CN115637085A - Water-based inorganic zinc-rich anticorrosive paint and preparation method thereof - Google Patents
Water-based inorganic zinc-rich anticorrosive paint and preparation method thereof Download PDFInfo
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Abstract
An aqueous inorganic zinc-rich anticorrosive paint and a preparation method thereof relate to the technical field of paint. The water-based inorganic zinc-rich anticorrosive paint comprises the following components in parts by weight: 5-15 parts of potassium silicate; 10-30 parts of silica sol; 5-10 parts of gamma-glycidyl ether oxypropyl trimethoxy silane; 20-40 parts of silicone-acrylate emulsion; 20-40 parts of modified zinc powder; 1-5 parts of a curing agent; 0.5-1.5 parts of thickening agent; the preparation method of the modified zinc powder comprises the following steps: 1, preparing a silane modified solution; 2, preparing a phytic acid modified solution; and 3, preparing the modified zinc powder. Compared with the existing water-based inorganic zinc-rich anticorrosive coating, the modified zinc powder is selected to replace the common zinc powder in the preparation raw materials, so that the coating has better corrosion resistance and water resistance.
Description
Technical Field
The invention relates to the technical field of coatings, in particular to a water-based inorganic zinc-rich anticorrosive coating and a preparation method thereof.
Background
On one hand, metal corrosion is the most important cause of waste of steel resources, which causes a great amount of economic loss every year, and on the other hand, metal corrosion increases the risk of serious dangerous accidents, such as cracks or holes in natural gas or petroleum transportation pipelines due to metal corrosion, and collapse of steel structures in tower cranes due to cracks caused by metal corrosion, so that the research on corrosion prevention of steel and the application of advanced corrosion prevention technology are urgent.
The coating of the anticorrosive paint on the surface of the steel is a common technical means for avoiding metal corrosion, and not only can play a certain anticorrosive role, but also can bring a decorative effect. Among various anticorrosive coatings, the zinc-rich anticorrosive coating not only has a physical shielding effect (preventing a corrosive medium from directly contacting with the surface of a substrate), but also has electrochemical protection, self-repairing and passivating effects of a coating film, so that the zinc-rich anticorrosive coating is widely applied to the field of corrosion prevention.
The zinc-rich anticorrosive paint can be divided into two categories of organic zinc-rich anticorrosive paint and inorganic zinc-rich anticorrosive paint, and the two categories of zinc-rich anticorrosive materials have the characteristics and the application occasions thereof. The inorganic zinc-rich paint is divided into solvent type and water type, the solvent type inorganic zinc-rich paint is a paint composed of ethyl orthosilicate as a base material, and the water type inorganic zinc-rich paint is a bi-component paint composed of water-based inorganic silicate (sodium, potassium and lithium) resin, zinc powder and an auxiliary agent. The water-based inorganic zinc-rich anticorrosive coating is widely used by virtue of excellent adhesive force, wear resistance, heat resistance, radiation resistance, solvent resistance, safety and antistatic property.
However, the traditional water-based inorganic anti-corrosion zinc-rich paint still has the following defects: 1. the zinc powder is too active, so that the coating fails prematurely, and the corrosion resistance is still to be improved; 2. the surface of the zinc powder is rough, and gully gaps exist between the zinc powder and the adjacent zinc powder, so that water stain is easy to permeate into the zinc powder, the coating is difficult to dry completely quickly, bubbling is easy to occur, and the quality of the coating is influenced.
Disclosure of Invention
The invention aims to overcome the defects of the prior art, provides a water-based inorganic zinc-rich anticorrosive paint and a preparation method thereof, and solves the problems of poor corrosion resistance and water resistance of the existing water-based inorganic zinc-rich anticorrosive paint.
The technical scheme of the invention is as follows: the water-based inorganic zinc-rich anticorrosive paint comprises the following components in parts by weight: 5-15 parts of potassium silicate; 10-30 parts of silica sol; 5-10 parts of gamma-glycidyl ether oxypropyl trimethoxy silane; 20-40 parts of silicone-acrylate emulsion; 20-40 parts of modified zinc powder; 1-5 parts of a curing agent; 0.5-1.5 parts of thickening agent;
the preparation method of the modified zinc powder comprises the following steps:
s01, preparing a silane modified solution: respectively taking gamma-methacryloxypropyltrimethoxysilane and 1,2-bis (triethoxysilyl) ethane, dispersing the gamma-methacryloxypropyltrimethoxysilane and the 1,2-bis (triethoxysilyl) ethane in a No. 1 solution formed by ethanol and distilled water to obtain a No. 2 solution, fully stirring the No. 2 solution, and preserving the temperature at 20-30 ℃;
in the step, the volume ratio of the gamma-methacryloxypropyltrimethoxysilane to the 1,2-bis (triethoxysilyl) ethane is 2: (2-3); the volume ratio of ethanol to distilled water in solution No. 1 is 1: (4-5);
s02, preparing a phytic acid modified solution: mixing the No. 2 solution with phytic acid to form a No. 3 solution, dispersing the No. 3 solution into a No. 4 solution formed by ethanol and distilled water to obtain a No. 5 solution, adjusting the pH value of the No. 5 solution to 7-10, fully stirring the No. 5 solution, and keeping the temperature at 30-40 ℃;
in the step, the volume ratio of the No. 2 solution to the phytic acid is (3-20): 2; the volume ratio of ethanol to distilled water in solution No. 4 was 1: (4-5);
s03, preparing modified zinc powder: adding zinc powder into the No. 5 solution, fully stirring to enable the surface of the zinc powder to be fully infiltrated by the No. 5 solution, so as to attach a silane film and a phytic acid group on the surface of the zinc powder, and evaporating the No. 5 solution to dryness to obtain the modified zinc powder.
The further technical scheme of the invention is as follows: in the step S01 for preparing the modified zinc powder, stirring and heat preservation of the No. 2 solution are carried out simultaneously for 20-40 min; in the step S02 of preparing the modified zinc powder, stirring and heat preservation of the No. 5 solution are carried out simultaneously for 20-40 min; in the step of preparing the modified zinc powder S02, the concentration of phytic acid is 45-55 percent; in the step of preparing the modified zinc powder S03, the particle size of the added zinc powder is 250-800 meshes.
The invention further adopts the technical scheme that: the water-based inorganic zinc-rich anticorrosive paint comprises the following components in parts by weight: 10 parts of potassium silicate; 20 parts of silica sol; 7 parts of gamma-glycidyl ether oxypropyl trimethoxy silane; 30 parts of silicone-acrylate emulsion; 30 parts of modified zinc powder; 3 parts of a curing agent; 1 part of a thickening agent; the curing agent is triethylene tetramine, and the thickening agent is sodium polyacrylate.
The technical scheme of the invention is as follows: a method for preparing the water-based inorganic zinc-rich anticorrosive paint comprises the following steps:
s01, pouring 5-15 parts by weight of potassium silicate solution into a container, dropwise adding 10-30 parts by weight of silica sol into the container to obtain No. 6 solution, stirring and heating while dropwise adding, and controlling the heating temperature to be 50-70 ℃;
s02, adding 5-10 parts by weight of gamma-glycidoxypropyltrimethoxysilane to the solution No. 6 under stirring to obtain a solution No. 7, and standing the solution No. 7 to naturally cool the solution No. 7 to room temperature;
s03, adding 20-40 parts by weight of silicone-acrylic emulsion into the No. 7 solution under a stirring state to obtain No. 8 solution;
and S04, sequentially adding 20-40 parts by weight of modified zinc powder, 1-5 parts by weight of curing agent and 0.5-1.5 parts by weight of thickening agent into the No. 8 solution under a stirring state to obtain the water-based inorganic zinc-rich anticorrosive paint.
Compared with the prior art, the invention has the following advantages: compared with the existing water-based inorganic zinc-rich anticorrosive coating, the coating has better corrosion resistance and water resistance by selecting the modified zinc powder to replace the common zinc powder in the preparation raw materials. Compared with the rough surface form of common zinc powder, the modified zinc powder is coated with a silane film and phytic acid groups, so that a smooth and compact protective film is formed. Based on the protective film, on one hand, direct contact between a corrosive medium and zinc powder is avoided, the speed of corroding the zinc powder by the corrosive medium is delayed, premature failure of the coating is avoided, and on the other hand, the characteristic of smoothness and compactness effectively avoids water stain infiltration, so that the water resistance of the coating is improved.
The invention is further described below with reference to the figures and examples.
Drawings
FIG. 1 is an SEM image of a common zinc powder magnified 10000 times;
FIG. 2 is an SEM image of a modified zinc powder magnified 10000 times;
FIG. 3 is a photograph of the surface topography of a control sample;
fig. 4 is a surface topography photograph of the experimental group of samples.
Detailed Description
Example 1:
the water-based inorganic zinc-rich anticorrosive paint comprises the following components in parts by weight: 10 parts of potassium silicate; 20 parts of silica sol; 7 parts of gamma-glycidyl ether oxypropyl trimethoxy silane; 30 parts of silicone-acrylate emulsion; 30 parts of modified zinc powder; 3 parts of a curing agent; 1 part of thickening agent.
The preparation method of the modified zinc powder comprises the following steps:
s01, preparing a silane modified solution: respectively taking gamma-methacryloxypropyltrimethoxysilane and 1,2-bis (triethoxysilyl) ethane, dispersing the gamma-methacryloxypropyltrimethoxysilane and the 1,2-bis (triethoxysilyl) ethane in a No. 1 solution formed by ethanol and distilled water to obtain a No. 2 solution, fully stirring the No. 2 solution, and preserving the temperature at 25 ℃;
in the step, the volume ratio of the gamma-methacryloxypropyltrimethoxysilane to the 1,2-bis (triethoxysilyl) ethane is 2:3; the volume ratio of ethanol to distilled water in solution No. 1 is 1:4.
s02, preparing a phytic acid modified solution: mixing the No. 2 solution with phytic acid to form a No. 3 solution, dispersing the No. 3 solution into a No. 4 solution formed by ethanol and distilled water to obtain a No. 5 solution, adjusting the pH value of the No. 5 solution to 9, fully stirring the No. 5 solution, and keeping the temperature at 35 ℃;
in the step, the volume ratio of the No. 2 solution to the phytic acid is 8.8:2; the volume ratio of ethanol to distilled water in solution No. 4 was 1:4.
s03, preparing modified zinc powder: adding zinc powder into the No. 5 solution, fully stirring to enable the surface of the zinc powder to be fully infiltrated by the No. 5 solution, so as to attach a silane film and phytic acid groups on the surface of the zinc powder, and evaporating the No. 5 solution to dryness to obtain the modified zinc powder.
Preferably, in the step S01 of preparing the modified zinc powder, stirring and heat preservation of the No. 2 solution are carried out simultaneously, and the duration is 30min; in the step S02 of preparing the modified zinc powder, stirring and heat preservation of the No. 5 solution are carried out simultaneously, and the time duration is 30min; in the step of preparing the modified zinc powder S02, the concentration of phytic acid is 50 percent; in the step of preparing the modified zinc powder S03, the particle size of the added zinc powder is 500 meshes.
Preferably, the curing agent is triethylene tetramine, and the thickening agent is sodium polyacrylate.
The preparation method of the water-based inorganic zinc-rich anticorrosive paint comprises the following steps:
s01, pouring 10 parts of potassium silicate solution into a container, dropwise adding 20 parts of silica sol into the container to obtain No. 6 solution, stirring and heating while dropwise adding, and controlling the heating temperature to be 50-70 ℃;
s02, adding 7 parts of gamma-glycidoxypropyltrimethoxysilane to the solution No. 6 under a stirring state to obtain a solution No. 7, and standing the solution No. 7 to naturally cool the solution No. 7 to room temperature;
s03, adding 30 parts of silicone-acrylic emulsion into the solution No. 7 under a stirring state to obtain a solution No. 8;
and S04, sequentially adding 30 parts of modified zinc powder, 3 parts of curing agent and 1 part of thickening agent into the No. 8 solution under a stirring state to obtain the water-based inorganic zinc-rich anticorrosive paint.
The parts in the preparation method of the water-based inorganic zinc-rich anticorrosive paint are the parts by weight.
Example 2:
compared with example 1, the difference of this example is only the weight parts of the components of the water-based inorganic zinc-rich anticorrosive paint. The water-based inorganic zinc-rich anticorrosive paint comprises the following components in parts by weight: 10 parts of potassium silicate; 20 parts of silica sol; 7 parts of gamma-glycidyl ether oxypropyl trimethoxy silane; 30 parts of silicone-acrylic emulsion; 20 parts of modified zinc powder; 3 parts of a curing agent; 1 part of thickening agent.
Example 3:
compared with example 1, the difference of the present example is only in the weight parts of the components of the water-based inorganic zinc-rich anticorrosive paint. The water-based inorganic zinc-rich anticorrosive paint comprises the following components in parts by weight: 10 parts of potassium silicate; 20 parts of silica sol; 7 parts of gamma-glycidyl ether oxypropyl trimethoxy silane; 30 parts of silicone-acrylate emulsion; 40 parts of modified zinc powder; 3 parts of a curing agent; 1 part of thickening agent.
The coating formed by coating the water-based inorganic zinc-rich anticorrosive paint disclosed by the invention has a smooth and compact surface, and is improved in quick drying property, water resistance and corrosion resistance, and the technical effect of the coating is proved by an SEM (scanning electron microscope) comparison graph and a plurality of comparison experiments.
The quick-drying properties of the coating were analyzed by SEM comparison:
FIG. 1 is an SEM picture of a plain zinc powder at 50000 times magnification, and FIG. 2 is an SEM picture of a modified zinc powder at 5000 times magnification. As is apparent from fig. 1, the conventional zinc powder has a rough surface and many gaps, which results in a relatively rough coating surface, easy water accumulation and relatively long drying time. As is apparent from fig. 2, the modified zn powder surface is covered with micelle example to form a smooth and dense protective film with less gaps, which results in a relatively smooth coating surface, less water retention, and relatively short drying time.
Comparative experiment 1 (determination of coating drying time):
the experimental group is the sample coated with the aqueous inorganic zinc-rich anticorrosive paint in example 1, and the control group is the sample coated with the conventional aqueous inorganic zinc-rich anticorrosive paint (unmodified zinc powder). According to GB/T1728-2020 'determination method for drying time of paint film and putty film', the surface drying time of the coating is measured by a finger touch method, and the actual drying time of the coating is measured by a cotton ball pressing method. The finger touch method is mainly to determine whether the coating surface is dry or not based on the sticky feeling of the finger tip touching the coating surface layer. The cotton ball pressing method is mainly used for judging whether a coating is actually dried or not through the trace left by the cotton balls on the surface of a paint film (the specific operation is that after the coating is brushed on the surface of a base material, the cotton balls are forcibly pressed on the surface of the paint film, and then the cotton balls are removed, if 1-2 cotton threads are left on the surface of the paint film and can be blown off, the earliest time is determined as the actual drying time of the coating).
Referring to the experimental results in table 1, it can be seen from table 1 that the surface drying time and the actual drying time (actual drying time) of the experimental group are both significantly shorter than those of the control group, which indicates that the quick-drying property of the experimental group is better.
Table 1:
| test items | Control group | Experimental group |
| Time to surface dry (min) | 15 | 10 |
| Actual drying time (min) | 60 | 50 |
Comparative experiment 2 (determination of the water resistance of the coating):
the experimental group 1 is the sample coated by the water-based inorganic zinc-rich anti-corrosive paint in the example 1, the experimental group 2 is the sample coated by the water-based inorganic zinc-rich anti-corrosive paint in the example 2, the experimental group 3 is the sample coated by the water-based inorganic zinc-rich anti-corrosive paint in the example 3, and the control group is the sample coated by the traditional water-based inorganic zinc-rich anti-corrosive paint (zinc powder is not modified). The water resistance of the coatings was tested according to the method of resistance to immersion in distilled water as described in GB/T1733-1993 "paint film Water resistance assay". Three parallel plates of samples were selected for experimental group 1, experimental group 2, experimental group 3 and control group. Under the condition of normal temperature, each group of parallel samples are respectively immersed into different beakers, and two thirds of the samples are ensured to be immersed in distilled water. After the specified time is finished, observing whether the sample has the phenomena of rusting, wrinkling, color loss and light change, and if the sample with two or more than two parallel plates in the three-plate parallel real sample meets the specified standard, determining that the sample is qualified.
The experimental results are shown in table 2, and the combination of table 2 shows that the samples of experimental group 1, experimental group 2 and experimental group 3 all meet the standard, are qualified products, and have better water resistance than the control group.
Table 2:
comparative experiment 3 (determination of the corrosion resistance of the coating):
the experimental group is the sample coated with the aqueous inorganic zinc-rich anticorrosive paint in example 1, and the control group is the sample coated with the conventional aqueous inorganic zinc-rich anticorrosive paint (unmodified zinc powder). 3.5 percent sodium chloride solution simulating artificial seawater is prepared according to the national standard GB/T10834-2008 'determination of salt water resistance of marine paint'. Clamping and hanging the sample in the solution by using a clamping plate under the normal temperature condition, ensuring that three-fourth of the sample is soaked in the solution, taking out the sample after soaking for 24 hours, wiping the moisture on the outer surface layer of the sample, and observing whether the corrosion phenomenon occurs on the coating of the sample.
Referring to fig. 3-4, fig. 3 is a photograph of the surface topography of the control group of samples, and fig. 4 is a photograph of the surface topography of the experimental group of samples. As can be seen from fig. 3, the surface of the control sample generates a large amount of rusts, and the corrosion resistance is relatively poor. As can be seen from FIG. 4, the surface morphology of the test sample of the experimental group is intact, no corrosion occurs, and the corrosion resistance is relatively good.
Comparative experiment 4 (coating hardness determination):
the experimental group is the sample coated with the aqueous inorganic zinc-rich anticorrosive paint in example 1, and the control group is the sample coated with the conventional aqueous inorganic zinc-rich anticorrosive paint (unmodified zinc powder). The hardness grade of the coating is determined by testing different grades of pencils in a QHQ-A pencil hardness tester according to GB/T6739-2006 determination of paint film hardness by the colored paint and varnish pencil method.
The experimental results show that the hardness of the sample coatings of the experimental group and the control group reaches 6H, and the process requirements can be met.
Comparative experiment 5 (impact strength measurement):
the experimental group is the sample coated with the aqueous inorganic zinc-rich anticorrosive paint in example 1, and the control group is the sample coated with the conventional aqueous inorganic zinc-rich anticorrosive paint (unmodified zinc powder). According to GB/T1732-2020 & lt & gt paint film impact resistance determination method & gt, the impact strength of a sample is determined, the sample is fixed on a test board table, a weight of 1kg is used as a heavy hammer to vertically fall on the prepared sample at normal temperature, three positions of each sample are selected for carrying out three times of impact tests (each position is used for carrying out one time of impact tests), and the position with the largest damage degree is selected from the three positions for determining the impact strength of the sample.
The experimental results show that the impact strength of the sample coatings of the experimental group and the control group is more than or equal to 50kg cm, and the process requirements can be met.
Claims (6)
1. The water-based inorganic zinc-rich anticorrosive paint is characterized by comprising the following components in parts by weight: the paint comprises the following components in parts by weight: 5-15 parts of potassium silicate; 10-30 parts of silica sol; 5-10 parts of gamma-glycidyl ether oxypropyl trimethoxy silane; 20-40 parts of silicone-acrylic emulsion; 20-40 parts of modified zinc powder; 1-5 parts of a curing agent; 0.5-1.5 parts of thickening agent;
the preparation method of the modified zinc powder comprises the following steps:
s01, preparing a silane modified solution: respectively taking gamma-methacryloxypropyltrimethoxysilane and 1,2-bis (triethoxysilyl) ethane, dispersing the gamma-methacryloxypropyltrimethoxysilane and the 1,2-bis (triethoxysilyl) ethane in a No. 1 solution formed by ethanol and distilled water to obtain a No. 2 solution, fully stirring the No. 2 solution, and preserving the temperature at 20-30 ℃;
in the step, the volume ratio of the gamma-methacryloxypropyltrimethoxysilane to the 1,2-bis (triethoxysilyl) ethane is 2: (2-3); the volume ratio of ethanol to distilled water in solution No. 1 is 1: (4-5);
s02, preparing a phytic acid modified solution: mixing the No. 2 solution with phytic acid to form a No. 3 solution, dispersing the No. 3 solution into a No. 4 solution formed by ethanol and distilled water to obtain a No. 5 solution, adjusting the pH value of the No. 5 solution to 7-10, fully stirring the No. 5 solution, and keeping the temperature at 30-40 ℃;
in the step, the volume ratio of the No. 2 solution to the phytic acid is (3-20): 2; the volume ratio of ethanol to distilled water in solution No. 4 was 1: (4-5);
s03, preparing modified zinc powder: adding zinc powder into the No. 5 solution, fully stirring to enable the surface of the zinc powder to be fully infiltrated by the No. 5 solution, so as to attach a silane film and phytic acid groups on the surface of the zinc powder, and evaporating the No. 5 solution to dryness to obtain the modified zinc powder.
2. The water-based inorganic zinc-rich anticorrosive paint according to claim 1, characterized in that: in the step S01 for preparing the modified zinc powder, stirring and heat preservation of the No. 2 solution are carried out simultaneously for 20-40 min; in the step S02 of preparing the modified zinc powder, stirring and heat preservation of the No. 5 solution are carried out simultaneously, and the time duration is 20-40 min; in the step of preparing the modified zinc powder S02, the concentration of phytic acid is 45-55 percent; in the step of preparing the modified zinc powder S03, the particle size of the added zinc powder is 250-800 meshes.
3. The aqueous inorganic zinc-rich anticorrosive coating according to claim 1 or 2, characterized in that: the paint comprises the following components in parts by weight: 10 parts of potassium silicate; 20 parts of silica sol; 7 parts of gamma-glycidyl ether oxypropyl trimethoxy silane; 30 parts of silicone-acrylate emulsion; 30 parts of modified zinc powder; 3 parts of a curing agent; 1 part of thickening agent.
4. The aqueous inorganic zinc-rich anticorrosive coating of claim 1 or 2, characterized in that: the paint comprises the following components in parts by weight: 10 parts of potassium silicate; 20 parts of silica sol; 7 parts of gamma-glycidyl ether oxypropyl trimethoxy silane; 30 parts of silicone-acrylate emulsion; 20 parts of modified zinc powder; 3 parts of a curing agent; 1 part of thickening agent.
5. The aqueous inorganic zinc-rich anticorrosive coating according to claim 1 or 2, characterized in that: the paint comprises the following components in parts by weight: 10 parts of potassium silicate; 20 parts of silica sol; 7 parts of gamma-glycidyl ether oxypropyl trimethoxy silane; 30 parts of silicone-acrylic emulsion; 40 parts of modified zinc powder; 3 parts of a curing agent; 1 part of thickening agent.
6. A process for preparing the aqueous inorganic zinc-rich anticorrosive coating as claimed in claim 1, characterized by the following steps:
s01, pouring 5-15 parts by weight of potassium silicate solution into a container, dropwise adding 10-30 parts by weight of silica sol into the container to obtain No. 6 solution, stirring and heating while dropwise adding, and controlling the heating temperature to be 50-70 ℃;
s02, adding 5-10 parts by weight of gamma-glycidoxypropyltrimethoxysilane to the solution No. 6 under stirring to obtain a solution No. 7, and standing the solution No. 7 to naturally cool the solution No. 7 to room temperature;
s03, adding 20-40 parts by weight of silicone-acrylic emulsion into the No. 7 solution under a stirring state to obtain No. 8 solution;
and S04, sequentially adding 20-40 parts by weight of modified zinc powder, 1-5 parts by weight of curing agent and 0.5-1.5 parts by weight of thickening agent into the No. 8 solution under a stirring state to obtain the water-based inorganic zinc-rich anticorrosive paint.
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