CN113337179A - Water-based nano epoxy zinc-rich coating and preparation method thereof - Google Patents
Water-based nano epoxy zinc-rich coating and preparation method thereof Download PDFInfo
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- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
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Abstract
The invention discloses a preparation method of a water-based nano epoxy zinc-rich coating, which comprises the following steps: s01, mixing the epoxy resin, the mica iron oxide and the ferrophosphorus powder, and performing ball milling; s02, mixing zinc phosphate and talcum powder, and ball milling; s03, mixing triethylene tetramine and zinc powder, and ball-milling; s04, adding the ball-milled epoxy resin, mica iron oxide and ferrophosphorus powder into water, and mixing to obtain a dispersion liquid A; s05, adding ball-milled zinc phosphate and talcum powder into the dispersion liquid A, and mixing to obtain a dispersion liquid B; and S06, adding ball-milled triethylene tetramine and zinc powder into the dispersion liquid B, and mixing to obtain the water-based nano epoxy zinc-rich coating. The water-based nano epoxy zinc-rich coating adopts nano raw material particles, and the adhesive force, impact resistance and salt mist resistance of the coating are all obviously superior to those of micron-sized raw material particles.
Description
Technical Field
The invention belongs to the technical field of coatings, and particularly relates to a water-based nano epoxy zinc-rich coating and a preparation method thereof.
Background
Most of containers are steel structures, play a very important role in international cargo transportation, and are equipment for providing transportation for ships, railways, automobiles and the like, and are applied very much. The container needs to bear the influence of temperature difference from high temperature to low temperature, direct sunlight and erosion of rainwater, and the influence of seawater impact and salt fog in the shipping container, and must adapt to the severe environment of each place on the earth. The corrosion protection requirements of the container under such a severe influence of a corrosive environment are very high.
The water-based epoxy zinc-rich primer can be suitable for metal primers in various heavy-duty anticorrosion fields, such as bridge steel structures, chemical storage tanks, underground pipelines, power transmission towers, mechanical equipment and the like, and can also be used as a workshop primer to be matched with a water-based epoxy micaceous iron intermediate paint and a water-based polyurethane finish paint for use.
Among the performances of the primer, one of the key indexes of adhesion, impact resistance and salt spray resistance is provided. The inventors of the present application developed a waterborne epoxy zinc rich primer in CN108517140A, the particle size of the powder raw material is all in the micrometer scale.
Disclosure of Invention
On the basis of the patents, the researchers of the invention process the micron-sized raw materials into the nanometer grade, and find that the adhesion, impact resistance and salt fog resistance of the obtained coating are all greatly improved.
The first aspect of the invention discloses a preparation method of a water-based nano epoxy zinc-rich coating, which comprises the following steps:
s01, mixing the epoxy resin, the mica iron oxide and the ferrophosphorus powder, and performing ball milling;
s02, mixing zinc phosphate and talcum powder, and ball milling;
s03, mixing triethylene tetramine and zinc powder, and ball-milling;
s04, adding the ball-milled epoxy resin, mica iron oxide and ferrophosphorus powder into water, and mixing to obtain a dispersion liquid A;
s05, adding ball-milled zinc phosphate and talcum powder into the dispersion liquid A, and mixing to obtain a dispersion liquid B;
and S06, adding ball-milled triethylene tetramine and zinc powder into the dispersion liquid B, and mixing to obtain the water-based nano epoxy zinc-rich coating.
In some preferred embodiments of the present invention, in S01, the weight ratio of the grinding balls to the material is (10-20):1, the rotation speed of the ball mill is 30-60rpm, and the ball milling is performed for 1-5h, preferably for 2-4 h.
In some preferred embodiments of the present invention, in S02, the weight ratio of the grinding balls to the material is (10-20):1, the rotation speed of the ball mill is 30-60rpm, and the ball milling is performed for 0.5-1.5h, preferably, the weight ratio of the grinding balls to the material is (10-15):1, the rotation speed of the ball mill is 50-60rpm, and the ball milling is performed for 1-1.5 h.
In some preferred embodiments of the present invention, in S03, the weight ratio of the grinding balls to the material is (10-20):1, the rotation speed of the ball mill is 30-60rpm, and the ball milling is performed for 0.1-2h, preferably for 0.4-1 h.
In some preferred embodiments of the present invention, the mixing in S04 and S06 is 200-400rpm mechanical stirring for 10-30min, preferably 300rpm mechanical stirring for 20 min.
In some preferred embodiments of the present invention, the mixing comprises mechanical stirring and ultrasonic dispersion in S05, preferably mechanical stirring at 300rpm for 20min and ultrasonic dispersion at 200W for 30 min.
In some preferred embodiments of the present invention, the particle size of the ball-milled epoxy resin particles, mica iron oxide and ferrophosphorus powder, zinc phosphate and talc, triethylene tetramine and zinc powder is below 150nm, the ratio of the particle size of 30-50nm is not less than 50%, and the ratio of the particle size of 10nm is less than 10%.
In some preferred embodiments of the invention, the raw materials of the water-based nano epoxy zinc-rich paint comprise (1.5-2.5) 1 weight part of A component and B component;
the component A comprises the following raw materials in parts by weight:
20-30 parts of water, 25-35 parts of epoxy resin, 5-10 parts of mica iron oxide, 1.5-3 parts of ferrophosphorus powder, 350 parts of zinc phosphate 300-350 parts and 1.5-2.5 parts of talcum powder;
the component B comprises the following raw materials in parts by weight:
20-35 parts of triethylene tetramine and 20-40 parts of zinc powder.
In some preferred embodiments of the present invention, in S05, the time of ultrasonic dispersion is determined by the following formula:
wherein T1 is the time of mechanical stirring, and the value is 10-30 min; r1 is the rotation speed of mechanical stirring, the value is 200-400rpm, RS is the standard value of the rotation speed of mechanical stirring, and the value is 250-300 rpm; w is ultrasonic power, the value is 150-.
In some preferred embodiments of the present invention, in S04 and S06, the speed control of the mechanical agitation controls the voltage by the following PID algorithm:
wherein, Δ u (c) corresponds to the variation of the voltage within the time interval of two test voltages; kc is a constant, 11-15; f (C) is the deviation at the time of sampling C, f (C-1) is the deviation at the time of sampling C-1, and f (C-2) is the deviation at the time of sampling C-2; TS is sampling period, 2.0-2.5 s; TD is differential time, 1.0-1.5 min; TI is integration time, 1.5-2.5 min.
The second aspect of the invention is to disclose the water-based nano epoxy zinc-rich paint obtained by the preparation method of the first aspect.
The invention has the beneficial effects that:
(1) the water-based nano epoxy zinc-rich coating adopts nano raw material particles, and the adhesive force, impact resistance and salt mist resistance of the coating are all obviously superior to those of micron-sized raw material particles.
(2) The preparation method of the water-based nano epoxy zinc-rich coating adopts a ball milling technology to obtain nano raw material particles.
(3) According to the preparation method of the water-based nano epoxy zinc-rich coating, the micaceous iron oxide and the ferrophosphorus powder are used as the accelerating agent for ball milling of the epoxy resin, so that the nano granulation process of the epoxy resin is accelerated.
Detailed Description
The embodiments of the present invention are described below with reference to specific embodiments, and other advantages and effects of the present invention will be easily understood by those skilled in the art from the disclosure of the present specification. The invention is capable of other and different embodiments and of being practiced or of being carried out in various ways, and its several details are capable of modification in various respects, all without departing from the spirit and scope of the present invention. In the following examples and comparative examples, the particle size of the epoxy resin waterborne epoxy resin is about 4 um. The particle size of each powder raw material belongs to the micron order.
Unless otherwise specified, the examples and comparative examples are parallel tests with the same components, component contents, preparation steps, preparation parameters.
Example 1
Water-based nano epoxy zinc-rich coating and preparation method thereof
The water-based nano epoxy zinc-rich paint comprises 2:1 parts by weight of a component A and a component B.
Component A formula (by weight)
25 parts of water, 30 parts of epoxy resin, 8 parts of mica iron oxide, 2 parts of ferrophosphorus powder, 325 parts of zinc phosphate and 2 parts of talcum powder.
B component formula (by weight)
30 parts of triethylene tetramine and 30 parts of zinc powder.
The preparation method comprises the following steps:
(1) mixing epoxy resin, mica iron oxide and ferrophosphorus powder, adding liquid nitrogen, and ball-milling in a ball mill at a ball-milling speed of 50rpm for 3h at a weight ratio of 15: 1;
(2) mixing zinc phosphate and talcum powder, adding liquid nitrogen, and placing into a ball mill for ball milling, wherein the weight ratio of grinding balls to materials is 15:1, the rotating speed of the ball mill is 50rpm, and the ball milling is carried out for 1h for later use;
(3) mixing triethylene tetramine and zinc powder, adding liquid nitrogen, and placing the mixture into a ball mill for ball milling, wherein the weight ratio of grinding balls to materials is 15:1, the rotating speed of the ball mill is 50rpm, and the ball milling is carried out for 0.5h for later use;
(4) adding the ball-milled epoxy resin, mica iron oxide and ferrophosphorus powder into water, and mechanically stirring at 300rpm for 20 min;
(5) adding the ball-milled zinc phosphate and talcum powder into the aqueous dispersion, mechanically stirring at 300rpm for 20min, and ultrasonically dispersing at 200W for 30 min;
(6) and then adding the ball-milled triethylene tetramine and zinc powder into the aqueous dispersion, and mechanically stirring at 300rpm for 20 min.
In the ball-milled epoxy resin particles, mica iron oxide and ferrophosphorus powder, zinc phosphate and talcum powder, triethylene tetramine and zinc powder, the particle size is below 150nm, the proportion of the particle size of 30-50nm is not less than 50%, and the proportion of the particle size of 10nm is less than 10%.
Example 2
Water-based nano epoxy zinc-rich coating and preparation method thereof
The water-based nano epoxy zinc-rich paint comprises 2:1 parts by weight of a component A and a component B.
Component A formula (by weight)
25 parts of water, 30 parts of epoxy resin, 8 parts of mica iron oxide, 2 parts of ferrophosphorus powder, 325 parts of zinc phosphate and 2 parts of talcum powder.
B component formula (by weight)
30 parts of triethylene tetramine and 30 parts of zinc powder.
The preparation method comprises the following steps:
(1) mixing epoxy resin, mica iron oxide and ferrophosphorus powder, adding liquid nitrogen, and ball-milling in a ball mill at a ball-milling speed of 60rpm for 4h, wherein the weight ratio of the grinding balls to the materials is 10: 1;
(2) mixing zinc phosphate and talcum powder, adding liquid nitrogen, and placing into a ball mill for ball milling, wherein the weight ratio of grinding balls to materials is 10:1, the rotating speed of the ball mill is 60rpm, and the ball milling is carried out for 1.5 hours for later use;
(3) mixing triethylene tetramine and zinc powder, adding liquid nitrogen, and placing the mixture into a ball mill for ball milling, wherein the weight ratio of grinding balls to materials is 10:1, the rotating speed of the ball mill is 60rpm, and the ball milling is carried out for 1h for later use;
(4) adding the ball-milled epoxy resin, mica iron oxide and ferrophosphorus powder into water, and mechanically stirring at 300rpm for 20 min;
(5) adding the ball-milled zinc phosphate and talcum powder into the aqueous dispersion, mechanically stirring at 300rpm for 20min, and ultrasonically dispersing at 200W for 30 min;
(6) and then adding the ball-milled triethylene tetramine and zinc powder into the aqueous dispersion, and mechanically stirring at 300rpm for 20 min.
In the ball-milled epoxy resin particles, mica iron oxide and ferrophosphorus powder, zinc phosphate and talcum powder, triethylene tetramine and zinc powder, the particle size is below 150nm, the proportion of the particle size of 30-50nm is not less than 50%, and the proportion of the particle size of 10nm is less than 10%.
Example 3
Water-based nano epoxy zinc-rich coating and preparation method thereof
The water-based nano epoxy zinc-rich paint comprises 2:1 parts by weight of a component A and a component B.
Component A formula (by weight)
25 parts of water, 30 parts of epoxy resin, 8 parts of mica iron oxide, 2 parts of ferrophosphorus powder, 325 parts of zinc phosphate and 2 parts of talcum powder.
B component formula (by weight)
30 parts of triethylene tetramine and 30 parts of zinc powder.
The preparation method comprises the following steps:
(1) mixing epoxy resin, mica iron oxide and ferrophosphorus powder, adding liquid nitrogen, and ball-milling in a ball mill at a ball-milling speed of 30rpm for 2h at a weight ratio of 20: 1;
(2) mixing zinc phosphate and talcum powder, adding liquid nitrogen, and ball-milling in a ball mill at a ball milling ball-material rotation speed of 30rpm for 0.4h at a weight ratio of 20:1 for later use;
(3) mixing triethylene tetramine and zinc powder, adding liquid nitrogen, and placing the mixture into a ball mill for ball milling, wherein the weight ratio of grinding balls to materials is 20:1, the rotating speed of the ball mill is 30rpm, and the ball milling is carried out for 0.4h for later use;
(4) adding the ball-milled epoxy resin, mica iron oxide and ferrophosphorus powder into water, and mechanically stirring at 300rpm for 20 min;
(5) adding the ball-milled zinc phosphate and talcum powder into the aqueous dispersion, mechanically stirring at 300rpm for 20min, and ultrasonically dispersing at 200W for 30 min;
(6) and then adding the ball-milled triethylene tetramine and zinc powder into the aqueous dispersion, and mechanically stirring at 300rpm for 20 min.
In the ball-milled epoxy resin particles, mica iron oxide and ferrophosphorus powder, zinc phosphate and talcum powder, triethylene tetramine and zinc powder, the particle size is below 150nm, the proportion of the particle size of 30-50nm is not less than 50%, and the proportion of the particle size of 10nm is less than 10%.
Example 4
Water-based nano epoxy zinc-rich coating and preparation method thereof
The water-based nano epoxy zinc-rich paint comprises 2:1 parts by weight of a component A and a component B.
Component A formula (by weight)
25 parts of water, 30 parts of epoxy resin, 8 parts of mica iron oxide, 2 parts of ferrophosphorus powder, 325 parts of zinc phosphate and 2 parts of talcum powder.
B component formula (by weight)
30 parts of triethylene tetramine and 30 parts of zinc powder.
The preparation method comprises the following steps:
(1) mixing epoxy resin, mica iron oxide and ferrophosphorus powder, adding liquid nitrogen, and ball-milling in a ball mill at a ball-milling speed of 50rpm for 1h, wherein the weight ratio of the grinding balls to the materials is 15: 1;
(2) mixing zinc phosphate and talcum powder, adding liquid nitrogen, and placing into a ball mill for ball milling, wherein the weight ratio of grinding balls to materials is 15:1, the rotating speed of the ball mill is 50rpm, and the ball milling is carried out for 0.5h for later use;
(3) mixing triethylene tetramine and zinc powder, adding liquid nitrogen, and placing the mixture into a ball mill for ball milling, wherein the weight ratio of grinding balls to materials is 15:1, the rotating speed of the ball mill is 50rpm, and the ball milling is carried out for 0.1h for later use;
(4) adding the ball-milled epoxy resin, mica iron oxide and ferrophosphorus powder into water, and mechanically stirring at 300rpm for 20 min;
(5) adding the ball-milled zinc phosphate and talcum powder into the aqueous dispersion, mechanically stirring at 300rpm for 20min, and ultrasonically dispersing at 200W for 30 min;
(6) and then adding the ball-milled triethylene tetramine and zinc powder into the aqueous dispersion, and mechanically stirring at 300rpm for 20 min.
The particle diameters of the epoxy resin particles, the mica iron oxide and the ferrophosphorus powder, the zinc phosphate and the talcum powder, the triethylene tetramine and the zinc powder after ball milling are all below 150nm, the proportion of the particle diameters of 30-50nm is about 40%, and the proportion of the particle diameters below 10nm is lower than 10%. The particle size was slightly larger than in examples 1-3.
Example 5
Water-based nano epoxy zinc-rich coating and preparation method thereof
The water-based nano epoxy zinc-rich paint comprises 2:1 parts by weight of a component A and a component B.
Component A formula (by weight)
25 parts of water, 30 parts of epoxy resin, 8 parts of mica iron oxide, 2 parts of ferrophosphorus powder, 325 parts of zinc phosphate and 2 parts of talcum powder.
B component formula (by weight)
30 parts of triethylene tetramine and 30 parts of zinc powder.
The preparation method comprises the following steps:
(1) mixing epoxy resin, mica iron oxide and ferrophosphorus powder, adding liquid nitrogen, and ball-milling in a ball mill at a ball-milling speed of 50rpm for 5h, wherein the weight ratio of the grinding balls to the materials is 15: 1;
(2) mixing zinc phosphate and talcum powder, adding liquid nitrogen, and placing into a ball mill for ball milling, wherein the weight ratio of grinding balls to materials is 15:1, the rotating speed of the ball mill is 50rpm, and the ball milling is carried out for 3 hours for later use;
(3) mixing triethylene tetramine and zinc powder, adding liquid nitrogen, and placing the mixture into a ball mill for ball milling, wherein the weight ratio of milling balls to materials is 15:1, the rotating speed of the ball mill is 50rpm, and the ball milling is carried out for 2 hours for later use;
(4) adding the ball-milled epoxy resin, mica iron oxide and ferrophosphorus powder into water, and mechanically stirring at 300rpm for 20 min;
(5) adding the ball-milled zinc phosphate and talcum powder into the aqueous dispersion, mechanically stirring at 300rpm for 20min, and ultrasonically dispersing at 200W for 30 min;
(6) and then adding the ball-milled triethylene tetramine and zinc powder into the aqueous dispersion, and mechanically stirring at 300rpm for 20 min.
The particle size of the epoxy resin particles, mica iron oxide and ferrophosphorus powder, zinc phosphate and talcum powder, triethylene tetramine and zinc powder after ball milling is below 100nm, and the ratio of the particle size of 30-50nm is about 50%. About 20% of the total amount of the particles having a particle size of 10nm or less. The particle size was slightly smaller than in examples 1-3.
Example 6
Water-based nano epoxy zinc-rich coating and preparation method thereof
The water-based nano epoxy zinc-rich paint comprises 2:1 parts by weight of a component A and a component B.
Component A formula (by weight)
25 parts of water, 30 parts of epoxy resin, 8 parts of mica iron oxide, 2 parts of ferrophosphorus powder, 325 parts of zinc phosphate and 2 parts of talcum powder.
B component formula (by weight)
30 parts of triethylene tetramine and 30 parts of zinc powder.
The preparation method comprises the following steps:
(1) adding liquid nitrogen into the epoxy resin, and placing the epoxy resin into a ball mill for ball milling, wherein the weight ratio of grinding balls to materials is 15:1, the rotating speed of the ball mill is 50rpm, and the ball milling is carried out for 3 hours for later use;
(2) mixing mica iron oxide, ferrophosphorus powder, zinc phosphate and talcum powder, adding liquid nitrogen, and putting into a ball mill for ball milling, wherein the weight ratio of grinding balls to materials is 15:1, the rotating speed of the ball mill is 50rpm, and the ball milling is carried out for 1h for later use;
(3) mixing triethylene tetramine and zinc powder, adding liquid nitrogen, and placing the mixture into a ball mill for ball milling, wherein the weight ratio of grinding balls to materials is 15:1, the rotating speed of the ball mill is 50rpm, and the ball milling is carried out for 0.5h for later use;
(4) adding the ball-milled epoxy resin into water, and mechanically stirring at 300rpm for 20 min;
(5) adding the ball-milled mica iron oxide, the ferrophosphorus zinc phosphate and the talcum powder into the aqueous dispersion, mechanically stirring at 300rpm for 20min, and ultrasonically dispersing at 200W for 30 min;
(6) and then adding the ball-milled triethylene tetramine and zinc powder into the aqueous dispersion, and mechanically stirring at 300rpm for 20 min.
The ball-milled epoxy resin particles were equivalent to example 4 and slightly larger than example 1. The remaining particles were similar to example 1. The effect of ball milling is promoted after mica iron oxide and ferrophosphorus powder are added into the epoxy resin.
Example 7
A method for preparing a waterborne nano epoxy zinc-rich paint, which is different from the preparation method of the paint in example 1, wherein in S05, the ultrasonic dispersion time is determined by the following formula:
wherein T1 is the time of mechanical stirring, and the value is 10-30 min; r1 is the rotation speed of mechanical stirring, the value is 200-400rpm, RS is the standard value of the rotation speed of mechanical stirring, and the value is 250-300 rpm; w is ultrasonic power, the value is 150-.
In the present embodiment, the time for determining the ultrasonic dispersion is set such that the dispersion effect is significantly better than the time outside the range. Not only ensures the sufficient dispersion of the system, but also avoids the excessive time waste.
Example 8
A method for preparing a waterborne nano epoxy zinc-rich paint, which is different from the preparation method of the paint in example 1, wherein in S04 and S06, the speed control of mechanical stirring controls the voltage through the following PID algorithm:
wherein, Δ u (c) corresponds to the variation of the voltage within the time interval of two test voltages; kc is a constant, 11-15; f (C) is the deviation at the time of sampling C, f (C-1) is the deviation at the time of sampling C-1, and f (C-2) is the deviation at the time of sampling C-2; TS is sampling period, 2.0-2.5 s; TD is differential time, 1.0-1.5 min; TI is integration time, 1.5-2.5 min.
The speed control method for mechanical stirring can quickly and stably reach the designated speed, reduces the system error caused by instability, and provides a good research platform.
Comparative example 1
Water-based nano epoxy zinc-rich coating and preparation method thereof
The water-based nano epoxy zinc-rich paint comprises 2:1 parts by weight of a component A and a component B.
Component A formula (by weight)
25 parts of water, 30 parts of epoxy resin, 8 parts of mica iron oxide, 2 parts of ferrophosphorus powder, 325 parts of zinc phosphate and 2 parts of talcum powder.
B component formula (by weight)
30 parts of triethylene tetramine and 30 parts of zinc powder.
The preparation method comprises the following steps:
(1) epoxy resin, mica iron oxide, ferrophosphorus powder, zinc phosphate, talcum powder, triethylene tetramine and zinc powder, and sieving with a 200-mesh sieve;
(2) adding the sieved epoxy resin, mica iron oxide, ferrophosphorus powder, zinc phosphate and talcum powder into water, and mechanically stirring at 300rpm for 20min to obtain a dispersion liquid;
(3) mixing the sieved triethylene tetramine and zinc powder, mechanically stirring at 300rpm for 20min, and ultrasonically dispersing at 200W for 30 min;
(4) and adding the mixed triethylene tetramine and zinc powder into the dispersion liquid, and mechanically stirring at 300rpm for 20 min.
Epoxy resin, mica iron oxide, ferrophosphorus powder, zinc phosphate, talcum powder, triethylene tetramine and zinc powder, and the epoxy resin, the mica iron oxide, the ferrophosphorus powder, the zinc phosphate, the talcum powder, the triethylene tetramine and the zinc powder are sieved by a 200-mesh sieve, wherein the particle sizes are all smaller than 75um, and the proportion of the particle sizes smaller than 100nm is less than 5%.
Examples of the experiments
The coatings obtained in examples and comparative examples were measured for adhesion, impact resistance and salt spray resistance (5% NaCl) according to "HG/T3668-2009 Zinc-rich primer" type II 2. And carrying out sand blasting or shot blasting treatment on the substrate to remove rust on the substrate to Sa2.5 grade, wherein the roughness is 40-70 um. The results are shown in Table 1.
TABLE 1
| adhesion/MPa | Impact resistance/px | Salt spray resistance per hour | |
| Example 1 | ≥11d | 1350d | 480c |
| Example 2 | ≥11d | 1621e | 470c |
| Example 3 | ≥14e | 1372d | 480c |
| Example 4 | ≥10c | 1308c | 450b |
| Example 5 | ≥10c | 1293c | 460b |
| Example 6 | ≥8b | 1285b | 450b |
| Comparative example 1 | ≥7a | 1265a | 400a |
The results show that the adhesion and impact resistance of examples 1-6 after ball milling particle size reduction are significantly better than those of micron-sized comparative example 1 without ball milling treatment. In examples 1 to 6, examples 1 to 3 were significantly superior to examples 4 and 5 in both adhesion and impact resistance. Adhesion, example 3, far surpassed example 1/2 with the unexpected technical effect. The impact resistance of example 2 is far superior to that of examples 1 and 3, and an unexpected technical effect is obtained. The results for salt spray resistance were similar to adhesion and impact resistance except that there were no significant differences between examples 1-3, and examples 4-6.
While the preferred embodiments and examples of the present invention have been described in detail, the present invention is not limited to the embodiments and examples, and various changes can be made without departing from the spirit of the present invention within the knowledge of those skilled in the art.
Claims (10)
1. A preparation method of a water-based nano epoxy zinc-rich coating comprises the following steps:
s01, mixing the epoxy resin, the mica iron oxide and the ferrophosphorus powder, and performing ball milling;
s02, mixing zinc phosphate and talcum powder, and ball milling;
s03, mixing triethylene tetramine and zinc powder, and ball-milling;
s04, adding the ball-milled epoxy resin, mica iron oxide and ferrophosphorus powder into water, and mixing to obtain a dispersion liquid A;
s05, adding ball-milled zinc phosphate and talcum powder into the dispersion liquid A, and mixing to obtain a dispersion liquid B;
and S06, adding ball-milled triethylene tetramine and zinc powder into the dispersion liquid B, and mixing to obtain the water-based nano epoxy zinc-rich coating.
2. The preparation method according to claim 1, wherein in S01, the weight ratio of grinding balls to materials is (10-20):1, the rotation speed of the ball mill is 30-60rpm, and the ball milling is carried out for 1-5h, preferably for 2-4 h.
3. The preparation method according to claim 1 or 2, wherein in S02, the weight ratio of grinding balls to materials is (10-20):1, the rotation speed of the ball mill is 30-60rpm, and the ball milling is carried out for 0.5-1.5h, preferably the weight ratio of the grinding balls to the materials is (10-15):1, the rotation speed of the ball mill is 50-60rpm, and the ball milling is carried out for 1-1.5 h.
4. The preparation method according to any one of claims 1 to 3, wherein in S03, the weight ratio of grinding balls to materials is (10-20):1, the rotation speed of the ball mill is 30-60rpm, and the ball milling is carried out for 0.1-2h, preferably for 0.4-1 h.
5. The method according to any one of claims 1 to 4, wherein the mixing in S04 and S06 is mechanical stirring at 200-400rpm for 10-30min, preferably at 300rpm for 20 min.
6. The method according to any one of claims 1 to 5, wherein the mixing in S05 comprises mechanical stirring and ultrasonic dispersion, preferably mechanical stirring at 300rpm for 20min and ultrasonic dispersion at 200W for 30 min.
7. The method according to any one of claims 1 to 6, wherein the particle size of the ball-milled epoxy resin particles, mica iron oxide and ferrophosphorus powder, zinc phosphate and talc, triethylene tetramine and zinc powder is less than 150nm, the ratio of the particle size of 30 to 50nm is not less than 50%, and the ratio of the particle size of 10nm is less than 10%.
8. The production method according to any one of claims 1 to 7, wherein in S05, the time for ultrasonic dispersion is determined by the following formula:
wherein T1 is the time of mechanical stirring, and the value is 10-30 min; r1 is the rotation speed of mechanical stirring, the value is 200-400rpm, RS is the standard value of the rotation speed of mechanical stirring, and the value is 250-300 rpm; w is ultrasonic power, the value is 150-.
9. The method of any one of claims 1 to 8, wherein the speed control of the mechanical agitation in S04 and S06 controls the voltage by the following PID algorithm:
wherein, Δ u (c) corresponds to the variation of the voltage within the time interval of two test voltages; kc is a constant, 11-15; f (C) is the deviation at the time of sampling C, f (C-1) is the deviation at the time of sampling C-1, and f (C-2) is the deviation at the time of sampling C-2; TS is sampling period, 2.0-2.5 s; TD is differential time, 1.0-1.5 min; TI is integration time, 1.5-2.5 min.
10. The water-based nano epoxy zinc-rich paint obtained by the preparation method according to any one of claims 1 to 9.
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| Publication number | Priority date | Publication date | Assignee | Title |
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102031054A (en) * | 2010-12-30 | 2011-04-27 | 东莞市高能磁电技术有限公司 | Preparation method and product of high-frequency high-efficiency electromagnetic interference (EMI) composite protective coating |
| CN106566377A (en) * | 2016-10-19 | 2017-04-19 | 安徽菱湖漆股份有限公司 | High-performance waterborne epoxy zinc-rich paint and preparation method thereof |
-
2021
- 2021-06-07 CN CN202110632318.1A patent/CN113337179B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102031054A (en) * | 2010-12-30 | 2011-04-27 | 东莞市高能磁电技术有限公司 | Preparation method and product of high-frequency high-efficiency electromagnetic interference (EMI) composite protective coating |
| CN106566377A (en) * | 2016-10-19 | 2017-04-19 | 安徽菱湖漆股份有限公司 | High-performance waterborne epoxy zinc-rich paint and preparation method thereof |
Non-Patent Citations (3)
| Title |
|---|
| 张国忠等: "《现代混凝土搅拌输送车及应用》", 30 June 2006, 中国建材工业出版社 * |
| 杜卫民: "《纳米材料化学的理论与工程应用研究》", 31 May 2018, 电子科技大学出版社 * |
| 薛茹君等: "《无机纳米材料的表面修饰改性与物性研究》", 31 October 2009, 合肥工业大学出版社 * |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115058134A (en) * | 2022-08-17 | 2022-09-16 | 潍坊学院 | Water-based inorganic zinc-rich primer and preparation method thereof |
| CN115058134B (en) * | 2022-08-17 | 2022-10-28 | 潍坊学院 | Water-based inorganic zinc-rich primer and preparation method thereof |
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