CN115612325A - Metal inorganic coating and preparation method and application thereof - Google Patents
Metal inorganic coating and preparation method and application thereof Download PDFInfo
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- CN115612325A CN115612325A CN202211330041.8A CN202211330041A CN115612325A CN 115612325 A CN115612325 A CN 115612325A CN 202211330041 A CN202211330041 A CN 202211330041A CN 115612325 A CN115612325 A CN 115612325A
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D1/00—Coating compositions, e.g. paints, varnishes or lacquers, based on inorganic substances
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/86—Catalytic processes
- B01D53/8668—Removing organic compounds not provided for in B01D53/8603 - B01D53/8665
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D1/00—Coating compositions, e.g. paints, varnishes or lacquers, based on inorganic substances
- C09D1/02—Coating compositions, e.g. paints, varnishes or lacquers, based on inorganic substances alkali metal silicates
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/32—Radiation-absorbing paints
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/20—Diluents or solvents
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2255/00—Catalysts
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- B01D2255/802—Photocatalytic
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Abstract
The invention discloses a metal inorganic coating and a preparation method and application thereof. The metal inorganic coating comprises 5-20% of sodium silicate, 10-35% of silica sol, 10-40% of titanium dioxide powder and 20-70% of water. The metal inorganic coating has strong adhesive force and does not influence the activity of the nano titanium dioxide.
Description
Technical Field
The invention relates to a metal inorganic coating, a preparation method and application thereof.
Background
The photocatalyst net used by the ETC air sterilizer is used for attaching nano-scale titanium dioxide powder to a metal net to play a role in purifying air; however, the binding force between the water-based titanium dioxide powder and carriers such as metal is weak, and a base coating with higher viscosity is required to play a transition role. The base layer coating with high viscosity has certain adhesion with a metal matrix and the like, also has adhesion with water-based titanium dioxide, and does not influence the activity of the titanium dioxide. Alcohol-based base coating sold in the market is already used for ETC air disinfectors, and has certain adhesive force with metal mesh and titanium dioxide solution, but the base coating is easy to crack after being sprayed on a substrate, so that the base coating is easy to fall off, and the photocatalyst net with titanium dioxide powder attached to the surface is easy to fall off during installation and transportation.
Fig. 1 (cracking, X100) shows the morphology of some commercially available alcohol-based base coating sprayed on metal mesh, which has the disadvantages of poor adhesion, easy cracking, severe dusting, etc.
Disclosure of Invention
An object of the present invention is to provide a metallic inorganic paint having strong adhesion without affecting the activity of nano titanium dioxide.
The metal inorganic coating provided by the invention comprises 5-20% of sodium silicate, 10-35% of silica sol, 10-40% of titanium dioxide powder and 20-70% of water.
In one embodiment, the titanium dioxide powder is rutile titanium dioxide.
In one embodiment, the sodium silicate is a liquid sodium silicate.
In one embodiment, the silica sol is a liquid neutral silica sol.
In one embodiment, the silica sol has a particle size of 10-20nm and 30% SiO 2 And (4) content.
In one embodiment, the liquid sodium silicate has a sodium silicate content of 42%.
It is another object of the present invention to provide the use of the metallic inorganic coating material in the preparation of a coated metallic article.
It is still another object of the present invention to provide a metal article comprising a coating layer made of the metallic inorganic paint.
In one embodiment, the metal article is a photocatalyst mesh.
It is still another object of the present invention to provide a method for preparing the metallic inorganic paint, comprising: 5 to 20 percent of sodium silicate, 10 to 35 percent of silica sol, 10 to 40 percent of titanium dioxide powder and 20 to 70 percent of water are mixed to obtain the metal inorganic coating.
The metal inorganic coating has better adhesion and equivalent formaldehyde treatment efficiency to the existing base coating.
Drawings
Fig. 1 shows the appearance of a commercial alcohol-based base coat sprayed on a metallic aluminum mesh.
Figure 2 shows a summary of the results of adhesion and water resistance tests in the film former ratio screen.
Fig. 3 shows a metallic aluminum mesh sprayed with a metallic inorganic coating according to an embodiment of the present invention.
FIG. 4 illustrates a metallic inorganic coating sprayed honeycomb aluminum according to one embodiment of the present invention.
Detailed Description
The invention aims to provide a metal inorganic coating. The metal inorganic coating has strong adhesive force and is an inorganic coating which does not influence the activity of the nano titanium dioxide. The metallic inorganic coating is selected to avoid the defect that ultraviolet rays break the organic long chain and prevent the coating from aging.
The formula design principle of the metal inorganic coating is as follows: composition = film former + filler + solvent. The commercial organic coating comprises organic resin, titanium dioxide and alcohol, wherein the long chain of the organic resin is easy to break and age under ultraviolet rays, the resin and the titanium dioxide are easy to shrink and crack after forming a film, the adhesion with a metal substrate is poor, and the alcohol solvent is volatilized, so that the problems of occupational safety and environmental protection exist.
The metal inorganic coating comprises an inorganic film-forming agent, rutile titanium dioxide and water. The inorganic film-forming agent resists ultraviolet rays and is a combination of sodium silicate and silica sol after screening. Sodium silicate of formula Na 2 O.nSiO 2 An inorganic silicate, which is a commonly used inorganic binder; silica sol, a dispersion of nanoscale silica particles in water or solvent, of the formula mSiO 2 .nH 2 When the silica sol loses moisture, monomer silicic acid is gradually polymerized into high polymer silica gel, and colloid molecules are enlarged along with the evaporation of the moisture. The filler isThe rutile titanium dioxide has the advantages of low cost, compact crystal structure, stability, small optical activity and high ultraviolet absorption efficiency. Water is more environmentally friendly as a solvent.
Recipe determination
Sodium silicate used below was a liquid, modulus: 2.31, content: 42%, baume degree: 50;
the used silica sol is liquid neutral silica sol, and the content of the components is as follows: siO 2 2 :30 percent; pH value: 7.8 to 8.4; particle size: (10-20) nm;
the rutile titanium dioxide is white and rutile type, and the crystal structure of the rutile titanium dioxide is compact and relatively stable, the optical activity is small, and the efficiency of absorbing ultraviolet rays is relatively high;
the water used was laboratory grade three-stage water, pH (25 ℃): 5.0 to 7.5; conductivity (25 ℃ C.)/(mS/m): less than or equal to 0.50 percent.
The specific process for preparing the metal inorganic coating comprises the following steps:
step one, adding a sodium silicate aqueous solution into a container A;
step two, adding a silica sol aqueous solution into the container B;
step three, adding rutile titanium dioxide into the container C;
step four, adding tertiary water into the container D;
step five, adding the sodium silicate aqueous solution in the container A into the container D, and stirring for 2min;
step six, adding the silica sol aqueous solution in the container B into the container D, and stirring for 2min;
step seven, adding the powder in the container C into the container D, and stirring for 5min;
step eight, immersing the container D into an ultrasonic water tank, and carrying out ultrasonic vibration at 40,000Hz for 30min.
Oxidizable substance content (in terms of O)/(mg/L) of the metallic inorganic coating material: less than or equal to 0.50 percent; content of evaporation residue (105 ℃ C. +. 2 ℃ C.)/(mg/L): less than or equal to 2.0.
1. Screening of film-forming agent proportion
In order to determine the influence of different proportions of sodium silicate and silica sol on the adhesion and water resistance, the amounts of rutile titanium dioxide and water were fixed, and a metal inorganic coating was prepared according to the following table and applied to the surface of a metal aluminum plate.
TABLE 1
| Numbering | Sodium silicate | Silica sol | Rutile titanium dioxide | Water (W) |
| 8～A | 20％ | 20％ | 20％ | 40％ |
| 8～B | 43％ | 14％ | 14％ | 29％ |
| 8～C | 10％ | 30％ | 20％ | 40％ |
| 8～D | 35％ | 5％ | 20％ | 40％ |
| 8～E | 5％ | 35％ | 20％ | 40％ |
| 8～F | 25％ | 15％ | 20％ | 40％ |
| 8～G | 15％ | 25％ | 20％ | 40％ |
| 8～H | 38％ | 2％ | 20％ | 40％ |
| 8～ |
2％ | 38％ | 20％ | 40％ |
| 8～J | 40％ | 0％ | 20％ | 40％ |
| 8～ |
0％ | 40％ | 20％ | 40％ |
Tape peeling test
Adhering the coating on a metal aluminum plate coated with different metal inorganic coatings by using an adhesive tape, then removing the adhesive tape by using a certain force, and observing the residue of the coating on the adhesive tape to judge the adhesion force of the coating 。
The rutile titanium dioxide is arranged on the adhesive tapes of 8-I and 8-K, which indicates that the adhesive force is poor.
Water resistance test
And (3) immersing the metal aluminum plate coated with the metal inorganic coating in water, observing the change of the metal aluminum plate just after being immersed in the water, and observing the change of the amount of rutile titanium dioxide on the surface of the metal aluminum plate after being immersed in the water for 24 hours and naturally dried to judge the water resistance of the metal aluminum plate.
Wherein, 8-B, 8-D, 8-F, 8-H, 8-I, 8-J and 8-K are just immersed in water, the rutile titanium dioxide on the surface immersed in the water begins to slide off and drift to the water in a smoke state, and the water slowly becomes turbid; after the aluminum plate is immersed in water for 24 hours and naturally aired, all rutile titanium dioxide of the part, immersed in water, of some metal aluminum plates falls off, such as 8-J, and the rutile titanium dioxide of the part, immersed in water, of some metal aluminum plates falls off, and the color of the rutile titanium dioxide is darker than that of the part, not immersed in water, such as 8-I.
8 to A, 8 to C, 8 to E and 8 to G are immersed in water, and the water is clear and unchanged.
Summary of the invention
The above test results show that the metallic inorganic paint has poor adhesion when the content of sodium silicate in the metallic inorganic paint is less than 5%, and has poor water resistance when the content of silica sol in the metallic inorganic paint is more than 20%, as shown in table 2 and fig. 2 below.
TABLE 2
2. Filler proportion screening
The result of screening the proportion of the film forming agent obtains the boundary point of the adhesion and the water resistance, namely when the lower boundary of the sodium silicate is 5 percent and the upper boundary is 20 percent, the adhesion and the water resistance are good.
In the test, the two boundary points are used, the amount of rutile titanium dioxide is changed to screen the proportion of the filler, and the metal inorganic coating is prepared according to the following table 3 and coated on the surface of the metal aluminum plate.
TABLE 3
| Number of | Sodium silicate | Silica sol | Rutile titanium dioxide | Water (W) |
| 8～L | 20％ | 20％ | 5％ | 55％ |
| 8～M | 20％ | 20％ | 30％ | 30％ |
| 8～P | 20％ | 20％ | 40％ | 20％ |
| 8～N | 5％ | 35％ | 5％ | 55％ |
| 8～O | 5％ | 35％ | 30％ | 30％ |
Tape peeling test
The adhesive tape is adhered to a metal aluminum plate coated with different metal inorganic coatings, the adhesive tape is removed by a certain force, and the residue of the coatings on the adhesive tape is observed to judge the adhesive force.
The rutile titanium dioxide is coated on the 8-N adhesive tape and the 8-O adhesive tape, which indicates that the adhesion force is poor.
Water resistance test
And (3) immersing the metal aluminum plate coated with the metal inorganic coating in water, observing the change of the metal aluminum plate just after the metal aluminum plate is immersed in the water, and observing the layering and the color change of the rutile titanium dioxide on the surface of the metal aluminum plate after the metal aluminum plate is immersed in the water for 24 hours and naturally aired to judge the water resistance of the metal aluminum plate.
When 8-L is just immersed in water, the layering phenomenon occurs between the part immersed in water and the part not immersed in water, but no rutile titanium dioxide falls off, and the water is clear. After the titanium dioxide powder is naturally dried after being immersed in water for 24 hours, the titanium dioxide powder has layering phenomenon and no other color change, which indicates that the rutile-free titanium dioxide powder falls off.
The metal aluminum plate coated with other metal inorganic coatings has no change before and after being immersed in water, the water is clear, and the rutile-free titanium dioxide powder slides off.
Summary of the invention
The above test results show that when the contents of sodium silicate and silica sol in the metallic inorganic coating are both 20% and the content of rutile titanium dioxide in the metallic inorganic coating is 30% -40%, the adhesion and water resistance of the metallic inorganic coating are both good, and the results are shown in table 4.
TABLE 4
3. Solvent ratio screening
The solvent plays a role in dilution, in order to enable the inorganic coating to have certain fluidity and facilitate painting or spraying on the metal surface, the inorganic coating needs to be diluted by the solvent, the metal inorganic coating is coated on the surface of the metal aluminum plate for multiple times after being diluted by 8-A, the adhesive force and the water resistance of the metal inorganic coating are verified through a tape stripping test and a soaking test, and the metal inorganic coating is prepared according to the following table 5 and coated on the surface of the metal aluminum plate.
TABLE 5
| Numbering | Sodium silicate | Silica sol | Rutile titanium dioxide | Water (I) |
| 8-A-dilution | 10％ | 10％ | 10％ | 70％ |
No rutile titanium dioxide remained on the tape. Upon immersion in water, the water was clear with no change before and after. The rutile titanium dioxide does not fall off after being naturally dried after being immersed in water for 24 hours.
The test shows that water only has a diluting effect, and the metal inorganic coating can volatilize after being formed into a film and dried, so that the adhesion force and the water resistance test of the metal inorganic coating are not influenced.
4. Preliminary screening results and other Performance tests
The metallic inorganic paint in table 6 below has good adhesion and good water resistance after preliminary screening. The following metallic inorganic coatings were coated on metallic aluminum panels and tested for other properties.
TABLE 6
Reflectance test
A plain aluminum plate was used as a substrate, and coated with a metallic inorganic paint selected from those listed in Table 6 and a commercially available base paint, and a metallic aluminum plate coated with a commercially available base paint was used as a comparative example. Because the content of rutile titanium dioxide in the metal inorganic coating 8-A-diluted is lower, the reflectivity test is carried out after each brushing and airing.
The test results are shown in table 7 below, where the reflectance is related to the content of rutile titanium dioxide in the coated metallic inorganic paint, and when the content of rutile titanium dioxide is higher, the reflectance is lower, indicating that the paint has good absorption of ultraviolet rays, and the metallic inorganic paint in table 6 has lower reflectance to ultraviolet rays.
TABLE 7
Aging test
The metallic inorganic paint in Table 6 was coated on a metal aluminum plate, then a half of the metal aluminum plate was masked, and it was irradiated for 168 hours under UVC, and its anti-aging property was judged by cracking, color change, etc.
The test result shows that after 168h of UVC irradiation, the front and back of the coated metal aluminum plate have no color change and no cracking lamp, and the aging resistance of the metal inorganic coating in the table 6 is good.
Comparative test with commercially available base coating
In order to test adhesion, water resistance, aging resistance and reflectance of the metallic inorganic coatings in table 6 and the commercially available base layer coatings, the commercially available base layer coatings and the metallic inorganic coatings in table 6 were coated or sprayed on a metallic aluminum mesh. Meanwhile, the powder dropping rate of the coated metal aluminum mesh and the efficiency of treating formaldehyde were tested.
1. Adhesion, water resistance test, reflectance and aging resistance test of commercially available base coating materials
Tape peel testing of commercially available base coatings showed that much white powder adhered to the black tape, which was seen to have poor adhesion; the immersion test of the commercial base coating shows that no powder falls off and the water is clear; after being immersed in water for 24 hours, the paint has no crack and good water resistance.
After the metal aluminum mesh coated by the commercially available base layer coating is subjected to ultraviolet radiation for 168 hours, no color change and no cracking occur before and after the metal aluminum mesh is irradiated by ultraviolet radiation, which indicates that the metal aluminum mesh has good ageing resistance.
The reflectivity test of the commercially available base coating showed a reflectivity of 2.07%, indicating that it absorbs ultraviolet light well and has a low reflectivity.
2. Powder falling rate test
The metallic inorganic coating materials in table 6 and commercially available base coating materials were coated or sprayed on a metallic aluminum mesh to test the dusting rate thereof. The aluminum mesh was placed in a ferrous metal pan and dropped freely 5 times from a height of 1 meter, and its loss of mass was tested to characterize its dusting rate.
For commercially available base coat coated metallic aluminum mesh, a clear white powder was visible in the tested ferrous metal pan; whereas, for the metallic aluminum mesh coated with the metallic inorganic paint in Table 6, substantially no white powder was visible in the ferrous metal pan after the test. The results of the weight difference of the tests also show that the dusting rate of the aluminum metal mesh coated with the metallic inorganic coating in table 6 is significantly better than that of the aluminum metal mesh coated with the commercially available base coating (JRCJ 5), as shown in table 8.
TABLE 8
3. Testing the efficiency of Formaldehyde treatment
The metallic inorganic coatings in table 6 and the commercially available base coat were coated or sprayed on an equal size metallic aluminum mesh and then tested in a square bin test at the same time. The test results show that the efficiency of treating formaldehyde with metallic aluminum mesh sprayed with the metallic inorganic coating in table 6 is comparable to the efficiency of treating formaldehyde with metallic aluminum mesh sprayed with a commercially available base coating.
TABLE 9
As shown in FIG. 3 (x 100), the inorganic metallic paint of the present invention has strong adhesion to the substrate and no cracking or peeling.
FIG. 4 shows a honeycomb aluminum sprayed with the metallic inorganic coating of the present invention, showing that the metallic inorganic coating of the present invention has good adhesion to the substrate, no peeling off, and better UV resistance.
Summary of test results
The metallic inorganic coating of the present invention has better adhesion and other equivalent properties compared to commercially available base coatings.
Watch 10
| Examples | Numbering | Sodium silicate | Silica sol | Rutile titanium dioxide | Water (W) | Adhesion force | Water resistance | Reflectance% | Anti-aging agent | Powder falling rate | Efficiency K for treating |
| 1 | 8～A | 20％ | 20％ | 20％ | 40％ | Good taste | Good taste | 2.15 | Good taste | Is low with | 0.024 |
| 2 | 8～C | 10％ | 30％ | 20％ | 40％ | Good taste | Good taste | 2.04 | Good taste | Is low in | 0.021 |
| 3 | 8～E | 5％ | 35％ | 20％ | 40％ | Good taste | Good taste | 2.01 | Good taste | Is low with | 0.022 |
| 4 | 8～G | 15％ | 25％ | 20％ | 40％ | Good taste | Good taste | 1.94 | Good taste | Is low with | 0.025 |
| 5 | 8～M | 20％ | 20％ | 30％ | 30％ | Good taste | Good taste | 1.47 | Good taste | Is low with | 0.022 |
| 6 | 8～P | 20％ | 20％ | 40％ | 20％ | Good taste | Good taste | 1.10 | Good taste | Is low in | 0.023 |
| 7 | Commercial primer | ～ | ～ | ～ | ～ | Difference (D) | Good taste | 2.07 | Good taste | Height of | 0.023 |
Examples
Based on the screening, the metal inorganic coating which has better adhesive force, better water resistance, lower reflectivity and lower dusting rate and does not influence the capability of the nano titanium dioxide powdery mildew on treating formaldehyde is obtained.
Table 11 shows the compositions of the metallic inorganic coatings of examples 1 to 7.
TABLE 11
| Examples | Numbering | Sodium silicate | Silica sol | Rutile titanium dioxide | Water (W) |
| 1 | 8～A | 20％ | 20％ | 20％ | 40％ |
| 2 | 8 to A dilution | 10％ | 10％ | 10％ | 70％ |
| 3 | 8～C | 10％ | 30％ | 20％ | 40％ |
| 4 | 8～E | 5％ | 35％ | 20％ | 40％ |
| 5 | 8～G | 15％ | 25％ | 20％ | 40％ |
| 6 | 8～M | 20％ | 20％ | 30％ | 30％ |
| 7 | 8～P | 20％ | 20％ | 40％ | 20％ |
Claims (10)
1. A metallic inorganic paint contains sodium silicate (5-20%), silica sol (10-35%), titanium dioxide powder (10-40%) and water (20-70%).
2. The metallic inorganic coating of claim 1, wherein the titanium dioxide powder is rutile titanium dioxide.
3. The metallic inorganic coating material of claim 1, wherein the sodium silicate is liquid sodium silicate.
4. The metallic inorganic coating material of claim 1, wherein the silica sol is a liquid neutral silica sol.
5. The metallic inorganic coating of claim 4, wherein the silica sol has a particle size of 10-20nm and 30% SiO 2 And (4) content.
6. The metallic inorganic coating of claim 3, wherein the liquid sodium silicate has a sodium silicate content of 42%.
7. Use of the metallic inorganic coating of any one of claims 1 to 6 in the preparation of a coated metallic article.
8. A metal article comprising a coating layer made of the metallic inorganic coating material according to any one of claims 1 to 6.
9. The photocatalyst net according to claim 8, wherein the metal product is a photocatalyst net.
10. A method for preparing the metallic inorganic coating of claim 1, comprising:
5 to 20 percent of sodium silicate, 10 to 35 percent of silica sol, 10 to 40 percent of titanium dioxide powder and 20 to 70 percent of water are mixed to obtain the metal inorganic coating.
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