CN113073286A - Composite material, electric appliance and method for preparing composite material - Google Patents

Composite material, electric appliance and method for preparing composite material Download PDF

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Publication number
CN113073286A
CN113073286A CN202010009212.1A CN202010009212A CN113073286A CN 113073286 A CN113073286 A CN 113073286A CN 202010009212 A CN202010009212 A CN 202010009212A CN 113073286 A CN113073286 A CN 113073286A
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insulating layer
alloy coating
composite material
electrothermal alloy
profile
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CN113073286B (en
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万鹏
曹达华
杨玲
许智波
黄韦铭
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Foshan Shunde Midea Electrical Heating Appliances Manufacturing Co Ltd
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Foshan Shunde Midea Electrical Heating Appliances Manufacturing Co Ltd
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    • CCHEMISTRY; METALLURGY
    • C23COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23CCOATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C4/00Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge
    • C23C4/12Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge characterised by the method of spraying
    • C23C4/126Detonation spraying
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    • C23CCOATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C24/00Coating starting from inorganic powder
    • C23C24/02Coating starting from inorganic powder by application of pressure only
    • C23C24/04Impact or kinetic deposition of particles
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    • C23CCOATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C28/00Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
    • C23C28/30Coatings combining at least one metallic layer and at least one inorganic non-metallic layer
    • C23C28/32Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one pure metallic layer
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    • C23C28/00Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
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    • C23C28/00Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
    • C23C28/30Coatings combining at least one metallic layer and at least one inorganic non-metallic layer
    • C23C28/34Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one inorganic non-metallic material layer, e.g. metal carbide, nitride, boride, silicide layer and their mixtures, enamels, phosphates and sulphates
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    • C23C28/00Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
    • C23C28/30Coatings combining at least one metallic layer and at least one inorganic non-metallic layer
    • C23C28/34Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one inorganic non-metallic material layer, e.g. metal carbide, nitride, boride, silicide layer and their mixtures, enamels, phosphates and sulphates
    • C23C28/345Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one inorganic non-metallic material layer, e.g. metal carbide, nitride, boride, silicide layer and their mixtures, enamels, phosphates and sulphates with at least one oxide layer
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    • C23CCOATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C4/00Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge
    • C23C4/04Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge characterised by the coating material
    • C23C4/06Metallic material
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    • C23CCOATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C4/00Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge
    • C23C4/04Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge characterised by the coating material
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    • C23C4/08Metallic material containing only metal elements
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    • C23CCOATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C4/00Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge
    • C23C4/04Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge characterised by the coating material
    • C23C4/10Oxides, borides, carbides, nitrides or silicides; Mixtures thereof
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    • C23COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23CCOATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C4/00Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge
    • C23C4/04Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge characterised by the coating material
    • C23C4/10Oxides, borides, carbides, nitrides or silicides; Mixtures thereof
    • C23C4/11Oxides
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    • C23CCOATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C4/00Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge
    • C23C4/12Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge characterised by the method of spraying
    • C23C4/129Flame spraying
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    • C23C4/00Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge
    • C23C4/12Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge characterised by the method of spraying
    • C23C4/131Wire arc spraying
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    • C23C4/00Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge
    • C23C4/12Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge characterised by the method of spraying
    • C23C4/134Plasma spraying
    • HELECTRICITY
    • H05ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05BELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
    • H05B3/00Ohmic-resistance heating
    • H05B3/10Heating elements characterised by the composition or nature of the materials or by the arrangement of the conductor

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Abstract

The invention discloses a composite material, an electric appliance and a method for preparing the composite material. The composite material comprises: a substrate, the material of which comprises metal, ceramic or glass; an insulating layer formed on a surface of the base; and the electrothermal alloy coating is formed on the surface of the insulating layer far away from the substrate, and on at least one section of the composite material perpendicular to the plane of the substrate, the interface profile of the electrothermal alloy coating and the insulating layer has a profile arithmetic mean deviation Ra of not less than 5 micrometers. According to the roughness of the interface, a structure that the electrothermal alloy coating and the insulating layer are embedded with each other can be formed, so that the bonding force of the electrothermal alloy coating and the insulating layer can be effectively improved.

Description

Composite material, electric appliance and method for preparing composite material
Technical Field
The invention relates to the field of household appliances, in particular to a composite material, an electric appliance adopting the composite material and a method for preparing the composite material.
Background
Heating units are used in various household electrical appliances, such as air conditioners, electric heaters, cookers and stoves. Currently, the main heating modes of the heating unit include electromagnetic heating, hot plate heating and infrared heating. However, the current electromagnetic heating usually needs to adopt a relatively complex heating system, the heat transfer efficiency of the hot plate heating mode is relatively low, and in addition, the infrared heating is only suitable for partial cookware with high infrared absorption coefficient.
The electrothermal alloy coating is a novel heating mode, namely the resistance alloy of a heating body is manufactured by utilizing the resistance characteristic of metal, and the electrothermal alloy coating has higher heat exchange efficiency, higher reliability, lower cost and better manufacturability.
However, the current technology of electrothermal alloy coating still needs to be improved.
Disclosure of Invention
The present invention is directed to solving at least one of the problems of the prior art. To this end, an object of the present invention is to propose a composite material that can be effectively applied to household electrical appliances, having an electrothermal alloy coating, with at least one of the following advantages:
the binding force between the electrothermal alloy coating and the conductive coating, or the binding force between the substrate and the insulating layer, or the binding force between the electrothermal alloy coating and the insulating layer is remarkably improved;
the insulating layer has high electrical insulation and can resist high voltage of 1250 volts and even 2500 volts without breakdown; and
the expansion coefficient of the electrothermal alloy coating is close to that of the insulating layer, the electrothermal alloy coating is not easy to deform, and the heating power of the electrothermal alloy coating can be improved.
In view of the above, the present invention provides a composite material having an electrothermal alloy coating layer, which can be effectively applied to a household appliance.
In one aspect of the invention, the invention proposes a composite material comprising, according to an embodiment of the invention: a substrate, the material of which comprises metal, ceramic or glass; an insulating layer formed on a surface of the base; and the electrothermal alloy coating is formed on the surface of the insulating layer far away from the substrate, and on at least one section of the composite material perpendicular to the plane of the substrate, the interface profile of the electrothermal alloy coating and the insulating layer has a profile arithmetic mean deviation Ra of not less than 5 micrometers. According to an embodiment of the invention, the profile of the interface of the electrocaloric alloy coating and the insulating layer has an arithmetic mean deviation Ra of the profile of not less than 20 micrometers. According to an embodiment of the invention, the interface profile of the electrocaloric alloy coating and the insulating layer has a maximum height Rz of not less than 8 microns. According to an embodiment of the invention, the interface profile of the electrocaloric alloy coating and the insulating layer has a maximum height Rz of not less than 25 microns. Because the types of materials adopted by the electrothermal alloy coating layer and the insulating layer are different, the inventor carries out intensive research for improving the binding force between the electrothermal alloy coating layer and the insulating layer, and finds that the binding force between the electrothermal alloy coating layer and the insulating layer can be effectively improved under the same spraying condition by improving the roughness of the interface between the electrothermal alloy coating layer and the insulating layer. Specifically, according to the roughness of the interface, a structure that the electrothermal alloy coating and the insulating layer are embedded with each other can be formed, so that the bonding force of the electrothermal alloy coating and the insulating layer can be effectively improved. Therefore, the phenomenon of separation between layers caused by thermal stress between the electrothermal alloy coating and the insulating layer can be reduced, the contact area between the electrothermal alloy coating and the insulating layer can be increased, the transfer of heat to a matrix through the insulating layer can be accelerated, further, the mutually embedded transition connection is adopted, the heat generated by the electrothermal alloy coating is more, the heat conduction speed of the electrothermal alloy coating is higher, the heat conduction speed of the insulating layer is relatively lower, the mutually embedded transition structure connection is arranged, the contact area is increased, the heat transfer efficiency between the electrothermal alloy coating and the insulating layer is improved, on one hand, the phenomenon of separation between the electrothermal alloy coating and the insulating layer caused by the large thermal stress generated by the overlarge temperature difference between the electrothermal alloy coating and the insulating layer is prevented, on the other hand, the corrosion phenomenon generated by the thermal stress of the electrothermal alloy coating can be reduced, and the service life of the electrothermal alloy coating is prolonged, furthermore, the heat of the electrothermal alloy coating can be quickly led into the insulating layer, so that the heat conduction efficiency of the insulating layer is accelerated, and the heating efficiency of the substrate is improved.
According to an embodiment of the present invention, the electrothermal alloy coating layer contains a metal element and an oxygen element, and the atomic percentage of the oxygen element is 5 to 30 at% in at least a part of the electrothermal alloy coating layer. According to an embodiment of the invention, the metal element comprises: 15 to 25 at% of chromium element; 10 to 20 at% of aluminum element; 0.1 to 1.5 at% of yttrium element; and the balance of iron. Therefore, the expansion coefficient between the insulating layer and the electrothermal alloy coating is close to that between the insulating layer and the electrothermal alloy coating, and deformation and even cracking between the insulating layer and the electrothermal alloy coating when the insulating layer is subjected to cold and hot changes are avoided.
According to an embodiment of the invention, the insulating layer is an insulating coating, the porosity of the insulating layer not exceeding 5% in at least a part of the area. Therefore, the insulating property of the insulating layer can be effectively improved, the insulating layer is prevented from being broken down by high voltage, the withstand voltage can meet the safe use requirement of 1250V-2500V, and meanwhile, the harsh preparation process is avoided.
According to an embodiment of the invention, the profile of the interface of the substrate and the insulating layer has an arithmetic mean deviation Ra of the profile not lower than 20 microns, in at least one section of the composite material perpendicular to the plane of the substrate. According to an embodiment of the present invention, the profile of the interface of the substrate and the insulating layer has an arithmetic mean deviation Ra of the profile of not less than 30 μm. According to an embodiment of the invention, the interface profile of the substrate and the insulating layer has a maximum height Rz of not less than 25 μm. According to an embodiment of the invention, the interface profile of the substrate and the insulating layer has a maximum height Rz of not less than 35 micrometer. Therefore, the bonding force between the insulating layer and the substrate, the heat transfer and the uniformity of heat transfer can be improved, the interface heat conductivity coefficient between the insulating layer and the substrate is improved, and the heat transfer speed is improved.
According to an embodiment of the present invention, further comprising an electrically conductive layer formed on at least a portion of a surface of the electrothermal alloy coating, a material constituting the electrically conductive layer comprising silver or copper. Therefore, the electrothermal alloy coating can be connected with an external circuit through the conducting layer, so that the composite material has good electrothermal performance.
According to an embodiment of the invention, the electrically conductive layer is an electrically conductive coating, and the profile of the interface of the electrically conductive coating and the electrothermal alloy coating has an arithmetic mean deviation Ra of the profile of not less than 5 micrometers in at least one section of the composite material perpendicular to the plane of the substrate. According to an embodiment of the invention, the interface profile of the electrically conductive coating and the electrothermal alloy coating has an arithmetic mean deviation Ra of the profile of not less than 20 micrometers. According to an embodiment of the invention, the interface profile of the electrically conductive coating and the electrocaloric alloy coating has a maximum height Rz of not less than 8 microns. According to an embodiment of the invention, the interface profile of the electrically conductive coating and the electrocaloric alloy coating has a maximum height Rz of not less than 25 microns. According to the roughness of above-mentioned interface, can form the structure that electrothermal alloy coating and conductive coating inlayed each other, thereby can improve the cohesion of the two effectively, can improve the flow efficiency of electric current between electrothermal alloy coating and the conductive coating, thereby improve the heating power of electrothermal alloy coating, and can improve the cohesion between electrothermal alloy coating and the conductive coating, improve area of contact, reduce both interface resistance, thereby reduce because both the electric conductivity is different, and the less technical problem of electric current leading-in speed appears, and can further improve the heating power of electrothermal alloy coating, reduce generating heat of conductive coating, the utilization ratio of the improvement energy.
According to the embodiment of the invention, the electrothermal alloy coating has a preset pattern, and the electrothermal alloy coating is distributed at intervals on the section perpendicular to the plane of the substrate. The electrothermal alloy coating and the insulating layer are not completely covered, so that heat is generated locally, the heat at the corresponding position of the insulating layer is higher, then the heat is diffused and transferred at other positions of the insulating layer, and the heat at the corresponding position of the corresponding substrate is also possibly relatively higher.
According to an embodiment of the invention, the composite material satisfies at least one of the following conditions: the thickness of the insulating layer is 50-500 microns; the thickness of the electrothermal alloy coating is 10-150 microns; the thickness of the conductive layer is 30-150 microns. Therefore, the composite material has good use performance.
In a second aspect of the invention, an electrical appliance is presented. According to an embodiment of the invention, the appliance comprises: a heating assembly having the composite material described previously. Therefore, the electric appliance can utilize the high-efficiency heat generation efficiency of the composite material. In addition, as described above, by increasing the roughness of the interface between adjacent coating layers, the bonding force between adjacent coating layers can be effectively increased under the same spray condition. Specifically, according to the roughness of the interface, a structure that the electrothermal alloy coating and the insulating layer are embedded with each other can be formed, so that the bonding force of the electrothermal alloy coating and the insulating layer can be effectively improved. Therefore, the electric appliance adopting the composite material has high safety and use reliability.
According to an embodiment of the invention, the appliance is a cooking appliance or a liquid heating vessel, the appliance comprising: the composite material described above; a body, a portion of an outer wall of the body constituting a matrix of the composite material, and the electrothermal alloy coating being disposed on the outer wall of the body. Therefore, the electric appliance has high safety and use reliability.
It should be noted that the features and advantages described above for the composite material are also applicable to the electrical appliance according to the embodiment of the present invention, and are not described herein again.
In a third aspect of the invention, the invention proposes a method for preparing a composite material as described above. According to an embodiment of the invention, the method comprises: (1) forming the insulating layer on a surface of the base; (2) forming the electrothermal alloy coating on the surface of the insulating layer far from the substrate, and enabling the interface profile of the electrothermal alloy coating and the insulating layer to have the profile arithmetic mean deviation Ra of not less than 5 microns so as to obtain the composite material. By this method, the aforementioned composite material can be efficiently obtained. As described above, by increasing the roughness of the interface between the insulating layer and the electrothermal alloy coating layer, the bonding force between the insulating layer and the electrothermal alloy coating layer can be effectively increased under the same spraying conditions. Specifically, according to the roughness of the interface, a structure that the electrothermal alloy coating and the insulating layer are embedded with each other can be formed, so that the bonding force of the electrothermal alloy coating and the insulating layer can be effectively improved. Therefore, the electric appliance adopting the composite coating has high safety and use reliability. Thereby, it can be ensured that the composite material can be used for a heating unit of an appliance, such as a household appliance.
According to an embodiment of the present invention, the step (1) further comprises: (1-a) roughening at least a part of the surface of the substrate; and (1-b) forming the insulating layer on the roughened surface by explosion spraying or plasma spraying. According to an embodiment of the present invention, in the step (1), the roughening treatment is performed by at least one of sand blasting, grinding, and chemical etching, and in the step (2), the electrothermal alloy layer is formed by supersonic spraying or plasma spraying. According to an embodiment of the present invention, further comprising: forming a conductive coating on at least a portion of the surface of the electrothermal alloy coating by arc spraying or cold spraying. Therefore, an insulating layer, an electrothermal alloy coating and a conductive coating with an embedded structure at the interface can be formed.
It should be noted that the features and advantages described above for the composite material are also applicable to the method for preparing the composite material according to the embodiment of the present invention, and will not be described herein again.
Additional aspects and advantages of the invention will be set forth in part in the description which follows and, in part, will be obvious from the description, or may be learned by practice of the invention.
Drawings
The above and/or additional aspects and advantages of the present invention will become apparent and readily appreciated from the following description of the embodiments, taken in conjunction with the accompanying drawings of which:
FIG. 1 is a schematic structural view of a composite material according to one embodiment of the present invention;
FIG. 2 is a schematic structural view of a composite material according to another embodiment of the present invention;
FIG. 3 is a schematic structural diagram of a composite material according to yet another embodiment of the present invention;
FIG. 4 is a schematic structural diagram of a composite material according to yet another embodiment of the present invention;
FIG. 5 is a schematic structural view of a composite material according to yet another embodiment of the present invention;
FIG. 6 is a schematic structural view of a composite material according to yet another embodiment of the present invention;
FIG. 7 is a schematic structural diagram of a composite material according to yet another embodiment of the present invention;
FIG. 8 is a schematic structural view of a composite material according to yet another embodiment of the present invention;
FIG. 9 is a perspective view of a pot according to one embodiment of the present invention;
FIG. 10 is a bottom view of a pot according to one embodiment of the present invention;
fig. 11 is a bottom view of a pot according to yet another embodiment of the present invention.
Reference numerals:
a substrate 100, an insulating layer 200, an electrothermal alloy coating 300,
the number of the apertures 201 is such that,
an electrothermal alloy coating sublayer 310, an electrothermal alloy coating sublayer 320, an electrothermal alloy coating sublayer 330, an electrothermal alloy coating sublayer 340,
insulating layer sublayer 210, insulating layer sublayer 220, insulating layer sublayer 230, insulating layer sublayer 240,
conductive layer 400, conductive connection 410, power source 420,
interface profile L10, interface profile L20, interface profile L30,
a protective coating 500a, an insulating protective shell 500b,
the cooker 1000, the cooker body 10, the cooker edge 11,
the first insulating layer 20 is formed of a first insulating material,
a heat-generating layer 30, a heat-generating section 31, a circular arc section 311, a first transition section 312, a straight section 313, a second transition section 314,
a first conductive layer 41, a second conductive layer 42.
Detailed Description
Reference will now be made in detail to embodiments of the present invention, examples of which are illustrated in the accompanying drawings, wherein like or similar reference numerals refer to the same or similar elements or elements having the same or similar function throughout. The embodiments described below with reference to the accompanying drawings are illustrative only for the purpose of explaining the present invention, and are not to be construed as limiting the present invention.
A composite material according to an embodiment of the present invention is described below with reference to fig. 1 to 8.
Referring to fig. 1, in one aspect of the present invention, the present invention provides a composite material, which includes a substrate 100, an insulation layer 200, and an electrothermal alloy coating layer 300 according to an embodiment of the present invention, wherein a material constituting the substrate 100 may include metal, ceramic, or glass, the insulation layer 200 is formed on a surface of the substrate 100, and the electrothermal alloy coating layer 300 is formed on a surface of the insulation layer 200 away from the substrate 100.
According to the embodiment of the invention, the inventor of the invention finds that in the process of researching the electrothermal alloy coating, the household appliance adopting the electrothermal alloy coating has the possibility that the electrothermal alloy coating is separated from the insulating layer after being subjected to a plurality of cold and hot cycles in the using process. After the inventor conducts an in-depth analysis, the inventor finds that the bonding force between the insulating layer and the electrothermal alloy coating layer is not easily improved due to the different types of materials used for the insulating layer and the electrothermal alloy coating layer. Therefore, the inventors have conducted intensive studies and found that the bonding force between the insulating layer and the electrothermal alloy coating layer can be effectively improved under the same spray coating conditions by improving the roughness of the interface between the insulating layer and the electrothermal alloy coating layer.
According to an embodiment of the invention, with reference to fig. 6, the profile L30 of the interface of the electrocaloric alloy coating and the insulating layer has an arithmetic mean deviation Ra of the profile not lower than 5 microns, in at least one section of the composite material perpendicular to the plane of the substrate. According to an embodiment of the invention, the electrothermal alloy coating and insulating layer interface profile L30 has an arithmetic mean deviation Ra of the profile of not less than 20 microns, such as 20 microns, 25 microns, 30 microns, 40 microns. In other words, for example, the thickness of the electrothermal alloy coating is 100 μm, the arithmetic mean deviation Ra of the interface profile of the electrothermal alloy coating and the insulating layer is 20%, 25%, 30%, 40% of the thickness of the electrothermal alloy coating. According to an embodiment of the present invention, the electrothermal alloy coating and insulating layer interface profile L30 has a maximum height Rz of not less than 8 microns. According to an embodiment of the present invention, the electrothermal alloy coating and insulating layer interface profile L30 has a maximum height Rz of not less than 25 microns. Therefore, the phenomenon of separation between layers caused by thermal stress between the electrothermal alloy coating and the insulating layer can be reduced, the contact area between the electrothermal alloy coating and the insulating layer can be increased, the transfer of heat to a matrix through the insulating layer can be accelerated, further, the mutually embedded transition connection is adopted, the heat generated by the electrothermal alloy coating is more, the heat conduction speed of the electrothermal alloy coating is higher, the heat conduction speed of the insulating layer is relatively lower, the mutually embedded transition structure connection is arranged, the contact area is increased, the heat transfer efficiency between the electrothermal alloy coating and the insulating layer is improved, on one hand, the phenomenon of separation between the electrothermal alloy coating and the insulating layer caused by the large thermal stress generated by the overlarge temperature difference between the electrothermal alloy coating and the insulating layer is prevented, on the other hand, the corrosion phenomenon generated by the thermal stress of the electrothermal alloy coating can be reduced, and the service life of the electrothermal alloy coating is prolonged, furthermore, the heat of the electrothermal alloy coating can be quickly led into the insulating layer, so that the heat conduction efficiency of the insulating layer is accelerated, and the heating efficiency of the substrate is improved.
In the present invention, the term "composite material" refers to a composite body composed of a multilayer structure.
According to an embodiment of the present invention, referring to fig. 6, the composite material further includes: and a conductive layer 400, the conductive layer 400 being formed on at least a portion of a surface of the electrothermal alloy coating layer 300, a material constituting the conductive layer 400 including silver or copper. Therefore, the electrothermal alloy coating can be connected with an external circuit through the conducting layer, so that the composite material has good electrothermal performance.
According to an embodiment of the present invention, the insulating layer and the conductive layer may be formed by spraying, respectively, that is, the insulating layer is an insulating coating and the conductive layer is a conductive coating. The inventor finds that the situation that peeling easily occurs between the insulating layer and the substrate and between the electrothermal alloy coating and the conductive coating in the using process of the composite material is also caused by different types of materials between the two adjacent layers.
According to an embodiment of the present invention, referring to fig. 6, in order to improve the bonding force and the contact area of the conductive coating 400 and the electrothermal alloy coating 300, the inventors of the present invention propose a structure in which the conductive coating 400 and the electrothermal alloy coating 300 are inlaid with each other. According to an embodiment of the invention, the interface profile L20 of the electrically conductive coating 400 and the electrothermal alloy coating 300 has an arithmetic mean deviation Ra of the profile of not less than 5 micrometers in at least one cross section of the composite material perpendicular to the plane of the substrate. According to an embodiment of the present invention, the interface profile L20 of the electrically conductive coating 400 and the electrothermal alloy coating 300 has an arithmetic mean deviation Ra of the profile of not less than 20 microns, such as 20 microns, 25 microns, 30 microns, 40 microns. In other words, for example, for a 100 μm thick electrocaloric alloy coating, the arithmetic mean deviation Ra of the interface profile of the electrocaloric alloy coating and the conductive coating is 20%, 25%, 30%, 40% of the thickness of the electrocaloric alloy coating. According to an embodiment of the present invention, the interface profile L20 of the conductive coating 400 and the electrocaloric alloy coating 300 has a maximum height Rz of not less than 8 microns. According to an embodiment of the present invention, the interface profile L20 of the conductive coating 400 and the electrocaloric alloy coating 300 has a maximum height Rz of not less than 25 microns. Because the types of materials used for the conductive coating 400 and the electrothermal alloy coating 300 are different, a structure in which the conductive coating 400 and the electrothermal alloy coating 300 are inlaid into each other can be formed according to the roughness of the interface, so that the bonding force between the conductive coating 400 and the electrothermal alloy coating 300 can be effectively improved, the contact area can be effectively increased, and the transmission efficiency of current can be improved.
According to an embodiment of the present invention, referring to fig. 6, in order to improve the bonding force between the insulating layer and the substrate, in at least one section of the composite material perpendicular to the plane of the substrate, the interface profile L10 of the substrate 100 and the insulating layer 200 has a profile arithmetic mean deviation Ra of not less than 20 μm. According to an embodiment of the present invention, the interface profile L10 of the substrate 100 and the insulating layer 200 has an arithmetic mean deviation Ra of the profile of not less than 30 micrometers, such as 40 micrometers, 50 micrometers, 60 micrometers. In other words, for an insulating layer having a thickness of 200 μm, the arithmetic mean deviation Ra of the interface profile between the insulating layer and the substrate is 20%, 25%, 30% of the thickness of the insulating layer. According to an embodiment of the present invention, the interface profile L10 of the substrate 100 and the insulating layer 200 has a maximum height Rz of not less than 25 μm. According to an embodiment of the present invention, the interface profile L10 of the substrate 100 and the insulating layer 200 has a maximum height Rz of not less than 35 μm. Therefore, the roughness of the interface between the insulating layer and the substrate is improved, so that the bonding force between the insulating layer and the substrate can be effectively improved under the same spraying condition. Specifically, according to the roughness of the interface, the insulating layer 200 may be embedded in the substrate 100, so that the bonding force between the insulating layer and the substrate may be effectively improved. In addition, under the condition that the cross section between the substrate 100 and the insulating layer 200 has a certain roughness, the outer surface of the formed insulating layer 200, which is far away from the substrate 100, also has a certain roughness, so that the bonding force between the electrothermal alloy coating 300 and the insulating layer 200 sprayed on the outer surface is further enhanced, and further, the method is also helpful for promoting the bonding force between the electrothermal alloy coating 300 and the conductive coating 400, increasing the bonding area of the electrothermal alloy coating 300 and the conductive coating 400, and improving the current transmission efficiency.
The surface of the substrate 100 may be roughened by a blasting process or a sanding process, preferably a blasting process, as required before the insulating layer 200 is formed, so that the degree of roughness can be easily controlled, and for example, blasting with a particle size of 50 to 100 μm may be performed at a pressure of 0.8 to 1.5MPa for 10 to 200 seconds.
According to an embodiment of the invention, the arithmetic mean deviation Ra of the profile of the interface between the insulating layer and the substrate is greater than the arithmetic mean deviation Ra of the profile of the interface between the insulating layer and the electrothermal alloy coating and greater than the arithmetic mean deviation Ra of the profile of the interface between the electrothermal alloy coating and the conductive coating. Therefore, the binding force between layers can be improved, heat generated by the electrothermal alloy coating can be quickly transferred to the insulating layer, the efficiency and uniformity of heat transfer from the insulating layer to the substrate are improved, the thermal stress between the substrate and the insulating layer is reduced, and the delamination phenomenon between the substrate and the insulating layer is prevented.
It will be understood by those skilled in the art that the terms arithmetic mean deviation Ra and maximum height Rz of the profile as used herein are common parameters for evaluating the surface profile of an object, and those skilled in the art can perform detection by well-known means after acquiring an interface image, for example, the national standard GB/T1031-: the arithmetic mean deviation Ra of the profile is the arithmetic mean of the absolute values of the distances from each point on the measured profile to the datum line in the sampling length; the maximum height Rz is the sum of the average of the peak heights of the five maximum profiles and the average of the valley bottoms of the five maximum profiles over the measured profile over the sample length.
According to an embodiment of the present invention, in order to further improve the bonding force between the electrothermal alloy coating layer and the insulating layer, the electrothermal alloy coating layer contains a metal element and an oxygen element, and the atomic percent of the oxygen element does not exceed 40 at% in at least a part of the area of the electrothermal alloy coating layer.
According to the embodiment of the invention, by adopting the electrothermal alloy coating 300, electric energy can be effectively converted into heat energy, the heating efficiency is high, uniform heating is easy, and the use and preparation cost can be reduced. However, in the process of studying the electrothermal alloy coating 300, the inventor of the present invention found that, in the use process of the household appliance using the electrothermal alloy coating 300, after a plurality of cooling and heating cycles, deformation may occur between the insulating layer 200 and the electrothermal alloy coating 300, and a fracture may seriously occur to cause electric leakage or short circuit. The inventor of the present invention has conducted extensive studies and found that, due to the different compositions of the insulating layer 200 and the electrothermal alloy coating 300, a large difference in thermal expansion coefficient exists between the insulating layer 200 and the electrothermal alloy coating 300, and then after multiple hot and cold cycles, the insulating layer 200 and the electrothermal alloy coating 300 are deformed, thereby causing a series of adverse effects. Therefore, the inventors have conducted intensive studies and unexpectedly found that the introduction of oxygen into the electrothermal alloy coating layer 300 can reduce the difference in the expansion coefficient between the electrothermal alloy coating layer 300 and the insulating layer 200, thereby reducing the thermal stress between the electrothermal alloy coating layer 300 and the insulating layer 200, and improving the bonding strength between the electrothermal alloy coating layer 300 and the insulating layer 200 and the life span during thermal cycling. And it has been unexpectedly found that the introduction of oxygen also contributes to the improvement of the resistance and heat generation efficiency of the electrothermal alloy coating 300. The oxygen content can be controlled by the spraying atmosphere, and with the increase of the oxygen element content, the expansion coefficient of the electrothermal alloy coating 300 and the expansion coefficient of the insulating layer 200 tend to be consistent, so that the deformation between the insulating layer 200 and the electrothermal alloy coating 300 is avoided when the electrothermal alloy coating undergoes cold and heat changes. In addition, as the inventors have conducted extensive studies, it has been found that as the oxygen content increases, particularly when the oxygen content exceeds 40% (atomic number percentage, which may be directly expressed as "at%", herein), the electric resistance of the electrothermal alloy coating layer 300 becomes too high, which may lower the heat generation efficiency of the electrothermal alloy coating layer, may overheat the electrothermal alloy coating layer 300 to shorten the life, and may rapidly deteriorate the electrical conductivity of the electrothermal alloy coating layer. Therefore, by controlling the content of oxygen element in the electrothermal alloy coating 300 within 40% (atomic number percentage), the electrothermal alloy coating can have high heat generation efficiency under the condition of avoiding the deformation or cracking between the insulating layer and the electrothermal alloy coating, and the electric conductivity of the electrothermal alloy coating 300 can be prevented from being deteriorated, so that the composite material can be ensured to be used for heating units of electric appliances such as household electric appliances.
Further, according to an embodiment of the present invention, in at least a part of the area of the electrothermal alloy coating layer, the atomic percent of oxygen element is not less than 5 at%. According to the embodiment of the invention, in at least one part of the electrothermal alloy coating layer, the atomic percent of oxygen element is 5-30 at%. Therefore, the expansion coefficient between the insulating layer and the electrothermal alloy coating is further ensured to be close, and deformation and even cracking between the insulating layer and the electrothermal alloy coating are avoided when the electrothermal alloy coating undergoes cold and hot changes.
It is noted that the content of a specific element (including but not limited to oxygen element, metal element, etc.) in the coating layer can be determined by means well known to those skilled in the art, such as X-ray fluorescence spectroscopy, X-ray diffraction spectroscopy, scanning electron microscopy spectroscopy, atomic emission spectroscopy, inductively coupled plasma emission spectroscopy, ultraviolet-visible spectrophotometry, and electrochemical methods. It will be understood by those skilled in the art that for a given material, when determining the content of a specific element, it is not necessary to determine the content of the whole material, but one or more sites may be detected, and an arithmetic average may be taken as a detection result, for example, the content of oxygen may be determined by performing elemental analysis on more than 3 sites of the material to be detected, and the average of the oxygen content at these sites may be taken as a final detection result. In addition, one skilled in the art can use in situ detection or sample a particular coating before performing the detection, as the case may be.
According to the embodiment of the present invention, the type of metal of the electrothermal alloy coating that can be used is not particularly limited as long as it can be adapted to form a stable coating on the surface of the insulator and can generate a desired amount of heat when an electric current is passed. The electrothermal alloy coating which can be used includes both Ni-Cr system and Fe-Cr-Al system alloys, and some rare metal elements such as yttrium element may be added according to circumstances. To this end, according to an embodiment of the present invention, the metal element for forming the electrothermal alloy coating layer includes at least one selected from the group consisting of chromium element, aluminum element, yttrium element, iron element, manganese element, and nickel element. According to an embodiment of the present invention, the metal element includes: 15 to 25 at% of chromium element; 10 to 20 at% of aluminum element; 0.1 to 1.5 at% of yttrium element; and the balance of iron. Thus, high heating efficiency is achieved, and the cost is relatively low, and such elemental proportioning enables good compatibility between the electrothermal alloy coating 300 and the adjacent layers (insulating layer 200, conductive coating 400, or protective coating 500a) in the composite material.
The means for forming the electrothermal alloy coating layer 300 according to the embodiment of the present invention is not particularly limited, and various known spraying methods may be employed. According to an embodiment of the present invention, the electrothermal alloy coating 300 may be formed by thermal spraying, such as supersonic spraying or plasma spraying. In the process of forming the electrothermal alloy coating layer 300, a desired oxygen element content can be easily obtained by controlling the supply amount of oxygen. The oxygen element content can be obtained, for example, by adjusting the ratio of air and inert gas. Additionally, referring to FIG. 3, an electrothermal alloy coating 300 may include a plurality of electrothermal alloy coating sub-layers 310, 320, 330, and 340 disposed in a sequential stack, according to an embodiment of the present invention. One skilled in the art may use different elemental oxygen contents for these electrothermal alloy coating sublayers 310, 320, 330, and 340 as desired. According to some examples of the invention, the amount of oxygen in the electrocaloric alloy coating sublayers 310, 320, 330, and 340 decreases in a direction away from the insulating layer (i.e., bottom-to-top in fig. 3) in at least one region of the electrocaloric alloy coating 300. Thus, regions proximate to the insulating layer 200, such as the electrothermal alloy coating sub-layer 340, having a relatively high oxygen content, may have a coefficient of expansion close to that of the insulating layer 200, while regions distal from the insulating layer 200, such as the electrothermal alloy coating sub-layer 310, may have a relatively low oxygen content, which may ensure good electrical conductivity of the electrothermal alloy coating 300. It should be noted that the 4 electrothermal alloy coating sublayers 310, 320, 330 and 340 illustrated in FIG. 3 are for convenience of description only, and those skilled in the art may arrange the electrothermal alloy coating sublayers 310, 320, 330 and 340 according to the total thickness of the electrothermal alloy coating 300 or according to the need, for example, more than ten electrothermal alloy coating sublayers may be used. In addition, it should be noted that, for the plurality of electrothermal alloy coating sub-layers 310, 320, 330 and 340, the oxygen content in the electrothermal alloy coating sub-layers 310, 320, 330 and 340 decreases along the direction away from the insulating layer (i.e. the direction from bottom to top in fig. 3), and it does not mean that the oxygen content of the upper layer is lower than that of the lower layer between any two adjacent electrothermal alloy coating sub-layers, and here, only the trend of the oxygen content is described as a whole, and generally, the oxygen content of the outermost layer, such as the electrothermal alloy coating sub-layer 310 in the figure, is lower than that of the innermost layer, such as the electrothermal alloy coating sub-layer 340, and the fluctuation of the oxygen content of one or several layers may exist in the middle, which is allowed.
In addition, according to the embodiment of the invention, the thickness of the electrothermal alloy coating layer 300 is 10 to 150 micrometers in at least a partial region. According to the embodiment of the invention, the thickness of the electrothermal alloy coating layer 300 is 30-150 microns. According to an embodiment of the present invention, the thickness of the electrocaloric alloy coating 300 is 50 microns. Thus, the electrothermal alloy coating 300 can effectively meet the heat requirement of household appliances such as cookware. It should also be noted that, for composite materials, the thickness of each coating layer can also be detected by various known means, and the final detection result can be determined by a method of arithmetic mean of multipoint detection. One skilled in the art will appreciate that different thicknesses of the electrothermal alloy coating 300 will result in different resistances and different heating powers.
The type of material that may be used for the matrix 100 of the composite material is not particularly limited, according to embodiments of the present invention. According to some specific examples of the present invention, the base 100 is formed of at least one selected from the group consisting of metal, ceramic, and glass. According to some embodiments of the present invention, the metal may include at least one selected from aluminum, aluminum alloy, stainless steel, iron alloy and iron, such as 304 stainless steel, 430 stainless steel, and the like. These materials are commonly used in electric appliances such as home appliances, and have a good heat conduction property, and thus, can effectively conduct heat generated from the electrothermal alloy coating layer. Further, when the composite material is applied to a household appliance, it may be convenient to directly use a part of the structure or component existing in the appliance as the substrate 100, for example, according to some embodiments of the present invention, the outer wall of the pot body of an electric cooker may be used as the substrate 100, and further, other coatings of the composite material may be formed on such substrate 100.
In addition, regarding the insulating layer 200, according to an embodiment of the present invention, the insulating layer 200 may be formed using thermal spraying, and particularly, the insulating layer 200 is formed by thermal spraying. According to an embodiment of the present invention, the insulating layer 200 may be formed of aluminum oxide, silicon oxide, or aluminum nitride. Alumina can be present in the form of ceramic materials, which have good insulating properties, and can have good compatibility with a variety of metal alloys and matrix materials. According to an embodiment of the invention, the insulation voltage of the composite material is not less than 1250 volts. According to an embodiment of the invention, the insulation voltage of the composite material is not less than 2500 volts. Therefore, the insulating layer can have satisfactory insulating performance, so that the situation that the insulating layer is broken down by high voltage cannot occur in the using process of household appliances adopting the composite coating. It should be noted that the insulation voltage of the composite material is not lower than 1250V, which means that after 1250V is applied to the composite material, the composite material is not broken down, and the voltage of the composite material which is not broken down can reach 2500V at most.
Referring to fig. 2, in accordance with an embodiment of the present invention, the insulating layer 200 has a porosity of no more than 5% in at least a portion of the region. According to an embodiment of the present invention, the porosity of the insulating layer 200 is not less than 0.1%. According to an embodiment of the present invention, the porosity of the insulating layer 200 does not exceed 2%. According to an embodiment of the invention, the porosity of the composite material is 0.1 to 3% in at least a part of the area. The inventor of the present invention has found that, in the process of studying the electrothermal alloy coating 300, the household appliance using the electrothermal alloy coating 300 may have a high voltage breakdown of the insulating layer 200 during the use. In order to avoid this, the inventors conducted an in-depth analysis of the insulating layer 200, and found that, although the material itself used to form the insulating layer 200 has good insulating properties, voids 201 are present between particles due to melt stacking of the particles during thermal spraying. When the porosity in the insulating layer reaches a certain value, the insulating layer may be broken down resulting in a safety risk. Therefore, under the same porosity, the thicker the insulating layer thickness is, the better; the lower the porosity in the insulating layer, the better the same thickness of the insulating layer. However, when the porosity is less than 0.1%, the required flame temperature of thermal spraying is as high as 10000 ℃ or more, the particle velocity for forming the insulating layer is more than 1000m/s, which is difficult to be achieved by the prior art, and the conditions of the preparation process become severe. In addition, the inventors have found that, when the thickness of the insulating layer exceeds 500 μm, the bonding force between the insulating layer and the substrate 100 or the electrothermal alloy coating layer 300 is drastically reduced. In addition, the inventors have found that the pores 201 are hygroscopic during use of the appliance, thereby further reducing the insulation of the insulating layer. For this reason, the inventors have conducted intensive studies on the porosity of the insulating layer, and found that when the porosity of the insulating layer exceeds 5%, the insulating property of the insulating layer 200 is deteriorated, and the moisture absorption of the insulating layer 200 is increased, and there is a possibility that the insulating layer is broken down even by high voltage. According to the embodiment of the invention, the inventor finds that the insulating property of the insulating layer can be effectively improved by controlling the porosity of the insulating layer within a certain range, the insulating layer is prevented from being broken down by high voltage, and meanwhile, a harsh spraying process is also avoided.
According to the embodiment of the invention, the thickness of the insulating layer 200 is 50 to 500 micrometers in at least one part of the region. According to the embodiment of the invention, the thickness of the insulating layer is 100-300 microns. According to an embodiment of the invention, the thickness of the insulating layer is 200 microns. The inventors of the present invention have found that, by controlling the thickness of the insulating layer within the above range, the insulating layer still has satisfactory insulating properties with a porosity higher than 0.1%, for example, higher than 0.2%, and can ensure a strong bonding strength between the insulating layer 200 and other coating layers, for example, the electrothermal alloy coating 300 or the substrate 100.
In addition, one skilled in the art can form the insulating layer 200 by spray coating, such as a plasma spray coating process, and can achieve a range of porosity (also sometimes referred to as porosity) by controlling parameters of the plasma spray coating process. Referring to fig. 4, the insulating layer 200 may include a plurality of insulating layer sub-layers 210, 220, 230, and 240 sequentially stacked according to an embodiment of the present invention. One skilled in the art may employ different porosities for the insulating layer sub-layers 210, 220, 230, and 240 as desired. According to some examples of the invention, the porosity in the insulating layer sub-layers 210, 220, 230, and 240 increases in a direction away from the insulating layer (a bottom-up direction in the drawing). Thus, the insulating layer sub-layer 240 has relatively low porosity and high insulating performance in a region close to the substrate 100, and the insulating layer sub-layer 210 has relatively high porosity in a region far from the substrate 100, so that the manufacturing cost can be reduced and the bonding force between the insulating layer and the electrothermal alloy coating can be improved. It should be noted that the 4 insulating layer sub-layers 210, 220, 230 and 240 shown in the drawings are only for convenience of description, and those skilled in the art may set the number of the insulating layer sub-layers according to the desired total thickness of the insulating layer 200 or according to the need, for example, ten or more stacked insulating layer sub-layers may be used. In addition, it should be particularly noted that, for the plurality of insulating layer sub-layers 210, 220, 230 and 240, the porosity in the insulating layer sub-layers 210, 220, 230 and 240 increases along the direction away from the substrate, and does not mean that the requirement is satisfied between any two adjacent insulating layer sub-layers, and the trend is only described as a whole.
The porosity of the insulating layer can be determined by one skilled in the art using techniques known in the art, for example, by taking a cross-sectional view of the composite coating and measuring the area fraction of pores 201 in the insulating layer 200 per unit area. It will be appreciated by those skilled in the art that by taking an average of a plurality of porosity values based on a plurality of cross sections, the porosity of the final insulating layer 200 may be determined. In addition, one skilled in the art can also refer to drainage methods to determine the porosity of the composite material as a whole. Thus, according to embodiments of the present invention, the porosity of the composite material is 0.1 to 3% in at least a part of the region. Therefore, the breakdown voltage resistance of the composite material can be improved, and the safety of the composite material in the using process can be improved.
Referring to fig. 5 and 8, the electrothermal alloy coating 300 can generate a large amount of heat when current passes through it, and in the embodiment of the present invention, it is proposed that the current is supplied to the electrothermal alloy coating 300 through the conductive coating 400, and the conductive coating 400 has a large contact area with the electrothermal alloy coating 300, so that the current transmission efficiency can be improved. According to embodiments of the present invention, the conductive coating may have a thickness of 30-150 microns. Therefore, the conductive coating has good conductive performance. According to an embodiment of the present invention, the composite material further comprises a conductive connector 410, one end of the conductive connector 410 is connected to the conductive coating 400, and the other end of the conductive connector 410 is adapted to be connected to a power source 420. According to an embodiment of the present invention, at least one of the conductive connecting member 410 and the conductive coating 400 is a low heat generating material, for example, formed of copper or silver. Therefore, in the process that the power supply 420 supplies power to the electrothermal alloy coating 300 through the conductive connecting piece 410 and the conductive coating 400, the conductive connecting piece 410 does not generate excessive heat, so that the phenomenon that the conductive connecting piece 410 is connected with the power supply 420 and hot melting does not occur in the working process of the electrothermal alloy coating 300 is avoided, and further the conductive connecting piece 410 and the power supply 420 can be connected by adopting a metal material with a relatively low melting point, for example, in a soldering mode, so that the production cost is reduced.
According to an embodiment of the invention, the electrocaloric alloy coating has a predetermined pattern. According to the embodiment of the invention, the electrothermal alloy coatings are distributed at intervals on the interface vertical to the plane of the substrate. The electrothermal alloy coating and the insulating layer are not completely covered, so that heat is generated locally, the heat at the corresponding position of the insulating layer is higher, then the heat is diffused and transferred at other positions of the insulating layer, and the heat at the corresponding position of the corresponding substrate is also possibly relatively higher.
Referring to fig. 7 and 8, the composite material may also have protective means, such as protectors 500a, 500b, according to embodiments of the invention, the protectors 500a, 500b covering at least a portion of the electrocaloric alloy coating 300. According to an embodiment of the present invention, the protection member is a protective coating 500a, and the protective coating 500a covers at least a portion of the surface of the electrothermal alloy coating 300 remote from the substrate 100. According to an embodiment of the present invention, the protection member is an insulating protective shell 500b, and the insulating protective shell 500b may cover at least a portion of the surface of the electrothermal alloy coating 300 away from the substrate 100. Therefore, the electrothermal alloy coating can be further protected, electric shock of a user in the use process is avoided, and short circuit of the electrothermal alloy coating caused by air or other materials in the use process can also be avoided. It will be appreciated by those skilled in the art that the protector is preferably made of an insulating material. For example, the protective member may be a ceramic coating, an insulating varnish, or an insulating structure such as a plastic shell.
It should be noted that the features and advantages described above for the respective coatings or components may be combined with each other and are described separately for convenience only and will not be described again here.
As previously mentioned, the composite materials described herein may be used in the field of home appliances as heating elements for home appliances and can exert their various advantages. Thus, in a second aspect of the invention, the invention proposes an electrical appliance. According to an embodiment of the invention, the appliance comprises: a heating assembly having the composite material described previously. Thus, according to embodiments of the present invention, the appliance may utilize the efficient heat generation efficiency of the composite material. In addition, as described above, by increasing the roughness of the interface between adjacent coating layers, the bonding force between adjacent coating layers can be effectively increased under the same spray condition. Specifically, according to the roughness of the interface, a structure that the conductive coating and the electrothermal alloy coating are embedded with each other can be formed, so that the bonding force of the conductive coating and the electrothermal alloy coating can be effectively improved. Therefore, the electric appliance adopting the composite coating has high safety and use reliability.
According to the embodiment of the present invention, the field to which the composite material can be applied is not particularly limited, and applicable appliances include cooking appliances or liquid heating containers, and specifically, air conditioners, cleaning appliances, kitchen appliances, electric warming appliances, and cosmetic health care appliances.
Referring to fig. 9 to 11, according to an embodiment of the present invention, the electric appliance is a pot 1000, the pot includes the composite material and the pot body 10, a portion of the outer wall of the pot body 10 constitutes a matrix of the composite material, and the electric heating alloy coating 300 is disposed on the outer wall of the pot body 10.
In order to improve the heating efficiency of the electrothermal alloy coating, according to the embodiment of the invention, the electrothermal alloy coating 300 forms the heat generating layer 30 of the pot 1000 on the pot body, the heat generating layer comprises a plurality of heat generating sections 31 connected end to end in sequence, the head end of the first heat generating section 31 in the plurality of heat generating sections 31 is suitable for being connected with the power input end of the heating circuit, and the tail end of the last heat generating section 31 in the plurality of heat generating sections 31 is suitable for being connected with the power output end of the heating circuit.
Therefore, the heating layer 30 is divided into the plurality of heating sections 31 which are connected in series, a loop can be formed during electrification, wherein the heating sections 31 can be one or two combinations of straight lines and circular arcs, so that the heating layer 30 is attractive in arrangement, simple in manufacturing process and high in utilization rate.
In some embodiments, a portion of the plurality of heat-generating segments 31 is an arc segment 311, another portion of the plurality of heat-generating segments 31 is a first transition segment 312, a center of a circle corresponding to the plurality of arc segments 311 is a center of a bottom wall of the pot body, and at least a portion of the plurality of arc segments 311 is arranged at intervals in a radial direction of a circumference with the center of the bottom wall of the pot body as a center, that is, a circle corresponding to at least a portion of the plurality of arc segments 311 is arranged concentrically. In the extending direction of the heat generating layer 30, the plurality of arc segments 311 are arranged at intervals, the plurality of first transition segments 312 are arranged at intervals, two adjacent arc segments 311 are connected through the first transition segment 312, and the arc segments 311 are connected between two adjacent first transition segments 312. The plurality of arc sections 311 and the plurality of first transition sections 312 are connected in series, so that a loop can be formed during electrification, uniform heating is realized, the heating layer 30 is attractive in arrangement, the manufacturing process is simple, and the utilization rate is high. In some examples, the first transition section 312 is a straight or arcuate section. Specifically, in the present embodiment, two adjacent circular arc segments 311 are connected by a straight line segment. In the present embodiment, two adjacent circular arc segments 311 are connected by a circular arc transition.
In some embodiments, a portion of the plurality of heat-emitting segments 31 is a straight segment 313, another portion of the plurality of heat-emitting segments 31 is a second transition segment 314, and at least a portion of the plurality of straight segments 313 are arranged in parallel or in line. In the extending direction of the heat generating layer 30, a plurality of straight sections 313 are arranged at intervals, a plurality of second transition sections 314 are arranged at intervals, two adjacent straight sections 313 are connected through the second transition sections 314, and two adjacent second transition sections 314 are connected through the straight sections 313. The plurality of straight sections 313 and the plurality of second transition sections 314 are connected in series, so that a loop can be formed when the power is on, uniform heating is realized, the heating layer 30 is beautiful in arrangement, the manufacturing process is simple, and the utilization rate is high.
In some examples, the second transition section 314 forms an arc section and the circle center corresponding to the arc section is the center of the bottom wall of the pan body; and/or the second transition section 314 forms a straight line segment. Specifically, two adjacent straight sections 313 may be connected by a circular arc section and a straight section.
Since the current always flows along the path with the shortest distance, if the corner formed between two adjacent heating sections 31 is a right angle, especially the current is easily accumulated at the position where the inner corner is the right angle, which results in the right angle current being too high, the local temperature of the heating layer 30 is too high if light, and the local heating section 31 of the heating layer 30 is easily burned out if heavy, and even a short circuit is easily caused. Therefore, in some embodiments, two adjacent heat generation sections 31 are connected in a circular arc transition manner.
In order to prevent the heating section 31 from being worn or damaged to affect the heating effect of the pan body 10, in some embodiments, the width D2 of the heating section 31 is set to be 0.1mm to 30 mm. For example, the width D2 of the heat emitting segment 31 may be 0.1mm, 10mm, 15mm, 20mm, 25mm, 30 mm. In some examples, the width D2 of the heat emitting segment 31 is set to be 5mm to 12 mm.
It should be noted that too large a distance D1 between two adjacent heat generating segments 31 will result in poor uniformity of heating temperature, too small a distance D1 between two adjacent heat generating segments 31 will result in small creepage distance for the first heat generation, and if there is a foreign matter between two adjacent heat generating segments 31 or the environment is wet, an arc is easily generated, thereby damaging the heat generating layer 30.
Therefore, in some embodiments, the distance D1 between two adjacent heat generating segments 31 arranged at intervals is set to be 0.1mm to 20 mm. For example, the distance D1 between two adjacent spaced-apart heat emitting segments 31 may be 0.1mm, 5mm, 8mm, 12mm, 15mm, 20 mm. In some examples, the distance D1 between two adjacent spaced-apart heat emitting segments 31 is 5mm to 10mm, for example, the distance D1 between two adjacent spaced-apart heat emitting segments 31 may be 5mm, 7mm, 10 mm.
Other components of the appliance according to embodiments of the present invention, such as power supplies, control components, etc., and operations, are known to those of ordinary skill in the art and will not be described in detail herein.
It should be noted that the features and advantages described above for the composite material are also applicable to the electrical appliance according to the embodiment of the present invention, and are not described herein again.
In a third aspect of the invention, the invention proposes a method for preparing a composite material as described above.
According to an embodiment of the invention, the method comprises:
(1) an insulating layer is formed on a surface of the base. According to an embodiment of the present invention, the step (1) further comprises; (1-a) roughening at least a part of a surface of a substrate; (1-b) forming an insulating layer on the roughened surface by explosion spraying or plasma spraying. Since the surface of the substrate has a certain roughness, the bonding force between the insulating layer and the substrate can be further enhanced. According to an embodiment of the present invention, the roughening treatment is performed by at least one of sand blasting, grinding and chemical etching. The degree of roughness can be easily controlled by preferably performing a blasting treatment, and for example, the blasting treatment may be performed for 10 to 200 seconds under a pressure of 0.8 to 1.5MPa with a particle size of 50 to 100 μm.
(2) Forming an electrothermal alloy coating on the surface of the insulating layer remote from the substrate, and making the interface profile of the electrothermal alloy coating and the insulating layer have an arithmetic mean deviation Ra of profile not less than 5 μm, so as to obtain the composite material. According to an embodiment of the present invention, the electrothermal alloy coating layer may be formed by supersonic spraying or plasma spraying.
By this method, the aforementioned composite material can be efficiently obtained. As described above, in addition, as described above, by increasing the roughness of the interface between the adjacent coating layers, the bonding force between the adjacent coating layers can be effectively increased under the same spray condition. Specifically, according to the roughness of the interface, a structure that the electrothermal alloy coating and the insulating layer are embedded with each other can be formed, so that the bonding force of the electrothermal alloy coating and the insulating layer can be effectively improved. Therefore, the electric appliance adopting the composite coating has high safety and use reliability.
Thereby, it can be ensured that the composite material can be used for a heating unit of an appliance, such as a household appliance.
According to the embodiment of the present invention, it is further possible to include: and forming a conductive coating on the surface of the electrothermal alloy coating layer far away from the insulating layer by electric arc spraying or cold spraying.
It should be noted that the features and advantages described above for the composite material are also applicable to the method for preparing the composite material according to the embodiment of the present invention, and will not be described herein again. In addition, regarding the formation process of the coating layer, it is well known in the art, and those skilled in the art can accomplish it according to the process conditions selected as described herein without inventive labor.
The scheme of the invention will be explained with reference to the examples.
It will be appreciated by those skilled in the art that the following examples are illustrative of the invention only and should not be taken as limiting the scope of the invention. The examples, where specific techniques or conditions are not indicated, are to be construed according to the techniques or conditions described in the literature in the art or according to the product specifications. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products commercially available.
Example 1
Preparation of composite Material
After the surface cleaning treatment of the stainless steel material, the surface of the stainless steel was subjected to a sand blasting treatment, and the surface profile of the stainless steel substrate was allowed to have an arithmetic mean deviation Ra of the profile of 40 μm by controlling the conditions of the sand blasting treatment.
And spraying an insulating layer on the surface of the stainless steel material subjected to sand blasting through a plasma spraying process, wherein the insulating layer is made of aluminum oxide, and the porosity of the insulating layer is ensured to be 3% by adjusting spraying parameters, and the thickness of the insulating layer is 200 microns. The interface profile of the insulating layer and the stainless steel substrate had an arithmetic mean deviation Ra of the profile of 40 micrometers.
On the surface of the formed insulating layer, 35-45 at% of FeCrAlY powder (iron (Fe), 15-25 at% of chromium (Cr), 10-20 at% of aluminum (Al), 0.1-1.5 at% of yttrium (Y)) was spray-coated with supersonic flame, and the amount of oxygen supplied was controlled so that the oxygen content of the electrothermal alloy coating was 20 at%, thereby forming an electrothermal alloy coating having a thickness of 50 μm. The profile of the interface of the electrocaloric alloy coating and the insulating layer has an arithmetic mean deviation Ra of the profile of 20 microns.
Copper is sprayed on the surface of the formed electrothermal alloy coating by cold spraying, so that a conductive coating with the thickness of 50 microns is formed. The interface profile of the conductive coating and the electrothermal alloy coating has an arithmetic mean deviation Ra of the profile of 20 microns.
Cross section detection
The cross section of the obtained composite material is detected, and the result shows that an obvious mutual mosaic structure is formed between the copper layer (conductive coating) and the FeCrAlY layer (electrothermal alloy coating), and in addition, a cross structure is also formed between the alumina layer (insulating layer), the FeCrAlY layer (electrothermal alloy coating) and the stainless steel layer (substrate).
Performance detection
In this example, the composite obtained in example 1 was examined for bond strength by hot and cold cycles (room temperature-400 degrees celsius) 1000 times, and it was found that no significant cracking occurred between the layers.
In the embodiment, the breakdown of the composite material is also detected, and the composite material can withstand the voltage of 1250-2500V without being broken down.
Example 2 to example 6
The composite materials of examples 2 to 6 were prepared by substantially the same procedure as in example 1, except that the surface of the stainless steel was not subjected to the sand blast treatment and the oxygen content in the electrothermal alloy coatings of examples 2 to 6 was controlled to 10 at%, 15 at%, 25 at%, 30 at%, and 35 at% when the surface of the insulating layer was subjected to the supersonic flame spraying of the FeCrAlY powder.
The bonding strength of the composite materials obtained in examples 2-6 was tested by hot and cold cycles (room temperature-400 ℃)1000 times, and it was found that no significant cracking occurred between the insulating layer and the electrothermal alloy coating in the composite materials.
Example 7 example 10
Examples 7-10 were prepared substantially the same as in example 1, except that, when the insulating layer was sprayed by a plasma spraying process, the spraying parameters (e.g., spraying speed, spraying pressure, spraying temperature) were adjusted such that the porosity of the insulating layer in example 7 was 1% and the thickness was 100 μm, the porosity of the insulating layer in example 8 was 2% and the thickness was 200 μm, the porosity of the insulating layer in example 9 was 4% and the thickness was 400 μm, and the porosity of the insulating layer in example 10 was 5% and the thickness was 400 μm.
The breakdown resistance of the composite materials obtained in examples 7 to 10 was examined, and it was found that the composite materials were able to withstand a voltage of 1250 to 2500V without being broken down.
Examples 11 and 12
The composite materials of examples 11 and 12 were prepared in substantially the same manner as in example 1, except that the stainless steel substrate and the insulating layer in example 11 were made to have an arithmetic mean deviation of profile Ra of 30 μm in the profile of the interface between the insulating layer and the electrocaloric alloy coating layer and the profile of the interface between the electrocaloric alloy coating layer and the conductive coating layer, respectively, 10 μm in the profile of the interface between the electrocaloric alloy coating layer and the conductive coating layer by controlling the conditions of the blasting treatment when the stainless steel surface was subjected to the blasting treatment; let the profile of the interface of the stainless steel substrate and the insulating layer in example 12 have an arithmetic mean deviation Ra of profile of 50 micrometers, the profile of the interface of the insulating layer and the electrocaloric alloy coating layer, and the profile of the interface of the electrocaloric alloy coating layer and the conductive coating layer have an arithmetic mean deviation Ra of profile of 30 micrometers, respectively.
When the cross sections of the composite materials obtained in the examples 11 and 12 are detected, obvious mutual mosaic structures are formed between the conductive coating and the electrothermal alloy coating, and in addition, cross structures are also formed between the insulating layer and the electrothermal alloy coating as well as between the insulating layer and the substrate.
The composite materials obtained in examples 11 and 12 were tested for bond strength by hot and cold cycles (room temperature-400 degrees celsius) 1000 times, and it was found that no significant cracking occurred between the layers.
In the description herein, references to the description of the term "one embodiment," "some embodiments," "an illustrative embodiment," "an example," "a specific example," or "some examples" or the like mean that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the invention. In this specification, the schematic representations of the terms used above do not necessarily refer to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples.
While embodiments of the invention have been shown and described, it will be understood by those of ordinary skill in the art that: various changes, modifications, substitutions and alterations can be made to the embodiments without departing from the principles and spirit of the invention, the scope of which is defined by the claims and their equivalents.

Claims (24)

1. A composite material, comprising:
a substrate, the material of which comprises metal, ceramic or glass;
an insulating layer formed on a surface of the base;
an electrothermal alloy coating formed on the surface of the insulating layer remote from the substrate,
and on at least one section of the composite material, which is perpendicular to the plane of the substrate, the profile of the interface of the electrothermal alloy coating and the insulating layer has the profile arithmetic mean deviation Ra of not less than 5 microns.
2. The composite material of claim 1, wherein the interface profile of the electrocaloric alloy coating and the insulating layer has an arithmetic mean deviation Ra of profile of not less than 20 microns.
3. The composite of claim 1, wherein the interface profile of the electrocaloric alloy coating and the insulating layer has a maximum height Rz of not less than 8 microns.
4. The composite of claim 1, wherein the electrothermal alloy coating and the insulating layer have an interface profile with a maximum height Rz of not less than 25 microns.
5. The composite material according to claim 1, wherein the electrocaloric alloy coating contains a metal element and an oxygen element, and an atomic percentage of the oxygen element is 5 to 30 at% in at least a part of the electrocaloric alloy coating.
6. The composite material according to claim 5, characterized in that said metallic element comprises:
15 to 25 at% of chromium element;
10 to 20 at% of aluminum element;
0.1 to 1.5 at% of yttrium element; and
the balance of iron element.
7. The composite material of claim 1, wherein the insulating layer is an insulating coating and the insulating layer has a porosity of no more than 5% in at least a portion of the area.
8. The composite material according to claim 7, wherein the profile of the interface of the substrate with the insulating layer has an arithmetic mean deviation Ra of the profile not lower than 20 μm in at least one section of the composite material perpendicular to the plane of the substrate.
9. The composite material of claim 8, wherein the interface profile of the substrate and the insulating layer has an arithmetic mean deviation Ra of the profile of not less than 30 microns.
10. The composite material of claim 8, wherein the interface profile of the matrix and the insulating layer has a maximum height Rz of not less than 25 microns.
11. The composite material of claim 8, wherein the interface profile of the matrix and the insulating layer has a maximum height Rz of not less than 35 microns.
12. The composite of claim 1, further comprising an electrically conductive layer formed on at least a portion of a surface of the electrocaloric alloy coating, the electrically conductive layer comprising a material comprising silver or copper.
13. The composite material according to claim 12, wherein the electrically conductive layer is an electrically conductive coating, and the profile of the interface of the electrically conductive coating with the electrothermal alloy coating has an arithmetic mean deviation Ra of the profile of not less than 5 μm in at least one cross section of the composite material perpendicular to the plane of the substrate.
14. The composite material of claim 13, wherein the interface profile of the electrically conductive coating and the electrocaloric alloy coating has an arithmetic mean deviation Ra of profile of not less than 20 microns.
15. The composite of claim 13, wherein the interface profile of the electrically conductive coating and the electrocaloric alloy coating has a maximum height Rz of not less than 8 microns.
16. The composite of claim 13, wherein the interface profile of the electrically conductive coating and the electrocaloric alloy coating has a maximum height Rz of no less than 25 microns.
17. The composite material of claim 1, wherein the electrocaloric alloy coating has a predetermined pattern, and the electrocaloric alloy coating is spaced apart in a cross-section perpendicular to a plane of the substrate.
18. The composite material according to claim 12, wherein the composite material satisfies at least one of the following conditions:
the thickness of the insulating layer is 50-500 microns;
the thickness of the electrothermal alloy coating is 10-150 microns;
the thickness of the conductive layer is 30-150 microns.
19. An electrical appliance, comprising:
a heating element having the composite material of any one of claims 1 to 18.
20. The appliance according to claim 19, wherein the appliance is a cooking appliance or a liquid heating vessel, the appliance comprising:
a composite material according to any one of claims 1 to 18;
a body, a portion of an outer wall of the body constituting a matrix of the composite material, and the electrothermal alloy coating being disposed on the outer wall of the body.
21. A method of making the composite material of any one of claims 1 to 18, comprising:
(1) forming the insulating layer on a surface of the base;
(2) forming the electrothermal alloy coating on the surface of the insulating layer far from the substrate, and enabling the interface profile of the electrothermal alloy coating and the insulating layer to have the profile arithmetic mean deviation Ra of not less than 5 microns so as to obtain the composite material.
22. The method of claim 21, wherein step (1) further comprises;
(1-a) roughening at least a part of the surface of the substrate; and
(1-b) forming the insulating layer on the roughened surface by explosion spraying or plasma spraying.
23. The method according to claim 22, wherein in the step (1), the roughening treatment is performed by at least one of blasting, grinding and chemical etching,
in the step (2), the electrothermal alloy coating is formed by supersonic spraying or plasma spraying.
24. The method of claim 21, further comprising:
forming a conductive coating on at least a portion of the surface of the electrothermal alloy coating by arc spraying or cold spraying.
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