A method for preparing titanium-based non-stick cookware

Abstract

This application discloses a method for preparing titanium-based non-stick cookware, belonging to the field of cookware manufacturing technology. The method for preparing titanium-based non-stick cookware includes the following steps: (1) degreasing, cleaning, and drying the titanium-based pot body; (2) placing the titanium-based pot body obtained in step (1) in a first electrolyte for a first micro-arc oxidation to form a first micro-arc oxide film; (3) polishing the titanium-based pot body obtained in step (2), and then placing it in a second electrolyte for a second micro-arc oxidation to form a second micro-arc oxide film; the first electrolyte includes silicates, phosphates, titanium salts, and metal salts, and the second electrolyte includes silicates, phosphates, metal salts, and antibacterial particles; titanium ions are formed in the titanium salts in the first electrolyte; and silver or copper ions are formed in the antibacterial particles in the second electrolyte. This preparation method can improve the non-stick cookware's resistance to discoloration, non-stick properties, and hardness, and the two-stage micro-arc oxidation process can also improve the consistency of non-stick properties.

Description

Technical Field

[0001] This application relates to a method for preparing titanium-based non-stick cookware, belonging to the field of cookware manufacturing technology. Background Technology

[0002] Pure titanium cookware generally suffers from poor resistance to discoloration, insufficient substrate hardness, and inadequate anti-stick properties, resulting in overall performance issues that need improvement. To enhance the anti-stick properties of pure titanium cookware, a fluoropolymer coating is often applied to the surface of the pure titanium substrate. However, fluoropolymer coatings suffer from weak substrate adhesion, low hardness, and poor wear resistance, making them prone to scratches, peeling, and flaking during long-term cooking. They are also susceptible to aging, degradation, discoloration, and loss of gloss under high temperatures. Furthermore, the fluoropolymer coating lacks sufficient temperature stability, potentially leading to the release of harmful substances at high temperatures and limitations in food contact safety.

[0003] The ceramic coating suffers from drawbacks such as low hardness and easy wear. It also has problems such as high brittleness, poor thermal shock resistance, weak bonding between the coating and the titanium substrate, easy cracking and peeling, and limited processing and forming. Both traditional modification schemes are difficult to simultaneously meet the comprehensive needs of cookware for long-term non-stick, high hardness, wear resistance, discoloration resistance and safety and durability.

[0004] Existing technologies include micro-arc oxidation to generate zirconia / titanium oxide ceramic films on titanium-based cookware to improve the wear resistance of titanium-containing cookware. However, its anti-discoloration performance cannot be effectively improved, and micro-interface separation can occur between the zirconia and titanium oxide ceramic films, making it difficult to improve non-stick consistency. Furthermore, current micro-arc oxidation processes also involve sealing the ceramic film, which improves its density but results in limited improvement in anti-stick and antibacterial properties.

[0005] Therefore, there is an urgent need for a preparation process that can effectively improve the anti-discoloration, hardness, and anti-stick properties of pure titanium cookware. Summary of the Invention

[0006] To address the aforementioned issues, a method for preparing titanium-based non-stick cookware is provided. This method generates rutile-type dark titanium dioxide ceramic on the surface of the titanium-based cookware, which not only improves its resistance to discoloration but also enhances its non-stick properties and hardness. Furthermore, the two-stage micro-arc oxidation process generates more uniform pores to improve the consistency of non-stick coating.

[0007] This application provides a method for preparing titanium-based non-stick cookware, comprising the following steps: (1) The titanium-based pot body is degreased, cleaned, and dried; (2) The titanium-based pot body obtained in step (1) is placed in the first electrolyte to undergo micro-arc oxidation to form the first micro-arc oxide film; (3) Polish the titanium-based pot body obtained in step (2), and then place it in the second electrolyte for secondary micro-arc oxidation to form a second micro-arc oxide film; The first electrolyte includes silicates, phosphates, titanium salts, and metal salts, and the second electrolyte includes silicates, phosphates, metal salts, and antibacterial particles; the metal salt is selected from at least one of sodium salt, potassium salt, and calcium salt; the titanium salt in the first electrolyte forms titanium ions; and the antibacterial particles in the second electrolyte form silver ions or copper ions.

[0008] To prevent cracking in the micro-arc oxidation ceramic layer and ensure its growth rate, this application employs a two-stage micro-arc oxidation process on the titanium-based cookware body. The first stage of micro-arc oxidation forms a rutile titanium dioxide matrix, while the second stage yields a first and a second micro-arc oxidation film with different pore distributions. This two-stage micro-arc oxidation process improves the density and uniformity of the pores in both the first and second micro-arc oxidation films, thereby enhancing the oil retention capacity of the non-stick cookware surface and improving its non-stick properties.

[0009] Currently, in the process of generating oxide films through micro-arc oxidation, the generated titanium dioxide is anatase, which has problems such as insufficient thermodynamic stability and poor high-temperature aging and discoloration resistance. At the same time, the structure of anatase titanium dioxide is loose, and it is prone to crystal transformation and large volume change at high temperatures, which leads to easy cracking of the oxide film.

[0010] In the above preparation method, adding titanium salt to the first electrolyte provides sufficient raw materials for the nucleation of rutile titanium dioxide, increasing the precipitation probability of rutile titanium dioxide. Even if no titanium salt is added to the second electrolyte after the formation of the first micro-arc oxide film, it can still induce the formation of rutile titanium dioxide in the second micro-arc oxide film on the titanium plate substrate, making the first and second micro-arc oxide films dark ceramic, thereby significantly improving the anti-discoloration properties of non-stick cookware. Furthermore, reducing the titanium ion concentration in the second electrolyte can prevent the deposition of antibacterial particles. In addition, compared to anatase titanium dioxide, rutile titanium dioxide has lower surface energy, higher hardness, and thermochemical stability, which can simultaneously improve the non-stick properties, scratch resistance, and high-temperature anti-aging and discoloration capabilities of titanium-based non-stick cookware.

[0011] The addition of antibacterial particles to the second electrolyte can give non-stick cookware good antibacterial properties. Antibacterial ions are evenly distributed in the second micro-arc oxidation film and on the surface of the non-stick cookware along with the formation of the second micro-arc oxidation film, which can improve the antibacterial consistency of the non-stick cookware.

[0012] Optionally, the concentrations of silicate and phosphate in the first electrolyte are both 5-30 g / L, and the concentrations of silicate and phosphate in the second electrolyte are both 5-30 g / L.

[0013] Specifically, the concentrations of silicate and phosphate in the first electrolyte are selected from any concentrations between 5 g / L, 8 g / L, 10 g / L, 11 g / L, 12 g / L, 13 g / L, 14 g / L, 15 g / L, 16 g / L, 17 g / L, 18 g / L, 19 g / L, 20 g / L, 23 g / L, 25 g / L, 28 g / L, and 30 g / L; and the concentrations of silicate and phosphate in the second electrolyte are selected from any concentrations between 5 g / L, 8 g / L, 10 g / L, 11 g / L, 12 g / L, 13 g / L, 14 g / L, 15 g / L, 16 g / L, 17 g / L, 18 g / L, 19 g / L, 20 g / L, 23 g / L, 25 g / L, 28 g / L, and 30 g / L.

[0014] The micro-arc oxidation process in this application utilizes an electrolyte in which silicates promote outward film growth by providing a large amount of film-forming material instantaneously, while phosphates promote inward film growth, generating compounds with high density that can participate in the formation of the substrate oxide. Therefore, silicates determine the film thickness, while phosphates determine the film density and adhesion. When the concentrations of silicates and phosphates in the electrolyte are set to the same value, a microscopic balance is achieved between the outward deposition and inward metallurgical bonding of the pot body, resulting in a more balanced corrosion resistance and wear resistance on the pot surface.

[0015] The concentrations of silicates and phosphates mentioned above can ensure the moderate stability of the electrolyte system, avoiding the loosening and pulverization of the first and second micro-arc oxide films caused by a strongly alkaline environment; at the same time, the intensity of the micro-arc discharge reaction is controlled to promote the formation of dense and uniform rutile titanium dioxide on the titanium surface, which synergistically enhances the wear resistance, high-temperature discoloration resistance and anti-stick properties of the non-stick pan, and can also reduce electrolyte ablation failure, improve process controllability and production repeatability.

[0016] Optionally, the metal salt is selected from NaOH and / or K2CO3. The addition of the above metal salt can reduce the phase transformation activation energy of titanium dioxide and accelerate the transformation of the anatase phase to the rutile phase, so as to form a micro-arc oxide film of rutile titanium dioxide.

[0017] Preferably, the metal salt is NaOH with a concentration of 0.1-0.3 mol / L.

[0018] Specifically, the concentration of NaOH is selected from 0.1 mol / L, 0.15 mol / L, 0.2 mol / L, 0.25 mol / L, 0.3 mol / L, and any concentration between these values.

[0019] The concentration of NaOH mentioned above can both adjust the pH of the electrolyte and provide Na+. + Furthermore, it can ensure the consistency of the micro-arc oxidation film growth rate.

[0020] Optionally, the titanium ions formed by the titanium salt in the first electrolyte are tetravalent titanium ions (Ti). 4+ The titanium salt is at least one of Ti(SO4)2, TiCl4, (NH4)2TiF6, K2TiF6, and Na2TiF6. Optionally, the concentration of titanium salt in the first electrolyte is 0.03-0.3 mol / L.

[0021] Specifically, the concentration is selected from 0.03 mol / L, 0.05 mol / L, 0.06 mol / L, 0.07 mol / L, 0.08 mol / L, 0.09 mol / L, 0.1 mol / L, 0.15 mol / L, 0.2 mol / L, 0.25 mol / L, 0.3 mol / L, and any concentration between these values.

[0022] The titanium salt added in this application forms titanium ions in the first electrolyte. Within the aforementioned titanium salt concentration range, the concentration of titanium ions in the first electrolyte is sufficient, providing ample raw materials for the nucleation of the rutile phase, increasing its precipitation probability, and effectively improving the density of the film after the first micro-arc oxidation. If the titanium salt concentration is too low, the amount of rutile titanium dioxide generated in the first and second micro-arc oxidation films will be low, weakening the sealing effect on the pores of the pot body. It will not significantly affect the improvement of the corrosion resistance and wear resistance of the first and second micro-arc oxidation films, mainly leading to a decrease in the non-stick properties and high-temperature discoloration resistance of the cookware. If the titanium salt concentration is too high, the excessively high titanium salt concentration will cause a sharp increase in the conductivity of the electrolyte, thereby increasing the porosity of the film layer, surface roughness, causing destructive ablation, and affecting the film-substrate bonding strength, reducing the adhesion of the first micro-arc oxidation film.

[0023] Because this application uses a titanium-based pot, which has stable performance, the micro-arc oxidation electrolyte of pure silicate and phosphate systems produces a mild spark, but the energy is insufficient to support a deep phase transition. Therefore, in the TiO2 generated in situ by micro-arc oxidation, the amorphous and anatase phases dominate the film. The anatase phase is a metastable phase, and the transformation from the anatase phase to the high-temperature stable rutile phase requires extremely high local activation energy, typically requiring a macroscopic ambient temperature of 600℃-800℃. In this application, the addition of titanium salt to the first electrolyte not only allows it to directly participate in film formation as an exogenous titanium source, but also strongly alters the plasma discharge dynamics, rapidly transforming the micro-arc discharge from dense small sparks to a strong arc with high-energy large sparks. The local microscopic temperature of these high-energy arcs provides the absolute thermal energy for the anatase-to-rutile phase transition. Therefore, the first micro-arc oxidation film prepared in this application is a dark rutile phase titanium dioxide. In the presence of the first micro-arc oxide film of rutile phase, even if no titanium salt is added to the second electrolyte, the second micro-arc oxide film will be induced to tend to form rutile phase titanium dioxide.

[0024] Optionally, the antibacterial particles are Ag3PO4 particles, and the concentration of the Ag3PO4 particles is 5-40 g / L.

[0025] Specifically, the concentration of the Ag3PO4 particles is selected from 5 g / L, 10 g / L, 15 g / L, 20 g / L, 25 g / L, 30 g / L, 35 g / L, 40 g / L, and any concentration between these values.

[0026] Preferably, the concentration of the Ag3PO4 particles is 10-20 g / L.

[0027] Ag3PO4 particles form silver ions in the second electrolyte, giving the non-stick cookware an antibacterial silver ion coating and providing it with excellent antibacterial properties. The concentration of Ag3PO4 particles ensures both the antibacterial properties of the non-stick cookware and improves the adhesion between the first and second micro-arc oxidation films, preventing delamination of the non-stick cookware.

[0028] Optionally, the second electrolyte further includes EDTA-2Na, wherein the Ag3PO4 particles contain Ag + The molar ratio with EDTA-2Na is less than 1.

[0029] Specifically, the Ag3PO4 particles contain Ag + The molar ratio with EDTA-2Na is selected from any value between 0.01, 0.05, 0.1, 0.15, 0.2, 0.25, 0.3, 0.35, 0.4, 0.45, 0.5, 0.55, 0.6, 0.65, 0.7, 0.75, 0.8, 0.85, 0.9, 0.95, and 0.99.

[0030] The EDTA-2Na (disodium ethylenediaminetetraacetate) added to the second electrolyte stabilizes silver ions through complexation, preventing premature precipitation and thus improving the dispersion uniformity of silver ions in the second micro-arc oxidation film. This allows for uniform dispersion along the thickness of the film, enhancing the antibacterial uniformity and durability of the non-stick cookware. (Ag in Ag3PO4 particles) + If the molar ratio of EDTA-2Na to Ag is greater than 1, the discharge intensity cannot be effectively suppressed, thus weakening the effect on Ag. + Electrophoretic migration regulation, reducing Ag + This reduces deposition efficiency, thereby decreasing the density of the film.

[0031] Optionally, the voltage for a single micro-arc oxidation is 350-500V, the oxidation time is 20-30min, and the bath temperature is 20-40℃. The voltage for secondary micro-arc oxidation is 500-650V, the oxidation time is 5-15min, and the bath temperature is 20-40℃.

[0032] The voltage of the secondary micro-arc oxidation is higher than that of the primary micro-arc oxidation, which increases the formation rate of the second micro-arc oxidation film and enhances the micro-arc discharge energy. It also optimizes the crystal composition and microstructure of titanium dioxide, making the porosity of the second micro-arc oxidation film higher than that of the first micro-arc oxidation film.

[0033] Specifically, the voltage for one micro-arc oxidation is selected from any voltage between 350V, 360V, 370V, 380V, 400V, 410V, 420V, 430V, 440V, 450V, 460V, 470V, 480V, 490V, and 500V; the time for one micro-arc oxidation is selected from any time between 20min, 21min, 22min, 23min, 24min, 25min, 26min, 27min, 28min, 29min, and 30min; and the bath temperature is selected from any temperature between 20℃, 21℃, 22℃, 23℃, 24℃, 25℃, 26℃, 27℃, 28℃, 29℃, 30℃, 31℃, 32℃, 33℃, 34℃, 35℃, 36℃, 37℃, 38℃, 39℃, and 40℃.

[0034] Specifically, the voltage for secondary micro-arc oxidation is selected from any voltage between 500V, 510V, 520V, 530V, 540V, 550V, 560V, 570V, 580V, 590V, 600V, 610V, 620V, 630V, 640V, and 650V; the time for secondary micro-arc oxidation is selected from any time between 5min, 6min, 7min, 8min, 9min, 10min, 11min, 12min, 13min, 14min, and 15min; and the bath temperature is selected from any temperature between 20℃, 21℃, 22℃, 23℃, 24℃, 25℃, 26℃, 27℃, 28℃, 29℃, 30℃, 31℃, 32℃, 33℃, 34℃, 35℃, 36℃, 37℃, 38℃, 39℃, and 40℃.

[0035] Optionally, at least a portion of the surface of the titanium-based pot body in step (1) is provided with a plurality of protrusions, and a recessed area is formed between adjacent protrusions; After polishing in step (3), the first micro-arc oxide film on the raised surface is removed. After secondary micro-arc oxidation, the raised surface is provided with a second micro-arc oxide film. The surface of the recessed area includes the second micro-arc oxide film and the first micro-arc oxide film from top to bottom.

[0036] Optionally, the raised and recessed areas are formed by embossing, etching or laser engraving processes, preferably by embossing.

[0037] The aforementioned raised and recessed areas serve several purposes: first, the raised areas act as a spatula and the recessed areas, improving the adhesion of the first and second micro-arc oxide films in the recessed areas; second, the raised areas divide the titanium-based cookware body, enhancing stress dispersion and reducing the risk of localized deformation and cracking; and third, the recessed areas can function as oil storage areas during non-stick cookware use, storing and evenly releasing oil during cooking to form a uniform lubricating oil film, significantly improving the non-stick performance of the cookware and enabling low-oil cooking, preventing scorching, and easy cleaning.

[0038] Optionally, before step (1), the pot body substrate is formed into the titanium-based pot body by embossing process, and the protrusions are continuous patterns so that the recessed area forms multiple segmented independent regions; after secondary micro-arc oxidation, the recessed area forms multiple segmented independent double-film regions of the second micro-arc oxidation film plus the first micro-arc oxidation film.

[0039] The second micro-arc oxidation film formed by the secondary micro-arc oxidation process in this application can further improve the non-stick performance of non-stick cookware, but it may suffer from reduced adhesion. This application addresses this by using raised sections to divide the recessed area into several independent spaces, which significantly improves the anti-peeling performance of the second micro-arc oxidation film and extends the service life of the non-stick cookware. Furthermore, this method can also disperse stress, reduce the risk of cracking in the oxide film layer on the surface of the non-stick cookware, and extend its service life.

[0040] Optionally, the pot body substrate can be preheated to 500-600℃ and held for 5-10 minutes before embossing.

[0041] Pure titanium pot substrates exhibit significant elastic deformation. Direct embossing can lead to issues such as noticeable springback in the embossed patterns, low dimensional accuracy, and poor contour clarity. Furthermore, it can easily cause localized stress concentration on the substrate, resulting in microcracks and damaging the surface structure of the titanium-based pot. This reduces the bonding strength between the subsequent first and second micro-arc oxide films and the titanium-based pot, increasing the risk of delamination and peeling. Therefore, preheating before embossing improves the processing performance and accuracy of the pot substrate, reduces stress concentration, and facilitates the adhesion of the first and second micro-arc oxide films.

[0042] Optionally, the oxide film thickness of the single-film region on the raised surface is 5-20 μm, the oxide film thickness of the double-film region on the recessed region is 15-70 μm, and the single-film region and the double-film region on the surface of the titanium-based pot are arranged alternately.

[0043] The thickness of the oxide film on the raised surface is the thickness of the second micro-arc oxide film formed on the raised surface through a secondary micro-arc oxidation process. The thickness of the oxide film in the recessed area is the total thickness of the first and second micro-arc oxide films. The above thickness setting can ensure that the non-stick cookware has the best non-stick properties, anti-discoloration properties, hardness and adhesion, and significantly extend the service life of the non-stick cookware.

[0044] Specifically, the oxide film thickness of the single-film region on the raised surface is 5μm, 6μm, 7μm, 8μm, 9μm, 10μm, 11μm, 12μm, 13μm, 14μm, 15μm, 16μm, 17μm, 18μm, 19μm, 20μm, or any thickness between these values.

[0045] Specifically, the oxide film thickness in the double-film region of the recessed area is 15μm, 20μm, 25μm, 30μm, 35μm, 40μm, 45μm, 50μm, 55μm, 60μm, 65μm, 70μm, or any thickness between these values.

[0046] Optionally, after one micro-arc oxidation, the first micro-arc oxidation film has a porosity of φ1, and after polishing in step (3), the second micro-arc oxidation film on the raised surface has a porosity of φ2, and the second micro-arc oxidation film on the surface of the recessed area has a porosity of φ3, wherein φ1 < φ3 and φ2 < φ3.

[0047] In this application's two-stage micro-arc oxidation process, the porosity of the second micro-arc oxidation film is higher than that of the first micro-arc oxidation film, and the porosity of the second micro-arc oxidation film is also more uniform. This improves the oil retention capacity of the non-stick cookware surface, thereby enhancing its non-stick performance. The secondary micro-arc oxidation process, by creating larger porosity in the recessed areas, further enhances the oil retention and anti-stick properties of the non-stick cookware. In addition, the porosity of the raised areas is smaller than that of the second micro-arc oxidation film in the recessed areas, which improves the heat transfer efficiency of the raised areas and enhances the heating uniformity of the non-stick cookware.

[0048] Specifically, the value of φ1 ranges from 5% to 30%, φ2 varies depending on the polishing process, and the value of φ3 ranges from 10% to 60%.

[0049] Optionally, the polishing in step (3) includes rough polishing, fine polishing and finishing.

[0050] Preferably, the coarse polishing uses 120# soft cloth-based ceramic sandpaper, the fine polishing uses 180# soft cloth-based ceramic sandpaper, and the finishing uses a scouring pad.

[0051] Optionally, the degreasing in step (1) is performed by ultrasonic treatment with an alkaline cleaning agent, and the cleaning is performed by rinsing with clean water.

[0052] The treatment in step (1) can ensure the cleanliness of the surface of the titanium-based pot, so as to ensure the adhesion of the first micro-arc oxide film and the second micro-arc oxide film.

[0053] Optionally, the steps also include: (4) Anneal the titanium-based pot body obtained in step (3); place the titanium-based pot body into the annealing equipment at room temperature, the annealing process adopts a preset heating rate, after reaching the preset annealing temperature, maintain the annealing temperature for the preset annealing time, and take out the titanium-based pot body after naturally cooling down to room temperature to form the titanium-based non-stick cookware.

[0054] This application describes an annealing treatment of non-stick cookware with a first micro-arc oxide film and a second micro-arc oxide film. This process promotes the complete transformation of residual anatase titanium dioxide in the first and second micro-arc oxide films into rutile titanium dioxide, thereby improving the non-stick cookware's anti-discoloration properties, hardness, and anti-stick properties. After annealing, the titanium-based cookware is naturally cooled to room temperature and then removed. This process stabilizes the microstructure of the first and second micro-arc oxide films and prevents changes in the oxidizing atmosphere from affecting the phase structure of the titanium dioxide.

[0055] Optionally, the preset heating rate of the annealing process is 5-10℃ / min, the preset annealing temperature is 600-800℃, and the preset annealing time is 1-3h.

[0056] The preset heating rate of the annealing process enables slow heating, preventing stress cracking of the first and second micro-arc oxide films and improving the adhesion between the first and second micro-arc oxide films in the recessed area. The aforementioned annealing temperature and time can improve the conversion efficiency and uniformity of titanium dioxide from the anatase phase to the rutile phase, thereby improving the quality uniformity of non-stick cookware.

[0057] Specifically, the preset heating rate of the annealing process is 5℃ / min, 6℃ / min, 7℃ / min, 8℃ / min, 9℃ / min, 10℃ / min, or any heating rate between these values; the preset annealing temperature is 600℃, 620℃, 640℃, 660℃, 680℃, 700℃, 720℃, 740℃, 760℃, 780℃, 800℃, or any temperature between these values; and the preset annealing duration is 1h, 15h, 2h, 2.5h, 3h, or any time between these values.

[0058] The beneficial effects of this application include, but are not limited to: 1. According to the preparation method of titanium-based non-stick cookware of this application, the two-stage micro-arc oxidation process improves the density and uniformity of the pores of the first and second micro-arc oxidation films, thereby improving the oil retention of the non-stick cookware surface and thus improving the non-stick performance of the non-stick cookware.

[0059] 2. According to the preparation method of titanium-based non-stick cookware of this application, titanium salt is added to the first electrolyte so that the first micro-arc oxidation film and the second micro-arc oxidation film form rutile titanium dioxide, thereby simultaneously improving the non-stick properties, scratch resistance and high-temperature anti-aging and discoloration ability of the titanium-based non-stick cookware.

[0060] 3. According to the preparation method of titanium-based non-stick cookware of this application, the addition of antibacterial particles in the second electrolyte can endow the non-stick cookware with good antibacterial properties, and the antibacterial ions are evenly distributed in the second micro-arc oxidation film and on the surface of the non-stick cookware along with the formation of the second micro-arc oxidation film, which can improve the antibacterial consistency of the non-stick cookware.

[0061] 4. According to the preparation method of the titanium-based non-stick cookware of this application, the raised and recessed areas can divide the micro-arc oxide film and isolate the spatula from the micro-arc oxide film, thereby dispersing stress and improving the adhesion of the first and second micro-arc oxide films. This, in turn, improves the service life of the non-stick cookware.

[0062] 5. According to the preparation method of titanium-based non-stick cookware of this application, annealing the non-stick cookware with the first micro-arc oxide film and the second micro-arc oxide film can promote the complete transformation of the anatase phase titanium dioxide remaining in the first micro-arc oxide film and the second micro-arc oxide film into rutile phase titanium dioxide, thereby improving the non-stick cookware's anti-discoloration performance, hardness and anti-stick performance. Attached Figure Description

[0063] The accompanying drawings, which are included to provide a further understanding of this application and form part of this application, illustrate exemplary embodiments and are used to explain this application, but do not constitute an undue limitation of this application. In the drawings: Figure 1 This is a schematic diagram of the structure of the non-stick cookware involved in Embodiment 7 of this application.

[0064] Figure 2 This is a porosity test diagram of the non-stick cookware surface obtained in step (2) of Embodiment 1 of this application.

[0065] Figure 3 This is a porosity test diagram of the non-stick cookware surface obtained in step (3) of Embodiment 1 of this application.

[0066] Figure 4 This is an appearance drawing of the non-stick cookware of Comparative Example 7 of this application.

[0067] Figure 5 This is a test diagram of the non-stick cookware used in Example 1 of this application to demonstrate the non-stick properties of fried eggs.

[0068] Figure 6 This is a test diagram of the non-stick cookware used in Example 6 of this application to demonstrate the non-stick properties of fried eggs.

[0069] Figure 7 This is a test image of the non-stick cookware used in Comparative Example 3 of this application to demonstrate the non-stick properties of fried eggs.

[0070] Figure 8 This is a test diagram of the non-stick cookware used in Comparative Example 5 of this application to demonstrate the non-stick properties of fried eggs.

[0071] Figure 9 This is an image of the non-stick cookware after its anti-discoloration test according to Embodiment 7 of this application.

[0072] Figure 10 This is a picture of the non-stick cookware of Comparative Example 1 after the anti-discoloration test.

[0073] List of components and reference numerals: 1. A raised area; 2. A recessed area. Detailed Implementation

[0074] The present application is described in detail below with reference to the embodiments, but the present application is not limited to these embodiments.

[0075] Unless otherwise specified, the raw materials used in the embodiments and comparative examples of this application were all purchased commercially.

[0076] Unless otherwise specified, the methods used in the embodiments and comparative examples of this application are conventional methods in the prior art.

[0077] The degreasing and cleaning of the titanium-based pot body in the following embodiments and comparative examples are as follows: The titanium-based pot body was ultrasonically treated with an alkaline cleaning agent for 10 minutes, and then rinsed with clean water three times after treatment.

[0078] The polishing in step (3) of the following examples and comparative examples includes rough polishing, fine polishing and finishing. Rough polishing uses 120# soft cloth-based ceramic sandpaper, fine polishing uses 180# soft cloth-based ceramic sandpaper, and finishing uses a scouring pad.

[0079] Example 1 This embodiment relates to a method for preparing titanium-based non-stick cookware, characterized by comprising the following steps: (1) The titanium-based pot body is degreased, cleaned, and dried; (2) The titanium-based pot obtained in step (1) is placed in the first electrolyte for a first micro-arc oxidation to form a first micro-arc oxidation film; the first electrolyte includes silicate, phosphate, Ti(SO4)2 and NaOH, the concentration of silicate is 10 g / L, the concentration of phosphate is 20 g / L, the concentration of Ti(SO4)2 is 0.1 mol / L, the concentration of NaOH is 0.1 mol / L, the voltage of the first micro-arc oxidation is 350 V, the oxidation time is 30 min, and the temperature of the bath is 40 °C; (3) Polish the titanium-based pot body obtained in step (2), and then place it in the second electrolyte for secondary micro-arc oxidation to form a second micro-arc oxidation film; the second electrolyte includes silicate, phosphate, NaOH and Ag3PO4 antibacterial particles, the concentration of silicate is 10 g / L, the concentration of phosphate is 20 g / L, the concentration of NaOH is 0.1 mol / L, the concentration of Ag3PO4 antibacterial particles is 15 g / L, the voltage of secondary micro-arc oxidation is 500 V, the oxidation time is 15 min, and the temperature of the bath is 40 °C.

[0080] Example 2 This embodiment relates to a method for preparing titanium-based non-stick cookware, characterized by comprising the following steps: (1) The titanium-based pot body is degreased, cleaned, and dried; (2) The titanium-based pot body obtained in step (1) is placed in the first electrolyte for a single micro-arc oxidation to form a first micro-arc oxidation film. The first electrolyte includes silicate, phosphate, TiCl4 and NaOH. The concentration of silicate is 20 g / L, the concentration of phosphate is 10 g / L, the concentration of TiCl4 is 0.05 mol / L, and the concentration of NaOH is 0.3 mol / L. The voltage of the single micro-arc oxidation is 500 V, the oxidation time is 20 min, and the temperature of the bath is 20 °C. In this embodiment, the concentration of silicate is higher than that of phosphate, which promotes the pot body to have a higher growth rate and a thicker outer film layer with higher hardness. The surface hardness is high, and the wear resistance, drop resistance and discoloration resistance are better.

[0081] (3) Polish the titanium-based pot body obtained in step (2), and then place it in the second electrolyte for secondary micro-arc oxidation to form a second micro-arc oxidation film; the second electrolyte includes silicate, phosphate, NaOH and CuSO4 antibacterial particles, the concentration of silicate is 20 g / L, the concentration of phosphate is 10 g / L, the concentration of NaOH is 0.3 mol / L, the concentration of Ag3PO4 antibacterial particles is 5 g / L, the voltage of secondary micro-arc oxidation is 650 V, the oxidation time is 5 min, and the temperature of the bath is 20 °C.

[0082] Example 3 The difference between this embodiment and Example 1 is that the concentration of titanium salt Ti(SO4)2 is selected as 0.05 mol / L, and the concentration of Ag3PO4 particles is 40 g / L.

[0083] Example 4 The difference between this embodiment and Embodiment 1 is that the second electrolyte also includes EDTA-2Na, and the Ag3PO4 particles contain Ag. + The molar ratio of EDTA-2Na to EDTA-2Na is 0.99, and the rest is the same as in Example 1.

[0084] Example 5 The difference between this embodiment and Embodiment 1 is that the second electrolyte also includes EDTA-2Na, and the Ag3PO4 particles contain Ag. + The molar ratio of EDTA-2Na to EDTA-2Na is 0.01, and the rest is the same as in Example 1.

[0085] Example 6 refer to Figure 1 The difference between this embodiment and embodiment 4 is that, before step (1), a large-tonnage hydraulic press (6000T) is used to apply pressure to the surface of the pot body substrate sheet to emboss and form a titanium-based pot body, so that the surface of the titanium-based pot body is provided with several protrusions 1, and a recessed area 2 is formed between adjacent protrusions 1. The protrusions 1 are continuous patterns, so that the recessed area 2 forms multiple segmented independent areas. After polishing in step (3), the first micro-arc oxide film on the surface of the protrusions 1 is removed. After secondary micro-arc oxidation, the surface of the protrusions 1 is provided with a second micro-arc oxide film. The recessed area 2 forms multiple segmented independent double-film areas of the second micro-arc oxide film plus the first micro-arc oxide film. The rest is the same as in embodiment 1.

[0086] Example 7 The difference between this embodiment and embodiment 6 is that it also includes the following steps: (4) Anneal the titanium-based pot body obtained in step (3); place the titanium-based pot body into the annealing equipment at room temperature, and use a preset heating rate of 5℃ / min for the annealing process. After reaching the preset annealing temperature of 800℃, maintain the annealing temperature for the preset annealing time of 1h. After the titanium-based pot body is naturally cooled to room temperature, it is taken out to form a titanium-based non-stick cookware. The rest is the same as in Example 7.

[0087] Example 8 The difference between this embodiment and embodiment 7 is that it also includes the following steps: (4) Anneal the titanium-based pot body obtained in step (3); place the titanium-based pot body into the annealing equipment at room temperature, and use a preset heating rate of 10℃ / min for the annealing process. After reaching the preset annealing temperature of 600℃, maintain the annealing temperature for the preset annealing time of 3h. After the titanium-based pot body is naturally cooled to room temperature, it is taken out to form a titanium-based non-stick cookware. The rest is the same as in Example 7.

[0088] Example 9 The difference between this embodiment and Example 4 is that the amount of EDTA-2Na added is increased, and the Ag in the Ag3PO4 particles is increased. + The molar ratio of EDTA-2Na to EDTA-2Na is 1.2, and the rest is the same as in Example 4.

[0089] Comparative Example 1 The difference between this comparative example and Example 1 is that step (3) is omitted, while the rest is the same as Example 1.

[0090] Comparative Example 2 The difference between this comparative example and Comparative Example 1 is that, before step (1), the pot body substrate is formed into a titanium-based pot body through an embossing process. At least part of the surface of the titanium-based pot body is provided with several protrusions, and a recessed area is formed between adjacent protrusions. The protrusions are continuous patterns so that the recessed area forms multiple segmented independent regions. In step (3), only a polishing operation is performed, the first micro-arc oxide film on the surface of the protrusion is removed, and multiple segmented independent first micro-arc oxide film covered areas are formed in the recessed area. The rest is the same as Comparative Example 1.

[0091] Comparative Example 3 (New comparative example, no titanium salt added to the first electrolyte) The difference between this comparative example and Example 1 is that Ti(SO4)2 is not added to the first electrolyte, while the rest is the same as in Example 1.

[0092] Comparative Example 4 The difference between this comparative example and Example 1 is that the second electrolyte also includes Ti(SO4)2, and the concentration of Ti(SO4)2 is 0.1 mol / L. The rest is the same as in Example 1.

[0093] Comparative Example 5 The difference between this comparative example and Example 6 is that NaOH is not added to the first electrolyte, while the rest is the same as in Example 1.

[0094] Comparative Example 6 The difference between this comparative example and Example 1 is that Ag3PO4 antibacterial particles are not added to the second electrolyte; otherwise, it is the same as Example 1.

[0095] Comparative Example 7 The difference between this comparative example and Example 1 is that the Ag3PO4 particles in the second electrolyte are replaced with ZnCl2, while the rest is the same as in Example 1.

[0096] Comparative Example 8 The difference between this comparative example and Example 1 is that Ti(SO4)2 in the first electrolyte is replaced with K2ZrF6, while the rest is the same as in Example 1.

[0097] Comparative Example 9 The difference between this comparative example and Example 7 is that the preset annealing temperature is 500°C and the annealing time is maintained at the preset annealing temperature for 4 hours. The rest is the same as Example 7.

[0098] Comparative Example 10 The difference between this comparative example and Example 7 is that the preset heating rate is 15°C / min, and the annealing temperature is maintained at the preset annealing time for 50 minutes. The rest is the same as Example 7.

[0099] Comparative Example 11 The difference between this embodiment and Example 1 is that the concentration of Ti(SO4)2 is 0.4 mol / L, while the rest is the same as in Example 1.

[0100] Test Example 1: Non-stickiness test The non-stick cookware obtained from the above embodiments and comparative examples was subjected to non-stick performance testing. The test results are shown in Table 2. The specific test methods are as follows: Non-stick properties are divided into non-stick for fried eggs and non-stick for stir-frying, specifically: Non-stick properties of fried eggs: Spray soybean oil 5 times on the surface of the pan using an oil sprayer, spread it evenly on the inner surface of the pan, and when the inner surface is heated to 150℃-170℃, conduct 3 more fried egg tests. When the egg white is basically solidified, remove the egg and observe the egg residue. Determine the non-stick level according to the requirements of GB / T32095 for non-stick properties of fried eggs. Simulated stir-frying: Spray soybean oil 5 times on the surface of the pan using an oil sprayer, spread it evenly on the inner surface of the non-stick pan, and then stir-fry potato shreds to observe the sticking state. Determine the non-stick level according to Table 1 below.

[0101] Table 1

[0102] Table 2

[0103] Figure 2 This is a porosity test diagram of the non-stick cookware surface obtained in step (2) of Example 1. Figure 3 The porosity test diagram of the non-stick cookware surface obtained in step (3) of Example 1 is based on... Figure 2 and Figure 3 The comparison shows that the porosity of the second micro-arc oxidation film obtained by two micro-arc oxidations is higher than that of the first micro-arc oxidation film obtained by one micro-arc oxidation, and the pores of the second micro-arc oxidation film are more uniform. Figure 4 This is a picture of the non-stick cookware in Comparative Example 7. You can see that the surface of the cookware in this comparative example has rough micro-pores.

[0104] Furthermore, the porosity of the first micro-arc oxide film after the first micro-arc oxidation in Example 7 was tested, and the porosity φ1 was obtained for the surface porosity of the oxide film. After polishing in step (3), the porosity of the first micro-arc oxide film on the raised surface changed slightly, and the porosity φ2 was obtained. φ2 will vary depending on the cutting degree of the polishing process. Usually, the porosity decreases slightly after the polishing process. After the second micro-arc oxidation in step (3), the porosity of the surface of the second micro-arc oxide film on the surface of the recessed area was tested, and the porosity φ3 was obtained. The comparison concluded that φ1 < φ3 and φ2 < φ3. As for the material inside the oxide film, after the first micro-arc oxidation, the material inside the first micro-arc oxide film has a porosity φ1'. After polishing in step (3), the porosity φ2' inside the first micro-arc oxide film on the raised surface is not affected. After the second micro-arc oxidation in step (3), the material inside the second micro-arc oxide film on the surface of the recessed area has a porosity φ3'. φ1' > φ3' and φ2' > φ3'. In this embodiment, φ1 is 5%~30%, φ3 is 10%~60%; φ1' is 5%~20%, and φ3' is 3%~15%.

[0105] The cookware of this application, after the above-described process, exhibits a two-stage porosity expansion process on its outer surface. This expansion occurs as follows: after the first micro-arc oxidation process, the porosity increases; after polishing, the porosity decreases; and after the second micro-arc oxidation process, the outer surface becomes even more porous and uniform. Meanwhile, within the material of the first micro-arc oxidation film, the porosity increases after the first micro-arc oxidation process, remains unchanged after polishing, and then decreases after the second micro-arc oxidation process. The material deposition from the secondary micro-arc oxidation preferentially acts on the interior of the primary pores, creating a self-sealing effect within the first micro-arc oxidation film. Simultaneously, the energy release from the secondary micro-arc oxidation on the surface of the first micro-arc oxidation film creates a pore-expanding effect. The process of this application creates a gradient change in the porosity of the oxide film from large to small from the outside to the inside.

[0106] Figure 5 This is a test image of non-stick cookware used in Example 1 to demonstrate the non-stick properties of fried eggs. Figure 4 Achieve Grade I non-stick coating when frying eggs; Figure 6 This is a test image of non-stick cookware used in Example 6 to demonstrate the non-stick properties of fried eggs. Figure 6 Achieve Grade II non-stick coating when frying eggs; Figure 7 This is a test image showing the non-stick properties of non-stick cookware in Comparative Example 3, which demonstrates the non-stick properties of frying eggs. Figure 7 The fact that the egg stuck to the pan indicates that it failed the non-stick test for frying eggs. Figure 8 This is a test chart showing the non-stick properties of non-stick cookware in Comparative Example 5, which tests the non-stick properties of fried eggs. Figure 8 The fact that the egg stuck to the pan indicates that it failed the non-stick test for frying eggs.

[0107] Test Example 2 Antibacterial Test The non-stick cookware obtained in the above embodiments and comparative examples was subjected to antibacterial tests. The test results are shown in Table 3. The specific test methods are as follows: Antibacterial properties: The antibacterial rate of the cookware material surface after 24 hours of testing according to the film application method of GB / T2188 is evaluated as having antibacterial efficacy and reaching Class II antibacterial properties if the antibacterial rate against Escherichia coli and Staphylococcus aureus is ≥ 90%, and if the antibacterial rate is ≥ 99%, it is evaluated as having strong antibacterial efficacy and reaching Class I antibacterial properties.

[0108] Table 3

[0109] Test Example 3: Drop Resistance and Discoloration Resistance Test The non-stick cookware obtained in the above embodiments and comparative examples were subjected to drop resistance and discoloration resistance tests. The test results are shown in Table 4. The specific test methods are as follows: Drop resistance: Drop a pot containing a standard counterweight (such as a standard volume of water or steel shot) from a height of 0.8 meters to 1 meter onto the base plate and determine whether the pot body is obviously deformed, whether there are cracks, whether the handle is broken or detached, and whether there is water leakage at the joints.

[0110] Anti-discoloration test: Prepare two samples of the same material, one as a control sample, and place the other sample in a 250℃ oven for 30 minutes. After cooling, observe the color difference between the two samples under a standard light source.

[0111] Table 4

[0112] Figure 9 This is an appearance image of the non-stick cookware of Embodiment 7 after the anti-discoloration test. It can be seen that the non-stick cookware of Embodiment 7 has no obvious color difference. Figure 10 The image shows the appearance of the non-stick cookware of Comparative Example 1 after the color change test. It can be seen that the non-stick cookware of Comparative Example 1 has a significant color difference.

[0113] According to the test results of Examples 1-9 of this application, the non-stick cookware of this application has good non-stick properties, hardness, and anti-discoloration properties. In Example 1, the phosphate concentration of the first electrolyte and the second electrolyte is higher than the silicate concentration, which can promote the inward growth of the film layer in the pot body, reduce its porosity and make it more uniformly distributed, so as to ensure that the metal pot body forms a higher metallurgical structure, thereby significantly improving the corrosion resistance of the cookware.

[0114] A comparison of Examples 1 and 3 shows that increasing the concentration of antibacterial particles significantly improves antibacterial performance and also improves non-stickiness to some extent.

[0115] Based on the comparison between Examples 1 and Examples 4 and 5, it can be seen that Ag + The change in the molar ratio of EDTA-2Na mainly affects the antibacterial properties and can also affect the non-stick properties to some extent. However, according to the comparison between Examples 4 and 9, due to the active chemical properties of silver ions in the antibacterial particles, excessive EDTA-2Na will cause silver ions to deposit in the second electrolyte, making the electrolyte turbid and reducing its service life; at the same time, it will produce complexes of excessive silver ions, which will cause uneven pitting corrosion on the surface of the cookware during micro-arc discharge. Therefore, it is necessary to control the amount of Ag. + The molar ratio with EDTA-2Na is less than 1.

[0116] A comparison of Examples 4 and 6 shows that embossing the pot body can further improve the non-stick properties of the cookware and enhance the anti-peeling performance of the second micro-arc oxide film, thereby reducing the risk of cracking of the oxide film layer on the surface of the non-stick cookware.

[0117] A comparison of Examples 6 and 7 and 8 reveals that the micro-arc oxidation process, under high voltage, sintersects a ceramic layer in situ on the metal surface via plasma micro-arc discharge. This process results in the presence of a large amount of amorphous substances, metastable phases (such as anatase and brookite phases), and extremely high residual thermal stress in the ceramic layer. Therefore, annealing after micro-arc oxidation can drive the metastable phase to transform into the most thermodynamically stable crystalline phase (rutile phase), thus promoting inorganic non-metallic phase transformation. Especially when the cookware substrate uses a relatively soft titanium substrate, this significantly improves the lattice density of the cookware surface, optimizes the microscopic hardness and wear resistance of the cookware surface, and not only improves drop resistance but also significantly enhances non-stick properties.

[0118] According to the comparison between Example 1 and Comparative Example 1, without the secondary micro-arc oxidation in step (3), the surface of the non-stick cookware only has a single micro-arc oxidation film, which significantly reduces the non-stick and anti-discoloration effects of the non-stick cookware.

[0119] The comparison between Comparative Example 1 and Comparative Example 2 shows that when the cookware substrate is embossed, and the first micro-arc oxidation is followed by polishing to remove the first micro-arc oxidation film on the raised surface, the first micro-arc oxidation film only exists in the recessed area. Therefore, the non-stick and anti-discoloration effects of the cookware are stronger than those of Comparative Example 1, proving that the embossing operation can improve the non-stick and anti-discoloration properties of the cookware.

[0120] A comparison of Example 1 and Comparative Example 3 shows that without the addition of Ti(SO4)2 to the first electrolyte, the sealing effect on the micropores formed by the primary micro-arc oxidation film is weakened, resulting in a decrease in the porosity of the primary micro-arc oxidation film. This is detrimental to the formation of a pore size gradient from large to small from the outside to the inside in the non-stick cookware after the second micro-arc oxidation, thus reducing the non-stick performance. Furthermore, the absence of Ti(SO4)2 reduces the proportion of rutile phase titanium dioxide, leading to insufficient hardness in the non-stick cookware formed from the relatively soft titanium-based pot body. In the drop test, the pot body exhibited slight deformation.

[0121] As can be seen from the comparison between Example 1 and Comparative Example 4, since antibacterial particles are added to the second electrolyte, if Ti(SO4)2 is also added to the second electrolyte, the second electrolyte is prone to high conductivity, which leads to a large amount of antibacterial particles agglomerating and precipitating, reducing the content of substances adhering to and forming on the surface of the cookware. This not only wastes materials but also reduces the antibacterial properties of the non-stick cookware.

[0122] According to the comparison between Example 6 and Comparative Example 5, adding NaOH to the first electrolyte can effectively reduce the arc-starting voltage of the process. In Comparative Example 5, no NaOH was added, resulting in a weakened conductivity effect, which would cause poor quality phenomena such as local conductivity and uneven porosity on the surface of the cookware. Therefore, the effect was poor in the non-stick test.

[0123] As can be seen from the comparison between Example 1 and Comparative Example 6, the absence of Ag3PO4 antibacterial particles reduces the antibacterial performance of cookware, making it difficult to achieve a sustained antibacterial effect.

[0124] As can be seen from the comparison between Example 1 and Comparative Example 7, replacing Ag3PO4 particles with ZnCl2 can also achieve a good antibacterial effect. However, ZnCl2 has high corrosivity, which increases pitting corrosion on the titanium plate surface during micro-arc oxidation and significantly reduces the surface porosity uniformity, thus significantly reducing the non-stick properties.

[0125] As can be seen from the comparison between Example 1 and Comparative Example 8, zirconium salt was used to replace titanium salt in the first electrolyte because zirconium cannot be converted into simple free cations (such as Zr). 4+ While fluoride ions in potassium fluorozirconate (K2ZrF6) exist stably in their stable form, the high corrosiveness and toxicity resulting from the detachment of fluoride ions from the matrix make it unsuitable as a food contact material, and the waste liquid treatment would pose a significant environmental burden. Furthermore, ZrO2's hydrophilicity and oil-resistant properties are significantly weaker than TiO2, resulting in less non-stick cookware.

[0126] A comparison of Example 7 and Comparative Example 9 reveals that when alternative tests were conducted by lowering the annealing temperature and extending the annealing time, excessive grain growth was observed in the material, resulting in coarse internal grains. This significantly weakens the impact resistance of the cookware and, during subsequent hole-making processes on the sidewalls of the cookware, a "orange peel" defect is easily observed around the openings. Testing of the annealed samples from Comparative Example 9 showed that lowering the preset annealing temperature and extending the annealing time resulted in material deformation and leakage at the rivet connections of the cookware during drop tests, causing it to fail the drop test.

[0127] According to the comparison between Example 7 and Comparative Example 10, the faster the preset heating rate of the annealing process, the greater the temperature gradient between the surface of the cookware material and the center of the cookware when heat is transferred from the surface of the cookware to the center. This leads to asynchronous volume expansion of the inner and outer layers, which can easily cause defects such as increased internal thermal stress in the material. Therefore, in the drop test of the annealed sample of Comparative Example 10, there were slight cracks on the surface of the cookware.

[0128] As can be seen from the comparison between Example 1 and Comparative Example 11, increasing the concentration of titanium salt in the first electrolyte helps to achieve a better sealing deposition effect on the discharge micropores generated in the first micro-arc oxidation process in the second micro-arc oxidation process. However, excessively high titanium salt concentration will increase the conductivity of the electrolyte, easily causing local large arc ablation and poor surface porosity. At the same time, local huge thermal stress is prone to producing film cracks, resulting in poor surface film performance in the second micro-arc oxidation process, and thus significantly reduced non-stick properties.

[0129] The above description is merely an embodiment of this application, and the scope of protection of this application is not limited to these specific embodiments, but is determined by the claims of this application. Various modifications and variations can be made to this application by those skilled in the art. Any modifications, equivalent substitutions, improvements, etc., made within the technical concept and principles of this application should be included within the scope of protection of this application.

Claims

1. A method for preparing titanium-based non-stick cookware, characterized in that, Includes the following steps: (1) The titanium-based pot body is degreased, cleaned, and dried; (2) The titanium-based pot body obtained in step (1) is placed in the first electrolyte to undergo micro-arc oxidation to form the first micro-arc oxide film; (3) Polish the titanium-based pot body obtained in step (2), and then place it in the second electrolyte for secondary micro-arc oxidation to form a second micro-arc oxide film; The first electrolyte includes silicates, phosphates, titanium salts, and metal salts, and the second electrolyte includes silicates, phosphates, metal salts, and antibacterial particles; the metal salt is selected from at least one of sodium salt, potassium salt, and calcium salt; the titanium salt in the first electrolyte forms titanium ions; and the antibacterial particles in the second electrolyte form silver ions or copper ions.

2. The method for preparing titanium-based non-stick cookware according to claim 1, characterized in that, The titanium ions formed by the titanium salt in the first electrolyte are tetravalent titanium ions (Ti). 4+ The titanium salt is at least one of Ti(SO4)2, TiCl4, (NH4)2TiF6, K2TiF6, and Na2TiF6.

3. The method for preparing titanium-based non-stick cookware according to claim 1, characterized in that, The antibacterial particles are Ag3PO4 antibacterial particles, and the concentration of the Ag3PO4 antibacterial particles is 5-40 g / L.

4. The method for preparing titanium-based non-stick cookware according to claim 3, characterized in that, The second electrolyte also includes EDTA-2Na, and the Ag3PO4 antibacterial particles contain Ag + The molar ratio with EDTA-2Na is less than 1.

5. The method for preparing titanium-based non-stick cookware according to any one of claims 1-4, characterized in that, The titanium-based pot body in step (1) has at least a number of protrusions on a portion of its surface, and a recessed area is formed between adjacent protrusions; After polishing in step (3), the first micro-arc oxide film on the raised surface is removed. After secondary micro-arc oxidation, the raised surface is provided with a second micro-arc oxide film. The surface of the recessed area includes the second micro-arc oxide film and the first micro-arc oxide film from top to bottom.

6. The method for preparing titanium-based non-stick cookware according to claim 5, characterized in that, Before step (1), the pot body substrate is formed into the titanium-based pot body by embossing process, and the protrusions are continuous patterns so that the recessed area forms multiple segmented independent regions; After secondary micro-arc oxidation, the recessed area forms several separate dual-film regions consisting of a second micro-arc oxidation film and a first micro-arc oxidation film.

7. The method for preparing titanium-based non-stick cookware according to claim 6, characterized in that, The oxide film thickness of the single-film region on the raised surface is 5-20 μm, and the oxide film thickness of the double-film region in the recessed area is 15-70 μm. The single-film region and the double-film region on the surface of the titanium-based pot are arranged alternately.

8. The method for preparing titanium-based non-stick cookware according to claim 5, characterized in that, After one micro-arc oxidation, the surface of the first micro-arc oxidation film has a porosity of φ1. After polishing in step (3), the surface of the second micro-arc oxidation film on the raised surface has a porosity of φ2. After a second micro-arc oxidation in step (3), the surface of the second micro-arc oxidation film in the recessed area has a porosity of φ3, where φ1 < φ3 and φ2 < φ3.

9. The method for preparing titanium-based non-stick cookware according to any one of claims 1-4, characterized in that, It also includes the following steps: (4) Anneal the titanium-based pot body obtained in step (3); place the titanium-based pot body into the annealing equipment at room temperature, the annealing process adopts a preset heating rate, after reaching the preset annealing temperature, maintain the annealing temperature for the preset annealing time, and take out the titanium-based pot body after naturally cooling down to room temperature to form the titanium-based non-stick cookware.

10. The method for preparing the titanium-based non-stick cookware according to claim 9, characterized in that, The preset heating rate of the annealing process is 5-10℃ / min, the preset annealing temperature is 600-800℃, and the preset annealing time is 1-3h.

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