CN110304853B - Geopolymer coating suitable for metal substrate and preparation method thereof - Google Patents
Geopolymer coating suitable for metal substrate and preparation method thereof Download PDFInfo
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- CN110304853B CN110304853B CN201910303414.4A CN201910303414A CN110304853B CN 110304853 B CN110304853 B CN 110304853B CN 201910303414 A CN201910303414 A CN 201910303414A CN 110304853 B CN110304853 B CN 110304853B
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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
- C04B12/00—Cements not provided for in groups C04B7/00 - C04B11/00
- C04B12/005—Geopolymer cements, e.g. reaction products of aluminosilicates with alkali metal hydroxides or silicates
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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
- C04B28/00—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements
- C04B28/006—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements containing mineral polymers, e.g. geopolymers of the Davidovits type
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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
- C04B28/00—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements
- C04B28/24—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements containing alkyl, ammonium or metal silicates; containing silica sols
- C04B28/26—Silicates of the alkali metals
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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
- C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
- C04B2111/00474—Uses not provided for elsewhere in C04B2111/00
- C04B2111/00482—Coating or impregnation materials
- C04B2111/00525—Coating or impregnation materials for metallic surfaces
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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
- C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
- C04B2111/00474—Uses not provided for elsewhere in C04B2111/00
- C04B2111/00482—Coating or impregnation materials
- C04B2111/00577—Coating or impregnation materials applied by spraying
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- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P40/00—Technologies relating to the processing of minerals
- Y02P40/10—Production of cement, e.g. improving or optimising the production methods; Cement grinding
Abstract
The invention discloses a gold-plating solution suitable for goldBelongs to a geopolymer coating of a substrate and a preparation method thereof. The preparation method of the geopolymer coating comprises the following steps: 1) sodium silicate, NaOH and H2Mixing and drying O uniformly to obtain a transparent alkali activator; 2) weighing geopolymer synthesis raw materials and an alkali activator, and then mixing and stirring to obtain a flowing geopolymer precursor; 3) spraying a geopolymer precursor on the surface of the metal to obtain a geopolymer coating; 3) the obtained coating is cured in the air to obtain a geopolymer coating. The preparation method is simple, easy to operate and low in raw material cost; the prepared real geopolymer coating has uniform thickness, firm combination with a metal substrate and no defects such as cracks and the like after curing. In addition, the geopolymer coating on the surface of the metal substrate obtained by the invention is beneficial to improving the heat resistance and the corrosion resistance of the metal, and has wide industrial application prospect.
Description
Technical Field
The invention belongs to the field of preparation of geopolymer coatings, and particularly relates to a geopolymer coating suitable for a metal substrate and a preparation method thereof.
Technical Field
The geopolymer (called geopolymer for short) is a gel material which is prepared by taking natural minerals or solid wastes, artificial silicon-aluminum compounds and the like as raw materials and adding an exciting agent and has a three-dimensional network structure of silicon-oxygen tetrahedron and aluminum-oxygen tetrahedron, and has the advantages of wide main raw material source, relatively simple preparation process (no need of high-temperature roasting), low cost, energy conservation and environmental protection. The geopolymer has the characteristics of high strength, high temperature resistance, acid and alkali corrosion resistance, excellent radiation resistance and the like, so that the geopolymer can be widely applied to various industrial fields.
The geopolymer coating is deposited on the metal surface, which is beneficial to improving the heat resistance and the corrosion resistance of the metal. Therefore, the preparation of geopolymer coatings for metal substrates is of great significance for improving the properties of the metal substrates.
However, since the geopolymer is mainly composed of silicon-oxygen and aluminum-oxygen bonds, the difference in properties from metals is large. For the preparation of the geopolymer coating on the surface of the metal substrate, common methods are spin coating and dip coating methods, both of which face the problem of cracks caused by shrinkage of the geopolymer coating during curing, and in addition, when the viscosity of the geopolymer precursor is high, the problems of large coating thickness, low bonding strength with the metal substrate after curing, peeling off and the like can be caused.
Disclosure of Invention
The invention aims to overcome the defects in the prior art and provide a geopolymer coating suitable for a metal substrate and a preparation method thereof. The preparation method of the coating is simple, the cost of raw materials is low, the coating is suitable for industrial large-scale production, the thickness of the obtained geopolymer coating is thin, the geopolymer coating is firmly combined with a metal substrate, and the cured coating has no cracks.
In order to achieve the purpose, the technical scheme provided by the invention is as follows:
a method of preparing a geopolymer coating suitable for use on a metal substrate, comprising the steps of:
1) mixing geopolymer synthesis raw materials with an alkali activator, and stirring to obtain a flowing geopolymer precursor;
2) spraying the geopolymer precursor prepared in the step 1) on the surface of metal, and then carrying out non-sealing type curing treatment to obtain the geopolymer coating.
According to the scheme, preferably, the mole ratio of Si/Al in the geopolymer precursor obtained in the step 1) is 2.4-2.6, and H is2O/Al2O3In a molar ratio of 25 to 27, Na2O/Al2O3Is 1.
According to the scheme, preferably, the geopolymer synthetic raw material in the step 1) is one or more of metakaolin, fly ash, clay or slag. More preferably, the metakaolin comprises the following components in percentage by weight: SiO 22 55wt%，Al2O339wt%, and the balance oxide impurities; the mass ratio of the metakaolin to the alkali activator is (94-110): (247-294).
According to the scheme, preferably, the alkali-activating agent in the step 1) is prepared by the following method: sodium silicate, NaOH and H2O is mixed uniformly, 40oStanding for 24h under C to obtain the transparent alkali activator. More preferably, the sodium silicate, NaOH and H2The mass ratio of O is 100: (4.8-9.6): (142-184). More preferably, the sodium silicate consists of the following substances in percentage by weight: na (Na)2O·3.35SiO2 80wt%；H2O 20wt%。
According to the scheme, preferably, the rotating speed of stirring in the step 1) is 500-800 r/min, and the stirring time is 10-20 min.
According to the scheme, preferably, the metal surface in the step 2) is subjected to surface treatment, including grinding or cleaning to remove oil or surface oxidation.
According to the scheme, preferably, the spraying in the step 2) is air spraying, the air pressure is 0.5-3 MPa when the spraying is carried out, and the spraying time is 5-10 s.
According to the scheme, preferably, the curing temperature in the step 2) is 70-150 DEG CoC, the time is 1-3 h.
The invention also provides a geopolymer coating suitable for the metal substrate, which is characterized in that the coating is prepared by the method and has the thickness of about 10-1000 mu m. More preferably, the thickness of the coating is 50-60 μm.
The basic principle of the invention is as follows:
the geopolymer precursor is generated by the reaction of alkali activator and synthetic raw materials of geopolymer such as metakaolin or fly ash, the liquid geopolymer precursor is coated on a metal matrix by air compression, and then the uniform geopolymer coating is formed by further reaction through open-type low-temperature curing.
Compared with the prior art, the invention has the main advantages that:
(1) the preparation method is simple, easy to operate and low in raw material cost;
(2) no true geopolymer coatings suitable for metal substrates have been found in the prior art; in the preparation method, the real geopolymer coating suitable for the metal substrate is finally obtained by adopting proper raw materials and proportion and combining the processes of spraying and open-type curing.
(3) The geopolymer prepared by the method has uniform coating thickness, is firmly combined with a metal substrate, and has no obvious cracks.
(4) The geopolymer coating prepared on the surface of the metal is beneficial to improving the heat resistance and the corrosion resistance of the metal.
Drawings
FIG. 1 is an infrared spectrum of a metakaolin based geopolymer coating prepared in example 1 and the raw metakaolin.
FIG. 2 is an electron microscope scan of the surface topography of the metakaolin-based geopolymer coating made in example 1.
FIG. 3 is a microscopic topography of the metakaolin-based geopolymer coating prepared in example 1 on an aluminum substrate.
FIG. 4 is an infrared spectrum of a metakaolin based geopolymer type coating prepared in comparative example 1 and the raw metakaolin
Detailed Description
The present invention is further illustrated by the following examples, which are merely illustrative of the feasibility of the present invention and are not intended to limit the scope of the claims of the present invention.
All the starting materials mentioned in the examples below are, unless otherwise specified, commercially available.
Example 1
The preparation method of the metakaolin-based geopolymer coating on the surface of the Al alloy comprises the following specific steps:
1) 100 g of sodium silicate (containing 80 wt% of Na) was weighed2O·3.35SiO220 wt% of H2O), 6.7g of NaOH and 150 g of H2O, then mixing uniformly and placing at 40oC, in an oven for 24 hours, obtaining a transparent alkali activator; 99 g of metakaolin (containing 55% by weight of SiO) were weighed out239wt% of Al2O3And 6 wt% of impurities) and 256.7g of the alkali-activator were mixed in a stirrer at a rotational speed of 700 r/min for a stirring time of 10 min. The precursor of the metakaolin-based geopolymer is obtained and evenly mixed and flows.
2) Pouring the metakaolin-based geopolymer precursor prepared in the step 1) into a container, and spraying the surface of the deoiled Al alloy by using an air spray gun, wherein the air pressure during spraying is 0.6 MPa, and the spraying time is 5 s; to obtain the geopolymer precursor coating.
3) Curing the geopolymer precursor coating obtained in the step 2), specifically in an oven, 80oAnd C, curing for 1.5 h in a non-sealed mode (in an open mode) to obtain the metakaolin-based geopolymer coating.
FIG. 1 is an infrared spectrum of the metakaolin based geopolymer coating prepared in this example and the raw metakaolin, from which it can be seen that the Si-O-Si bonds are significantly shifted, illustrating the formation of geopolymer.
FIG. 2 shows the surface morphology of the metakaolin-based geopolymer coating prepared in this example, which is relatively uniform.
FIG. 3 is a microscopic image of the metakaolin-based geopolymer coating prepared in this example on an aluminum substrate, and it can be seen from the image that the coating and the aluminum substrate are firmly bonded without significant cracks and have a thickness of about 50 to 60 μm.
Example 2
The metakaolin-based geopolymer coating is prepared on the surface of steel, and the method comprises the following specific steps:
1) 100 g of sodium silicate (containing 80 wt% of Na) was weighed2O·3.35SiO220 wt% of H2O), 9.2g NaOH and 160H2O, then mixing uniformly and placing at 40oC, in an oven for 24 hours, obtaining a transparent alkali activator; 107 g of metakaolin (containing 55% by weight of SiO) were weighed out239wt% of Al2O3And 6 wt% impurities) and 269.2g of the alkali activator were mixed in a stirrer at a speed of 500 r/min for a period of 20 min. The precursor of the metakaolin-based geopolymer is obtained and evenly mixed and flows.
2) Pouring the metakaolin-based geopolymer precursor prepared in the step 1) into a container, and spraying the degreased steel surface by using an air spray gun, wherein the air pressure is 0.5 MPa and the spraying time is 10 s; to obtain the geopolymer precursor coating.
3) Curing the geopolymer precursor coating obtained in the step 2), specifically in an oven, 150%oAnd C, curing for 1 h in a non-sealed mode (in an open mode) to obtain the metakaolin-based geopolymer coating.
Comparative example 1
The metakaolin-based geopolymer type coating is prepared on the surface of the Al alloy, and the method comprises the following specific steps:
1) 100 g of sodium silicate (containing 80 wt% of Na) was weighed2O·3.35SiO220 wt% of H2O), 6.7g of NaOH and 150 g of H2O, then mixing uniformly and placing at 40oC, in an oven for 24 hours, obtaining a transparent alkali activator; 99 g of metakaolin (containing 55% by weight of SiO) were weighed out239wt% of Al2O3And 6 wt% of impurities) and 256.7g of the alkali-activator were mixed in a stirrer at a rotational speed of 700 r/min for a stirring time of 10 min. The precursor of the metakaolin-based geopolymer is obtained and evenly mixed and flows.
2) Pouring the geopolymer precursor prepared in the step 1) into a container, and carrying out dip-coating on the surface of the deoiled Al alloy to obtain the geopolymer precursor coating.
3) Curing the coating obtained in the step 2, specifically in an oven, 80%oAnd C, solidifying for 1.5 h in a sealed mode (namely putting the Al alloy deposited with the coating into a sealed container), and obtaining the metakaolin-based geopolymer coating.
FIG. 4 is an infrared spectrum of a metakaolin based geopolymer type coating prepared in this comparative example and metakaolin as a starting material, from which it can be seen that the product has Si-O-Si bonds in wavenumber positions substantially identical to metakaolin, indicating that no true geopolymer is obtained. This is because the precursor has a high water content, and if the sealing solidification is adopted, the water participating in the geopolymer polymerization reaction is excessive, so that the formation of the geopolymer network structure is weakened, and the real geopolymer cannot be obtained. Furthermore, due to the hermetic curing, water vapor in the precursor may remain in the container, causing corrosion of the metal substrate.
Claims (10)
1. A method of preparing a geopolymer coating suitable for use on a metal substrate, comprising the steps of:
1) mixing geopolymer synthesis raw materials with an alkali activator, and stirring to obtain a geopolymer precursor; molar ratio of Si/Al in the Geopolymer precursorThe ratio is 2.4 to 2.6, H2O/Al2O3In a molar ratio of 25 to 27, Na2O/Al2O3Is 1; the geopolymer synthetic raw material is one or more of metakaolin, fly ash, clay or slag; the alkali activator is prepared by the following method: sodium silicate, NaOH and H2O is mixed uniformly, 40oStanding for 24h under C to obtain an alkali activator;
2) spraying the geopolymer precursor prepared in the step 1) on the surface of metal, and then carrying out non-sealing type curing treatment to obtain a geopolymer coating, wherein the thickness of the geopolymer coating is 10-1000 microns.
2. The method of claim 1, wherein the metakaolin has a composition comprising, in weight percent:
SiO2 55wt%，Al2O339wt%, and the balance oxide impurities;
the mass ratio of the metakaolin to the alkali activator is (94-110): (247-294).
3. The method of claim 1, wherein said sodium silicate, NaOH and H are selected from sodium silicate, NaOH and H2The mass ratio of O is 100 (4.8-9.6): (142-184).
4. The method for preparing a geopolymer coating suitable for metal substrates according to claim 1, characterized in that said sodium silicate consists of, in weight percentages:
Na2O·3.35SiO2 80 wt%；
H2O 20 wt%。
5. the method for preparing the geopolymer coating suitable for the metal substrate as claimed in claim 1, wherein the rotation speed of the stirring in step 1) is 500-800 r/min, and the stirring time is 10-20 min.
6. The method of claim 1, wherein the metal surface in step 2) is subjected to a surface treatment comprising grinding or cleaning to remove oil or surface oxidation.
7. The method for preparing the geopolymer coating suitable for the metal substrate as claimed in claim 1, wherein the spraying in step 2) is air spraying, the air pressure in the spraying is 0.5-3 MPa, and the spraying time is 5-10 s.
8. The method for preparing a geopolymer coating suitable for a metal substrate according to claim 1, wherein the curing temperature in step 2) is 70-150%oC, the time is 1-3 h.
9. A geopolymer coating suitable for a metal substrate, wherein the coating is prepared by the preparation method of the geopolymer coating according to any one of claims 1 to 8, and has a thickness of 10 to 1000 μm.
10. The geopolymer coating suitable for use on a metal substrate according to claim 9, wherein said thickness is 50 to 60 μm.
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