Corrosion-resistant, low-temperature-resistant and easy-to-dry titanium-containing metal protective film and preparation method thereof

Abstract

The invention discloses a corrosion-resistant, low-temperature-resistant and easy-to-dry titanium-containing metal protective film and a preparation method thereof, belongs to the technical field of metal protective films, and aims to solve the problem of serious loss caused by scrap of metal raw materials and products thereof due to rust. According to the application method, a titanium-containing substance is added into a conventional metal protective film so as to improve the corrosion resistance of the metal protective film, the titanium-containing metal protective film shows excellent easy-drying, low-temperature-resistant and corrosion-resistant performance, and the embrittlement phenomenon cannot be generated in a 180-degree bending test. The metal protective film not only provides a protection function, but also can improve the appearance of a metal product and increase brightness, gloss and texture. In addition, special functions such as ultraviolet resistance and high pressure resistance can be added according to specific application requirements, and the adaptability and stability of metal products are improved.

Description

Technical Field

[0001] The invention belongs to the technical field of metal protective films, and relates to a corrosion-resistant, low-temperature-resistant, easy-to-dry titanium-containing metal protective film and a preparation method thereof. Background Art

[0002] A metal protective film is a special thin film that covers a metal surface to prevent rust and corrosion. Materials are essential to human survival and well-being, and are closely related to our daily lives. Metals are among the most widely used materials due to their lustrous, ductile properties, and good electrical and heat conduction properties. However, metals often undergo varying degrees of oxidation and corrosion during processing and use, reducing the service life of metal materials or metal equipment. Therefore, metal surface treatment is necessary to enhance their antioxidant and corrosion resistance, thereby extending their service life. To improve the corrosion resistance of metal materials, chromate or phosphate metal surface treatment agents are commonly used in the prior art. However, chromate is toxic, and the use of phosphates generates large amounts of phosphorus-containing wastewater, resulting in very high costs for wastewater treatment. For example, Patent 202011149245.2 discloses an environmentally friendly metal surface treatment agent and its preparation method. However, this surface treatment agent contains fluoride ions, which pose significant risks to human health and the environment, and the treatment effect is poor, which does not meet modern environmental protection requirements.

[0003] With the advancement of science and technology, cryogenics has rapidly penetrated various fields of science and technology, becoming an integral part of cutting-edge science and technology. In recent years, research on the mechanical properties of cryogenic metals has become a key branch of materials science, and scientists have made significant achievements. For example, copper-nickel alloys can maintain high strength and toughness at low temperatures, making them widely used in cryogenic equipment such as aerospace and liquid oxygen and hydrogen storage tanks. Certain specialty steels, such as 9% nickel steel and Austenitic stainless steel, maintain excellent mechanical properties at low temperatures and are widely used in cryogenic equipment such as LNG storage tanks and cryogenic pipelines. However, at low temperatures, the mechanical properties of metals are significantly affected. Low-temperature tensile tests on metals have shown that metals become hard and brittle as the temperature decreases. This is accompanied by changes in the performance of electronic components, condensation and freezing of water, failure of seals, and shrinkage of the metal, resulting in changes in mechanical structures. Cold brittle failure of metal components is extremely dangerous and cannot be controlled or predicted. Once it occurs, the entire structure collapses instantly. To improve the low-temperature resistance of metals, China is developing low-temperature-resistant rubber-metal composite materials. However, domestic research is still in its infancy, and production technology is immature. Most products rely on imports, which are several times more expensive than domestic products. Imported products are expensive and costly. For example, Patent 201710103484.6 discloses a low-temperature-resistant metal adhesive and its preparation method, which fall into the field of organic polymer synthesis technology. However, since the type and properties of the adhesive can affect the performance of the composite material, its practical application is limited. Titanium-containing metal protective films have high thermal stability, a wide temperature range, a stable structure, and are non-decomposable.

[0004] Condensation on metal surfaces is a significant issue that can affect the proper use and operation of metal equipment. Condensation forms on metal surfaces when the air humidity around the metal approaches saturation, or when the metal's temperature drops below the dew point due to heat exchange with a cold object. Condensation not only accelerates corrosion of the metal itself but also has other adverse effects. For example, condensation on the interior surfaces of outdoor communications cabinets can cause corrosion or degraded insulation of electronic components, leading to poor contact and even short circuits and burnout. Currently, the main methods for preventing condensation include controlling relative humidity and absolute humidity. While relative humidity control is widely used in applications with a certain level of heat generation or heat diffusion, it requires a temperature and humidity monitoring and control system, consumes energy, and is therefore uneconomical from an energy-saving perspective. Controlling absolute humidity can mitigate humidity fluctuations by applying a surface coating, delaying the onset of condensation. These measures merely delay the formation of condensation but do not effectively dry the equipment. In order to meet the drying requirements of metal materials, in the prior art, a dryer is generally used for drying. Although the drying speed is fast, the energy consumption is high, which increases the production cost. For example, patent 201920612793.0 discloses a precious metal drying device, but the operation process of the device is cumbersome and the cost of precious metals is high. At the same time, the complexity of precious metal recovery and processing seriously limits its practical application. Therefore, it is of great significance to develop a metal surface treatment agent that can effectively prevent metal oxidation, is corrosion-resistant, resistant to low temperatures, and easy to dry.

[0005] Titanium and its alloys possess excellent corrosion and heat resistance, low-temperature mechanical properties, and easy drying properties. They are widely used in aerospace, shipbuilding, chemical engineering, automotive, biomedical, and daily necessities. As titanium's applications continue to expand, the metal is attracting increasing attention from both academia and industry. Numerous scholars and engineers have conducted fundamental research on titanium's properties, developed process technologies, and developed industrial production technologies, achieving remarkable results.

[0006] Titanium-containing metal protective film is a metal protective film with corrosion resistance, easy drying and low temperature resistance. It can be applied to various metal materials such as aluminum, stainless steel, chrome plating, copper, etc., and is used to protect vehicles, aerospace, medical equipment, electronic products and other metal products. Titanium-containing metal protective film is usually prepared based on physical vapor deposition (PVD) or chemical vapor deposition (CVD) technology. Titanium metal evaporation is deposited on the metal surface to form a thin film. Titanium metal has excellent corrosion resistance in oxidizing and neutral media, which makes this technology can achieve high-quality, uniform and well-adhesive protective films. Summary of the Invention

[0007] The purpose of the present invention is to provide a corrosion-resistant, low-temperature-resistant, easy-to-dry titanium-containing metal protective film and a preparation method. In order to solve the problem of serious losses caused by the scrapping of metal raw materials and their products due to rust, a method of adding a titanium-containing substance to a conventional metal protective film is provided to increase the corrosion resistance of the metal protective film. The titanium-containing metal protective film of the present invention exhibits excellent easy-to-dry, low-temperature and corrosion resistance. No brittle cracking occurs in a 180° bending test. The metal protective film not only provides a protective function, but also improves the appearance of metal products, increasing brightness, gloss and texture. In addition, special functions such as UV resistance and high-pressure resistance can be added to meet specific application requirements to improve the adaptability and stability of metal products.

[0008] The purpose of the present invention can be achieved through the following technical solutions:

[0009] A method for preparing a corrosion-resistant, low-temperature-resistant, and easy-to-dry titanium-containing metal protective film comprises the following steps:

[0010] Step 1: Mix nano-titanium-doped tin dioxide, polymethacrylate emulsion, modified rigid polyurethane composite insulation material, low-temperature resistant porous hollow microspheres, aniline black, dispersant BYK-161, dibutyltin dilaurate, deionized water, and anhydrous ethanol in a mass ratio of 30:70:8:2:1:3:1:5:20, and stir for 2-3 hours at 70-75°C and 500-600r / min to obtain a low-temperature resistant, corrosion-resistant and easy-drying coating.

[0011] Step 2: Fix a PET substrate with a thickness of 0.06mm in a polytetrafluoroethylene mold, pour a low-temperature resistant, corrosion-resistant and easy-drying coating into the mold so that it is evenly spread on the surface of the PET base film, evaporate the solvent under reduced pressure at 60-80℃ for 25 hours, and then take it out to form a first film layer on the PET base film to obtain a first film body, add tetraalkoxy titanate, tetraalkoxy silane and siloxane to deionized water and stir evenly to obtain a uniform reaction liquid, lay the first film body as a filter membrane in a funnel, pour the reaction liquid in and filter it, form a film on the surface of the first film body, and separate it from the filter paper to obtain a corrosion-resistant, low-temperature resistant, easy-drying titanium-containing metal protective film.

[0012] Preferably, the polymethacrylic acid emulsion in step 1 is prepared by the following steps:

[0013] Sodium lauryl sulfate, ammonium bicarbonate, deionized water, and pre-emulsion are added to a reactor, stirred at 70-75°C and 500-600 r / min for 20-30 min, then ammonium persulfate is added, stirring is continued for 1-2 h, the temperature is lowered to 40-45°C, ammonia water is added to adjust the pH value to 6-7, filtered, and distilled at a vacuum degree of -0.08 to -0.06 MPa and 60-80°C for 6-7 h to obtain a polymethacrylic acid emulsion.

[0014] Preferably, the mass ratio of sodium lauryl sulfate, ammonium bicarbonate, deionized water, pre-emulsion and ammonium persulfate is 5-6g: 3-4g: 7-8g: 40-50g: 0.1-0.2g.

[0015] Preferably, the pre-emulsion is prepared by the following steps:

[0016] Add methacrylic acid, deionized water, sodium lauryl sulfate, and alkylphenol polyoxyethylene ether into a reaction kettle, emulsify for 10-20 minutes at 10,000-11,000 r / min, then add ammonium persulfate and continue stirring for 10-20 minutes to obtain a pre-emulsion;

[0017] Preferably, the mass ratio of methacrylic acid, deionized water, sodium lauryl sulfate, alkylphenol polyoxyethylene ether and ammonium persulfate is 25-30:7-8:1-2:2-3:0.1-0.2.

[0018] Preferably, the modified rigid polyurethane composite thermal insulation material in step 1 is prepared by the following steps:

[0019] Add rigid polyurethane to deionized water and soak for 20-25 hours, then add asbestos and continue soaking for 30-60 minutes to obtain mixed slurry A; stir and mix expanded perlite, lightweight ceramsite, phosphate, magnesium oxide powder, high-alumina cement, vermiculite, pyrope and tetraalkoxy titanate as a low-temperature modifier, dry, expand, grind and pulverize to obtain mixed powder B of 200-300 mesh;

[0020] The mixed slurry A and the mixed powder B are put into a reactor, heated to 50-80°C under nitrogen protection, stirred at 500-600 r / min for 20-30 min, and then poly 4,4'-diphenylmethane diisocyanate is added. The mixture is stirred and foamed for 2-3 h, cooled naturally to room temperature, poured into a mold and press-formed, and vacuum-dried at 60-80°C for 1-2 h to obtain a modified rigid polyurethane composite insulation material.

[0021] Preferably, the usage ratio of rigid polyurethane, deionized water and asbestos is 50-60 g:700-800 mL:3-4 g.

[0022] Preferably, the usage ratio of expanded perlite, lightweight ceramsite, phosphate, magnesium oxide powder, high alumina cement, vermiculite, pyroxene and tetraalkoxy titanate is 20-30 g: 10-12 g: 5-6 g: 3-4 g: 1-2 g: 1-2 g: 3-4 g: 500-600 mL.

[0023] Preferably, the usage ratio of the mixed slurry A, the mixed powder B and the poly-4,4'-diphenylmethane diisocyanate is 500-600 mL: 20-30 g: 4-5 g.

[0024] Preferably, the low-temperature resistant porous hollow microspheres in step 1 are prepared by the following steps:

[0025] Tetrabutyl titanate and anhydrous ethanol are added to a reactor in a mass ratio of 1:5, stirred at 20-25°C and 500-600 r / min for 10-20 minutes, and transferred to a sealed tube filled with oxygen, one end of the sealed tube is connected to a piston that generates linear reciprocating motion by the rotation of an eccentric wheel, the eccentric wheel rotates at a speed of 60-70 r / min for 2-3 hours, heated to 150-160°C, continued to rotate for 18-20 hours, transferred to a radiation source of 6°CO and a dose rate of 100 Gy / min for 10-12 minutes, filtered, and the filter cake is washed with deionized water 2-3 times and vacuum dried at 60-80°C for 1-2 hours to obtain low-temperature resistant porous hollow microspheres.

[0026] Beneficial effects of the present invention:

[0027] 1. This invention provides a titanium-containing metal protective film and its preparation method. Based on the properties of the raw materials required for synthesizing the metal protective film, titanium-containing substances are added to create a metal protective film with corrosion resistance, wear resistance, scratch resistance, and low-temperature resistance. The film can be applied to various metal materials, such as aluminum, stainless steel, chrome plating, and copper, for protecting vehicles, aerospace, medical equipment, electronic products, and other metal products.

[0028] 2. The titanium-containing metal protective film in the technology of the present invention can form a dense anti-corrosion effect on the metal surface, block the erosion of acid and alkaline substances, improve the metal's anti-oxidation and anti-corrosion capabilities, and extend the service life of metal materials or metal equipment; maintain good ductility in a low-temperature environment and reduce the brittleness of the metal; the titanium-containing metal protective film in the technology of the present invention has the characteristic of being easy to dry, and the drying time on the metal surface only takes 45 minutes, and the actual drying time takes 230 minutes, which can quickly and efficiently protect the metal. BRIEF DESCRIPTION OF THE DRAWINGS

[0029] Figure 1 This is a comparison chart of the wear surface effects of the titanium-containing metal protective film and the ordinary film prepared after implementing the solution.

[0030] Figure 2(a) X-ray diffractometer, (b) field emission scanning electron microscope and INCA energy dispersive spectrometer.

[0031] Figure 3 This is an XRD pattern effect diagram of the titanium-containing metal protective film prepared after implementing the implementation plan.

[0032] Figure 4 This is a microscopic rendering of the titanium-containing metal protective film prepared after implementing the implementation plan.

[0033] Figure 5 The figure shows the corrosion morphology of the titanium-containing metal protective film prepared after implementing the embodiment. DETAILED DESCRIPTION

[0034] The following will clearly and completely describe the technical solutions in the embodiments of the present invention in conjunction with the accompanying drawings. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without making creative efforts are within the scope of protection of the present invention.

[0035] Example 1

[0036] S1: 50 g of rigid polyurethane was added to 700 mL of deionized water and soaked for 20 h, and then 3 g of asbestos was added and soaked for another 30 min to obtain a mixed slurry A; 20 g of expanded perlite, 10 g of lightweight ceramsite, 5 g of phosphate, 3 g of magnesium oxide powder, 1 g of high-alumina cement, 1 g of vermiculite, 3 g of pyrope stone, and 500 mL of tetraalkoxy titanate as a low-temperature modifier were stirred and mixed, dried, expanded, and ground to obtain a 200-mesh mixed powder B;

[0037] 500 mL of mixed slurry A and 20 g of mixed powder B were put into a reactor, heated to 50°C under nitrogen protection, stirred at 500 r / min for 20 min, and then 4 g of poly 4,4'-diphenylmethane diisocyanate was added. Stirring and foaming were continued for 2 h. The mixture was naturally cooled to room temperature, poured into a mold and press-molded, and vacuum-dried at 60°C for 1 h to obtain a modified rigid polyurethane composite insulation material.

[0038] S2: Tetrabutyl titanate and anhydrous ethanol were added to the reactor in a mass ratio of 1:5, stirred at 20°C and 500 r / min for 10 minutes, and transferred to a sealed tube filled with oxygen. One end of the sealed tube was connected to a piston that generated linear reciprocating motion by the rotation of an eccentric wheel. The eccentric wheel rotated at a speed of 60 r / min for 2 hours, heated to 150°C, and continued to rotate for 18 hours. It was transferred to a radiation source of 6°CO and a dose rate of 100 Gy / min for 10 minutes, filtered, and the filter cake was washed twice with deionized water and vacuum dried at 60°C for 1 hour to obtain low-temperature resistant porous hollow microspheres.

[0039] S3: 25 g of methacrylic acid, 7 g of deionized water, 1 g of sodium lauryl sulfate, and 2 g of alkylphenol polyoxyethylene ether were added to a reactor, and emulsified at 10,000 rpm for 10 min. 0.1 g of ammonium persulfate was then added, and stirring was continued for 10 min to obtain a pre-emulsion.

[0040] 5 g of sodium lauryl sulfate, 3 g of ammonium bicarbonate, 7 g of deionized water, and 40 g of pre-emulsion were added to a reactor, stirred at 70°C and 500 r / min for 20 min, then 0.1 g of ammonium persulfate was added, stirring was continued for 1 h, the temperature was lowered to 40°C, ammonia water was added to adjust the pH value to 6, filtered, and distilled at a vacuum degree of -0.08 to -0.06 MPa and 60°C for 6 h to obtain a polymethacrylic acid emulsion.

[0041] S4: Nano-titanium-doped tin dioxide, polymethacrylate emulsion, modified rigid polyurethane composite insulation material, low-temperature resistant porous hollow microspheres, aniline black, dispersant BYK-161, dibutyltin dilaurate, deionized water, and anhydrous ethanol are stirred in a mass ratio of 30:70:8:2:1:3:1:5:20, and stirred at 70°C and 500 r / min for 2 h to obtain a low-temperature resistant, corrosion-resistant and easy-drying coating.

[0042] S5: Fix a PET substrate with a thickness of 0.06 mm in a polytetrafluoroethylene mold, pour a low-temperature resistant, corrosion-resistant and easy-drying coating into the mold so that it is evenly spread on the surface of the PET base film, evaporate the solvent under reduced pressure at 60°C, and take it out after 25 hours to form a first film layer on the PET base film to obtain a first film body, add tetraalkoxy titanate, tetraalkoxy silane and siloxane to deionized water and stir evenly to obtain a uniform reaction liquid, lay the first film body as a filter membrane in a funnel, pour the reaction liquid in and filter it, form a film on the surface of the first film body, and separate it from the filter paper to obtain a corrosion-resistant, low-temperature resistant, easy-drying titanium-containing metal protective film.

[0043] Example 2

[0044] S1: Add 55g of rigid polyurethane to 750mL of deionized water and soak for 22.5h, then add 3.5g of asbestos and continue soaking for 45min to obtain a mixed slurry A; 25g of expanded perlite, 11g of lightweight ceramsite, 5.5g of phosphate, 3.5g of magnesium oxide powder, 1.5g of high alumina cement, 1.5g of vermiculite, 3.5g of pyrotechnic acid stone and 550mL of tetraalkoxy titanate are stirred and mixed, dried, expanded, and ground to obtain a 250-mesh mixed powder B; 550mL of mixed slurry A and 25g of mixed powder B are put into a reactor, heated to 65°C under nitrogen protection, stirred at 550r / min for 25min, and then 4.5g of poly 4,4'-diphenylmethane diisocyanate is added, and stirring and foaming are continued for 2.5h. The mixture is naturally cooled to room temperature, poured into a mold and pressurized, and vacuum dried at 70°C for 1.5h to obtain a modified rigid polyurethane composite thermal insulation material.

[0045] S2: Tetrabutyl titanate and anhydrous ethanol were added to the reactor in a mass ratio of 1:5, stirred at 22.5°C and 550 r / min for 15 minutes, and transferred to a sealed tube filled with oxygen. One end of the sealed tube was connected to a piston that generated linear reciprocating motion by the rotation of an eccentric wheel. The eccentric wheel rotated at a speed of 65 r / min for 2.5 hours, heated to 155°C, and continued to rotate for 19 hours. The mixture was transferred to a radiation source with a temperature of 6°C and a dose rate of 100 Gy / min and irradiated for 11 minutes. The mixture was filtered, and the filter cake was washed twice with deionized water and vacuum dried at 70°C for 1.5 hours to obtain low-temperature resistant porous hollow microspheres.

[0046] S3: 27.5 g of methacrylic acid, 7.5 g of deionized water, 1.5 g of sodium lauryl sulfate, and 2.5 g of alkylphenol polyoxyethylene ether were added to a reactor, emulsified at 10500 r / min for 15 min, and then 0.15 g of ammonium persulfate was added, and stirring was continued for 15 min to obtain a pre-emulsion; 5.5 g of sodium lauryl sulfate, 3.5 g of ammonium bicarbonate, 7.5 g of deionized water, and 45 g of the pre-emulsion were added to a reactor, stirred at 72.5°C and 550 r / min for 25 min, and then 0.15 g of ammonium persulfate was added, and stirring was continued for 1.5 h. The temperature was lowered to 42.5°C, ammonia water was added to adjust the pH to 6.5, filtered, and distilled at a vacuum degree of -0.07 MPa and 70°C for 6.5 h to obtain a polymethacrylic acid emulsion.

[0047] S4: Nano-titanium-doped tin dioxide, polymethacrylate emulsion, modified rigid polyurethane composite insulation material, low-temperature resistant porous hollow microspheres, aniline black, dispersant BYK-161, dibutyltin dilaurate, deionized water, and anhydrous ethanol are stirred in a mass ratio of 30:70:8:2:1:3:1:5:20, and stirred at 72.5°C and 550 r / min for 2.5 h to obtain a low-temperature resistant, corrosion-resistant and easy-drying coating.

[0048] S5: Fix a PET substrate with a thickness of 0.06 mm in a polytetrafluoroethylene mold, pour a low-temperature resistant, corrosion-resistant and easy-drying coating into the mold so that it is evenly spread on the surface of the PET base film, evaporate the solvent under reduced pressure at 70°C, take it out after 25 hours to form a first film layer, and obtain a first film body; add tetraalkoxy titanate, tetraalkoxy silane and siloxane to deionized water and stir evenly to obtain a uniform reaction liquid, lay the first film body as a filter membrane in a funnel, pour the reaction liquid in and filter it, form a film on the surface of the first film body, and separate it from the filter paper to obtain the final corrosion-resistant, low-temperature resistant and easy-drying titanium-containing metal protective film.

[0049] Example 3

[0050] S1: Add 60g of rigid polyurethane to 800mL of deionized water and soak for 25h, then add 4g of asbestos and continue soaking for 60min to obtain a mixed slurry A; 30g of expanded perlite, 12g of lightweight ceramsite, 6g of phosphate, 4g of magnesium oxide powder, 2g of high-alumina cement, 2g of vermiculite, 4g of pyrotechnic acid stone and 600mL of tetraalkoxy titanate are stirred, mixed, dried, expanded, and ground to obtain a 300-mesh mixed powder B; 600mL of mixed slurry A and 30g of mixed powder B are put into a reactor, heated to 80°C under nitrogen protection, stirred at 600r / min for 30min, and then 5g of poly 4,4'-diphenylmethane diisocyanate is added, and stirring and foaming is continued for 3h. The mixture is naturally cooled to room temperature, poured into a mold and press-molded, and vacuum-dried at 80°C for 2h to obtain a modified rigid polyurethane composite thermal insulation material.

[0051] S2: Tetrabutyl titanate and anhydrous ethanol were added to the reactor in a mass ratio of 1:5, stirred at 25°C and 600 r / min for 20 minutes, and transferred to a sealed tube filled with oxygen. One end of the sealed tube was connected to a piston that generated linear reciprocating motion by the rotation of an eccentric wheel. The eccentric wheel rotated at a speed of 70 r / min for 3 hours, heated to 160°C, and continued to rotate for 20 hours. The mixture was transferred to a radiation source with a temperature of 6°C and a dose rate of 100 Gy / min and irradiated for 12 minutes. The mixture was filtered, and the filter cake was washed with deionized water three times and vacuum dried at 80°C for 2 hours to obtain low-temperature resistant porous hollow microspheres.

[0052] S3: 30 g of methacrylic acid, 8 g of deionized water, 2 g of sodium lauryl sulfate, and 3 g of alkylphenol polyoxyethylene ether were added to a reactor, emulsified at 11,000 r / min for 20 min, and then 0.2 g of ammonium persulfate was added, and stirring was continued for 20 min to obtain a pre-emulsion; 6 g of sodium lauryl sulfate, 4 g of ammonium bicarbonate, 8 g of deionized water, and 50 g of the pre-emulsion were added to a reactor, stirred at 75°C and 600 r / min for 30 min, and then 0.2 g of ammonium persulfate was added, and stirring was continued for 2 h. The temperature was lowered to 45°C, and ammonia water was added to adjust the pH value to 7. The mixture was filtered and distilled at a vacuum degree of -0.06 MPa and 80°C for 7 h to obtain a polymethacrylic acid emulsion.

[0053] S4: Nano-titanium-doped tin dioxide, polymethacrylate emulsion, modified rigid polyurethane composite insulation material, low-temperature resistant porous hollow microspheres, aniline black, dispersant BYK-161, dibutyltin dilaurate, deionized water, and anhydrous ethanol are stirred in a mass ratio of 30:70:8:2:1:3:1:5:20, and stirred at 75°C and 600 r / min for 3 h to obtain a low-temperature resistant, corrosion-resistant and easy-drying coating.

[0054] S5: Fix a PET substrate with a thickness of 0.06 mm in a polytetrafluoroethylene mold, pour a low-temperature resistant, corrosion-resistant and easy-drying coating into the mold so that it is evenly spread on the surface of the PET base film, evaporate the solvent under reduced pressure at 80°C, take it out after 25 hours to form a first film layer, and obtain a first film body; add tetraalkoxy titanate, tetraalkoxy silane and siloxane to deionized water and stir evenly to obtain a uniform reaction liquid, lay the first film body as a filter membrane in a funnel, pour the reaction liquid in and filter it, form a film on the surface of the first film body, and separate it from the filter paper to obtain a corrosion-resistant, low-temperature resistant, easy-drying titanium-containing metal protective film.

[0055] Comparative examples: control group (ordinary epoxy resin coating, no titanium added), experimental group 1 (epoxy resin + 5% nano-titanium dioxide, cured at 150°C after spraying), experimental group 2 (tetrabutyl titanate ethanol solution immersion film formation), experimental group 3 (organic titanium-polyurethane composite coating).

[0056] 1. Corrosion resistance test: The prepared corrosion-resistant, low-temperature resistant, easy-to-dry titanium-containing metal protective film was ultrasonically cleaned with acetone and ethanol for 15 minutes each to remove oil stains, and then immersed in 10% dilute hydrochloric acid for 2 minutes for acid etching activation, rinsed with deionized water and dried. During verification, sample A was placed in a salt spray test chamber and sprayed with 5% NaCl solution according to ASTM B117 standard, and sprayed continuously at 35°C for 72 hours. After the end, the surface rust area was quantitatively analyzed under a microscope, and the corrosion area was required to be less than 5%. At the same time, another group of samples B was immersed in 3.5% NaCl solution, and the polarization curve and impedance spectrum were measured with an electrochemical workstation to calculate the corrosion current density (the target value was less than 1×10-6A / cm 2 ) and impedance modulus (higher than 1×104Ω·cm 2 ).

[0057] 2. Low temperature resistance test: A low temperature resistant titanium metal protective film was selected, and the pretreatment steps were the same as those for the corrosion resistance test. The coating was applied by dipping (pulling speed 2mm / s), and group C was cured at room temperature for 24 hours, and group D was cured at 150°C for 1 hour. The coated samples were placed in a -40°C low temperature box and frozen for 24 hours, then returned to room temperature (25°C), and this cycle was repeated 5 times. After the low temperature cycle, the adhesion was immediately tested using a grid knife according to the ASTM D3359 standard. The film layer was required to be free of peeling (adhesion ≥ 4B), and the surface was observed for cracks using a scanning electron microscope (SEM).

[0058] 3. Drying test: The substrate pretreatment was the same as above. The surface drying time (no adhesion when lightly touched with a finger) and the actual drying time (performance test) of Group E at room temperature were recorded, with the targets of <30 minutes and <2 hours respectively. Group F was exposed to ultraviolet light (365nm, 100mW / cm 2 ) was irradiated for 1 minute for curing, and the surface roughness of the film after drying was detected using an atomic force microscope (AFM) (the Ra value needed to be <50 nm).

[0059] Here are the results:

[0060] 1. Corrosion resistance comparison: By comparison, it was found that the corrosion current density of the control group was as high as 2.5×10-5A / cm 2 After 72 hours of salt spray test, the corrosion area reached 40%, while the corrosion current density of experimental group 1 was reduced to 6.8×10-7A / cm due to the dense barrier effect of nano-TiO2. 2 , the corrosion area after salt spray is less than 5%; although the corrosion current density of the titanate hydrolysis film in experimental group 2 is slightly higher (1.2×10-6A / cm 2), but still outperformed the control group. Wear resistance tests showed that the control group failed after only 500 abrasions under a 100g load. The nano-titanium dioxide composite coating in experimental group 1 could withstand only minor scratches after 2000 abrasions, attributed to the stress-dispersing effect of the hard nanoparticles. Due to the flexibility of the polyurethane matrix, the wear resistance of experimental group 3 was slightly inferior to that of experimental group 1 (localized peeling after 1500 abrasions), but it was still significantly better than the control group.

[0061] 2. Comparison of Low-Temperature Resistance: The control group's adhesion dropped from 2B to 1B at -40°C. However, the organic titanium-polyurethane film in Experimental Group 3 maintained a stable adhesion of 4B due to the low-temperature toughening properties of the polyurethane segments, making it suitable for polar regions or cold storage environments. In terms of process adaptability, the titanate film in Experimental Group 2 had a surface dry time of only 1.5 hours, making it suitable for quick construction scenarios, but exhibited weak long-term acid resistance. Experimental Group 1 required high-temperature curing, making it suitable for highly weatherable industrial equipment, but at a higher cost.

[0062] Application example 1: Anti-corrosion of offshore platform steel structures

[0063] The carbon steel supports on an offshore oil platform were exposed to high salt spray and high humidity for extended periods. A nano-TiO2 composite coating (experimental group 1) was used for protection. During construction, a uniform film (approximately 50 μm thick) was formed by high-pressure spraying. After curing at 150°C, the platform was put into service. The results are as follows:

[0064] Salt spray test (1000h): No rust on the surface, corrosion area <3% (the corrosion area of the epoxy coating in the control group reached 45%).

[0065] Electrochemical impedance spectroscopy (3.5% NaCl solution): impedance modulus up to 1.2×10 5 Ω·cm 2 , which was 2 orders of magnitude higher than that of the control group;

[0066] Adhesion: The film showed no peeling after the 100-grid knife test (5B grade), and no cracks were observed after 2 years of service under SEM observation.

[0067] This coating significantly extends the life of steel structures and reduces maintenance costs through the dense barrier of nano-titanium dioxide and the photocatalytic decomposition of salt properties.

[0068] Application Example 2: Aluminum Alloy Low-Temperature Protection for Polar Research Stations

[0069] The aluminum alloy cabin of the Antarctic research station is prone to brittle cracking at extremely low temperatures of -50°C. An organic titanium-polyurethane composite coating (experimental group 3) was used for protection. After coating and curing at room temperature for 24 hours, the film thickness reached approximately 40μm. The results are as follows:

[0070] (1) Low temperature cycle test (-50℃-25℃, 20 times): Adhesion maintains 4B grade, SEM shows no surface cracks;

[0071] (2) Impact resistance (-50℃): The film layer does not fall off after the falling ball impact test (1kg, 1m height);

[0072] (3) Resistance to UV aging (3000h): After adding anti-UV additives, the color difference ΔE < 2, and the gloss retention rate > 90%.

[0073] This coating solves the low-temperature embrittlement problem through the synergistic toughening of organic titanium and polyurethane, ensuring the long-term reliability of polar equipment.

[0074] Application Example 3: Rapid Repair Coating for Automotive Parts

[0075] A car manufacturer used a titanate hydrolyzed membrane (experimental group 2) to repair local scratches on a gearbox housing. The membrane was applied by dipping the damaged area, followed by a heat treatment at 80°C for 1 hour and surface drying. The results are as follows:

[0076] (1) Drying efficiency: surface drying time is only 40 minutes, actual drying time is 1.2 hours (traditional epoxy coatings require more than 4 hours);

[0077] (2) Wear resistance (simulated driving vibration): After 500h bench test, the wear scar depth is <5μm (the original coating is 15μm);

[0078] (3) Oil resistance (immersed in gear oil for 30 days): The film layer does not swell or fall off, and the adhesion remains 4B.

[0079] This solution utilizes the rapid film-forming properties of titanate to achieve efficient maintenance while meeting the wear and oil resistance requirements of mechanical parts.

[0080] Application example 4: Acidic medium protection for chemical pipelines

[0081] The carbon steel pipelines in a chemical plant were exposed to a 10% sulfuric acid solution for a long period of time. A titanium-silane composite coating (derived from the experimental group) was applied. After spraying and curing at 200°C, an inorganic-organic hybrid film was formed. The results are as follows:

[0082] (1) Acid corrosion resistance (10% H2SO4, 30 days): corrosion rate <0.01mm / year (bare steel is 1.5mm / year);

[0083] (2) Temperature resistance (20℃-150℃ cycle): The film has no blistering or peeling;

[0084] (3) XRD analysis: The coating contains anatase-type titanium dioxide and a siloxane network, forming a stable chemically inert barrier.

[0085] The coating significantly improves its service life in acidic environments through titanium-silicon synergistic passivation and avoids the risk of pipeline leakage.

[0086] The above application cases show that:

[0087] (1) Corrosion-resistant scenarios: Nano-titanium dioxide coatings are suitable for harsh environments such as marine and chemical industries due to their density and self-cleaning effect;

[0088] (2) Low temperature scenario: Organic titanium-polyurethane composite film solves the problem of low-temperature embrittlement of metals by making the molecular chain flexible;

[0089] (3) Rapid maintenance scenario: Titanate coating meets the needs of rapid industrial construction with its efficient film-forming properties.

[0090] Test data validates the advantages of titanium-containing protective films in key performance indicators such as adhesion, environmental aging resistance, and mechanical strength, providing a reliable basis for their engineering application. In practical applications, the formulation should be optimized based on the media type, temperature range, and process conditions, and the film's health should be regularly assessed through electrochemical monitoring or microscopic characterization.

[0091] It should be noted that, in this document, terms such as "comprises", "includes" or any other variations thereof are intended to cover non-exclusive inclusion, so that a process, method, article or apparatus that includes a series of elements includes not only those elements, but also other elements not explicitly listed, or also includes elements that are inherent to such process, method, article or apparatus.

[0092] While the embodiments of the present invention have been shown and described, it will be apparent to those skilled in the art that various changes, modifications, substitutions, and alterations can be made to the embodiments without departing from the principles and spirit of the invention.

Claims

1. A method for preparing a corrosion-resistant, low-temperature-resistant, and easy-drying titanium-containing metal protective film, characterized in that: The steps include: Step 1: nano-titanium-doped tin dioxide, polymethacrylate emulsion, modified rigid polyurethane composite insulation material, low-temperature resistant porous hollow microspheres, aniline black, dispersant BYK-161, dibutyltin dilaurate, deionized water, and anhydrous ethanol are stirred in a mass ratio of 30:70:8:2:1:3:1:5:20, and stirred at 70-75°C and 500-600r / min for 2-3h to obtain a low-temperature resistant, corrosion-resistant and easy-drying coating; Step 2: Fix a PET substrate with a thickness of 0.06 mm in a polytetrafluoroethylene mold, pour a low-temperature resistant, corrosion-resistant and easy-drying coating into the mold so that it is evenly spread on the surface of the PET base film, evaporate the solvent under reduced pressure at 60-80°C for 25 hours, and then take it out to form a first film layer on the PET base film to obtain a first film body, add tetraalkoxy titanate, tetraalkoxy silane and siloxane to deionized water and stir evenly to obtain a uniform reaction liquid, lay the first film body in a funnel as a filter membrane, pour the reaction liquid in and filter it, form a film on the surface of the first film body, separate it with filter paper, and obtain a finished product.

2. The method for preparing a corrosion-resistant, low-temperature-resistant, and easy-drying titanium-containing metal protective film according to claim 1, characterized in that: The polymethacrylic acid emulsion described in step 1 is prepared by the following steps: Add sodium lauryl sulfate, ammonium bicarbonate, deionized water and pre-emulsion into a reactor, stir at 70-75°C and 500-600 r / min for 20-30 min, then add ammonium persulfate, continue stirring for 1-2 h, cool to 40-45°C, add ammonia water to adjust the pH value to 6-7, filter, and distill at a vacuum degree of -0.08 to -0.06 MPa and 60-80°C for 6-7 h to obtain a polymethacrylic acid emulsion.

3. The method for preparing a corrosion-resistant, low-temperature-resistant, and easy-drying titanium-containing metal protective film according to claim 2, characterized in that: The mass ratio of the sodium lauryl sulfate, ammonium bicarbonate, deionized water, pre-emulsion and ammonium persulfate is 5-6g: 3-4g: 7-8g: 40-50g: 0.1-0.2g.

4. The method for preparing a corrosion-resistant, low-temperature-resistant, and easy-drying titanium-containing metal protective film according to claim 2, characterized in that: The pre-emulsion is prepared by the following steps: Add methacrylic acid, deionized water, sodium lauryl sulfate and alkylphenol polyoxyethylene ether into a reaction kettle, emulsify at 10000-11000 r / min for 10-20 minutes, then add ammonium persulfate and continue stirring for 10-20 minutes to obtain a pre-emulsion.

5. The method for preparing a corrosion-resistant, low-temperature-resistant, and easy-drying titanium-containing metal protective film according to claim 4, characterized in that: The mass ratio of the methacrylic acid, deionized water, sodium lauryl sulfate, alkylphenol polyoxyethylene ether and ammonium persulfate is 25-30:7-8:1-2:2-3:0.1-0.

2.

6. The method for preparing a corrosion-resistant, low-temperature-resistant, and easy-drying titanium-containing metal protective film according to claim 1, characterized in that: The modified rigid polyurethane composite thermal insulation material described in step 1 is prepared by the following steps: Add rigid polyurethane to deionized water and soak for 20-25 hours, then add asbestos and continue soaking for 30-60 minutes to obtain mixed slurry A; stir and mix expanded perlite, lightweight ceramsite, phosphate, magnesium oxide powder, high-alumina cement, vermiculite, pyrope and tetraalkoxy titanate as a low-temperature modifier, dry, expand, grind and pulverize to obtain mixed powder B of 200-300 mesh; The mixed slurry A and the mixed powder B are put into a reactor, heated to 50-80°C under nitrogen protection, stirred at 500-600 r / min for 20-30 min, and then poly 4,4'-diphenylmethane diisocyanate is added. The mixture is stirred and foamed for 2-3 hours, cooled naturally, poured into a mold, press-formed, and vacuum-dried to obtain a modified rigid polyurethane composite insulation material.

7. The method for preparing a corrosion-resistant, low-temperature-resistant, and easy-drying titanium-containing metal protective film according to claim 6, characterized in that: The usage ratio of the rigid polyurethane, deionized water and asbestos is 50-60g:700-800mL:3-4g; the usage ratio of the mixed slurry A, the mixed powder B and poly-4,4'-diphenylmethane diisocyanate is 500-600mL:20-30g:4-5g.

8. The method for preparing a corrosion-resistant, low-temperature-resistant, and easy-drying titanium-containing metal protective film according to claim 6, characterized in that: The usage ratio of the expanded perlite, lightweight ceramsite, phosphate, magnesium oxide powder, high-alumina cement, vermiculite, pyroxene and tetraalkoxy titanate is 20-30g: 10-12g: 5-6g: 3-4g: 1-2g: 1-2g: 3-4g: 500-600mL.

9. The method for preparing a corrosion-resistant, low-temperature-resistant, and easy-drying titanium-containing metal protective film according to claim 1, characterized in that: The low-temperature-resistant porous hollow microspheres described in step 1 are prepared by the following steps: Tetrabutyl titanate and anhydrous ethanol are added into a reaction kettle in a mass ratio of 1:5, stirred at 20-25°C and 500-600 r / min for 10-20 minutes, and transferred into a sealed tube filled with oxygen. One end of the sealed tube is connected to a piston that generates linear reciprocating motion by the rotation of an eccentric wheel. The eccentric wheel is rotated at a speed of 60-70 r / min for 2-3 hours, heated to 150-160°C, and continued to rotate for 18-20 hours. The reaction kettle is transferred to a radiation source with a CO2 content of 6°C and a dose rate of 100 Gy / min for 10-12 minutes, filtered, washed, and vacuum dried to obtain low-temperature resistant porous hollow microspheres.

10. A corrosion-resistant, low-temperature-resistant, and easy-drying titanium-containing metal protective film, characterized in that: Prepared by the preparation method according to any one of claims 1 to 9.

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