CN109988440B - High-temperature-resistant, anti-corrosion and wear-resistant coating and preparation method thereof - Google Patents
High-temperature-resistant, anti-corrosion and wear-resistant coating and preparation method thereof Download PDFInfo
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Abstract
The invention relates to a high-temperature-resistant anticorrosive wear-resistant coating and a preparation method thereof. The coating consists of a bottom coating and a surface coating, wherein the bottom coating slurry consists of potassium silicate, potassium titanate fiber, kaolin, alumina, mica powder, silicon dioxide, yttrium oxide, a dispersing agent, a defoaming agent and a thickening agent; the top coating slurry consists of zirconium sol, aluminum borate whisker, barium sulfate, aluminum oxide, silicon carbide, silicon nitride, cerium oxide, a dispersing agent, a defoaming agent and a thickening agent, wherein the bottom coating is coated on the metal and has the thickness of 100-300 mu m, and the top coating is coated on the bottom coating and has the thickness of 100-200 mu m.
Description
Technical Field
The invention relates to the field of materials, in particular to a high-temperature-resistant, anti-corrosion and wear-resistant coating and a preparation method thereof.
Background
With the development of industrial technology, the corrosion of metal substrate engineering equipment and components is increasingly prominent, especially the high-temperature corrosion with powder scouring. In order to protect metal substrates from corrosion wear, high temperature corrosion resistant coating techniques have been rapidly developed.
The high-temperature anticorrosive paint can be divided into three categories in terms of molecular composition, namely organic high-temperature resistant anticorrosive paint, inorganic high-temperature resistant anticorrosive paint and organic-inorganic composite high-temperature resistant anticorrosive paint. The organic high-temperature resistant anticorrosive paint has various varieties, including heterocyclic polymers such as polyimides, polyamide imides, heterochain polymers such as polyether sulfones, polyphenylene sulfides and the like, and elemental organic polymers such as organic silicon, organic fluorine, organic titanium and the like. The inorganic high-temperature resistant anticorrosive paint comprises water glass-based inorganic paint and silica sol paint, wherein the former is alkali metal silicate, and the latter is water dispersion of silica colloid as film forming matter.
At present, metal anticorrosive paint products with the working temperature of more than 300 ℃ are mainly inorganic anticorrosive paints, wherein silicate high-temperature-resistant anticorrosive paints are widely applied, and particularly high-temperature metal anticorrosive paints with potassium silicate as a binder.
However, in the practical application process, potassium silicate is singly used as the binder of the anti-corrosion coating, and particularly, the potassium silicate has a plurality of defects in the high-temperature environment. Firstly, the corrosion resistance is poor, a network pore channel is formed after the single potassium silicate corrosion-resistant coating is cured at high temperature, and corrosive media enter the bottom of the base material along the pore channel, so that the base material is corroded. Secondly, the thermal shock resistance is poor, and the single potassium silicate anti-corrosion coating is easy to crack under the high-temperature environment. Thirdly, the wear resistance is poor, the wear resistance of the single potassium silicate anti-corrosion coating is reduced in a high-temperature environment, and the single potassium silicate anti-corrosion coating is easily worn away to lose the anti-corrosion effect in a corrosive environment with powder abrasion. Meanwhile, the coating is easy to yellow under high temperature, and the elasticity of the coating is easy to age.
Aiming at the problems, resin is usually added to solve the problems, but the high-temperature resistance of the potassium silicate anticorrosive coating after the resin is added is poor (the resin has low temperature resistance), and the potassium silicate anticorrosive coating is difficult to continuously use in a high-temperature environment, researchers give related formulas such as 201310585452.6 with the publication number of CN 103602107A, and the formulas specifically comprise 56-65 parts of potassium silicate, 9-16 parts of silica sol, 9-13 parts of water, 2-3 parts of lithium silicate, 2-3 parts of coupling agent, 8-13 parts of emulsion, 0.03-0.04 part of auxiliary agent and 0.5-0.8 part of stabilizing agent. The finally obtained coating has excellent corrosion resistance, flexibility, high hardness and wear resistance. However, the coating layer has difficulty in realizing the anticorrosion function in the high-temperature field due to the poor temperature resistance of the resin.
Based on the problems, the invention provides a novel high-temperature-resistant anti-corrosion wear-resistant coating.
Disclosure of Invention
According to the invention, the high-temperature-resistant, anti-corrosion and wear-resistant coating is prepared on the surface of the metal substrate, so that on one hand, the substrate can be protected from being corroded by oxygen, chlorine, hydrogen chloride, hydrogen sulfide and alkali metal salt in a high-temperature environment; on the other hand, the high-temperature-resistant, corrosion-resistant and wear-resistant coating formed on the surface of the metal base material can greatly improve the wear-resistant capability of the metal base material and prolong the service life of the base material.
The first invention of the invention is to provide a high-temperature resistant, anti-corrosive and wear-resistant coating, which consists of a primary coating slurry and a top coating slurry, wherein the primary coating slurry consists of potassium silicate, potassium titanate fiber, kaolin, alumina, mica powder, silicon dioxide, yttrium oxide, a dispersing agent, a defoaming agent and a thickening agent; the top coating slurry consists of zirconium sol, aluminum borate whisker, barium sulfate, aluminum oxide, silicon carbide, silicon nitride, cerium oxide, a dispersing agent, a defoaming agent and a thickening agent, wherein the thickness of the bottom coating coated on the metal is 100-300 mu m, and the thickness of the top coating coated on the bottom coating is 100-200 mu m.
The priming paint comprises the following components in parts by weight: 50-70 parts of potassium silicate, 5-10 parts of potassium titanate fiber, 3-10 parts of kaolin, 3-12 parts of alumina, 5-10 parts of mica powder, 5-10 parts of silicon dioxide, 0.5-1 part of yttrium oxide, 0.05-0.1 part of dispersing agent, 0.05-0.1 part of defoaming agent and 0.1-0.3 part of thickening agent.
The top coating slurry comprises the following components in parts by weight: 50-60 parts of zirconium sol, 5-10 parts of aluminum borate whisker, 3-10 parts of barium sulfate, 3-12 parts of aluminum oxide, 5-10 parts of silicon carbide, 5-10 parts of silicon nitride, 0.5-1 part of cerium oxide, 0.05-0.1 part of dispersing agent, 0.05-0.1 part of defoaming agent and 0.1-0.3 part of thickening agent.
Preferably, the primer coating slurry comprises the following components in parts by weight: 55-70 parts of potassium silicate, 5-10 parts of potassium titanate fiber, 3-10 parts of kaolin, 3-12 parts of alumina, 5-10 parts of mica powder, 5-8.5 parts of silicon dioxide, 0.5-1 part of yttrium oxide, 0.05-0.08 part of dispersing agent, 0.05-0.08 part of defoaming agent and 0.15-0.3 part of thickening agent.
More preferably, the primer slurry comprises the following components in parts by weight: 60-65 parts of potassium silicate, 6-10 parts of potassium titanate fiber, 8-10 parts of kaolin, 6-10 parts of alumina, 5-7 parts of mica powder, 5-8 parts of silicon dioxide, 1 part of yttrium oxide, 0.06-0.08 part of dispersant, 0.07-0.08 part of defoaming agent and 0.15-0.2 part of thickener.
Preferably, the top coating slurry comprises the following components in parts by weight: 57-60 parts of zirconium sol, 8-10 parts of aluminum borate whisker, 3-9 parts of barium sulfate, 3-11 parts of aluminum oxide, 5-9 parts of silicon carbide, 5-10 parts of silicon nitride, 0.5-1 part of cerium oxide, 0.05-0.08 part of dispersing agent, 0.05-0.09 part of defoaming agent and 0.15-0.3 part of thickening agent.
More preferably, the top-coating slurry comprises the following components in parts by weight: 57-58 parts of zirconium sol, 8-10 parts of aluminum borate whisker, 7-9 parts of barium sulfate, 10-11 parts of aluminum oxide, 5-9 parts of silicon carbide, 5-9 parts of silicon nitride, 1 part of cerium oxide, 0.06-0.08 part of dispersing agent, 0.07-0.09 part of defoaming agent and 0.15-0.2 part of thickening agent.
In the above coating slurry:
the modulus of the potassium silicate is 3.1-4.8 (SiO)216-23% of content and 20-35% of solid content);
the length-diameter ratio of the potassium titanate fibers is 100: 1-200: 1;
the concentration of the zirconium sol is 15-30%, the preferable particle size is 10nm, the concentration is 20%, and the pH is 5;
the length-diameter ratio of the aluminum borate whisker is 150: 1-200: 1;
the particle size of the rest fillers is 0.2-5 mu m;
the dispersing agent is sodium polycarboxylate, potassium polyacrylate or sodium polyacrylate;
the defoaming agent is emulsified silicone oil, paraffin hydrocarbon oil or metal stearate;
the thickening agent is fumed silica, hydroxyethyl cellulose or carboxymethyl cellulose.
The invention also provides a preparation method of the priming paint, which comprises the following steps:
(1) firstly, adding a dispersing agent into a potassium silicate binder, and stirring and mixing at a stirring speed of 100-200 r/min for 5-30 min;
(2) adding kaolin, alumina, mica powder, silicon dioxide, yttrium oxide powder and potassium titanate crystal whiskers into the mixture obtained in the step (1), and stirring and dispersing for 30-60 min at a stirring and dispersing speed of 600-1200 r/min;
(3) and finally, adding a defoaming agent and a thickening agent, and stirring to obtain the base coating slurry, wherein the stirring speed is 60-100 r/min, and the stirring time is 5-30 min.
The invention also provides a preparation method of the topcoat slurry, which comprises the following steps:
(1) firstly, adding a dispersing agent into a zirconium sol binder, and stirring and mixing at a stirring speed of 100-200 r/min for 5-30 min;
(2) then adding barium sulfate, aluminum oxide, silicon carbide, silicon nitride, cerium oxide powder and aluminum borate crystal whiskers into the step (1), and stirring and dispersing at a stirring and dispersing speed of 800-1200 r/min for 30-60 min;
(3) and finally, adding a defoaming agent and a thickening agent, and stirring to obtain the base coating slurry, wherein the stirring speed is 80-120 r/min, and the stirring time is 5-30 min.
The invention also provides application of the coating on a metal surface.
The metal substrate may be cast iron, stainless steel, aluminum alloy, or the like.
When in coating, the primary coating slurry and the surface coating slurry can be coated by a spraying or brushing method;
specifically, the coating method provided by the invention comprises the following steps:
(1) cleaning greasy dirt on the surface of a metal substrate, and performing sand blasting treatment to Sa2.5 or Sa3 grade;
(2) preparing a base coating slurry, coating the base coating slurry on the surface of a metal base material, wherein the thickness of the base coating slurry is 100-300 mu m, and naturally drying or drying and curing to obtain a base coating;
(3) preparing a top coating slurry, coating the top coating slurry on the surface of the primary coating with the thickness of 100-200 mu m, and drying and curing to obtain the high-temperature-resistant, corrosion-resistant and wear-resistant coating with a double-layer structure.
The method comprises the following steps:
in the step 2): the natural drying time is 24-48 h, the drying and curing temperature is 80-150 ℃, and the drying and curing time is 2-6 h.
In the step 3): the drying and curing temperature of the top coating is 600-800 ℃, and the drying and curing time is 6-12 h.
The invention has the following innovative effects:
1. the formula of the invention comprises:
1) the single potassium silicate coating has the defects of poor corrosion resistance and thermal shock resistance in a high-temperature environment, and the abrasion resistance of the coating is reduced along with the increase of the working temperature. Therefore, the potassium silicate binder coating is required to be modified and improved in corrosion resistance, thermal shock resistance and wear resistance as a high-temperature corrosion-resistant wear-resistant coating. Relevant researches show that the zirconium sol binder coating has excellent characteristics of high temperature resistance, corrosion resistance, wear resistance, oxidation resistance and the like, but the problem of poor thermal shock resistance exists when a single zirconium sol coating is directly coated on a metal matrix. Researchers have attempted to mix potassium silicate binders with zirconium sol binders for performance enhancement. However, in practice, it has been found that the physical and chemical properties such as surface potential of colloidal particles in the potassium silicate binder and the zirconium sol binder (potassium silicate and zirconium sol are binders themselves) and pH of the binder are very different, and that if the two are simply mixed, gelation occurs and the binder fails.
The mixing of the potassium silicate and zirconium sol directly leads to gel failure, and the direct mixing is not feasible in principle, no matter what other components are added.
The invention adopts the steps of firstly preparing a potassium silicate anti-corrosion coating on a metal substrate, and then coating a zirconium sol anti-corrosion coating on the potassium silicate anti-corrosion coating. The advantages of this are: on one hand, the zirconium sol can be effectively filled into network pore channels of the solidified potassium silicate coating, so that the compactness is improved, and the corrosion prevention effect is improved. On the other hand, the zirconium sol coating on the surface has excellent wear resistance after being cured, and the overall wear resistance effect of the coating can be improved. Finally, the zirconium sol coating/potassium silicate coating which is a special double-layer structure coating combined with each other (the zirconium sol partially permeates into network pore channels of the solidified potassium silicate coating) has the controllability of the thermal expansion coefficient and the thermal expansion matching performance which is similar to that of the metal base material at high temperature, thereby obviously improving the overall thermal shock resistance of the coating. On one hand, the controllability of thermal expansion controls the zirconium sol to permeate into network pore channels of the solidified potassium silicate coating so as to effectively combine the two coatings; on the other hand, the method is realized by adding powder and whiskers into the potassium silicate base coating slurry and the zirconium sol surface coating slurry. Specifically, kaolin, alumina, mica powder, silicon dioxide, yttrium oxide powder and potassium titanate whiskers in a certain proportion are added into the potassium silicate primary coating slurry, and barium sulfate, alumina, silicon carbide, silicon nitride, cerium oxide and aluminum borate whiskers in a certain proportion are added into the zirconium sol surface coating slurry. Wherein, the added potassium titanate whisker and aluminum borate whisker can also play a role in toughening and improving the thermal shock resistance. Finally, the metal substrate, the potassium silicate coating and the zirconium sol coating synchronously expand in the temperature changing process without peeling or cracking.
2) Selecting the filler:
the thermal expansion matching between the coating and the metal substrate is better after the coating is solidified by adding the kaolin, the alumina, the mica powder, the silicon dioxide, the yttrium oxide powder and the potassium titanate crystal whisker into the potassium silicate binder.
The coating prepared by adding the barium sulfate, the alumina, the silicon carbide, the silicon nitride, the cerium oxide powder and the aluminum borate whisker into the zirconium sol binder after curing can be firmly combined with the base coating on one hand, and can further adjust the thermal expansion matching property of the base coating and the metal matrix on the other hand (part of the surface coating slurry permeates into network pore channels of the base coating), so that the overall thermal shock resistance of the coating is obviously improved.
2. Partial slurry components of the top coating slurry can permeate into a network structure formed by curing the bottom coating before curing, and fine pore channels in the bottom coating are filled to form a more compact anticorrosion transition layer, so that the anticorrosion capability of the whole coating is greatly improved.
3. The coating material is different from the common protective coating in functional singleness, the base coating layer of the coating material with the double-layer structure formed by different components provides high-temperature adhesive force and corrosion resistance, the top coating layer provides high-temperature wear resistance, and the whole coating has excellent comprehensive performance of high temperature resistance, corrosion resistance and wear resistance.
4. The reticular structure formed after the bottom coating is solidified can be firmly combined with the metal base material, the toughness of the coating can be adjusted by adding the potassium titanate fiber into the coating, and the adding amount of the potassium titanate fiber can be adjusted and controlled according to the material quality of the metal base material.
5. The top coating slurry contains a large amount of silicon carbide and silicon nitride wear-resistant base materials, and the cured coating has excellent wear resistance. In addition, the aluminum borate whisker added into the top coating slurry can enhance the matching property of the thermal expansion coefficients of the top coating and the bottom coating, thereby improving the thermal shock resistance of the whole coating, and the whole coating does not crack or fall off on different metal substrates.
Detailed Description
The following examples are intended to illustrate the invention but are not intended to limit the scope of the invention.
Examples 1 to 5: first coat
1. Consists of the following components: see Table 1
Table 1: each component (unit: kg) in examples 1 to 5
2. The preparation method comprises the following steps:
(1) firstly, adding a dispersing agent into a potassium silicate binder, and stirring and mixing at a stirring speed of 100r/min for 30 min;
(2) adding kaolin, alumina, mica powder, silicon dioxide, yttrium oxide powder and potassium titanate crystal whiskers into the mixture obtained in the step (1), and stirring and dispersing the mixture at the stirring and dispersing speed of 1200r/min for 30 min;
(3) and finally, adding a defoaming agent and a thickening agent, and stirring to obtain the base coating slurry, wherein the stirring speed is 60r/min, and the stirring time is 30 min.
Examples 6 to 10: top coat
1. Consists of the following components: see Table 2
Table 2: each component (unit: kg) in examples 6 to 10
2. The preparation method comprises the following steps:
(1) firstly, adding a dispersing agent into a zirconium sol binder, and stirring and mixing at a stirring speed of 100r/min for 30 min;
(2) then adding barium sulfate, aluminum oxide, silicon carbide, silicon nitride, cerium oxide powder and aluminum borate crystal whisker into the step (1), stirring and dispersing at the stirring and dispersing speed of 1200r/min for 30 min;
(3) and finally, adding a defoaming agent and a thickening agent, and stirring to obtain the base coating slurry, wherein the stirring speed is 80r/min, and the stirring time is 30 min.
Example 11: coating method
(1) Cleaning greasy dirt on the surface of a metal substrate (the metal substrate can be cleaned by using a degreasing cleaning agent), and performing sand blasting treatment to Sa2.5 or Sa3 grade;
(2) preparing a base coat slurry (as in examples 1-5), coating the base coat slurry on the surface of a metal base material, and naturally drying or drying and curing to obtain a base coat;
(3) preparing a top coating slurry, coating the top coating slurry (as in examples 6-10) on the surface of the primary coating, and drying and curing to obtain the high-temperature-resistant, corrosion-resistant and wear-resistant coating with a double-layer structure.
Experimental example 1: performance index
1. The performance indexes of the coating are inspected, and the inspection items are as follows:
table 3: investigation item, performance index and detection method standard
1. Sample preparation:
sample 1: the primer of example 1 is matched with the top coat of example 6 and coated by the method of example 11;
sample 2: example 2 the basecoat was applied using the method of example 11 in combination with the topcoat of example 7;
sample 3: example 3 the basecoat was applied using the method of example 11 in combination with the topcoat of example 8;
sample 4: example 4 the basecoat was applied using the method of example 11 in combination with the topcoat of example 9;
sample 5: example 5 the basecoat was applied using the method of example 11 in combination with the topcoat of example 10;
control 1: reference is made to the following formulations: application No. 200510080488.4, publication No. CN1709988A, was selected for example 2, which is resistant to high temperatures of 600 ℃.
Control 2: reference is made to the following formulations: application No. 201010580684.9, publication No. CN102558924B, see example 5 for formulation.
Control 3: in the invention, no potassium titanate whisker is added into the bottom coating slurry or no aluminum borate whisker is added into the top coating slurry.
Control 4: the painting sequence of the invention is changed, namely, zirconium sol binder slurry is adopted as a base coat, and potassium silicate binder slurry is adopted as a top coat.
3. The experimental results are as follows:
control 1: the coating has excellent acid resistance, alkali resistance, salt spray resistance, oil resistance, weather resistance and strong adhesive force. However, the temperature resistance limit of the anticorrosive coating is 600 ℃, which is lower than the temperature resistance performance (more than 1000 ℃) of the anticorrosive coating prepared by the formula.
Control 2: the coating has the advantages of high temperature resistance, corrosion resistance, water resistance and good thermal shock resistance. However, compared with the high-temperature corrosion-resistant wear-resistant coating, the coating has poor wear resistance in a high-temperature environment and is difficult to be applied in a corrosion environment with powder erosion for a long time.
Control 3: the finally obtained coating has poor thermal shock resistance, and the coating is easy to crack and lose efficacy.
Control 4: the prepared coating has poor bonding force with a metal matrix, and the high-temperature wear resistance is obviously reduced.
The performance results for the other samples are shown in Table 4
Table 4: results of the experiment
Table 4 the results show that: the coating provided by the invention has excellent high temperature resistance, corrosion resistance and wear resistance, can protect metal matrix equipment in a high-temperature, powder scouring and corrosive working environment for a long time, and greatly prolongs the service life of the metal equipment.
Although the invention has been described in detail hereinabove by way of general description, specific embodiments and experiments, it will be apparent to those skilled in the art that many modifications and improvements can be made thereto based on the invention. Accordingly, such modifications and improvements are intended to be within the scope of the invention as claimed.
Claims (4)
1. The high-temperature-resistant, anti-corrosion and wear-resistant coating for the surface of the metal substrate consists of a base coating and a surface coating, wherein the base coating slurry consists of the following components in parts by weight: 60-65 parts of potassium silicate, 6-10 parts of potassium titanate fiber, 8-10 parts of kaolin, 6-10 parts of alumina, 5-7 parts of mica powder, 5-8 parts of silicon dioxide, 1 part of yttrium oxide, 0.06-0.08 part of dispersant, 0.07-0.08 part of defoaming agent and 0.15-0.2 part of thickener; the top coating slurry comprises the following components in parts by weight: 50-60 parts of zirconium sol, 5-10 parts of aluminum borate whisker, 3-10 parts of barium sulfate, 3-12 parts of aluminum oxide, 5-10 parts of silicon carbide, 5-10 parts of silicon nitride, 0.5-1 part of cerium oxide, 0.05-0.1 part of dispersing agent, 0.05-0.1 part of defoaming agent and 0.1-0.3 part of thickening agent, wherein the bottom coat is coated on the metal and has the thickness of 100-300 mu m, and the top coat is coated on the bottom coat and has the thickness of 100-200 mu m; in the primer coating slurry, the modulus of the potassium silicate is 3.1-4.8, and SiO is2The content is 16-23%, and the solid content is 20-35%; the length-diameter ratio of the potassium titanate fibers is 100: 1-200: 1; in the topcoat slurry, the concentration of the zirconium sol is 15-30%, the particle size is 10nm, and the pH value is 5; the length-diameter ratio of the aluminum borate whisker is 150: 1-200: 1; the particle size of the rest fillers is 0.2-5 mu m.
2. The coating according to claim 1, wherein the top-coating slurry comprises the following components in parts by weight: 57-60 parts of zirconium sol, 8-10 parts of aluminum borate whisker, 3-9 parts of barium sulfate, 3-11 parts of aluminum oxide, 5-9 parts of silicon carbide, 5-10 parts of silicon nitride, 0.5-1 part of cerium oxide, 0.05-0.08 part of dispersing agent, 0.05-0.09 part of defoaming agent and 0.15-0.3 part of thickening agent.
3. The coating according to claim 2, wherein the top-coating slurry comprises the following components in parts by weight: 57-58 parts of zirconium sol, 8-10 parts of aluminum borate whisker, 7-9 parts of barium sulfate, 10-11 parts of aluminum oxide, 5-9 parts of silicon carbide, 5-9 parts of silicon nitride, 1 part of cerium oxide, 0.06-0.08 part of dispersing agent, 0.07-0.09 part of defoaming agent and 0.15-0.2 part of thickening agent.
4. Use of a coating as claimed in any one of claims 1 to 3 for coating a metal surface.
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| CN112209727A (en) * | 2020-09-02 | 2021-01-12 | 珠海弘德表面技术有限公司 | Ceramic coating for heating surface of power plant boiler and preparation method thereof |
| CN112331391B (en) * | 2020-10-28 | 2022-04-22 | 江苏亿致通信科技有限公司 | High-compression-resistance, noise-resistant, flame-retardant and high-temperature-resistant cable |
| CN114958100A (en) * | 2022-06-08 | 2022-08-30 | 安徽佐藤精密机械有限公司 | Corrosion-resistant and wear-resistant automobile piston ring and machining method thereof |
| CN115160896B (en) * | 2022-08-11 | 2023-09-08 | 浙江万丰摩轮有限公司 | Preparation method of motorcycle hub with three-dimensional phantom coating |
| CN115895311B (en) * | 2022-12-02 | 2023-08-04 | 中国科学院兰州化学物理研究所 | Protective coating suitable for blending high-sulfur high-alkali coal and preparation method of coating |
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