CN110129851B - Thermocouple, preparation method thereof and electric appliance - Google Patents

Thermocouple, preparation method thereof and electric appliance Download PDF

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Publication number
CN110129851B
CN110129851B CN201810113795.5A CN201810113795A CN110129851B CN 110129851 B CN110129851 B CN 110129851B CN 201810113795 A CN201810113795 A CN 201810113795A CN 110129851 B CN110129851 B CN 110129851B
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spraying
electrode
thermocouple
insulating coating
oxide film
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CN110129851A (en
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成乐
王慷慨
熊玉明
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Midea Group Co Ltd
Guangdong Midea White Goods Technology Innovation Center Co Ltd
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Midea Group Co Ltd
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    • A—HUMAN NECESSITIES
    • A47—FURNITURE; DOMESTIC ARTICLES OR APPLIANCES; COFFEE MILLS; SPICE MILLS; SUCTION CLEANERS IN GENERAL
    • A47J—KITCHEN EQUIPMENT; COFFEE MILLS; SPICE MILLS; APPARATUS FOR MAKING BEVERAGES
    • A47J36/00—Parts, details or accessories of cooking-vessels
    • C—CHEMISTRY; METALLURGY
    • C23—COATING 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
    • C23C—COATING 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
    • C23C4/00—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge
    • C23C4/04—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge characterised by the coating material
    • C23C4/06—Metallic material
    • C—CHEMISTRY; METALLURGY
    • C23—COATING 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
    • C23C—COATING 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
    • C23C4/00—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge
    • C23C4/04—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge characterised by the coating material
    • C23C4/06—Metallic material
    • C23C4/08—Metallic material containing only metal elements
    • C—CHEMISTRY; METALLURGY
    • C23—COATING 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
    • C23C—COATING 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
    • C23C4/00—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge
    • C23C4/12—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge characterised by the method of spraying
    • C23C4/129—Flame spraying
    • C—CHEMISTRY; METALLURGY
    • C23—COATING 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
    • C23C—COATING 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
    • C23C4/00—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge
    • C23C4/12—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge characterised by the method of spraying
    • C23C4/131—Wire arc spraying
    • C—CHEMISTRY; METALLURGY
    • C23—COATING 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
    • C23C—COATING 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
    • C23C4/00—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge
    • C23C4/12—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge characterised by the method of spraying
    • C23C4/134—Plasma spraying
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
    • C25D11/02—Anodisation
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
    • C25D11/02—Anodisation
    • C25D11/026—Anodisation with spark discharge
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01K—MEASURING TEMPERATURE; MEASURING QUANTITY OF HEAT; THERMALLY-SENSITIVE ELEMENTS NOT OTHERWISE PROVIDED FOR
    • G01K7/00—Measuring temperature based on the use of electric or magnetic elements directly sensitive to heat ; Power supply therefor, e.g. using thermoelectric elements
    • G01K7/02—Measuring temperature based on the use of electric or magnetic elements directly sensitive to heat ; Power supply therefor, e.g. using thermoelectric elements using thermoelectric elements, e.g. thermocouples

Abstract

The invention discloses a thermocouple, a preparation method thereof and an electric appliance. The thermocouple includes: a metal substrate; an oxide film layer covering at least a portion of a surface of the metal substrate; an insulating coating covering the surface of the oxide film layer; and the electrode layer is arranged on one side of the insulating coating layer far away from the metal substrate, wherein the pore diameter of the insulating coating layer is not more than 10 nanometers. Therefore, the insulating layer in the thermocouple has excellent bonding performance with the metal base material, and has good high temperature resistance, corrosion resistance and stability; and the insulating layer has good compactness and excellent insulating property.

Description

Thermocouple, preparation method thereof and electric appliance
Technical Field
The invention relates to the technical field of household appliances, in particular to a thermocouple, a preparation method thereof and an electric appliance.
Background
With the transformation and upgrade and the technical development of the household appliance industry, the intelligent electric appliance becomes an important development direction of the household appliance technology. The thin-film thermocouple has the advantages of being small in mass, high in response speed, small in environmental disturbance, free of damage to the structure of a measured piece and the like, becomes an advanced surface temperature measuring technology, can be widely applied to surface temperature measurement of household appliances, can achieve accurate and real-time temperature display, and can effectively improve product performance and user experience. Compared with the traditional bulk phase thermocouple material, the film thermocouple can be directly prepared on the surface of a measured object, the requirements of accurate and real-time temperature sensing are really met, and the integrity and the attractiveness of the product structure are not influenced.
However, the existing thermocouple, the preparation method thereof and the electric appliance still need to be improved.
Disclosure of Invention
The present invention is based on the discovery and recognition by the inventors of the following facts and problems:
the inventor finds that the insulating layer in the current thin-film thermocouple generally has the problems of poor insulating performance, poor high-temperature resistance, poor bonding force with a base material and the like. The inventor finds that, through intensive research and a large number of experiments, the reason is that when the thin-film thermocouple is prepared, an insulating layer needs to be prepared on a metal substrate firstly, and the existing insulating layer is generally prepared by a method of coating organic matters or sintering ceramics, on one hand, the insulating layer prepared by the method has poor high-temperature resistance; on the other hand, the bonding force between the insulating layer and the substrate is poor, the insulating layer is easy to separate from the metal substrate, the possibility of insulating failure is easy to occur under severe working conditions, and the insulating property is poor. In order to further improve the corrosion resistance, the wear resistance and the insulating property of the insulating layer, in the prior art, an oxide film layer with a certain thickness is directly formed on a metal substrate through anodic oxidation treatment, however, the oxide film layer is still in a porous structure, holes with the diameter of 10-3000 nm can still be formed according to the difference of an electrolysis process and solution proportion, and when a conductive layer is formed on the oxide film layer subsequently, for example, when a solution or a melt with good conductivity is coated, particles can penetrate into nano holes to cause insulation failure, so that the insulating property is not outstanding enough.
The present invention aims to alleviate or solve at least to some extent at least one of the above mentioned problems.
In one aspect of the invention, a thermocouple is provided. According to an embodiment of the present invention, the thermocouple includes: a metal substrate; an oxide film layer covering at least a portion of a surface of the metal substrate; an insulating coating covering the surface of the oxide film layer; and the electrode layer is arranged on one side of the insulating coating layer far away from the metal substrate, wherein the pore diameter of the insulating coating layer is not more than 10 nanometers. Therefore, the insulating layer in the thermocouple has excellent bonding performance with the metal base material, and has good high temperature resistance, corrosion resistance and stability; and the insulating layer has good compactness and excellent insulating property.
According to the embodiment of the invention, the thickness of the oxide film layer is 10-200 microns. Therefore, the bonding performance of the insulating layer and the metal base material is excellent, and the performance of the thermocouple can be further improved.
According to an embodiment of the present invention, a material forming the insulating coating layer includes at least one of inorganic silica gel, potassium silicate, sodium silicate, lithium silicate, zirconium oxide, titanium oxide, and aluminum oxide. Therefore, the compactness of an insulating layer in the thermocouple can be improved, the insulating property is improved, and the performance of the thermocouple is further improved.
According to the embodiment of the invention, the thickness of the insulating coating is 1-200 microns. Therefore, the bonding performance of the insulating layer and the metal base material is excellent, and the performance of the thermocouple can be further improved.
According to an embodiment of the present invention, the electrode layer further includes a first electrode and a second electrode, and at least a portion of the first electrode and the second electrode are overlapped. Therefore, the performance of the thermocouple can be further improved.
In another aspect of the invention, the invention provides a method of making a thermocouple as described above. The method comprises the following steps: carrying out oxidation treatment on the metal substrate so as to form an oxide film layer; forming an insulating coating on the oxide film layer so as to form a metal plate; forming an electrode layer on the insulating coating based on the metal plate material to form the thermocouple. The thermocouple prepared by the method can be the thermocouple described above, so that all the characteristics and advantages of the thermocouple described above can be achieved, and the description is omitted. In general, the insulating layer in the thermocouple prepared by the method has excellent bonding performance with a metal base material, and the insulating layer has high temperature resistance, good corrosion resistance and good stability; and the insulating layer has good compactness and excellent insulating property.
According to an embodiment of the present invention, the oxidation treatment is an anodic oxidation treatment, and the electrolytic solution used in the anodic oxidation treatment includes: 100-220 g/L sulfuric acid, 5-15 g/L oxalic acid, 2-16 g/L glycerol and 2-5 g/L additive; the temperature of the electrolyte is 3-10 ℃, the reaction time is 30-120 minutes, and the voltage range is 12-18 volts. Therefore, the anodic oxidation treatment can be simply and conveniently carried out, and the performance of the prepared thermocouple is further improved.
According to the embodiment of the invention, the oxidation treatment is micro-arc oxidation, and the electrolyte used in the micro-arc oxidation treatment comprises: 1-20 g/L sodium phosphate, 4-35 g/L sodium silicate, 4-10 g/L potassium silicate, 1-20 g/L sodium hydroxide, 0.5-4 g/L glycerol, 0-3 g/L boric acid, 1-5 g/L nano aluminum oxide and 1-5 g/L silicon carbide; the temperature of the electrolyte is 3-50 ℃, the reaction time is 30-120 minutes, and the voltage range is 400-550 volts. Therefore, micro-arc oxidation treatment can be simply and conveniently carried out, and the performance of the prepared thermocouple is further improved.
According to an embodiment of the present invention, the insulating coating layer is formed by disposing an insulating material on the oxide film layer and drying, the insulating material being disposed on the oxide film layer by at least one of roll coating, spin coating, electrostatic spraying. Therefore, the insulating coating can be formed simply and conveniently, and the performance of the prepared thermocouple is further improved.
According to the embodiment of the invention, the drying is vacuum drying, wherein the drying temperature is 200-600 ℃, the drying time is 10-60 minutes, and the pressure is not higher than 5000 Pa. Therefore, the insulating coating can fully permeate into the oxide film layer, the bonding performance of the insulating layer and the metal base material in the thermocouple can be further improved, the compactness of the insulating layer can be improved, and the insulating performance is more excellent.
According to an embodiment of the present invention, based on the metal plate material, forming an electrode layer on the insulating coating is achieved by: spraying a first thermoelectric material on the surface of the insulating coating of the metal plate by a thermal spraying method to form a first electrode; spraying a second thermoelectric material on the surface of the insulating coating by using the thermal spraying method to form a second electrode; wherein the second electrode and the first electrode have at least one contact area therebetween, and the first thermoelectric material and the second thermoelectric material have different compositions. The inventor finds that the method for forming the electrode layer is simple and convenient to operate, easy to implement, low in requirement on control precision of process parameters, high in process feasibility, good in reliability, low in cost, high in production efficiency, and easy to realize actual industrial production, a thermocouple utilizing the electrode layer can be in direct contact with a measured object, the method is particularly suitable for the field of household appliances, the structure is simple, the production period is short, the temperature measurement precision is high, the sensitivity is high, the thermal response speed is high, the real-time and accurate temperature measurement and control functions can be realized, and the product performance and the user experience are good.
According to an embodiment of the invention, the thermal spray method includes at least one of arc spraying, flame spraying, and plasma spraying.
According to the embodiment of the invention, the carrier gas adopted by the electric arc spraying is nitrogen or inert gas, and at least one of the following is satisfied: the voltage is 20-45V; the current is 50-400A; the spraying distance is 50-400 mm; the spraying air pressure is more than or equal to 0.2 MPa; the moving speed of the spray gun is 50-2000 mm/S.
According to an embodiment of the invention, the flame spraying satisfies at least one of: the preheating temperature of the metal plate is more than 40 ℃; the spraying angle is 60-90 degrees; the spraying distance is 50-300 mm; the oxygen pressure is more than or equal to 0.5 MPa; the acetylene pressure is more than or equal to 0.1 MPa; the moving speed of the spray gun is 50-1000 mm/S; the powder feeding amount is 0.5-2.0 Kg/h; the particle size of the powder is 15-45 μm.
According to an embodiment of the invention, the plasma spraying satisfies at least one of: the current is 300-700A; the voltage is 30-100V; the flow rate of argon gas is 30-70L/min; the flow rate of hydrogen or helium is 4-25L/min; the flow rate of the powder feeding carrier gas is 3-15L/min; the spraying distance is 50-250 mm; the moving speed of the spray gun is 50-1000 mm/S; the powder feeding speed is 5-50 g/min.
According to an embodiment of the present invention, the first electrode and the second electrode each have a rough surface; the average thickness of the first electrode and the second electrode is each independently 5-100 microns; the area of the contact area is 0.5-200 square millimeters.
According to an embodiment of the present invention, the first thermoelectric material includes at least one of platinum-rhodium alloy, nickel-chromium alloy, iron, copper, nickel-chromium-silicon alloy, and tungsten-rhenium alloy; the second thermoelectric material includes at least one of platinum-rhodium alloy, platinum, nickel-silicon alloy, nickel-aluminum alloy, nickel-silicon-magnesium alloy, and tungsten-rhenium alloy.
In yet another aspect of the present invention, an appliance is presented. The appliance includes a thermocouple as described above. Thus, the appliance may have all the features and advantages of the previously described thermocouple, which are not described in detail herein. In general, the thermocouple used in the electric appliance has excellent bonding performance of the insulating layer and the metal base material, and the insulating layer has high temperature resistance, good corrosion resistance and good stability; and the insulating layer has good compactness and excellent insulating property.
According to an embodiment of the present invention, the electric appliance is a cooking apparatus, and the thermocouple is disposed at a side of the cooking apparatus directly contacting food. The inventor finds that the thermocouple directly contacts with the measured object, is particularly suitable for the field of household appliances, and has the advantages of simple structure, short production period, high temperature measurement precision, high sensitivity, high thermal response speed, capability of realizing real-time and accurate temperature measurement and control functions, and good product performance and user experience. When the thermocouple is used for cooking equipment, the cooking effect is good, real intelligent cooking can be realized, and all the characteristics and advantages of the thermocouple are achieved, and the thermocouple is not repeated.
According to an embodiment of the present invention, the cooking apparatus further includes a protective layer covering the thermocouple and directly contacting the food; wherein the protective layer is a Teflon coating or a ceramic non-stick coating; the thickness of the protective layer is 10-100 microns.
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 shows a schematic structural diagram of a thermocouple according to one embodiment of the present invention;
FIG. 2 shows a schematic structural diagram of a thermocouple according to another embodiment of the present invention;
FIG. 3 shows a schematic structural diagram of a thermocouple according to yet another embodiment of the present invention;
FIG. 4 shows a schematic flow diagram of a method of making a thermocouple according to one embodiment of the present invention; and
FIG. 5 shows a schematic flow diagram of a method of making a thermocouple according to another embodiment of the invention;
FIG. 6 shows a schematic partial flow diagram of a method of making a thermocouple according to one embodiment of the present invention;
FIG. 7 is a schematic view showing a partial structure of a thermocouple according to an embodiment of the present invention;
FIG. 8 shows a physical photograph of a first mask and a second mask according to an embodiment of the present invention;
FIG. 9 shows a physical photograph of a thermocouple according to one embodiment of the invention;
FIG. 10 is a schematic sectional view showing the structure of a thermocouple temperature measuring accuracy apparatus according to an embodiment of the present invention;
FIGS. 11 to 13 are graphs showing temperature changes of room temperature to 300 ℃ of the thermocouple and the standard temperature measuring sensor according to embodiments 1 to 3 of the present invention; and
FIG. 14 shows a scanning electron micrograph of a thermocouple cross section according to one embodiment of the present invention.
Description of reference numerals:
100: a metal substrate; 200: oxidizing the film layer; 300: an insulating coating; 400: an electrode layer; 410: a first electrode; 420: a second electrode; 1000: a ceramic plate; 2000: a heater; 3000: a thermal insulation material; 4000: and a temperature collector.
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.
In one aspect of the invention, a thermocouple is provided. According to an embodiment of the present invention, referring to fig. 1, the thermocouple includes: a metal substrate 100, an oxide film layer 200, an insulating coating 300, and an electrode layer 400. According to an embodiment of the present invention, the oxide film layer 200 covers at least a portion of the surface of the metal substrate 100. According to the embodiment of the present invention, the insulating coating 300 covers the surface of the oxide film layer 200, and the electrode layer 400 is disposed on the side of the insulating coating 300 away from the metal substrate 100. According to an embodiment of the present invention, the pore size of the insulating coating 300 is not greater than 10 nm. Therefore, the insulating layer in the thermocouple has excellent bonding performance with the metal base material, and has good high temperature resistance, corrosion resistance and stability; and the insulating layer has good compactness and excellent insulating property.
For the sake of understanding, the following is a detailed description of the principle of the oxide film layer and the insulating coating layer to achieve the above technical effects:
as described above, even in the oxide film layer formed by sintering ceramic, a porous structure having a diameter of 10 to 3000nm still exists, and when a conductive paste having a high fluidity is coated on the surface of the oxide film layer, the conductive paste permeates from the porous structure to the metal substrate side, and finally, insulation failure is caused. The inventor finds that if a dense insulating coating (for example, the pore diameter is not more than 10 nanometers) can be formed on the formed oxide film layer, the porous structure in the oxide film layer can be effectively blocked, and after the insulating coating is formed on the oxide film layer, the insulating layer is more dense, so that the insulating property of the metal substrate can be remarkably improved, even if moisture and melt are extremely difficult to permeate into the porous structure in the oxide film layer through the insulating coating, and the problem of short circuit between a subsequently formed conductive layer and the metal substrate does not exist. Because the relatively compact insulating coating exists on the oxide film layer, even if the subsequent processes of coating silver paste, spraying a conductive coating, sputtering conductive particles and the like are required to be carried out on the surface of the insulating layer, the preparation of electronic elements such as a sensor and the like or related circuits can be realized, and the problems of short circuit and the like caused by the contact between the formed electrical structures such as the circuits and the like and the metal base material can be solved.
According to an embodiment of the present invention, the specific material of the metal substrate 100 is not particularly limited, and may be selected by those skilled in the art according to actual needs. For example, according to an embodiment of the present invention, the metal substrate 100 may be at least one of an aluminum alloy, a titanium alloy, and a stainless steel alloy. Specifically, the metal alloy may be at least one of an antibacterial stainless steel alloy, 300 series stainless steel, 400 series stainless steel, die-cast aluminum alloy, spun aluminum alloy, and 5 series aluminum alloy. Therefore, the material source is wide and easy to obtain, the cost is low, and the electrode layer is formed by the subsequent process.
According to an embodiment of the present invention, the thickness of the oxide film layer 200 is not particularly limited, and may be selected by one skilled in the art according to actual requirements. For example, according to the embodiment of the invention, the thickness of the oxide film layer 200 may be 10 to 200 μm. The inventors found that, if the thickness is too small, the insulating property of the oxide film layer 200 is not good, and if the thickness is too large, the bonding property between the oxide film layer 200 and the metal substrate 100 is poor, and the oxide film layer is easily peeled off in the subsequent process or use. Under the above thickness condition, the oxide film layer 200 has a strong bonding force with the metal substrate 100, and also has excellent insulating properties, so that the performance of the thermocouple can be further improved. According to the embodiment of the present invention, the specific manner and the specific material for forming the oxide film layer 200 are not particularly limited, for example, when the metal substrate 100 is an aluminum alloy, the oxide film layer 200 may be formed by an anodic oxidation process or a micro-arc oxidation process, and the formed oxide film layer 200 is aluminum oxide.
According to an embodiment of the present invention, the specific material forming the insulating coating 300 is not particularly limited, and may be selected by those skilled in the art according to actual needs. For example, according to an embodiment of the present invention, the material forming the insulating coating 300 includes at least one of inorganic silica gel, potassium silicate, sodium silicate, lithium silicate, zirconium oxide, titanium oxide, and aluminum oxide. Therefore, the compactness of an insulating layer in the thermocouple can be improved, the insulating property is improved, and the performance of the thermocouple is further improved. The thickness of the insulating coating 300 is not particularly limited according to an embodiment of the present invention, and may be selected by those skilled in the art according to actual needs. For example, according to an embodiment of the present invention, the thickness of the insulating coating 300 may be 1 to 200 μm. The thickness is too small, the improvement of the insulating layer compactness performance of the insulating coating 300 is limited, so that the insulating performance is poor, the thickness is too large, and the bonding performance of the insulating coating 300 with the oxide film layer 200 and the metal base material 100 is poor, so that the bonding force between the insulating coating 300 and the oxide film layer 200 and the metal base material 100 is strongest under the thickness condition, the excellent insulating performance is considered, and the performance of the thermocouple is further improved. According to an embodiment of the present invention, a specific manner of forming the insulating coating 300 is not particularly limited, and may be formed by at least one of roll coating, spin coating, and electrostatic spraying, for example.
In addition, the inventor finds that the oxide film layer and the insulating coating formed by the materials can be better integrated with a metal base material from the aspects of materials and preparation processes, so that the bonding force is more excellent, the high-temperature resistance and the corrosion resistance of the oxide film layer and the insulating coating are good, and the formed thermocouple can work under severe conditions such as high temperature for a long time, and the stability of the thermocouple is further improved.
According to an embodiment of the present invention, referring to fig. 2 (a) is a schematic cross-sectional structure, (b) is a schematic plan-view structure) and fig. 3 (a) is a schematic cross-sectional structure, and fig. 3 (b) is a schematic plan-view structure), the electrode layer 400 further includes a first electrode 410 and a second electrode 420, at least a portion of the first electrode 410 and the second electrode 420 are overlapped, that is, the first electrode 410 and the second electrode 420 have at least one contact area. It should be noted that, referring to fig. 2, the contact area may only include a contact surface (as shown in fig. 2 a) perpendicular to the metal substrate 100; alternatively, referring to fig. 3, the contact region may include both a contact surface perpendicular to the metal substrate 100 and a contact surface parallel to the metal substrate 100 (B shown as (a) in fig. 3). Therefore, the performance of the thermocouple can be further improved. According to the embodiment of the present invention, the specific forming materials, the specific shapes, the thicknesses, the resistance values, and the forming manners of the first electrode 410 and the second electrode 420 are not particularly limited, and those skilled in the art can select the forming materials according to actual requirements. According to the embodiment of the present invention, the specific size of the contact area between the first electrode and the second electrode and the specific number of the contact areas are not particularly limited, and those skilled in the art can select the size and the number according to actual needs.
According to an embodiment of the present invention, the first electrode 410 and the second electrode 420 each have a rough surface. It should be noted that the rough surface of the present invention should be a rough surface that can be distinguished by naked eyes. In some embodiments of the present invention, the surface roughness of both the first electrode 410 and the second electrode 420 is greater than 1 micron. Therefore, the thermocouple prepared is particularly suitable for the field of household appliances, and has the advantages of simple structure, short production period, high temperature measurement precision, high sensitivity and high thermal response speed, can realize real-time and accurate temperature measurement and control functions, and has good product performance and user experience.
The thicknesses of the first electrode 410 and the second electrode 420 are not particularly limited according to an embodiment of the present invention, and may be flexibly selected as needed by those skilled in the art as long as the requirements are satisfied. In some embodiments of the present invention, the average thickness of the first electrode 410 and the second electrode 420 may be 5-100 micrometers. In some more preferred embodiments of the present invention, the average thickness of the first electrode 410 and the second electrode 420 may be 10 to 60 micrometers. In some embodiments of the invention, the average thickness of the first electrode 410 and the second electrode 420 may be 10 microns, 20 microns, 30 microns, 40 microns, 50 microns, 60 microns. Therefore, the prepared thermocouple has a good temperature measuring effect, so that the first electrode 410 and the second electrode 420 have higher reliability and better wear resistance, better uniformity and more attractive vision.
In another aspect of the invention, the invention provides a method of making a thermocouple as described above. The thermocouple prepared by the method can be the thermocouple described above, so that all the characteristics and advantages of the thermocouple described above can be achieved, and the description is omitted. In general, the insulating layer in the thermocouple prepared by the method has excellent bonding performance with a metal base material, and the insulating layer has high temperature resistance, good corrosion resistance and good stability; and the insulating layer has good compactness and excellent insulating property. According to an embodiment of the invention, referring to fig. 4, the method comprises:
s100: subjecting a metal substrate to an oxidation treatment
In this step, the metal base material is subjected to oxidation treatment to form an oxide film layer. The specific material of the metal substrate according to the embodiment of the present invention is not particularly limited, and may be selected by those skilled in the art according to actual needs. For example, according to an embodiment of the present invention, the metal substrate may be at least one of an aluminum alloy, a titanium alloy, and a stainless steel alloy. Specifically, the metal alloy may be at least one of an antibacterial stainless steel alloy, 300 series stainless steel, 400 series stainless steel, die-cast aluminum alloy, spun aluminum alloy, and 5 series aluminum alloy. Therefore, the material source is wide and easy to obtain, the cost is low, and the electrode layer is formed by the subsequent process.
The specific type of oxidation treatment according to the embodiment of the present invention is not particularly limited, and those skilled in the art may select different oxidation treatment processes according to the requirements of the workpiece. For example, according to the embodiment of the present invention, the oxidation treatment may be an anodic oxidation treatment, and when the anodic oxidation treatment is performed, the specific type of the electrolyte solution configured is not particularly limited, and may include: 100-220 g/L sulfuric acid, 5-15 g/L oxalic acid, 2-16 g/L glycerol and 2-5 g/L additive; according to the embodiment of the present invention, the temperature of the electrolyte, the reaction time of the anodic oxidation treatment, and the voltage range used are not particularly limited, for example, the temperature of the electrolyte may be 3 to 10 degrees celsius, the reaction time may be 30 to 120 minutes, and the voltage range may be 12 to 18 volts. Therefore, the anodic oxidation treatment can be simply and conveniently carried out, and the performance of the prepared thermocouple is further improved. Alternatively, according to an embodiment of the present invention, the oxidation treatment may be micro-arc oxidation, and when the micro-arc oxidation treatment is performed, the specific type of the configured electrolyte is not particularly limited, and may include: 1-20 g/L sodium phosphate, 4-35 g/L sodium silicate, 4-10 g/L potassium silicate, 1-20 g/L sodium hydroxide, 0.5-4 g/L glycerol, 0-3 g/L boric acid, 1-5 g/L nano aluminum oxide and 1-5 g/L silicon carbide; according to the embodiment of the invention, the temperature of the electrolyte, the reaction time of the micro-arc oxidation treatment and the voltage range are not particularly limited, for example, the temperature of the electrolyte may be 3 to 50 ℃, the reaction time may be 30 to 120 minutes, and the voltage range may be 400 to 550 volts. Therefore, micro-arc oxidation treatment can be simply and conveniently carried out, and the performance of the prepared thermocouple is further improved. According to the embodiment of the invention, when the anodic oxidation treatment or the micro-arc oxidation treatment is utilized, the solution is required to be inflated or circulated in the electrolysis process in order to ensure the uniform electrolysis.
The specific thickness of the oxide film formed by the oxidation process according to the embodiment of the present invention has been described in detail above, and will not be described herein again. According to an embodiment of the present invention, a specific material for forming the oxide film layer is not particularly limited, for example, when the metal substrate is an aluminum alloy, the oxide film layer formed by the anodic oxidation treatment or the micro-arc oxidation treatment is aluminum oxide.
In order to further improve the performance of the thermocouple manufactured by the method, referring to fig. 5, before the oxidation treatment is performed on the metal base material, the method further includes:
s10: pretreating metal substrates
In this step, the metal substrate is pretreated. According to an embodiment of the present invention, a specific manner of the preprocessing may specifically include: the method comprises the following steps of firstly removing oil from a metal base material, secondly conducting alkaline washing on the metal base material, then conducting light emission on the metal base material, and finally conducting chemical polishing on the metal base material. According to the embodiment of the invention, the specific modes of oil removal, alkaline cleaning, light extraction and chemical polishing are not particularly limited, and can be selected by a person skilled in the art according to actual requirements. The following will describe the specific treatment method of the above pretreatment in detail by taking an aluminum alloy workpiece as an example:
(1) oil removal
And (3) dipping the aluminum alloy workpiece in a common commercially available degreasing solution for 3-10 minutes and cleaning, wherein the temperature of the solution is 60-70 ℃.
(2) Alkali washing
And (2) soaking the workpiece obtained in the step (1) in a 10-20% sodium hydroxide solution for 3-6 min at the temperature of 20-30 ℃, and then placing the workpiece in flowing clear water for cleaning for 2-8 min.
(3) Light emission
And (3) soaking the workpiece obtained in the step (2) in a 5-10% nitric acid solution for 3-10 minutes at the temperature of 20-30 ℃, and then placing the workpiece in flowing clear water for cleaning for 2-8 minutes.
(4) Chemical polishing
And (3) soaking the workpiece obtained in the step (3) in 85% phosphoric acid solution or mixed solution of phosphoric acid and sulfuric acid in a volume ratio of 9:1 for 30-200 seconds at the temperature of 85 +/-15 ℃, and then placing the workpiece in flowing clear water for cleaning for 2-8 minutes.
The surface of the metal base material after the pretreatment is clean and flat, and the quality of subsequent processes is favorably improved.
S200: forming an insulating coating on the oxide film layer
In this step, an insulating coating is formed on the oxide film layer to form a metal plate. According to the embodiment of the invention, the aperture of the insulating coating formed on the oxide film layer is not more than 10 nanometers, so that the thermocouple prepared by the method has excellent bonding performance between the insulating layer and the metal base material, and the insulating layer has good high temperature resistance, corrosion resistance and stability; and the insulating layer has good compactness and excellent insulating property.
According to an embodiment of the present invention, a specific manner of forming the insulating coating layer is not particularly limited, and for example, the insulating coating layer may be formed by disposing an insulating material on the oxide film layer and drying, wherein the insulating material is disposed on the oxide film layer by at least one of roll coating, spin coating, and electrostatic spraying. Therefore, the insulating coating can be formed simply and conveniently, and the performance of the prepared thermocouple is further improved. The specific material (i.e., the insulating material) for forming the insulating coating and the specific thickness of the film layer according to the embodiment of the present invention have been described in detail above, and will not be described in detail herein. According to the embodiment of the invention, the specific manner of drying is not particularly limited, for example, the drying may be vacuum drying, so that the insulating coating can sufficiently penetrate into the oxide film layer in the vacuum drying process, the bonding performance of the insulating layer and the metal base material in the thermocouple can be further improved, the compactness of the insulating layer can be improved, and the insulating performance is more excellent. According to the embodiment of the present invention, the drying temperature, the drying time, and the drying pressure of the vacuum drying are not particularly limited, and those skilled in the art can select the drying temperature, the drying time, and the drying pressure according to actual requirements, for example, the drying treatment can be performed under a vacuum condition, for example, the drying temperature can be 200 to 600 degrees celsius, the drying time can be 10 to 60 minutes, and the pressure is not higher than 5000 Pa. According to an embodiment of the present invention, the drying temperature may be 300 degrees celsius, the drying time may be 30 minutes, and the pressure during drying may be 1000 Pa. Specifically, the metal substrate on which the insulating material is formed can be placed in a vacuum oven for baking, firstly, the vacuum is pumped, the insulating material is made to fully permeate into the porous structure of the oxide film layer through negative pressure, then, the baking is carried out again to solidify the insulating material so as to form the insulating coating, therefore, the bonding force between the insulating coating and the oxide film layer and the metal substrate can be improved, and the insulating coating can completely cover the porous structure of the oxide film layer to realize the hole sealing effect.
In order to further improve the performance of the thermocouple manufactured by the method, referring to fig. 5, after the metal base material is subjected to the oxidation treatment, before the insulating coating is formed on the oxide film layer, the method further includes:
s20: cleaning treatment
In this step, the metal base material subjected to the oxidation treatment is subjected to a cleaning treatment. According to an embodiment of the present invention, the cleaning process may further include: rinsing with clear water, ultrasonic cleaning and drying. Specifically, firstly, the metal base material subjected to peroxidation treatment is placed in flowing clear water for cleaning for 2-5 minutes, then the metal base material is placed in pure water for cleaning for 3-8 minutes by using ultrasonic waves, the water temperature can be 25 +/-5 ℃, and finally, the cleaned metal base material is dried so as to form an insulating coating on an oxide film layer of the metal base material in the next step.
S300: forming an electrode layer on the insulating coating
In this step, an electrode layer is formed on the insulating coating based on the metal plate material so as to form a thermocouple. According to an embodiment of the present invention, referring to fig. 6, the electrode layer may be implemented by:
s1: forming a first electrode
In this step, a first thermoelectric material is sprayed on the surface of the insulating coating of the metal plate material by a thermal spraying method to form a first electrode. Specifically, referring to fig. 7 (a) is a schematic cross-sectional structure, and fig. 2 (b) is a schematic plan-view structure), a schematic structural diagram is shown, in which the first electrode 410 is formed on the surface of the insulating coating 300 of the metal plate (including the metal substrate 100, the oxide film layer 200, and the insulating coating 300).
According to an embodiment of the present invention, the specific material type of the first thermoelectric material is not particularly limited, and may be flexibly selected by those skilled in the art as needed as long as the requirement is satisfied, and may include, for example, but not limited to, platinum-rhodium alloy, nickel-chromium alloy, iron, copper, nickel-chromium-silicon alloy, tungsten-rhenium alloy, and the like. In some embodiments of the present invention, the first thermoelectric material may be embodied as Pt90Rh10、Pt87Rh13、Pt70Rh30、Ni90Cr10Iron, copper, Ni84.5Cr14Si1.5、W97Re3And W95Re5. Therefore, the material source is wide and easy to obtain, and the prepared thermocouple has good temperature measurement effect, and better stability and sensitivityHigh.
According to the embodiment of the present invention, the supply form of the first thermoelectric material is not particularly limited, and one skilled in the art can flexibly select the first thermoelectric material as needed as long as the requirement is satisfied. In some embodiments of the invention, the first thermoelectric material is provided in the form of a first wire. In other embodiments of the present invention, the first thermoelectric material is provided in the form of an alloy powder. This makes thermal spraying more suitable.
According to an embodiment of the present invention, the gauge of the first wire is not particularly limited, and one skilled in the art can flexibly select it as needed as long as the requirement is satisfied. In some embodiments of the invention, the diameter of the first wire may be 1.0-2.5 millimeters. In some embodiments of the invention, the diameter of the first wire may be 1.0 mm, 1.5 mm, 2.0mm, 2.5 mm. Therefore, the diameter of the first wire rod is moderate, and the first wire rod is more suitable for thermal spraying treatment.
According to the embodiment of the present invention, the particle size of the alloy powder is not particularly limited, and those skilled in the art can flexibly select the particle size as needed as long as the requirement is satisfied. The particle size of the alloy powder of the present invention is within the particle size distribution range, and the particle sizes of the alloy powder particles are different from each other but all within the particle size distribution range. In some embodiments of the invention, the alloy powder may have a particle size of 15-45 μm. In some embodiments of the invention, the alloy powder may have a particle size of 20 μm or 30 μm. Therefore, the alloy powder has moderate particle size and is more suitable for thermal spraying treatment.
The specific method of thermal spraying is not particularly limited according to embodiments of the present invention, and one skilled in the art can flexibly select the method as needed, as long as the requirements are met, such as but not limited to arc spraying, flame spraying, plasma spraying, and the like. In some embodiments of the invention, the specific method of thermal spraying is arc spraying. Therefore, the method is simple and convenient to operate, easy to realize, low in control precision requirement on technological parameters, high in feasibility, good in reliability, low in cost, high in production efficiency, easy to realize actual industrial production, and particularly suitable for the field of household appliances, and has the advantages of simple structure, short production period, high temperature measurement precision, high sensitivity, high thermal response speed, capability of realizing real-time and accurate temperature measurement and control functions, and good product performance and user experience.
According to the embodiments of the present invention, the inventors have conducted extensive and intensive studies and experimental verification on the carrier gas for arc spraying, and found that the carrier gas for arc spraying is nitrogen or an inert gas (referred to as a rare gas, i.e., helium (He), neon (Ne), argon (Ar), krypton (Kr), xenon (Xe), and radioactive radon (Rn)), which can effectively prevent the first electrode and the second electrode from being oxidized during the arc spraying process, resulting in low temperature measurement accuracy and poor product performance of the prepared thermocouple. The inventors found that the temperature measurement accuracy of the thermocouple prepared using nitrogen or an inert gas can be significantly improved as compared to a thermocouple prepared using no nitrogen or an inert gas as a carrier gas. In some embodiments of the invention, the carrier gas for the arc spraying is nitrogen. Therefore, the temperature measuring precision of the prepared thermocouple is obviously improved, and the cost is low.
According to the embodiments of the invention, the inventor conducts a great deal of intensive investigation and experimental verification on the voltage of the arc spraying, and finds that the voltage of the arc spraying is 20-45V, and in some specific embodiments of the invention, the voltage of the arc spraying is 20V, 25V, 30V, 35V, 40V and 45V, so that the method has high reliability and high production efficiency, and the prepared thermocouple product has good performance and user experience. Moreover, the voltage of the arc spraying is in the range, so that the first thermoelectric material can be sprayed more sufficiently on the premise of ensuring the technical effect, the quality of the formed first electrode 200 is higher, and the bonding force between the first electrode and the metal plate is better; meanwhile, the temperature in the process of arc spraying is moderate, more first thermoelectric materials are not oxidized, the purity of the formed first electrode is higher, and the thermoelectric performance is more excellent.
According to the embodiments of the present invention, the inventors have conducted a great deal of intensive research and experimental verification on the current of the arc spraying, and found that the current of the arc spraying is 50-400A, and in some embodiments of the present invention, the current of the arc spraying is specifically 50A, 100A, 150A, 200A, 250A, 300A, 350A, 400A, and 450A, which further enables the method to have high reliability and high production efficiency, and the product performance and user experience of the prepared thermocouple are good. Moreover, the electric current of the electric arc spraying is in the range mentioned above, so that the efficiency of forming the first electrode by the first thermoelectric material is higher on the premise of ensuring the technical effect mentioned above; meanwhile, the first electrode is formed to have high uniformity.
According to the embodiments of the present invention, the inventors have conducted a great deal of intensive investigation and experimental verification on the spraying distance of the arc spraying (which refers to the linear distance between the air outlet of the spray gun and the metal plate), and found that the spraying distance of the arc spraying is 50-400 mm, and in some specific embodiments of the present invention, the spraying distance of the arc spraying is specifically 50mm, 100mm, 150mm, 200mm, 250mm, 300mm, 350 mm, 400mm, and 450 mm, so that the method has high reliability and high production efficiency, and the prepared thermocouple product has good performance and user experience. Moreover, the spraying distance of the electric arc spraying is in the range, so that the shape of the metal plate is more complete on the premise of ensuring the technical effect, and the shape of the metal plate is not obviously changed before the electric arc spraying and after the electric arc spraying; meanwhile, higher production efficiency can be guaranteed, the bonding force of the first electrode and the metal plate is higher, more first thermoelectric materials cannot be oxidized, the purity of the formed first electrode is higher, and the thermoelectric performance is more excellent.
According to the embodiments of the present invention, the inventor has conducted a great deal of intensive investigation and experimental verification on the spraying pressure of the arc spraying, and found that the spraying pressure of the arc spraying is greater than or equal to 0.2MPa, and in some specific embodiments of the present invention, the spraying pressure of the arc spraying is specifically 0.2MPa, 0.4MPa, 0.6MPa, 0.8MPa, 1MPa, 1.2MPa, which can further make the method highly reliable and efficient, and the performance and user experience of the prepared thermocouple product are good. Moreover, the spraying pressure of the electric arc spraying is in the range, so that the spraying speed of the first thermoelectric material is higher and the bonding force between the formed first electrode and the metal plate is better when the electric arc spraying is carried out on the premise of ensuring the technical effect.
According to the embodiments of the invention, the inventor conducts a great deal of thorough research and experimental verification on the moving speed of the spray gun for electric arc spraying, and finds that the moving speed of the spray gun for electric arc spraying is 50-2000mm/S, and in some specific embodiments of the invention, the moving speed of the spray gun for electric arc spraying is specifically 50mm/S, 400mm/S, 800mm/S, 1200mm/S, 1600mm/S and 2000mm/S, so that the method has high reliability and high production efficiency, and the prepared thermocouple product has good performance and good user experience. Moreover, the moving speed of the spray gun of the electric arc spraying is in the range, the thickness of the formed first electrode is moderate on the premise of ensuring the technical effect, and more excellent uniformity and continuity are ensured.
According to the embodiment of the invention, in order to make the preparation method of the thermocouple lower in cost, higher in production efficiency, better in reliability and capable of obtaining the thermocouple with more excellent performance, the inventor comprehensively considers the carrier gas, the voltage, the current, the spraying distance, the spraying air pressure and the moving speed of the spray gun adopted by the electric arc spraying, and the inventor finds that when the carrier gas adopted by the electric arc spraying is nitrogen or inert gas, the carrier gas and the inert gas simultaneously meet the following requirements: the voltage is 20-45V; the current is 50-400A; the spraying distance is 50-400 mm; the spraying air pressure is more than or equal to 0.2 MPa; when the moving speed of the spray gun is 50-2000mm/S, all parameters of the spray gun are mutually influenced and have a synergistic effect, so that the preparation method of the thermocouple can be shortened to be within 2 minutes, the thermocouple is shortened by hundreds of times compared with the prior art, the cost is only one tenth of the cost of the prior art, the prepared thermocouple is extremely high in temperature measurement precision, sensitivity and thermal response speed, real-time and accurate temperature measurement and control functions can be realized, and the product performance and the user experience are extremely good.
In other embodiments of the present invention, the specific method of thermal spraying is flame spraying. Therefore, the method is simple and convenient to operate, easy to realize, low in control precision requirement on process parameters, high in feasibility, good in reliability, low in cost, high in production efficiency, easy to realize actual industrial production, and particularly suitable for the field of household appliances, and has the advantages of simple structure, short production period, high temperature measurement precision, high sensitivity, high thermal response speed, capability of realizing real-time and accurate temperature measurement and control functions, and good product performance and user experience.
According to the embodiments of the invention, the inventor conducts a great deal of intensive investigation and experimental verification on the preheating temperature of the flame sprayed metal plate, and finds that the preheating temperature of the flame sprayed metal plate is more than 40 ℃, and in some specific embodiments of the invention, the preheating temperature of the flame sprayed metal plate is specifically 50 ℃, 60 ℃, 70 ℃, 80 ℃, 90 ℃ and 100 ℃, so that the method has high reliability and high production efficiency, and the prepared thermocouple product has good performance and user experience. Moreover, the preheating temperature of the flame sprayed metal plate is in the range, so that the first electrode and the metal plate can be better combined on the premise of ensuring the technical effect.
According to the embodiments of the invention, the inventor conducts a great deal of intensive investigation and experimental verification on the spraying angle (the included angle between the spraying direction and the metal plate) of the flame spraying, and finds that the spraying angle of the flame spraying is 60-90 degrees, and in some specific embodiments of the invention, the spraying angle of the flame spraying is 60 degrees, 70 degrees, 80 degrees and 90 degrees, so that the method is further high in reliability and production efficiency, and the prepared thermocouple product is good in performance and user experience. Moreover, the spraying angle of the flame spraying is within the range, so that on the premise of ensuring the technical effect, the shadow effect is basically avoided when the flame spraying is carried out, and the formed first electrode has higher density.
According to the embodiments of the invention, the inventor conducts a great deal of intensive investigation and experimental verification on the spraying distance of flame spraying (the distance between a spray gun for flame spraying and a metal plate), and finds that the spraying distance of flame spraying is 50-300mm, and in some specific embodiments of the invention, the spraying distance of flame spraying is specifically 50mm, 100mm, 150mm, 200mm, 250mm and 300mm, so that the method is further high in reliability and production efficiency, and the prepared thermocouple product is good in performance and user experience. Moreover, the spraying distance of the flame spraying is within the range, so that the shape of the metal plate is more complete on the premise of ensuring the technical effect, and the shape of the metal plate is not obviously changed before the flame spraying and after the flame spraying; meanwhile, higher production efficiency can be guaranteed, the bonding force of the first electrode and the metal plate is higher, more first thermoelectric materials cannot be oxidized, the purity of the formed first electrode is higher, and the thermoelectric performance is more excellent.
According to the embodiments of the present invention, the inventors have conducted a great deal of intensive investigation and experimental verification on the oxygen pressure of flame spraying, and found that the oxygen pressure of flame spraying is greater than or equal to 0.5MPa, and in some specific embodiments of the present invention, the oxygen pressure of flame spraying is specifically 0.5MPa, 0.7MPa, 0.9MPa, 1.1MPa, and 1.3MPa, which can further make the method highly reliable and efficient, and the prepared thermocouple product has good performance and user experience. Moreover, the oxygen pressure of the flame spraying is in the range, so that the first electrode and the metal plate have better bonding force on the premise of ensuring the technical effect.
According to the embodiments of the present invention, the inventor has conducted a great deal of intensive investigation and experimental verification on the acetylene pressure of the flame spraying, and found that the acetylene pressure of the flame spraying is greater than or equal to 0.1MPa, and in some specific embodiments of the present invention, the acetylene pressure of the flame spraying is specifically 0.1MPa, 0.3MPa, 0.5MPa, 0.7MPa, 0.9MPa, 1.1MPa, and 1.3MPa, so that the method has high reliability and high production efficiency, and the performance and user experience of the prepared thermocouple product are good. Moreover, the acetylene pressure of the flame spraying is in the range, so that the first electrode and the metal plate have better bonding force on the premise of ensuring the technical effect.
According to the embodiments of the invention, the inventor conducts a great deal of thorough research and experimental verification on the moving speed of the flame spraying spray gun, and finds that the moving speed of the flame spraying spray gun is 50-1000mm/S, and in some specific embodiments of the invention, the moving speed of the flame spraying spray gun is specifically 50mm/S, 100mm/S, 200mm/S, 400mm/S, 600mm/S, 800mm/S and 1000mm/S, so that the method can be further high in reliability and production efficiency, and the prepared thermocouple product is good in performance and user experience. Moreover, the moving speed of the spray gun for flame spraying is in the range, so that the thickness of the formed first electrode is moderate on the premise of ensuring the technical effect, and the excellent uniformity and continuity are ensured.
According to the embodiments of the present invention, the inventor has conducted a great deal of intensive investigation and experimental verification on the powder feeding rate (the mass of the consumed alloy powder material in unit time) of the flame spraying, and found that the powder feeding amount of the flame spraying is 0.5 to 2.0Kg/h, and in some embodiments of the present invention, the powder feeding amount of the flame spraying is specifically 0.5Kg/h, 0.6Kg/h, 0.7Kg/h, 0.8Kg/h, 0.9Kg/h, 1.0Kg/h, 1.5Kg/h, and 2.0Kg/h, which can further improve the reliability and the production efficiency of the method, and the product performance and the user experience of the prepared thermocouple are good. Moreover, the powder feeding amount of the flame spraying is within the range, so that the efficiency of forming the first electrode is higher, the thickness of the first electrode 200 is more uniform on the premise of ensuring the technical effect, and meanwhile, the device for flame spraying is not easy to block.
According to the embodiments of the present invention, the inventors have conducted a lot of close examination and experimental verification on the particle size of the flame sprayed powder (it should be noted that the particle size of the powder herein refers to the particle size of the alloy powder), and found that the particle size of the flame sprayed powder is 15-45 μm, and in some embodiments of the present invention, the particle size of the flame sprayed powder is specifically 20 μm and 30 μm, which further enables the method to have high reliability and high production efficiency, and the prepared thermocouple product has good performance and user experience. Moreover, the particle size of the flame sprayed powder material is in the range, so that on the premise of ensuring the technical effect, more first thermoelectric materials are not oxidized, the purity of the formed first electrode is higher, and the thermoelectric property is more excellent; and the first thermoelectric material is more fully sprayed, the quality of the formed first electrode is higher, and the bonding force between the first electrode and the metal plate is better.
According to the embodiment of the invention, in order to make the preparation method of the thermocouple lower in cost, higher in production efficiency, better in reliability and capable of obtaining the thermocouple with more excellent performance, the inventor comprehensively considers the preheating temperature of the base material, the spraying angle, the spraying distance, the oxygen pressure, the acetylene pressure, the moving speed of the spray gun, the powder feeding amount and the particle size of the powder material adopted by flame spraying, and finds that when the preheating temperature of the base material of the flame spraying is more than 40 ℃, and simultaneously the following conditions are met: the spraying angle is 60-90 degrees; the spraying distance is 50-300 mm; the oxygen pressure is more than or equal to 0.5 MPa; the acetylene pressure is more than or equal to 0.1 MPa; the moving speed of the spray gun is 50-1000 mm/s; the powder feeding amount is 0.5-2.0 Kg/h; when the particle size of the powder is 15-45 mu m, all parameters of the powder are mutually influenced and have a synergistic effect, so that the preparation method of the thermocouple can be greatly shortened, the cost is greatly reduced, the prepared thermocouple is high in temperature measurement precision, high in sensitivity and high in thermal response speed, real-time and accurate temperature measurement and control functions can be realized, and the product performance and the user experience are good.
In still other embodiments of the present invention, the specific method of thermal spraying is plasma spraying. Therefore, the method is simple and convenient to operate, easy to realize, low in control precision requirement on process parameters, high in feasibility, good in reliability, low in cost, high in production efficiency, easy to realize actual industrial production, and particularly suitable for the field of household appliances, and has the advantages of simple structure, short production period, high temperature measurement precision, high sensitivity, high thermal response speed, capability of realizing real-time and accurate temperature measurement and control functions, and good product performance and user experience.
According to the embodiments of the present invention, the inventors have conducted a lot of intensive research and experimental verification on the current of plasma spraying, and found that the current of plasma spraying is 300-. Moreover, the current of the plasma spraying is in the range mentioned above, so that the efficiency of forming the first electrode by the first thermoelectric material is higher on the premise of ensuring the technical effect mentioned above; meanwhile, the first electrode is formed to have high uniformity.
According to the embodiments of the invention, the inventor conducts a great deal of intensive investigation and experimental verification on the voltage of the plasma spraying, and the inventor finds that the voltage of the plasma spraying is 30-100V, and in some specific embodiments of the invention, the voltage of the plasma spraying is 30V, 50V, 70V, 90V and 100V, so that the method has high reliability and high production efficiency, and the prepared thermocouple product has good performance and user experience. Moreover, the voltage of the plasma spraying is in the range, so that the first thermoelectric material can be sprayed more sufficiently on the premise of ensuring the technical effect, the quality of the formed first electrode is higher, and the bonding force between the first electrode and the metal plate is better; meanwhile, the temperature in the process of arc spraying is moderate, more first thermoelectric materials are not oxidized, the purity of the formed first electrode is higher, and the thermoelectric performance is more excellent.
According to the embodiments of the invention, the inventor conducts a large amount of thorough investigation and experimental verification on the argon flow rate of plasma spraying, and finds that the argon flow rate of plasma spraying is 30-70L/min, and in some specific embodiments of the invention, the argon flow rate of plasma spraying is 30L/min, 40L/min, 50L/min, 60L/min and 70L/min, so that the method is further high in reliability and production efficiency, and the prepared thermocouple product is good in performance and user experience. Moreover, the argon flow of the plasma spraying is in the range, so that the plasma gas is sufficient, the first thermoelectric material is sprayed more sufficiently, the efficiency is higher, the energy consumption is low, the quality of the formed first electrode is more excellent, and the performance is better on the premise of ensuring the technical effect.
According to the embodiments of the invention, the inventor conducts a large amount of thorough investigation and experimental verification on the flow rate of hydrogen or helium sprayed by plasma, and the inventor finds that the flow rate of hydrogen or helium sprayed by plasma is 4-25L/min, and in some specific embodiments of the invention, the flow rates of hydrogen or helium sprayed by plasma are 4L/min, 10L/min, 15L/min, 20L/min and 25L/min, so that the method can be further high in reliability and production efficiency, and the performance and user experience of the prepared thermocouple product are good. Moreover, the flow rate of the hydrogen or the helium gas sprayed by the plasma is in the range, so that the production efficiency is higher, the first thermoelectric material substrate cannot be oxidized on the premise of ensuring the technical effect, and the formed first electrode has better quality and better performance.
According to the embodiments of the invention, the inventor conducts a great deal of intensive investigation and experimental verification on the flow rate of powder feeding and carrier gas of plasma spraying (the gas flow rate for conveying alloy powder, usually nitrogen), and the inventor finds that the flow rate of the powder feeding and carrier gas of the plasma spraying is 3-15L/min, and in some specific embodiments of the invention, the flow rates of the powder feeding and carrier gas of the plasma spraying are specifically 3L/min, 6L/min, 9L/min, 12L/min and 15L/min, so that the method has high reliability and high production efficiency, and the prepared thermocouple product has good performance and user experience. Moreover, the flow rate of the powder feeding carrier gas for plasma spraying is in the range, so that the first thermoelectric material can be effectively fed into the plasma spraying equipment on the premise of ensuring the technical effect, the blockage is not easy to cause, the spraying efficiency is high, and the plasma degree of the equipment is not influenced.
According to the embodiments of the invention, the inventor conducts a great deal of intensive investigation and experimental verification on the spraying distance of the plasma spraying, and finds that the spraying distance of the plasma spraying is 50-250mm, and in some specific embodiments of the invention, the spraying distance of the plasma spraying is specifically 50mm, 100mm, 150mm, 200mm and 250mm, so that the method has high reliability and high production efficiency, and the prepared thermocouple product has good performance and user experience. Moreover, the spraying distance of the plasma spraying is within the range, so that the shape of the metal plate is more complete on the premise of ensuring the technical effect, and the shape of the metal plate is not obviously changed before flame spraying and after flame spraying; meanwhile, higher production efficiency can be guaranteed, the bonding force of the first electrode and the metal plate is higher, more first thermoelectric materials cannot be oxidized, the purity of the formed first electrode is higher, and the thermoelectric performance is more excellent.
According to the embodiments of the present invention, the inventors have conducted a great deal of intensive research and experimental verification on the moving speed of the plasma spraying spray gun, and found that the moving speed of the plasma spraying spray gun is 50-1000mm/S, and in some specific embodiments of the present invention, the moving speed of the plasma spraying spray gun is specifically 50mm/S, 100mm/S, 200mm/S, 400mm/S, 600mm/S, 800mm/S, or 1000mm/S, which can further make the method highly reliable and efficient, and the performance and user experience of the prepared thermocouple product are good. Moreover, the moving speed of the spray gun for plasma spraying is in the range, so that the thickness of the formed first electrode is moderate on the premise of ensuring the technical effect, and the more excellent uniformity and continuity are ensured.
According to the embodiments of the invention, the inventor conducts a great deal of intensive investigation and experimental verification on the powder feeding speed (the mass of the alloy powder consumed in unit time) of the plasma spraying, and finds that the powder feeding speed of the plasma spraying is 5-50g/min, and in some specific embodiments of the invention, the powder feeding speed of the plasma spraying is 5g/min, 10g/min, 20g/min, 30g/min, 40g/min and 50g/min, so that the method has high reliability and high production efficiency, and the prepared thermocouple product has good performance and user experience. Moreover, the powder feeding speed of the plasma spraying is in the range, the efficiency of forming the first electrode is higher on the premise of ensuring the technical effect, the thickness of the first electrode is more uniform, and meanwhile, the device for flame spraying is not easy to block.
According to the embodiment of the invention, in order to make the preparation method of the thermocouple lower in cost, higher in production efficiency, better in reliability and capable of obtaining the thermocouple with more excellent performance, the inventor comprehensively considers the current, the voltage, the argon gas flow, the hydrogen or helium gas flow, the powder feeding carrier gas flow, the spraying distance, the moving speed of the spray gun and the powder feeding speed adopted by plasma spraying, and finds that when the current of the plasma spraying is 300-700A, and simultaneously the following conditions are met: the voltage is 30-100V; the flow rate of argon gas is 30-70L/min; the flow rate of hydrogen or helium is 4-25L/min; the flow rate of the powder feeding carrier gas is 3-15L/min; the spraying distance is 50-250 mm; the moving speed of the spray gun is 50-1000 mm/s; when the powder feeding speed is 5-50g/min, all parameters of the thermocouple are mutually influenced and have a synergistic effect, so that the preparation method of the thermocouple can be greatly shortened, the cost is greatly reduced, the prepared thermocouple is high in temperature measurement precision, high in sensitivity and high in thermal response speed, real-time and accurate temperature measurement and control functions can be realized, and the product performance and the user experience are good.
The specific manner of spraying the first thermoelectric material on the surface of the insulating coating of the metal plate material to form the first electrode according to the embodiment of the present invention is not particularly limited, and those skilled in the art can flexibly select the first thermoelectric material as needed as long as the requirements are met. In some embodiments of the present invention, a first mask (a shown in fig. 8) may be used to cover the metal plate, and then spraying is performed, and the hollow portion of the first mask forms the first electrode.
In some specific embodiments of the invention, the oxidized portion of the surface of the first wire is previously removed prior to performing the thermal spraying. Therefore, the first thermoelectric material can be ensured to remove impurities on the surface before thermal spraying, and the spraying effect is better.
According to the embodiment of the present invention, the specific method for removing the oxidized portion is not particularly limited, and one skilled in the art may flexibly select according to the requirement as long as the requirement is satisfied, and for example, may include but not limited to grinding, sand blasting, and the like. In some embodiments of the invention, the specific method of removing the oxidized portion may be grit blasting. Therefore, the surfaces of the first wire and the second wire can be completely treated, and the method is simple and convenient to operate and easy for industrial production.
According to the embodiment of the present invention, the specific kind of sand used for the sand blasting is not particularly limited, and may be flexibly selected by those skilled in the art as long as the requirement is satisfied, and may include, but is not limited to, quartz sand, brown corundum, iron sand, white corundum, etc., for example. In some embodiments of the present invention, the specific type of sand used for the blasting process may be brown corundum or white corundum. Therefore, the sand blasting effect can be better.
According to the embodiment of the present invention, the particle size of the sand used for the blasting treatment is not particularly limited, and one skilled in the art can flexibly select the sand as needed as long as the requirement is satisfied. In some embodiments of the present invention, the grit used in the grit blasting may be 20-800 mesh in size. In some more preferred embodiments of the present invention, the grit used for the grit blasting may be 40-120 mesh in size. In some embodiments of the invention, the grit used in the grit blasting may be 40 mesh, 60 mesh, 80 mesh, 100 mesh, 120 mesh. Therefore, oxidized parts of the surfaces of the first wire and the second wire can be processed to the utmost extent under the condition of ensuring that the surfaces of the first wire and the second wire are not abraded. If the grit size of the sand used for the blasting is too low, it is difficult to clean the oxidized portions of the surfaces of the first wire and the second wire, and if the grit size of the sand used for the blasting is too high, it is easy to leave grinding marks on the surfaces of the first wire and the second wire.
According to the embodiment of the present invention, the shape of the first electrode is not particularly limited, and one skilled in the art can flexibly select the shape as needed as long as the requirement is satisfied. In some embodiments of the present invention, the first electrode may have a bar shape.
According to the embodiment of the present invention, the thickness of the first electrode is not particularly limited, and one skilled in the art can flexibly select the thickness as needed as long as the requirement is satisfied. In some embodiments of the invention, the average thickness of the first electrode may be 5-100 microns. In some more preferred embodiments of the present invention, the average thickness of the first electrode may be 10 to 60 micrometers. In some embodiments of the invention, the first electrode may have an average thickness of 10 microns, 20 microns, 30 microns, 40 microns, 50 microns, 60 microns. Therefore, the prepared thermocouple is good in temperature measurement effect, the first electrode has higher reliability and better wear resistance, the uniformity is better, and the appearance is more attractive visually.
According to the embodiment of the present invention, the resistance of the first electrode is not particularly limited, and one skilled in the art can flexibly select the resistance as needed as long as the requirement is satisfied. In some embodiments of the invention, the first electrode has a resistance of no more than 1000 ohms. In some embodiments of the invention, the first electrode may have a resistance of 100 ohms, 200 ohms, 400 ohms, 600 ohms, 800 ohms, 1000 ohms. Therefore, the electric conductivity is good, the prepared thermocouple is high in sensitivity, good in temperature measurement effect and high in thermal response speed, and real-time and accurate temperature measurement and control functions can be realized.
According to an embodiment of the invention, the first electrode has a rough surface. It should be noted that the rough surface of the present invention should be a rough surface that can be distinguished by naked eyes. In some embodiments of the invention, the surface roughness of the first electrode is greater than 1 micron. Therefore, the thermocouple prepared is particularly suitable for the field of household appliances, and has the advantages of simple structure, short production period, high temperature measurement precision, high sensitivity and high thermal response speed, can realize real-time and accurate temperature measurement and control functions, and has good product performance and user experience.
S2: forming a second electrode
In this step, a second thermoelectric material is sprayed on the surface of the insulating coating using a thermal spraying method to form a second electrode. According to an embodiment of the invention, there is at least one contact area between the second electrode and the first electrode, and the first thermoelectric material and the second thermoelectric material are of different composition. Specifically, referring to fig. 2 (a) is a schematic cross-sectional structure, fig. 2 (b) is a schematic plan-view structure) or fig. 3 (a) is a schematic cross-sectional structure, fig. 3 (b) is a schematic plan-view structure), the schematic structural diagram is a structure in which the second electrode 420 is formed on the surface of the insulating coating 300 of the metal plate (including the metal substrate 100, the oxide film layer 200, and the insulating coating 300). Fig. 9 shows a photograph of a thermocouple prepared after the second electrode was formed. The method forms a first electrode 410 and a second electrode 420 on an insulating coating 300 in a metal plate material, the second electrode 420 and the first electrode 410 having at least one contact area therebetween (a as shown in fig. 2), and the first thermoelectric material forming the first electrode 410 and the second thermoelectric material forming the second electrode 420 are different in composition.
According to an embodiment of the present invention, the specific material type of the second thermoelectric material should be different from the specific composition of the first thermoelectric material, and may include, but is not limited to, for example, platinum-rhodium alloy, platinum, nickel-silicon alloy, nickel-aluminum alloy, nickel-silicon-magnesium alloy, tungsten-rhenium alloy, and the like. In some embodiments of the present invention, the second thermoelectric material may specifically be Pt in its kind94Rh6Platinum, Ni97Si3、Ni97Al3、Cu55Ni45、Ni95.5Si4.5Mg1、W75Re25And W74Re26. Therefore, the material source is wide and easy to obtain, and the prepared thermocouple has good temperature measurement effect and high stability and sensitivity.
According to the embodiment of the present invention, the first thermoelectric material and the second thermoelectric material are not particularly limited in combination as long as they are one selected from the above-described materials. The foregoing first thermoelectric material and second thermoelectric material may be freely combined. For example, in some specific embodiments of the invention, Ni90Cr10As the first thermoelectric material, Ni97Si3The first electrode and the second electrode are respectively formed by the second thermoelectric material. Therefore, the prepared thermocouple has a good temperature measuring effect and good stability.
According to the embodiment of the present invention, the supply form of the second thermoelectric material is not particularly limited, and one skilled in the art can flexibly select it as needed as long as the requirement is satisfied. In some embodiments of the invention, the second thermoelectric material is provided in the form of a second wire. In other embodiments of the present invention, the second thermoelectric material is provided in the form of an alloy powder. This makes thermal spraying more suitable.
According to the embodiment of the present invention, the specification of the second wire, the method for removing the oxidized part on the surface of the second wire in advance, the particle size of the alloy powder, the second mask (b shown in fig. 8), the thickness, the resistance, the roughness and other characteristics of the second electrode are the same as those of the first thermoelectric material, the first wire, the first electrode, the first mask and other characteristics and advantages described above, and thus, redundant description is omitted here.
According to an embodiment of the present invention, the contact region may include only a contact surface (as shown in fig. 2 a) perpendicular to the metal substrate; alternatively, the contact region may include both a contact surface perpendicular to the metal base material and a contact surface parallel to the metal base material (B shown as (a) in fig. 3). According to the embodiment of the present invention, the area of the contact region (e.g. a shown in fig. 2 a) is not particularly limited, and one skilled in the art can flexibly select the area as needed as long as the requirement is met. In some embodiments of the invention, the area of the contact region may be 0.5 to 200 square millimeters. In some embodiments of the invention, the contact area may have an area of 0.5 mm, 1mm, 10 mm, 50mm, 100mm, 150mm, 200 mm. Therefore, the prepared contact temperature sensor has good linearity, large thermoelectromotive force and high sensitivity, and can realize higher temperature measurement reliability on the premise of ensuring accurate judgment of the position of the temperature measurement point.
In yet another aspect of the present invention, an appliance is presented. The appliance includes a thermocouple as described previously. Thus, the appliance may have all the features and advantages of the previously described thermocouple, which are not described in detail herein. In general, the thermocouple used in the electric appliance has excellent bonding performance of the insulating layer and the metal base material, and the insulating layer has high temperature resistance, good corrosion resistance and good stability; and the insulating layer has good compactness and excellent insulating property. The inventor finds that the thermocouple directly contacts with the measured object, is particularly suitable for the field of household appliances, and has the advantages of simple structure, short production period, high temperature measurement precision, high sensitivity, high thermal response speed, capability of realizing real-time and accurate temperature measurement and control functions, and good product performance and user experience.
According to an embodiment of the present invention, the electric appliance may be a cooking apparatus, and the thermocouple is provided on a surface of the cooking apparatus directly contacting the food. According to the embodiment of the present invention, the specific kind of the cooking apparatus is not particularly limited, and those skilled in the art can flexibly select the cooking apparatus as needed, as long as the requirements are satisfied, for example, including but not limited to an induction cooker, an electric pressure cooker, an electric hot pot, an electric scissors pot, an electric stewpan, and an electric kettle. According to the embodiment of the invention, the induction cooker, the electric pressure cooker, the electric heating pot, the electric scissors pot, the electric stewpot and the electric heating pot all have the general structures of the induction cooker, the electric pressure cooker, the electric scissors pot, the electric stewpot and the electric heating pot in the field, and redundant description is omitted. When the thermocouple is used for cooking equipment, the cooking effect is good, real intelligent cooking can be realized, and all the characteristics and advantages of the thermocouple in the front are realized, so that the thermocouple is not repeated.
According to an embodiment of the present invention, the cooking apparatus further includes a protective layer covering the thermocouple and directly contacting the food. According to the embodiment of the present invention, the specific material of the protective layer is not particularly limited, and one skilled in the art can flexibly select the material as needed as long as the requirement is satisfied. In some embodiments of the present invention, the specific material type of the protective layer may be a teflon coating or a ceramic non-stick coating. Therefore, on the one hand, the thermocouple can be protected in the cooking process to prevent the thermocouple from being damaged in the cooking process to influence the temperature measurement effect, and on the other hand, the Teflon coating and the ceramic non-stick coating are food-grade coatings and cannot damage the human body after being used for a long time.
According to the embodiment of the present invention, the thickness of the protective layer is not particularly limited, and one skilled in the art can flexibly select the thickness as needed as long as the requirement is satisfied. In some embodiments of the present invention, the protective layer may have a thickness of 10-50 microns. In some embodiments of the present invention, the thickness of the protective layer may be 10 microns, 20 microns, 30 microns, 40 microns, 50 microns. Therefore, the thermocouple cannot be protected due to the fact that the thickness of the protective layer is too thin, and the temperature measurement accuracy of the thermocouple cannot be influenced due to the fact that the thickness of the protective layer is too thick.
The following describes embodiments of the present invention in detail.
Precision testing of thermocouples
The temperature measuring accuracy of the thermocouple of the invention is tested by using the device shown in fig. 10, the thermocouple (not shown in the figure) and a standard temperature measuring sensor (a standard temperature measuring sensor made of the same material as the thermocouple of the invention, not shown in the figure) are formed on a ceramic wafer 1000, the ceramic wafer 1000 is placed on a heater 2000, the temperature measuring point of the thermocouple of the invention is T, the temperature measuring point of the standard temperature measuring sensor is T mark, the T mark is as close as possible to the T mark, a heat insulating material 3000 is covered outside, the heater 2000 is opened, the temperature is gradually increased, the temperature of the two points of the T mark and the T mark is collected by using a temperature collector 4000, and the temperature change curve of the thermocouple of the invention and the standard temperature measuring sensor at room temperature-300 ℃.
Example 1
Method for producing thermocouple
1. Carrying out sand blasting treatment on a stainless steel alloy (200 × 1mm) by adopting 80-mesh brown corundum, and then carrying out surface insulation treatment;
2. covering a first mask plate with a hollowed first electrode pattern on the stainless steel alloy with the surface subjected to insulation treatment;
3. removing the first wire (Ni component)90Cr102.0mm in diameter) oxidized part of the surface;
4. in the presence of a carrier gas of N2Under the condition, an electric arc spraying device is adopted to spray a first wire material on the ceramic covered with the first mask plate, the spraying voltage is 20V,the current is 100A, the spraying distance is 300mm, the spraying air pressure is 0.6MPa, the moving speed of the spray gun is 100mm/S, a first electrode of the thermocouple is formed, the average thickness is 35 mu m, and the resistance is 150 omega;
5. covering a second mask plate with a hollowed second electrode pattern on the stainless steel alloy with the surface subjected to insulation treatment, wherein the hollowed pattern on the second mask plate and the hollowed pattern on the first mask plate have an overlapping region with an area of 5 x 5mm2Forming a contact region within the overlap region;
6. removing the second wire (Cu as the component)55Ni452.0mm in diameter) oxidized part of the surface;
7. in the presence of a carrier gas of N2Under the conditions, spraying a second wire material on the ceramic covered with the second mask plate by adopting electric arc spraying equipment, wherein the spraying voltage is 30V, the current is 400A, the spraying distance is 200mm, the spraying air pressure is 0.8MPa, the moving speed of a spray gun is 300mm/S, a second electrode of the thermocouple is formed, the average thickness is 45 mu m, and the resistance is 120 omega;
8. the temperature change curve of the thermocouple is tested to be in accordance with the temperature change curve of the standard temperature measuring sensor at room temperature to 300 ℃ (shown in figure 11), and the temperature change curve of the thermocouple is almost consistent with the temperature change curve of the standard temperature measuring sensor, and the error is about 1%.
Example 2
Method for producing thermocouple
1. Carrying out insulation treatment on the surface of an aluminum alloy (200 x 400 x 2 mm);
2. covering a first mask plate with a hollowed first electrode pattern on the aluminum alloy with the surface subjected to insulation treatment;
3. removing oxidized portions of the surface of a first wire (Cu component, 1.8mm in diameter);
4. under the condition that the carrier gas is Ar, spraying a first wire material on the ceramic covered with the first mask plate by adopting electric arc spraying equipment, wherein the spraying voltage is 40V, the current is 100A, the spraying distance is 400mm, the spraying air pressure is 0.4MPa, the moving speed of a spray gun is 100mm/S, a first electrode of a thermocouple is formed, the average thickness is 25 mu m, and the resistance is 150 omega;
5. will hollow out the second electrode patternThe second mask plate is covered on the aluminum alloy with the surface subjected to insulation treatment, and the hollow patterns on the second mask plate and the hollow patterns on the first mask plate have an overlapping region with an area of 2 x 2mm2Forming a contact region within the overlap region;
6. removing the second wire (composition Ni)97Si31.8mm in diameter) oxidized part of the surface;
7. spraying a second wire material on the ceramic covered with the second mask plate by adopting electric arc spraying equipment under the condition that the carrier gas is Ar, wherein the spraying voltage is 20V, the current is 50A, the spraying distance is 100mm, the spraying air pressure is 0.2MPa, the moving speed of a spray gun is 400mm/S, a second electrode of the thermocouple is formed, the average thickness is 45 mu m, and the resistance is 15 omega;
8. the temperature change curve of the thermocouple is tested to be between room temperature and 300 ℃ of the standard temperature measurement sensor (as shown in figure 12), and the graph shows that the temperature change curve of the thermocouple is approximately consistent with the temperature change curve of the standard temperature measurement sensor, and the error is about 1%.
Example 3
Method for producing thermocouple
1. Carrying out sand blasting treatment on a stainless steel alloy (200 × 1mm) by adopting 100-mesh brown corundum, and then carrying out insulation treatment on the surface of the stainless steel alloy;
2. covering a first mask plate with a hollowed first electrode pattern on the stainless steel alloy with the surface subjected to insulation treatment;
3. removing the first wire (Ni component)90Cr102.0mm in diameter) oxidized part of the surface;
4. in the presence of a carrier gas of N2Under the conditions, spraying a first wire material on the ceramic covered with the first mask plate by adopting electric arc spraying equipment, wherein the spraying voltage is 20V, the current is 100A, the spraying distance is 300mm, the spraying air pressure is 0.6MPa, the moving speed of a spray gun is 100mm/S, a first electrode of a thermocouple is formed, the average thickness is 35 mu m, and the resistance is 150 omega;
5. covering a second mask plate with a second electrode pattern hollowed out on the aluminum alloy with the surface subjected to insulation treatment, wherein the hollowed-out pattern on the second mask plate and the hollowed-out pattern on the first mask plateThe pattern has an overlapping area of 2 x 2mm2Forming a contact region within the overlap region;
6. removing the second wire (composition Ni)97Si31.8mm in diameter) oxidized part of the surface;
7. spraying a second wire material on the ceramic covered with the second mask plate by adopting electric arc spraying equipment under the condition that the carrier gas is Ar, wherein the spraying voltage is 20V, the current is 50A, the spraying distance is 100mm, the spraying air pressure is 0.2MPa, the moving speed of a spray gun is 400mm/S, a second electrode of the thermocouple is formed, the average thickness is 45 mu m, and the resistance is 15 omega;
8. the temperature change curve of the thermocouple is tested to be between room temperature and 300 ℃ of the standard temperature measurement sensor (as shown in figure 13), and the graph shows that the temperature change curve of the thermocouple is approximately consistent with the temperature change curve of the standard temperature measurement sensor, and the error is about 1%.
Example 4
Method for producing thermocouple
1. Insulating the surface of the stainless steel alloy (200 × 1 mm);
2. covering a first mask plate with a hollowed first electrode pattern on the stainless steel alloy with the surface subjected to insulation treatment, and heating to 60 ℃;
3. preparing alloy powder (with Ni as component)90Cr10Particle size distribution 15-45 μm);
4. spraying alloy powder on the stainless steel alloy covered with the first mask plate by adopting flame spraying equipment, wherein the spraying angle is more than 80 degrees, the spraying distance is 250mm, the oxygen pressure is 0.8MPa, the acetylene pressure is 0.15MPa, the moving speed of a spray gun is 400mm/s, the powder feeding amount is 1.5Kg/h, and a first electrode of a thermocouple is formed, the average thickness is 35 mu m, and the resistance is 120 omega;
5. covering a second mask plate with a hollowed second electrode pattern on the stainless steel alloy with the surface subjected to insulation treatment, wherein the hollowed pattern on the second mask plate and the hollowed pattern on the first mask plate have an overlapping region with an area of 5 x 5mm2Forming a contact region within the overlap region;
6. preparing alloy powder (Cu as component)55Ni45The particle size distribution is 15-45 μm);
7. spraying alloy powder on the stainless steel alloy covered with the second mask plate by adopting flame spraying equipment, wherein the spraying angle is more than 90 degrees, the spraying distance is 100mm, the oxygen pressure is 0.9MPa, the acetylene pressure is 0.10MPa, the moving speed of a spray gun is 400mm/s, the powder feeding amount is 1.5Kg/h, and a second electrode of the thermocouple is formed, the average thickness is 50 microns, and the resistance is 15 omega;
8. the temperature change curve between the temperature measuring device and a standard temperature measuring sensor at room temperature and 300 ℃ is tested, and the temperature measuring error is about 1 percent.
Example 5
Method for producing thermocouple
1. Carrying out sand blasting treatment on aluminum alloy (200 × 400 × 2mm) by adopting 50-mesh white corundum, and then carrying out insulation treatment on the surface of the aluminum alloy;
2. covering a first mask plate with a hollowed first electrode pattern on the surface of the aluminum alloy subjected to insulation treatment, and heating to 80 ℃;
3. preparing alloy powder (with Ni as component)84.5Cr14Si1.5Particle size distribution 15-45 μm);
4. spraying alloy powder on the aluminum alloy covered with the first mask plate by adopting flame spraying equipment, wherein the spraying angle is 85 degrees, the spraying distance is 150mm, the oxygen pressure is 0.7MPa, the acetylene pressure is 0.15MPa, the moving speed of a spray gun is 500mm/s, the powder feeding amount is 1.0Kg/h, a first electrode of a thermocouple is formed, the average thickness is 15 microns, and the resistance is 150 ohms;
5. covering a second mask plate with a hollowed second electrode pattern on the aluminum alloy with the surface subjected to insulation treatment, wherein the hollowed pattern on the second mask plate and the hollowed pattern on the first mask plate have an overlapping region with an area of 2 x 2mm2Forming a contact region within the overlap region;
6. preparing alloy powder (with Ni as component)97Si3The particle size distribution is 15-45 μm);
7. spraying alloy powder on the stainless steel alloy covered with the second mask plate by adopting flame spraying equipment, wherein the spraying angle is 85 degrees, the spraying distance is 150mm, the oxygen pressure is 0.8MPa, the acetylene pressure is 0.10MPa, the moving speed of a spray gun is 200mm/s, the powder feeding amount is 1.0Kg/h, a second electrode of the thermocouple is formed, the average thickness is 45 mu m, and the resistance is 15 omega;
8. the temperature change curve between the temperature measuring device and a standard temperature measuring sensor at room temperature and 300 ℃ is tested, and the temperature measuring error is about 1 percent.
Example 6
Method for producing thermocouple
1. Carrying out sand blasting treatment on a stainless steel alloy (200 × 1mm) by using 80-mesh white corundum, and then carrying out insulation treatment on the surface of the stainless steel alloy;
2. covering a first mask plate with a hollowed first electrode pattern on the stainless steel alloy with the surface subjected to insulation treatment;
3. preparing alloy powder (with Ni as component)90Cr10Particle size distribution 15-45 μm);
4. spraying alloy powder on the stainless steel alloy covered with the first mask plate by using plasma spraying equipment, wherein the spraying current is 700A, the spraying voltage is 40V, the argon flow is 60L/min, the hydrogen flow is 20L/min, the powder feeding carrier flow is 10L/min, the spraying distance is 100mm, the moving speed of a spray gun is 500mm/s, the powder feeding amount is 10g/min, a first electrode of a thermocouple is formed, the average thickness is 15 mu m, and the resistance is 300 omega;
5. covering a second mask plate with a hollowed second electrode pattern on the stainless steel alloy with the surface subjected to insulation treatment, wherein the hollowed pattern on the second mask plate and the hollowed pattern on the first mask plate have an overlapping region with an area of 5 x 5mm2Forming a contact region within the overlap region;
6. preparing alloy powder (Cu as component)55Ni45The particle size distribution is 15-45 μm);
7. spraying alloy powder on the microcrystalline glass covered with the second mask plate by using plasma equipment, wherein the spraying current is 300A, the spraying voltage is 70V, the argon flow is 50L/min, the helium flow is 4L/min, the powder conveying and carrying flow is 15L/min, the spraying distance is 100mm, the moving speed of a spray gun is 400mm/s, the powder conveying amount is 50g/min, a second electrode of the thermocouple is formed, the average thickness is 50 mu m, and the resistance is 20 omega;
8. the temperature change curve between the temperature measuring device and a standard temperature measuring sensor at room temperature and 300 ℃ is tested, and the temperature measuring error is about 1 percent.
Example 7
Method for producing thermocouple
1. Carrying out surface insulation treatment on an aluminum alloy (200 × 400 × 2 mm);
2. covering a first mask plate with a hollowed first electrode pattern on the aluminum alloy with the surface subjected to insulation treatment;
3. preparing alloy powder (with Ni as component)84.5Cr14Si1.5Particle size distribution 15-45 μm);
4. spraying alloy powder on the aluminum alloy covered with the first mask plate by using plasma spraying equipment, wherein the spraying current is 300A, the spraying voltage is 50V, the argon flow is 40L/min, the hydrogen flow is 15L/min, the powder conveying and carrying flow is 10L/min, the spraying distance is 200mm, the moving speed of a spray gun is 100mm/s, the powder conveying amount is 25g/min, a first electrode of a thermocouple is formed, the average thickness is 25 mu m, and the resistance is 150 omega;
5. covering a second mask plate with a hollowed second electrode pattern on the aluminum alloy with the surface subjected to insulation treatment, wherein the hollowed pattern on the second mask plate and the hollowed pattern on the first mask plate have an overlapping region with an area of 2 x 2mm2Forming a contact region within the overlap region;
6. preparing alloy powder (with Ni as component)97Si3The particle size distribution is 15-45 μm);
7. spraying alloy powder on the aluminum alloy covered with the second mask plate by using plasma equipment, wherein the spraying current is 600A, the spraying voltage is 70V, the argon flow is 60L/min, the hydrogen flow is 25L/min, the powder conveying and carrying flow is 15L/min, the spraying distance is 250mm, the moving speed of a spray gun is 200mm/s, the powder conveying amount is 30g/min, a second electrode of the thermocouple is formed, the average thickness is 50 mu m, and the resistance is 30 omega;
8. the temperature change curve between the temperature measuring device and a standard temperature measuring sensor at room temperature and 300 ℃ is tested, and the temperature measuring error is about 2 percent.
Example 8
Thermocouple (structure schematic view, refer to fig. 2 and 3)
1. Metal matrix: carrying out sand blasting treatment on the surface of the 5 series aluminum alloy, wherein the particle size of sand is 40 meshes so as to carry out insulation treatment;
2. buffer layer: the layer is an interpenetration layer between the surface of the metal matrix subjected to sand blasting and the insulating coating, is combined in a canine-tooth staggered manner and has the thickness of about 40 mu m;
3. insulating coating: the layer is ZrO2A layer having a thickness of 300 μm, prepared by plasma spraying, having a porosity of 10%;
4. a first electrode: iron; second electrode Ni97Si3The thickness is 40 μm; the preparation method is plasma spraying.
Fig. 14 shows a scanning electron micrograph of the thermocouple cross section.
The temperature change curve between the temperature measuring device and a standard temperature measuring sensor at room temperature and 300 ℃ is tested, and the temperature measuring error is about 1 percent.
Example 9
Thermocouple (structure schematic view, refer to fig. 2 and 3)
1. Metal matrix: carrying out sand blasting treatment on the surface of the titanium alloy, wherein the particle size of sand is 80 meshes so as to carry out surface insulation treatment;
2. buffer layer: the layer is an interpenetration layer between the surface of the metal matrix subjected to sand blasting and the insulating coating, is combined in a canine-tooth staggered manner, and has the thickness of about 30 mu m;
3. insulating coating: the layer is Al2O3A layer having a thickness of 200 μm, prepared by plasma spraying, having a porosity of 10%;
4. a first electrode: ni90Cr10(ii) a Second electrode Cu55Si45The thickness is 30 μm; the preparation method is electric arc spraying.
The temperature change curve between the temperature measuring device and a standard temperature measuring sensor at room temperature and 300 ℃ is tested, and the temperature measuring error is about 1 percent.
In the description of the present invention, the terms "upper", "lower", and the like indicate orientations or positional relationships based on those shown in the drawings, and are only for convenience of describing the present invention but do not require that the present invention must be constructed and operated in a specific orientation, and thus, should not be construed as limiting the present invention.
In the description herein, references to the description of "one embodiment," "another embodiment," etc., mean that a particular feature, structure, material, or characteristic described in connection with the embodiment is included in at least one embodiment of the invention. In this specification, the schematic representations of the terms used above are not necessarily intended to 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. Furthermore, various embodiments or examples and features of different embodiments or examples described in this specification can be combined and combined by one skilled in the art without contradiction. In addition, it should be noted that the terms "first" and "second" in this specification are used for descriptive purposes only and are not to be construed as indicating or implying relative importance or implying any number of technical features indicated.
Although embodiments of the present invention have been shown and described above, it is understood that the above embodiments are exemplary and should not be construed as limiting the present invention, and that variations, modifications, substitutions and alterations can be made to the above embodiments by those of ordinary skill in the art within the scope of the present invention.

Claims (19)

1. A thermocouple, comprising:
a metal substrate;
an oxide film layer covering at least a portion of a surface of the metal substrate;
an insulating coating layer covering a surface of the oxide film layer, the insulating coating layer being formed by disposing an insulating material on the oxide film layer and drying under a pressure of not more than 5000 Pa;
an electrode layer disposed on a side of the insulating coating layer away from the metal substrate,
wherein the pore size of the insulating coating is not greater than 10 nanometers.
2. The thermocouple according to claim 1, wherein the thickness of the oxide film layer is 10 to 200 μm.
3. The thermocouple of claim 1, wherein a material forming the insulating coating includes at least one of inorganic silica gel, potassium silicate, sodium silicate, lithium silicate, zirconia, titania, and alumina.
4. The thermocouple according to claim 1, wherein the insulating coating has a thickness of 1 to 200 μm.
5. The thermocouple of claim 1, wherein the electrode layers further include a first electrode and a second electrode, at least a portion of the first electrode and the second electrode being disposed in an overlapping arrangement.
6. A method of making a thermocouple according to any one of claims 1 to 5, comprising:
carrying out oxidation treatment on the metal substrate so as to form an oxide film layer;
forming an insulating coating on the oxide film layer so as to form a metal plate material, wherein the insulating coating is formed by arranging an insulating material on the oxide film layer and drying the insulating material under the condition that the pressure does not exceed 5000Pa, the insulating material is arranged on the oxide film layer through at least one of roll coating, spin coating and electrostatic spraying, and the pore diameter of the insulating coating is not more than 10 nanometers;
forming an electrode layer on the insulating coating based on the metal plate material to form the thermocouple.
7. The method according to claim 6, wherein the oxidation treatment is an anodic oxidation treatment, and an electrolytic solution used in the anodic oxidation treatment includes: 100-220 g/L sulfuric acid, 5-15 g/L oxalic acid, 2-16 g/L glycerol and 2-5 g/L additive; the temperature of the electrolyte is 3-10 ℃, the reaction time is 30-120 minutes, and the voltage range is 12-18 volts.
8. The method according to claim 6, wherein the oxidation treatment is micro-arc oxidation, and the electrolyte used in the micro-arc oxidation treatment comprises: 1-20 g/L sodium phosphate, 4-35 g/L sodium silicate, 4-10 g/L potassium silicate, 1-20 g/L sodium hydroxide, 0.5-4 g/L glycerol, 0-3 g/L boric acid, 1-5 g/L nano aluminum oxide and 1-5 g/L silicon carbide; the temperature of the electrolyte is 3-50 ℃, the reaction time is 30-120 minutes, and the voltage range is 400-550 volts.
9. The method according to claim 6, wherein the drying is vacuum drying,
wherein the drying temperature is 200-600 ℃, and the drying time is 10-60 minutes.
10. The method of claim 6, wherein forming an electrode layer on the insulating coating based on the metal plate material is performed by:
spraying a first thermoelectric material on the surface of the insulating coating of the metal plate by a thermal spraying method to form a first electrode;
spraying a second thermoelectric material on the surface of the insulating coating by using the thermal spraying method to form a second electrode;
wherein the second electrode and the first electrode have at least one contact area therebetween, and the first thermoelectric material and the second thermoelectric material have different compositions.
11. The method of claim 10, wherein the thermal spray method comprises at least one of arc spraying, flame spraying, and plasma spraying.
12. The method of claim 11, wherein the arc spraying uses a carrier gas that is nitrogen or an inert gas and satisfies at least one of:
the voltage is 20-45V;
the current is 50-400A;
the spraying distance is 50-400 mm;
the spraying air pressure is more than or equal to 0.2 MPa;
the moving speed of the spray gun is 50-2000 mm/S.
13. The method of claim 11, wherein the flame spraying is at least one of:
the preheating temperature of the metal plate is more than 40 ℃;
the spraying angle is 60-90 degrees;
the spraying distance is 50-300 mm;
the oxygen pressure is more than or equal to 0.5 MPa;
the acetylene pressure is more than or equal to 0.1 MPa;
the moving speed of the spray gun is 50-1000 mm/S;
the powder feeding amount is 0.5-2.0 Kg/h;
the particle size of the powder is 15-45 μm.
14. The method of claim 11, wherein the plasma spraying satisfies at least one of:
the current is 300-700A;
the voltage is 30-100V;
the flow rate of argon gas is 30-70L/min;
the flow rate of hydrogen or helium is 4-25L/min;
the flow rate of the powder feeding carrier gas is 3-15L/min;
the spraying distance is 50-250 mm;
the moving speed of the spray gun is 50-1000 mm/S;
the powder feeding speed is 5-50 g/min.
15. The method of claim 10, wherein the first electrode and the second electrode each have a rough surface;
the average thickness of the first electrode and the second electrode is each independently 5-100 microns;
the area of the contact area is 0.5-200 square millimeters.
16. The method of claim 10, wherein the first thermoelectric material comprises at least one of platinum-rhodium alloy, nickel-chromium alloy, iron, copper, nickel-chromium-silicon alloy, and tungsten-rhenium alloy; the second thermoelectric material includes at least one of platinum-rhodium alloy, platinum, nickel-silicon alloy, nickel-aluminum alloy, nickel-silicon-magnesium alloy, and tungsten-rhenium alloy.
17. An electrical appliance comprising a thermocouple according to any one of claims 1 to 5.
18. The appliance according to claim 17, wherein the appliance is a cooking appliance and the thermocouple is provided at a side of the cooking appliance that is in direct contact with food.
19. The electric appliance according to claim 18, characterized in that the cooking device further comprises a protective layer covering the thermocouple and in direct contact with the food,
wherein the protective layer is a Teflon coating or a ceramic non-stick coating;
the thickness of the protective layer is 10-100 microns.
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