CN109053158B - Thermosensitive ceramic powder, NTC thermosensitive chip, temperature sensor and preparation method - Google Patents
Thermosensitive ceramic powder, NTC thermosensitive chip, temperature sensor and preparation method Download PDFInfo
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- CN109053158B CN109053158B CN201810990546.4A CN201810990546A CN109053158B CN 109053158 B CN109053158 B CN 109053158B CN 201810990546 A CN201810990546 A CN 201810990546A CN 109053158 B CN109053158 B CN 109053158B
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- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C12/00—Powdered glass; Bead compositions
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- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C8/00—Enamels; Glazes; Fusion seal compositions being frit compositions having non-frit additions
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- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- 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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Abstract
The application discloses a thermosensitive ceramic powder, an NTC thermosensitive chip, a temperature sensor and a preparation method, wherein the ceramic powder comprises, by weight, 18-38% of manganese dioxide powder, 12-20% of cobaltous oxide powder, 4-14% of ferric oxide powder, 21-41% of nickel oxide powder and 2-10% of rare earth oxide powder. The temperature sensor prepared by the application has the advantages of extremely good flexibility, bending resistance, vibration resistance, wear resistance, corrosion resistance and the like, meets the requirement that the environments such as oil stain, EMI (electro-magnetic interference), mechanical pressure and the like in the motor are extremely severe, and can stably work under severe conditions for a long time to meet the requirement of the temperature sensor.
Description
Technical Field
The invention relates to the technical field of electronic components, in particular to thermosensitive ceramic powder, an NTC thermosensitive chip, a temperature sensor and a preparation method.
Background
NTC (negative temperature coefficient) thermistor is a thermal semiconductor resistor made of polycrystalline ceramic mixed with oxide, the resistance value of which decreases with the rise of temperature, has the advantages of low price, excellent quality, stable performance and the like, and is widely used for preparing temperature sensors for measuring temperature.
In recent years, the NTC temperature sensor is more and more widely applied to battery packs, motors, electric control systems and thermal management systems of new energy vehicles. The NTC thermal chip is used as a core component of the temperature sensor, which puts new requirements on the NTC thermal chip. In a severe environment with continuous high temperature, high pressure and high vibration in a new energy automobile, the NTC temperature sensor is required to be small in size, high in precision, high in response speed and high in reliability.
An electric machine, which is one of three key components in an electric vehicle, is a device that ultimately converts stored electrical energy into mechanical energy. Any energy conversion device generates heat when working, the power of the electric automobile is different from 30KW to 200KW, and a large amount of heat is generated in the conversion process. The internal power of the motor is too high due to heating, and the magnetism of the rotor of the motor is affected and even lost. It is very important to monitor the temperature of the motor in its operating state. And the environments such as oil stain, EMI (electro-magnetic interference), mechanical pressure and the like in the motor are very severe, and the requirement of the temperature sensor is that the motor can stably work under severe conditions for a long time. The research and development of products (B is less than 2300K) with wide temperature zone detection temperature is inevitably required, and the requirements on small volume, high precision and high response speed are also met; and is required to have good consistency, strong EMI resistance, and high long-term stability.
Disclosure of Invention
The application provides thermosensitive ceramic powder, an NTC thermosensitive chip, a temperature sensor and a preparation method.
In order to achieve the purpose, the following technical scheme is adopted in the application:
according to a first aspect, the application discloses a heat-sensitive ceramic powder, which comprises, by weight, 18-38% of manganese dioxide powder, 12-20% of cobalt trioxide powder, 4-14% of iron oxide powder, 21-41% of nickel oxide powder and 2-10% of rare earth oxide powder.
Preferably, the heat-sensitive ceramic powder comprises, by weight, 22-34% of manganese dioxide powder, 14-18% of cobalt trioxide powder, 4-12% of iron oxide powder, 25-35% of nickel oxide powder and 2-10% of rare earth oxide powder.
Preferably, the heat-sensitive ceramic powder comprises, by weight, 26-30% of manganese dioxide powder, 15-17% of cobaltous oxide powder, 7-10% of ferric oxide powder, 28-32% of nickel oxide powder and 4-8% of rare earth oxide powder.
Further, the rare earth oxide powder is one or a mixture of oxides of rare earth metals of scandium (Sc), yttrium (Y), lanthanum (La), cerium (Ce), praseodymium (Pr), neodymium (Nd), samarium (Sm), europium (Eu) and gadolinium (Gd).
According to a second aspect, the present application discloses a thermal sensitive ceramic slurry comprising the thermal sensitive ceramic powder disclosed in the first aspect of the present application, and a binder, a plasticizer, a surface auxiliary agent, and an organic solvent.
Furthermore, the heat-sensitive ceramic powder accounts for 55-88% of the weight of the heat-sensitive ceramic slurry, the adhesive accounts for 3-16% of the weight of the heat-sensitive ceramic slurry, the plasticizer accounts for 1.2-5.6% of the weight of the heat-sensitive ceramic slurry, the surface additive accounts for 0.3-1.5% of the weight of the heat-sensitive ceramic slurry, and the solvent accounts for 7-25% of the weight of the heat-sensitive ceramic slurry;
preferably, the binder is at least one selected from the group consisting of polyvinyl butyral, butyl cellulose, ethyl cellulose, methyl cellulose, polymethyl methacrylate, polyethyl methacrylate, and polyalkyl methacrylate.
Preferably, the plasticizer is selected from at least one of glycerol citrate, glycerol nitrate, glycerol, dioctyl phthalate, dibutyl phthalate and dibutyl sebacate.
Preferably, the surface auxiliary agent is at least one selected from polyether modified silicone oil type surface auxiliary agents, mineral oil type surface auxiliary agents, mixed silicone oil type surface auxiliary agents, phenyl silicone oil type surface auxiliary agents and dimethyl silicone oil type surface auxiliary agents.
Preferably, the solvent is at least one selected from the group consisting of absolute ethanol, terpineol, DBE, ethylene glycol, butyl carbitol, methyl ethyl ketone, amyl acetate, isoamyl acetate, methyl carbonate, ethyl carbonate and N-methyl-2-pyrrolidone.
According to a third aspect, an NTC thermal chip is prepared by using the thermal sensitive ceramic powder of the first aspect of the present application or the thermal sensitive ceramic slurry disclosed in the second aspect.
According to a fourth aspect, the application discloses a method for preparing an NTC thermal sensitive chip, comprising casting a thermal sensitive ceramic slurry disclosed in the second aspect of the application into a ceramic green sheet by using a casting machine, and then performing isostatic pressing on the ceramic green sheet to obtain a solid green sheet for preparing an ultra-thin NTC thermal sensitive chip;
preferably, the temperature isostatic pressing condition is that the temperature is 60-80 ℃, the pressure is 40-60 MPa, and the temperature pressing time is 80-150 seconds.
Further, electrode and protective glass glaze printing is carried out on the green sheet subjected to warm isostatic pressing, and then the printed electrode, protective glass glaze and the green sheet are sintered together to form the NTC thermosensitive chip with an integrated structure;
preferably, the sintering temperature is 900-1200 ℃.
Further, the method comprises the steps of cutting the sintered product into a required size, and then carrying out intermediate heat treatment to eliminate stress in the NTC heat-sensitive chip; the heat treatment is carried out under the conditions that the temperature is increased to 450-650 ℃ at the speed of 5-15 ℃/min, the temperature is kept for 1-24 h, and then the temperature is naturally cooled to the room temperature.
According to a fourth aspect, the application discloses an NTC thermal chip prepared by the preparation method disclosed in the third aspect of the application.
According to a fifth aspect, the present application discloses a temperature sensor employing an NTC thermosensitive chip disclosed in the third or fourth aspect of the present application.
Further, the NTC thermosensitive chip is sequentially wrapped with high-thermal-conductivity silica gel, organic silicon modified epoxy resin and high-thermal-conductivity epoxy resin from inside to outside;
preferably, the high thermal conductivity silica gel is prepared by mixing common silica gel with 30-60 wt% of boron nitride powder based on the total weight of the high thermal conductivity silica gel;
preferably, the organic silicon modified epoxy resin is prepared by mixing common organic siloxane epoxy resin with 30-60 wt% of aluminum nitride powder based on the total weight of the organic silicon modified epoxy resin;
preferably, the high thermal conductive epoxy resin is prepared by mixing common bisphenol F epoxy resin with 30-60 wt% of aluminum nitride powder based on the total weight of the high thermal conductive epoxy resin.
According to a sixth aspect, the present application discloses a method for manufacturing a temperature sensor disclosed in the fifth aspect of the present application, comprising the steps of sequentially dipping an NTC thermosensitive chip with a soldered lead wire in a highly heat conductive silica gel, an organosilicon modified epoxy resin, and a highly heat conductive epoxy resin, and then putting the NTC thermosensitive chip in absolute ethyl alcohol to be cleaned by ultrasonic waves, so as to obtain the temperature sensor;
preferably, the high-thermal-conductivity silica gel is soaked under the conditions of 110-130 ℃ hardening for 1-3 h, the organosilicon modified epoxy resin is soaked under the conditions of 120-140 ℃ hardening for 0.5-2 h, and the high-thermal-conductivity epoxy resin is soaked under the conditions of 110-130 ℃ hardening for 0.5-2 h;
more preferably, the high thermal conductive silica gel is immersed in the silicone modified epoxy resin at 120 ℃ for 2 hours, the silicone modified epoxy resin at 130 ℃ for 1 hour, and the high thermal conductive epoxy resin at 120 ℃ for 1 hour.
Due to the adoption of the technical scheme, the beneficial effects of the application are as follows:
the utility model provides a thermal sensitive ceramic powder, each layer material composition of ceramic powder, the powder particle diameter, powder appearance and solid content reasonable in design, the ceramic thick liquids of this ceramic powder configuration are adopted, in preparing NTC heat-sensitive chip, thereby can satisfy and prepare with high temperature electrode thick liquids and glass protective layer frit at 900 ~ 1200 ℃ high temperature down integrative sintering and obtain intensity and toughness high, the resistance to welding is strong, NTC heat-sensitive chip that the reliability is high, this NTC heat-sensitive chip does not appear superior properties such as damaged, fracture, softening in paster and welding process.
According to the NTC chip thermosensitive sensor prepared by the application, multiple materials such as ceramics, electrodes, glass protective layers and the like and a multilayer structure are co-fired under the same sintering curve to form a thermosensitive sensing element with functionality, high mechanical strength and high process size accuracy, and in the preparation process, a ceramic green body is pressed by adopting a warm isostatic pressing technology to be combined with a ceramic green body to sinter the printed ceramic green body in inert gas, so that an ultrathin NTC thermosensitive chip which is uniform, solid, good in compactness, good in mechanical property and electrical property and 0.08-0.5 mm in thickness is obtained. The motor temperature sensor prepared by the application is sequentially made of high-thermal-conductivity epoxy resin, organic silicon modified epoxy resin and high-thermal-conductivity silica gel from outside to inside. The high-thermal-conductivity epoxy resin, the organic silicon modified epoxy resin and the high-thermal-conductivity silica gel chip packaging material have good thermal conductivity, so that the NTC chip can quickly detect the change of the motor temperature; structural design makes the sensor have fabulous compliance, resistant buckling, advantages such as resistant vibration, wearability, corrosion-resistant simultaneously, satisfies the inside greasy dirt of motor, EMI, environment such as mechanical pressure very abominable, and it is the requirement to temperature sensor to work stably under adverse conditions for a long time.
Drawings
Fig. 1 is a schematic structural view of an NTC thermal sensitive chip according to an embodiment, in which 1 is an electrode, 2 is an NTC thermal sensitive ceramic, and 3 is a glass coating protection;
FIG. 2 is a schematic structural view of a temperature sensor according to an embodiment, in which 1 is an NTC thermal sensitive chip, 2 is a high thermal conductive silica gel wrapping layer, 3 is an organic silicon modified epoxy resin wrapping layer, 4 is a high thermal conductive epoxy resin wrapping layer, and 5 is a lead wire;
FIG. 3 is a process flow diagram of another embodiment of a temperature sensor.
Detailed Description
The present invention will be described in further detail with reference to the following detailed description and accompanying drawings.
In the traditional NTC heat-sensitive chip preparation technology, cold isostatic pressing forming of a blank, high-temperature sintering, cutting, electrode coating and glass glaze encapsulation processes are commonly adopted. The NTC thermal sensitive chip prepared by the traditional process cannot meet the new requirements of the battery pack, the motor and the electric control and thermal management system on the temperature sensor made of the NTC thermal sensitive chip in the aspects of volume, precision, response speed, EMI resistance and long-term stability, and particularly provides new challenges for the temperature sensor adopting the NTC thermal sensitive chip in the battery pack, the motor and the electric control and thermal management system of the new energy automobile in the severe environment of continuous high-temperature, high-pressure and high-vibration in the new energy automobile in the aspects of volume, precision, response speed and reliability.
The NTC heat-sensitive chip is characterized in that heat-sensitive ceramic powder composed of manganese dioxide powder, cobaltous oxide powder, ferric oxide powder, nickel oxide powder and rare earth oxide powder is creatively selected, the material components of each layer of the ceramic powder, the powder particle size, the powder morphology and the solid content are reasonable in design, and ceramic slurry prepared by the ceramic powder can be integrally sintered with high-temperature electrode slurry and glass protective layer glaze at the high temperature of 900-1200 ℃ in preparation of the NTC heat-sensitive chip, so that the NTC heat-sensitive chip is high in strength and toughness, strong in welding resistance and high in reliability and does not have the superior performances of breakage, cracking, softening and the like in the process of surface mounting and welding.
The rare earth oxide powder is one or a mixture of oxides of rare earth metals of scandium (Sc), yttrium (Y), lanthanum (La), cerium (Ce), praseodymium (Pr), neodymium (Nd), samarium (Sm), europium (Eu) and gadolinium (Gd).
The content of each component of the above-mentioned heat-sensitive ceramic powder can be varied within a wide range. In a preferred embodiment of the present invention, the powder comprises, by weight, 18 to 38% of manganese dioxide powder, 12 to 20% of cobalt trioxide powder, 4 to 14% of iron oxide powder, 21 to 41% of nickel oxide powder, and 2 to 10% of rare earth oxide powder.
In a more preferred embodiment, the heat-sensitive ceramic powder comprises, by weight, 22-34% of manganese dioxide powder, 14-18% of cobalt trioxide powder, 4-12% of iron oxide powder, 25-35% of nickel oxide powder and 2-10% of rare earth oxide powder.
In a more preferred embodiment, the heat-sensitive ceramic powder comprises, by weight, 26-30% of manganese dioxide powder, 15-17% of cobaltous oxide powder, 7-10% of ferric oxide powder, 28-32% of nickel oxide powder and 4-8% of rare earth oxide powder.
The application also discloses thermosensitive ceramic slurry, which comprises the thermosensitive ceramic powder, an adhesive, a plasticizer, a surface auxiliary agent and an organic solvent.
The content of the various components of the above-mentioned heat-sensitive ceramic slurry may vary within wide ranges. In a preferred embodiment of the invention, the heat-sensitive ceramic powder accounts for 55-88 wt% of the heat-sensitive ceramic slurry, the adhesive accounts for 3-16 wt% of the heat-sensitive ceramic slurry, the plasticizer accounts for 1.2-5.6 wt% of the heat-sensitive ceramic slurry, the surface auxiliary agent accounts for 0.3-1.5 wt% of the heat-sensitive ceramic slurry, and the solvent accounts for 7-25 wt% of the heat-sensitive ceramic slurry;
preferably, the binder is at least one selected from the group consisting of polyvinyl butyral, butyl cellulose, ethyl cellulose, methyl cellulose, polymethyl methacrylate, polyethyl methacrylate, and polyalkyl methacrylate.
Preferably, the plasticizer is at least one selected from the group consisting of glycerol citrate, glycerol nitrate, glycerol, dioctyl phthalate, dibutyl phthalate and dibutyl sebacate.
Preferably, the surface auxiliary agent is at least one selected from polyether modified silicone oil type surface auxiliary agents, mineral oil type surface auxiliary agents, mixed silicone oil type surface auxiliary agents, phenyl silicone oil type surface auxiliary agents and dimethyl silicone oil type surface auxiliary agents, such as GLH-71130-3R and Federal B-329/B-293/294/295 of Jiangxi Linghu company.
Preferably, the solvent is at least one selected from the group consisting of absolute ethanol, terpineol, DBE, ethylene glycol, butyl carbitol, methyl ethyl ketone, amyl acetate, isoamyl acetate, methyl carbonate, ethyl carbonate and N-methyl-2-pyrrolidone.
In the preparation of the NTC heat-sensitive chip, the ceramic green body is pressed by creatively adopting a warm isostatic pressing technology and the printed ceramic green body is sintered into a whole in inert gas, so that the NTC heat-sensitive chip with uniformity, firmness, good compactness, good mechanical property and good electrical property is obtained.
The preparation method of the NTC thermosensitive chip provided by the application comprises the following steps:
preparing a ceramic green sheet, wherein the ceramic green sheet is prepared from the thermosensitive ceramic slurry, and the thickness of the ceramic green sheet is 0.1-0.6 mm;
preparing a ceramic green body, namely pressing the ceramic green body into the ceramic green body by adopting a warm isostatic pressing technology;
preparing an NTC heat-sensitive chip, printing electrode slurry and glass protective glaze on the ceramic green body, and sintering the printed ceramic green body in an inert gas atmosphere furnace to form a whole to obtain the NTC heat-sensitive chip.
The electrode slurry adopts silver-coated palladium powder to replace silver powder as a conductive agent. The silver-coated palladium is a binary alloy which takes palladium as a base and is added with silver, palladium and silver can be dissolved in each other infinitely to form a continuous solid solution, the resistance value is stable, the oxidation resistance is good at room temperature, the oxidation resistance is improved along with the increase of the palladium content at high temperature, the silver-coated palladium does not change color in a sulfur-containing atmosphere, and the corrosion and aging are not easy to occur.
The glass protective glaze comprises the following components in parts by weight: b is2O318-25% of aluminum silicate Al2SiO54-10％、SiO215-30％、Bi2O3 45-60％、ZnO 6-12％、CeO2 0.5-2.0％、K2O 0.4-1％、Li20.8 to 2 percent of O and 0.3 to 3 percent of CaO. The glass powder contains B2O3While being Al2SiO5Substituted for Al203The paint does not contain heavy metal elements such as copper elements and the like, does not contain harmful substances and elements, and is green and environment-friendly; b is2O3And Al2SiO5The glass powder has the characteristic of high temperature resistance, the softening and melting temperature exceeds 800 ℃, and the high temperature resistance of the NTC chip green body can be realizedAnd (5) sintering at a temperature.
The working principle of the temperature isostatic pressing is the Pascal law, namely, the pressure of a medium (liquid or gas) in a closed container can be transmitted to all directions equally, the manufactured product has good isotropy and good effect on parts with high performance requirements, complex shapes and larger three-dimensional sizes. The temperature is raised to enable the ceramic powder to flow along with the deformation of the organic matter binder, internal pores are filled, a uniform and solid blank is obtained, the warm isostatic pressing technology is adopted, the forming pressure is low, and the warm isostatic pressing pressure is far smaller than the cold isostatic pressing, so that the internal stress of the ceramic blank is low, no crack exists in the interior, the equipment investment is greatly reduced, and the equipment operation safety is high; the NTC chip is directly manufactured into a formed ultra-bulk thin sheet, the thickness of the finally manufactured NTC chip is 0.08-0.5 mm, and the NTC chip cannot be cut by the traditional large strip column process.
The method adopts inert gas as protective atmosphere, can ensure the stability and the consistency of the contents of Mn, Ni, Fe, Co and other elements in the NTC thermistor formula, simultaneously ensure that the chemical valence states of the transition metals are not changed, and do not generate decomposition reaction during high-temperature sintering to separate out NiO and other harmful substances. The resistivity and the material constant B value of the thermistor material are ensured not to change. The invention adopts inert gas as pressure medium to carry out high-pressure sintering, and applies pressure to the thermal sensitive ceramic blank in the sintering process, so that the powder is subjected to the action of high temperature and balanced pressure, the densification process is accelerated, the hot-pressing sintering temperature is reduced, the sintering time is shortened, the growth of crystal grains is inhibited, residual air holes in a sintered body are eliminated, and surface cracks are healed; the product with good mechanical property and electrical property is obtained.
According to the method, the thermal sensitive ceramic slurry is made into the ceramic green sheet by adopting the casting machine, and the ceramic green sheet with the thick bottom of 0.1-0.6 mm is made by adopting the casting machine.
The temperature isostatic pressing technology is carried out in a liquid-phase pressure medium, the pressure medium is selected from one of purified water, heat-conducting silicon oil or hydraulic oil, the pressure medium has a prominent effect, other media cannot be brought in the temperature isostatic pressing process, the temperature isostatic pressing technology cannot chemically react with a ceramic green sheet, and most preferably, the pressure medium is purified water.
The temperature isostatic pressing condition is that the temperature and the pressure are 80-150 s in a temperature and pressure environment with the temperature of 60-80 ℃ and the pressure of 40-60 MPa. The temperature isostatic pressure is 40-60 MPa and is far less than the cold isostatic pressure of 200-400 MPa, the internal stress of the ceramic green body is small, no crack is generated in the ceramic green body, the equipment investment is greatly reduced, and the equipment operation safety is high.
In the present application, the inert gas is selected from one of He, Ne, Ar, Kr and Xe, and the sintering temperature is 900 to 1200 ℃. The inert gas is used as a protective atmosphere, the stability and the consistency of the contents of Mn, Ni, Fe, Co and other element components in the NTC thermistor formula can be realized, the chemical valence states of the transition metals are ensured not to be changed, and the decomposition reaction is not generated during high-temperature sintering to precipitate harmful substances such as NiO and the like. The resistivity and the material constant B value of the thermistor material are ensured not to change. One gas of He, Ne, Ar, Kr or Xe is used as a pressure medium to carry out high-pressure sintering, and pressure is applied to the thermal sensitive ceramic blank in the sintering process, so that the powder is subjected to the action of high temperature and balanced pressure, the densification process is accelerated, the hot-pressing sintering temperature is reduced, the sintering time is shortened, the growth of crystal grains is inhibited, residual air holes in a sintered body are eliminated, and surface cracks are healed; the product with good mechanical property and electrical property is obtained. Proved by verification, when Ar gas is used as protective atmosphere, the prepared NTC chip has better mechanical property and electrical property.
In order to eliminate stress in the prepared NTC chip, the NTC chip is subjected to heat treatment after the NTC chip is obtained, namely, the NTC heat-sensitive chip is heated to 450-650 ℃ in a programming manner, is subjected to heat preservation for 1-24 hours in an environment of 450-650 ℃, and is then naturally cooled.
In order to meet the requirements for different sizes of NTC chips, the NTC chips may also be cut before the heat treatment step to obtain the required size.
The NTC chip prepared by the method is used for preparing the temperature sensor, and the method comprises the following steps:
welding a lead: welding the lead on the end electrode of the NTC thermosensitive chip;
wrapping with high-thermal-conductivity silica gel: wrapping the NTC thermosensitive chip with high-thermal-conductivity silica gel to obtain a first inclusion, wherein the high-thermal-conductivity silica gel contains 30-60% by weight of boron nitride powder;
coating with organic silicon modified epoxy resin: coating the first inclusion with organosilicon modified epoxy resin to obtain a second inclusion, wherein the organosilicon modified epoxy resin contains 30-60 wt% of aluminum nitride powder;
and (3) coating the high-thermal-conductivity epoxy resin, and coating the second inclusion with the high-thermal-conductivity epoxy resin to obtain the temperature sensor, wherein the high-thermal-conductivity epoxy resin contains 30-60% by weight of aluminum nitride powder.
Welding the lead in a dip soldering mode, and then ultrasonically cleaning and drying the lead by using absolute ethyl alcohol after welding;
the wrapping condition of the high-thermal-conductivity silica gel wrapping is that the high-thermal-conductivity silica gel is hardened at 110-130 ℃ for 1-3 h, the wrapped high-thermal-conductivity silica gel has better integrity and consistency and good thermal conductivity, and in order to obtain better effect, the wrapping condition is that the high-thermal-conductivity silica gel is hardened at 120 ℃ for 2 h.
The coating condition of the organic silicon modified epoxy resin coating is that the organic silicon modified epoxy resin is hardened for 0.5-2 h at 120-140 ℃, the organic silicon modified epoxy resin coated under the condition has better integrity and consistency, and in order to obtain better effect, the coating condition is that the organic silicon modified epoxy resin is hardened for 1h at 130 ℃.
The wrapping condition of the high-thermal-conductivity epoxy resin wrapping is that the high-thermal-conductivity epoxy resin is hardened at 110-130 ℃ for 0.5-2 h, the thermal-conductivity epoxy resin wrapped under the condition has better integrity and consistency and good thermal conductivity, and in order to obtain a better effect, the wrapping condition is that the high-thermal-conductivity epoxy resin is hardened at 120 ℃ for 1 h.
In order to remove impurities such as dust and the like remained on the temperature sensor in the preparation process, the temperature sensor obtained by preparation can be put into absolute ethyl alcohol to be cleaned by ultrasonic waves in the step of preparing the temperature sensor.
The present invention is described in detail below with reference to specific examples. It should be understood that these examples are illustrative only and are not to be construed as limiting the scope of the invention.
Examples
1. For preparing NTC heat-sensitive chip
1) The thermistor comprises the following components in parts by weight according to a design formula: 35% of manganese dioxide powder, 16% of cobalt oxide powder, 8.5% of iron oxide powder, 36% of nickel oxide powder and 4.5% of rare earth oxide powder, mixing, ball-milling, drying at low temperature, calcining at high temperature, ball-milling and crushing to obtain the thermal sensitive ceramic powder.
2) The thermal sensitive ceramic slurry is prepared from the following components in parts by weight: mixing 76% of thermal sensitive ceramic powder with 10% of organic solvent (butyl carbitol 4%, amyl acetate 3%, isoamyl acetate 3%), 9% of adhesive polyvinyl butyral, 4% of plasticizer dibutyl sebacate and federal B-3291.0% of surface auxiliary agent, ball-milling by a planetary ball mill, sieving and defoaming in vacuum to obtain thermal sensitive ceramic slurry.
3) And (3) forming the thermal sensitive ceramic slurry into a ceramic green sheet by using a casting machine, wherein the thick bottom is 0.1-0.6 mm.
4) Rubber or plastic is put into the ceramic green sheet which is formed by tape casting to be used as a sheathing die material, and purified water is used as a pressure medium. And (3) carrying out warm pressing for 100s in a warm-pressing environment with the temperature of 70 ℃ and the pressure of 50MPa, and pressing and forming the thermosensitive ceramic powder material to obtain a uniform and firm blank.
5) And printing an upper electrode and glass protective glaze on the formed ceramic green sheet subjected to warm pressing treatment by adopting a screen printing process, and sintering the upper electrode and the NTC ceramic together into a whole at one time in the environment of 1000 ℃.
The electrode slurry adopts 73% of silver-coated palladium powder as a conductive agent instead of silver powder, the silver-coated palladium powder is spherical, the particle size of the powder is 3-6 um, and the thickness of the silver-coated palladium is 15-20 nm; 6% of oxidized metal powder, wherein the oxidized metal powder is a combination of iron oxide and manganese dioxide metal oxide powder, the weight ratio of the iron oxide to the manganese dioxide metal oxide powder is 2:1, and the particle size of the powder is 120-500 nm; 9% of solvent, wherein the solvent is butyl carbitol and DBE, and the weight ratio of the two solvents is 1: 1; 10.5 percent of organic binder, wherein the organic binder is American eastman butyl cellulose CAB551-0.01 and Japanese Kuraray company Mowital B60H, and the weight ratio of the butyl cellulose CAB551-0.01 to the Mowital B60H is 4: 1; 0.3% of dispersant, DISPERBYK-190 from BYK company; 0.7% of defoaming agent, BYK-055 of BYK; leveling agent 0.5%, BYK company: BYK-333.
The glass protective glaze consists of glass powder 45 wt%, nanometer titania 3 wt%, nanometer zirconia powder with cerium oxide and stable content 22 wt% and Al2O312 percent of solvent, 10 percent of adhesive, 6 percent of plasticizer and 0.2 percent of dispersant, wherein the glass powder comprises the following components in percentage by weight: b is2O3 20％、Al2SiO5 4％、SiO2 17％、Bi2O3 46％、ZnO 8％、CeO20.5％、K2O 0.7％、Li2O1% and CaO 2%.
6) And (4) putting the formed compact block containing the terminal electrode and the glass protective layer obtained in the step (5) into an Ar atmosphere furnace for solid solution sintering at the temperature of 1050 ℃ under the pressure of 5MPa to obtain a sintered block, and preparing the thermosensitive ceramic body.
7) And scribing the thermosensitive ceramic body into a required size to obtain the ultrathin high-precision high-reliability NTC thermosensitive chip with the thickness of 0.08-0.5 mm.
8) Carrying out heat treatment on an ultrathin high-precision high-reliability NTC thermosensitive chip: heating to 550 ℃ at the heating rate of 10 ℃/min, preserving heat for 10h, and naturally cooling to room temperature to eliminate the stress in the chip.
2. Temperature sensor using NTC thermosensitive chip
1) Welding a lead: and welding the lead wire and the terminal electrode of the NTC thermosensitive chip together in a dip soldering mode, and then carrying out ultrasonic cleaning and drying by using absolute ethyl alcohol.
2) Wrapping high-thermal-conductivity silica gel: adopt the impregnation mode with NTC chip with high heat conduction silica gel parcel, at 120 degrees 2 hours of sclerosis, wherein: the high-heat-conductivity silica gel is prepared by mixing common silica gel on the market with 45 wt% of boron nitride powder.
3) Coating organic silicon modified epoxy resin: and (3) immersing the NTC heat-sensitive chip wrapped with the high-thermal-conductivity silica gel into the organic silicon modified epoxy resin in an immersion mode, and hardening at 130 ℃ for 1 hour. Is prepared by mixing common organic siloxane epoxy resin on the market with 45 percent by weight of aluminum nitride powder.
4) Wrapping high-thermal-conductivity epoxy resin: and (3) immersing the NTC heat-sensitive chip prepared in the step into high-heat-conductivity epoxy resin in an impregnation mode, and hardening at 120 ℃ for 1 hour. Wherein: the high-conductivity epoxy resin is prepared by mixing common bisphenol F epoxy resin on the market with 45 wt% of aluminum nitride powder.
5) Putting the temperature sensor obtained in the step 4 into absolute ethyl alcohol, and cleaning by ultrasonic waves; and then carrying out performance test and calibration to obtain the temperature sensor.
And (3) measuring a reference resistance value: the temperature sensor is placed in a constant temperature oil tank at the temperature of 25 +/-0.03 ℃, a stirring instrument is needed during the oil tank test, the oil temperature difference of all parts in the oil tank is smaller than 0.1 ℃, the sensor is placed in the constant temperature oil tank for 1 hour, then the resistance of the sensor is measured by a digital bridge, and data is recorded. And (3) testing results: r25 is 10 k.OMEGA. + -. 0.5%.
B value determination: the temperature sensors are placed in a constant temperature oil tank, the resistance values R1 and R2 of the temperature sensors at 25 ℃ and 85 ℃ are respectively measured by a digital bridge, and then the B value is calculated according to the following formula: and B is T1 multiplied by T2/(T2-T1). times Ln (R1/R2), wherein T1 and T2 are standard temperatures, namely the value of T1 is (25+273) K, the value of T2 is (85+273) K, and data are recorded. And (3) testing results: b is 3435K. + -. 0.5%.
Insulation resistance: the temperature sensing head of the temperature sensor is placed in water with the temperature of 25 +/-1 ℃, the other end of the temperature sensing head is placed in water with the temperature of 25 +/-1 ℃ on another disc, then the anode of the voltage-resistance/insulation resistance tester is placed in the water with the temperature sensing head of the temperature sensor, the cathode of the voltage-resistance/insulation resistance tester is placed in the water with the temperature sensing head of the temperature sensor, and the insulation resistance is used for measuring the insulation resistance of the insulation resistance. And (3) testing results: the insulation resistance between the shell of the temperature sensing head and the lead is more than or equal to 100M omega.
And (3) voltage resistance test: the temperature sensor temperature sensing head is placed in water with the temperature of 25 +/-2 ℃, the other end of the temperature sensor is placed in water with the temperature of 25 +/-2 ℃, then the anode of the insulation withstand voltage tester is placed in the water with the temperature sensor temperature sensing head, the cathode is placed in the water of the other disc, 1800V and 50Hz alternating voltage is applied to the two discs of water to keep 60s, the initial leakage current is set to be 2mA, and the result meets the requirement.
And (3) testing results: the lead-out end and 1800VAC/50Hz water are added for 60s without the phenomena of breakdown, discharge, arcing and the like.
And (3) mechanical pressure resistance test: the temperature sensor was subjected to a vertical downward pressure of 5kg for 10 seconds, and the appearance and electrical properties of the sample were examined. Appearance, insulation resistance, withstand voltage, reference resistance, and B value after the operation according to the prescribed method. And (3) testing results: the insulation resistance is more than or equal to 100M omega, the voltage resistance test has no phenomena of breakdown, discharge, arcing and the like, the resistance value change delta R is less than or equal to +/-1 percent R, and the B constant change delta B is less than or equal to +/-1 percent B.
And (3) drop test: the sensor was dropped from 1m high onto a hard object placed on wood floor or thicker, without packaging, and repeated 5 times to check the appearance of the sample, electrical properties. Appearance, insulation resistance, withstand voltage, reference resistance, and B value after the operation according to the prescribed method. And (3) testing results: the insulation resistance is more than or equal to 100M omega, the voltage resistance test has no phenomena of breakdown, discharge, arcing and the like, the resistance value change delta R is less than or equal to +/-1 percent R, and the B constant change delta B is less than or equal to +/-1 percent B.
Moisture and heat resistance test: the temperature sensor is placed in air with the ambient temperature of 60 ℃ and the humidity of 93-95% RH for 48h, then the temperature sensor is placed at the room temperature of 25 ℃ for 1h, the resistance value of the temperature sensor is tested, the B constant is calculated, and data are recorded. And (3) testing results: the resistance change delta R is less than or equal to +/-1% R, and the B constant change delta B is less than or equal to +/-1% B.
And (3) cold and heat shock resistance test: and (3) placing the temperature sensor in a thermostat at minus 30 ℃ for 30min, then placing the temperature sensor in an environment at 105 ℃ for 30min as a period, circulating for 5 periods, then placing the temperature sensor at room temperature of 25 ℃ for 1h, testing the resistance value of the temperature sensor, calculating the B constant, and recording data. The test result requires that: the resistance change delta R is less than or equal to +/-1% R, and the B constant change delta B is less than or equal to +/-1% B.
And (3) vibration resistance test: the vibration frequency is 20-200 Hz, the vibration is carried out for 4 hours respectively in the vertical, front-back, left-right directions, and the appearance and the electrical property meet the requirements. After testing according to the specified method, the following requirements are met: appearance, insulation resistance, withstand voltage, reference resistance, and B-strike.
And (3) testing results: the appearance is not damaged, the insulation resistance is not less than 100M omega, the voltage resistance test is not punctured, discharged, flashover and other phenomena, the resistance value change delta R is not more than +/-1 percent R, and the B constant change delta B is not more than +/-1 percent B.
The present invention has been described in terms of specific examples, which are provided to aid understanding of the invention and are not intended to be limiting. For a person skilled in the art to which the invention pertains, several simple deductions, modifications or substitutions may be made according to the idea of the invention.
Claims (15)
1. An NTC heat-sensitive chip prepared from heat-sensitive ceramic slurry is characterized in that the NTC heat-sensitive chip is prepared from heat-sensitive ceramic powder and a silver-coated palladium electrode, wherein the heat-sensitive ceramic powder comprises 18-38% of manganese dioxide powder, 12-20% of cobalt trioxide powder, 4-14% of iron oxide powder, 21-41% of nickel oxide powder and 2-10% of rare earth oxide powder, the silver-coated palladium electrode comprises silver-coated palladium powder, iron oxide powder and manganese dioxide powder, the particle size of the silver-coated palladium powder is 3-6 um, and the thickness of the silver-coated palladium is 15-20 nm; the NTC heat-sensitive chip is an integrated structure formed by integrally sintering the heat-sensitive ceramic powder and the silver-coated palladium electrode at 900-1200 ℃.
2. The NTC thermal chip of claim 1, wherein: the ceramic powder is prepared from thermal sensitive ceramic slurry, and the thermal sensitive ceramic slurry comprises the thermal sensitive ceramic powder.
3. The NTC thermal chip of claim 2, wherein: the thermosensitive ceramic slurry also comprises an adhesive, a plasticizer, a surface auxiliary agent and an organic solvent; the heat-sensitive ceramic powder accounts for 55-88% of the weight of the heat-sensitive ceramic slurry, the adhesive accounts for 3-16% of the weight of the heat-sensitive ceramic slurry, the plasticizer accounts for 1.2-5.6% of the weight of the heat-sensitive ceramic slurry, the surface auxiliary agent accounts for 0.3-1.5% of the weight of the heat-sensitive ceramic slurry, and the organic solvent accounts for 7-25% of the weight of the heat-sensitive ceramic slurry;
the adhesive is selected from at least one of polyvinyl butyral, butyl cellulose, ethyl cellulose, methyl cellulose, polymethyl methacrylate, polyethyl methacrylate and polyalkyl methacrylate; the plasticizer is selected from at least one of glycerol citrate, glycerol nitrate, glycerol, dioctyl phthalate, dibutyl phthalate and dibutyl sebacate; the surface auxiliary agent is at least one of polyether modified silicone oil type surface auxiliary agents, mineral oil type surface auxiliary agents, mixed silicone oil type surface auxiliary agents, phenyl silicone oil type surface auxiliary agents and dimethyl silicone oil type surface auxiliary agents; the organic solvent is at least one selected from absolute ethyl alcohol, terpineol, DBE, ethylene glycol, butyl carbitol, butanone, amyl acetate, isoamyl acetate, methyl carbonate, ethyl carbonate and N-methyl-2-pyrrolidone.
4. A preparation method of an NTC heat-sensitive chip is characterized by comprising the following steps: casting the thermosensitive ceramic slurry of claim 2 or 3 into a ceramic green sheet by a casting machine, then carrying out warm isostatic pressing on the ceramic green sheet to obtain a solid green sheet, carrying out electrode and protective glass glaze printing on the warm isostatic pressed green sheet, and then sintering the printed electrode, protective glass glaze and green sheet together in an inert atmosphere to form an NTC thermosensitive chip with an integrated structure; the sintering temperature is 900-1200 ℃;
the electrode is a silver-coated palladium electrode, the silver-coated palladium electrode comprises silver-coated palladium powder, iron oxide powder and manganese dioxide powder, the particle size of the silver-coated palladium powder is 3-6 um, and the thickness of the silver-coated palladium is 15-20 nm.
5. The method of claim 4, wherein: the conditions of the warm isostatic pressing are that the temperature is 60-80 ℃, the pressure is 40-60 MPa, and the warm pressing time is 80-150 seconds.
6. The method of claim 5, wherein: cutting the sintered product into a required size, and then carrying out medium heat treatment to eliminate stress in the NTC heat-sensitive chip; the heat treatment is carried out under the conditions that the temperature is increased to 450-650 ℃ at the speed of 5-15 ℃/min, the temperature is kept for 1-24 h, and then the temperature is naturally cooled to the room temperature.
7. An NTC thermosensitive chip prepared by the preparation method of any one of claims 4 to 6.
8. A temperature sensor using the NTC thermal chip of any one of claims 1 to 3 or claim 7.
9. The temperature sensor of claim 8, wherein: the NTC heat-sensitive chip is wrapped by high-thermal-conductivity silica gel, organic silicon modified epoxy resin and high-thermal-conductivity epoxy resin from inside to outside in sequence.
10. The temperature sensor of claim 9, wherein: the high-thermal-conductivity silica gel is prepared by adding boron nitride powder accounting for 30-60 wt% of the total weight of the high-thermal-conductivity silica gel into common silica gel and mixing.
11. The temperature sensor of claim 9, wherein: the organic silicon modified epoxy resin is prepared by mixing common organic siloxane epoxy resin with 30-60 wt% of aluminum nitride powder based on the total weight of the organic silicon modified epoxy resin.
12. The temperature sensor of claim 9, wherein: the high-thermal-conductivity epoxy resin is prepared by mixing common bisphenol F epoxy resin with 30-60 wt% of aluminum nitride powder based on the total weight of the high-thermal-conductivity epoxy resin.
13. The method for manufacturing a temperature sensor according to any one of claims 9 to 12, wherein: the NTC heat-sensitive chip welded with the lead wire is sequentially immersed in high-heat-conductivity silica gel, organic silicon modified epoxy resin and high-heat-conductivity epoxy resin, and then is placed in absolute ethyl alcohol to be cleaned by ultrasonic waves, so that the temperature sensor is obtained.
14. The method for manufacturing a temperature sensor according to claim 13, wherein: the high-thermal-conductivity silica gel is dipped in the high-thermal-conductivity silica gel under the condition of hardening for 1-3 h at 110-130 ℃, dipped in the organic silicon modified epoxy resin under the condition of hardening for 0.5-2 h at 120-140 ℃, and dipped in the high-thermal-conductivity epoxy resin under the condition of hardening for 0.5-2 h at 110-130 ℃.
15. The method for manufacturing a temperature sensor according to claim 14, wherein: the high heat-conducting silica gel is soaked in the high heat-conducting silica gel under the condition of curing at 120 ℃ for 2 hours, the organosilicon modified epoxy resin is soaked in the organosilicon modified epoxy resin under the condition of curing at 130 ℃ for 1 hour, and the high heat-conducting epoxy resin is soaked in the high heat-conducting epoxy resin under the condition of curing at 120 ℃ for 1 hour.
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