CN115058132B - Negative carbon self-cleaning inorganic coating, preparation method thereof and obtained coating - Google Patents

Negative carbon self-cleaning inorganic coating, preparation method thereof and obtained coating Download PDF

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CN115058132B
CN115058132B CN202210779046.2A CN202210779046A CN115058132B CN 115058132 B CN115058132 B CN 115058132B CN 202210779046 A CN202210779046 A CN 202210779046A CN 115058132 B CN115058132 B CN 115058132B
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coating
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CN115058132A (en
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杨露
方勇乐
王发洲
胡曙光
刘志超
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Wuhan University of Technology WUT
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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
    • 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
    • C09D7/60—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
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W30/00—Technologies for solid waste management
    • Y02W30/50—Reuse, recycling or recovery technologies
    • Y02W30/91—Use of waste materials as fillers for mortars or concrete

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Catalysts (AREA)
  • Paints Or Removers (AREA)

Abstract

The invention discloses a negative carbon self-cleaning inorganic coating, a preparation method thereof and an obtained coating. The negative carbon self-cleaning inorganic coating comprises the following raw materials in parts by weight: 40-90 parts of inorganic cementing material, 1-15 parts of composite photocatalytic medium, 0-50 parts of auxiliary carbonizing agent, 0-15 parts of thickening agent and 30-60 parts of water. The invention can be used in CO by selecting the cementing material with carbonization active ingredient 2 Calcium carbonate and silica gel are generated in the atmosphere, so that the paint has the effects of protecting buildings and bonding materials, has good weather resistance, has stable self-cleaning effect in the long-term rain wash, and provides a stable chemical environment for the composite photocatalytic medium; meanwhile, the phenomenon that the coating substrate is decomposed by superoxide ions and hydroxyl radicals generated by the composite photocatalytic medium under the excitation of ultraviolet light is avoided; by controlling the mixing amount of the composite photocatalytic medium and the solid content of the coating, the self-cleaning effect of the coating is further improved on the basis of ensuring the mechanical property of the coating.

Description

Negative carbon self-cleaning inorganic coating, preparation method thereof and obtained coating
Technical Field
The invention relates to the technical field of building materials, in particular to a negative carbon self-cleaning inorganic coating, a preparation method thereof and an obtained coating.
Background
Since the human society has stepped into a high-speed development stage, CO in the atmosphere has been caused due to excessive use of fossil fuels 2 The concentration of (A) is directly over 400ppm from around 300 ppm. This has brought about a series of disasters for humans: natural disasters such as sea level elevation leading to flooding in local areas, ocean acidification leading to species disappearance, and high temperatures. The deep emission reduction of greenhouse gases needs to be strictly controlled, and zero emission is realized.
Under the repeated action of factors such as sunlight, rain, haze, sand and the like, the traditional building coating material is gradually aged, and some organic or inorganic dust can be deposited on the surface of the coating. This not only causes the coating surface to continue to deteriorate, but also affects the cleanliness of the coating appearance. Therefore, a new self-cleaning building coating material is urgently needed to change the current situation.
At present, there are many researches on self-cleaning coating materials, mainly focusing on self-cleaning and super-cleaning by photocatalytic effectThe hydrophilic (hydrophobic) effect is self-cleaning. An organic self-cleaning coating material with a photocatalytic effect is prepared by the patent (CN 111004531A), and has a good self-cleaning effect. But when incorporated into TiO 2 When the content of (b) is low, the self-cleaning effect of the photocatalytic effect is not obvious; when doped with TiO 2 At higher contents of (B), too much TiO 2 Superoxide ions and hydroxyl radicals generated under the action of ultraviolet light can decompose the organic coating substrate, and the service life of the coating is shortened. Furthermore, the mere photocatalytic effect of self-cleaning relies entirely on ultraviolet light, which affects the range of applications for self-cleaning coatings. The patent (CN 103468086B) prepares a super-hydrophilic SiO 2 Based on self-cleaning coating materials. Technically, the cost is reduced by replacing the spin coating method with the spray coating method, but complicated surface drying and curing treatment are needed at the later stage, and particularly the temperature of the curing treatment is about 400 ℃.
With the development of building materials towards the direction of energy conservation and emission reduction, the current situation is changed by needing a self-cleaning coating material which is environment-friendly and has a lasting self-cleaning effect.
Disclosure of Invention
The invention aims to overcome the technical defects, provides a negative carbon self-cleaning inorganic coating, a preparation method thereof and an obtained coating, and solves the technical problems that the self-cleaning coating in the prior art cannot achieve good self-cleaning effect and durability and is not environment-friendly enough.
The invention provides a negative carbon self-cleaning inorganic coating, which comprises the following raw materials in parts by weight: 40-90 parts of inorganic cementing material, 1-15 parts of composite photocatalytic medium, 0-50 parts of auxiliary carbonizing agent, 0-15 parts of thickening agent and 30-60 parts of water; the inorganic cementing material is carbonization active ingredient or industrial solid waste at least containing 60 percent of carbonization active ingredient, and the carbonization active ingredient is at least one of dicalcium silicate, monocalcium silicate, tricalcium disilicate, calcium hydroxide and magnesium hydroxide; the composite photocatalytic medium consists of photocatalytic material and SiO-containing material 2 The carrier is compounded.
The second aspect of the invention provides a preparation method of a negative carbon self-cleaning inorganic coating, which comprises the following steps:
and uniformly mixing the inorganic cementing material, the composite photocatalytic medium, the auxiliary carbonizing agent, the thickening agent and water according to the proportion to obtain the negative carbon self-cleaning inorganic coating.
The third aspect of the invention provides a negative carbon self-cleaning inorganic coating, which is obtained by coating the negative carbon self-cleaning inorganic coating provided by the first aspect of the invention on the surface of a substrate and carrying out in-situ carbon mineralization reaction.
Compared with the prior art, the invention has the beneficial effects that:
the invention can be used in CO by selecting the cementing material with carbonization active ingredient 2 Calcium carbonate and silica gel are generated in the atmosphere, so that the paint has the effects of protecting buildings and bonding materials, has good weather resistance, has stable self-cleaning effect in the long-term rain wash, and provides a stable chemical environment for the composite photocatalytic medium; meanwhile, the phenomenon that the coating substrate is decomposed by superoxide ions and hydroxyl radicals generated by the composite photocatalytic medium under the excitation of ultraviolet light is avoided; by controlling the mixing amount of the composite photocatalytic medium and the solid content of the coating, the self-cleaning effect of the coating is further improved on the basis of ensuring the mechanical property of the coating; the invention has good self-cleaning effect, and can store a large amount of CO in the preparation process 2 The method has the characteristics of carbon-negative environmental protection and simple construction; the raw materials of the invention are all inorganic materials, the process flow is simple, the weather resistance is good, the invention is an environment-friendly self-cleaning inorganic coating, and the coating can be applied to the coating of the surface of a building and the self-cleaning of the inner surface of the building.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail with reference to the following embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and do not limit the invention.
The invention provides a negative carbon self-cleaning inorganic coating, which comprises the following raw materials in parts by weight: 40-90 parts of inorganic cementing material, 1-15 parts of composite photocatalytic medium, 0-50 parts of auxiliary carbonizing agent, 0-15 parts of thickening agent and 30-60 parts of water.
In the invention, the inorganic gel material has carbon mineralization activity and can absorb part of CO in the carbon mineralization process 2 The aim of 'carbon negative' in the production and preparation of the building coating material can be realized, and the composite photocatalytic material has a stable chemical environment after mineralization reaction, does not influence the catalytic activity of the composite photocatalytic medium, and can be chemically combined with the composite photocatalytic medium material; in addition, the carbon mineralized coating has certain strength and forms a porous structure, so that the composite photocatalytic medium can be exposed, and the formed coating has better self-cleaning performance. The inorganic cementing material may be directly active carbonization components such as dicalcium silicate, monocalcium silicate, tricalcium disilicate, calcium hydroxide, magnesium hydroxide, etc., or may be industrial solid waste containing at least 60% of the active carbonization components, such as steel slag powder containing not less than 70% of active carbonization components, magnesium slag powder containing not less than 70% of active carbonization components, etc., which is not limited in the present invention.
In some embodiments of the present invention, the particle size of the inorganic gelling material is 50nm to 8 μm.
In the present invention, the mass ratio of the inorganic gelling material to water is (0.9 to 1.5): 1, and more preferably (1.2 to 1.5): 1. The inventors have found that the mass ratio of inorganic gelling material to water has a large influence on the coating properties. With the reduction of the mass ratio of the inorganic cementing material to water, the porosity of the formed coating is increased, which is beneficial to exposing more composite photocatalytic media, and finally the obtained coating has a better photocatalytic self-cleaning effect, but the mechanical property is obviously reduced.
In the invention, the composite photocatalytic medium consists of a photocatalytic material and SiO-containing 2 The carrier is compounded. On one hand, the composite photocatalytic medium has a good photocatalytic self-cleaning effect, for example, in some embodiments of the present invention, the photoelectron efficiency of NO of 1g of the composite photocatalytic medium can reach 0.86%; on the other hand, the modified epoxy resin can form chemical bond with a cementing material, and the durability is improved. Further, the photocatalytic material can be one of nano titanium dioxide, nano zinc oxide and nano ferric oxideAt least one of; the main component of the carrier is SiO 2 So as to form a chemical bond with the cementitious material during the carbon mineralization, which may be, for example, hydrophilic SiO 2 At least one of aerogel, hydrophilic silica sol, modified quartz powder, modified fly ash and modified zeolite. In some more specific embodiments of the present invention, the modified quartz powder, the modified fly ash and the modified zeolite are respectively obtained by soaking the quartz powder, the fly ash and the zeolite in an alkaline solution, and then washing and drying.
In the present invention, in the composite photocatalytic medium, the photocatalytic material accounts for 10% to 90% of the total mass of the composite photocatalytic medium, including but not limited to 10%, 20%, 30%, 40%, 50%, 60%, 70%, 80%, 90%, etc., which is not limited in this respect, and those skilled in the art can select the photocatalytic material according to actual situations. The inventor finds that in the test process, with the increase of the photocatalytic material, the photocatalytic effect in the composite photocatalytic medium is increased and then basically kept unchanged, a small amount of photocatalyst can improve the mechanical property, and the mechanical property of the coating can be reduced by excessive doping.
In some preferred embodiments of the present invention, the mass ratio of the inorganic gelling material to the composite photocatalytic medium is (3-9): 1, further (6 to 9): 1. in the invention, the inventor finds that under the condition of the same mass ratio of the inorganic cementing material to water, the porosity of the formed coating is reduced along with the increase of the composite photocatalytic medium, and both the photocatalytic effect and the mechanical property show the trend of increasing before decreasing. When the mass ratio of the inorganic cementing material to the composite photocatalytic medium is (6-7): 1, the coating formed has optimal performance.
In the present invention, the auxiliary carbonizing agent is carbonate or bicarbonate. For example, the auxiliary carbonizing agent may be one or more of magnesium bicarbonate, nano calcium carbonate and ammonium bicarbonate. According to the invention, the hardness and the photocatalytic effect of the coating can be improved by adding the auxiliary carbonizing agent. Further, the mass ratio of the inorganic cementing material to the auxiliary carbonizing agent is 1: (0.4-0.7).
In the invention, the thickener is one or more of lithium magnesium silicate, bentonite, silica fume, diatomite and kaolin. The invention can adjust the fluidity of the coating by adding the thickening agent and improve the bleeding phenomenon of the coating. Further, the mass ratio of the inorganic cementing material to the thickening agent is 1: (0.1-0.2).
In some embodiments of the present invention, the negative carbon self-cleaning inorganic coating comprises the following raw materials in parts by weight: 45-80 parts of inorganic cementing material, 8-13 parts of composite photocatalytic medium, 1-50 parts of auxiliary carbonizing agent, 5-12 parts of thickening agent and 40-55 parts of water.
The second aspect of the invention provides a preparation method of a negative carbon self-cleaning inorganic coating, which comprises the following steps:
and uniformly mixing the inorganic cementing material, the composite photocatalytic medium, the auxiliary carbonizing agent, the thickening agent and water according to the proportion to obtain the negative carbon self-cleaning inorganic coating.
The third aspect of the invention provides a negative carbon self-cleaning inorganic coating, which is obtained by coating the negative carbon self-cleaning inorganic coating provided by the first aspect of the invention on the surface of a substrate and carrying out in-situ carbon mineralization reaction.
In the invention, the negative carbon self-cleaning inorganic coating can be coated on the surface of a base material in a spraying, brushing or other modes, and the formed coating has good weather resistance. In some embodiments of the invention, the coating is applied at a thickness of 0.2 to 0.35mm.
In some preferred embodiments of the present invention, the above-mentioned negative carbon self-cleaning inorganic coating is applied to the surface of the substrate by spraying, and CO-containing is adopted in the spraying process 2 The gas is used as a spraying gas source to realize in-situ carbon mineralization. The invention adopts a certain concentration of CO 2 The gas is used as a spraying gas source to realize in-situ carbon mineralization, so that the formed coating has certain hardness and a porous structure. Further, the mass concentration of carbon dioxide in the carbon dioxide-containing gas is 30 to 100%, including but not limited to 30%, 40%, 50%, 60%, 70%, 80%, 90%, 100%, and the like. The invention does not limit the spraying gas source, and the spraying gas source is not only high-purity CO 2 The gas may also be a gas containing a higher concentrationCO of 2 The waste gas or the mixed gas of (2) such as cement kiln tail gas, thermal power generation tail gas and the like.
The present invention is not limited to the kind of the above-mentioned base material, and may be, for example, a cement-based material.
In the following embodiments of the present invention, some of the raw materials are summarized as follows:
modified fly ash: 10g of fly ash was added to 100ml of 6mol/L sodium hydroxide solution and pretreated for 4h at 85 ℃. Then, washing the fly ash subjected to alkali excitation for three times by using tap water and deionized water respectively, and drying in an oven at 105 ℃ for 24 hours;
modifying quartz powder: 10g of quartz powder is soaked in 100ml of 0.1mol/L sodium hydroxide aqueous solution for pretreatment for 24 hours; then, washing the quartz powder subjected to alkali excitation for three times by using tap water and deionized water respectively, and drying in an oven at 105 ℃ for 24 hours;
composite photocatalytic medium: the carrier is soaked in titanium dioxide sol, and then the mixture obtained by filtering is dried for 24 hours at 105 ℃, so that the composite photocatalytic medium is prepared. Wherein, when the carrier is quartz powder, the soaking time is 5min, and when the carrier is fly ash or aerogel, the soaking time is 3h.
Example 1
The negative carbon self-cleaning inorganic coating comprises the following components in parts by weight: 50 parts of dicalcium silicate and 8 parts of TiO 2 /SiO 2 The composite photocatalyst comprises a composite photocatalytic medium, 20 parts of ammonium bicarbonate, 5 parts of bentonite and 40 parts of water. TiO 2 2 /SiO 2 In the composite photocatalytic medium, the carrier is modified flyash or TiO 2 The content is 60%.
Adopting CO with the mass concentration of 80 percent 2 And (3) spraying the negative carbon self-cleaning inorganic coating on the surface of the cement matrix by using gas as a spraying gas source, and forming the self-cleaning inorganic coating on the surface of the cement matrix through an in-situ carbon mineralization process.
Example 2
The negative carbon self-cleaning inorganic coating comprises the following components in parts by weight: 65 parts of dicalcium silicate and 8 parts of TiO 2 /SiO 2 Composite photocatalytic medium, 30 parts of ammonium bicarbonate and 8 parts of silica fumeAnd 50 parts of water. TiO 2 2 /SiO 2 In the composite photocatalytic medium, the carrier is hydrophilic SiO 2 Aerogels, tiO 2 The content is 40%.
Adopting CO with the mass concentration of 100 percent 2 And (3) spraying the negative carbon self-cleaning inorganic coating on the surface of the cement matrix by using gas as a spraying gas source, and forming the self-cleaning inorganic coating on the surface of the cement matrix through an in-situ carbon mineralization process.
Example 3
The negative carbon self-cleaning inorganic coating comprises the following components in parts by weight: 80 parts of dicalcium silicate and 12 parts of TiO 2 /SiO 2 The composite photocatalytic medium comprises 50 parts of ammonium bicarbonate, 12 parts of kaolin and 55 parts of water. TiO 2 2 /SiO 2 In the composite photocatalytic medium, the carrier is modified quartz powder or TiO 2 The content is 40%.
Adopting CO with the mass concentration of 100 percent 2 And (3) spraying the negative carbon self-cleaning inorganic coating on the surface of the cement matrix by using gas as a spraying gas source, and forming the self-cleaning inorganic coating on the surface of the cement matrix through an in-situ carbon mineralization process.
Example 4
The negative carbon self-cleaning inorganic coating comprises the following components in parts by weight: 50 parts of dicalcium silicate and 13 parts of TiO 2 /SiO 2 The composite photocatalyst comprises a composite photocatalytic medium, 20 parts of ammonium bicarbonate, 5 parts of bentonite and 40 parts of water. TiO 2 2 /SiO 2 In the composite photocatalytic medium, the carrier is modified flyash or TiO 2 The content is 60%.
The coating preparation was the same as in example 1.
Example 5
The negative carbon self-cleaning inorganic coating comprises the following components in parts by weight: 50 parts of dicalcium silicate and 8 parts of TiO 2 /SiO 2 The composite photocatalyst comprises a composite photocatalytic medium, 20 parts of ammonium bicarbonate, 5 parts of bentonite and 40 parts of water. TiO 2 2 /SiO 2 In the composite photocatalytic medium, the carrier is modified flyash or TiO 2 The content is 80%.
The coating preparation was the same as in example 1.
Example 6
The negative carbon self-cleaning inorganic coating comprises the following components in parts by weight: 50 parts of dicalcium silicate and 8 parts of TiO 2 /SiO 2 The composite photocatalyst comprises a composite photocatalytic medium, 20 parts of ammonium bicarbonate, 5 parts of bentonite and 40 parts of water. TiO 2 2 /SiO 2 In the composite photocatalytic medium, the carrier is modified flyash or TiO 2 The content is 40%.
The coating preparation was the same as in example 1.
Example 7
The negative carbon self-cleaning inorganic coating comprises the following components in parts by weight: 45 parts of dicalcium silicate and 8 parts of TiO 2 /SiO 2 The composite photocatalyst comprises a composite photocatalytic medium, 30 parts of ammonium bicarbonate, 8 parts of silica fume and 50 parts of water. TiO 2 2 /SiO 2 In the composite photocatalytic medium, the carrier is hydrophilic SiO 2 Aerogels, tiO 2 The content is 40%.
The coating preparation was the same as in example 2.
Example 8
The negative carbon self-cleaning inorganic coating comprises the following components in parts by weight: 50 parts of dicalcium silicate and 8 parts of TiO 2 /SiO 2 The composite photocatalytic medium comprises 30 parts of ammonium bicarbonate, 8 parts of silica fume and 50 parts of water. TiO 2 2 /SiO 2 In the composite photocatalytic medium, the carrier is hydrophilic SiO 2 Aerogels, tiO 2 The content is 40%.
The coating preparation was the same as in example 2.
Example 9
The negative carbon self-cleaning inorganic coating comprises the following components in parts by weight: 80 parts of dicalcium silicate and 12 parts of TiO 2 /SiO 2 The composite photocatalyst comprises a composite photocatalytic medium, 50 parts of ammonium bicarbonate, 12 parts of kaolin and 55 parts of water. TiO 2 2 /SiO 2 In the composite photocatalytic medium, modified quartz powder and TiO are used as carriers 2 The content is 40%.
Air was used as the source of the spray air, and the other conditions were the same as in example 3.
Example 10
The negative carbon self-cleaning inorganic coating material set of the embodiment is calculated by weightThe method comprises the following steps: 80 parts of dicalcium silicate and 12 parts of TiO 2 /SiO 2 The composite photocatalyst comprises a composite photocatalytic medium, 0 part of ammonium bicarbonate, 12 parts of kaolin and 55 parts of water. TiO 2 2 /SiO 2 In the composite photocatalytic medium, the carrier is modified quartz powder or TiO 2 The content is 40%.
The coating preparation was the same as in example 3.
Comparative example 1
The negative carbon self-cleaning inorganic coating comprises the following components in parts by weight: 50 parts of dicalcium silicate and 0 part of TiO 2 /SiO 2 The composite photocatalytic medium comprises 20 parts of ammonium bicarbonate, 5 parts of bentonite and 40 parts of water.
The coating preparation was the same as in example 1.
Comparative example 2
The negative carbon self-cleaning inorganic coating comprises the following components in parts by weight: 50 parts of dicalcium silicate and 8 parts of hydrophilic SiO 2 Aerogel, 20 parts of ammonium bicarbonate, 5 parts of bentonite and 40 parts of water.
The coating preparation was the same as in example 1.
Comparative example 3
The negative carbon self-cleaning inorganic coating comprises the following components in parts by weight: 65 parts of dicalcium silicate and 8 parts of TiO 2 The photocatalyst consists of a photocatalytic medium, 30 parts of ammonium bicarbonate, 8 parts of silica fume and 50 parts of water.
The coating preparation was the same as in example 2.
Test group
Performing coating microhardness test and NO degradation on the different coatings x The method comprises the following main test conditions of a test, a rhodamine B self-cleaning test, a rain erosion durability test and a contact angle test:
1. and (3) microhardness testing: detecting the hardness of the coating by using a microhardness tester, fixing a sample by using epoxy resin, preparing the sample into a cylinder, and polishing for multiple times to expose the side surface of the coating; the final results were averaged using test conditions of 0.1kgf loading force and 10s loading time.
2. Degradation of NO x And (3) testing: the sample to be tested is put into a standard reactor (ISO 22197-1) 2 . The total flow rate of the mixed gas is 3L-min by adjusting the flow rates of the dry air, the wet air and the NO gas -1 Wherein the relative humidity is 50% and the NO gas concentration is about 1 ppm. And (3) detecting the concentration of the NO gas in the whole testing process by adopting an HN-CK5001 type nitrogen oxide analyzer in the whole process.
3. Self-cleaning test of rhodamine B: 2ml of rhodamine B solution (20 mg/L) is uniformly added dropwise to a square sample (2.5X 2.5 cm) 2 ) A surface. And placing the sample under a xenon lamp, and after illumination for 3h, comparing the color change of the surface of the sample to evaluate the efficiency of degrading rhodamine B by the sample.
4. Testing the durability of rain wash: the carbon-negative self-cleaning inorganic coating material is placed under the water flow with the flow rate of 450 ml/min for flushing for 1d, and then the degradation of NO is tested x The ability of the cell to perform.
5. Contact angle test: the negative carbon self-cleaning inorganic coating material was horizontally placed under ultraviolet irradiation, and the contact angle of water at equilibrium was measured using an optical contact angle measuring instrument (OCA 20).
6. And (3) porosity testing: and shooting a back scattering image of the coating surface through a field emission scanning electron microscope, and calculating the porosity of the coating surface through software image J processing.
TABLE 1 results of the experiments of the above examples 1 to 10 and comparative examples 1 to 3
Figure SMS_1
Figure SMS_2
As can be seen from Table 1, the coatings formed by the examples of the present invention have good self-cleaning effect, mechanical properties and durability, compared with the comparative examples.
Compared with the prior art, the invention has the beneficial effects that:
(1) The negative carbon self-cleaning inorganic coating prepared by the inventionThe composite photocatalytic medium is used as main self-cleaning substance, and on one hand, the used composite photocatalytic medium is SiO 2 As a carrier, the catalyst can reduce the agglomeration of the photocatalyst, improve the utilization rate of the catalyst and ensure that the composite photocatalytic medium degrades NO x The photoelectron efficiency is as high as 0.86%; on the other hand, in the absence of ultraviolet light, siO has hydrophilic properties 2 The hydrophilic characteristic of the coating surface can be maintained, the contact angle is 25 degrees, and finally the self-cleaning effect is realized through two aspects of the photocatalysis effect and the super-hydrophilic effect.
(2) The negative carbon self-cleaning inorganic coating prepared by the invention adopts carbonization active ingredients such as dicalcium silicate, monocalcium silicate, tricalcium silicate, calcium hydroxide, magnesium hydroxide and the like as a cementing material, has carbon mineralization activity, and can be applied to CO 2 Calcium carbonate and silica gel are generated in the atmosphere, the coating has the functions of protecting the coating and bonding materials, the self-cleaning effect is stable in the long-term rain washing, and a stable chemical environment is provided for the composite photocatalytic medium. Meanwhile, the composite photocatalytic medium is prevented from generating superoxide ions and hydroxyl radicals to decompose the coating substrate under the excitation of ultraviolet light. In addition, CO can be sequestered 2 In the presence of CO 2 Can absorb 40 percent of CO of the mass of the reactor during reaction 2 Is an environment-friendly material.
(3) The carbon-negative self-cleaning inorganic coating material prepared by the invention has the advantages that the surface of the coating has higher porosity on the basis of ensuring the mechanical property of the coating by controlling the mixing amount of the composite photocatalytic medium and the solid content of the coating, and more composite photocatalytic media can be exposed, so that the photocatalytic degradation property of the coating is improved.
(4) The negative carbon self-cleaning inorganic coating prepared by the invention adopts CO with a certain concentration 2 The gas is used as a spraying gas source to realize in-situ carbon mineralization and a small amount of auxiliary carbonizing agent is added, so that the coating can be gradually carbonated and cured while the construction is carried out on the surface of the building, and the phenomenon that CO is generated at the later stage is avoided 2 The carbonation curing process in the atmosphere reduces the cost.
The above-described embodiments of the present invention should not be construed as limiting the scope of the present invention. Any other corresponding changes and modifications made according to the technical idea of the present invention should be included in the protection scope of the claims of the present invention.

Claims (9)

1. The negative carbon self-cleaning inorganic coating is characterized by comprising the following raw materials in parts by weight: 40 to 90 parts of inorganic cementing material, 1 to 15 parts of composite photocatalytic medium, 0 to 50 parts of auxiliary carbonizing agent, 0 to 15 parts of thickening agent and 30 to 60 parts of water; wherein the content of the first and second substances,
the inorganic cementing material is a carbonization active ingredient or industrial solid waste at least containing 60 percent of the carbonization active ingredient, and the carbonization active ingredient is at least one of dicalcium silicate, monocalcium silicate, tricalcium disilicate, calcium hydroxide and magnesium hydroxide;
the composite photocatalytic medium is prepared from a photocatalytic material and SiO-containing 2 The photocatalytic material is at least one of nano titanium dioxide, nano zinc oxide and nano ferric oxide;
the auxiliary carbonizing agent is one or more of magnesium bicarbonate, nano calcium carbonate and ammonium bicarbonate.
2. The carbon-negative self-cleaning inorganic coating as claimed in claim 1, wherein the mass ratio of the inorganic cementing material to water is (1.2 to 1.5): 1.
3. The negative-carbon self-cleaning inorganic coating of claim 1, wherein the SiO-containing material is selected from the group consisting of 2 The carrier is hydrophilic SiO 2 At least one of aerogel, hydrophilic silica sol, modified quartz powder, modified fly ash and modified zeolite; in the composite photocatalytic medium, the photocatalytic material accounts for 10-90% of the total mass of the composite photocatalytic medium.
4. The carbon-negative self-cleaning inorganic coating of claim 1, wherein the mass ratio of the inorganic cementing material to the composite photocatalytic medium is (3~9): 1.
5. the negative-carbon self-cleaning inorganic coating according to claim 1, wherein the mass ratio of the inorganic cementing material to the auxiliary carbonizing agent is 1: (0.4 to 0.7).
6. The negative carbon self-cleaning inorganic coating of claim 1, wherein the thickener is one or more of lithium magnesium silicate, bentonite, silica fume, diatomite and kaolin; the mass ratio of the inorganic cementing material to the thickening agent is 1: (0.1 to 0.2).
7. A method for preparing the negative carbon self-cleaning inorganic coating of any one of claims 1~6, comprising the steps of:
and uniformly mixing the inorganic cementing material, the composite photocatalytic medium, the auxiliary carbonizing agent, the thickening agent and water according to a proportion to obtain the negative carbon self-cleaning inorganic coating.
8. A negative carbon self-cleaning inorganic coating, which is obtained by coating the negative carbon self-cleaning inorganic coating of 1~6 on the surface of a substrate and performing in-situ carbon mineralization reaction.
9. The negative carbon self-cleaning inorganic coating of claim 8, wherein the negative carbon self-cleaning inorganic coating is coated on the surface of a substrate by spraying, and carbon dioxide with the mass concentration of 30-100% and containing CO is adopted in the spraying process 2 The gas is used as a spraying gas source to realize in-situ carbon mineralization.
CN202210779046.2A 2022-07-04 2022-07-04 Negative carbon self-cleaning inorganic coating, preparation method thereof and obtained coating Active CN115058132B (en)

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Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107903667A (en) * 2017-10-25 2018-04-13 伍淼 A kind of multi-functional super-hydrophilic coating and preparation method thereof
CN114656811A (en) * 2022-04-12 2022-06-24 武汉理工大学 Fireproof heat-preservation heat-insulation inorganic coating material and preparation method thereof

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107903667A (en) * 2017-10-25 2018-04-13 伍淼 A kind of multi-functional super-hydrophilic coating and preparation method thereof
CN114656811A (en) * 2022-04-12 2022-06-24 武汉理工大学 Fireproof heat-preservation heat-insulation inorganic coating material and preparation method thereof

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