CN113149597A - Potassium phosphate magnesium-based steel anticorrosive coating material and preparation method thereof - Google Patents
Potassium phosphate magnesium-based steel anticorrosive coating material and preparation method thereof Download PDFInfo
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- CN113149597A CN113149597A CN202110382778.3A CN202110382778A CN113149597A CN 113149597 A CN113149597 A CN 113149597A CN 202110382778 A CN202110382778 A CN 202110382778A CN 113149597 A CN113149597 A CN 113149597A
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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
- C04B28/34—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 cold phosphate binders
- C04B28/344—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 cold phosphate binders the phosphate binder being present in the starting composition solely as one or more phosphates
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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
- C04B2111/20—Resistance against chemical, physical or biological attack
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- Preventing Corrosion Or Incrustation Of Metals (AREA)
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Abstract
The invention discloses a potassium phosphate magnesium-based steel anticorrosive coating material and a preparation method thereof. The potassium phosphate magnesium-based steel anticorrosive coating material is formed by mixing a potassium phosphate magnesium cementing material, a setting time regulating component, a corrosion inhibition component and a toughening component, and the raw materials of the potassium phosphate magnesium cementing material, a composite retarder component, a corrosion inhibition component and a toughening component. The potassium phosphate magnesium-based steel anticorrosive coating material has excellent performances of normal-temperature curing, quick hardening, high strength, low shrinkage, freezing and salt freezing resistance, salt corrosion resistance, high temperature resistance, strong environmental adaptability and the like, and also has excellent toughness and impact resistance.
Description
Technical Field
The invention belongs to the technical field of anticorrosive coatings, and particularly relates to a potassium phosphate magnesium-based steel anticorrosive coating material and a preparation method thereof.
Background
Steel is an important raw material in industrial development and is widely applied to the fields of construction, traffic, mechanical manufacturing and the like. The steel is an iron-carbon alloy with carbon content less than 2.11%, and mainly consists of ferrite, carbide or graphite two phases. Since the two phases are unevenly distributed in the steel and the carbide potential is higher than the ferrite potential, the steel is susceptible to corrosive media (H) in industrial or natural environments2O、O2、CI-、SO4 2-Etc.) to form numerous micro-corrosion cells on the steel surface, causing electrochemical corrosion.The steel structure facilities inevitably contact substances such as water vapor, acid, alkali, salt and the like in the using process, and the corrosion speed of the steel is further accelerated in the severe environment. Statistical data show that the economic loss caused by steel corrosion accounts for about 3% -5% of the total value of national production.
The method for coating the anticorrosive paint on the surface of the steel is one of effective methods for preventing corrosion of steel facilities, and the inorganic non-metallic paint does not release toxic gas and age and has more advantages than organic paint. If the coating is coated on a steel substrate, the inorganic non-metallic coating can protect the surface of a steel structure from abrasion through a physical barrier, and can also form a layer of chemically combined inorganic polymerization anticorrosive coating through chemical combination of self-permeation and iron atoms on the surface of the steel structure, so that the surface of the steel structure is continuously protected. However, most inorganic non-metallic coatings have the defects of harsh construction conditions, low-temperature film formation, slow curing speed, easy volume shrinkage in the curing process, brittle coatings and the like, and the application range of the inorganic non-metallic coatings is limited.
For example, a magnesium potassium phosphate cement can be coagulated and hardened to form a dense structure similar to a sintered ceramic in a short time by stirring with water. Has the excellent performances of normal temperature curing, quick hardening, high strength, low shrinkage, freezing and salt freezing resistance, salt corrosion resistance, high temperature resistance, strong environmental adaptability and the like. But the potassium phosphate magnesium adhesive also has the defects of too fast setting time, concentrated release of hydration heat, high brittleness and the like.
Disclosure of Invention
The invention provides a potassium phosphate magnesium-based steel anticorrosive coating material which has excellent performances of normal-temperature curing, quick hardening, high strength, low shrinkage, freezing and salt freezing resistance, salt corrosion resistance, high temperature resistance, strong environmental adaptability and the like, and also has excellent toughness and impact resistance.
The potassium phosphate magnesium-based steel anticorrosive coating material is prepared by mixing a potassium phosphate magnesium cementing material, a setting time regulating component, a corrosion inhibition component and a toughening component, and comprises the following raw materials:
82-88 parts of a potassium magnesium phosphate cementing material,
8-10 parts of a composite retarder component,
4-6 parts of corrosion inhibition component
1-2 parts of toughening component
The potassium magnesium phosphate cementing material is composed of an acid component (monopotassium phosphate) and an alkali component (dead-burned magnesium oxide + mineral admixture), wherein the mass ratio of the acid component to the alkali component is 1: 1.5-2.5. The mineral admixture is metakaolin and/or silica fume, the dead burned oxide powder accounts for 80-95% of the alkali component, and the metakaolin and/or silica fume accounts for 5-20% of the alkali component.
The coagulation time regulating and controlling component comprises the following components in percentage by mass: 10-15% of calcium nitrite, 30-35% of borax, 50-60% of disodium hydrogen phosphate dodecahydrate and 100% of 3 components in total. The coagulation time regulating and controlling component is powder, and the particle size is within the range of 180-250 mu m.
The setting time regulating and controlling component consists of calcium nitrite, borax and disodium hydrogen phosphate dodecahydrate, and through regulating the proportion of 3 components and the mixing amount in the potassium magnesium phosphate cementing material, the setting time of the slurry of the potassium magnesium phosphate cementing material can be regulated effectively within the range of 20-120 min, and the hydration heat is released in two stages during the hydration reaction of the slurry of the potassium magnesium phosphate cementing material, and the hydration heat release amount in the initial stage of hydration is small. The novel composite retarder can meet the construction operation requirements of coating materials in various environments, does not contain chloride ions, and can avoid the corrosion of the coating materials to steel substrates.
The corrosion inhibition component consists of binary oxide (zinc oxide and/or aluminum oxide) and molybdate (sodium molybdate and/or ammonium molybdate), and the mass ratio of the two components is 3: 2, wherein the zinc oxide and/or the aluminum oxide are colorless powder, the purity is not less than 92.0 wt%, and the particle size is 0.1-20 mu m; the sodium molybdate and/or ammonium molybdate are white crystal powder with the particle size of 100-.
The toughening component is re-dispersible latex powder and/or polyvinyl alcohol powder, white solid powder, and has an average particle size of 80-125 μm.
The pH value of the dispersible latex powder is 5-7, the average particle size is 70-80 mu m, and the viscosity is 0.5-2 mPa.s;
the pH value of the polyvinyl alcohol powder is 5-7, the average particle size is 150-200 mu m, and the viscosity is 20-26 mPa.s.
The preparation method of the potassium phosphate magnesium-based steel anticorrosive coating material comprises the following steps:
1) mixing the coagulation time regulating and controlling components of calcium nitrite, borax and disodium hydrogen phosphate dodecahydrate with the acid component of the potassium magnesium phosphate adhesive;
2) mixing the corrosion inhibition component binary oxide (zinc oxide and/or aluminum oxide), molybdate (sodium molybdate and/or ammonium molybdate), the toughening component (re-dispersible latex powder and/or polyvinyl alcohol powder) and the alkali component of the potassium-magnesium phosphate adhesive;
3) and (3) mixing the mixture obtained in the steps 1) and 2) with water to obtain the slurry of the potassium phosphate magnesium-based steel anticorrosive coating material.
The preparation method of the potassium phosphate magnesium-based steel anticorrosive coating material slurry comprises the following steps
Under the natural environment condition (10-30 ℃, 40-70% RH) the method comprises the following steps:
(1) nitrite, borax, disodium hydrogen phosphate dodecahydrate and potassium dihydrogen phosphate are mixed in certain proportion to produce the acid component mixture.
(3) And adding the acid component mixture into water, and fully stirring to obtain a uniform acid component mixed solution.
(4) Adding zinc oxide and/or aluminum oxide, molybdate (sodium molybdate and/or ammonium molybdate) and redispersible latex powder and/or polyvinyl alcohol powder into dead-burned magnesium oxide and mineral admixture to obtain alkali component mixture.
(5) Adding the alkali component mixture into the acid component mixed solution, and stirring to uniformly mix the slurry and release gas; obtaining the slurry of the potassium phosphate magnesium-based steel anticorrosive coating material.
(6) The coating slurry can be coated on the surface of a steel base material through a spraying or brushing process to form an anticorrosive coating hardened body.
The magnesium phosphate cementing material is prepared from dead-burned magnesium oxide powder, phosphate, an admixture, a retarder and the like, the magnesium phosphate cementing material has the characteristics of rapid hardening, high early strength and strong environmental adaptability, the defects of long curing time and maintenance requirement of silicate adhesives can be overcome, the defects of large curing shrinkage and easy cracking of other inorganic adhesives can be overcome due to the low shrinkage characteristic of the magnesium phosphate adhesive in the hardening process, and soluble phosphate in the magnesium phosphate adhesive can be combined with iron elements on the surface of a steel structure to form a compact iron phosphate compound protective layer, so that the corrosion on the surface of the steel structure can be protected, and the adhesive force of a coating on the surface of the steel structure is enhanced. The coating material prepared from the magnesium phosphate cementing material can be cured at normal temperature, and forms a phosphate ceramic coating through acid-base neutralization reaction, the linear expansion coefficient of a hardened body of the coating material is in the same order of magnitude as that of steel, and the coating material has good compatibility with a steel substrate.
The invention takes the magnesium potassium phosphate cementing material as a matrix, and prepares the magnesium potassium phosphate cementing material based steel anticorrosive coating by doping a novel composite retarder, a toughening agent, a corrosion inhibitor and the like, wherein the main hydration product magnesium phosphate has a corrosion inhibition effect, and a solidified body of the magnesium potassium phosphate cementing material has a self-repairing function to a certain extent.
The invention has the advantages that
(1) The potassium phosphate magnesium cementing material based anticorrosive paint is two-component solid powder and is convenient to store. The coating slurry has simple preparation process and can be constructed at normal temperature. The slurry can ensure good workability within 20-60 min, steel facilities can be conveniently coated and secondarily repaired on a construction site, and after construction is finished, the coating can be automatically cured in a normal atmospheric environment so as to avoid the need of special curing equipment and heating process.
(2) The hydration heat is dispersed and released in the process of curing the slurry of the potassium magnesium phosphate cementing material-based anticorrosive coating, the volume shrinkage is reduced in the curing process, and the phenomenon of cracking of a large-area coating in the curing process caused by the concentrated release of the hydration heat and plastic shrinkage is avoided. Because the coating is an inorganic coating material, no harmful components are released in the construction process and after curing, the coefficient of linear expansion of a cured body is close to that of a steel substrate, the compatibility is good, and the coating can be prevented from cracking caused by inconsistent linear expansion when the temperature changes too much.
(3) Soluble phosphate in the potassium magnesium phosphate cementing material-based anticorrosive coating slurry can be combined with iron elements on the surface of a steel substrate to form a compact iron phosphate compound protective layer, so that the corrosion of the surface of a steel structure can be protected, and the adhesive force of the coating on the surface of the steel structure is enhanced. The steel corrosion inhibition component in the coating realizes a second steel protective layer outside a coating hardened body by forming a passive film on the surface of the steel, thereby effectively improving the corrosion resistance of the steel substrate. Wherein, the molybdate plays the dual roles of isolating rust prevention and passive corrosion prevention. The conversion time of the anticorrosion process is longer, so the later anticorrosion effect is particularly obvious.
(4) The potassium magnesium phosphate cementing material-based anticorrosive paint adopts the redispersible latex powder and/or polyvinyl alcohol powder as a toughness improving component, can effectively improve the flexibility of the coating, and ensures that a hardened body of the coating can cooperatively and consistently deform with a base material without cracking when a steel facility is under the action of elastic stress. And the solid powdery re-dispersible latex powder and/or polyvinyl alcohol powder can be directly doped into the potassium magnesium phosphate cementing material-based anticorrosive paint dry powder, so that the operation is simple and the construction is convenient.
Detailed Description
For a better understanding of the present invention, the following examples are given to further illustrate the present invention, but the present invention is not limited to the following examples of dead-burned magnesium oxide.
The dispersible latex powder used in the examples is a product of Hebei Yanxing chemical Co., Ltd.
The polyvinyl alcohol powder used in the examples was a product of three-dimensional group corporation, and the product type was polyvinyl alcohol powder 17 to 88.
Example 1
An anti-corrosion coating material of potassium phosphate magnesium-based steel and a preparation method thereof, which comprises the following steps:
the cementing material is prepared by mixing a potassium magnesium phosphate cementing material, a setting time regulating component, a corrosion inhibiting component and a toughening component. The mass ratio of each component is as follows: 86. 8, 5 and 1, for a total of 100. The magnesium potassium phosphate cementing material consists of an alkali component (dead-burned magnesium oxide and metakaolin, wherein the mass ratio of the dead-burned magnesium oxide to the metakaolin is 4: 1) and an acid component (monopotassium phosphate), wherein the mass ratio of the alkali component to the acid component is 2: 1. the setting time regulating and controlling component consists of calcium nitrite, borax and disodium hydrogen phosphate dodecahydrate, wherein the mass ratio of the calcium nitrite to the borax to the disodium hydrogen phosphate dodecahydrate is 1: 2.5: 4.5. the corrosion inhibition component consists of zinc oxide and sodium molybdate, and the mass ratio of the zinc oxide to the sodium molybdate is 3: 2. the toughening component is redispersible latex powder.
Adding calcium nitrite, borax and disodium hydrogen phosphate dodecahydrate into a certain amount of water, fully stirring to obtain a uniform mixed solution, adding an acid component potassium dihydrogen phosphate of the potassium magnesium phosphate cementing material into the mixed solution, and fully stirring uniformly to obtain an acid component reaction solution of the potassium magnesium phosphate cementing material. Adding an alkali component (dead burned magnesium oxide and metakaolin), a corrosion inhibition component (zinc oxide and sodium molybdate) and a toughening component (redispersible latex powder) of the potassium magnesium phosphate cementing material into an acid component reaction solution of the potassium magnesium phosphate cementing material, and fully and uniformly stirring to obtain the potassium magnesium phosphate cementing material based steel anticorrosive paint slurry. The coating slurry can be coated on the surface of a steel base material through a spraying or brushing process to form an anticorrosive coating hardened body. Table 1 shows the results of the coating hardened body and the steel substrate in terms of adhesion strength, polarization resistance of Electrochemical Impedance (EIS) test, and salt spray test.
Example 2
An anti-corrosion coating material of potassium phosphate magnesium-based steel and a preparation method thereof, which comprises the following steps:
the steel material is prepared by mixing a potassium magnesium phosphate cementing material, a setting time regulating component, a steel corrosion inhibition component and a toughening component. The mass ratio of each component is as follows: 85. 10, 4 and 1, for a total of 100. The magnesium potassium phosphate cementing material consists of an alkali component (dead-burned magnesium oxide and metakaolin, wherein the mass ratio of the dead-burned magnesium oxide to the metakaolin is 4: 1) and an acid component (monopotassium phosphate), wherein the mass ratio of the alkali component to the acid component is 2: 1. the setting time regulating and controlling component consists of calcium nitrite, borax and disodium hydrogen phosphate dodecahydrate, wherein the mass ratio of the calcium nitrite to the borax to the disodium hydrogen phosphate dodecahydrate is 1: 2.0: 4.0. the corrosion inhibition component consists of aluminum oxide and ammonium molybdate, and the mass ratio of the aluminum oxide to the ammonium molybdate is 1: 1. the toughening component is redispersible latex powder.
The slurry of the potassium phosphate magnesium-based adhesive based steel anticorrosive coating material was prepared in example 1, and the bonding strength of the coating hardened body to the steel substrate, the polarization resistance of Electrochemical Impedance (EIS) test and the salt spray test results are shown in table 1.
Example 3
An anti-corrosion coating material of potassium phosphate magnesium-based steel and a preparation method thereof, which comprises the following steps:
the cementing material is prepared by mixing a potassium magnesium phosphate cementing material, a setting time regulating component, a corrosion inhibiting component and a toughening component. The mass ratio of each component is as follows: 86. 8, 5 and 1, for a total of 100. The magnesium potassium phosphate cementing material consists of an alkali component (dead-burned magnesium oxide and metakaolin, wherein the mass ratio of the dead-burned magnesium oxide to the metakaolin is 4: 1) and an acid component (monopotassium phosphate), wherein the mass ratio of the alkali component to the acid component is 2: 1. the setting time regulating and controlling component consists of calcium nitrite, borax and disodium hydrogen phosphate dodecahydrate, wherein the mass ratio of the calcium nitrite to the borax to the disodium hydrogen phosphate dodecahydrate is 1: 2.5: 4.5. the corrosion inhibition component consists of zinc oxide and sodium molybdate, and the mass ratio of the zinc oxide to the sodium molybdate is 3: 2. the toughening component is polyvinyl alcohol powder. The slurry of the potassium phosphate magnesium-based adhesive based steel anticorrosive coating material was prepared in example 1, and the bonding strength of the coating hardened body to the steel substrate, the polarization resistance of Electrochemical Impedance (EIS) test and the salt spray test results are shown in table 1.
Application performance detection
The Electrochemical Impedance Spectroscopy (EIS) test adopts a steel base material with the size of 15mm multiplied by 2mm, the thickness of the anti-corrosion coating of the potassium phosphate magnesium cementing material base steel material on the steel base material is 800 mu m, the soaking solution is NaCl solution, and the mass concentration is 3.5 +/-0.3%.
The dimensions of the steel plate used in the salt spray corrosion test are 150mm × 70mm × 2mm, and the thickness of the coating is 800 μm. The mass concentration of the NaCl solution is 5.0 +/-0.5%, and the spraying is continuously carried out for 1440 h.
According to the GB/T5210-2006 standard for the bonding strength of the coating, the end face of a columnar sample with the diameter of 25mm is coated with the coating and then maintained for 2 d at room temperature (25 ℃); and (4) adopting a universal material testing machine to stretch at a speed of 1mm/min until the bonding surface is broken, and calculating the bonding strength of the coating and the substrate according to the breaking load.
Reference 1 is a 250 μm thick zinc rich epoxy coating primer;
and the reference group 2 is a potassium magnesium phosphate cementing material containing a traditional retarder borax, wherein the acid-base mass ratio (P/M) of the potassium magnesium phosphate cementing material is 1: 2, the mass ratio of borax is 8%;
reference group 3 is a magnesium potassium phosphate gelled material containing a novel setting time regulating component, and the acid-base mass ratio (P/M) of the magnesium potassium phosphate gelled material is 1: 2, the novel setting time regulating component consists of calcium nitrite, borax and disodium hydrogen phosphate dodecahydrate (the mass ratio is 1: 2.5: 4.5), and the mass ratio is 8%.
TABLE 1 test results of test pieces coated with potassium magnesium phosphate-based steel anticorrosive coating material
Claims (7)
1. The potassium phosphate magnesium-based steel anticorrosive coating material is characterized by comprising the following raw materials in parts by mass:
82-88 parts of a potassium magnesium phosphate cementing material,
8-10 parts of a composite retarder component,
4-6 parts of a corrosion inhibition component,
1-2 parts of toughening component;
the potassium magnesium phosphate cementing material is composed of an acid component and an alkali component, wherein the mass ratio of the acid component to the alkali component is 1: 1.5-2.5;
the acid component is potassium dihydrogen phosphate;
80-95% of the alkali component by mass is dead-burned magnesia powder;
the coagulation time regulating and controlling component comprises the following components in percentage by mass: 10-15% of calcium nitrite, 30-35% of borax, 50-60% of disodium hydrogen phosphate dodecahydrate and 100% of 3 components in total;
the corrosion inhibition component consists of binary oxide and molybdate, and the mass ratio of the two components is 3: 2,
the divalent oxide is zinc oxide and/or aluminum oxide;
the molybdate is sodium molybdate and/or ammonium molybdate;
the toughening component is re-dispersible latex powder and/or polyvinyl alcohol powder;
the pH value of the dispersible latex powder is 5-7, the average particle size is 70-80 mu m, and the viscosity is 0.5-2 mPa.s;
the pH value of the polyvinyl alcohol powder is 5-7, the average particle size is 150-200 mu m, and the viscosity is 20-26 mPa.s.
2. The potassium phosphate magnesium based steel corrosion resistant coating material of claim 1, wherein the alkali component further comprises a mineral admixture, wherein the mineral admixture is metakaolin and/or silica fume, and the mineral admixture accounts for 5-20% of the alkali component.
3. The potassium phosphate magnesium-based steel anticorrosive coating material according to claim 1, wherein the zinc oxide and/or aluminum oxide has a purity of not less than 92.0 wt% and a particle diameter of 0.1 to 20 μm;
the potassium phosphate magnesium based steel corrosion protection coating material as claimed in claim 1, wherein the particle size of the sodium molybdate and/or ammonium molybdate is 100-250 μm.
4. The potassium phosphate magnesium-based steel anticorrosive coating material as claimed in claim 1, wherein the setting time controlling component is powder with a particle size within the range of 180-250 μm.
5. The potassium phosphate magnesium based steel corrosion resistant coating material of claim 1, wherein the toughening component has an average particle size of 80-150 μm.
6. The method for preparing potassium phosphate magnesium-based steel anticorrosive coating material as claimed in claim 1, comprising the steps of:
mixing the setting time regulating component with the acid component of the potassium magnesium phosphate adhesive;
mixing the corrosion inhibition component, the toughening component and the alkali component of the potassium-magnesium phosphate adhesive;
and (3) mixing the mixture obtained in the steps 1) and 2) with water to obtain the slurry of the potassium phosphate magnesium-based steel anticorrosive coating material.
7. The method according to claim 7, characterized in that it comprises in particular the following steps
The method is operated under the natural environment condition of 10-30 ℃ and 40-70% RH according to the following steps:
mixing the components with water to obtain a mixture, stirring to uniformly mix the slurry and release gas; obtaining the slurry of the potassium phosphate magnesium-based steel anticorrosive coating material;
the potassium phosphate magnesium-based steel anti-corrosion coating material slurry can be coated on the surface of a steel substrate through a spraying or brushing process to form an anti-corrosion coating hardened body.
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| CN115975422A (en) * | 2022-10-20 | 2023-04-18 | 中建八局第三建设有限公司 | Anticorrosion and fireproof integrated coating and application thereof |
| CN116855108A (en) * | 2023-05-29 | 2023-10-10 | 三江学院 | Ammonium phosphate magnesium-based steel base material anti-corrosion coating and preparation method thereof |
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