Composite material and manufacturing method thereof, composite coating, appliance and manufacturing method thereof

Abstract

The invention provides a composite material, a manufacturing method of the composite material, a composite coating, an appliance and a manufacturing method of the appliance. Wherein the composite material is composite particles comprising an inorganic non-metallic material and polyaryletherketone resin, the inorganic non-metallic material has a hollow closed-pore structure, and the surface of the inorganic non-metallic material is grafted with hydroxyl, a fluorine-containing group or a siloxane-containing group. The composite coating formed by the composite material has good heat insulation performance and mechanical integrity.

Description

Technical Field

[0001] This application relates to the technical field of composite materials with low thermal conductivity, and in particular to a composite material and its manufacturing method, a composite coating, an appliance and its manufacturing method. Background Technology

[0002] Polyaryletherketone (PEEK) resins possess excellent high-temperature resistance, mechanical strength, and chemical stability, making them valuable in the manufacture of wear-resistant coatings. As a type of polyaryletherketone resin, PEEK is typically used as a high-performance specialty engineering plastic, and its superior wear resistance gives it a significant advantage.

[0003] In the prior art, polyetheretherketone resin layer is usually used as wear-resistant layer. The wear-resistant layer formed has good wear resistance. However, the thermal conductivity of this wear-resistant layer is usually above 0.25 W / (m·K). Therefore, due to the high thermal conductivity, the heat insulation effect of the wear-resistant layer is not good during use, and it cannot meet the urgent need for efficient heat insulation of household utensils (such as cookware handles).

[0004] Based on this, attempts have been made in the field to combine fillers with low thermal conductivity and polyaryletherketone resins to form composite layers. However, the compatibility between fillers and polyaryletherketone resins is poor, and the resulting composite layers are difficult to achieve both thermal insulation and mechanical integrity.

[0005] Therefore, providing a composite material with good thermal insulation performance based on this resin layer remains a technical problem that urgently needs to be solved in this field. Summary of the Invention

[0006] The purpose of this application is to provide a composite material and its manufacturing method, composite coating, and appliance, so as to solve the technical problem that the composite layer of existing kitchen appliances is difficult to achieve both heat insulation and mechanical integrity.

[0007] According to a first aspect of this application, this application provides a composite material, wherein the composite material is a composite particle comprising an inorganic non-metallic material and a polyaryletherketone resin, wherein the inorganic non-metallic material has a hollow closed-cell structure and its surface is grafted with at least one of hydroxyl groups, fluorine-containing groups, and siloxane-containing groups.

[0008] The low thermal conductivity composite material provided according to the embodiments of this application comprises composite particles of inorganic non-metallic material and polyaryletherketone resin. The surface of the inorganic non-metallic material is grafted with at least one of hydroxyl, fluorine-containing, and siloxane-containing groups. This inorganic non-metallic material enables good compatibility between the components of the composite material, thereby reducing defects in the composite coating caused by component incompatibility (e.g., large pore defects, crack defects, delamination), improving the overall adhesion of the composite coating, and thus ensuring the mechanical integrity of the formed composite coating. Furthermore, compared to the corresponding polyaryletherketone resin material, the hollow closed-cell structure of the inorganic non-metallic material in this composite material relatively reduces the thermal conductivity of the polyaryletherketone resin, thereby obtaining a low thermal conductivity composite material. Moreover, the organic-inorganic transition layer formed on the surface of the grafted and modified inorganic non-metallic material further increases the interfacial thermal resistance and inhibits heat conduction, thus further reducing the thermal conductivity of the composite material, thereby ensuring that the composite coating formed from the composite material has good thermal insulation performance. In summary, the composite coating formed from the composite material according to this application can have both good thermal insulation performance and mechanical integrity.

[0009] According to this application, in the composite material, polyaryletherketone resin is the main component, and inorganic non-metallic materials are the auxiliary component. As an example, when the composite material is composed of polyaryletherketone resin and inorganic non-metallic materials, taking the total mass of the composite material as 100%, the mass of the inorganic non-metallic materials is 10%-30% of the total mass of the composite particles, and the mass of the polyaryletherketone resin is 70%-90% of the total mass of the composite particles, and the sum of the mass percentages of the inorganic non-metallic materials and the polyaryletherketone resin is 100%.

[0010] In these embodiments, each component has a suitable mass ratio, enabling the composite material to simultaneously possess low thermal conductivity, good mechanical properties, good dispersion properties, and material compatibility.

[0011] In some embodiments, the polyaryletherketone resin includes at least one of polyetherketone resin, polyetheretherketone resin, polyetherketone resin, polyetheretherketone resin, and polyetherketone etherketone resin. Compared with fluorocarbon resins, these polyaryletherketone resins have superior mechanical strength, hardness, high temperature resistance, and inherent fluorine-free properties. This ensures that the main body of the composite material has good performance in all aspects, and ensures its stability and environmental friendliness in the corresponding appliance's operating environment.

[0012] In some embodiments, the inorganic non-metallic material includes at least one of silicon dioxide, tin dioxide, cobalt tetroxide, titanium dioxide, calcium carbonate, aluminum oxide, and magnesium oxide. These inorganic non-metallic materials can combine the advantages of low thermal conductivity, low cost, and certain mechanical strength.

[0013] In some embodiments, the polyaryletherketone resin has a particle size of 20 μm-120 μm, which is considered a medium particle size. This avoids the agglomeration of excessively fine particles (<20 μm) due to their high surface energy, while also preventing excessively coarse particles (>120 μm) from forming stress concentration points in the resulting composite coating. Furthermore, during the composite material manufacturing stage, this particle size provides a sufficiently large specific surface area for contact with the grafted modified inorganic non-metallic material, allowing for adequate contact between the two materials and the formation of a composite material with stable and uniform dispersion. Moreover, during the stage of coating the composite material to form the initial composite layer, this particle size of polyaryletherketone resin meets the powder flowability requirements of the coating process (e.g., the powder flowability requirements for electrostatic spraying, which will be described below) and allows for synchronous flow with the inorganic non-metallic material as a solid filler, thereby reducing local defects (such as voids and delamination) in the initial composite layer. Meanwhile, during the initial sintering stage of the composite layer, the melt of polyaryletherketone resin with this particle size can have suitable fluidity, thus avoiding unevenness of the composite coating due to excessively high viscosity or sagging of the composite coating due to excessively low viscosity.

[0014] In some embodiments, the particle size of the inorganic non-metallic material is 20μm-50μm, and the hollow closed-cell structure of the inorganic non-metallic material is a spherical shape with a diameter of 20μm-50μm. Such an inorganic non-metallic material can provide sufficient surface active sites (such as hydroxyl groups and defect sites) to connect with polyaryletherketone resin, and will not cause agglomeration due to excessive surface energy.

[0015] In some embodiments, the composite material is composed of inorganic non-metallic materials and polyaryletherketone resin, wherein, based on the total mass of the composite material as 100%, the mass of the inorganic non-metallic materials is 10%-30% of the total mass of the composite material, and the mass of the polyaryletherketone resin is 70%-90% of the total mass of the composite material.

[0016] In these embodiments, each component has a suitable mass ratio, enabling the composite material to simultaneously possess low thermal conductivity, good mechanical properties, good dispersion properties, and material compatibility.

[0017] In some embodiments, the polyaryletherketone resin has a melting point of 305°C-390°C, a characteristic that provides sufficient thermal stability safety margin for composite coatings formed from composite materials with low thermal conductivity.

[0018] In some embodiments, the intrinsic viscosity of the polyaryletherketone resin is 0.60 dL / g-1.2 dL / g. Polyaryletherketone resins with intrinsic viscosities in this range exhibit good melt flowability and thermal stability above their melting point. Thus, the polyaryletherketone resin in the initial composite layer formed by the low thermal conductivity composite material obtained from this resin can possess good melt leveling properties during high-temperature sintering, allowing it to fully melt, flow, and spread, forming a dense, defect-free composite coating with sufficient mechanical strength. It can also carry inorganic non-metallic materials to form the composite coating. If the intrinsic viscosity of the polyaryletherketone resin is too low, the molecular chains are short, resulting in insufficient cohesion in the formed composite coating and easily leading to performance degradation. If the intrinsic viscosity of the polyaryletherketone resin is too high, it will be difficult for the resin to fully flow and fuse during sintering, similarly affecting the density of the coating.

[0019] In some embodiments, the polyaryletherketone resin has a crystallinity of 30%-40%, and is a semi-crystalline polymer. The high crystallinity region forms hard micro-regions during friction to resist surface scratches and adhesive wear, thus exhibiting good wear resistance. In this way, the wear resistance of the composite coating formed by the low thermal conductivity composite material obtained by polyaryletherketone resin can be improved.

[0020] In some embodiments, the glass transition temperature of the polyaryletherketone resin is 143°C-180°C. Such a glass transition temperature ensures that the composite coating formed therefrom can maintain dimensional stability and hardness at high temperatures, making it suitable for appliances that need to withstand high-temperature friction environments.

[0021] In some embodiments, the polyaryletherketone resin in the composite material has a low coefficient of friction. For example, the coefficient of friction of the polyaryletherketone resin is 0.2-0.25, so the surface of the composite coating formed therefrom is smooth and has good self-lubricating properties, which can reduce the possibility of other substances adhering to the surface.

[0022] In some embodiments, the fluorinated group is a perfluorinated substituted alkyl chain, and the siloxane-containing alkyl group is polymethylsiloxane; and / or, the molecular weight of the fluorinated group is 500 g / mol-1000 g / mol, and the molecular weight of the siloxane-containing alkyl group is 1000 g / mol-10000 g / mol. Thus, these modified groups can promote the compatibility between inorganic non-metallic materials and polyaryletherketone resins, thereby solving a series of defects in composite coatings caused by poor compatibility between the various components of the composite material.

[0023] In some embodiments, the inorganic non-metallic material and the polyaryletherketone resin are respectively spherical or near-spherical.

[0024] In these embodiments, the macroscopic morphology of the polyaryletherketone resin in the composite material is spherical or near-spherical. The spherical particles have smooth surfaces and can weaken the interaction forces between the particles of different components of the composite material through a "point contact mode" with the inorganic non-metallic material that also has spherical or near-spherical shapes, thus inhibiting the tendency of agglomeration. This can improve the compatibility and certain bonding between the inorganic non-metallic material and the polyaryletherketone resin in the composite material when the inorganic non-metallic material has a high filler content, thereby improving the thermal insulation performance and mechanical integrity of the composite coating formed by the composite material.

[0025] In some embodiments, the thermal conductivity of the composite material is 0.06 W / (m·K)-0.17 W / (m·K), which is suitable as a heat-insulating coating or heat-resistant coating for appliances.

[0026] According to a second aspect of this application, a method for manufacturing a composite material is provided, wherein the method comprises: providing a polyaryletherketone resin and an inorganic non-metallic material having hydroxyl groups, fluorine-containing groups, or siloxane groups grafted onto its surface and having a hollow closed-cell structure; mixing the polyaryletherketone resin and the inorganic non-metallic material to form composite particles in which at least the inorganic non-metallic material is dispersed in the polyaryletherketone resin, thereby manufacturing the composite material.

[0027] According to the manufacturing method of the composite material with low thermal conductivity provided in the embodiments of this application, by mixing an inorganic non-metallic material with hydroxyl, fluorine-containing, or siloxane-containing groups grafted onto its surface and a polyaryletherketone resin in a particulate state, stable and dispersed composite particles can be formed. The modified groups (hydroxyl, fluorine-containing, or siloxane-containing groups) grafted onto the surface of the inorganic non-metallic material enable good compatibility between the various components of the composite material, thereby reducing defects caused by component incompatibility in the composite coating formed by the composite material (e.g., large pore defects, crack defects, delamination), improving the overall adhesion of the composite coating, and thus ensuring the mechanical integrity of the formed composite coating. In addition, compared with the corresponding polyaryletherketone resin material, the inorganic non-metallic material with a hollow closed-cell structure in this composite material can relatively reduce the thermal conductivity of the polyaryletherketone resin, thereby obtaining a composite material with low thermal conductivity. Furthermore, the organic-inorganic transition layer formed on the surface of the grafted and modified inorganic non-metallic material can further increase the interfacial thermal resistance and inhibit heat conduction, thereby further reducing the thermal conductivity of the composite material, thus ensuring that the composite coating formed by the composite material has good thermal insulation performance. In summary, the composite coating formed from the composite material according to this application can have both good thermal insulation performance and mechanical integrity.

[0028] In some embodiments, the step of forming an inorganic non-metallic material with fluorine-containing groups grafted on its surface and having a hollow closed-cell structure includes: providing hollow closed-cell inorganic particles; grafting hydroxyl groups onto the surface of the inorganic particles; and coupling the inorganic particles with the hydroxyl groups on the surface of the inorganic particles through a perfluorinated substituted alkyl acyl chloride or a perfluorinated substituted alkyl siloxane coupling agent to form an inorganic non-metallic material with fluorine-containing groups grafted on its surface and having a hollow closed-cell structure.

[0029] In some embodiments, the step of forming an inorganic non-metallic material with fluorine-containing groups grafted on its surface and having a hollow closed-cell structure includes: providing hollow closed-cell inorganic particles; grafting hydroxyl groups onto the surface of the inorganic particles; performing a coupling reaction between a silane coupling agent having epoxy groups and the surface hydroxyl groups of the inorganic particles to graft epoxy groups onto the surface of the inorganic particles; and then performing an epoxy-amino coupling reaction between a terminal amino-substituted polymethylsiloxane or a side-chain amino-substituted polymethylsiloxane and the inorganic particles having epoxy groups to form an inorganic non-metallic material with siloxane-containing groups grafted on its surface and having a hollow closed-cell structure.

[0030] In some embodiments, the step of forming an inorganic non-metallic material with hydroxyl groups grafted onto its surface and having a hollow closed-cell structure includes: providing hollow closed-cell inorganic particles; and plasma treating the surface of the inorganic particles to graft hydroxyl groups onto the surface of the inorganic particles, thereby forming the inorganic non-metallic material with hydroxyl groups grafted onto its surface and having a hollow closed-cell structure.

[0031] In these embodiments, the inorganic non-metallic materials obtained by the above three methods have good compatibility with the particles of polyaryletherketone resin, thus reducing the possibility of agglomeration of the same component in the composite material, thereby reducing the defects caused by poor compatibility and agglomeration of different materials in the composite coating formed by the composite material.

[0032] In some embodiments, the step of mixing the inorganic non-metallic material and the polyaryletherketone resin includes: placing the inorganic non-metallic material and the polyaryletherketone resin in a mixing device and stirring, wherein the stirring speed is 120 rpm to 160 rpm and the stirring time is 4 hours to 6 hours.

[0033] In these embodiments, mixing the inorganic non-metallic material and polyaryletherketone resin at the aforementioned rotational speed for 4-6 hours avoids the rupture of the hollow closed-cell structure of the inorganic non-metallic material due to collision or compression during the mixing process. This ensures the integrity of the hollow closed-cell structure, laying the foundation for achieving low and uniform thermal conductivity in the composite material. Furthermore, this mixing process requires no solvent; only controlled mechanical force is used to achieve the initial uniform dispersion of the inorganic non-metallic material in the polyaryletherketone resin, resulting in a composite material with good flowability and good mixing uniformity.

[0034] In some embodiments, the polyaryletherketone resin has a particle size of 20 μm-120 μm, which is considered a medium particle size. This avoids the agglomeration of excessively fine particles (<10 μm) due to their high surface energy, while also preventing excessively coarse particles (>120 μm) from forming stress concentration points in the resulting composite coating. Furthermore, during the composite material manufacturing stage, this particle size provides a sufficiently large specific surface area for contact with the grafted modified inorganic non-metallic material, allowing for adequate contact between the two materials and the formation of a composite material with stable and uniform dispersion. Moreover, during the stage of coating the composite material to form the initial composite layer, this particle size of polyaryletherketone resin meets the powder flowability requirements of the coating process (e.g., the powder flowability requirements for electrostatic spraying, which will be described below) and allows for synchronous flow with the inorganic non-metallic material as a solid filler, thereby reducing local defects (such as voids and delamination) in the initial composite layer. Meanwhile, during the initial sintering stage of the composite layer, the melt of polyaryletherketone resin with this particle size can have suitable fluidity, thus avoiding unevenness of the composite coating due to excessively high viscosity or sagging of the composite coating due to excessively low viscosity.

[0035] In some embodiments, the polyaryletherketone resin includes at least one of polyetherketone resin, polyetheretherketone resin, polyetherketone resin, polyetheretherketone resin, and polyetherketone etherketone resin. Compared with fluorocarbon resins, these polyaryletherketone resins have superior mechanical strength, hardness, high temperature resistance, and inherent fluorine-free properties. This ensures that the main body of the composite material has good performance in all aspects, and ensures its stability and environmental friendliness in the corresponding appliance's operating environment.

[0036] In some embodiments, the inorganic non-metallic material includes at least one of silicon dioxide, tin dioxide, cobalt tetroxide, titanium dioxide, calcium carbonate, aluminum oxide, and magnesium oxide. These inorganic non-metallic materials can combine the advantages of low thermal conductivity, low cost, and certain mechanical strength.

[0037] In some embodiments, the particle size of the inorganic non-metallic material is 20μm-50μm, and the hollow closed-cell structure of the inorganic non-metallic material is a spherical shape with a diameter of 20μm-50μm. Such an inorganic non-metallic material can provide sufficient surface active sites (such as hydroxyl groups and defect sites) to connect with polyaryletherketone resin, and will not cause agglomeration due to excessive surface energy.

[0038] In some embodiments, the fluorinated group is a perfluorinated alkyl chain, and the siloxane group is a polymethylsiloxane chain; and / or, the number average molecular weight of the perfluorinated alkyl chain is 500 g / mol-1000 g / mol, and the number average molecular weight of the polymethylsiloxane chain is 1000 g / mol-10000 g / mol. Thus, these modified groups can promote the compatibility between inorganic non-metallic materials and polyaryletherketone resins, thereby solving a series of defects in composite coatings caused by poor compatibility between the various components of the composite material.

[0039] In some embodiments, the mass ratio of the polyaryletherketone resin to the inorganic non-metallic material during mixing is (70-90):(10-30).

[0040] In these embodiments, each component has a suitable mass ratio, enabling the composite material to simultaneously possess low thermal conductivity, good mechanical properties, good dispersion properties, and material compatibility.

[0041] According to a third aspect of this application, a composite coating is provided, wherein the composite coating comprises a polyaryletherketone resin layer and particulate matter dispersed in the interior and surface of the polyaryletherketone resin layer, the particulate matter comprising an inorganic non-metallic material having a hollow closed-cell structure.

[0042] In some embodiments, the density of the composite coating is not higher than 1.1 g / cm³. 3 Its density is much lower than that of conventional metals and solid ceramics, and also lower than that of the selected polyaryletherketone resin, thus enabling the formed composite coating to be lighter.

[0043] In some embodiments, the thickness of the composite coating is 100μm-400μm. This thickness can ensure the thermal insulation performance of the composite coating while avoiding the possibility of the coating cracking due to thermal stress due to excessive thickness.

[0044] In some embodiments, the Vickers hardness of the composite coating is 35HV-45HV, which can further improve the wear resistance of the composite coating.

[0045] In some embodiments, the coefficient of friction of the composite coating is 0.1-0.2, which can further improve the wear resistance of the composite coating.

[0046] In some embodiments, the polyaryletherketone resin layer and the inorganic non-metallic material are chemically bonded at the contact interface. Specifically, the product is a cross-linking product of the surface groups of the hydroxylated polyaryletherketone and the inorganic non-metallic material. In this way, the bonding between different components inside the composite coating can be further optimized due to chemical bonding.

[0047] According to one embodiment of this application, the composite coating uses a polyaryletherketone resin layer as the continuous phase (main layer or base layer) and an inorganic non-metallic material as the dispersed phase (added in small amounts). This balances the overall performance of the composite coating, including its wear resistance and strength. As an example, in some embodiments, the mass of the polyaryletherketone resin layer is 70%-90% of the total mass of the composite coating, and the mass of the inorganic non-metallic material is 10%-30% of the total mass of the composite coating. It can be seen that in the composite coating, the polyaryletherketone resin layer is the main component, and the inorganic non-metallic material is the auxiliary component. The appropriate mass ratio of the polyaryletherketone resin layer and the inorganic non-metallic material allows for a balance between the mechanical properties, bonding performance, and other quality requirements of the composite coating while ensuring its low thermal conductivity.

[0048] In some embodiments, the inorganic non-metallic material and the polyaryletherketone resin layer have a gap at the contact interface, which can further reduce the thermal conductivity of the composite coating and further improve the thermal insulation effect of the composite coating, making it close to thermal insulation.

[0049] According to a fourth aspect of this application, an apparatus is provided, wherein the apparatus includes an apparatus substrate and a composite coating formed on the apparatus substrate, wherein the composite coating includes the composite coating described above.

[0050] In some embodiments, the appliance includes a thermos, a thermos flask, a thermos cup, or a kitchen utensil handle, and the composite coating serves as the heat insulation layer of the appliance to meet the heat insulation needs of various daily necessities and achieve the purpose of preventing scalding or keeping warm.

[0051] In some embodiments, the appliance further includes a non-stick layer formed on the composite coating, thereby improving the ease of cleaning of the appliance surface.

[0052] According to a fifth aspect of this application, a method for manufacturing an appliance is provided, wherein the method comprises: providing the aforementioned composite material or a composite material manufactured by the method for manufacturing composite materials; coating the composite material onto an appliance substrate to form an initial composite layer; and sintering the initial composite layer at a sintering temperature not lower than the melting point of the polyaryletherketone resin in the initial composite layer to obtain a composite coating in which an inorganic non-metallic material with at least a hollow closed-cell structure is dispersed in the polyaryletherketone resin layer, thereby manufacturing the appliance. Attached Figure Description

[0053] The above and other aspects, features, and other advantages of this application will become clearer and more readily understood from the following detailed description of exemplary embodiments in conjunction with the accompanying drawings, in which: Figure 1 A schematic diagram illustrating the formation principle of a composite coating provided according to an exemplary embodiment of this application is shown; Figure 2 A photograph of the surface of the composite coating provided according to Embodiment 9 of this application is shown; Figure 3 SEM images of the surface of the composite coating provided according to Embodiment 9 of this application are shown; Figure 4 An SEM image of a cross section of the composite coating provided according to Embodiment 9 of this application is shown; Figure 5 A schematic diagram showing the results of a low thermal conductivity test analysis of the composite coating provided according to Example 9 of this application is illustrated. Detailed Implementation

[0054] The following will combine Figures 1 to 5 This application describes the composite materials, manufacturing methods thereof, composite coatings, and appliances and manufacturing methods thereof provided in the embodiments of this application.

[0055] The thermal conductivity of natural polyaryletherketone resins in the prior art is high, which cannot meet the heat insulation requirements of household utensils (e.g., cookware handles).

[0056] The inventors discovered that the thermal conductivity of materials containing natural polyaryletherketone resins can be reduced by incorporating hollow, closed-cell inorganic fillers (such as hollow silica microspheres) into polyaryletherketone resins.

[0057] However, the inventors discovered that when attempting to composite polyaryletherketone resin and hollow closed-cell inorganic fillers into a liquid coating, a series of mixing uniformity problems caused by the hollow structure were encountered. First, considering the inherent characteristics of the hollow closed-cell inorganic filler, its unique hollow structure gives it a tendency to float and agglomerate. When mixed with polyaryletherketone resin to form a liquid coating, this tendency significantly affects the mixing effect. Specifically, due to the special forces generated by the hollow structure, polyaryletherketone resin and hollow closed-cell inorganic fillers are difficult to mix fully and uniformly in the liquid system, resulting in uneven distribution of components within the mixed coating. Second, this uneven mixing further affects the coating's performance. During the coating application process, the hollow closed-cell inorganic filler is more prone to agglomeration on the coating surface due to buoyancy. This prevents the filler from being uniformly dispersed throughout the coating, making it difficult to form a uniform thermal insulation structure. Ultimately, the coating cannot achieve ideal, uniform thermal insulation performance and fails to meet the thermal insulation requirements of relevant application scenarios.

[0058] When attempting to combine polyaryletherketone resin with hollow, closed-cell inorganic fillers to form solid composite materials, certain dispersion issues arise. Specifically, natural polyaryletherketone resin has high chemical inertness and poor compatibility with inorganic fillers. During the blending process to form composite materials and the sintering process to form coatings, the composite inorganic fillers are prone to agglomeration and phase separation from the polyaryletherketone resin (this separation can be macroscopic or microscopic; for example, when polyaryletherketone resin is mixed with inorganic fillers, resin-rich areas and particle-aggregated areas may appear). These phase-separated areas become stress concentration points, easily triggering crack propagation and reducing the strength and toughness of the composite layer. This leads to coating defects, decreased adhesion, and affects the thermal insulation and mechanical integrity of the coating. Especially when the inorganic filler content is high, it becomes more difficult to prepare a coating that combines both thermal insulation and mechanical integrity.

[0059] This application proposes to combine polyaryletherketone resin with inorganic non-metallic materials that have hydroxyl, fluorine, or siloxane groups grafted onto their surface and have a hollow closed-cell structure to obtain a composite material with high compatibility. The composite material is then used to form a composite coating that can simultaneously possess low thermal conductivity and mechanical integrity, thereby solving the problem of local defects caused by poor compatibility in existing composite materials and avoiding a series of problems such as cracking or reduced impact resistance of the composite coating due to local defects.

[0060] According to a first aspect of this application, a method for manufacturing a composite material with low thermal conductivity is provided, wherein the composite material with low thermal conductivity is used to manufacture a heat insulation layer for insulated pots, thermos flasks, thermos cups or anti-scalding handles, so as to meet the heat insulation needs in various daily necessities and achieve the purpose of anti-scalding or heat preservation.

[0061] In this application, a method for manufacturing a composite material with low thermal conductivity includes providing a polyaryletherketone resin and an inorganic non-metallic material with at least one of hydroxyl, fluorine-containing groups and siloxane-containing groups grafted onto its surface and having a hollow closed-cell structure; mixing the inorganic non-metallic material and the polyaryletherketone resin to form composite particles in which at least one of the inorganic non-metallic material having a hollow closed-cell structure is dispersed in the polyaryletherketone resin, thereby obtaining a composite material with low thermal conductivity.

[0062] According to the manufacturing method of the low thermal conductivity composite material provided in the embodiments of this application, by mixing inorganic non-metallic materials and polyaryletherketone resin in a particulate state, stable and dispersed composite particles can be formed. The modified groups (at least one of hydroxyl, fluorine-containing groups, and siloxane-containing groups) grafted onto the surface of the inorganic non-metallic material can enable good compatibility between the components of the composite material, thereby reducing defects (e.g., large pore defects, crack defects, delamination) caused by component incompatibility in the composite coating formed by the composite material, improving the overall adhesion of the composite coating, and thus ensuring the mechanical integrity of the formed composite coating. In addition, compared with the corresponding polyaryletherketone resin material, the inorganic non-metallic material with a hollow closed-cell structure in this composite material can relatively reduce the thermal conductivity of the polyaryletherketone resin, thereby obtaining a low thermal conductivity composite material. Furthermore, the organic-inorganic transition layer formed on the surface of the grafted and modified inorganic non-metallic material can further increase the interfacial thermal resistance and suppress heat conduction, thereby further reducing the thermal conductivity of the composite material, thus ensuring that the composite coating formed by the composite material has good thermal insulation performance. In summary, the composite coating formed from the composite material according to this application can have both good thermal insulation performance and mechanical integrity.

[0063] Compared with metallic materials, polyaryletherketone resin has a low thermal conductivity. Its hollow closed-cell structure (high heat barrier efficiency) with inorganic non-metallic materials can work together to form a composite coating with a double thermal barrier, which significantly reduces the thermal conductivity of the composite coating and improves the thermal insulation performance.

[0064] In this application, a hollow closed-cell structure refers to an inorganic non-metallic material having a hollow interior. This means that the particles of the inorganic non-metallic material are not solid, but rather contain one or more closed cavities. Here, the closed cavities indicate that the hollow closed-cell structure is completely isolated from the outside world and has no connecting channels. This prevents the penetration of polyaryletherketone resin or polyaryletherketone resin melt, and the hollow closed-cell structure can remain in the final composite coating without being damaged by external forces, thus maintaining its thermal insulation properties.

[0065] In the embodiments of this application, the hollow closed-cell structure can be a regular sphere, an ellipsoid, or an irregular shape, depending on the preparation method and process conditions of the inorganic non-metallic material. For example, when preparing an inorganic non-metallic material with a hollow closed-cell structure using a template method, the shape and size of the hollow closed-cell structure can be controlled by selecting a suitable template.

[0066] In this application, polyaryletherketone resin particles serve as the continuous phase in the composite material, while inorganic non-metallic material particles with a hollow closed-cell structure serve as the dispersed phase. The air trapped inside the hollow closed-cell structure acts as an excellent thermal insulator, effectively hindering heat conduction. Therefore, this application utilizes the thermal resistance effect of the hollow closed-cell structure of the inorganic non-metallic material dispersed in the polyaryletherketone resin particles to obtain a composite material with low thermal conductivity. Furthermore, using inorganic non-metallic material particles with a hollow closed-cell structure as the dispersed phase in the composite material can relatively reduce the density of the composite material, thereby enabling the composite coating formed by this composite material to possess both the advantages of being lightweight and having low thermal conductivity.

[0067] The following describes a method for manufacturing a composite material with low thermal conductivity according to this application, with reference to specific embodiments.

[0068] Provide inorganic non-metallic materials According to this application, the step of providing inorganic non-metallic materials includes providing inorganic particles with hollow closed pores, and grafting modification of the surface of the inorganic particles (specifically grafting at least one of hydroxyl, fluorine-containing groups, and siloxane-containing groups) to obtain the inorganic non-metallic material of this application having a hollow closed-pore structure and having at least one of hydroxyl, fluorine-containing, and siloxane-containing groups grafted onto its surface. In this application, the inorganic non-metallic material is used as a heat-insulating reinforcing phase, dispersed in a composite coating, which can maintain the hollow closed-pore structure. The composite coating as a whole has a low thermal conductivity, and the air inside the hollow closed-pore structure effectively blocks heat transfer, thereby achieving a heat insulation effect.

[0069] In these embodiments, by selecting an inorganic non-metallic material with a hollow closed-cell structure and at least one of hydroxyl, fluorine-containing, and siloxane-containing groups grafted onto its surface, the hydroxyl, fluorine-containing, or siloxane-containing groups grafted onto the surface of the inorganic non-metallic material enable the contact interface between the inorganic non-metallic material and the polyaryletherketone resin to have compatibility and a certain bonding force. This ensures that the particles of the inorganic non-metallic material are uniformly and stably dispersed in the particles of the polyaryletherketone resin, avoiding the agglomeration of particles of the same component in the composite material and the formation of local defects. Thus, a composite coating with both good mechanical properties and thermal conductivity can be obtained through this composite material.

[0070] In this application, inorganic non-metallic materials and polyaryletherketone resin are mixed in particulate form so that they can exist in uniformly dispersed particulate form before forming a composite coating. This lays the foundation for the uniform dispersion of each component in the composite coating, thereby avoiding local defects in the composite coating and improving the durability of the composite coating.

[0071] According to some embodiments of this application, the method for manufacturing a composite material with low thermal conductivity further includes the step of providing an inorganic non-metallic material with hydroxyl groups grafted onto its surface. Specifically, the step of providing an inorganic non-metallic material with hydroxyl groups grafted onto its surface includes the following steps.

[0072] Step S101: Provide hollow closed-cell inorganic particles.

[0073] Step S102: Plasma treatment is performed on the surface of inorganic particles to graft hydroxyl groups onto the surface of the inorganic particles, thereby obtaining an inorganic non-metallic material with a hollow closed-cell structure and hydroxyl groups grafted onto the surface according to the present application.

[0074] In step S101, the hollow closed-cell inorganic particles include one or more of the following: hollow closed-cell silica particles, hollow closed-cell tin dioxide particles, hollow closed-cell cobalt tetroxide particles, hollow closed-cell titanium dioxide particles, hollow closed-cell calcium carbonate particles, hollow closed-cell alumina particles, hollow closed-cell ceramic microspheres, and hollow closed-cell glass microspheres. These hollow closed-cell inorganic particles are distinct from hollow open-cell inorganic particles (e.g., hollow open-cell silica aerogel). This is because, during the formation of the composite coating, the open-cell structure of hollow open-cell inorganic particles results in the polyaryletherketone resin melt sealing the internal hollow portion, leading to a less significant improvement in thermal insulation. These inorganic non-metallic materials possess advantages such as low thermal conductivity, low cost, and certain mechanical strength. As a specific example, the particle size of the inorganic particles can be controlled at the micrometer scale.

[0075] As an example, the melting point of hollow, closed-cell inorganic particles is higher than that of polyaryletherketone resin. Therefore, the melting point of the resulting inorganic non-metallic material with a hollow, closed-cell structure and surface grafted groups is also higher than that of polyaryletherketone resin. Thus, in the process of forming a composite coating from composite materials, a dense composite coating with low thermal conductivity can be formed by melting only the polyaryletherketone resin without affecting the inorganic non-metallic material and by taking advantage of the fluidity of the polyaryletherketone resin melt.

[0076] As specific examples, the melting point of hollow closed-cell silica particles is 1710℃-1723℃, the melting point of hollow closed-cell tin dioxide particles is 1500℃-1630℃, the melting point of hollow closed-cell cobalt tetroxide particles is 895℃, the melting point of hollow closed-cell titanium dioxide particles is 1830℃-1879℃, the melting point of hollow closed-cell calcium carbonate particles is 1339℃, the melting point of hollow closed-cell alumina particles is 2054℃-2060℃, the melting point of hollow closed-cell ceramic microspheres is 1400℃-1800℃, and the melting point of hollow closed-cell glass microspheres is 600℃-1200℃.

[0077] In step S101, the thermal conductivity of the hollow closed-cell inorganic particles is no greater than 0.1 W / (m·K). For example, the thermal conductivity of the hollow closed-cell inorganic particles can be between 0.020 W / (m·K) and 0.050 W / (m·K). Correspondingly, the inorganic non-metallic material in the composite material has a correspondingly low thermal conductivity. Thus, the overall thermal conductivity of the composite material can be reduced by using this inorganic non-metallic material as an auxiliary filler in the polyaryletherketone resin.

[0078] It should be noted that, in addition to the plasma treatment method described above for grafting hydroxyl groups onto the surface of inorganic particles, other methods such as ammonia immersion treatment or hydrogen peroxide immersion treatment can also be used to graft hydroxyl groups onto the surface of inorganic particles. As a specific example, hollow closed-cell inorganic microspheres are added to a solution containing hydrogen peroxide, and after stirring at a low speed for a certain period of time, an inorganic non-metallic material with a hollow closed-cell structure and hydroxyl groups grafted onto its surface can be obtained.

[0079] According to some other embodiments of this application, the method for manufacturing a composite material with low thermal conductivity further includes providing an inorganic non-metallic material with fluorine-containing groups grafted onto its surface. Here, the fluorine-containing groups can be lipophilic molecules or low surface energy molecules. Specifically, the step of providing an inorganic non-metallic material with fluorine-containing groups grafted onto its surface and having a hollow closed-cell structure includes the following steps.

[0080] Step S201: Provide hollow closed-cell inorganic particles.

[0081] Step S202: Graft hydroxyl groups onto the surface of inorganic particles.

[0082] Step S203 involves a coupling reaction between a perfluorinated alkyl acyl chloride or a perfluorinated alkylsiloxane coupling agent and the hydroxyl groups on the surface of the inorganic particles, thereby forming an inorganic non-metallic material with at least fluorinated groups grafted onto its surface and possessing a hollow closed-cell structure. In these embodiments, the inorganic non-metallic material may only have fluorinated groups grafted onto it, or it may have both hydroxyl and fluorinated groups. The hydroxyl groups in the inorganic non-metallic material represent the remaining hydroxyl portion that has not been reacted by the perfluorinated alkyl acyl chloride or the perfluorinated alkylsiloxane coupling agent. That is, in step S203, a portion of the hydroxyl groups grafted onto the surface of the inorganic particles react with the perfluorinated alkyl acyl chloride or the perfluorinated alkylsiloxane coupling agent, while the other portion remains in the final inorganic non-metallic material, thus forming an inorganic non-metallic material that simultaneously possesses hydroxyl and fluorinated groups. When this inorganic non-metallic material is used to form a composite coating, the hydroxyl groups in the inorganic non-metallic material can tightly bind with the matrix material or other components through hydrogen bonds and other forces, effectively filling the micropores inside the coating and making the composite coating structure more compact, thereby significantly improving the protective performance and stability of the coating. At the same time, the fluorine-containing groups have low surface energy, which can form a low surface energy interface layer on the coating surface, greatly reducing the adhesion between the coating and other substances, thus endowing the composite coating with good non-stick properties.

[0083] According to some embodiments of this application, the method for manufacturing a composite material with low thermal conductivity further includes providing an inorganic non-metallic material with siloxane-containing groups grafted onto its surface. Here, the siloxane-containing groups can be lipophilic molecules or low surface energy molecules. Specifically, the step of forming an inorganic non-metallic material with siloxane-containing groups grafted onto its surface and having a hollow closed-cell structure includes the following steps.

[0084] Step S301: Provide hollow closed-cell inorganic particles.

[0085] Step S302: Graft hydroxyl groups onto the surface of inorganic particles.

[0086] Step S303 involves a coupling reaction between a silane coupling agent containing epoxy groups and the surface hydroxyl groups of the inorganic particles, grafting epoxy groups onto the surface of the inorganic particles. Then, a terminal amino-substituted polymethylsiloxane or a side-chain amino-substituted polymethylsiloxane is used to perform an epoxy-amino coupling reaction with the inorganic particles containing epoxy groups, thereby forming an inorganic non-metallic material with at least siloxane-containing alkyl groups grafted onto its surface and possessing a hollow closed-cell structure. In these embodiments, the inorganic non-metallic material may only have siloxane-containing alkyl groups grafted onto it, or it may simultaneously possess hydroxyl and siloxane-containing alkyl groups. The hydroxyl groups in the inorganic non-metallic material represent the remaining hydroxyl portion that has not undergone the coupling reaction. That is, in step S303, a portion of the hydroxyl groups grafted onto the surface of the inorganic particles react with the silane coupling agent containing epoxy groups, while the other portion remains in the final inorganic non-metallic material, thus forming an inorganic non-metallic material simultaneously possessing hydroxyl and siloxane-containing alkyl groups. When this inorganic non-metallic material is used to form a composite coating, the hydroxyl groups in the inorganic non-metallic material can tightly bind with the matrix material or other components through hydrogen bonds and other forces, effectively filling the micropores inside the coating. This makes the composite coating structure denser, thus significantly improving the protective performance and stability of the coating. At the same time, the siloxane groups have low surface energy, which can form a low surface energy interface layer on the coating surface, greatly reducing the adhesion between the coating and other substances. This gives the composite coating excellent non-stick properties, making it a promising candidate for applications in anti-fouling and anti-sticking fields.

[0087] In some embodiments, the fluorinated group is a perfluorinated substituted alkyl chain, and the siloxane group is a polymethylsiloxane chain. The number average molecular weight of the perfluorinated alkyl chain is 500 g / mol-1000 g / mol, and the number average molecular weight of the polymethylsiloxane chain is 1000 g / mol-10000 g / mol. Thus, these modified groups can promote the compatibility between inorganic non-metallic materials and polyaryletherketone resins, thereby solving a series of defects in composite coatings caused by poor compatibility between the various components of the composite material.

[0088] It should be noted that the hollow closed-cell inorganic particles in step S201 have the same or similar properties or structures as the hollow closed-cell inorganic particles in step S101.

[0089] According to this application, the inorganic non-metallic material belongs to at least one of the inorganic non-metallic materials. After flotation purification, its sphericity and particle size distribution are ensured to be uniform, and it has a low thermal conductivity. The inorganic particles can be grafted with hydroxyl groups on their surface, and after grafting hydroxyl groups, they have more active sites, which is conducive to further grafting with various organic molecules (such as silane coupling agents, polymer segments, etc.), thereby forming more active groups on their surface. On the one hand, the surface of the grafted inorganic particles (inorganic non-metallic material) is wrapped with an organic layer, which can reduce the van der Waals forces between the inorganic non-metallic material particles and reduce the tendency of inorganic non-metallic material to agglomerate, so that the inorganic non-metallic material particles can be more uniformly dispersed in polyaryletherketone resin. On the other hand, the grafted organic segments have similar or complementary molecular chain structures to polyaryletherketone, and can form strong interfacial bonds through physical entanglement or chemical bonding, reducing phase separation. Thus, the inorganic non-metallic materials obtained through the above two methods can have good compatibility with the particles of polyaryletherketone resin, thereby reducing the possibility of agglomeration of the same component in the composite material, and thus reducing the defects caused by poor compatibility and agglomeration of different materials in the composite coating formed by the composite material.

[0090] According to this application, the particle size of the inorganic particles is in the range of 15 μm to 45 μm. In some embodiments, the thickness of the fluorine-containing groups or siloxane-containing groups grafted onto the surface of the inorganic particles is no greater than 10 nm. In other embodiments, the thickness of the hydroxyl groups grafted onto the surface of the inorganic particles is no greater than 10 nm, thus making the size of the inorganic non-metallic material formed from the inorganic particles larger than the size of the inorganic particles themselves. For example, in an exemplary embodiment, the size of the inorganic non-metallic material is in the range of 20 μm to 50 μm. Such a particle size of inorganic non-metallic material can provide sufficient surface active sites (such as hydroxyl groups and defect sites) to connect with the polyaryletherketone resin without causing agglomeration due to excessively high surface energy.

[0091] Provide polyaryletherketone resin According to this application, the molecular backbone of polyaryletherketone resin is composed of alternating benzene rings, ether bonds (—O—), and ketone bonds (—CO—). As the main component of the composite material with low thermal conductivity, the rigid structure of the benzene rings endows the polyaryletherketone resin with high modulus and high compressive strength, making it less prone to plastic deformation during friction, thereby reducing wear. The ether bonds endow the polyaryletherketone resin with flexibility, forming a "rigid-flexible" balanced structure, making the polyaryletherketone resin both resistant to deformation and not easily brittle during friction.

[0092] As an example, the thermal conductivity of polyaryletherketone resin in the composite material is greater than that of the inorganic non-metallic material. Specifically, the thermal conductivity of polyaryletherketone resin exceeds that of the inorganic non-metallic material by 0.2 W / (m·K). Thus, with the same amount of inorganic non-metallic material added, the thermal conductivity of the composite material formed by the two can be significantly reduced, resulting in a composite coating with a significantly lower thermal conductivity. More specifically, the thermal conductivity of the inorganic non-metallic material is 0.020 W / (m·K)-0.050 W / (m·K), while that of the polyaryletherketone resin is 0.24 W / (m·K)-0.26 W / (m·K).

[0093] In some embodiments, the polyaryletherketone (PAEK) resin includes at least one of polyetherketone (PEK) resin, polyetheretherketone (PEEK) resin, polyetherketoneketone (PEKK) resin, polyetheretherketoneketone (PEEKK) resin, and polyetherketoneetherketoneketone (PEKEKK) resin. Compared with fluorocarbon resins, these polyaryletherketone resins have superior mechanical strength, hardness, high temperature resistance, and inherent fluorine-free properties. This ensures that the main body of the composite material has good performance in all aspects, and ensures its stability and environmental friendliness in the corresponding appliance's operating environment.

[0094] In some embodiments, the polyaryletherketone resin in the composite material has a particle size of 20 μm-120 μm, which is considered a medium particle size. This avoids the agglomeration of excessively fine particles (<20 μm) due to their high surface energy, while also preventing excessively coarse particles (>120 μm) from forming stress concentration points in the resulting composite coating. Furthermore, during the composite material manufacturing stage, this particle size provides a sufficiently large specific surface area for contact with the grafted modified inorganic non-metallic material, allowing for adequate contact between the two materials and the formation of a composite material with stable and uniform dispersion. Moreover, during the coating stage to form the initial composite layer, this particle size of polyaryletherketone resin meets the powder flowability requirements of the coating process (e.g., the powder flowability requirements for electrostatic spraying, which will be described below) and allows for synchronous flow with the inorganic non-metallic material as a solid filler, thereby reducing local defects (such as voids and delamination) in the initial composite layer. Meanwhile, during the initial sintering stage of the composite layer, the melt of polyaryletherketone resin with this particle size can have suitable fluidity, thus avoiding unevenness of the composite coating due to excessively high viscosity or sagging of the composite coating due to excessively low viscosity.

[0095] In a preferred embodiment, the polyaryletherketone resin in the composite material has a particle size of 20μm-50μm, which, while possessing the advantages already described above, also has higher deposition efficiency and can save costs.

[0096] In some embodiments, the macroscopic morphology of the polyaryletherketone resin in the composite material is spherical or near-spherical. The spherical particles have smooth surfaces and can weaken the interaction forces between the particles of different components of the composite material through a "point contact mode" with the inorganic non-metallic material that also has spherical or near-spherical shapes, thus inhibiting the tendency of agglomeration. This can improve the compatibility and certain bonding between the inorganic non-metallic material and the polyaryletherketone resin in the composite material when the inorganic non-metallic material has a high filler content, thereby improving the thermal insulation performance and mechanical integrity of the composite coating formed by the composite material.

[0097] In some embodiments, the polyaryletherketone resin in the composite material has a crystallinity of 30%-40%, and is a semi-crystalline polymer. The highly crystalline regions will form hard micro-regions during friction to resist surface scratches and adhesive wear, thus exhibiting good wear resistance. In this way, the wear resistance of the composite coating formed by the low thermal conductivity composite material obtained by polyaryletherketone resin can be improved.

[0098] In some embodiments, the degree of polymerization of the polyaryletherketone resin in the composite material is 100-300, which has a medium degree of polymerization. By selecting polyaryletherketone with this degree of polymerization, the molecular chains have formed a sufficient number of entanglement points (about 10-30 entanglement points per chain), which can significantly improve the melt viscosity and melt strength of the composite coating formed by the composite material with low thermal conductivity during the sintering process, avoid melt cracking or drooling during sintering, and have good tensile strength, heat resistance and corrosion resistance.

[0099] In some embodiments, the glass transition temperature (Tg) of the polyaryletherketone resin in the composite material is in the range of 143°C-180°C. As specific examples, the glass transition temperature of polyetherketone (PEK) resin is 155°C-165°C, that of polyetheretherketone (PEEK) resin is 143°C-155°C, that of polyetherketoneketone (PEKK) resin is 162°C-165°C, that of polyetheretherketoneketone (PEEKK) resin is 165°C-175°C, and that of polyetherketoneetherketoneketone (PEKEKK) resin is 170°C-180°C. Below Tg, polyaryletherketone resins exhibit rigidity; above Tg, they exhibit increased toughness due to chain segment movement, softening only near their melting point. This glass transition temperature ensures that the resulting composite coating maintains dimensional stability and hardness at high temperatures, making it suitable for appliances requiring high-temperature friction environments.

[0100] In some embodiments, the polyaryletherketone resin in the composite material has a low coefficient of friction. For example, the coefficient of friction of the polyaryletherketone resin is 0.2-0.25, so the surface of the composite coating formed therefrom is smooth and has good self-lubricating properties, which can reduce the possibility of other substances adhering to the surface.

[0101] In the appliances involved in this application, the normal operating temperature is typically no higher than 280°C. According to this application, the polyaryletherketone resin in the low thermal conductivity composite material has a melting point of 305°C-390°C. This characteristic provides sufficient thermal stability safety margin for the composite coating formed by the low thermal conductivity composite material. Since the operating temperature of the appliance is much lower than the melting point of the polyaryletherketone resin, it can be ensured that the composite coating formed by this low thermal conductivity composite material will not undergo structural changes due to high-temperature environments, thereby guaranteeing reliable integrity, mechanical strength, and wear resistance of the composite coating during subsequent long-term use.

[0102] In some embodiments, the intrinsic viscosity of the polyaryletherketone resin is 0.60 dL / g-1.2 dL / g. Polyaryletherketone resins with intrinsic viscosities in this range exhibit good melt flowability and thermal stability above their melting point. Thus, the polyaryletherketone resin in the initial composite layer formed by the low thermal conductivity composite material obtained from this resin can possess good melt leveling properties during high-temperature sintering, allowing it to fully melt, flow, and spread, forming a dense, defect-free composite coating with sufficient mechanical strength. It can also carry inorganic non-metallic materials to form the composite coating. If the intrinsic viscosity of the polyaryletherketone resin is too low, the molecular chains are short, resulting in insufficient cohesion in the formed composite coating and easily leading to performance degradation. If the intrinsic viscosity of the polyaryletherketone resin is too high, it will be difficult for the resin to fully flow and fuse during sintering, similarly affecting the density of the coating.

[0103] Here, intrinsic viscosity is used to characterize the specific viscosity limit of polyetheretherketone (PEEK) polymer chains when infinitely diluted in a specific solvent. It can be determined using specialized instruments and methods. For example, the intrinsic viscosity of PEEK can be determined using an automated Ubbelohde viscometer via extrapolation. The testing process typically involves dissolving the PEEK sample in 96% concentrated sulfuric acid, measuring the flow time of the solution at a specific temperature, and then calculating the intrinsic viscosity value.

[0104] According to this application, the polyetheretherketone (PEEK) resin can be either the original resin without any modification or a hydroxylated PEEK resin. The hydroxylation modification of the PEEK resin can be achieved by plasma treatment, resulting in a PEEK resin with reactive groups capable of crosslinking with inorganic non-metallic materials, thereby improving the overall density of the final composite coating.

[0105] Specifically, plasma treatment can be performed using oxygen (O2), argon (Ar) or a mixture thereof to form plasma, and the treatment power can be 300W-500W, the treatment time can be 5 minutes-30 minutes, and the gas flow rate can be 60mL / min-200mL / min. In addition, plasma treatment of polyetheretherketone resin can be carried out under low vacuum conditions.

[0106] Manufacturing composite materials with low thermal conductivity According to this application, an inorganic non-metallic material with a hollow closed-cell structure and a polyaryletherketone resin are mixed to obtain composite particles as a composite material. It should be noted that the hollow closed-cell structure of the inorganic non-metallic material can be retained in the composite material. Thus, in the composite coating formed by this composite material, the inorganic non-metallic material is uniformly dispersed in the polyaryletherketone resin layer. The hollow closed-cell structure of the inorganic non-metallic material can act as a heat conduction barrier, significantly reducing the heat transfer efficiency of the composite coating. The uniformly dispersed inorganic non-metallic material can form "heat-resistant units" in the composite coating, thereby obtaining a composite coating with low thermal conductivity as a heat-insulating or insulating coating for appliances.

[0107] In some embodiments, the step of mixing inorganic non-metallic materials and polyaryletherketone resin includes: placing the inorganic non-metallic materials and polyaryletherketone resin in a dry powder state into a mixing device rotating at a mixing speed of 120 rpm to 160 rpm for mixing, and the mixing time of the inorganic non-metallic materials and polyaryletherketone resin is 4 hours to 6 hours.

[0108] In these embodiments, mixing the inorganic non-metallic material and polyaryletherketone resin at the aforementioned rotational speed for 4-6 hours avoids the breakage of the hollow closed-cell structure of the inorganic non-metallic material due to collision or compression during the mixing process. This ensures the integrity of the hollow closed-cell structure of the inorganic non-metallic material, laying the foundation for achieving low and uniform thermal conductivity in the composite material. Furthermore, this mixing process requires no solvent; only controlled mechanical force is used to achieve the initial uniform dispersion of the inorganic non-metallic material in the polyaryletherketone resin, resulting in a composite material (composite powder) with good flowability and good mixing uniformity.

[0109] According to a second aspect of this application, a composite material with low thermal conductivity is provided, wherein the composite material with low thermal conductivity is a solid coating, wherein the composite material with low thermal conductivity is a composite particle comprising an inorganic non-metallic material and a polyaryletherketone resin, wherein the inorganic non-metallic material has a hollow closed-cell structure, and wherein the surface of the inorganic non-metallic material is grafted with at least one of hydroxyl groups, fluorine-containing groups and siloxane-containing groups.

[0110] The low thermal conductivity composite material provided in the embodiments of this application comprises composite particles of inorganic non-metallic materials and polyaryletherketone resin. The surface of the inorganic non-metallic material is grafted with hydroxyl groups, fluorine-containing groups, or siloxane-containing groups. This inorganic non-metallic material enables good compatibility between the components of the composite material, thereby reducing defects in the composite coating caused by component incompatibility (e.g., large pores, cracks, delamination), improving the overall adhesion of the composite coating, and thus ensuring the mechanical integrity of the formed composite coating. Furthermore, compared to the corresponding polyaryletherketone resin material, the hollow closed-cell structure of the inorganic non-metallic material in this composite material relatively reduces the thermal conductivity of the polyaryletherketone resin, thereby obtaining a low thermal conductivity composite material. Moreover, the organic-inorganic transition layer formed on the surface of the grafted and modified inorganic non-metallic material further increases the interfacial thermal resistance and inhibits heat conduction, thus further reducing the thermal conductivity of the composite material, thereby ensuring that the composite coating formed from the composite material has good thermal insulation performance. In summary, the composite coating formed from the composite material according to this application possesses both good thermal insulation performance and mechanical integrity.

[0111] According to this application, in the composite material, polyaryletherketone resin is the main component, and inorganic non-metallic materials are the auxiliary component. As an example, the mass ratio of inorganic non-metallic materials to polyaryletherketone resin is (10-30):(70-90). It should be noted that the composite material of this application can be composed of polyaryletherketone resin and inorganic non-metallic materials, or it can contain trace amounts or minor amounts of impurities or non-sticky particles in addition to polyaryletherketone resin and inorganic non-metallic materials.

[0112] When the composite material is composed of polyaryletherketone resin and inorganic non-metallic materials, taking the total mass of the composite material as 100%, the mass of inorganic non-metallic materials is 10%-30% of the total mass of the composite particles, and the mass of polyaryletherketone resin is 70%-90% of the total mass of the composite particles.

[0113] In these embodiments, each component has a suitable mass ratio, enabling the composite material to simultaneously possess low thermal conductivity, good mechanical properties, good dispersion properties, and material compatibility.

[0114] In some embodiments, the thermal conductivity of the composite material is 0.06 W / (m·K)-0.17 W / (m·K), which is suitable as a heat-insulating coating or heat-resistant coating for appliances.

[0115] According to a third aspect of this application, a composite coating is provided, wherein the composite coating is obtained by coating and sintering a composite material having a low thermal conductivity and including polyaryletherketone resin and an inorganic non-metallic material having a hollow closed-cell structure. Therefore, the composite coating is a composite coating of polyaryletherketone resin / hollow microspheres, and also has the advantages of low thermal conductivity, fluorine-free, and lightweight, making it suitable for use as heat insulation for household appliances.

[0116] In some embodiments, the composite coating comprises a polyaryletherketone resin layer and particulate matter uniformly dispersed in the polyaryletherketone resin layer. It should be noted that, in this application, uniform dispersion of particulate matter in the polyaryletherketone resin layer means that the particulate matter is dispersed within and on the surface of the polyaryletherketone resin layer, or that the particulate matter is uniformly distributed throughout the entire area of ​​the polyaryletherketone resin layer, wherein the particulate matter comprises inorganic non-metallic materials having a hollow closed-cell structure.

[0117] It should be noted that the inorganic non-metallic materials in the composite coating can be the same as or slightly different from those in the composite coating of the low thermal conductivity composite material. This is because, during the process of forming the composite coating by sintering the initial composite layer formed by the low thermal conductivity composite material, some grafted segments of the grafted groups of the inorganic non-metallic materials may react. For example, at high temperatures, if the grafted segments contain carbonyl groups, the carbonyl groups may be oxidized to carboxyl groups (-COOH) or further decarboxylated to generate carbon dioxide, thereby reducing the molecular weight of the inorganic non-metallic materials present in the composite coating. However, this only changes some groups or molecular weight of the inorganic non-metallic materials and does not destroy the hollow closed-cell structure of the inorganic non-metallic materials.

[0118] Compared to a solid polyaryletherketone resin layer, the composite coating of inorganic non-metallic materials with a hollow closed-cell structure dispersed in the polyaryletherketone resin layer according to the embodiments of this application can have a relatively low thermal conductivity. Furthermore, the composite coating is formed from a composite material, and the inorganic non-metallic material surface of the composite material is grafted with hydroxyl, fluorine-containing, or siloxane-containing groups, which enables good compatibility between the various components of the composite material. During the sintering process of forming the composite coating from this composite material, the groups grafted onto the surface of the inorganic non-metallic material can be compatible with the melt of the polyaryletherketone resin, thus reducing defects (e.g., large pore defects) caused by component incompatibility in the composite coating formed by the composite material. Moreover, the inorganic non-metallic material with various groups grafted onto its surface can bond with the polyaryletherketone resin layer through, for example, hydrogen bonds or chemical bonds, thereby further improving the overall adhesion of the composite coating and ensuring the mechanical integrity of the formed composite coating.

[0119] When an inorganic non-metallic material with low thermal conductivity is uniformly dispersed in a polyaryletherketone resin layer, it can act as a "heat transfer barrier layer" in the composite coating, interrupting the continuous thermal conduction path of the polyaryletherketone molecular chain and forcing heat to be transferred through an interface with higher impedance. Furthermore, the organic-inorganic transition layer formed on the surface of the grafted inorganic non-metallic material further increases the interfacial thermal resistance and inhibits heat conduction, thereby enabling the composite coating formed from the composite material according to this application to possess both good thermal insulation performance and mechanical integrity.

[0120] In this application, the polyaryletherketone resin layer has a crystalline structure, and the inorganic non-metallic material can work synergistically with the crystalline structure of the polyaryletherketone resin layer to form a "hard matrix-flexible interface" composite system, which maintains mechanical strength and suppresses microcracks caused by thermal expansion mismatch between the two materials.

[0121] In some embodiments, the density of the composite coating is not higher than 1.3 g / cm³. 3 Specifically, it can be 1.0 g / cm 3 -1.1g / cm 3 Within this range, the density is much lower than that of conventional metals, solid ceramics, etc., and lower than that of the selected polyaryletherketone resin, thus enabling the formed composite coating to be lighter.

[0122] In some embodiments, the thickness of the composite coating is 100μm-400μm. This thickness can ensure the thermal insulation performance of the composite coating while avoiding the possibility of the coating cracking due to thermal stress due to excessive thickness.

[0123] In some embodiments, the Vickers hardness of the composite coating is 35HV-45HV, which can further improve the wear resistance of the composite coating.

[0124] In some embodiments, the coefficient of friction of the composite coating is 0.1-0.2, which can further improve the wear resistance of the composite coating.

[0125] In some embodiments, the polyaryletherketone resin layer and the inorganic non-metallic material are chemically bonded at the contact interface. Specifically, the product is a cross-linking product of the surface groups of the hydroxylated polyaryletherketone and the inorganic non-metallic material. In this way, the bonding between different components inside the composite coating can be further optimized due to chemical bonding.

[0126] According to this application, the composite coating uses a polyaryletherketone resin layer as the continuous phase (main layer or base layer) and inorganic non-metallic materials as the dispersed phase (added in small amounts). This balances the overall performance of the composite coating, including its wear resistance and strength. As an example, in some embodiments, the mass of the polyaryletherketone resin layer is 70%-90% of the total mass of the composite coating, and the mass of the inorganic non-metallic materials is 10%-30% of the total mass of the composite coating. It can be seen that in the composite coating, the polyaryletherketone resin layer is the main component, and the inorganic non-metallic materials are the auxiliary component. The appropriate mass ratio of the polyaryletherketone resin layer and the inorganic non-metallic materials allows for a balance between the mechanical properties, bonding performance, and other quality requirements of the composite coating while ensuring its low thermal conductivity.

[0127] Furthermore, it should be noted that when the mass percentage of inorganic non-metallic materials in the composite coating is 10%-15%, the composite coating exhibits a significantly reduced thermal conductivity while maintaining good mechanical properties. When the mass percentage of inorganic non-metallic materials in the composite coating reaches 20% or more, the composite coating can achieve excellent thermal insulation performance, with a thermal conductivity as low as 0.06 W / (m·K)-0.17 W / (m·K), while the density does not exceed 1.3 g / cm³. 3 In this way, it can fully meet the dual requirements of household appliances for lightweight and efficient heat insulation.

[0128] In some embodiments, the inorganic non-metallic material and the polyaryletherketone resin layer have a gap at the contact interface, which can further reduce the thermal conductivity of the composite coating and further improve the thermal insulation effect of the composite coating, making it close to thermal insulation.

[0129] As an example, the gap size is at the micrometer level, or as an example, the gap size is in the range of 0.1μm-1μm.

[0130] The composite coating according to this application has low thermal conductivity, and therefore can be used as a heat insulation coating for anti-scalding handles to prevent users from getting burned when holding the handles of utensils, or as a heat insulation coating for containers to ensure that the temperature of the container does not drop easily during use, thereby maintaining it within a preset temperature range for a certain period of time.

[0131] In addition, the contact area between the inorganic non-metallic material and the polyaryletherketone resin layer in the composite coating has gaps, which can further reduce the thermal conductivity of the composite coating due to the heat insulation properties of the gaps.

[0132] According to a fourth aspect of this application, an appliance is provided, wherein the appliance includes an appliance substrate and a composite coating formed on the appliance substrate, wherein the composite coating includes the composite coating of the above embodiments.

[0133] In some embodiments, the appliance includes an insulated pot, a thermos, a thermos cup, or a kitchen utensil handle. The composite coating is applicable to a wide variety of appliances, thereby enabling the creation of various types of appliances to meet market demands.

[0134] According to a fifth aspect of this application, a method for manufacturing an appliance is provided. (See also...) Figure 1 The method for manufacturing the appliance includes: Step S301, providing an appliance substrate. Step S302, providing a composite material with low thermal conductivity, wherein the composite material with low thermal conductivity is a composite particle comprising an inorganic non-metallic material and a polyaryletherketone resin, wherein the inorganic non-metallic material has a hollow closed-cell structure and its surface is grafted with hydroxyl, fluorine-containing groups, or siloxane-containing groups. Step S303, electrostatically spraying the composite material with low thermal conductivity onto the appliance substrate to form an initial composite layer. Step S304, sintering the initial composite layer at a sintering temperature not lower than the melting point of the polyaryletherketone resin in the initial composite layer, thereby obtaining a composite coating in which at least a hollow closed-cell structure of inorganic non-metallic material is dispersed in the polyaryletherketone resin layer, thereby manufacturing the appliance.

[0135] In this embodiment, coating refers to the method of uniformly covering the surface of the appliance substrate with a composite material (liquid coating) with a low thermal conductivity by electrostatic spraying. Compared with other layer formation methods (e.g., plasma spraying, laser cladding, hot pressing), this application, through electrostatic spraying, can avoid affecting the hollow closed-cell structure of inorganic non-metallic materials, and can ensure the integrity of the hollow closed-cell structure in the composite coating. Unlike plasma spraying, laser cladding, and hot pressing, it will not damage the hollow closed-cell structure of inorganic non-metallic materials, causing the pores to collapse or disappear completely, thereby preventing the composite coating from losing its lightweight, heat insulation, and other properties.

[0136] According to the manufacturing method of the appliance provided in the embodiments of this application, a composite material with low thermal conductivity, comprising inorganic non-metallic materials and polyaryletherketone resin in the form of composite particles, can have dispersion stability due to the grafting of hydroxyl, fluorine-containing groups or siloxane-containing groups on the surface of the inorganic non-metallic materials. It can also form an initial composite layer with uniformly dispersed components through coating. Furthermore, under the influence of sintering temperature, the polyaryletherketone resin in the initial composite layer can melt and carry the inorganic non-metallic materials to flow synchronously, thereby forming a composite coating with both good thermal insulation performance and mechanical integrity.

[0137] The following describes the manufacturing method of the appliance according to this application, with specific steps.

[0138] Provide appliance base According to the present invention, the utensil base includes a pot base, a kettle base, a cup base, or a handle base, and the corresponding utensil can be formed as an insulated pot, an insulated kettle, an insulated cup, or a kitchen utensil handle, respectively. Here, the utensil base has a prototype structure similar to the corresponding utensil. As a specific example, the utensil base is formed by stretching or spinning a metal material, wherein the metal material includes magnesium, aluminum, iron, or titanium.

[0139] According to some embodiments of this application, the bonding surface between the appliance substrate and the composite coating is a micron-level rough surface, and the composite coating is conformally disposed on the appliance substrate. In this way, the bonding performance between the appliance substrate and the composite coating can be improved by utilizing the rough surface of the appliance substrate, and the surface of the composite coating can be made to have a smaller unevenness, such as nano-level unevenness, so as to ensure the easy cleaning performance of the surface of the composite coating.

[0140] Preheating (optional) According to this application, the method for manufacturing the appliance may further include a step of preheating the appliance substrate. As an example, the preheating temperature may be 80℃-110℃, and the preset time may be 20min-40min. Through preheating treatment, the composite coating formed by the composite material with low thermal conductivity can have better bonding performance with the appliance substrate.

[0141] Formation of the initial composite layer According to this application, the composite material can form a composite coating on an appliance substrate through a particle forming layer. As an example, the particle forming layer is formed by electrostatic spraying, wherein the electrostatic spraying voltage is 30kV-50kV, the powder feeding pressure is 0.3MPa-0.6MPa, the temperature of the appliance substrate is 25℃-30℃, and the spraying time is 3s-5s. Through the electrostatic effect, the composite material can be uniformly adsorbed onto the appliance substrate, forming a uniform initial composite layer with controllable thickness.

[0142] According to this application, there are two modes in the electrostatic spraying process. The first mode is to ground the tool substrate (conventional mode), and the second mode is to charge the tool substrate (reverse mode). The first mode is suitable for flat tool substrates, while the second mode is more suitable for tool substrates with complex shapes. For example, for handles, the surface usually has grooves or curved parts. If the first mode is used, the electric field is easily shielded, while the second mode will not be affected by this.

[0143] The second mode will be described in detail below.

[0144] In the electrostatic spraying of composite materials, a high-voltage electrode contacts the substrate, charging it while the composite material particles remain neutral or grounded. During spraying, neutral composite material particles are transported through insulated pipes to prevent premature discharge with the high-voltage substrate. The particles, under the influence of the electric field, move towards and are attracted to the charged substrate. Grounded particles are grounded through conductive pipes, creating a reverse electric field with the charged substrate. The particles become negatively charged due to friction or induction, attracting the positively charged substrate and resulting in higher deposition efficiency.

[0145] Furthermore, after the particles of the composite material are adsorbed onto the appliance matrix, the polyaryletherketone resin in the composite material can melt on the charged appliance matrix and carry the inorganic non-metallic material particles to be deposited together on the appliance matrix to form an initial composite layer. Here, the inorganic non-metallic material is dispersed in the polyaryletherketone resin due to the modified groups, forming a structure of "polyaryletherketone resin encapsulating inorganic non-metallic material".

[0146] Sintering to form a composite coating According to this application, after obtaining the initial composite layer, sintering is performed to solidify the initial composite layer and form an integrated composite coating. In this application, the initial composite layer is sintered at a sintering temperature not lower than the melting point of the polyaryletherketone resin in the initial composite layer. This allows the polyaryletherketone resin to fully melt and solidify, while maintaining the uniform dispersion of inorganic non-metallic materials in the polyaryletherketone resin matrix, forming a composite coating with polyaryletherketone resin as the continuous phase and inorganic non-metallic materials as the dispersed phase, ultimately resulting in an appliance with significantly improved surface wear resistance.

[0147] Specifically, the appliance substrate with the initial composite layer is transferred to a sintering furnace and sintered at a high temperature of 380℃-420℃ for 10-30 minutes. During this process, the polyaryletherketone resin in the initial composite layer can fully melt and level, and coat the uniformly dispersed inorganic non-metallic materials. Then, by naturally cooling to room temperature, a robust, integrated, fluorine-free, lightweight, and low thermal conductivity composite coating is formed on the appliance substrate.

[0148] In a preferred embodiment, the sintering temperature is 50°C-100°C higher than the melting point of the polyaryletherketone resin in the initial composite layer. For example, the sintering temperature is 380°C-420°C, and the curing time is 10-30 minutes. Performing sintering at this temperature and time allows the polyaryletherketone resin in the initial composite layer to further melt and form a polyaryletherketone resin melt. After natural cooling, the polyaryletherketone resin melt crystallizes and shrinks in volume, creating gaps at the interface with the inorganic non-metallic material. This further reduces the thermal conductivity of the composite coating according to this application, thereby producing a composite coating with good thermal insulation properties.

[0149] In some embodiments, the thickness of the composite coating is 30 micrometers to 200 micrometers. This thickness can ensure the thermal insulation performance of the composite coating while avoiding excessive stress that could cause the composite coating to delaminate or crack.

[0150] In this application, the polyetheretherketone resin layer is the main structure of the composite coating. It has advantages such as high temperature resistance, light weight, environmental protection, and chemical corrosion resistance. It can complement the functions of inorganic non-metallic materials with modified groups and hollow closed-cell structures, and finally form a composite coating that combines "light weight, high temperature resistance, high-efficiency heat insulation and environmental protection" to meet the comprehensive needs of household appliances (e.g., cookware handles) for safety, lightness and durability.

[0151] According to this application, inorganic non-metallic materials containing hydroxyl groups, fluorinated groups, or siloxane groups in low thermal conductivity composite materials can interact with polyaryletherketone resins during the formation of composite coatings, thereby bonding together. For example, when the surface of the inorganic non-metallic material contains hydroxyl groups, these hydroxyl groups can form hydrogen bonds or covalent bonds with polar groups (such as ether bonds in polyaryletherketone) in the polyaryletherketone resin, thereby improving interfacial shear strength. As another example, when the surface of the inorganic non-metallic material contains fluorinated groups, the high electronegativity of the fluorine atoms in the fluorinated groups can form van der Waals forces or induced dipole interactions with the hydrocarbon chains in the polyaryletherketone resin, reducing interfacial defects. Furthermore, when the surface of the inorganic non-metallic material contains siloxane groups, these siloxane groups can undergo polycondensation reactions with organic groups (such as hydroxyl groups) in the polyaryletherketone resin to enhance interfacial bonding.

[0152] According to this application, when the appliance also includes other coatings (e.g., non-stick layers), non-stick materials can be added to the composite material so that the composite coating formed by the composite material itself can have both wear resistance and non-stick properties to meet the usage requirements of the appliance (e.g., cookware). Alternatively, a non-stick layer can be rearranged on the composite coating after it has been formed.

[0153] Spraying to create a non-stick layer on the composite coating In some embodiments, the appliance further includes a non-stick layer formed on the composite coating. Correspondingly, the method of manufacturing the appliance includes coating a non-stick material on the composite coating to form a non-stick layer on the composite coating, wherein the composite coating serves as an intermediate layer.

[0154] As a specific example, the non-stick material can be a liquid fluorine coating, a liquid ceramic coating, or a solid non-stick material, as is available in the prior art.

[0155] In some embodiments, when a non-stick material is coated on top of the composite coating, the surface of the composite coating is made into a viscous flow state and bonded with the coated non-stick material, thereby greatly improving the bonding performance between the composite coating and the non-stick layer.

[0156] In addition, the surface of the composite coating of this application may contain active groups such as hydroxyl (-OH) and amino (-NH2). Therefore, in some embodiments, a non-stick material that can chemically bond or hydrogen bond with the composite coating can also be used to further improve the bonding performance between the composite coating and the non-stick layer by chemically bonding the composite coating and the non-stick layer.

[0157] According to this application, the appliance obtained through the above steps includes an appliance substrate and a composite coating formed on the surface of the appliance substrate.

[0158] The beneficial effects of the present invention will be described below with reference to specific examples.

[0159] Example 1 The low thermal conductivity composite material of Example 1 was formed by the following method.

[0160] Step S401: Provide polyaryletherketone resin and inorganic non-metallic material. The selected polyaryletherketone resin is polyetheretherketone resin with an average particle size of 20 μm, a melting point of 343℃, and an intrinsic viscosity of 0.60 dL / g. The selected inorganic non-metallic material is hydroxyl-modified hollow silica microspheres, model HMS-20, with an average particle size of 20 μm and a hollow closed-cell structure exhibiting a near-spherical shape with a size of 20 μm.

[0161] In step S402, polyaryletherketone resin and inorganic non-metallic materials are added to a curing machine in a dry powder state and mechanically mixed by stirring at a speed of 160 rpm for 6 hours, thereby forming a composite material in the form of composite particles with uniform dispersion of each component. The mass ratio of inorganic non-metallic materials to polyaryletherketone resin is 20:80, thereby producing a composite material with low thermal conductivity according to Example 1.

[0162] Example 2 Except for using a different polyaryletherketone resin to replace the polyaryletherketone resin of Example 1 to form a composite material (the polyaryletherketone resin of Example 2 is a polyetherketone resin), the low thermal conductivity composite material of Example 2 according to this application is formed by the same method as in Example 1.

[0163] Example 3 Except for using a different polyaryletherketone resin to replace the polyaryletherketone resin of Example 1 to form a composite material (the polyaryletherketone resin of Example 3 is a polyetherketone resin), the low thermal conductivity composite material of Example 3 according to this application is formed using the same method as in Example 1.

[0164] Example 4 Except for using a different polyaryletherketone resin to replace the polyaryletherketone resin of Example 1 to form a composite material (the polyaryletherketone resin of Example 4 is a polyetheretherketone resin), the low thermal conductivity composite material of Example 4 according to this application is formed using the same method as in Example 1.

[0165] Example 5 Except for using a different polyaryletherketone resin to replace the polyaryletherketone resin of Example 1 to form a composite material (the polyaryletherketone resin of Example 5 is a polyetherketone etherketone resin), the low thermal conductivity composite material of Example 5 according to this application is formed using the same method as in Example 1.

[0166] Example 6 Except for using different inorganic non-metallic materials to replace the inorganic non-metallic material of Example 1 to form a composite material (the inorganic non-metallic material of Example 6 is titanium dioxide), the low thermal conductivity composite material of Example 6 according to this application is formed using the same method as in Example 1.

[0167] Example 7 Except for using different inorganic non-metallic materials to replace the inorganic non-metallic material of Example 1 to form a composite material with low thermal conductivity (the inorganic non-metallic material in this example is tin dioxide), the composite material with low thermal conductivity according to Example 7 of this application is formed using the same method as in Example 1.

[0168] Example 8 Except for using different components to form a low thermal conductivity composite material (the components of the low thermal conductivity composite material in Example 8 include not only the components of Example 1, but also non-stick particles made of polysiloxane, wherein the mass ratio of inorganic non-metallic material, polyaryletherketone resin and non-stick particles is 20:80:5), the low thermal conductivity composite material of Example 8 according to this application is formed using the same method as in Example 1.

[0169] Comparative Example 1 Except for omitting the inorganic non-metallic material in Example 1, the material of Comparative Example 1 was manufactured using the same method as in Example 1.

[0170] Comparative Example 2 Except for omitting the polyetheretherketone resin in Example 1, the material of Comparative Example 2 was manufactured using the same method as in Example 1.

[0171] Comparative Example 3 Except that the inorganic non-metallic material in Example 1 was replaced with the same type of solid inorganic non-metallic material (specifically, solid silica microspheres were used in Comparative Example 3), the material of Comparative Example 3 was manufactured using the same method as in Example 1.

[0172] Comparative Example 4 Except that the inorganic non-metallic material in Example 1 was replaced with the same type of hollow open-cell inorganic non-metallic material (specifically, hollow open-cell silica microspheres were used in Comparative Example 4), the material of Comparative Example 4 was manufactured using the same method as in Example 1.

[0173] Comparative Example 5 Except that the polyaryletherketone resin of Example 1 was replaced with epoxy resin, the material of Comparative Example 5 was manufactured using the same method as in Example 1.

[0174] Comparative Example 6 Except that the polyaryletherketone resin of Example 1 was replaced with a metal material (specifically nickel powder), the material of Comparative Example 6 was manufactured using the same method as in Example 1.

[0175] The properties of the low thermal conductivity composite materials of Examples 1 to 8 and the materials of Comparative Examples 1 to 6 were tested and the results are recorded in Table 1 below.

[0176] The dispersion uniformity of each component of the composite material and the structural integrity of the inorganic non-metallic material were determined by scanning electron microscopy to confirm that the structural integrity of the inorganic non-metallic material was not compromised before the formation of the layer.

[0177] Table 1 Performance Test Record Table

[0178] As can be seen from Table 1 above, the inorganic non-metallic materials in the composite materials of this application embodiment possess a complete hollow closed-cell structure and are uniformly mixed. This indicates that the mixing process does not damage the hollow closed-cell structure, laying the foundation for maintaining the hollow closed-cell structure in the subsequent composite coating and meeting the requirements of subsequent processing.

[0179] Cooking Utensil Manufacturing Example 9 The shovel of Example 9 is formed by the following method.

[0180] Step S401: Provide a pre-treated aluminum plate with a thickness of 1.5 mm, a length of 10 cm, and a width of 3 cm as the handle base, and pre-set the handle base to 100°C and maintain it for 30 min.

[0181] In step S402, the low thermal conductivity composite material of Example 1 is deposited on the preheated handle substrate by electrostatic spraying (electrostatic spraying voltage is 40kV, powder feeding pressure is 0.5MPa) to obtain an initial composite layer. Then, the handle with the initial composite layer is placed in a sintering furnace and sintered at 400°C for 15 minutes to form a composite coating with a thickness of 100 micrometers on the handle substrate to obtain the handle. The handle is then connected to the shovel head to obtain the shovel provided according to Example 1 of this application.

[0182] Example 10 Except that the low thermal conductivity composite material of Example 9 was replaced with the low thermal conductivity composite material of Example 2, the shovel of Example 10 was manufactured using the same method as that of Example 9.

[0183] Example 11 Except that the low thermal conductivity composite material of Example 9 was replaced with the low thermal conductivity composite material of Example 3, the shovel of Example 11 was manufactured using the same method as that of Example 9.

[0184] Example 12 Except that the low thermal conductivity composite material of Example 9 was replaced with the low thermal conductivity composite material of Example 4, the shovel of Example 12 was manufactured using the same method as that of Example 9.

[0185] Example 13 Except that the low thermal conductivity composite material of Example 9 was replaced with the low thermal conductivity composite material of Example 5, the shovel of Example 13 was manufactured using the same method as that of Example 9.

[0186] Example 14 Except that the low thermal conductivity composite material of Example 9 was replaced with the low thermal conductivity composite material of Example 6, the shovel of Example 14 was manufactured using the same method as that of Example 9.

[0187] Example 15 Except that the low thermal conductivity composite material of Example 9 was replaced with the low thermal conductivity composite material of Example 7, the shovel of Example 15 was manufactured using the same method as that of Example 9.

[0188] Example 16 Except that the low thermal conductivity composite material of Example 9 was replaced with the low thermal conductivity composite material of Example 8, the shovel of Example 16 was manufactured using the same method as that of Example 9.

[0189] Example 17 After step S402, step S403 is added, in which a non-stick layer with a thickness of 45 μm is formed on the composite coating using liquid ceramic coating. Otherwise, the shovel of Example 17 is manufactured using the same method as in Example 9.

[0190] Example 18 Between steps S402 and S403, the surface of the composite coating is heated to a viscous flow state at 385°C, and then a liquid ceramic coating is applied in this state. The shovel of Example 18 is then manufactured using the same method as in Example 17.

[0191] Comparative Example 6 Except that the low thermal conductivity composite material of Example 9 was replaced with the material of Comparative Example 1, the shovel of Comparative Example 6 was manufactured using the same method as that of Example 9.

[0192] Comparative Example 7 Except that the low thermal conductivity composite material of Example 9 was replaced with the material of Comparative Example 2, the shovel of Comparative Example 7 was manufactured using the same method as that of Example 9.

[0193] Comparative Example 8 Except that the low thermal conductivity composite material of Example 9 was replaced with the material of Comparative Example 3, the shovel of Comparative Example 8 was manufactured using the same method as that of Example 9.

[0194] Comparative Example 9 Except that the low thermal conductivity composite material of Example 9 was replaced with the material of Comparative Example 4, the shovel of Comparative Example 9 was manufactured using the same method as that of Example 9.

[0195] Comparative Example 10 Except that the low thermal conductivity composite material of Example 9 was replaced with the material of Comparative Example 5, the shovel of Comparative Example 10 was manufactured using the same method as that of Example 9.

[0196] Comparative Example 11 Except that the low thermal conductivity composite material of Example 9 was replaced with the material of Comparative Example 6, the shovel of Comparative Example 11 was manufactured using the same method as in Example 9. Regarding Comparative Example 11, it should be noted that the large surface tension of the nickel melt in Comparative Example 6 and the large density difference with the hollow closed-cell inorganic non-metallic material cause the hollow closed-cell material to completely float in the coating, ultimately forming a non-uniform composite film.

[0197] The performance of the shovels in Examples 9 to 18 and Comparative Examples 6 to 11 was tested, and the test results are shown in the table.

[0198] 1. Vickers Hardness Test Method for Coatings: The standard Vickers hardness test method is adopted. A diamond indenter with a 136° angle between its two opposing faces is vertically pressed into the coating surface of the specimen under a specified test force. After maintaining the pressure for a specified time, the test force is removed, and the lengths of the two diagonals of the residual indentation on the specimen surface are measured. The Vickers hardness value is obtained by calculating the test force per unit area of ​​the indentation. The coating of the specimen refers to the coating of the spatula in the examples and comparative examples (hereinafter the same).

[0199] 2. Cross-cut test method: Perform the cross-cut test according to the method specified in GB / T9286—2021 / ISO 2409:2020, determine the number of squares that fall off the sample, and calculate the retention rate. The higher the retention rate, the better the bonding strength.

[0200] II. The test results are shown in the table below.

[0201] Table 2 Performance Test Record Table

[0202] As can be seen from Table 2 above, the composite coatings formed by the composite materials in the embodiments of this application have low thermal conductivity and meet the requirements of cross-cut tests, etc., so they are suitable as materials for heat insulation or thermal insulation needs.

[0203] However, the thermal conductivity of the layers formed by the materials in Comparative Examples 6-11 is still relatively high, which does not meet the requirements for heat insulation or heat preservation.

[0204] Additionally, it should be noted that Comparative Example 7 is only an inorganic non-metallic material, without film-forming polymers, and has poor formability.

[0205] In Comparative Example 11, using corrosion-resistant and inert metallic Ni as the substrate for the inorganic non-metallic material resulted in significant differences in density and surface tension, causing the hollow, closed-cell inorganic non-metallic material to completely float to the top of the coating, thus losing uniformity. Furthermore, metallic Ni itself is a high-thermal-conductivity and high-density metal, leading to a high density (7.7 g / cm³) in the resulting composite film. 3Both the thermal conductivity (80 W / mK) and thermal conductivity are significantly higher than those of the composite coating in the examples. This indirectly suggests that when using hollow, closed-cell inorganic non-metallic materials to reduce the density of the composite coating and increase its thermal insulation performance, heat-resistant polymers (e.g., polyaryletherketone resins) should be selected as the substrate to achieve a synergistic effect, rather than materials with good thermal conductivity (e.g., metallic materials).

[0206] Figure 2 A photograph of the surface of the composite coating provided according to Embodiment 9 of this application is shown. Figure 2 It can be seen that the surface of the composite coating of this application is formed as a continuous and complete layer structure.

[0207] Figure 3 SEM images of the surface of the composite coating provided according to Embodiment 9 of this application are shown. Figure 3 It can be seen that the inorganic non-metallic material particles on the surface of the composite coating of this application are uniformly dispersed, the structure is intact, and there is no agglomeration.

[0208] Figure 4 SEM images of a cross-section of the composite coating provided according to Embodiment 9 of this application are shown. Figure 4 It can be seen that the inorganic non-metallic material particles on the surface of the composite coating of this application are not agglomerated, and gaps are formed in the contact area between the inorganic non-metallic material and the polyaryletherketone resin layer in the composite coating.

[0209] The thermal conductivity of air at room temperature is typically 0.026 W / (m·K). Figure 5 A schematic diagram showing the results of a low thermal conductivity test analysis of a composite coating provided according to an embodiment of this application is illustrated. Figure 5 It can be seen that the thermal conductivity of the composite coating of this application is 0.06 W / (m·K), which is close to that of air. Therefore, the composite coating of this application embodiment has a low thermal conductivity.

[0210] In addition, all the above tests were performed on other embodiments of this application besides Embodiment 9. As can be seen from the tests, the composite coatings of other embodiments of this application besides Embodiment 9 (Examples 10-18) also have all the excellent properties similar to those of Embodiment 9 (e.g., integrity, low thermal conductivity, uniform particle dispersion of inorganic non-metallic materials, and fewer defects).

Claims

1. A composite material, characterized in that, The composite material is a composite particle comprising an inorganic non-metallic material and a polyaryletherketone resin, wherein the inorganic non-metallic material has a hollow closed-cell structure and its surface is grafted with at least one of hydroxyl groups, fluorine-containing groups, and siloxane-containing groups.

2. The composite material according to claim 1, characterized in that, The polyaryletherketone resin includes at least one of polyetherketone resin, polyetheretherketone resin, polyetherketone-ketone resin, polyetheretherketone-ketone resin, and polyetherketone-ketone-ketone resin; and / or, The inorganic non-metallic material includes at least one of silicon dioxide, tin dioxide, cobalt tetroxide, titanium dioxide, calcium carbonate, aluminum oxide, and magnesium oxide.

3. The composite material according to claim 1, characterized in that, The polyaryletherketone resin has a particle size of 20 μm-120 μm; and / or, The particle size of the inorganic non-metallic material is 20μm-50μm.

4. The composite material according to claim 1, characterized in that, The composite material is composed of inorganic non-metallic materials and polyaryletherketone resin. The mass of the inorganic non-metallic materials is 10%-30% of the total mass of the composite material, and the mass of the polyaryletherketone resin is 70%-90% of the total mass of the composite material.

5. The composite material according to claim 1, characterized in that, The polyaryletherketone resin has a melting point of 305℃-390℃; and / or, the intrinsic viscosity of the polyaryletherketone resin is 0.60 dL / g-1.2 dL / g; and / or, the crystallinity of the polyaryletherketone resin is 30%-40%; and / or, the glass transition temperature of the polyaryletherketone resin is 143℃-180℃; and / or, the coefficient of friction of the polyaryletherketone resin is 0.2-0.25; and / or, the inorganic non-metallic material and the polyaryletherketone resin are respectively spherical or near-spherical.

6. The composite material according to claim 1, characterized in that, The fluorine-containing group is a perfluorinated substituted alkane chain, and the siloxane-containing group is a polymethylsiloxane chain.

7. The composite material according to claim 6, characterized in that, The perfluorinated alkane chain has a number average molecular weight of 500 g / mol to 1000 g / mol, and the polymethylsiloxane chain has a number average molecular weight of 1000 g / mol to 10000 g / mol.

8. The composite material according to any one of claims 1 to 7, characterized in that, The thermal conductivity of the composite material is 0.06 W / (m·K)-0.17 W / (m·K).

9. A method for manufacturing a composite material, characterized in that, The method for manufacturing the composite material includes: Provides polyaryletherketone resin and inorganic non-metallic materials with at least one of hydroxyl, fluorine-containing groups and siloxane-containing groups grafted onto their surfaces and having a hollow closed-cell structure; The composite material is manufactured by mixing the polyaryletherketone resin and the inorganic non-metallic material to form composite particles in which the inorganic non-metallic material is at least dispersed in the polyaryletherketone resin.

10. The method for manufacturing the composite material according to claim 9, characterized in that, The steps for forming an inorganic non-metallic material with fluorine-containing groups grafted onto its surface and possessing a hollow closed-cell structure include: Provides hollow, closed-cell inorganic particles; Hydroxyl groups are grafted onto the surface of the inorganic particles; An inorganic non-metallic material with at least fluorine-containing groups grafted onto its surface and possessing a hollow closed-cell structure is formed by coupling an inorganic particle with a perfluorinated substituted alkyl acyl chloride or a perfluorinated substituted alkyl siloxane coupling agent through a coupling reaction.

11. The method for manufacturing the composite material according to claim 9, characterized in that, The steps for forming an inorganic non-metallic material with surface grafted siloxane groups and a hollow closed-cell structure include: Provides hollow, closed-cell inorganic particles; Hydroxyl groups are grafted onto the surface of the inorganic particles; An inorganic non-metallic material with at least siloxane groups grafted onto its surface is formed by coupling a silane coupling agent containing epoxy groups to the surface of the inorganic particles. Then, an epoxy-amino coupling reaction is carried out with the inorganic particles containing epoxy groups using a terminal amino-substituted polymethylsiloxane or a side amino-substituted polymethylsiloxane.

12. The method for manufacturing the composite material according to claim 9, characterized in that, The steps for forming an inorganic non-metallic material with hydroxyl groups grafted onto its surface and possessing a hollow closed-cell structure include: Provides hollow, closed-cell inorganic particles; Plasma treatment is performed on the surface of the inorganic particles to graft hydroxyl groups onto the surface of the inorganic particles, thereby forming the inorganic non-metallic material with hydroxyl groups grafted onto the surface and having a hollow closed-cell structure.

13. The method for manufacturing the composite material according to claim 9, characterized in that, The step of mixing the inorganic non-metallic material and the polyaryletherketone resin includes: The inorganic non-metallic material and the polyaryletherketone resin are placed in a mixing device and stirred, wherein the stirring speed is 120 rpm to 160 rpm and the stirring time is 4 hours to 6 hours.

14. The method for manufacturing the composite material according to any one of claims 9 to 11, characterized in that, The polyaryletherketone resin has a particle size of 20 μm-120 μm; and / or, the polyaryletherketone resin includes at least one of polyetherketone resin, polyetheretherketone resin, polyetherketoneketone resin, polyetheretherketoneketone resin, and polyetherketoneetherketoneketone resin; and / or, the inorganic non-metallic material includes at least one of silicon dioxide, tin dioxide, cobalt tetroxide, titanium dioxide, calcium carbonate, aluminum oxide, and magnesium oxide; and / or, the inorganic non-metallic material has a particle size of 20 μm-50 μm, and the hollow closed-cell structure of the inorganic non-metallic material has a diameter of 20 μm-50 μm; and / or, the mass ratio of the polyaryletherketone resin to the inorganic non-metallic material is (70-90):(10-30).

15. A composite coating, characterized in that, The composite coating comprises a polyaryletherketone resin layer and particulate matter dispersed in the interior and surface of the polyaryletherketone resin layer. The particulate matter comprises an inorganic non-metallic material having a hollow closed-cell structure, and the surface of the inorganic non-metallic material is grafted with at least one of hydroxyl groups, fluorine-containing groups, and siloxane-containing groups.

16. The composite coating according to claim 15, characterized in that, The density of the composite coating is not higher than 1.1 g / cm³. 3 ; and / or, the Vickers hardness of the composite coating is 35HV-45HV; and / or, the coefficient of friction of the composite coating is 0.1-0.2; and / or, the thickness of the composite coating is 100μm-400μm.

17. The composite coating according to claim 15, characterized in that, The inorganic non-metallic material is bonded to the polyaryletherketone resin layer at the contact interface; and / or, the mass of the polyaryletherketone resin layer is 70%-90% of the total mass of the composite coating, and the mass of the inorganic non-metallic material is 10%-30% of the total mass of the composite coating.

18. The composite coating according to claim 15, characterized in that, The mass of the polyaryletherketone resin layer is 70%-90% of the total mass of the composite coating, the mass of the inorganic non-metallic material is 10%-30% of the total mass of the composite coating, and the sum of the mass percentage of the inorganic non-metallic material and the mass percentage of the polyaryletherketone resin layer is 100%.

19. The composite coating according to claim 15, characterized in that, There is a gap at the interface between the inorganic non-metallic material and the polyaryletherketone resin layer.

20. An appliance, characterized in that, The appliance includes an appliance substrate and a composite coating formed on the appliance substrate; Wherein, the composite coating includes the composite coating according to any one of claims 15 to 19; or, the composite coating is a composite coating formed of a composite material, and the composite material is a composite material manufactured by the manufacturing method of the composite material according to any one of claims 1 to 8 or the composite material according to any one of claims 9 to 14.

21. The appliance according to claim 20, characterized in that, The appliance includes an insulated pot, a thermos, an insulated cup, or a kitchen utensil handle, and the composite coating serves as the heat insulation layer of the appliance.

22. A method for manufacturing an appliance, characterized in that, The method for manufacturing the device includes: Provide a composite material obtained by a method for manufacturing a composite material according to any one of claims 1 to 8 or any one of claims 9 to 14; The composite material is electrostatically sprayed onto the appliance substrate to form an initial composite layer; The initial composite layer is sintered at a sintering temperature not lower than the melting point of the polyaryletherketone resin in the initial composite layer to obtain a composite coating in which inorganic non-metallic materials with at least a hollow closed-cell structure are dispersed in the polyaryletherketone resin layer, thereby manufacturing an appliance.

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