CN114921123A - Epoxy coating self-repairing microcapsule additive for steel sheet pile - Google Patents
Epoxy coating self-repairing microcapsule additive for steel sheet pile Download PDFInfo
- Publication number
- CN114921123A CN114921123A CN202210598057.0A CN202210598057A CN114921123A CN 114921123 A CN114921123 A CN 114921123A CN 202210598057 A CN202210598057 A CN 202210598057A CN 114921123 A CN114921123 A CN 114921123A
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- China
- Prior art keywords
- steel sheet
- epoxy coating
- sheet pile
- microcapsule
- additive
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- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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Classifications
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/08—Anti-corrosive paints
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J13/00—Colloid chemistry, e.g. the production of colloidal materials or their solutions, not otherwise provided for; Making microcapsules or microballoons
- B01J13/02—Making microcapsules or microballoons
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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
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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
- 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
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2206—Oxides; Hydroxides of metals of calcium, strontium or barium
Abstract
The invention relates to the technical field of metal material corrosion prevention and the field of constructional engineering, and particularly discloses an epoxy coating self-repairing microcapsule additive for a steel sheet pile, wherein the inner layer of the microcapsule is a calcium oxide inner core, and the outer layer of the microcapsule is a sodium metasilicate capsule shell; the preparation method comprises the steps of mechanically crushing and sieving the calcium hydroxide solid, mechanically stirring and mixing the calcium hydroxide solid with sodium metasilicate hydrate, and finally calcining the calcium hydroxide solid at high temperature under the condition of mechanical stirring; the calcium oxide microcapsule additive is simple in preparation method, convenient to use, environment-friendly and pollution-free, and can repair defects and damaged holes/gaps of the epoxy coating, so that pitting corrosion and perforation corrosion of the steel sheet pile are inhibited, and the service life of the epoxy coating is prolonged.
Description
Technical Field
The invention relates to the technical field of metal corrosion protection and the field of constructional engineering, in particular to an epoxy coating self-repairing microcapsule additive for a steel sheet pile.
Background
The steel sheet pile has the advantages of high strength, good water resistance, strong durability, reusability, capability of obviously reducing earth volume and construction amount and the like, and is widely applied to ocean engineering construction of wharfs, unloading yards, embankment revetments, breakwaters, diversion dikes, docks, gates, temporary bank expansion, bridge-building cofferdams and the like. The main materials of the steel sheet pile comprise carbon steel and low alloy steel, which can be seriously corroded in seawater, and the protection of a coating is one of important measures for corrosion protection of the steel sheet pile. The epoxy coating has good mechanical strength and adhesion, excellent impermeability and corrosion resistance, small curing shrinkage and excellent seawater corrosion resistance, and is widely applied to coating protection of steel sheet piles.
The epoxy coating is difficult to avoid a small amount of defects and partial damage in the construction processes of coating, hoisting, piling and the like. In the service process, local corrosion in the form of a large cathode and a small anode is easily induced in a seawater medium, pitting corrosion is easily formed at the defect and the damaged part, and even corrosion perforation occurs, so that the coating is peeled and falls off to lose the protection effect (figure 2). The pH value of the solution is increased, so that the pitting corrosion and the local corrosion of steel can be effectively inhibited, wherein CaO has strong alkalinity and low price, and can be used for improving the local corrosion of the steel sheet pile. However, if CaO is directly coated on the surface of the steel sheet pile, the CaO reacts with water and dissolved carbon dioxide quickly to be converted into CaCO 3 And the alkalinity disappears, leading to failure of the coating. The problem of CaO failure can be solved by adding CaO particles into the epoxy resin coating in a microcapsule form, and when the epoxy coating is damaged, the CaO microcapsules can repair the coating through two ways: (1) CaO particles with H 2 Reaction of O to Ca (OH) 2 And dissolved in the aqueous solution in the gap of the damaged coating, the pH value in the gap is increased, a compact iron oxide and iron hydroxide layer is generated when the iron element is oxidized under the condition of high pH value, and the solid iron oxide/hydroxide layer protects the steel matrix, therebyThe occurrence of pitting and local corrosion is suppressed (fig. 3); (2) CaO particles are converted into Ca (OH) by contacting with an aqueous solution 2 Then further converted into CaCO insoluble in water 3 The transition volume expands, filling up the damaged gap. Since CaO has strong basicity, it easily causes the epoxy resin to be denatured when it is in direct contact with the epoxy paint, thereby decreasing the strength of the coating layer. Sodium metasilicate (Na) 2 SiO 3 ) Is close to neutrality, can stably coexist with CaO and epoxy resin simultaneously, and prepares a layer of Na on the surface of calcium oxide particles 2 SiO 3 And a shell layer forms CaO microcapsules, so that the problem of epoxy resin denaturation can be effectively solved. In addition, Na 2 SiO 3 Readily soluble in water, Na when the epoxy coating is damaged 2 SiO 3 Can rapidly dissolve and release CaO.
The melting point of sodium metasilicate is higher (1088 ℃), the microcapsule core-shell structure is inconvenient to prepare, but the melting point of sodium metasilicate hydrate is lower (Na) 2 SiO 3 ·9H 2 Melting point of O is 48 ℃). Mixing Na 2 SiO 3 ·9H 2 The O temperature is controlled between the melting point (48 ℃) and the dehydration temperature (75 ℃) to prepare thick fluid, and the thick fluid can be coated on the surfaces of CaO particles through a mechanical stirring mode. Because CaO can be directly reacted with Na 2 SiO 3 ·9H 2 The crystal water in O reacts to generate Ca (OH) 2 Is not beneficial to the coating process, therefore, Ca (OH) is directly adopted 2 As a precursor, coating a layer of Na on the surface 2 SiO 3 ·9H 2 O, then calcining at high temperature to make Ca (OH) 2 And Na 2 SiO 3 ·9H 2 O is dehydrated to form CaO/NaSiO 3 Microcapsules with a core-shell structure. Ca (OH) 2 The initial temperature of conversion to CaO of (b) is 580 ℃, the calcination temperature should be higher than 580 ℃, and Ca (OH) 2 With Na 2 SiO 3 The initial temperature at which the reaction takes place is 800 c, so the calcination temperature should be below 800 c.
Disclosure of Invention
The invention aims to provide an epoxy coating self-repairing microcapsule additive for a steel sheet pile. The additive can repair the defects and damaged holes/gaps of the epoxy coating, thereby inhibiting the occurrence of pitting corrosion and perforation corrosion and prolonging the service life of the coating.
In order to achieve the purpose, the invention provides the following technical scheme: an epoxy coating self-repairing microcapsule additive for steel sheet piles is characterized by consisting of a microcapsule structure, wherein an inner layer is a calcium oxide (chemical formula CaO) inner core, and an outer layer is sodium metasilicate (chemical formula Na) 2 SiO 3 ) And (4) capsule shells. The preparation method comprises the following steps: firstly, mechanically crushing and sieving calcium hydroxide solid; then mechanically stirring and mixing the crushed calcium hydroxide particles and sodium metasilicate hydrate; and finally, calcining the mixed particles at high temperature under the condition of mechanical stirring to prepare the calcium oxide microcapsule.
Preferably, the size of the calcium oxide inner core is 10-500 μm, and the thickness of the sodium metasilicate capsule shell is 1-30 μm.
Preferably, the sodium metasilicate hydrate is Na 2 SiO 3 ·8H 2 O、Na 2 SiO 3 ·9H 2 Any one of O.
Preferably, the mechanical stirring mixing temperature is 48-75 ℃.
Preferably, the high-temperature calcination temperature is 580-800 ℃.
The invention has the following characteristics and beneficial effects:
the epoxy coating self-repairing microcapsule additive provided by the invention can repair the defects and damaged holes/gaps of the epoxy coating, thereby inhibiting the occurrence of pitting corrosion and perforation corrosion and prolonging the service life of the coating.
The final product of the epoxy coating self-repairing microcapsule additive for repairing the gap is Fe 2 O 3 、Fe(OH) 3 、CaCO 3 All the materials are nontoxic and harmless substances, and have no pollution to the surrounding environment.
The epoxy coating self-repairing microcapsule additive provided by the invention has the advantages of cheap and easily available raw materials, simple processing and preparation method and convenience in use.
Drawings
FIG. 1 is a schematic structural diagram of a self-repairing microcapsule of an epoxy coating according to the present invention;
FIG. 2 is a schematic view of a partial corrosion of a steel sheet pile coated with an epoxy paint;
FIG. 3 is a diagram of the repair mechanism of the calcium oxide microcapsules on the epoxy coating;
in the figure:
1. a calcium oxide core; 2. a metasilicic acid capsule shell; 3. steel sheet piles; 4. an epoxy coating;
5. calcium oxide microcapsules.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. The components of embodiments of the present invention generally described and illustrated in the figures herein may be arranged and designed in a wide variety of different configurations. Thus, the following detailed description of the embodiments of the present invention, as presented in the figures, is not intended to limit the scope of the invention, as claimed, but is merely representative of selected embodiments of the invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments of the present invention without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
In this case, calcium hydroxide is used as precursor, and is mechanically pulverized, sieved and mixed with Na 2 SiO 3 ·9H 2 Mixing and mechanically stirring (50 ℃), calcining at high temperature (600 ℃) under mechanical stirring and the like to prepare the calcium oxide microcapsule coated by the sodium metasilicate. Wherein the size of the calcium oxide inner core is 10 μm, and the thickness of the sodium metasilicate capsule shell is 1 μm. The calcium oxide microcapsule is added into an epoxy coating and coated on the surface of a wharf Steel sheet pile (Mariner type Steel sheet pile produced by Nippon Steel Corporation), and after 1-year service experiments, the epoxy coating is kept complete, and no obvious corrosion phenomenon occurs to the Steel sheet pile.
Comparative example 1
In the case, the epoxy coating is coated on the surface of a wharf Steel sheet pile (Mariner type Steel sheet pile produced by Nippon Steel Corporation), and after 1 year of service experiments, the epoxy coating generates serious foaming phenomenon, and the Steel sheet pile at the bubble part generates serious corrosion perforation phenomenon.
Example 2
In the case, calcium hydroxide is used as a precursor, and is mechanically crushed, sieved and mixed with Na 2 SiO 3 ·9H 2 Mixing and mechanically stirring (75 ℃), calcining at high temperature (800 ℃) under mechanical stirring and the like to prepare the calcium oxide microcapsule coated by the sodium metasilicate. Wherein the size of the calcium oxide inner core is 500 μm, and the thickness of the sodium metasilicate capsule shell is 20 μm. The calcium oxide microcapsule is added into an epoxy coating and coated on the surface of a wharf steel sheet pile (Q235B carbon steel), after 2 years of service experiments, the epoxy coating is found to be kept complete, the steel sheet pile has no obvious corrosion phenomenon, the cross section of the coating is cut open, and a repaired gap filled with iron oxide and hydroxide can be found, so that the calcium oxide microcapsule can better repair the damaged position and defects of the epoxy coating.
Comparative example 2
According to the scheme, the epoxy coating is coated on the surface of a wharf steel sheet pile (Q235B carbon steel), and after 2 years of service experiments, the epoxy coating is found to have a serious shedding phenomenon, so that the local corrosion is serious, and the coating fails wholly.
Example 3
In this case, calcium hydroxide is used as precursor, and is mechanically pulverized, sieved and mixed with Na 2 SiO 3 ·9H 2 O, mixing and mechanically stirring (60 ℃), calcining at high temperature (700 ℃) under mechanical stirring and the like to prepare the calcium oxide microcapsule coated with the sodium metasilicate. Wherein the size of the calcium oxide inner core is 200 μm, and the thickness of the sodium metasilicate capsule shell is 5 μm. The calcium oxide microcapsule is added into an epoxy coating and coated on the surface of a wharf steel sheet pile (Q345B carbon steel), and after 2 years of service experiments, the epoxy coating is kept complete, and the steel sheet pile has no obvious corrosion phenomenon.
Comparative example 3
In the scheme, the epoxy coating is coated on the surface of a wharf steel sheet pile (Q345B carbon steel), and after 2 years of service experiments, the epoxy coating is found to have a serious shedding phenomenon, so that the local corrosion is serious, and the coating fails integrally.
While embodiments of the invention have been shown and described, it will be understood by those of ordinary skill in the art that: numerous changes, modifications, substitutions and variations can be made to the embodiments without departing from the principles and spirit of the invention, the scope of which is defined by the claims and their equivalents.
Claims (5)
1. The epoxy coating self-repairing microcapsule additive for the steel sheet pile is characterized in that: the additive is composed of microcapsule structure, wherein the inner layer is calcium oxide core with chemical formula of CaO, and the outer layer is sodium metasilicate capsule shell with chemical formula of Na 2 SiO 3 (ii) a The preparation method comprises the following steps:
s1, mechanically crushing and sieving the calcium hydroxide solid;
s2, mechanically stirring and mixing the crushed calcium hydroxide particles and sodium metasilicate hydrate; the ratio of the calcium hydroxide particles to the sodium metasilicate hydrate is 4: 1-100: 1;
and S3, calcining the mixed particles at high temperature under the condition of mechanical stirring to obtain the calcium oxide microcapsule.
2. The epoxy coating self-repairing microcapsule additive for the steel sheet pile as claimed in claim 1, wherein the size of the calcium oxide inner core is 10 μm-500 μm, and the thickness of the sodium metasilicate capsule shell is 1 μm-30 μm.
3. The epoxy coating self-repairing microcapsule additive for steel sheet piles as claimed in claim 1, wherein the sodium metasilicate hydrate is Na 2 SiO 3 ·9H 2 O。
4. The epoxy coating self-repairing microcapsule additive for the steel sheet pile as claimed in claim 1, wherein the mechanical stirring mixing temperature in the preparation step S2 is 48-75 ℃.
5. The epoxy coating self-repairing microcapsule additive for the steel sheet pile as claimed in claim 1, wherein the preparation step S3 is carried out at a high-temperature calcination temperature of 580 ℃ -800 ℃, a calcination time of 10-100min and an air atmosphere.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210598057.0A CN114921123B (en) | 2022-05-30 | 2022-05-30 | Epoxy coating self-repairing microcapsule additive for steel sheet pile |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210598057.0A CN114921123B (en) | 2022-05-30 | 2022-05-30 | Epoxy coating self-repairing microcapsule additive for steel sheet pile |
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| CN114921123A true CN114921123A (en) | 2022-08-19 |
| CN114921123B CN114921123B (en) | 2023-02-10 |
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