portion of the material is as follows: 20-60 parts of epoxy resin, 5-20 parts of basalt flakes, 1-20 parts of nano-graphite alkyne, 1-10 parts of silane coupling agent, 1-3 parts of auxiliary agent, 5-50 parts of solvent A, 10-40 parts of curing agent and 5-50 parts of solvent B. The coating provided by the invention improves the corrosion resistance of the coating and obviously improves the chloride ion permeation resistance.

Description

Protective basalt flake coating capable of improving corrosion resistance of concrete and preparation method thereof
Technical Field
The invention relates to the field of corrosion-resistant coatings, in particular to a protective basalt flake coating for improving the corrosion resistance of concrete and a preparation method thereof.
Background
Reinforced concrete is widely used in various fields due to its excellent properties. However, concrete is subject to severe erosion in specific environments, which brings about severe economic loss, which statistically accounts for about 1.5-2.5% of GDP due to concrete corrosion each year. Chloride attack is a significant cause of concrete corrosion.
In the existing three-coating concrete protection system, for example, the coating system for dealing with the invasion of chloride ions in the guidance and explanation of the chloride ion countermeasure of roads and bridges published by the japan road association mostly adopts different matching modes such as epoxy resin or polyurethane, and plays a role in protecting chloride ions to a certain extent, but the effect is not good enough.
Disclosure of Invention
In view of the above, the invention provides a protective basalt flake coating for improving the corrosion resistance of concrete, and solves the above problems.
The technical scheme of the invention is realized as follows: the protective basalt flake coating capable of improving the corrosion resistance of concrete comprises a component A and a component B, wherein the component A is composed of epoxy resin, basalt flakes, nano-graphite alkyne, a silane coupling agent, an auxiliary agent and a solvent A, and the component B is composed of a curing agent and a solvent B; the weight portion of the material is as follows: 20-60 parts of epoxy resin, 5-20 parts of basalt flakes, 1-20 parts of nano-graphite alkyne, 1-10 parts of silane coupling agent, 1-3 parts of auxiliary agent, 5-50 parts of solvent A, 10-40 parts of curing agent and 5-50 parts of solvent B.
Further, the weight portions are as follows: 50 parts of epoxy resin, 15 parts of basalt flakes, 15 parts of nano-graphite alkyne, 5 parts of silane coupling agent, 2 parts of auxiliary agent, 30 parts of solvent A, 25 parts of curing agent and 10 parts of solvent B.
Further, the specific surface area of the nano-graphite alkyne is 210-230m2The graphite alkyne has the lamellar spacing of 0.36-0.42nm and the carbon content of more than 99 percent.
Further, the solvent A and the solvent B are one or more of dimethylbenzene, butanol and ethyl acetate.
Further, the solvent A is prepared from a solvent A and a solvent B in a volume ratio of 1: 2, mixing butanol and ethyl acetate; the solvent B is prepared from the following components in a volume ratio of 1: 3 butanol and ethyl acetate.
Further, the auxiliary agent is one or more of a dispersing agent, a defoaming agent and a flatting agent.
Further, the thickness of the basalt scales is 0.5-5 μm, and the mesh number is 200-1000 meshes.
Further, the epoxy resin is one or more of bisphenol A type epoxy resin, bisphenol F type epoxy resin and mixed type epoxy resin;
the silane coupling agent is one or more of KH550, KH560 and KH 570;
the curing agent is polyamide 300 and polyamide 650.
The invention also provides a preparation method of the coating for protecting basalt flakes, which comprises the following steps:
(1) adding the basalt flakes and the nano-graphite alkyne into a silane coupling agent for ultrasonic stirring to obtain modified basalt flakes and nano-graphite alkyne; mixing the modified basalt flakes and the nano-graphite alkyne with epoxy resin, an additive and a solvent to obtain a component A;
(2) mixing a curing agent and a solvent to obtain a component B;
(3) and mixing the component A and the component B to obtain the target coating.
Further, in the step (1), the ultrasonic stirring and heating are carried out simultaneously, the temperature is raised to 90-100 ℃ at the speed of 2-3 ℃/min, and the temperature is kept for 35-45 min; then heating to 150-; finally, the temperature is reduced to 50-60 ℃ at the speed of 9-11 ℃/min, and the temperature is preserved and heated for 60-70 min.
Compared with the prior art, the invention has the beneficial effects that:
(1) the invention mainly aims at the middle coating of a three-coating system, and the protective capability to chloride ions is further improved in a targeted manner on the basis of improving the corrosion resistance of the coating by adding basalt flakes and nano-graphite alkyne in the epoxy resin coating.
(2) The coating disclosed by the invention realizes effective adsorption of invasive chloride ions, remarkably improves the chloride ion permeation resistance and improves the corrosion resistance. According to the invention, the nano-graphite alkyne and the basalt flakes are compounded in a certain proportion, so that the chloride ion adsorption capacity of the coating is enhanced, and the acid and alkali resistance is improved.
(3) The invention adopts specific nano-graphite alkyne to further improve the corrosion resistance of the coating, and particularly improve the protective capability to chloride ions.
(4) The invention adopts the solvent with specific compounding proportion, further improves the corrosion resistance of the coating, and particularly improves the protective capability to chloride ions.
(5) The invention carries out three-stage gradient temperature stirring at a specific speed, is more beneficial to the formation of a honeycomb conductive network in the coating by the nano graphite alkyne, and further improves the corrosion resistance of the coating.
Detailed Description
In order to better understand the technical content of the invention, specific examples are provided below to further illustrate the invention.
The experimental methods used in the examples of the present invention are all conventional methods unless otherwise specified.
The materials, reagents and the like used in the examples of the present invention can be obtained commercially without specific description.
Example 1
1. Formulation of
Figure BDA0003315634850000031
2. Preparation method
(1) Adding the basalt flakes and the nano-graphite alkyne into a silane coupling agent, and carrying out ultrasonic stirring at the room temperature of 25 +/-5 ℃ to obtain modified basalt flakes and nano-graphite alkyne; mixing the modified basalt flakes and the nano-graphite alkyne with epoxy resin, an additive and a solvent to obtain a component A;
(2) mixing a curing agent and a solvent to obtain a component B;
(3) and mixing the component A and the component B to obtain the target coating.
Example 2
1. Formulation of
Figure BDA0003315634850000041
The component types were in accordance with example 1.
2. The preparation method comprises the following steps: in accordance with example 1.
Example 3
The amount of the raw materials was adjusted based on example 1. The specific formula is as follows:
components Formulation of Content (wt.)
A Epoxy resin 60 portions of
A Basalt scale 20 portions of
A Nano-graphite alkyne 20 portions of
A Silane coupling agent 10 portions of
A Auxiliary agent 3 portions of
A Solvent(s) 50 portions of
B Curing agent 40 portions of
B Solvent(s) 50 portions of
The preparation process was identical to example 1.
Example 4
The kinds of the solvent a and the solvent B were adjusted based on example 1. Solvent A is prepared from 1: 2, mixing butanol and ethyl acetate; solvent B is prepared from 1: 3 butanol and ethyl acetate. The preparation process was identical to example 1.
Example 5
On the basis of example 4, the preparation process was adjusted. The method specifically comprises the following steps:
(1) adding the basalt flakes and the nano-graphite alkyne into a silane coupling agent, carrying out ultrasonic stirring, heating while carrying out ultrasonic stirring, firstly heating to 90 ℃ at the speed of 2-3 ℃/min, and carrying out heat preservation and heating for 45 min; heating to 150 deg.C at a rate of 4-6 deg.C/min, and maintaining the temperature for 20 min; finally, cooling to 50 ℃ at the speed of 9-11 ℃/min, and keeping the temperature and heating for 70 min; obtaining modified basalt flakes and nano-graphite alkyne; mixing the modified basalt flakes and the nano-graphite alkyne with epoxy resin, an additive and a solvent to obtain a component A;
(2) mixing a curing agent and a solvent to obtain a component B;
(3) and mixing the component A and the component B to obtain the target coating.
Example 6
On the basis of example 4, the preparation process was adjusted. The method specifically comprises the following steps:
(1) adding the basalt flakes and the nano-graphite alkyne into a silane coupling agent, carrying out ultrasonic stirring, heating while carrying out ultrasonic stirring, firstly heating to 100 ℃ at the speed of 2-3 ℃/min, and carrying out heat preservation and heating for 35 min; heating to 200 deg.C at a rate of 4-6 deg.C/min, and maintaining the temperature for 15 min; finally, cooling to 60 ℃ at the speed of 9-11 ℃/min, and keeping the temperature and heating for 60 min; obtaining modified basalt flakes and nano-graphite alkyne; mixing the modified basalt flakes and the nano-graphite alkyne with epoxy resin, an additive and a solvent to obtain a component A;
(2) mixing a curing agent and a solvent to obtain a component B;
(3) and mixing the component A and the component B to obtain the target coating.
Comparative example 1
On the basis of the embodiment 1, the nano-graphite alkyne is replaced by the same amount of nano-graphene.
The preparation method comprises the following steps:
(1) adding the basalt flakes and the nano-graphene into a silane coupling agent, and carrying out ultrasonic stirring at the room temperature of 25 +/-5 ℃ to obtain modified basalt flakes and nano-graphene; mixing the modified basalt flakes and nano-graphene with epoxy resin, an additive and a solvent to obtain a component A;
(2) mixing a curing agent and a solvent to obtain a component B;
(3) and mixing the component A and the component B to obtain the target coating.
Comparative example 2
On the basis of the embodiment 1, the dosage of the nano graphite alkyne is increased. The dosage of the specific formula is as follows:
components Formulation of Content (wt.)
A Epoxy resin 50 portions of
A Basalt scale 15 portions of
A Nano-graphite alkyne 60 portions of
A Silane coupling agent 5 portions of
A Auxiliary agent 2 portions of
A Solvent A 30 portions of
B Curing agent 25 portions of
B Solvent B 10 portions of
The preparation process was identical to example 1.
Test examples
The coatings prepared in examples 1-6 and comparative examples 1-2 above were tested separately:
1.1 testing of the ability of the coating to resist penetration of chloride ions
1.1.1 coating sample, materials:
epoxy seal coat, midcoat (examples 1-6 and comparative examples 1-2 coatings), acrylic polyurethane topcoat; the fineness paper is 150mm multiplied by 150 mm; NaCl benchmark reagent (3% NaCl solution).
1.1.2 test instruments: LC-4 general microcomputer coulometer.
1.1.3 test plate preparation: the coating sheet for test is prepared by using coating fineness paper of 150mm multiplied by 150mm as a reinforcing material, spreading the reinforcing material on a glass plate, and applying a primer, a middle coating and a finish to the matched coating for test according to the plate preparation requirements. After each coating film is applied, the fine paper is immediately lifted off the glass plate and hung on a rope, and then the coating film is coated one more time after 24 hours. A total of 4 coated sheets were produced in this way. After being made, the product is hung in an indoor natural curing room 28 d.
1.1.4 test method the prepared movable coating sheet is cut into a circular test piece with the diameter of 60mm, and a chlorine ion permeability resistance test is carried out. The painted side of the test piece was faced with 3% NaCl solution and the other side of the fine paper was faced with distilled water, sharing 3 sets of devices. The test is carried out under the indoor normal temperature condition, and after 30 days, the content of the chloride ions in the distilled water is measured by an LC-4 general microcomputer coulometer. And a blank test was also determined.
1.1.5 test results show
The amount of chloride ion permeation was calculated as follows:
Figure BDA0003315634850000071
s-chloride ion Permeability, mg/(cm)2·d)；
CSample (A)-3% NaCl solution is permeated into distilled water to reach chloride ion concentration of mg/L;
Cair conditioner-the chloride ion concentration in the blank test distilled water, mg/L;
v is distilled water volume, mL;
d, the diameter of the contact surface of the paint film and the NaC1 solution or water is mm;
d-test days.
1.2 acid and alkali resistance test
After the coating was immersed for 30 days at an alkaline pH of 9, the coating was tested for a value of | Z |0.01Hz,
after the coating is immersed for 30 days under an acidic environment with pH of 3, the | Z |0.01Hz value of the coating is tested,
and the percentage reduction of the | Z |0.01Hz value of the coating was calculated by comparison with the | Z |0.01Hz value of the coating before immersion, respectively. Percent decrease in coating | Z |0.01Hz value (| Z |0.01Hz value of coating before immersion- | Z |0.01Hz value of coating after immersion)/| Z |0.01Hz value of coating before immersion 100%.
1.3 test results
Figure BDA0003315634850000081
The results show that the coatings prepared in examples 1-6 effectively reduce the chloride ion permeation amount and effectively improve the acid and alkali corrosion resistance of the coating. Wherein, the coating is prepared by further optimizing the process in the examples 5 to 6, and the performance of the coating is greatly improved. Therefore, the coating provided by the invention can obviously improve the corrosion resistance of the coating and simultaneously improve the chloride ion permeation resistance.
In the comparative example 1, the nano-graphite alkyne is replaced by the nano-graphene, so that the performance of the coating is greatly reduced. Compared with the prior art, the performance of the prepared coating is obviously reduced by using excessive nano-graphite alkyne, and a certain amount of nano-graphite alkyne and basalt scale are added into the epoxy resin coating, so that the corrosion resistance of the coating is effectively improved, and the protective capability to chloride ions is further improved.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like made within the spirit and principle of the present invention should be included in the scope of the present invention.

Claims (10)

1. The protective basalt flake coating capable of improving corrosion resistance of concrete is characterized by comprising a component A and a component B, wherein the component A is composed of epoxy resin, basalt flakes, nano-graphite alkyne, a silane coupling agent, an auxiliary agent and a solvent A, and the component B is composed of a curing agent and a solvent B; the weight portion of the material is as follows: 20-60 parts of epoxy resin, 5-20 parts of basalt flakes, 1-20 parts of nano-graphite alkyne, 1-10 parts of silane coupling agent, 1-3 parts of auxiliary agent, 5-50 parts of solvent A, 10-40 parts of curing agent and 5-50 parts of solvent B.
2. The protective basalt scale coating of claim 1, wherein the coating comprises, in parts by weight: 50 parts of epoxy resin, 15 parts of basalt flakes, 15 parts of nano-graphite alkyne, 5 parts of silane coupling agent, 2 parts of auxiliary agent, 30 parts of solvent A, 25 parts of curing agent and 10 parts of solvent B.
3. The coating for protecting basalt scales as recited in claim 1, wherein the specific surface area of the nano graphdiyne is 210-230m2The graphite alkyne has the lamellar spacing of 0.36-0.42nm and the carbon content of more than 99 percent.
4. The protective basalt flake coating of claim 1, wherein the solvent a and the solvent B are each one or more of xylene, butanol, and ethyl acetate.
5. The protective basalt scale coating of claim 4, wherein the solvent A is comprised of, by volume ratio, 1: 2, mixing butanol and ethyl acetate; the solvent B is prepared from the following components in a volume ratio of 1: 3 butanol and ethyl acetate.
6. The coating for protecting basalt flakes according to claim 1, wherein the auxiliary agent is one or more of a dispersant, a defoamer and a leveling agent.
7. The coating for protecting basalt scales as recited in claim 1, wherein the basalt scales have a thickness of 0.55 μm and a mesh size of 200-1000 meshes.
8. The protective basalt flake coating of claim 1, wherein,
the epoxy resin is one or more of bisphenol A type epoxy resin, bisphenol F type epoxy resin and mixed type epoxy resin;
the silane coupling agent is one or more of KH550, KH560 and KH 570;
the curing agent is polyamide 300 and polyamide 650.
9. The preparation method of the protective basalt scale coating of any one of claims 1 to 8, comprising the steps of:
(1) adding the basalt flakes and the nano-graphite alkyne into a silane coupling agent for ultrasonic stirring to obtain modified basalt flakes and nano-graphite alkyne; mixing the modified basalt flakes and the nano-graphite alkyne with epoxy resin, an additive and a solvent to obtain a component A;
(2) mixing a curing agent and a solvent to obtain a component B;
(3) and mixing the component A and the component B to obtain the target coating.
10. The preparation method of the coating for protecting basalt flakes according to claim 9, wherein in the step (1), the ultrasonic agitation is performed while heating, the temperature is raised to 90-100 ℃ at a speed of 2-3 ℃/min, and the heat is preserved and heated for 35-45 min; then heating to 150-; finally, the temperature is reduced to 50-60 ℃ at the speed of 9-11 ℃/min, and the temperature is preserved and heated for 60-70 min.
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CN116239916A (en) * 2022-09-05 2023-06-09 龙牌涂料(北京)有限公司 Ultraviolet-absorbing indoor coating and preparation method thereof
CN115895394B (en) * 2023-01-09 2023-05-23 广东腐蚀科学与技术创新研究院 Interface passivation type heavy-duty anticorrosive powder coating and preparation method and application thereof

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