Modified glass glaze, preparation method thereof, heating component and aerosol generating device

Abstract

The invention relates to the technical field of surface modification, in particular to modified glass glaze and a preparation method thereof, a heating assembly and an aerosol generating device. The modified glass glaze comprises a glass glaze base body, a transition layer and an oleophobic layer which are sequentially stacked in the thickness direction, wherein the transition layer comprises amorphous zirconium silicate; the oleophobic layer comprises a mesoporous inorganic material and a fluorinated organic polymer, and pores of the mesoporous inorganic material are filled with at least part of the fluorinated organic polymer. The thermal expansion coefficient of the transition layer is moderate, so that the whole structure forms a thermal stress gradient buffer system, and the risk of stripping of the oleophobic layer is reduced. The nano confinement effect of the mesoporous inorganic material can significantly improve the decomposition temperature of the fluorinated organic polymer, so that the fluorinated organic polymer can exert oleophobic performance for a long time. Therefore, the modified glass glaze is high in structural stability and excellent in thermal shock resistance, keeps excellent oleophobic performance at a long-term high temperature all the time, effectively inhibits tobacco tar adsorption and carbonization residues, and reduces the risk of cracking of a glass glaze matrix.

Description

Technical Field

[0001] This application relates to the field of surface modification technology, and in particular to modified glass glaze and its preparation method, heating components, and aerosol generating devices. Background Technology

[0002] An aerosol generator is an electronic device that generates aerosols through heating. It typically includes a heating element, a power supply, and a control unit. The heating element is the core of the aerosol generator and mainly consists of heating components. These components form an aerosol upon contact with an atomizing matrix, which can be liquid and stored in a liquid reservoir, or solid, such as a vaporizer stick. One type of heating component uses a ceramic substrate with a glass glaze containing metal particles on its surface. The area where the glass glaze is electrically connected to the wires is called a pad. The glass glaze surface easily absorbs e-liquid. When the e-liquid carbonizes at high temperatures, it expands, causing the glass glaze, especially at the pads, to crack. Therefore, current technology often applies an oleophobic layer to the glass glaze surface at the pads.

[0003] However, the large difference in thermal expansion coefficients between the oleophobic layer and the glass glaze makes the oleophobic layer prone to cracking and peeling under long-term high temperature, affecting its oleophobic properties. Furthermore, these oleophobic layers may decompose under long-term high temperature, which will also affect their oleophobic properties. Summary of the Invention

[0004] The purpose of this application is to provide modified glass glaze and its preparation method, heating element, and aerosol generating device, aiming to solve the problems in the prior art where residual soot on the surface of glass glaze makes it prone to cracking at high temperatures, while the oleophobic layer is prone to cracking or decomposition at high temperatures.

[0005] To achieve the above-mentioned objectives, the technical solution adopted in this application is as follows: In a first aspect, this application provides a modified glass glaze, comprising a glass glaze matrix, a transition layer and an oleophobic layer sequentially stacked along the thickness direction; The transition layer includes amorphous zirconium silicate; The oleophobic layer comprises a mesoporous inorganic material and a fluorinated organic polymer, with at least a portion of the fluorinated organic polymer filling the pores of the mesoporous inorganic material.

[0006] This application modifies the glass glaze by introducing a transition layer containing amorphous zirconium silicate between the glass glaze matrix and the oleophobic layer. This material has a thermal expansion coefficient between that of the glass glaze matrix and the oleophobic layer, forming a thermal stress gradient buffer system. This effectively alleviates the mismatch in thermal expansion coefficients between the oleophobic layer and the glass glaze matrix, making the volume expansion of adjacent layers more matched at high temperatures. This significantly reduces interfacial thermal stress concentration and lowers the risk of the oleophobic layer peeling off from the glass glaze matrix during thermal cycling. Amorphous zirconium silicate also exhibits good compatibility with both the glass glaze matrix and the mesoporous inorganic materials in the oleophobic layer, which is beneficial for further improving the interfacial bonding strength between layers. The oleophobic layer contains fluorinated organic polymers, whose fluorination structure endows the material surface with extremely low surface energy, giving the oleophobic layer excellent oleophobic properties. The mesoporous inorganic materials contain a large number of mesoporous pores, providing nanoscale confinement space for the fluorinated organic polymers. This significantly increases the decomposition temperature of the fluorinated organic polymers, making them less prone to decomposition and failure under long-term high-temperature conditions, allowing the oleophobic layer to continuously maintain its oleophobic properties. In summary, this modified glass glaze exhibits high structural stability and excellent thermal shock resistance. The oleophobic layer can stably exert its oleophobic effect on the surface of the modified glass glaze for a long time, and it maintains excellent oleophobic properties even under long-term high temperatures. This effectively inhibits the adsorption and carbonization of soy oil residue and reduces the risk of cracking in the glass glaze matrix.

[0007] Optionally, the transition layer satisfies at least one of the following characteristics: (1) Fluorine is doped into amorphous zirconium silicate; (2) The coefficient of thermal expansion of the transition layer is 2.8 × 10⁻⁶. -6 / ℃~4.5×10 -6 / ℃; (3) The thickness of the transition layer is 1 μm to 5 μm.

[0008] Optionally, the oleophobic layer satisfies at least one of the following characteristics: (1) The pore size of mesoporous inorganic materials is 5 nm to 20 nm; (2) Mesoporous inorganic materials include at least one of mesoporous silica, mesoporous alumina, mesoporous titanium dioxide, and mesoporous zirconium dioxide; (3) The mass ratio of mesoporous inorganic material to fluorinated organic polymer is (1-5):1; (4) Fluorinated organic polymers include at least one of perfluoropolyether and polytetrafluoroethylene; (5) The weight-average molecular weight of the fluorinated organic polymer is 500 to 5000; (6) The coefficient of thermal expansion of the oleophobic layer is 0.8 × 10⁻⁶. -6 / ℃~2.5×10 -6 / ℃; (7) The porosity of the oleophobic layer is 10%–50%; (8) The thickness of the oleophobic layer is 5 μm to 50 μm; (9) The oleophobic layer contains encapsulated repair material.

[0009] Optionally, the encapsulated repair material includes encapsulated fluorosiloxanes; and / or, The encapsulated repair material has a particle size of 1 μm to 5 μm; and / or, The mass ratio of mesoporous inorganic material to the encapsulated repair material is (5–25):1; and / or, The coefficient of thermal expansion of the glass enamel substrate is 5 × 10⁻⁶. -6 / ℃~7×10 -6 / ℃; and / or, The glass glaze substrate and the transition layer are covalently bonded with siloxanes.

[0010] Secondly, this application provides a method for preparing a modified glass glaze, comprising the following steps: The raw materials, including zirconium silicate sol, are subjected to a first film-forming treatment and annealing treatment on the surface of a glass glaze substrate to form a transition layer; Raw materials including mesoporous inorganic materials and fluorinated organic polymers are formulated into a slurry. The slurry is then subjected to a second film-forming treatment on the surface of the transition layer away from the glass glaze substrate to form an oleophobic layer, resulting in a modified glass glaze comprising a glass glaze substrate, a transition layer, and an oleophobic layer stacked sequentially.

[0011] The preparation method of this application first involves subjecting the raw materials, including zirconium silicate sol, to a first film-forming treatment, which uniformly distributes fine zirconium silicate particles on the surface of the glass glaze substrate. Following this, an annealing treatment is performed, which facilitates further bonding and densification of the amorphous inorganic network formed by silicon, oxygen, and zirconium atoms, resulting in a dense transition layer including amorphous zirconium silicate. Next, mesoporous inorganic materials and fluorinated organic polymers are formulated into a slurry, with at least a portion of the fluorinated organic polymer filling the pores of the mesoporous inorganic material. A second film-forming treatment is then performed to form an oleophobic layer. Therefore, the modified glass glaze of this application can be obtained, which not only possesses excellent oleophobic properties but also resists cracking and peeling under high-temperature impact, exhibiting high structural stability and durability.

[0012] Optionally, the preparation of the zirconium silicate sol includes the following steps: preparing a mixed solution from raw materials comprising silicate esters, zirconium salts, and a first solvent, and carrying out a hydrolysis-condensation reaction to obtain zirconium silicate sol; wherein, The molar ratio of silicates to zirconium salts is (1–5):1; and / or, Silicates include at least one of tetraethyl orthosilicate, tetramethyl orthosilicate, and silicone resin prepolymers; and / or, Zirconium salts include at least one of zirconium oxychloride and zirconate chlorochloride; and / or, The first solvent includes a mixture of water and alcohol; and / or, The pH of the solution is 3–5; and / or, The raw materials for preparing the mixed solution also include fluorinated organosilanes; and / or, The temperature for the hydrolysis-condensation reaction is 40℃~80℃.

[0013] Optionally, fluorinated organosilanes include fluoropropyltriethoxysilanes; and / or, The molar ratio of silicate esters to fluorinated organosilicones is (2-4):1.

[0014] Optionally, prior to the first film-forming treatment, a step of surface treatment of the glass enamel substrate is further included; and / or, The first film-forming treatment includes at least one of spin coating, dip coating, and blade coating; and / or, The annealing temperature is 380℃~500℃.

[0015] Optionally, the surface treatment includes at least one of silane coupling treatment, acid treatment, alkali treatment, plasma surface treatment, and ion implantation treatment.

[0016] Optionally, the second solvent for preparing the slurry includes a supercritical fluid, and the second film-forming treatment includes at least one of atmospheric plasma spraying and ultrasonic spraying; and / or, The raw materials for preparing the slurry also include the repair material being encapsulated.

[0017] Thirdly, this application provides a heating component, including the modified glass glaze described above, or the modified glass glaze prepared by the preparation method described above.

[0018] The areas in the heating element of this application that use the aforementioned modified glass glaze exhibit high oleophobicity, effectively reducing e-liquid retention and lowering the risk of cracking of the glass glaze layer due to high-temperature carbonization of e-liquid. Simultaneously, under the impact of high-temperature cycling, the transition layer and oleophobic layer in the modified glass glaze are not prone to cracking or peeling, and can provide long-term oleophobic protection, improving the reliability and service life of the heating element.

[0019] Fourthly, this application provides an aerosol generating device, including the heating component described above.

[0020] The aerosol generator provided in this application includes the aforementioned heating component, which can heat the atomizing matrix into an aerosol. At high temperatures, the heating component maintains excellent oleophobic properties, effectively reducing e-liquid residue and high-temperature carbonization. Under cyclic thermal shock, the heating component also exhibits high structural stability and durability. Therefore, this aerosol generator possesses high reliability, safety, and a long service life. Attached Figure Description

[0021] To more clearly illustrate the technical solutions in the embodiments of this application, the drawings used in the description of the embodiments or the prior art will be briefly introduced below. Obviously, the drawings described below are only some embodiments of this application. For those skilled in the art, other drawings can be obtained based on these drawings without creative effort.

[0022] Figure 1 This is a schematic diagram of the structure of one side of the thick film heating tube in Embodiment 1 of this application; Figure 2 This is a schematic diagram of the structure of other sides of the thick film heating tube in Embodiment 1 of this application; Figure 3 This is a schematic diagram of the pad area in the thick film heating tube of Embodiment 1 of this application; Figure 4 This is a schematic diagram showing that the thick film heating element of Embodiment 1 of this application has no residual smoke or carbonized components after long-term use; Figure 5 This is a schematic diagram showing the residue of e-liquid and carbonized components in the thick film heating element of Comparative Example 3 after long-term use. Figure label: 1-Ceramic substrate; 2-Heating path; 3-Pad; 31-Glass glaze substrate; 32-Transition layer; 33-Oleophobic layer; 4-Wire. Detailed Implementation

[0023] To make the technical problems, technical solutions, and beneficial effects of this application clearer, the following detailed description is provided in conjunction with embodiments. It should be understood that the specific embodiments described herein are merely illustrative and not intended to limit the scope of this application.

[0024] In this application, the term "and / or" describes the relationship between related objects, indicating that three relationships can exist. For example, A and / or B can represent: A existing alone, A and B existing simultaneously, or B existing alone. A and B can be singular or plural. The character " / " generally indicates that the preceding and following related objects have an "or" relationship.

[0025] In this application, "at least one" means one or more, and "more than one" means two or more. "At least one of the following" or similar expressions mean any combination of these items, including any combination of single or multiple items.

[0026] It should be understood that in the various embodiments of this application, the order of the above processes does not imply the order of execution. Some or all steps may be executed in parallel or sequentially. The execution order of each process should be determined by its function and internal logic, and should not constitute any limitation on the implementation process of the embodiments of this application.

[0027] The weights of the relevant components mentioned in the embodiments of this application can refer not only to the specific content of each component, but also to the proportional relationship between the weights of the components. Therefore, any scaling up or down of the content of the relevant components according to the embodiments of this application is within the scope disclosed in the embodiments of this application. Specifically, the mass in the embodiments of this application can be a well-known unit of mass in the chemical industry, such as µg, mg, g, or kg.

[0028] The terms "first" and "second" are used for descriptive purposes only, to distinguish objects, such as substances, from one another, and should not be construed as indicating or implying relative importance or implicitly specifying the number of technical features indicated. For example, without departing from the scope of the embodiments of this application, a first feature may also be referred to as a second feature, and similarly, a second feature may also be referred to as a first feature. Thus, a feature defined with "first" and "second" may explicitly or implicitly include one or more of that feature.

[0029] An aerosol generator is an electronic device that generates aerosols through heating. It typically includes a heating element, a power supply, and a control unit. The heating element is the core of the aerosol generator and mainly consists of heating components. The atomizing matrix can be solid, similar to a cigarette holder, and is heated and atomized by the heating component to form an aerosol. Among these heating components, thick-film heating tubes are a new type of device that differs from traditional heating wire coils. They generally use a metal tube as the substrate, coating it with glass powder, and then printing conductive paste onto the glass enamel surface to form the resistive layer of the heating circuit. This is usually printed in a meandering heating path to increase resistance and heating area. After initial curing, another layer of glass enamel is sprayed on, and the tube is sintered at high temperature to obtain a complete heating tube. Because it features a finely customizable thick-film resistor, this heating device is called a thick-film heating tube or thick-film heating element.

[0030] The area where the resistive layer is electrically connected to the external conductors is called the solder pad. It is typically connected to the positive and negative terminals of the external conductors via brazing or similar methods, with the soldering point usually located at the center of the pad. Generally, two solder pads are used, and their size is usually wider than the heating path, making them more suitable for connecting to thicker conductors. The solder pads serve two purposes: firstly, they act as the starting and ending points of the glass glaze heating circuit, supplying power to the entire circuit; secondly, they physically fix the conductors, ensuring a stable connection to the thick-film heating element even under external impact. The solder pads are also made of glass glaze printed and sintered using the aforementioned paste. The paste composition prioritizes the conductivity and solderability of the glass glaze, often increasing the metal particle content, while the paste for the heating path focuses on creating a glass glaze with stable resistance and heating performance.

[0031] The contact angle of the glass enamel surface is approximately 60°, making it prone to absorbing e-liquid. After the e-liquid carbonizes at high temperatures, it forms carbon residue and expands in volume. The stress caused by this expansion easily leads to cracking of the brittle glass enamel, especially at the solder pads. Therefore, existing technologies often incorporate an oleophobic layer, such as a perfluoropolyether layer, on the glass enamel surface at the solder pads. However, based on user habits, aerosol generators are frequently subjected to intermittent heating, rapid heating followed by a pause, and then rapid reheating, resulting in the thick-film heating element being subjected to continuous high-temperature shocks. Furthermore, the coefficient of thermal expansion of the glass enamel is significantly higher than that of the oleophobic layer, with a difference exceeding 5 × 10⁻⁶. -6 The temperature range of 300℃ can cause the oleophobic layer to crack and peel under long-term high-temperature cycling, such as an interfacial peeling rate >30% after thermal cycling at 300℃. On the other hand, these oleophobic layers may decompose under long-term high-temperature exposure. Both of these factors affect the oleophobic properties, causing the glass enamel surface to be re-exposed to the e-liquid environment, making it prone to cracking or even bursting at high temperatures.

[0032] To address the aforementioned problems, a first aspect of this application provides a modified glass glaze. The modified glass glaze comprises a glass glaze matrix, a transition layer, and an oleophobic layer sequentially stacked along the thickness direction. The transition layer includes amorphous zirconium silicate; The oleophobic layer comprises a mesoporous inorganic material and a fluorinated organic polymer, with at least a portion of the fluorinated organic polymer filling the pores of the mesoporous inorganic material.

[0033] This application's modified glass glaze introduces an amorphous zirconium silicate transition layer between the glass glaze matrix and the oleophobic layer. This material's coefficient of thermal expansion falls between that of the glass glaze matrix and the oleophobic layer, forming a thermal stress gradient buffer system. This effectively alleviates the mismatch in the coefficients of thermal expansion between the oleophobic layer and the glass glaze matrix, making the volume expansion of adjacent layers more matched at high temperatures. This significantly reduces interfacial thermal stress concentration and lowers the risk of the oleophobic layer peeling off from the glass glaze matrix during thermal cycling. Amorphous zirconium silicate also exhibits good compatibility with both the glass glaze matrix and the mesoporous inorganic materials in the oleophobic layer, further enhancing the interfacial bonding strength between layers. The oleophobic layer contains fluorinated organic polymers, whose fluorination structure imparts extremely low surface energy, resulting in excellent oleophobic properties. The mesoporous inorganic materials contain numerous mesoporous pores, providing nanoscale confinement space for the fluorinated organic polymers. This significantly increases the decomposition temperature of the fluorinated organic polymers, making them less prone to decomposition and failure under long-term high-temperature conditions, allowing the oleophobic layer to continuously maintain its oleophobic properties. In summary, this modified glass glaze exhibits high structural stability and excellent thermal shock resistance. The oleophobic layer can stably exert its oleophobic effect on the surface of the modified glass glaze for a long time, and it maintains excellent oleophobic properties even under long-term high temperatures. This effectively inhibits the adsorption and carbonization of soy oil residue and reduces the risk of cracking in the glass glaze matrix.

[0034] The following will provide a detailed description of each layer in the modified glass glaze.

[0035] Regarding the glass glaze substrate.

[0036] The glass glaze matrix is ​​the main structure of the modified glass glaze, and its main components may include, but are not limited to, a glaze formed by a solid solution of at least one of silicon oxide, calcium oxide, and aluminum oxide. In some embodiments, the thickness of the glass glaze matrix may be 5 μm to 10 μm. In exemplary cases, it may include, but is not limited to, any value or a range between any two of 5 μm, 7 μm, 8 μm, and 10 μm. These thickness ranges can ensure the mechanical strength of the glass glaze matrix and are also beneficial to the uniformity of heat conduction.

[0037] In some embodiments, the coefficient of thermal expansion of the glass glaze substrate can be 5 × 10⁻⁶. -6 / ℃~7×10 -6 / ℃, which may include, but is not limited to, 5×10 -6 / ℃, 5.7×10 -6 / ℃, 6.3×10 -6 / ℃, 7×10 -6 The range of any value or any two values ​​in / ℃. When the existing oleophobic layer is directly bonded to the glass glaze substrate, the difference in thermal expansion coefficients can easily cause interfacial stress concentration, leading to peeling or cracking of the oleophobic layer and affecting the durability of its oleophobic properties. Therefore, this application further provides a transition layer.

[0038] Regarding the transition layer.

[0039] The transition layer in the modified glass glaze of this application is located between the glass glaze matrix and the oleophobic layer, and includes amorphous zirconium silicate. As stated above, its coefficient of thermal expansion is between that of the glass glaze matrix and the oleophobic layer, which can form a thermal stress gradient buffer system. Moreover, the material has good compatibility with the mesoporous inorganic materials in the glass glaze matrix and the oleophobic layer, reducing the risk of oleophobic layer peeling during thermal cycling.

[0040] From a material perspective, in some embodiments, amorphous zirconium silicate comprises an amorphous system formed by Zr, Si, and O, exhibiting a network structure with short-range order and long-range disorder. It is rich in bonding structures such as Zr-O-Zr, Si-O-Si, and Zr-O-Si, which gives the transition layer excellent thermal stability, chemical inertness, and a suitable coefficient of thermal expansion.

[0041] In some embodiments, amorphous zirconium silicate is doped with fluorine. Fluorine atoms have extremely high electronegativity; introducing fluorine helps reduce the surface energy of the material, significantly improving the oleophobicity of amorphous zirconium silicate, further protecting the glass enamel matrix, and reducing the possibility of soot penetration and residue. Introducing fluorine also helps improve the compatibility of the fluorinated organic polymers in the transition layer and the oleophobic layer, increasing the interfacial bonding strength between the transition layer and the oleophobic layer, and further reducing the risk of oleophobic layer peeling. In an exemplary embodiment, the doped fluorine exists in the amorphous zirconium silicate network in the form of covalent bonds such as FO. In an exemplary embodiment, the doped fluorine is mixed in the amorphous zirconium silicate network in the form of fluorocarbon compounds. In an exemplary embodiment, the molar percentage of fluorine in the various elements of amorphous zirconium silicate is 0.05% to 5%, and can be, but is not limited to, any value or a range between any two of 0.05%, 0.1%, and 0.2%. This doping amount helps the transition layer to maintain both high thermal stability and oleophobic properties.

[0042] Structurally, in some embodiments, the thickness of the transition layer is 1 μm to 5 μm, including but not limited to any value or a range between any two of 1 μm, 2 μm, 3 μm, and 5 μm. This thickness range ensures that the transition layer has sufficient mechanical strength to effectively buffer thermal stress, and also provides stable bonding with the glass enamel substrate and the oleophobic layer, without being too thick and increasing the accumulation of thermal stress, which could lead to cracking.

[0043] In some embodiments, the coefficient of thermal expansion of the entire transition layer can be 2.8 × 10⁻⁶. -6 / ℃~4.5×10 -6 / ℃, which may include, but is not limited to, 2.8×10 -6 / ℃, 3.5×10 -6 / ℃, 4.0×10 -6 / ℃, 4.5×10 -6The range of any value or any two values ​​of / ℃, this coefficient of thermal expansion has good matching with the glass glaze substrate and the oleophobic layer, which can effectively alleviate the problem of easy cracking and peeling of the oleophobic layer due to the difference in the coefficient of thermal expansion.

[0044] In some embodiments, the glass glaze substrate and the transition layer include siloxane covalent bonds, which helps to further improve the interfacial bonding strength between the glass glaze substrate and the transition layer, thereby improving the structural stability of the entire modified glass glaze and giving full play to the buffering effect of the transition layer between the glass glaze substrate and the oleophobic layer.

[0045] Regarding the oleophobic layer.

[0046] The oleophobic layer comprises mesoporous inorganic materials and fluorinated organic polymers. As mentioned above, fluorinated organic polymers possess excellent oleophobic properties. The mesoporous inorganic materials not only share similarities with the amorphous zirconium silicate material in the transition layer, exhibiting good compatibility, but also, due to their mesoporous structure, can effectively support a large amount of fluorinated organic polymers. Furthermore, the nano-confining effect significantly increases the decomposition temperature of the fluorinated organic polymers. In addition, the mesoporous inorganic materials alter the thermal expansion coefficient of the entire oleophobic layer. Compared to oleophobic layers containing only fluorinated organic polymers, this inorganic-organic system's thermal expansion coefficient is closer to that of the transition layer, which is more beneficial in reducing the risk of cracking and delamination during thermal cycling.

[0047] From a material perspective, the mesoporous inorganic material and the fluorinated organic material form a modified oleophobic material. At least some of the fluorinated organic material is bound in the pores of the mesoporous inorganic material. Here, "at least some" means that it can be completely bound in the pores of the mesoporous inorganic material, or some of the fluorinated organic material can be bound on the surface of the mesoporous inorganic material, or some of the fluorinated organic material can be bound between the particles of the mesoporous inorganic material, such as being dispersed in the oleophobic layer.

[0048] In some embodiments, the pore size of the mesoporous inorganic material is 5 nm to 20 nm, and may include, but is not limited to, any value or a range between any two of 5 nm, 10 nm, 15 nm, and 20 nm, with 10 nm being a possible choice. Mesoporous inorganic materials with these pore size ranges are advantageous for fully supporting fluorinated organic polymers and significantly improve the decomposition temperature of fluorinated organic polymers through nanoconfinement. If the pore size is too small, fluorinated organic polymers have difficulty entering the pores, limiting the load-bearing capacity; if the pore size is too large, the nanoconfinement effect weakens, which is detrimental to improving the thermal stability of fluorinated organic polymers.

[0049] In some embodiments, the mesoporous inorganic material includes at least one of mesoporous silica, mesoporous alumina, mesoporous titanium dioxide, and mesoporous zirconium dioxide, with mesoporous silica being the preferred choice. These mesoporous inorganic materials possess a highly ordered pore structure and a large specific surface area, enabling them to support a large amount of fluorinated organic polymers. Furthermore, through the nanoconfining effect, they significantly suppress the molecular chain breakage and oxidation reactions of fluorinated organic polymers at high temperatures, thereby significantly increasing the decomposition temperature of the fluorinated organic polymers and facilitating their long-term oleophobic properties.

[0050] In some embodiments, the mass ratio of mesoporous inorganic material to fluorinated organic polymer can be (1–5):1, including but not limited to any ratio or any two of 1:1, 2:1, 3:1, 4:1, and 5:1. These mass ratios are beneficial for fully supporting the fluorinated organic polymer in the mesoporous structure and maintaining the mechanical strength and thermal stability of the oleophobic layer. If the mass ratio of fluorinated organic polymer is too low, the fluorinated organic polymer content will be insufficient, weakening the oleophobic performance; if it is too high, it may clog the pores, affecting the nano-confining effect and reducing the overall adhesion of the coating. In addition, such a mass ratio is also beneficial for making the thermal expansion coefficient of the oleophobic layer closer to that of the transition layer, which is beneficial for improving the bonding strength between the oleophobic layer and the transition layer and reducing the risk of cracking and peeling of the oleophobic layer during thermal cycling.

[0051] In some embodiments, the fluorinated organic polymer includes at least one of perfluoropolyether and polytetrafluoroethylene, optionally perfluoropolyether (PFPE). These fluorinated organic polymers have high chemical stability and oleophobic properties. The fluorinated structure in their molecular chains endows the material with extremely low surface energy, resulting in a contact angle greater than 90°, thereby exhibiting excellent oleophobic properties. The perfluorinated structure in PFPE further enhances its oleophobic properties.

[0052] In some embodiments, the weight-average molecular weight of the fluorinated organic polymer is 500 to 5000, and may include, but is not limited to, any value or a range between any two of 500, 1500, 3000, 4000, and 5000, with 3000 being a possible value. Fluorinated organic polymers in this molecular weight range have moderate chain lengths, which can balance high oleophobicity and high thermal stability. If the molecular weight is too low, the long-term thermal stability of the fluorinated organic polymer decreases; if the molecular weight is too high, the fluorinated organic polymer is difficult to uniformly bind in the mesoporous inorganic material, affecting the nano-confining effect of the mesoporous inorganic material and hindering the improvement of the decomposition temperature of the fluorinated organic polymer.

[0053] In some embodiments, the oleophobic layer includes encapsulated repair material. When the temperature is too high, microcracks may form in the oleophobic layer. These encapsulated repair materials can be released under high-temperature shock, rapidly repairing the microcracks and maintaining the structural integrity and oleophobic properties of the oleophobic layer. In some embodiments, the particle size of the encapsulated repair material is 1 μm to 5 μm, including but not limited to any value or a range between any two of 1 μm, 2 μm, 3 μm, 4 μm, and 5 μm. Encapsulated repair materials with these particle sizes have suitable capacity, capable of storing and releasing an appropriate amount of repair material, without affecting the compactness and surface smoothness of the oleophobic layer due to excessively large particle sizes.

[0054] In some embodiments, the encapsulated repair material comprises encapsulated fluorosiloxane. Upon rupture of the encapsulation capsule, the fluorosiloxane flows out and promptly fills the microcracks, forming strong bonds with mesoporous inorganic materials at high temperatures to repair the cracks. Simultaneously, the fluorosiloxane's main chain consists of silicon-oxygen segments, and its side chains include fluorocarbon groups, endowing it with strong oleophobicity, ensuring that the repaired crack retains high oleophobicity.

[0055] In the example, the fluorosiloxane may include, but is not limited to, at least one of fluorinated polymethylsiloxane, fluorinated polysiloxane, fluorinated dimethylsiloxane, and polytetrafluoroethylene. In the example, the encapsulating material may include, but is not limited to, at least one of gelatin, hydroxypropyl methylcellulose, and polyvinyl alcohol. These materials exhibit good thermal responsiveness at high temperatures, enabling precise rupture and release of the repair material. Encapsulation effectively isolates the fluorosiloxane from the external environment, preventing premature release under normal use conditions and waste. It allows for controlled release under thermal shock, promoting rapid crack healing and maintaining long-term stability of the oleophobic layer under continuous thermal shock. In the example, the encapsulated repair material can release the repair agent to repair cracks when subjected to thermal shock above 300°C, rapidly repairing cracks with a width <10 μm.

[0056] In some embodiments, the mass ratio of mesoporous inorganic material to encapsulated repair material is (5-25):1, which may include, but is not limited to, any value or any two of 5:1, 10:1, 15:1, 20:1, and 25:1. This ratio maintains the role of mesoporous inorganic material and fluorinated organic polymer as the main body of the oleophobic layer, maintains high structural strength and oleophobicity, and also realizes the crack repair function under high temperature impact, which is beneficial to improving the long-term thermal stability of the oleophobic layer.

[0057] In some embodiments, the coefficient of thermal expansion of the entire oleophobic layer containing the above-described mesoporous inorganic material and fluorinated organic polymer is 0.8 × 10⁻⁶. -6 / ℃~2.5×10 -6 / ℃, which may include, but is not limited to, 0.8×10 -6 / ℃, 1.5×10 -6 / ℃, 2×10 -6 / ℃, 2.5×10 -6 The range of any value or any two values ​​of / ℃, the coefficient of thermal expansion has good matching with the transition layer, and can effectively alleviate the problem of easy cracking and peeling of the oleophobic layer due to the difference in thermal expansion coefficient.

[0058] In some embodiments, the porosity of the entire oleophobic layer can be 10% to 50%, including but not limited to any value or a range between any two of 10%, 20%, 30%, 40%, and 50%. Oleophobic layers with these porosity ranges are beneficial for reducing the penetration of e-liquid and for accommodating repair materials, enabling timely repair of cracks caused by thermal shock.

[0059] Structurally, in some embodiments, the thickness of the oleophobic layer is 5 μm to 50 μm, which may include, but is not limited to, any value or any two of 5 μm, 10 μm, 20 μm, 40 μm, and 50 μm. This thickness can effectively block the penetration of e-liquid and provide sufficient mechanical strength.

[0060] A second aspect of this application provides a method for preparing a modified glass glaze. The preparation method includes the following steps S10 to S20: S10: The raw materials, including zirconium silicate sol, are subjected to a first film-forming treatment and annealing treatment on the surface of the glass glaze substrate to form a transition layer; S20: The raw materials, including mesoporous inorganic materials and fluorinated organic polymers, are formulated into a slurry. On the surface of the transition layer away from the glass glaze substrate, the slurry is subjected to a second film-forming treatment to form an oleophobic layer, thereby obtaining a modified glass glaze comprising a glass glaze substrate, a transition layer and an oleophobic layer stacked sequentially.

[0061] The preparation method of this application first involves subjecting the raw materials, including zirconium silicate sol, to a first film-forming treatment, which uniformly distributes fine zirconium silicate particles on the surface of the glass glaze substrate. Then, annealing is performed to further bond and densify the amorphous inorganic network formed by silicon, oxygen, and zirconium atoms, resulting in a dense transition layer including amorphous zirconium silicate. Next, mesoporous inorganic materials and fluorinated organic polymers are formulated into a slurry, with at least a portion of the fluorinated organic polymer filling the pores of the mesoporous inorganic material. A second film-forming treatment is then performed to form an oleophobic layer. Therefore, the modified glass glaze of this application embodiment can be obtained, which not only possesses excellent oleophobic properties but also resists cracking and peeling under high-temperature impact, exhibiting high structural stability and durability.

[0062] Step S10 is the step of forming an oleophobic layer. The glass glaze matrix can be referred to the relevant description of the glass glaze matrix in the modified glass glaze section above. The preparation of zirconium silicate sol may include the following steps: A mixed solution consisting of silicate esters, zirconium salts, and a first solvent is prepared and subjected to a hydrolysis-condensation reaction to obtain zirconium silicate sol.

[0063] This preparation method facilitates the first hydrolysis of silicate esters into silicate monomers, as well as the ionization and hydrolysis of zirconium salts, followed by condensation reactions between silicate monomers. This, combined with the intercalation of zirconium ion hydrolysis products, forms abundant Zr-O-Zr, Si-O-Si, and Zr-O-Si covalent bond structures, resulting in fine amorphous zirconium silicate particles on a macroscopic scale. This allows the mixed solution to form a sol, which is beneficial for the uniform dispersion of zirconium silicate in the sol system.

[0064] In some embodiments, the molar ratio of silicate ester to zirconium salt is (1-5):1, which may include, but is not limited to, any ratio or any two of 1:1, 2:1, 3:1, 4:1, and 5:1. These molar ratios of raw materials ensure that the Zr, Si, and O elements in the generated amorphous zirconium silicate particles are within a suitable range, which is beneficial for the final transition layer to achieve the required coefficient of thermal expansion and mechanical strength.

[0065] In some embodiments, the silicate esters include at least one of tetraethyl orthosilicate, tetramethyl orthosilicate, and silicone resin prepolymers, with tetraethyl orthosilicate being the preferred choice. These silicate ester raw materials hydrolyze in solution to generate silicic acid monomers, which can subsequently condense to form an amorphous zirconium silicate network structure. In some embodiments, the zirconium salts include at least one of zirconium oxychloride and zirconate chlorochloride, with zirconium oxychloride being the preferred choice. These zirconium oxychloride raw materials ionize in water and hydrolyze to generate components such as ZrO(OH)2, which can provide a zirconium source and subsequently participate in the condensation reaction of silicic acid.

[0066] In some embodiments, the first solvent comprises a mixture of water and alcohol, wherein the alcohol may include ethanol, and the volume ratio of water to alcohol may be 1:(0.03–0.1). Water, as a reaction medium, can participate in hydrolysis, while alcohol facilitates the condensation of silicic acid with the zirconium source to form an amorphous zirconium silicate sol system. In some embodiments, the pH value of the solution is 3–5, and may include, but is not limited to, any value or a range between any two of 3, 3.5, 4, and 5. An acidic environment is more conducive to accelerating the hydrolysis of the raw materials and improving the efficiency of the hydrolysis-condensation reaction.

[0067] In some embodiments, the temperature of the hydrolysis-condensation reaction is 40°C to 80°C, and may include, but is not limited to, any value or a range between any two of 40°C, 50°C, 60°C, 70°C, and 80°C, with 60°C being a possible choice. This temperature range is beneficial for promoting a fully stable hydrolysis-condensation reaction while preventing violent solvent evaporation. In an exemplary example, the hydrolysis-condensation reaction can proceed for 12 h to 36 h, optionally 24 h, to allow the reaction to proceed fully and form a stable sol system.

[0068] In some embodiments, the raw materials for preparing the solution also include fluorinated organosilanes. The fluorinated organosilanes are first hydrolyzed to generate fluorinated organosilicon alcohols, which then participate in the condensation reaction of silicic acid and a zirconium source. The silanol groups are bonded to the main chain of zirconium silicate, while the fluorinated organosilane groups form side chains bonded to the amorphous zirconium silicate system. Therefore, the addition of fluorinated organosilanes facilitates the introduction of fluorinated organosilane groups into the sol system. Subsequent annealing can form fluorine-doped amorphous zirconium silicate, significantly improving the oleophobicity of the transition layer and enhancing its compatibility with the fluorinated organic polymers in the oleophobic layer.

[0069] In some embodiments, the fluorinated organosilane includes fluoropropyltriethoxysilane. This fluorinated organosilane can effectively participate in the hydrolysis-condensation reaction, introducing fluorine into amorphous zirconium silicate and significantly improving the oleophobicity of the transition layer. In some embodiments, the molar ratio of silicate ester to fluorinated organosilane is (2–4):1, and may include, but is not limited to, any ratio or a range between any two of 2:1, 2.5:1, 3:1, 3.5:1, and 4:1, with 3:1 being a preferred ratio. These molar ratios are beneficial for controlling the distribution density of fluorine in the amorphous zirconium silicate network, and for ensuring that the transition layer balances oleophobicity, structural stability, and coefficient of thermal expansion.

[0070] In some embodiments, prior to the first film-forming treatment, a surface treatment step on the glass enamel substrate is included. Surface treatment may include at least one of silane coupling treatment, acid treatment, alkali treatment, plasma surface treatment, and ion implantation treatment. These surface treatment methods are beneficial for improving the cleanliness of the substrate surface, while simultaneously forming numerous active sites by binding active groups on the substrate surface, enhancing the adhesion between the substrate and the transition layer. In some embodiments, the silane coupling treatment may be performed as follows: first, a silane coupling agent is dissolved in ethanol to obtain a coupling agent solution. The silane coupling agent may be γ-aminopropyltriethoxysilane (APTES), with a mass percentage of 1.5 wt% to 2.5 wt% in the coupling agent solution. Then, the coupling agent solution is sprayed onto the surface of the glass enamel substrate and dried at 70°C to 90°C for 20 to 40 minutes, allowing the APTES to fully bond with the glass enamel substrate surface, forming numerous chemically active sites. The subsequent bonding strength with the transition layer can be significantly improved, and is expected to exceed 12 MPa according to ASTM D4541 standards. In some embodiments, ion implantation can be performed by bombarding the surface of a glass glaze substrate with high-energy ions, thereby attaching the ions to be implanted.

[0071] In some embodiments, the first film-forming process includes at least one of spin coating, dip coating, and blade coating, optionally spin coating. These first film-forming processes can form a uniform and dense transition layer film from the sol, and are particularly suitable for glass enamel substrates. In an exemplary example, spin coating can be performed by spin-coating the sol at a speed of 2000 rpm to 4000 rpm for a spin-coating time of 1200 s to 4800 s, resulting in a wet film of 1 μm to 5 μm, which is then dried at 70°C to 90°C.

[0072] Following the first film-forming treatment is an annealing process. Annealing promotes further bonding and densification of the amorphous inorganic network formed by silicon, oxygen, and zirconium atoms, resulting in a dense transition layer including amorphous zirconium silicate. In some embodiments, the annealing temperature is 300°C to 600°C, and may include, but is not limited to, any value or a range between any two of 300°C, 350°C, 450°C, 500°C, and 600°C. These annealing temperatures promote further bonding and densification of the amorphous inorganic network. The annealing time may be 30 min to 90 min, and optionally 1 hour.

[0073] Step S20 is the step of forming the oleophobic layer. The selection of mesoporous inorganic materials and the mass ratio of the fluorinated organic polymer can be referred to the description in the modified glass glaze above. The fluorinated organic polymer has high oleophobicity; the nano-confinement effect of the mesoporous structure in the mesoporous inorganic material can significantly improve the thermal stability of the fluorinated organic polymer; the mesoporous inorganic material also facilitates compatibility with the amorphous zirconium silicate material system of the transition layer; compared to an oleophobic layer containing only oleophobic materials, the mesoporous inorganic material also adjusts the coefficient of thermal expansion of the oleophobic layer, making it closer to the transition layer, reducing the risk of cracking and peeling of the oleophobic layer.

[0074] In some embodiments, the raw materials for preparing the slurry also include encapsulated repair material. The type and amount of encapsulated repair material can be referred to the description in the modified glass glaze above, which is beneficial for the oleophobic layer to release the repair material under high temperature shock, repair microcracks, reduce the risk of cracking and peeling, and improve the durability of the oleophobic layer under high temperature cycling.

[0075] To form an oleophobic layer from the raw materials of this inorganic-organic system, in some embodiments, the second solvent for preparing the slurry includes a supercritical fluid, and the second film-forming treatment includes at least one of atmospheric plasma spraying and ultrasonic spraying. The supercritical fluid can be selected from CO2 (pressure 15 MPa, temperature 50°C), which is beneficial for uniformly dispersing the mesoporous inorganic material filled with fluorinated organic polymers. Furthermore, such supercritical fluids are relatively environmentally friendly, and solvent removal during film formation is faster and gentler, which is conducive to forming a uniform oleophobic layer. Methods such as atmospheric plasma spraying can be used in conjunction with a supercritical fluid solution to form an oleophobic layer through a high-speed jet, and the supercritical fluid can be rapidly removed. In an exemplary example, atmospheric plasma spraying can use an Ar / H2 mixed gas, with a power of 20 kW to 40 kW, optionally 30 kW.

[0076] Finally, heat treatment of the oleophobic layer can facilitate better filling of the mesoporous structure of the fluorinated organic polymer into the mesoporous inorganic material, and promote stronger bonding between the fluorinated organic polymer and the mesoporous inorganic material. For example, fluorine forms covalent bonds with oxygen and silicon in the mesoporous inorganic material, further improving the filling degree and binding force of the fluorinated organic polymer in the pores of the mesoporous inorganic material. This is more conducive to the nano-confining effect, increases the decomposition temperature of the fluorinated organic polymer, and allows the oleophobic layer to maintain excellent oleophobic properties at long-term high temperatures. In the example, heat treatment can be performed in a protective atmosphere such as nitrogen at a temperature range of 260℃ to 290℃ for 1 h to 3 h.

[0077] A third aspect of this application provides a heating element. The heating element includes the modified glass glaze described in the above application embodiments, or includes the modified glass glaze prepared by the preparation method described in the above application embodiments.

[0078] In this embodiment, the area in the heating element using the modified glass glaze described above exhibits high oleophobicity, effectively reducing e-liquid retention and lowering the risk of cracking of the glass glaze layer due to high-temperature carbonization of e-liquid. Simultaneously, under the impact of high-temperature cycling, the transition layer and oleophobic layer in the modified glass glaze are not prone to cracking or peeling, and can provide long-term oleophobic protection, improving the reliability and service life of the heating element.

[0079] In some embodiments, the heating component may include a thick-film heating element, which is prepared by first providing a metal tube substrate, coating the surface of the metal tube with glass powder, then printing conductive paste onto the surface of the glass glaze to form a resistive layer for the heating circuit, after preliminary curing, spraying another layer of glass glaze, and finally sintering at high temperature to obtain the thick-film heating element. At least two pad areas are also provided in the thick-film heating element. The number of pads is adjustable according to the product's circuit design. The pads are used for electrical connection between the resistive layer and external wires, generally by brazing, with the welding position located at the center of the pad. The pad material is also a glass glaze containing metal, but the metal content is higher than that in the glass glaze heating path. Using the glass glaze in the pad as the glass glaze substrate, a transition layer and an oleophobic layer are provided around the solder joint, allowing the pad to form the aforementioned modified glass glaze. This effectively alleviates the problem that the pad area easily absorbs e-liquid, and the residual e-liquid easily causes the glass glaze substrate to crack after high-temperature carbonization. It also solves the problem that the traditional oleophobic layer is directly bonded to the surface of the glass glaze substrate, making it prone to cracking and peeling under thermal cycling. Therefore, the pad area of ​​this thick-film heating element can maintain its oleophobic properties at high temperatures, and still has high structural stability and service life even under cyclic thermal shock scenarios.

[0080] In some embodiments, the heating element can also be an industrial heating tube, etc. A transition layer and an oleophobic layer are formed on the surface of the glass glaze substrate of the industrial heating tube to create a modified glass glaze. This significantly improves oleophobicity, effectively reducing the carbonization and accumulation of oil at high temperatures, thereby reducing the risk of glaze cracking due to thermal stress concentration. Furthermore, the heating element maintains its oleophobic properties at high temperatures and exhibits high structural stability and a long service life even under cyclic thermal shock conditions.

[0081] A fourth aspect of this application provides an aerosol generating device. This aerosol generating device includes the heating element described in the above-described application.

[0082] The aerosol generator provided in this application includes the aforementioned heating component, which can heat the atomizing matrix into an aerosol. At high temperatures, the heating component maintains excellent oleophobic properties, effectively reducing e-liquid residue and high-temperature carbonization. Under cyclic thermal shock, the heating component also exhibits high structural stability and durability. Therefore, this aerosol generator has high reliability, safety, and a long service life.

[0083] The aerosol generating device may include, but is not limited to, an electronic atomizer, which may include the aforementioned heating component, as well as other key components such as a power supply component, a liquid storage component, and a control component.

[0084] The following description is based on specific embodiments.

[0085] Example 1 This embodiment provides a thick-film heating element, wherein the pad area is made of modified glass glaze.

[0086] like Figure 1 , Figure 2 As shown, the thick-film heating element includes a ceramic substrate 1, on which a heating path 2 is formed. The heating path 2 is made of a metal-containing glass glaze, and each end of the heating path 2 has a pad 3. The pad 3 is also made of a metal-containing glass glaze, but with a higher metal content than that in the heating path 2. The center of the pad 3 is soldered to a wire 4. Figure 3 As shown, in the thickness direction from the ceramic substrate 1 to the pad 3, the pad 3 sequentially includes a glass glaze substrate 31, a transition layer 32, and an oleophobic layer 33 stacked together. The transition layer 32 and the oleophobic layer 33 are disposed on the surrounding area of ​​the pad 3, except for the soldering point with the conductor 4. The pad 3 is approximately square in shape with rounded corners, and its area is approximately 8 mm². 2 The area of ​​the weld joint is approximately 6 mm. 2 The area where the transition layer 32 and the oleophobic layer 33 are set is approximately 2 mm. 2 .

[0087] The method for setting the transition layer and the oleophobic layer includes the following steps S1 to S3: S1: Surface treatment of the glass enamel substrate The glass glaze substrate is approximately 10 μm thick and has a coefficient of thermal expansion of approximately 6 × 10⁻⁶. -6 / ℃. Prepare a 2 wt% γ-aminopropyltriethoxysilane (APTES) ethanol solution, spray this solution onto the glass enamel surface, and dry at 80℃ for 30 minutes to complete surface cleaning and form a large number of chemically active sites on the surface.

[0088] S2: Formation of transition layer Tetraethyl orthosilicate (TEOS), fluoropropyltriethoxysilane (F-PTES), and zirconium oxychloride (ZrOCl2) were mixed in a molar ratio of 3:1:1. The mixture and a mixed solvent were added to an ethanol-water mixed solvent at a mass ratio of 1:3. The resulting solution had a pH of 3. The solution was then subjected to a hydrolysis-condensation reaction at 60°C for 24 hours to form a transparent sol.

[0089] On the surface of the surface-treated glass enamel substrate, a sol was spin-coated at 3000 rpm to form a film approximately 1 μm thick. After drying at 80°C, it was annealed at 450°C for 1 hour to form a transition layer 1 μm thick with a coefficient of thermal expansion of approximately 3.2 × 10⁻⁶. -6 / ℃.

[0090] S3: Forms an oleophobic layer Mesoporous SiO2 with an average pore size of 10 nm, perfluoropolyether (PFPE) with a molecular weight of 3000, and microencapsulated fluorosiloxane were dispersed in a supercritical CO2 fluid at a mass ratio of 15:5:1. The pressure of the supercritical fluid was 15 MPa and the temperature was 50 °C to obtain a slurry.

[0091] An atmospheric plasma spraying process was adopted, using an Ar / H2 mixed gas and a power setting of 30kW to deposit the slurry onto the surface of the transition layer, forming a film layer with a thickness of about 20 μm and a porosity of about 30%.

[0092] The film was heat-treated at 280℃ in a nitrogen atmosphere for 2 hours to further fill the mesopores of PFPE and form stronger covalent bonds, resulting in an oleophobic layer with a coefficient of thermal expansion of 2×10⁻⁶. -6 / ℃.

[0093] Example 2 This embodiment provides a thick-film heating tube, differing from Embodiment 1 only in that the molar ratio of TEOS, F-PTES, and ZrOCl2 in step S2 is changed from 3:1:1 to 6:2:1, resulting in a slight change in the thermal expansion coefficient of the transition layer from 3.2 × 10⁻⁶. -6 / ℃ becomes 4×10 -6 / ℃. All other steps are the same.

[0094] Example 3 This embodiment provides a thick-film heating tube, differing from Embodiment 1 only in that, in step S2, when preparing the solution, tetraethyl orthosilicate is replaced with an organosilicon resin prepolymer, resulting in a slight change in the coefficient of thermal expansion of the transition layer from 3.2 × 10⁻⁶. -6 / ℃ becomes 3.5×10 -6 / ℃. All other steps are the same.

[0095] Example 4 This embodiment provides a thick-film heating tube, which differs from Embodiment 1 only in that F-PTES is not added when preparing the solution in step S2, and the coefficient of thermal expansion of the transition layer changes slightly from 3.2 × 10⁻⁶. -6 / ℃ becomes 3.3×10 -6 / ℃. All other steps are the same.

[0096] Example 5 This embodiment provides a thick-film heating tube, which differs from Embodiment 1 only in that encapsulated fluorosiloxane is not added in step S3, and the coefficient of thermal expansion of the oleophobic layer changes slightly from 2×10⁻⁶. -6 / ℃ becomes 1.9×10 -6 / ℃. All other steps are the same.

[0097] Example 6 This embodiment provides a thick-film heating tube, which differs from Embodiment 1 only in that the average pore size of the mesoporous SiO2 in step S3 is changed from 10 nm to 15 nm, while the thermal expansion coefficient of the oleophobic layer remains almost unchanged. All other steps are the same.

[0098] Comparative Example 1 This comparative example provides a thick-film heating tube, which differs from Example 1 only in that zirconium oxychloride is not added in step S2, and the coefficient of thermal expansion of the transition layer is reduced from 3.2 × 10⁻⁶. -6 / ℃ becomes 2.6×10 -6 / ℃. All other steps are the same.

[0099] Comparative Example 2 This comparative example provides a thick-film heating tube, which differs from Example 1 only in that step S2 is omitted, i.e., the transition layer is not provided, and the oleophobic layer is directly applied to the surface of the glass glaze substrate. All other steps are the same.

[0100] Comparative Example 3 This comparative example provides a thick-film heating tube, which differs from Example 1 only in that the mesoporous silica in step S3 is replaced with macroporous silica, with a pore size distribution of 2000 nm to 3000 nm, and the thermal expansion coefficient of the oleophobic layer does not change significantly. All other steps are the same.

[0101] Comparative Example 4 This comparative example provides a thick-film heating tube, differing from Example 1 only in that the mesoporous silica in step S3 is replaced with macroporous zirconium dioxide, with a pore size distribution of 2000 nm to 3000 nm, and the thermal expansion coefficient of the oleophobic layer is slightly changed from 2 × 10⁻⁶. -6 / ℃ becomes 2.2×10 -6 / ℃. All other steps are the same.

[0102] The differences between Examples 1 to 6 and Comparative Examples 1 to 4 are shown in Table 1.

[0103]

[0104] Relevant performance tests and results analysis 1. Qualitative testing of materials The transition layer in each case was sampled and X-ray diffraction (XRD) and nuclear magnetic resonance spectroscopy (NMR) were used to qualitatively confirm the products of the hydrolysis-condensation reaction. For example, the transition layer in Example 1 was an amorphous zirconium silicate doped with fluorine.

[0105] 2. Morphological observation of the oleophobic layer The structure of the oleophobic layer in each case was observed using high-magnification transmission electron microscopy (TEM).

[0106] For each case, oleophobic layer samples were taken, and the porosity was determined using nitrogen adsorption method. At the same time, the pore size of the mesoporous inorganic material was also determined.

[0107] 3. Thermal expansion coefficient test The coefficients of thermal expansion of the transition layer and oleophobic layer in each embodiment were determined by thermomechanical analysis (TMA), and the results are recorded in Table 1.

[0108] 4. E-liquid residue on the oleophobic coating surface A thick-film heating element was used in an electronic atomizer, with a vaporizer stick as the atomizing matrix. Simulating the frequency of daily use, the heating element was powered on for 25 seconds and then de-powered for 9 seconds to cool, constituting one cycle. This process was repeated 10,000 times to atomize the vaporizer stick. The amount of e-liquid residue on the oleophobic layer surface was observed and rated. The results of Example 1 are as follows: Figure 4 As shown, the results of Comparative Example 3 are as follows: Figure 5 As shown.

[0109] 5. Thermal cycling shock test A thick-film heating element was used in an electronic atomizer, with a cigarette stick as the atomizing matrix. Simulating the frequency of daily use, a cycle was performed: the heating element was powered on for 25 seconds, then de-powered for 9 seconds to cool, and this cycle was repeated 10,000 times. This subjected the heating element to frequent high-temperature shocks, atomizing the cigarette stick. During the power-on phase, the temperature of the solder pads reached 360℃~380℃ without thermal runaway. After the test, the cracking of the oleophobic layer and its bonding with the transition layer were observed.

[0110] 6. Results Analysis Example 1, containing an amorphous zirconium silicate transition layer, exhibits a moderate coefficient of thermal expansion, effectively mitigating the thermal stress mismatch between the oleophobic layer and the glass enamel substrate, forming a gradient buffer. No interlayer delamination occurred under cyclic thermal shock of 360°C–380°C followed by cooling. Fluorine doping in the transition layer enhances its oleophobicity. The mesoporous silica in the oleophobic layer significantly improves the thermal stability of PFPE through a nano-confinement effect, raising its decomposition temperature to above 300°C, and in this case, above 380°C, allowing for long-term oleophobic performance. The microencapsulated fluorosiloxanes in the oleophobic layer rupture at high temperatures, releasing fluorosiloxanes and promptly repairing any potential cracks. Therefore, the pads in Example 1 exhibit the most ideal performance, showing no residue of soot, carbon residue, cracks, or delamination during continuous thermal shock cycles.

[0111] Compared to Example 1, Example 2 only adjusted the proportion of raw materials in the transition layer, while Example 3 only adjusted the raw materials for hydrolysis into silica monomers. The product obtained from the hydrolysis condensation is still fluorine-doped amorphous zirconium silicate material. Therefore, the performance test results in Example 3 are similar to those in Example 1, further demonstrating the excellent effect of amorphous zirconium silicate as a transition layer.

[0112] Compared to Example 1, F-PTES is not added in step S2 of Example 4, which results in the oleophobic performance of the transition layer being inferior to that of Example 1. However, since the oleophobic layer has good oleophobic performance, it can still effectively suppress e-liquid residue. Only after long-term use will there be slight e-liquid penetration in the transition layer, and there will still be no e-liquid residue on the surface of the oleophobic layer.

[0113] Compared to Example 1, Example 5 does not contain encapsulated fluorosiloxane. After long-term thermal shock cycling, the oleophobic layer develops a small number of microcracks and lacks self-healing ability, resulting in the cracks not healing in time. However, the number of microcracks is small and their size is also small. During 10,000 uses, the impact on the integrity and long-term performance of the oleophobic layer is limited.

[0114] Compared to Example 1, Example 6 adjusted the pore size of the oleophobic silica in the mesoporous layer, but it still remained within the mesoporous range, and could still exert its nano-confining effect to improve the thermal stability of PFPE. The decomposition temperature of PFPE could still reach above 300°C, and in this case it could reach above 380°C.

[0115] Compared to Example 1, in Comparative Example 1, zirconium oxychloride was not added in step S2. The hydrolysis-condensation reaction mainly involved the condensation between silica monomers, with fluorine doping. The final result was a fluorine-doped amorphous silica structure. The difference in thermal expansion coefficient between this structure and the glass glaze substrate was too large, significantly reducing its effectiveness as a transition layer. This failed to alleviate the thermal stress mismatch between the glass glaze and the oleophobic layer, leading to cracks and localized delamination of the oleophobic layer under thermal shock. Even with excellent properties, interface failure was still difficult to avoid.

[0116] Compared to Example 1, Comparative Example 2 does not have a transition layer, and the oleophobic layer is in direct contact with the glass glaze substrate. The difference in their coefficients of thermal expansion is large, which makes the oleophobic layer very easy to crack and peel off.

[0117] Compared to Example 1, Comparative Example 3 uses macroporous silica instead of mesoporous silica. Even with only a change in pore size, the e-liquid residue on the oleophobic layer surface is extremely severe. See details... Figure 4 and Figure 5 The comparison Figure 4 The results of 10,000 tests conducted on Example 1 show a smooth, reflective surface with no residue of soot or carbonized components. Figure 5 The results of 10,000 tests on Comparative Example 3 show a large amount of e-liquid residue on the surface, and significant carbonization residue. This demonstrates that simply replacing mesoporous silica with macroporous silica significantly reduces the decomposition temperature of PFPE. Under the same thermal shock, PFPE decomposes more easily, further proving the role of the nano-confinement effect of the mesoporous structure in improving the thermal stability of PFPE.

[0118] Compared to Example 1, the mesoporous silica in Comparative Example 4 was replaced with macroporous zirconium dioxide. The test results were similar to those in Comparative Example 3, both showing a large amount of residual soy oil and carbonized components. This demonstrates the role of the nano-confinence effect of the mesoporous structure in improving the thermal stability of PFPE.

[0119] The above description is merely a preferred embodiment of this application and is not intended to limit this application. Any modifications, equivalent substitutions, and improvements made within the spirit and principles of this application should be included within the protection scope of this application.

Claims

1. A modified glass glaze, characterized in that: It includes a glass glaze substrate, a transition layer, and an oleophobic layer that are sequentially stacked along the thickness direction; The transition layer includes amorphous zirconium silicate; The oleophobic layer comprises a mesoporous inorganic material and a fluorinated organic polymer, with at least a portion of the fluorinated organic polymer filling the pores of the mesoporous inorganic material.

2. The modified glass glaze according to claim 1, characterized in that, The transition layer satisfies at least one of the following characteristics: (1) The amorphous zirconium silicate is doped with fluorine; (2) The coefficient of thermal expansion of the transition layer is 2.8 × 10⁻⁶. -6 / ℃~4.5×10 -6 / ℃; (3) The thickness of the transition layer is 1 μm to 5 μm.

3. The modified glass glaze according to claim 1 or 2, characterized in that, The oleophobic layer satisfies at least one of the following characteristics: (1) The pore size of the mesoporous inorganic material is 5 nm to 20 nm; (2) The mesoporous inorganic material includes at least one of mesoporous silica, mesoporous alumina, mesoporous titanium dioxide, and mesoporous zirconium dioxide; (3) The mass ratio of the mesoporous inorganic material to the fluorinated organic polymer is (1-5):1; (4) The fluorinated organic polymer includes at least one of perfluoropolyether and polytetrafluoroethylene; (5) The weight-average molecular weight of the fluorinated organic polymer is 500 to 5000; (6) The coefficient of thermal expansion of the oleophobic layer is 0.8 × 10⁻⁶. -6 / ℃~2.5×10 -6 / ℃; (7) The porosity of the oleophobic layer is 10% to 50%; (8) The thickness of the oleophobic layer is 5 μm to 50 μm; (9) The oleophobic layer includes encapsulated repair material.

4. The modified glass glaze according to claim 3, characterized in that: The encapsulated repair material includes encapsulated fluorosiloxanes; and / or, The encapsulated repair material has a particle size of 1 μm to 5 μm; and / or, The mass ratio of the mesoporous inorganic material to the encapsulated repair material is (5-25):1; and / or, The coefficient of thermal expansion of the glass enamel substrate is 5 × 10⁻⁶. -6 / ℃~7×10 -6 / ℃; and / or, The glass glaze substrate and the transition layer are covalently bonded with siloxanes.

5. A method for preparing a modified glass glaze, characterized in that, Includes the following steps: The raw materials, including zirconium silicate sol, are subjected to a first film-forming treatment and annealing treatment on the surface of a glass glaze substrate to form a transition layer; A slurry is prepared by formulating raw materials including mesoporous inorganic materials and fluorinated organic polymers. The slurry is then subjected to a second film-forming treatment on the surface of the transition layer away from the glass glaze substrate to form an oleophobic layer, thereby obtaining a modified glass glaze comprising a glass glaze substrate, a transition layer and an oleophobic layer stacked sequentially.

6. The preparation method according to claim 5, characterized in that: The preparation of the zirconium silicate sol includes the following steps: preparing a mixed solution from raw materials comprising silicate esters, zirconium salts, and a first solvent, and carrying out a hydrolysis-condensation reaction to obtain the zirconium silicate sol; wherein, The molar ratio of the silicate ester to the zirconium salt is (1-5):1; and / or, The silicate esters include at least one of tetraethyl orthosilicate, tetramethyl orthosilicate, and organosilicon resin prepolymers; and / or, The zirconium salt includes at least one of zirconium oxychloride and zirconate chlorochloride; and / or, The first solvent includes a mixture of water and alcohol; and / or, The pH of the solution is 3–5; and / or, The raw materials for preparing the mixed solution also include fluorinated organosilanes; and / or, The hydrolysis-condensation reaction is carried out at a temperature of 40℃ to 80℃.

7. The preparation method according to claim 6, characterized in that, The fluorinated organosilane includes fluoropropyltriethoxysilane; and / or, The molar ratio of the silicate ester to the fluorinated organosilicon is (2-4):

1.

8. The preparation method according to any one of claims 5 to 7, characterized in that: Prior to the first film-forming process, the method further includes a surface treatment step on the glass glaze substrate; and / or, The first film-forming treatment includes at least one of spin coating, dip coating, and blade coating; and / or, The annealing temperature is 380℃~500℃.

9. The preparation method according to claim 8, characterized in that: The surface treatment includes at least one of silane coupling treatment, acid treatment, alkali treatment, plasma surface treatment, and ion implantation treatment.

10. The preparation method according to any one of claims 5 to 7 or 9, characterized in that: The second solvent for preparing the slurry includes a supercritical fluid, and the second film-forming treatment includes at least one of atmospheric plasma spraying and ultrasonic spraying; and / or, The raw materials for preparing the slurry also include the encapsulated repair material.

11. A heating element, characterized in that, It includes the modified glass glaze as described in any one of claims 1 to 4, or the modified glass glaze prepared by the preparation method as described in any one of claims 5 to 10.

12. An aerosol generating device, characterized in that: Includes the heating element as described in claim 11.

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