CN116535203B - NTC thermosensitive ceramic and ceramic chip for quick temperature measurement of electric water heater and preparation method - Google Patents
NTC thermosensitive ceramic and ceramic chip for quick temperature measurement of electric water heater and preparation method Download PDFInfo
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- CN116535203B CN116535203B CN202310351119.2A CN202310351119A CN116535203B CN 116535203 B CN116535203 B CN 116535203B CN 202310351119 A CN202310351119 A CN 202310351119A CN 116535203 B CN116535203 B CN 116535203B
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- 239000000919 ceramic Substances 0.000 title claims abstract description 148
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 81
- 238000009529 body temperature measurement Methods 0.000 title claims abstract description 43
- 238000002360 preparation method Methods 0.000 title abstract description 17
- 229910052761 rare earth metal Inorganic materials 0.000 claims abstract description 43
- 229910052500 inorganic mineral Inorganic materials 0.000 claims abstract description 41
- 239000011707 mineral Substances 0.000 claims abstract description 41
- 150000003839 salts Chemical class 0.000 claims abstract description 41
- 238000005520 cutting process Methods 0.000 claims abstract description 7
- 239000002994 raw material Substances 0.000 claims description 70
- 238000000498 ball milling Methods 0.000 claims description 62
- 238000001035 drying Methods 0.000 claims description 30
- 239000002002 slurry Substances 0.000 claims description 30
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum oxide Inorganic materials [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 claims description 24
- PLDDOISOJJCEMH-UHFFFAOYSA-N neodymium oxide Inorganic materials [O-2].[O-2].[O-2].[Nd+3].[Nd+3] PLDDOISOJJCEMH-UHFFFAOYSA-N 0.000 claims description 24
- KTUFCUMIWABKDW-UHFFFAOYSA-N oxo(oxolanthaniooxy)lanthanum Chemical compound O=[La]O[La]=O KTUFCUMIWABKDW-UHFFFAOYSA-N 0.000 claims description 24
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 23
- 229910052709 silver Inorganic materials 0.000 claims description 23
- 239000004332 silver Substances 0.000 claims description 23
- 238000007599 discharging Methods 0.000 claims description 20
- 238000007873 sieving Methods 0.000 claims description 19
- 238000000462 isostatic pressing Methods 0.000 claims description 17
- 238000000034 method Methods 0.000 claims description 15
- 238000005245 sintering Methods 0.000 claims description 12
- 239000000843 powder Substances 0.000 claims description 10
- 238000005303 weighing Methods 0.000 claims description 8
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 6
- 229910052726 zirconium Inorganic materials 0.000 claims description 6
- 238000004140 cleaning Methods 0.000 claims description 5
- 239000011248 coating agent Substances 0.000 claims description 5
- 238000000576 coating method Methods 0.000 claims description 5
- 238000009694 cold isostatic pressing Methods 0.000 claims description 5
- 238000000465 moulding Methods 0.000 claims description 5
- 238000007493 shaping process Methods 0.000 claims description 2
- 230000032683 aging Effects 0.000 abstract description 34
- 230000002195 synergetic effect Effects 0.000 abstract description 7
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 abstract description 5
- AMWRITDGCCNYAT-UHFFFAOYSA-L manganese oxide Inorganic materials [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 abstract description 3
- 230000000694 effects Effects 0.000 abstract description 2
- 230000000052 comparative effect Effects 0.000 description 34
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 19
- 150000002910 rare earth metals Chemical class 0.000 description 13
- 238000012360 testing method Methods 0.000 description 11
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 9
- 229910052596 spinel Inorganic materials 0.000 description 9
- 239000011029 spinel Substances 0.000 description 9
- 150000002500 ions Chemical class 0.000 description 8
- 238000011056 performance test Methods 0.000 description 6
- FKTOIHSPIPYAPE-UHFFFAOYSA-N samarium(III) oxide Inorganic materials [O-2].[O-2].[O-2].[Sm+3].[Sm+3] FKTOIHSPIPYAPE-UHFFFAOYSA-N 0.000 description 5
- 230000009286 beneficial effect Effects 0.000 description 4
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 description 4
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 description 4
- 238000012545 processing Methods 0.000 description 4
- 238000001514 detection method Methods 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- SZVJSHCCFOBDDC-UHFFFAOYSA-N ferrosoferric oxide Chemical compound O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 description 2
- 238000000227 grinding Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- -1 rare earth metal ions Chemical class 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 230000009191 jumping Effects 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- 238000009740 moulding (composite fabrication) Methods 0.000 description 1
- GNMQOUGYKPVJRR-UHFFFAOYSA-N nickel(III) oxide Inorganic materials [O-2].[O-2].[O-2].[Ni+3].[Ni+3] GNMQOUGYKPVJRR-UHFFFAOYSA-N 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- PZFKDUMHDHEBLD-UHFFFAOYSA-N oxo(oxonickeliooxy)nickel Chemical compound O=[Ni]O[Ni]=O PZFKDUMHDHEBLD-UHFFFAOYSA-N 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 238000003746 solid phase reaction Methods 0.000 description 1
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- C04B35/626—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B
- C04B35/62605—Treating the starting powders individually or as mixtures
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F24—HEATING; RANGES; VENTILATING
- F24H—FLUID HEATERS, e.g. WATER OR AIR HEATERS, HAVING HEAT-GENERATING MEANS, e.g. HEAT PUMPS, IN GENERAL
- F24H9/00—Details
- F24H9/18—Arrangement or mounting of grates or heating means
- F24H9/1809—Arrangement or mounting of grates or heating means for water heaters
- F24H9/1818—Arrangement or mounting of electric heating means
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- 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
- G01K7/16—Measuring temperature based on the use of electric or magnetic elements directly sensitive to heat ; Power supply therefor, e.g. using thermoelectric elements using resistive elements
- G01K7/22—Measuring temperature based on the use of electric or magnetic elements directly sensitive to heat ; Power supply therefor, e.g. using thermoelectric elements using resistive elements the element being a non-linear resistance, e.g. thermistor
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- H01—ELECTRIC ELEMENTS
- H01C—RESISTORS
- H01C7/00—Non-adjustable resistors formed as one or more layers or coatings; Non-adjustable resistors made from powdered conducting material or powdered semi-conducting material with or without insulating material
- H01C7/04—Non-adjustable resistors formed as one or more layers or coatings; Non-adjustable resistors made from powdered conducting material or powdered semi-conducting material with or without insulating material having negative temperature coefficient
- H01C7/042—Non-adjustable resistors formed as one or more layers or coatings; Non-adjustable resistors made from powdered conducting material or powdered semi-conducting material with or without insulating material having negative temperature coefficient mainly consisting of inorganic non-metallic substances
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- C04B2235/3262—Manganese oxides, manganates, rhenium oxides or oxide-forming salts thereof, e.g. MnO
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Abstract
The application relates to the field of thermal ceramics, and particularly discloses an NTC thermal ceramic for quick temperature measurement of an electric water heater, a ceramic chip and a preparation method thereof. The NTC heat-sensitive ceramic for quick temperature measurement of the electric water heater is prepared from Co 3O4、Mn3O4、NiO、Fe2O3, znO, mgO and rare earth element mineral salt, and has the effects of high compactness, damp heat resistance, low ageing rate due to the synergistic effect of the MgO and the rare earth element mineral salt. The NTC thermal sensitive ceramic chip for quick temperature measurement of the electric water heater, which is obtained by cutting and dicing the NTC thermal sensitive ceramic, has high density, low humidity and heat resistance and low aging rate, and solves the problem that the NTC thermal sensitive ceramic chip of the water outlet is easy to age and damage because the NTC thermal sensitive ceramic chip is in a humidity and heat environment for a long time.
Description
Technical Field
The application relates to the field of thermosensitive ceramics, in particular to NTC thermosensitive ceramics for quick temperature measurement of an electric water heater, a ceramic chip and a preparation method.
Background
Along with the improvement of national living standard, the requirements of people on comfortable water are also higher and higher, and the electric water heater becomes the first choice of household water for consumers due to constant temperature water outlet. In order to ensure the continuous constant-temperature water outlet and the safety of the electric water heater, NTC heat-sensitive ceramics are generally added as components for temperature monitoring.
The electric water heater is aimed to realize accurate temperature control, and is generally realized by an NTC heat-sensitive ceramic chip arranged at the water outlet. However, the NTC thermal sensitive ceramic chip of the water outlet is in a damp and hot environment for a long time, so that the NTC thermal sensitive ceramic chip is easy to age and damage.
Disclosure of Invention
In order to solve the problem that the NTC thermal sensitive ceramic chip of the water outlet is easy to age and damage because the NTC thermal sensitive ceramic chip is in a damp and hot environment for a long time, the application provides the NTC thermal sensitive ceramic for quickly measuring the temperature of the electric water heater, the ceramic chip and a preparation method.
The application provides an NTC thermal sensitive ceramic for quick temperature measurement of an electric water heater, a ceramic chip and a preparation method thereof, which adopts the following technical scheme:
In a first aspect, the present application provides an NTC thermal sensitive ceramic for rapid temperature measurement of an electric water heater, which adopts the following technical scheme: NTC thermosensitive ceramic for quick temp. measurement of electric water heater is prepared from following raw materials ：13-15％Co3O4、30-32％MCo3O4、24-26％NiO、14-17％Fe2O3、1-2％ZnO、5-7％MgO、 and rare-earth element mineral salt as rest.
By adopting the technical scheme, the NTC heat-sensitive ceramic prepared from 13-15％Co3O4、30-32％MCo3O4、24-26％NiO、14-17％Fe2O3、1-2％ZnO、5-7％MgO、 raw materials of the rest rare earth element mineral salt has good humidity resistance and heat resistance and low aging rate. Experiments show that Mg 2+ and rare earth element mineral salt can produce synergistic effect, so that the NTC thermal sensitive ceramic can improve the moisture and heat resistance of the NTC thermal sensitive ceramic on the basis of the resistivity and the B value suitable for an electric water heater, and the ageing rate is reduced, wherein the NTC thermal sensitive ceramic is in a spinel structure, partial ions such as Mn 3+ ions and Mn 4+ ions generally tend to enter the B site, and Mn 2+ ions tend to enter the A site, and electrons can jump between the Mn 3+ ions and the Mn 4+ ions with shorter distances due to the fact that the distance between the B site and the B site is slightly smaller than the distance between the a site and the a site in the spinel structure, so that jumping conductance is generated. At this time, the spinel structure is in a metastable state, mg 2+ and rare earth metal ions cooperate to occupy the a site in the spinel structure, and the Mn 3+ ions and Mn 4+ ions are kept to jump between B-sites instead of between a-sites, so that MgO and rare earth mineral salts have little influence on the resistivity and B value, but can maintain the spinel structure in a metastable state. When the spinelle structure breaks the metastable state, the metal ion position fluctuates greatly, resulting in dramatic changes in ceramic properties, i.e., aging. And Mg 2+ and rare earth metal ions cooperate to occupy the A position in the spinel structure, so that the spinel structure maintains a metastable state, the ceramic density is higher, the humidity and heat resistance is good, and the aging rate is low.
Optionally, the rare earth mineral salt is one or a combination of more than one of Y 2O3、Sm2O3、Nd2O3、La2O3.
Experiments show that one or more combinations of Y 2O3、Sm2O3、Nd2O3、La2O3 can cooperate with MgO to occupy the A site in the spinel structure, so that the spinel structure maintains a metastable state, the ceramic density is higher, the humidity and heat resistance is good, and the aging rate is low.
Optionally, the rare earth element mineral salt is a combination of Y 2O3、Nd2O3、La2O3 and Y 2O3、Nd2O3、La2O3 in a weight ratio of 1 (1-2) to 1-2.
Experiments show that when the rare earth element mineral salt is Y 2O3、Nd2O3、La2O3 and is combined according to a specific proportion, the synergistic effect with MgO is best, so that the heat-sensitive ceramic has higher density, better damp-heat resistance and lower aging rate.
In a second aspect, the present application provides a preparation method of the NTC thermal sensitive ceramic for rapid temperature measurement of an electric water heater, which adopts the following technical scheme:
a preparation method of NTC thermal sensitive ceramics for quick temperature measurement of an electric water heater comprises the following steps:
pretreatment of raw materials: placing the raw materials in a constant temperature and humidity box, and standing for 7-9 hours at the temperature of 24-26 ℃ and the relative humidity of 29-31%;
And (3) batching: accurately weighing raw materials;
ball milling: cleaning a ball milling tank and zirconium balls required by ball milling, and adding water balls into raw materials to grind into slurry;
discharging and drying: drying the slurry at 110-130 ℃ for 23-25 hours, and forming the slurry into blocks;
Sieving: the discharged and dried raw materials fall down to a screen mesh from top to bottom, and the blocks are changed into powder;
presintering: presintering the powdery raw materials at 800-900 ℃ for 4-6 hours;
and (3) forming: pouring the powdery raw materials into a die, and extruding and molding under the pressure condition of 3-5 MPa;
Isostatic pressing: isostatic pressing is carried out under the pressure of 150-250MPa to obtain ceramic core ingots, and isostatic pressing is carried out under normal temperature by adopting cold isostatic pressing;
sintering: sintering the ceramic core ingot at 1000-1200 deg.c for 5-7 hr.
Through the technical scheme, the raw material pretreatment step, the raw materials are placed in a constant temperature and humidity box for standing for 7-9 hours under the conditions of 24-26 ℃ and 29-31% relative humidity, so that the water content of the raw materials in different batches is the same as much as possible in production, errors are reduced, and the ceramic products in different batches are ensured to have stable performance. The batching step enables the balance to be in a horizontal position, the ball milling step cleans the ball milling tank and the zirconium balls to play a role in reducing errors of products in different batches, and the ceramic products in different batches are ensured to be stable in performance.
The discharging and drying step can evaporate the residual moisture after ball milling. The steps of ball milling, discharging, drying, sieving and the like can obtain fine, dry and uniform powdery raw materials, which is beneficial to subsequent processing. The presintering step can play a role in high-temperature solid-phase reaction, and the raw materials change color, thereby being beneficial to subsequent processing. The forming step can form the preliminary shape of the ceramic, which is beneficial to the subsequent processing. The isostatic pressing step can reduce pores in the produced ceramic, improve the density of ceramic green bodies, improve the density of the ceramic and ensure that the ceramic is not easy to crack. The sintering step can lead the ceramic green body to be ceramic, and the particles of the raw materials are melted into a whole to form a ceramic-like material for subsequent processing of ceramic chips.
Optionally, the ball milling in the ball milling step adopts a rotating speed of 170-190r/min for ball milling for 4-6 hours.
By adopting the technical scheme, the grinding quality is controlled by the time and the rotating speed of ball milling, the ball milling is performed for 4-6 hours by adopting the rotating speed of 170-190r/min, the grinding quality of raw materials is good, and the obtained raw materials have more uniform particle size and are suitable for sintering ceramic chips.
Optionally, the method further comprises the following steps after the sieving step and before the shaping step:
Secondary ball milling: adding pure water into the presintered raw materials, and ball-milling into slurry;
And (5) secondary discharging and drying: drying the slurry subjected to secondary ball milling at 110-130 ℃ for 23-25 hours, and forming the slurry into blocks;
And (3) secondary sieving: and (3) the raw materials subjected to secondary discharging and drying fall into a screen mesh from top to bottom, and the blocks are changed into powder.
By adopting the technical scheme, the steps of secondary ball milling, secondary discharging and drying, secondary sieving and the like can further improve the fineness and uniformity of the raw materials, and further the ceramic with higher density can be obtained after the sintering step.
Optionally, the ball milling in the secondary ball milling step adopts ball milling for 7-9 hours at a rotating speed of 170-190 r/min.
By adopting the technical scheme, the secondary ball milling adopts the rotating speed of 170-190r/min for ball milling for 7-9 hours, so that the fineness and uniformity of the raw materials can be further improved, and the ceramic chip with high density and uneasy cracking can be sintered in the subsequent step.
In a third aspect, the present application provides an NTC thermal sensitive ceramic chip for rapid temperature measurement of an electric water heater, which adopts the following technical scheme: the electric water heater comprises a body, wherein the body is made of the NTC thermal sensitive ceramic for quickly measuring the temperature of the electric water heater, and a silver layer is coated on the surface of the body.
By adopting the technical scheme, the NTC thermal sensitive ceramic chip for quick temperature measurement of the electric water heater, which is made of the NTC thermal sensitive ceramic for quick temperature measurement of the electric water heater, has high density, good damp-heat resistance and low aging rate, can adapt to the damp-heat environment of a water outlet, and is not easy to age to cause damage. The body and the silver layer form reliable ohmic contact, so that the conductivity, the weldability, the corrosion resistance and the oxidation resistance of the NTC heat-sensitive ceramic chip for quickly measuring the temperature of the electric water heater are improved.
Optionally, the thickness of the body is 0.25±0.005 mm.
By adopting the technical scheme, when the thickness of the body is 0.25+/-0.005 mm, the size of the NTC thermal sensitive ceramic chip is suitable for quick temperature measurement of the electric water heater, and moreover, the B value and the resistivity of the NTC thermal sensitive ceramic chip are also suitable for quick temperature measurement of the electric water heater.
In a fourth aspect, the present application provides a method for preparing the NTC thermal sensitive ceramic chip for rapid temperature measurement of an electric water heater, which adopts the following technical scheme:
the method comprises the following steps:
Dicing: cutting NTC heat sensitive ceramic for quick temperature measurement of electric water heater into ceramic sheet, coating silver paste on the ceramic sheet to form silver layer at 750-850 deg.C, tightly combining the ceramic sheet and silver layer, and cutting into ceramic chip.
Through the technical scheme, the silver layer has strong adhesive force on the ceramic chip, good weldability, compact surface, good compatibility between the silver layer and the NTC thermal sensitive ceramic for quick temperature measurement of the electric water heater, and good quality of the prepared NTC thermal sensitive ceramic chip.
In summary, the application has the following beneficial effects:
1. Because the thermosensitive ceramic is prepared from Co 3O4、Mn3O4、NiO、Fe2O3, znO, mgO and rare earth element mineral salt, the NTC thermosensitive ceramic for rapidly measuring the temperature of the electric water heater has the effects of high density, good humidity and heat resistance and low aging rate due to the synergistic effect of the MgO and the rare earth element mineral salt;
2. In the application, the rare earth mineral salt preferably adopts the combination of Y 2O3、Nd2O3、La2O3, and the combination of Y 2O3、Nd2O3、La2O3 and MgO have the best synergistic effect, so that the heat-sensitive ceramic has higher density, more moisture and heat resistance and lower aging rate;
3. According to the method, the NTC heat-sensitive ceramic for quickly measuring the temperature of the electric water heater, which is prepared through the steps of ball milling, forming, isostatic pressing, sintering and the like, has high density, low damp-heat resistance and aging rate, and the steps of secondary ball milling, secondary discharging drying, secondary sieving and the like can further improve the fineness and uniformity of raw materials, so that the ceramic with higher density can be obtained after the sintering step.
Detailed Description
The present application will be described in further detail below.
Examples
Example 1
An NTC thermal sensitive ceramic for quick temperature measurement of an electric water heater is prepared from the following raw materials in percentage by weight: 13% Co 3O4、32％Mn3O4、24％NiO、17％Fe2O3, 1% ZnO, 7% MgO, and the balance being rare earth mineral salt, namely 6% rare earth mineral salt, wherein the rare earth mineral salt is CeO 2.
The preparation method of the NTC thermal sensitive ceramic for rapid temperature measurement of the electric water heater comprises the following steps:
Pretreatment of raw materials: placing the raw materials in a constant temperature and humidity box, and standing for 7 hours at the temperature of 24 ℃ and the relative humidity of 31%; and (3) batching: firstly, confirming that a balance required for weighing is positioned at a horizontal position, namely, that water drops of the balance are in a circle range, and accurately weighing raw materials; ball milling: adopting a planetary ball mill, cleaning a required ball milling tank and zirconium balls, placing 250g of raw materials in each ball milling tank, adding 400mL of pure water, ball milling at a rotating speed of 170r/min for 6 hours, and ball milling the raw materials to obtain slurry;
discharging and drying: drying the slurry at 110 ℃ for 25 hours by adopting an oven, and forming the slurry into blocks;
Sieving: the discharged and dried raw materials fall down to a screen mesh from top to bottom, and the blocks are changed into powder;
presintering: the sieved raw materials are presintered for 6 hours at 800 ℃ by adopting a high Wen Zhongzhao furnace.
And (3) forming: pouring the powdery raw materials into a cylinder mould lightly, and performing molding operation under the pressure condition of 3 MPa;
Isostatic pressing: isostatic pressing is carried out under the pressure of 250MPa to obtain ceramic core ingots, and isostatic pressing is carried out under normal temperature by adopting cold isostatic pressing;
sintering: the ceramic core ingot was sintered at 1200 ℃ for 5 hours using a high Wen Zhongzhao furnace.
Example 2
An NTC thermal sensitive ceramic for quick temperature measurement of an electric water heater is prepared from the following raw materials in percentage by weight: 15% Co 3O4、30％Mn3O4、26％NiO、14％Fe2O3, 2% ZnO, 7% MgO and the balance of rare earth element mineral salts, namely 6% rare earth element mineral salts, wherein the rare earth element mineral salts are the combination of Lu 2O3、CeO2, and the weight part ratio of Lu 2O3、CeO2 is 1:1.
The preparation method of the NTC thermal sensitive ceramic for rapid temperature measurement of the electric water heater comprises the following steps:
pretreatment of raw materials: placing the raw materials in a constant temperature and humidity box, and standing for 9 hours at the temperature of 26 ℃ and the relative humidity of 29%; and (3) batching: firstly, confirming that a balance required for weighing is positioned at a horizontal position, namely, that water drops of the balance are in a circle range, and accurately weighing raw materials; ball milling: adopting a planetary ball mill, cleaning a required ball milling tank and zirconium balls, placing 250g of raw materials in each ball milling tank, adding 400mL of pure water, ball milling at a rotating speed of 190r/min for 4 hours, and ball milling the raw materials to obtain slurry;
discharging and drying: drying the slurry at 130 ℃ for 23 hours by adopting an oven, and forming the slurry into blocks;
Sieving: the discharged and dried raw materials fall down to a screen mesh from top to bottom, and the blocks are changed into powder;
presintering: the sieved raw materials are presintered for 4 hours at 900 ℃ by adopting a high Wen Zhongzhao furnace.
And (3) forming: pouring the secondarily sieved powdery raw materials into a cylinder mould lightly, and performing molding operation under the pressure condition of 5 MPa;
Isostatic pressing: isostatic pressing is carried out under the pressure of 150MPa to obtain ceramic core ingots, and isostatic pressing is carried out under normal temperature by adopting cold isostatic pressing;
Sintering: the ceramic core ingot was sintered at 1000 ℃ for 7 hours using a high Wen Zhongzhao furnace.
Example 3
An NTC thermal sensitive ceramic for quick temperature measurement of an electric water heater is prepared from the following raw materials in percentage by weight: 14% Co 3O4、31％Mn3O4、25％NiO、15.5％Fe2O3%, 1.5% ZnO, 6% MgO and the balance of rare earth mineral salts, namely 7% rare earth mineral salts, wherein the rare earth mineral salts are the combination of PrO and Lu 2O3、CeO2, and the weight part ratio of PrO to Lu 2O3、CeO2 is 1:1:1.
The preparation method of the NTC thermal sensitive ceramic for rapid temperature measurement of the electric water heater comprises the following steps:
Pretreatment of raw materials: placing the raw materials in a constant temperature and humidity box, and standing for 8 hours at the temperature of 25 ℃ and the relative humidity of 30%; and (3) batching: firstly, confirming that a balance required for weighing is positioned at a horizontal position, namely, that water drops of the balance are in a circle range, and accurately weighing raw materials; ball milling: adopting a planetary ball mill, cleaning a required ball milling tank and zirconium balls, placing 250g of raw materials in each ball milling tank, adding 400mL of pure water, ball milling for 5 hours at a rotating speed of 180r/min, and ball milling the raw materials to obtain slurry;
discharging and drying: drying the slurry at 120 ℃ for 24 hours by adopting an oven, and forming the slurry into blocks;
Sieving: the discharged and dried raw materials fall down to a screen mesh from top to bottom, and the blocks are changed into powder;
Presintering: the sieved raw materials are presintered for 5 hours at 800 ℃ by adopting a high Wen Zhongzhao furnace.
And (3) forming: pouring the secondarily sieved powdery raw materials into a cylinder mould lightly, and performing molding operation under the pressure condition of 4 MPa;
Isostatic pressing: isostatic pressing is carried out under the pressure of 200MPa to obtain ceramic core ingots, and isostatic pressing is carried out under normal temperature by adopting cold isostatic pressing;
sintering: the ceramic core ingot was sintered at 1100 ℃ for 6 hours using a high Wen Zhongzhao furnace.
Example 4
Example 4 differs from example 3 in that: the rare earth element mineral salt is a combination of Y 2O3、Sm2O3、Nd2O3、La2O3 and Y 2O3、Sm2O3、Nd2O3、La2O3 in a weight part ratio of 1:1:1:1.
Example 5
Example 5 differs from example 3 in that: the rare earth mineral salt is Y 2O3.
Example 6
Example 5 differs from example 3 in that: the rare earth element mineral salt is a combination of Y 2O3、Nd2O3、La2O3 and Y 2O3、Nd2O3、La2O3 in a weight part ratio of 2:1:1.
Example 7
Example 7 differs from example 6 in that: the rare earth element mineral salt is a combination of Y 2O3、Nd2O3、La2O3 and Y 2O3、Nd2O3、La2O3 in a weight part ratio of 1:1:1.
Example 8
Example 8 differs from example 6 in that: the rare earth element mineral salt is a combination of Y 2O3、Nd2O3、La2O3 and Y 2O3、Nd2O3、La2O3 in a weight part ratio of 1:2:2.
Example 9
Example 9 differs from example 6 in that: the rare earth element mineral salt is a combination of Y 2O3、Nd2O3、La2O3 and Y 2O3、Nd2O3、La2O3 in a weight part ratio of 1:1:2.
Example 10
Example 10 differs from example 9 in that:
the preparation method of the NTC thermal sensitive ceramic for rapid temperature measurement of the electric water heater further comprises the following steps after the sieving step and before the forming step:
Secondary ball milling: adding 400mL of pure water into the presintered raw materials, ball-milling for 9 hours at a rotating speed of 170r/min, and ball-milling into slurry;
And (5) secondary discharging and drying: drying the slurry subjected to secondary ball milling at 110 ℃ for 25 hours, and forming the slurry into blocks;
And (3) secondary sieving: and (3) the raw materials subjected to secondary discharging and drying fall into a screen mesh from top to bottom, and the blocks are changed into powder.
Example 11
Example 11 differs from example 9 in that:
the preparation method of the NTC thermal sensitive ceramic for rapid temperature measurement of the electric water heater further comprises the following steps after the sieving step and before the forming step:
Secondary ball milling: adding 400mL of pure water into the presintered raw materials, ball-milling for 7 hours at the rotating speed of 190r/min, and ball-milling into slurry;
and (5) secondary discharging and drying: drying the slurry subjected to secondary ball milling at 130 ℃ for 23 hours, and forming the slurry into blocks;
And (3) secondary sieving: and (3) the raw materials subjected to secondary discharging and drying fall into a screen mesh from top to bottom, and the blocks are changed into powder.
Example 12
Example 12 differs from example 9 in that:
the preparation method of the NTC thermal sensitive ceramic for rapid temperature measurement of the electric water heater further comprises the following steps after the sieving step and before the forming step:
Secondary ball milling: adding pure water into the presintered raw materials, ball-milling for 8 hours at a rotating speed of 180r/min, and ball-milling into slurry;
And (5) secondary discharging and drying: drying the slurry subjected to secondary ball milling at 120 ℃ for 24 hours, and forming the slurry into blocks;
And (3) secondary sieving: and (3) the raw materials subjected to secondary discharging and drying fall into a screen mesh from top to bottom, and the blocks are changed into powder.
Comparative examples
Comparative example 1
Comparative example 1 and example 12 are different in that an NTC thermosensitive ceramic for rapid temperature measurement of an electric water heater, which is free from MgO and rare earth mineral salt, is prepared from the following raw materials in percentage by weight ：16.092％Co3O4、35.632％Mn3O4、28.736％NiO、17.816％Fe2O3、1.724％ZnO.
Comparative example 2
The difference between the implementation of the comparative example 2 and the implementation of the example 12 is that the NTC thermosensitive ceramic for quick temperature measurement of the electric water heater is prepared from the following raw materials, by weight percent, ：14.894％Co3O4、32.979％Mn3O4、26.595％NiO、16.489％Fe2O3、1.596％ZnO,7.447％ rare earth element mineral salts, wherein the rare earth element mineral salts are the combination of Y 2O3、Nd2O3、La2O3, and the weight part ratio of Y 2O3、Nd2O3、La2O3 is 1:1:2.
Comparative example 3
Comparative example 3 is different from example 12 in that an NTC thermosensitive ceramic for rapid temperature measurement of electric water heater is prepared from the following raw materials (by weight percentage) without adding rare earth mineral salt ：15.054％Co3O4、33.333％Mn3O4、26.881％NiO、16.667％Fe2O3、1.613％ZnO、6.452％MgO.
Comparative example 4
Comparative example 4 is different from example 12 in that MgO is replaced with Al 2O3.
Application example
Application example 1
The NTC thermal sensitive ceramic chip for quickly measuring the temperature of the electric water heater comprises a body, wherein the body is made of the NTC thermal sensitive ceramic for quickly measuring the temperature of the electric water heater prepared in the embodiment 1, and a silver layer is coated on the surface of the body. The thickness of the body is 0.25 plus or minus 0.005 mm.
A preparation method of an NTC thermal sensitive ceramic chip for rapid temperature measurement of an electric water heater comprises the following steps:
dicing: cutting NTC heat sensitive ceramic for quick temperature measurement of electric water heater into ceramic sheet, coating silver paste on the ceramic sheet to form silver layer at 750 deg.C, tightly combining the ceramic sheet and silver layer, and cutting into ceramic chip.
Application examples 2 to 12
Application examples 2-12 differ from application example 1 in the source of the ontology, see in particular table 1 below;
TABLE 1 Source of the body of NTC thermal-sensitive ceramic chip of application examples 2-12
| Numbering device | Sources of body |
| Application example 2 | Example 2 |
| Application example 3 | Example 3 |
| Application example 4 | Example 4 |
| Application example 5 | Example 5 |
| Application example 6 | Example 6 |
| Application example 7 | Example 7 |
| Application example 8 | Example 8 |
| Application example 9 | Example 9 |
| Application example 10 | Example 10 |
| Application example 11 | Example 11 |
| Application example 12 | Example 12 |
Application example 13
Application example 13 differs from application example 12 in that in the preparation method, a silver layer is formed by coating a ceramic sheet with silver paste at 850 ℃ so that the ceramic sheet and the silver layer are tightly combined, and then the ceramic sheet and the silver layer are cut into ceramic chips.
Application example 14
Application example 14 differs from application example 12 in that in the preparation method, a silver layer is formed by coating a ceramic sheet with silver paste at a temperature of 800 ℃ so that the ceramic sheet and the silver layer are tightly combined, and then the ceramic sheet and the silver layer are cut into ceramic chips.
Comparative examples of application
Comparative examples 1 to 4 were used
Application comparative examples 1 to 4 differ from application example 12 in the source of the bulk, see in particular table 2 below;
TABLE 2 Source of the body of NTC thermal-sensitive ceramic chips applying comparative examples 1 to 4
| Numbering device | Sources of body |
| Comparative example 1 was used | Comparative example 1 |
| Comparative example 2 was used | Comparative example 2 |
| Comparative example 3 was used | Comparative example 3 |
| Comparative example 4 was used | Comparative example 4 |
Comparative example 5 was used
NTC thermal sensitive ceramic chip purchased from market is prepared from Co 3O4、Mn3O4、Ni2O3、Fe3O4 and ZnO as raw materials.
Performance detection
The NTC thermal sensitive ceramic chips of application examples 1 to 14 and application comparative examples 1 to 5 were subjected to density test, wet heat resistance test, and aging performance test to obtain Table 3.
And (3) density detection: adopting a PEM density tester to detect density, and pre-loading: 1.961N, main load weight: 10.58N, needle pressing size: 0.6mm, 0.01mm depth of press in, record meter reading.
Wet heat resistance test: the NTC thermal sensitive ceramic chip was tested for initial resistance R 0 and initial B value B 0, placed in air at an ambient temperature of 60℃and humidity of 93% R hours to 95% R hours for 48 hours, and then placed at room temperature of 25℃for 1 hour, and then tested for resistance R 25、B25 with a rate of change of resistance (R 25-R0)/R0. Times.100%) and a rate of change of B constant (B 25-B0)/B0. Times.100%).
Aging performance test: and testing the initial resistance value R 1 of the NTC heat-sensitive ceramic chip, placing the NTC heat-sensitive ceramic chip at 125 ℃, aging for 120 hours, measuring the resistance value R 2 of the NTC heat-sensitive ceramic chip at the room temperature after the aging is finished, and calculating to obtain the aging rate (R 2-R1)/R1 is 100 percent.
TABLE 3 detection results Table
As can be seen from the combination of application examples 1-14, application comparative examples 1-5 and tables 1-3, in the damp-heat resistance test of application examples 1-14, the change rate of the resistance and the change rate of the B constant are both less than 1%, the ageing rate is less than 0.5%, and the change rate of the resistance and the change rate of the B constant of application comparative example 1 are both greater than 1%, the damp-heat resistance test and the ageing performance test result of application examples 1-14 are obviously better than those of application comparative example 1, so that MgO and rare earth element mineral salts have larger influence on the compactness, the damp-heat resistance and the ageing performance of the NTC heat-sensitive ceramic chip, and the compactness, the damp-heat resistance and the ageing performance of the NTC heat-sensitive ceramic chip are obviously reduced due to the lack of MgO and rare earth element mineral salts.
Comparative application examples 1 to 14 and comparative application example 2, the results of the density, wet heat resistance test and aging performance test of application examples 1 to 14 are significantly better than those of application comparative example 2, which shows that MgO has a large influence on the density, wet heat resistance and aging performance of the NTC thermal ceramic chip, and that MgO is absent, and the density, wet heat resistance and aging performance of the NTC thermal ceramic chip are significantly reduced.
Comparing application examples 1-14 with application comparative example 3, the results of the density, the wet heat resistance test and the aging performance test of application examples 1-14 are obviously better than those of application comparative example 3, which shows that the rare earth element mineral salt has larger influence on the wet heat resistance and the aging performance of the NTC heat-sensitive ceramic chip, and the density, the wet heat resistance and the aging performance of the NTC heat-sensitive ceramic chip are obviously reduced due to the lack of the rare earth element mineral salt.
In conclusion, the method shows that MgO and rare earth element mineral salts have synergistic effect, and under the applied process conditions, the prepared NTC heat-sensitive ceramic chip has good humidity and heat resistance and good aging performance on the basis of high density, and is suitable for rapid temperature measurement of electric water heaters.
Comparative application examples 1 to 14 and comparative application example 4 show that Al 2O3 cannot produce a synergistic effect with rare earth mineral salts and cannot replace MgO.
The compactness, the damp-heat resistance test result and the aging rate of application examples 1-14 are obviously better than those of application comparative example 5, which shows that the NTC thermosensitive ceramic and ceramic chip for quick temperature measurement of the electric water heater of the application improves the compactness, the damp-heat resistance and the aging rate performance of the traditional ceramic chip.
Comparing application examples 4-6 with application example 3, the humidity resistance test result and aging rate of application examples 4-6 are better than those of application example 3, which shows that the rare earth element mineral salt is one or a combination of more than one of Y 2O3、Sm2O3、Nd2O3、La2O3, so that the heat-sensitive ceramic is more resistant to humidity and heat and has lower aging rate.
Comparing application examples 7-9 with application example 6, the compactness, the damp-heat resistance test result and the aging rate of application examples 7-9 are better than those of application example 6, which shows that the rare earth element mineral salt is a combination of Y 2O3、Nd2O3、La2O3, and the weight part ratio of Y 2O3、Nd2O3、La2O3 is 1 (1-2) when (1-2), so that the heat-sensitive ceramic is more resistant to damp heat and has lower aging rate.
Comparing application examples 10-14 with application example 9, the density of application examples 10-14 is better than application example 9, which shows that secondary ball milling, secondary discharging and drying and secondary sieving can improve the fineness and uniformity of the raw materials, and further improve the density of the ceramic.
Other performance tests:
B value determination: the NTC heat-sensitive ceramic chip is placed in a constant-temperature oil groove, the resistance R 1、R2 of the NTC heat-sensitive ceramic chip at 25 ℃ and 85 ℃ is measured by a digital bridge, and then the value B is calculated according to the following formula: b=t 1×T2/(T2-T1)×Ln(R1/R2), where T 1、T2 is a standard temperature, i.e. T 1 has a value of (25+273) K and T 2 has a value of (85+273) K.
2. Resistivity: the resistivity is the ratio of the product of the resistance R and the cross-sectional area S of the NTC thermal sensitive ceramic chip at room temperature to the length L.
| Project | B value determination/K | Resistivity/Ω.mm |
| Application example 1 | 3965 | 57154 |
| Application example 2 | 3932 | 56983 |
| Application example 3 | 3950 | 57006 |
| Application example 4 | 3941 | 57021 |
| Application example 5 | 3934 | 56997 |
| Application example 6 | 3951 | 57072 |
| Application example 7 | 3937 | 57149 |
| Application example 8 | 3942 | 57057 |
| Application example 9 | 3946 | 57124 |
| Application example 10 | 3937 | 56974 |
| Application example 11 | 3921 | 57142 |
| Application example 12 | 3941 | 56941 |
| Application example 13 | 3938 | 57098 |
| Application example 14 | 3920 | 56971 |
The B value of application examples 1-14 is stabilized at 3950 K+/-3%, the resistivity is stabilized at 5.7E4 Ω.mm+/-3%, and the NTC thermosensitive ceramic disclosed by the application is good in consistency and stability and suitable for quick temperature measurement of an electric water heater.
The above specific embodiments and examples are illustrative only and are not intended to limit the present application, and those skilled in the art, after having read the present specification, may make modifications without creative contribution to the present application as required, but all modifications are included in the protection scope of the present application.
Claims (8)
1. An NTC thermosensitive ceramic for quick temperature measurement of an electric water heater is characterized in that ：13-15%Co3O4、30-32%Mn3O4、24-26%NiO、14-17%Fe2O3、1-2%ZnO、5-7%MgO、 of rare earth element mineral salt is prepared from the following raw materials in percentage by weight;
The rare earth element mineral salt is a combination of Y 2O3、Nd2O3、La2O3 and Y 2O3、Nd2O3、La2O3 in a weight ratio of 1 (1-2) to 1-2.
2. A method for preparing the NTC thermal sensitive ceramic for rapid temperature measurement of electric water heater according to claim 1, comprising the steps of:
Pretreatment of raw materials: placing the raw materials in a constant temperature and humidity box, and standing for 7-9 hours at the temperature of 24-26 ℃ and the relative humidity of 29-31%;
And (3) batching: accurately weighing raw materials;
ball milling: cleaning a ball milling tank and zirconium balls required by ball milling, and adding water balls into raw materials to grind into slurry;
discharging and drying: drying the slurry at 110-130 ℃ for 23-25 hours, and forming the slurry into blocks;
Sieving: the discharged and dried raw materials fall down to a screen mesh from top to bottom, and the blocks are changed into powder;
presintering: presintering the powdery raw materials at 800-900 ℃ for 4-6 hours;
and (3) forming: pouring the powdery raw materials into a die, and extruding and molding under the pressure condition of 3-5 MPa;
Isostatic pressing: isostatic pressing is carried out under the pressure of 150-250MPa to obtain ceramic core ingots, and isostatic pressing is carried out under normal temperature by adopting cold isostatic pressing;
sintering: sintering the ceramic core ingot at 1000-1200 deg.c for 5-7 hr.
3. The method for preparing the NTC thermal sensitive ceramic for rapid temperature measurement of the electric water heater according to claim 2, wherein the method comprises the following steps: the ball milling in the ball milling step adopts a rotating speed of 170-190r/min for ball milling for 4-6 hours.
4. The method for preparing the NTC thermal sensitive ceramic for rapid temperature measurement of the electric water heater according to claim 2, wherein the method comprises the following steps:
The method further comprises the following steps after the sieving step and before the shaping step:
Secondary ball milling: adding pure water into the presintered raw materials, and ball-milling into slurry;
And (5) secondary discharging and drying: drying the slurry subjected to secondary ball milling at 110-130 ℃ for 23-25 hours, and forming the slurry into blocks;
And (3) secondary sieving: and (3) the raw materials subjected to secondary discharging and drying fall into a screen mesh from top to bottom, and the blocks are changed into powder.
5. The method for preparing the NTC thermal sensitive ceramic for rapidly measuring temperature of the electric water heater according to claim 4, wherein the method comprises the following steps: the ball milling in the secondary ball milling step adopts the rotating speed of 170-190r/min for 7-9 hours.
6. An NTC thermal sensitive ceramic chip for rapid temperature measurement of an electric water heater, comprising a body made of the NTC thermal sensitive ceramic for rapid temperature measurement of an electric water heater according to claim 1, wherein a silver layer is coated on the surface of the body.
7. The NTC thermal ceramic chip for rapid temperature sensing of electric water heater according to claim 6, wherein the thickness of the body is 0.25 ± 0.005 mm.
8. A method for preparing the NTC thermal sensitive ceramic chip for rapid temperature measurement of electric water heater as claimed in claim 6 or 7, comprising the steps of:
Dicing: cutting NTC heat sensitive ceramic for quick temperature measurement of electric water heater into ceramic sheet, coating silver paste on the ceramic sheet to form silver layer at 750-850 deg.C, tightly combining the ceramic sheet and silver layer, and cutting into ceramic chip.
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| 掺杂对Mn-Co-Ni-O及Mn-Ni-Cu-O系NTC热敏陶瓷电性能的影响研究;汶建彤;《中国学术期刊（光盘版）》;20131215;第B015-82页 * |
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