CN115073140B - Preparation method of copper-containing negative temperature coefficient thermosensitive ceramic material - Google Patents
Preparation method of copper-containing negative temperature coefficient thermosensitive ceramic material Download PDFInfo
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- 229910010293 ceramic material Inorganic materials 0.000 title claims abstract description 43
- 239000010949 copper Substances 0.000 title claims abstract description 35
- 229910052802 copper Inorganic materials 0.000 title claims abstract description 28
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 27
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims abstract description 48
- 238000000498 ball milling Methods 0.000 claims abstract description 27
- 239000000843 powder Substances 0.000 claims abstract description 23
- 238000001354 calcination Methods 0.000 claims abstract description 20
- 238000001035 drying Methods 0.000 claims abstract description 20
- 239000000463 material Substances 0.000 claims abstract description 18
- 235000006408 oxalic acid Nutrition 0.000 claims abstract description 16
- 239000000853 adhesive Substances 0.000 claims abstract description 15
- 230000001070 adhesive effect Effects 0.000 claims abstract description 15
- 238000001816 cooling Methods 0.000 claims abstract description 15
- 229940011182 cobalt acetate Drugs 0.000 claims abstract description 11
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 claims abstract description 11
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 claims abstract description 11
- 229940071125 manganese acetate Drugs 0.000 claims abstract description 11
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 claims abstract description 11
- 239000002270 dispersing agent Substances 0.000 claims abstract description 10
- 238000002156 mixing Methods 0.000 claims abstract description 10
- 238000000227 grinding Methods 0.000 claims abstract description 8
- 238000007873 sieving Methods 0.000 claims abstract description 8
- 238000000748 compression moulding Methods 0.000 claims abstract description 3
- 239000011572 manganese Substances 0.000 claims description 19
- 239000000203 mixture Substances 0.000 claims description 16
- 239000011812 mixed powder Substances 0.000 claims description 14
- 229910052748 manganese Inorganic materials 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 12
- 229910052751 metal Inorganic materials 0.000 claims description 9
- 239000002184 metal Substances 0.000 claims description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical group CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 7
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 7
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 7
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 2
- 229910017052 cobalt Inorganic materials 0.000 claims description 2
- 239000010941 cobalt Substances 0.000 claims description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 2
- 239000011230 binding agent Substances 0.000 claims 2
- 238000004519 manufacturing process Methods 0.000 claims 1
- 230000032683 aging Effects 0.000 abstract description 16
- 238000009529 body temperature measurement Methods 0.000 abstract description 4
- 238000009776 industrial production Methods 0.000 abstract description 2
- 230000005764 inhibitory process Effects 0.000 abstract description 2
- 239000000919 ceramic Substances 0.000 description 13
- 239000002994 raw material Substances 0.000 description 11
- 238000005303 weighing Methods 0.000 description 10
- 150000002500 ions Chemical class 0.000 description 7
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 5
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 5
- 238000011068 loading method Methods 0.000 description 5
- 238000000465 moulding Methods 0.000 description 5
- 229910052709 silver Inorganic materials 0.000 description 5
- 239000004332 silver Substances 0.000 description 5
- 229910052596 spinel Inorganic materials 0.000 description 4
- 239000011029 spinel Substances 0.000 description 4
- 238000005498 polishing Methods 0.000 description 3
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 2
- 229910001431 copper ion Inorganic materials 0.000 description 2
- RKTYLMNFRDHKIL-UHFFFAOYSA-N copper;5,10,15,20-tetraphenylporphyrin-22,24-diide Chemical compound [Cu+2].C1=CC(C(=C2C=CC([N-]2)=C(C=2C=CC=CC=2)C=2C=CC(N=2)=C(C=2C=CC=CC=2)C2=CC=C3[N-]2)C=2C=CC=CC=2)=NC1=C3C1=CC=CC=C1 RKTYLMNFRDHKIL-UHFFFAOYSA-N 0.000 description 2
- 229920002545 silicone oil Polymers 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 229910018663 Mn O Inorganic materials 0.000 description 1
- 229910003176 Mn-O Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000002431 foraging effect Effects 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical group [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 238000010532 solid phase synthesis reaction Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 238000003466 welding Methods 0.000 description 1
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- 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
- C04B35/01—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
- C04B35/016—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 based on manganites
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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
-
- H—ELECTRICITY
- 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
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
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- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/30—Constituents and secondary phases not being of a fibrous nature
- C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
- C04B2235/327—Iron group oxides, their mixed metal oxides, or oxide-forming salts thereof
- C04B2235/3275—Cobalt oxides, cobaltates or cobaltites or oxide forming salts thereof, e.g. bismuth cobaltate, zinc cobaltite
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- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/30—Constituents and secondary phases not being of a fibrous nature
- C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
- C04B2235/3281—Copper oxides, cuprates or oxide-forming salts thereof, e.g. CuO or Cu2O
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Abstract
The invention relates to a preparation method of copper-containing negative temperature coefficient thermal sensitive ceramic material, which comprises the steps of uniformly mixing cobalt acetate, copper acetate, manganese acetate and oxalic acid, ball milling with a grinding medium material and a dispersing agent, drying and calcining the obtained powder, then performing secondary ball milling, drying and sieving, then adding an adhesive for granulating, then performing compression molding, calcining the molded blank, and finally cooling. The copper-containing negative temperature coefficient heat-sensitive ceramic material prepared by the invention has the characteristics of good compactness, high stability, high precision, excellent conductivity, suitability for industrial production and the like, the room temperature resistivity is 2.15-578.33 ohm cm, the B value is 2247-3658K, the aging value is 1.63-3.82%, and the copper-containing negative temperature coefficient heat-sensitive ceramic material is particularly suitable for the technical fields of low-temperature measurement, surge current inhibition and the like.
Description
Technical Field
The invention relates to a preparation method of a copper-containing negative temperature coefficient thermal sensitive ceramic material with low resistance, high B value and high stability, and belongs to the technical field of negative temperature coefficient thermal sensitive ceramic materials.
Background
The Negative Temperature Coefficient (NTC) thermosensitive ceramic has the characteristics of high temperature measurement precision, good interchangeability, high reliability and the like, and has wide application in the aspects of temperature measurement, control, compensation and the like. In general, NTC thermal sensitive ceramic material is composed of a material with general formula AB 2 O 4 With the development of technology, higher demands are made on the low resistance and high B values of such materials, whereas it is often the case that the B value is also high when the resistivity of the material is high, and vice versa.
Studies have shown that doping with copper ions alone can reduce the room temperature resistivity to below 100 Ω cm, however, due to the transition of the valence state of copper ions and their ion and vacancyMigration and other factors lead to poor stability of the electrical properties of such materials, typically with a resistance drift of greater than 10%, e.g., ni 0.5 Mn 2.5 O 4 The room temperature resistivity of the ceramic was 2900Ω·cm, the aging value was 1.9%, and when a small amount of Cu ions was added, cu was contained 0.2 Ni 0.5 Mn 2.3 O 4 The room temperature resistivity of the ceramic is reduced by two orders of magnitude, namely 70 omega cm, and the ageing value is increased by one order of magnitude, namely 14.9%; ni (Ni) 0.66 Mn 2.34 O 4 The room temperature resistivity of the ceramic is 2037Ω·cm, and when a small amount of Cu ions is added, cu 0.2 Ni 0.66 Mn 2.14 O 4 The room temperature resistivity of the ceramic is reduced by two orders of magnitude to be 42 omega cm, and the ageing value is as high as 12.6%.
In order to improve the stability of the NTC thermosensitive ceramic containing Cu, zn which is a constant valence ion can be added 2+ However, although this method can increase the stability of the material, the room temperature resistivity of the material is also increased. For example, in Cu 0.2 Ni 0.66 Mn 2.14 O 4 Zn is added into ceramics 2+ ，Zn 0.4 Cu 0.2 Ni 0.66 Mn 2.14 O 4 The aging value of the ceramic is reduced to 4.2%, the room temperature resistivity is increased to 73.1 Ω & cm, and further, znCu 0.2 Ni 0.66 Mn 2.14 O 4 The aging value of the ceramic is reduced to 0.16%, and the room temperature resistivity is greatly increased to 980 Ω·cm. From this, it can be seen that for the Cu-based cubic spinel structure NTC thermal ceramics, the preparation of low resistance and high stability by ion doping is difficult to achieve. Therefore, it is urgent to explore a new technical scheme for preparing the NTC heat-sensitive material with low resistance and high stability.
Disclosure of Invention
The invention aims to provide a preparation method of a copper-containing negative temperature coefficient thermal sensitive ceramic material, aiming at the defects of the existing copper-containing negative temperature coefficient thermal sensitive ceramic material, and the prepared negative temperature coefficient thermal sensitive ceramic material has low resistance and high B value and high stability.
Technical proposal
A preparation method of a copper-containing negative temperature coefficient thermal sensitive ceramic material comprises the following steps:
(1) Uniformly mixing cobalt acetate, copper acetate, manganese acetate and oxalic acid to obtain a mixture, and then mixing the mixture with a grinding medium material and a dispersing agent according to a weight ratio of 1: (1-3): (1-3) adding the mixture into a ball milling tank for ball milling to obtain mixed powder;
(2) Drying the mixed powder, calcining, cooling, performing secondary ball milling for 6-24 hours, drying and sieving to obtain powder;
(3) Adding an adhesive into the powder material in the step (2) for granulating, then carrying out compression molding, calcining the molded blank, and finally cooling to obtain the copper-containing negative temperature coefficient thermal sensitive ceramic material.
Further, in the step (1), the dosage of the cobalt acetate, the copper acetate and the manganese acetate is measured according to the atomic percentage of metal, wherein the atomic percentage of cobalt is 32.67%, the atomic percentage of copper is 10-20%, the atomic percentage of manganese is 47.33-57.33%, and the dosage of oxalic acid is 1-1.5 times of the total molar weight of metal atoms.
Further, in the step (1), the dispersant is absolute ethyl alcohol.
Further, in the step (1), the rotating speed of the ball milling tank is 200-300 r/min, and the ball milling time is 3-12 h.
In the step (2), the drying temperature is 80 ℃ and the time is 12-24 hours.
Further, in the step (2), the calcination temperature is 600-900 ℃ and the time is 2-4 h.
Further, in the step (2), the drying temperature is 80 ℃.
In the step (3), the adhesive is a polyvinyl alcohol solution with the concentration of 5-8wt%, and the mass ratio of the adhesive to the powder is (5-8): (92-95).
Further, in the step (3), the calcination temperature is 1000-1200 ℃ and the time is 3-8 h.
The invention has the beneficial effects that:
the invention provides a preparation method of a copper-containing negative temperature coefficient thermal sensitive ceramic material, which takes cobalt acetate, copper acetate, manganese acetate and oxalic acid as raw materials, firstly prepares oxide powder with a spinel structure through a solid phase method, then prepares the negative temperature coefficient thermal sensitive ceramic material by adopting a ceramic preparation process, introduces Cu ions into Co-Mn-O with a tetragonal spinel structure, enhances the stability of the material by utilizing a special twin crystal structure of the tetragonal spinel structure, and reduces the resistivity of a system by utilizing the Cu ions. The method is simple to operate, and the prepared negative temperature coefficient thermal sensitive ceramic material has the characteristics of good compactness, high stability, high precision, excellent conductivity, suitability for industrial production and the like, has room temperature resistivity of 2.15-578.33 ohm cm, B value of 2247-3658K and aging value of 1.63-3.82%, and is particularly suitable for the technical fields of low-temperature measurement, surge current inhibition and the like.
Detailed Description
The technical scheme of the invention is further described below with reference to specific embodiments.
Example 1
A preparation method of a copper-containing negative temperature coefficient thermal sensitive ceramic material comprises the following steps:
(1) The method comprises the steps of taking analytically pure cobalt acetate, copper acetate, manganese acetate and oxalic acid as raw materials, accurately weighing the raw materials according to the atomic percentages of Co, cu and Mn of 32.67%, 10% and 7.33%, weighing the oxalic acid according to 1.1 times of the total molar weight of metal atoms (Co, cu and Mn), and mixing the mixture with agate balls serving as grinding medium materials and absolute ethyl alcohol serving as a dispersing agent according to the weight ratio of 1:2:3, loading the mixture into a ball milling tank for ball milling (the rotating speed is 250 r/min) for 5 hours to obtain mixed powder;
(2) Drying the mixed powder at 80 ℃ for 12 hours, calcining at 800 ℃ for 2 hours, cooling, performing secondary ball milling (the rotating speed is 250 r/min) for 12 hours, drying at 80 ℃ and sieving with a 80-mesh sieve to obtain powder;
(3) Adding an adhesive (5 wt% polyvinyl alcohol solution) into the powder in the step (2) for granulating, wherein the mass ratio of the adhesive to the powder is 8:92, then molding into a wafer with the diameter of 10mm under the pressure of 10MPa, calcining the molded blank for 3 hours at 1100 ℃, and finally cooling to obtain the copper-containing negative temperature coefficient thermal sensitive ceramic material.
1) The electrical performance test is carried out on the prepared negative temperature coefficient thermal sensitive ceramic material, and the test method comprises the following steps: firstly, polishing the surface of a negative temperature coefficient heat-sensitive ceramic material, wherein a polishing medium is silicon carbide, then, coating a layer of uniform silver paste on two surfaces, drying, then, sintering silver in a resistance furnace at 750 ℃ and preserving heat for 15min, and polishing the side surface of a ceramic sample after silver treatment, and then, testing the electrical property.
Resistance measurement: and (5) adding and welding a silver electrode lead on the silver-coated ceramic wafer sample. Resistance values were measured using an Agilent34401A digital multimeter, and resistances R at 25℃and 85℃were measured in silicone oil, respectively 25 And R is 85 The resistivity is calculated according to the formula:
wherein: ρ is the resistivity of the sample, Ω·cm; r is the resistance of the sample, omega; s is the area of the sample, cm 2 The method comprises the steps of carrying out a first treatment on the surface of the L is the thickness of the sample, cm.
B, calculating:
wherein R is 1 And R is 2 The resistance values of the samples at 25℃and 85℃respectively.
The electrical parameters of the negative temperature coefficient thermal sensitive ceramic material prepared by the embodiment are measured as follows: the resistivity at room temperature is 578.33 +/-1% omega cm, and the B value is 3658+/-2%K.
2) Aging value test: the negative temperature coefficient thermal sensitive ceramic material prepared in the embodiment is put into a baking oven at 150 ℃ for aging for 500 hours, then taken out, the resistance value at 25 ℃ is measured in silicone oil, and the aging value is calculated according to the following formula:
ageing value = (R 1 ’-R 1 )/R 1 *100％
Wherein R is 1 Resistance value of the sample at 25 ℃, R 1 ' is the resistance of the sample at 25℃after aging.
The aging value of the NTC thermal sensitive ceramic material prepared in this example was measured to be 2.61.+ -. 0.1%.
Example 2
A preparation method of a copper-containing negative temperature coefficient thermal sensitive ceramic material comprises the following steps:
(1) The method comprises the steps of taking analytically pure cobalt acetate, copper acetate, manganese acetate and oxalic acid as raw materials, accurately weighing the raw materials according to the atomic percentages of Co, cu and Mn of 32.67%, 13.33% and 54%, weighing the oxalic acid according to 1.5 times of the total molar weight of metal atoms (Co, cu and Mn), and mixing the mixture with agate balls serving as grinding medium materials and absolute ethyl alcohol serving as a dispersing agent according to the weight ratio of 1:2:3, loading the mixture into a ball milling tank, wherein the ball milling rotating speed is (the rotating speed is 250 r/min) for 5 hours, and obtaining mixed powder;
(2) Drying the mixed powder at 80 ℃ for 12 hours, calcining at 700 ℃ for 2 hours, cooling, performing secondary ball milling (the rotating speed is 250 r/min) for 12 hours, drying at 80 ℃ and sieving with a 80-mesh sieve to obtain powder;
(3) Adding an adhesive (5 wt% polyvinyl alcohol solution) into the powder in the step (2) for granulating, wherein the mass ratio of the adhesive to the powder is 8:92, then molding into a wafer with the diameter of 10mm under the pressure of 10MPa, calcining the molded blank for 3 hours at the temperature of 1000 ℃, and finally cooling to obtain the copper-containing negative temperature coefficient thermal sensitive ceramic material.
The electrical parameters of the negative temperature coefficient thermal sensitive ceramic material prepared by the embodiment are measured as follows: the resistivity at room temperature is 160.66 +/-1% omega cm, and the B value is 3338+/-2%K.
The aging value of the negative temperature coefficient thermal sensitive ceramic material prepared by the embodiment is measured to be 3.41 plus or minus 0.2 percent.
Example 3
A preparation method of a copper-containing negative temperature coefficient thermal sensitive ceramic material comprises the following steps:
(1) The method comprises the steps of taking analytically pure cobalt acetate, copper acetate, manganese acetate and oxalic acid as raw materials, accurately weighing the raw materials according to the atomic percentages of Co, cu and Mn of 32.67%, 13.33% and 54%, weighing the oxalic acid according to 1.5 times of the total molar weight of metal atoms (Co, cu and Mn), and mixing the mixture with agate balls serving as grinding medium materials and absolute ethyl alcohol serving as a dispersing agent according to the weight ratio of 1:2:3, loading the mixture into a ball milling tank for ball milling (the rotating speed is 250 r/min) for 5 hours to obtain mixed powder;
(2) Drying the mixed powder at 80 ℃ for 12 hours, calcining at 700 ℃ for 2 hours, cooling, performing secondary ball milling (the rotating speed is 250 r/min) for 12 hours, drying at 80 ℃ and sieving with a 80-mesh sieve to obtain powder;
(3) Adding an adhesive (5 wt% polyvinyl alcohol solution) into the powder in the step (2) for granulating, wherein the mass ratio of the adhesive to the powder is 8:92, then molding into a wafer with the diameter of 10mm under the pressure of 10MPa, calcining the molded blank for 3 hours at 1100 ℃, and finally cooling to obtain the copper-containing negative temperature coefficient thermal sensitive ceramic material.
The electrical parameters of the negative temperature coefficient thermal sensitive ceramic material prepared by the embodiment are measured as follows: the resistivity at room temperature is 16.97+ -0.5% Ω cm, and the B-value is 2832+ -1% K.
The aging value of the negative temperature coefficient thermal sensitive ceramic material prepared by the embodiment is measured to be 2.38 plus or minus 0.1 percent.
Example 4
A preparation method of a copper-containing negative temperature coefficient thermal sensitive ceramic material comprises the following steps:
(1) The method comprises the steps of taking analytically pure cobalt acetate, copper acetate, manganese acetate and oxalic acid as raw materials, accurately weighing the raw materials according to the atomic percentages of Co, cu and Mn of 32.67%, 13.33% and 54%, weighing the oxalic acid according to 1.5 times of the total molar weight of metal atoms (Co, cu and Mn), and mixing the mixture with agate balls serving as grinding medium materials and absolute ethyl alcohol serving as a dispersing agent according to the weight ratio of 1:2:3, loading the mixture into a ball milling tank for ball milling (the rotating speed is 250 r/min) for 5 hours to obtain mixed powder;
(2) Drying the mixed powder at 80 ℃ for 12 hours, calcining at 700 ℃ for 2 hours, cooling, performing secondary ball milling (the rotating speed is 250 r/min) for 12 hours, drying at 80 ℃ and sieving with a 80-mesh sieve to obtain powder;
(3) Adding an adhesive (5 wt% polyvinyl alcohol solution) into the powder in the step (2) for granulating, wherein the mass ratio of the adhesive to the powder is 8:92, then molding into a wafer with the diameter of 10mm under the pressure of 10MPa, calcining the molded blank for 3 hours at the temperature of 1200 ℃, and finally cooling to obtain the copper-containing negative temperature coefficient thermal sensitive ceramic material.
The electrical parameters of the negative temperature coefficient thermal sensitive ceramic material prepared by the embodiment are measured as follows: the resistivity at room temperature is 33.2+ -0.5% Ω & cm, and the B-value is 30005+ -1% K.
The ageing value of the negative temperature coefficient thermal sensitive ceramic material prepared by the embodiment is 1.63+/-0.05 percent.
Example 5
A preparation method of a copper-containing negative temperature coefficient thermal sensitive ceramic material comprises the following steps:
(1) The method comprises the steps of taking analytically pure cobalt acetate, copper acetate, manganese acetate and oxalic acid as raw materials, accurately weighing the raw materials according to the atomic percentages of Co, cu and Mn of 32.67%, 20% and 47.33%, weighing the oxalic acid according to 1.5 times of the total molar weight of metal atoms (Co, cu and Mn), and mixing the mixture with agate balls serving as a grinding medium material and absolute ethyl alcohol serving as a dispersing agent according to the weight ratio of 1:2:3, loading the mixture into a ball milling tank for ball milling (the rotating speed is 250 r/min) for 5 hours to obtain mixed powder;
(2) Drying the mixed powder at 80 ℃ for 12 hours, calcining at 700 ℃ for 2 hours, cooling, performing secondary ball milling (the rotating speed is 250 r/min) for 12 hours, drying at 80 ℃ and sieving with a 80-mesh sieve to obtain powder;
(3) Adding an adhesive (5 wt% polyvinyl alcohol solution) into the powder in the step (2) for granulating, wherein the mass ratio of the adhesive to the powder is 8:92, then molding into a wafer with the diameter of 10mm under the pressure of 10MPa, calcining the molded blank body at 1050 ℃ for 3 hours, and finally cooling to obtain the copper-containing negative temperature coefficient thermal sensitive ceramic material.
The electrical parameters of the negative temperature coefficient thermal sensitive ceramic material prepared by the embodiment are measured as follows: the resistivity at room temperature is 2.15+/-0.5% omega cm, and the B value is 2247+/-1% K.
The aging value of the negative temperature coefficient thermal sensitive ceramic material prepared by the embodiment is measured to be 3.82 plus or minus 0.1 percent.
Claims (6)
1. The preparation method of the copper-containing negative temperature coefficient thermosensitive ceramic material is characterized by comprising the following steps:
(1) Uniformly mixing cobalt acetate, copper acetate, manganese acetate and oxalic acid to obtain a mixture, and then mixing the mixture with a grinding medium material and a dispersing agent according to a weight ratio of 1: (1-3): (1-3) adding the mixture into a ball milling tank for ball milling to obtain mixed powder;
(2) Drying the mixed powder, calcining, cooling, performing secondary ball milling for 6-24 hours, drying, and sieving to obtain powder;
(3) Adding an adhesive into the powder material in the step (2) for granulating, then carrying out compression molding, calcining the molded blank, and finally cooling to obtain the copper-containing negative temperature coefficient thermal sensitive ceramic material;
in the step (1), the dosage of cobalt acetate, copper acetate and manganese acetate is measured according to the atomic percentage of metal, wherein the atomic percentage of cobalt is 32.67%, the atomic percentage of copper is 10-20%, the atomic percentage of manganese is 47.33-57.33%, and the dosage of oxalic acid is 1-1.5 times of the total molar weight of metal atoms;
in the step (2), the calcination temperature is 600-900 ℃ and the time is 2-4 hours;
in the step (3), the calcination temperature is 1000-1200 ℃ and the time is 3-8 hours.
2. The method of claim 1, wherein in step (1), the dispersant is absolute ethanol.
3. The method for preparing a copper-containing negative temperature coefficient thermal sensitive ceramic material according to claim 1, wherein in the step (1), the rotation speed of the ball milling tank is 200-300 r/min, and the ball milling time is 3-12 h.
4. The method of claim 1, wherein in the step (2), the drying temperature is 80 ℃ and the time is 12-24 hours.
5. The method of claim 1, wherein in step (2), the baking temperature is 80 ℃.
6. The method for producing a copper-containing negative temperature coefficient thermal sensitive ceramic material according to claim 1, wherein in the step (3), the binder is a polyvinyl alcohol solution having a concentration of 5 to 8wt%, and the mass ratio of the binder to the powder is (5 to 8): (92-95).
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