CN115505919A - Wear-resistant mildew-proof antibacterial cold-spraying additive coating and preparation method thereof - Google Patents
Wear-resistant mildew-proof antibacterial cold-spraying additive coating and preparation method thereof Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
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- C23C24/00—Coating starting from inorganic powder
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- C23C24/04—Impact or kinetic deposition of particles
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- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
- B22F1/12—Metallic powder containing non-metallic particles
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Abstract
The invention discloses a wear-resistant mildew-proof antibacterial cold-sprayed additive coating and a preparation method thereof, wherein the preparation method comprises the following steps: uniformly mixing main raw material powder, wear-resistant component powder and load-type antibacterial and mildew-proof component powder according to a weight ratio; spraying the mixed powder according to the following cold spraying parameters: inert atmosphere, working temperature is 350-800 ℃, gas pressure is 1.5-3.5MPa, powder feeding amount is 20-100g/min, and spraying distance is 10-50mm; and grinding and polishing the surface of the coating to obtain a finished product. The cold spraying wear-resistant coating has the advantages of thick thickness and good wear resistance, and the antibacterial rate can be returned to the original level by wiping and polishing the surface with dirt.
Description
Technical Field
The invention belongs to the technical field of coatings, and particularly relates to a wear-resistant, mildew-proof and antibacterial cold spraying additive coating and a preparation method thereof.
Background
People pay more and more attention to public environmental sanitation and family environmental sanitation. Therefore, products with antibacterial functional surfaces are greatly sought after in the market. The cold spraying additive technology has the advantages of wide process application range, thick thickness of the prepared coating, high binding force and strong durability, and becomes one of hot spots in the field of surface treatment.
In the prior patent CN201911101507.5, a container containing a composite coating is prepared by spraying a mixed powder composed of at least one of silver and copper micro powder and ceramic micro powder on the surface of a substrate by a cold spraying process, wherein the composite coating is composed of ceramic and at least one of copper micro powder and silver micro powder. The composite coating of the invention integrates the comprehensive properties of copper, silver and ceramic, and provides the container with the characteristics of wear resistance, antibiosis and good heat preservation. Patent CN202111446441.0 is a cold spray copper-containing stainless steel coating with antibacterial and antiviral functions, the copper stainless steel coating is prepared by mixing 304L stainless steel and pure Cu powder, and the cold spray coating with long-acting antibacterial and antiviral functions is obtained by controlling the speed and time of powder mixing, the carrier gas temperature, the spray distance, the spray pressure and the powder feeding temperature of cold spray.
According to the existing cold spraying antibacterial coating technology, metal powder such as silver powder and copper powder is mostly used as an antibacterial material in the scheme of preparing the antibacterial coating by using the cold spraying technology, and the defects of unstable actual antibacterial rate and poor mildew-proof effect exist, because the metal powder such as silver can quickly form free metal ions to perform the sterilization and disinfection effects when the metal powder reaches the nanometer size, the silver and copper metal powder in the existing raw material powder for cold spraying is in the micron level, and the real antibacterial rate is unstable after the product is really produced; from the cold spraying process, the size of the powder must be in the micron level due to the particularity of the process in the existing cold spraying technology, and the nano powder cannot be used for cold spraying because the first reason is too small in mass and low in powdering rate, and the nano powder is easier to sinter than micron-sized particles at the same temperature as the surface area in the second spraying process, so that the nano-sized antibacterial powder is difficult to directly use as a raw material.
Disclosure of Invention
The invention aims to overcome the defects in the prior art and provides a wear-resistant mildew-proof antibacterial cold-sprayed additive coating and a preparation method thereof.
In order to achieve the above purpose, one of the technical solutions of the present invention is: a preparation method of a wear-resistant, mildew-proof and antibacterial cold-sprayed additive coating specifically comprises the following steps:
(1) Preparing mixed powder: uniformly mixing main raw material powder, wear-resistant component powder and load-type antibacterial and mildewproof component powder according to a weight ratio;
(2) Preparing a cold spraying coating: spraying the mixed powder prepared in the step (1) according to the following cold spraying parameters: inert atmosphere, working temperature is 350-800 ℃, gas pressure is 1.5-3.5MPa, powder feeding amount is 20-100g/min, and spraying distance is 10-50mm;
(3) And (3) post-treatment: and (3) grinding and polishing the surface of the coating prepared in the step (2) to obtain a finished product.
In a preferred embodiment of the invention, the weight ratio of the main raw material powder, the wear-resistant component powder and the supported antibacterial and mildewproof component powder in the step (1) is 82-98.5.
In a preferred embodiment of the present invention, in the step (1), the main material powder is one of titanium particles, stainless steel particles, aluminum particles, copper particles, and silver particles.
In a preferred embodiment of the present invention, in the step (1), the average particle size of the main raw material powder particles is 10-80 μm.
In a preferred embodiment of the present invention, the powder of the wear-resistant component in step (1) is one or more of titanium dioxide particles, aluminum oxide particles, and silicon carbide particles.
In a preferred embodiment of the present invention, the powder of the wear-resistant component in step (1) has an average particle size of 5-40 μm.
In a preferred embodiment of the present invention, the powder of the antibacterial and antifungal components supported in step (1) is one or more of silver particles supported on zirconium phosphate, silver particles supported on silicate, zinc particles supported on silicate, and silver particles supported on silicate.
The zirconium phosphate silver-carrying particle carrier is mainly sheet zirconium phosphate or cubic zirconium phosphate, the silicate silver-carrying particle, the silicate zinc-carrying particle and the silicate zinc-carrying silver particle carrier are mainly silicate, silver ions or zinc ions are embedded into the carrier by means of intercalation, ion exchange and the like, and in the using process, the silver ions or the zinc ions carried by the load-type antibacterial agent can be dissociated out to kill bacteria.
In a preferred embodiment of the present invention, the average particle size of the powder particles of the supported antibacterial and antifungal components in step (1) is 1-30 μm.
In a preferred embodiment of the present invention, the inert atmosphere in step (2) is one of nitrogen or helium.
In a preferred embodiment of the present invention, the spraying in the step (2) is performed 10-20 times.
In a preferred embodiment of the present invention, the thickness of the coating layer prepared in the step (2) is 200-500 μm.
In order to achieve the above purpose, the second technical solution of the present invention is: a coating prepared by a preparation method of a wear-resistant, mildew-proof and antibacterial cold-spraying additive coating.
Compared with the prior art, the invention has the beneficial effects that:
1. the invention adopts the load type antibacterial mildew-proof powder as the antibacterial mildew-proof material, and the commercial load type antibacterial powder has more efficient and stable antibacterial effect than micron-sized silver and zinc particles because the load type antibacterial mildew-proof powder is loaded with the nano-sized silver and zinc, and the size of the load type antibacterial mildew-proof powder is micron-sized and can be used for a cold spraying process;
2. according to the invention, the metal powder with better plasticity (stainless steel, titanium, copper, aluminum, silver, gold and other metals) and the brittle load type antibacterial powder mixed powder are used, when the cold spraying powder impacts a substrate to obtain a uniform coating, the metal powder with better plasticity is used as a buffer layer and a wrapping layer of the brittle load type antibacterial powder, so that the powder loading rate of the load type antibacterial mildew-proof powder is improved, and the brittle load type antibacterial powder is protected from being broken; like the mud mixed small stones, the mixture of mud and small stones which is pounded on the wall is directly adhered to the wall, and if the small stones are directly pounded on the wall, the mixture of mud and small stones cannot be adhered to the wall certainly;
3. in the daily wear process, the fresh surface of the prepared coating is exposed, the new load-type antibacterial component on the lower layer is also exposed, the antibacterial performance of the product returns to the initial super-high antibacterial rate state again, and the antibacterial effect is maintained at a higher level all the time in such circulation;
4. many commercially available antibacterial coatings are contact type antibacterial coatings, the antibacterial rate of the coatings is seriously reduced when the surfaces of the coatings are stained, and thinner antibacterial coatings (the thickness of the common paint type antibacterial coatings is only 10-50 mu m) are damaged and fail if the coatings are wiped or polished.
Detailed Description
A preparation method of a wear-resistant, mildew-proof and antibacterial cold-sprayed additive coating specifically comprises the following steps:
(1) Preparing mixed powder: uniformly mixing main raw material powder, wear-resistant component powder and load-type antibacterial and mildewproof component powder according to a weight ratio;
(2) Preparing a cold spraying coating: spraying the mixed powder prepared in the step (1) according to the following cold spraying parameters: inert atmosphere, working temperature is 350-800 ℃, gas pressure is 1.5-3.5MPa, powder feeding amount is 20-100g/min, and spraying distance is 10-50mm;
(3) And (3) post-treatment: and (3) grinding and polishing the surface of the coating prepared in the step (2) to obtain a finished product.
The weight ratio of the main raw material powder, the wear-resistant component powder and the load-type antibacterial and mildewproof component powder in the step (1) is 82-98.5.
In the step (1), the main raw material powder is one of titanium particles, stainless steel particles, aluminum particles, copper particles and silver particles, and the average particle size is 10-80 μm.
The powder of the wear-resistant components in the step (1) is one or more of titanium dioxide particles, aluminum oxide particles and silicon carbide particles, and the average particle size of the particles is 5-40 mu m.
The powder of the loaded antibacterial and mildewproof component in the step (1) is one or more of zirconium phosphate silver-loaded particles, silicate zinc-loaded particles and silicate zinc-loaded particles.
The average grain diameter of the powder particles of the load type antibacterial and mildewproof components in the step (1) is 1-30 mu m.
And (3) in the step (2), the inert atmosphere is one of nitrogen or helium.
And (3) spraying for 10-20 times in the step (2).
The thickness of the coating prepared in the step (2) is 200-500 mu m.
A coating prepared by a preparation method of a wear-resistant, mildew-proof and antibacterial cold-spraying additive coating.
The zinc silicate-supported particles, silver zinc silicate-supported particles, and silver zirconium phosphate-supported particles used in the following examples are all commercially available.
Example 1:
the powder raw material is prepared by mechanically and uniformly mixing titanium particles with the average particle size of 50 microns, titanium dioxide particles with the average particle size of 20 microns and silicate zinc-loaded particles with the average particle size of 10 microns according to a weight ratio of 86. According to ATSM D4541 standard, tests show that the binding force of the coating on the surface of a stainless steel molten steel tank reaches 45MPa, the antibacterial performance and the mildew-proof performance are tested according to GB/T21510-2008 and GB/T1741-2020, the antibacterial rate on Escherichia coli reaches 76%, the antibacterial rate on Staphylococcus aureus reaches 70%, the mildew-proof rating on Aspergillus niger reaches 0 level, and the mildew-proof rating on Aspergillus flavus reaches 0 level; after the sample is boiled in water at 65 ℃ for 100 hours, the antibacterial rate to escherichia coli is 76%, the antibacterial rate to staphylococcus aureus is 70%, the mould resistance level to aspergillus niger is 0 grade, and the mould resistance level to aspergillus flavus is 0 grade; after the surface is rubbed by a steel wire ball for 1 ten thousand times by loading 1kg, the antibacterial rate to escherichia coli is 76%, the antibacterial rate to staphylococcus aureus is 70%, the mould resistance level to aspergillus niger is 0 grade, and the mould resistance level to aspergillus flavus is 0 grade.
Example 2:
the powder raw material is prepared by mechanically and uniformly mixing stainless steel particles with the average particle size of 60 microns, silicon carbide particles with the average particle size of 30 microns and silicate silver-loaded particles with the average particle size of 20 microns according to a weight ratio of 92. The gloss measured using a Meinenda MG-268 gloss Meter was 750GU (60 ℃). According to ATSM D4541 standard, tests show that the binding force of the coating on the surface of the stainless steel handle reaches 48MPa, the antibacterial performance and the mildew-proof performance are tested according to GB/T21510-2008 and GB/T1741-2020, the antibacterial rate on escherichia coli is more than 99%, the antibacterial rate on staphylococcus aureus is more than 99%, the mildew-resistant grade on aspergillus niger is 2, and the mildew-resistant grade on aspergillus flavus is 2; after the sample is boiled in water at 65 ℃ for 100 hours, the antibacterial rate of the sample to escherichia coli is more than 99%, the antibacterial rate to staphylococcus aureus is more than 99%, the level of aspergillus niger resistance to mold reaches level 2, and the level of aspergillus flavus resistance to mold reaches level 2; after the surface is rubbed by a steel wire ball for 1 ten thousand times by loading 1kg, the antibacterial rate of escherichia coli is more than 99 percent, the antibacterial rate of staphylococcus aureus is more than 99 percent, the level of aspergillus niger resistance to mildew is 2, and the level of aspergillus flavus resistance to mildew is 2.
Example 3:
the powder raw material is prepared by mechanically and uniformly mixing aluminum particles with the average particle size of 40 microns, titanium dioxide particles with the average particle size of 20 microns, silicate zinc-carrying particles with the average particle size of 10 microns and zirconium phosphate silver-carrying particles with the average particle size of 10 microns according to a weight ratio of 87. The gloss measured using a Meinenda MG-268 gloss Meter was 220GU (60 ℃). According to ATSM D4541 standard, tests show that the binding force of the coating on the surface of a stainless steel bathroom door frame reaches 42MPa, the antibacterial performance and the mildew-proof performance are tested according to GB/T21510-2008 and GB/T1741-2020, the antibacterial rate on escherichia coli is more than 99%, the antibacterial rate on staphylococcus aureus is more than 99%, the mildew-resistant grade on aspergillus niger is 1, and the mildew-resistant grade on aspergillus flavus is 1; after the sample is boiled in water at 65 ℃ for 100 hours, the antibacterial rate of the sample to escherichia coli is more than 99%, the antibacterial rate to staphylococcus aureus is more than 99%, the level of aspergillus niger resistance to mold reaches 1 level, and the level of aspergillus flavus resistance to mold reaches 1 level; after 1kg of steel wire ball is used for carrying and rubbing the surface for 1 ten thousand times, the antibacterial rate of Escherichia coli is more than 99 percent, the antibacterial rate of Staphylococcus aureus is more than 99 percent, the mould resistance level of Aspergillus niger reaches 1 grade, and the mould resistance level of Aspergillus flavus reaches 1 grade.
Example 4:
the powder raw material is prepared by mechanically and uniformly mixing silver particles with the average particle size of 30 microns, alumina particles with the average particle size of 30 microns and silicate zinc-loaded silver particles with the average particle size of 20 microns according to a weight ratio of 90. The gloss measured using a Meinenda MG-268 gloss meter was 340GU (60 ℃). According to the ATSM D4541 standard, through tests, the bonding force of the coating on the surface of the stainless steel bathroom door frame reaches 40MPa, the antibacterial performance and the mildew-proof performance are tested according to GB/T21510-2008 and GB/T1741-2020, the antibacterial rate to escherichia coli is more than 99%, the antibacterial rate to staphylococcus aureus is more than 99%, the mildew-resistant grade to aspergillus niger is 1 grade, and the mildew-resistant grade to aspergillus flavus is 1 grade; after being boiled in water at 65 ℃ for 100 hours, the sample is tested to have the antibacterial ratio to escherichia coli of more than 99 percent, the antibacterial ratio to staphylococcus aureus of more than 99 percent, the mould resistance grade to aspergillus niger of 1 grade and the mould resistance grade to aspergillus flavus of 1 grade; after 1kg of steel wire ball is used for carrying and rubbing the surface for 1 ten thousand times, the antibacterial rate of Escherichia coli is more than 99 percent, the antibacterial rate of Staphylococcus aureus is more than 99 percent, the mould resistance level of Aspergillus niger reaches 1 grade, and the mould resistance level of Aspergillus flavus reaches 1 grade.
Example 5:
the powder raw material is prepared by mechanically and uniformly mixing copper particles with the average particle size of 50 microns, alumina particles with the average particle size of 30 microns and silicate zinc-loaded silver particles with the average particle size of 20 microns according to a weight ratio of 90. The gloss measured using a Meinenda MG-268 gloss Meter was 400GU (60 ℃). According to ATSM D4541 standard, through testing, the binding force of the coating on the surface of the zinc alloy handle reaches 40MPa, the antibacterial performance and the mildew-proof performance are tested according to GB/T21510-2008 and GB/T1741-2020, the antibacterial rate to escherichia coli is 94%, the antibacterial rate to staphylococcus aureus is more than 92%, the mildew-resistant grade to aspergillus niger is 0 grade, and the mildew-resistant grade to aspergillus flavus is 0 grade; after a sample is boiled in water at 65 ℃ for 100 hours, the antibacterial rate of the sample on escherichia coli is measured to be 95%, the antibacterial rate on staphylococcus aureus is measured to be 92%, the mould resistance level on aspergillus niger reaches 0 grade, and the mould resistance level on aspergillus flavus reaches 0 grade; after 1kg of steel wire balls are used for carrying on surface and rubbing for 1 ten thousand times, the antibacterial rate of Escherichia coli reaches 94%, the antibacterial rate of Staphylococcus aureus reaches 92%, the mould resistance level of Aspergillus niger reaches 0 grade, and the mould resistance level of Aspergillus flavus reaches 0 grade.
Comparative example 1:
the powder raw material is prepared by mechanically and uniformly mixing titanium particles with the average particle size of 50 microns and titanium dioxide particles with the average particle size of 20 microns according to the weight ratio of 94. The measured glossiness of the coating is 560GU (60 degrees) according to ATSM D4541 standard by using a Meinengda MG-268 glossiness instrument, through testing, the bonding force of the coating on the surface of a stainless steel bathroom door frame reaches 40MPa, the antibacterial performance and the mildew resistance are tested according to GB/T21510-2008 and GB/T1741-2020, the antibacterial rate on escherichia coli is 65%, the antibacterial rate on staphylococcus aureus is more than 53%, the mildew resistance grade on aspergillus niger is 3, and the mildew resistance grade on aspergillus flavus is 3.
Comparative example 2:
the powder raw material is prepared by mechanically and uniformly mixing stainless steel particles with the average particle size of 60 mu m and silicon carbide particles with the average particle size of 30 mu m according to the weight ratio of 97 to 3, and the process parameters are consistent with those of the example 2, so that the wear-resistant coating with the particle size of 300 mu m is obtained. Gloss was measured to be 790GU (60 ℃ C.) using a Meinenda MG-268 gloss Meter. According to ATSM D4541 standard, tests show that the binding force of the coating on the surface of the stainless steel handle reaches 48MPa, the antibacterial performance and the mildew-proof performance are tested according to GB/T21510-2008 and GB/T1741-2020, the antibacterial rate on escherichia coli is 56%, the antibacterial rate on staphylococcus aureus is 50%, the mildew-resistant level on aspergillus niger is 3, and the mildew-resistant level on aspergillus flavus is 3.
Comparative example 3:
the powder raw material is prepared by mechanically and uniformly mixing aluminum particles with the average particle size of 40 mu m and titanium dioxide particles with the average particle size of 20 mu m according to the weight ratio of 97 to 3, and the process parameters are consistent with those of example 3 to obtain the wear-resistant coating with the particle size of 250 mu m. The gloss measured using a Meinenda MG-268 gloss Meter was 250GU (60 ℃). According to ATSM D4541 standard, through testing, the binding force of the coating on the surface of the stainless steel bathroom door frame reaches 42MPa, the antibacterial performance and the mildew-proof performance are tested according to GB/T21510-2008 and GB/T1741-2020, the antibacterial rate on Escherichia coli reaches 21%, the antibacterial rate on Staphylococcus aureus reaches 13%, the mildew-resistant level on Aspergillus niger reaches 4, and the mildew-resistant level on Aspergillus flavus reaches 4.
Comparative example 4:
the powder raw material is prepared by mechanically and uniformly mixing silver particles with the average particle size of 30 mu m and alumina particles with the average particle size of 30 mu m according to the weight ratio of 98. The gloss measured using a Meinenda MG-268 gloss meter was 360GU (60 ℃). According to ATSM D4541 standard, through testing, the binding force of the coating on the surface of the stainless steel bathroom door frame reaches 40MPa, the antibacterial performance and the mildew-proof performance are tested according to GB/T21510-2008 and GB/T1741-2020, the antibacterial rate on escherichia coli is 90%, the antibacterial rate on staphylococcus aureus is 86%, the mildew-resistant grade on aspergillus niger is 3, and the mildew-resistant grade on aspergillus flavus is 3.
Comparative example 5:
the raw materials of the powder are mechanically and uniformly mixed by copper particles with the average particle size of 50 mu m and alumina particles with the average particle size of 30 mu m according to the weight ratio of 95. The gloss measured using a Meinenda MG-268 gloss meter was 430GU (60 ℃). According to ATSM D4541 standard, tests show that the binding force of the coating on the surface of the zinc alloy handle reaches 40MPa, the antibacterial performance and the mildew-proof performance are tested according to GB/T21510-2008 and GB/T1741-2020, the antibacterial rate to escherichia coli is 87%, the antibacterial rate to staphylococcus aureus is 80%, the mildew-resistant level to aspergillus niger is 3, and the mildew-resistant level to aspergillus flavus is 3.
Table 1 shows the raw material components and the mixture ratio of the coatings of examples 1-5 and comparative examples 1-5, and the thickness, the antibacterial rate and the mildew-proof grade of the prepared coatings, and the comparative examples and comparative examples show that the samples with the supported antibacterial and mildew-proof component powder have better antibacterial and mildew-proof properties.
TABLE 1 coating raw material composition, proportioning and thickness, antibacterial rate and mildew-proof grade of the prepared coating
The above embodiments are merely preferred embodiments of the present invention, which are intended to illustrate the principles and functions of the present invention, and not to limit the present invention. It should be noted that modifications to the above-described embodiments can be made by persons skilled in the art without departing from the spirit and scope of the invention, and such modifications should also be considered as within the scope of the invention.
Claims (10)
1. A preparation method of a wear-resistant, mildew-proof and antibacterial cold spraying additive coating is characterized by comprising the following steps:
(1) Preparing mixed powder: uniformly mixing main raw material powder, wear-resistant component powder and load-type antibacterial and mildew-proof component powder according to a weight ratio;
(2) Preparing a cold spraying coating: spraying the mixed powder prepared in the step (1) according to the following cold spraying parameters: inert atmosphere, working temperature of 350-800 ℃, gas pressure of 1.5-3.5MPa, powder feeding amount of 20-100g/min and spraying distance of 10-50mm;
(3) And (3) post-treatment: and (3) grinding and polishing the surface of the coating prepared in the step (2) to obtain a finished product.
2. The preparation method of the coating according to claim 1, wherein the weight ratio of the main raw material powder, the wear-resistant component powder, and the supported antibacterial and mildewproof component powder in the step (1) is 82-98.5.
3. The method for preparing the coating according to claim 1, wherein the main raw material powder in the step (1) is one of titanium particles, stainless steel particles, aluminum particles, copper particles and silver particles, and the average particle diameter of the particles is 10 to 80 μm.
4. The method for preparing the coating according to claim 1, wherein the powder of the abrasion resistant component in the step (1) is one or more of titanium dioxide particles, aluminum oxide particles and silicon carbide particles, and the average particle size of the particles is 5-40 μm.
5. The method for preparing the coating according to claim 1, wherein the powder of the antibacterial and antifungal component supported in step (1) is one or more of silver-loaded zirconium phosphate particles, silver-loaded silicate particles, zinc-loaded silicate particles and zinc-loaded silicate particles.
6. The method for preparing the coating according to claim 1, wherein the average particle size of the powder particles of the supported antibacterial and antifungal ingredient in the step (1) is 1 to 30 μm.
7. The method of claim 1, wherein the inert atmosphere in step (2) is one of nitrogen or helium.
8. The method for preparing a coating according to claim 1, wherein the spraying in the step (2) is performed 10 to 20 times.
9. The method for preparing a coating according to claim 1, wherein the thickness of the coating prepared in the step (2) is 200 to 500 μm.
10. A coating obtainable by a process for the preparation of a coating according to any one of claims 1 to 9.
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