CN101838144A - BaTiO3-based PTC thermal sensitive ceramic material and preparation method thereof - Google Patents
BaTiO3-based PTC thermal sensitive ceramic material and preparation method thereof Download PDFInfo
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- CN101838144A CN101838144A CN201010188474A CN201010188474A CN101838144A CN 101838144 A CN101838144 A CN 101838144A CN 201010188474 A CN201010188474 A CN 201010188474A CN 201010188474 A CN201010188474 A CN 201010188474A CN 101838144 A CN101838144 A CN 101838144A
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Abstract
The invention provides a BaTiO3-based PTC thermal sensitive ceramic material and a preparation method thereof. The thermal sensitive ceramic material comprises the primary materials of TiO2, BaCO3, Bi2O3 and K2CO3 and the auxiliary materials of Nb2O5, Y2O3, Mn(NO3)2 and Sb2O3. The preparation method comprises the following steps of: mixing the primary materials and mixing the primary materials with zirconium ballstones and deionized water and roasting into pre-combined materials, mixing with the auxiliary materials, zirconium ballstones and deionized water to form complete dosing, then after mixing the complete dosing with zirconium ballstones and deionized water, ball-milling, drying, prilling and screening to press as samples, then transferring to the high temperature electric furnace in nitrogen atmosphere to raise the temperature and reduce the temperature, changing the in-furnace atmosphere to air with nitrogen when the temperature is reduced to 1100-900 DEG C and maintaining the temperature, then cooling along with the furnace and finally coating the electrode slurry to obtain the PTC thermal sensitive ceramic material. The ceramic material prepared by the method has higher room temperature which achieves 185 DEG C maximally, is non-poisonous and has low room temperature resistivity.
Description
[technical field]
The present invention relates to a kind of PTC thermal sensitive ceramic material and preparation method thereof, particularly a kind of BaTiO
3Based PTC thermal sensitive ceramic material and preparation method thereof.
[background technology]
The BaTiO that is used for (more than 120 ℃) under the hot conditions of commercial production at present
3Base positive temperature coefficient (PTC) thermal sensitive ceramics all contains lead, this leaded high-temp PTC stupalith can work the mischief to human and environment when producing and use, European Union also issued in 2006 and strict forbidden the use regulations of leaded material in electronic ceramics, therefore, and development lead-free high-temperature BaTiO
3Based PTC thermal sensitive ceramic material is extremely urgent.
Current, numerous scholars are to lead-free high-temperature BaTiO
3Based PTC thermal sensitive ceramic has carried out extensive studies.For example, T.Shimada[1] etc. the people in the PTC thermal sensitive ceramics, mix Bi
0.5Na
0.5TiO
3, so, this thermal sensitive ceramics is because unleaded, so, can not work the mischief to human body and environment, simultaneously, suitably the Curie temperature of raising thermal sensitive ceramics makes Curie temperature reach 175 ℃.(T.Shimada?and?et?al.Lead?free?PTCRceramics?and?its?electrical?properties，Journal?of?the?European?Ceramic?Society，2007，27(13-15)：3877-3882)。
Yet, above-mentioned BaTiO
3-Bi
0.5Na
0.5TiO
3Also there is the shortcoming of self in system's pottery:, promptly work as Bi
0.5Na
0.5TiO
3When content surpassed 2mol%, the ceramics sample that burns till under air atmosphere was difficult to the room temperature semiconductor.
In addition, though Bi
0.5Na
0.5TiO
3Curie temperature up to 320 ℃, and when low doping concentration, can obviously improve the Curie temperature of barium titanate; Yet, when high-concentration dopant,, in addition, also make the room temperature resistivity of ceramic sample enlarge markedly to the obvious reduction of raising the efficiency of Curie temperature.Therefore, the simple Bi that directly mixes
0.5Na
0.5TiO
3Limited to the raising degree of its ceramic Curie temperature in the barium titanate.
In view of above problem, be necessary to provide a kind of BaTiO that can solve the problems of the technologies described above in fact
3Based PTC thermal sensitive ceramic material and preparation method thereof.
[summary of the invention]
Technical problem to be solved by this invention provides a kind of BaTiO
3Based PTC thermal sensitive ceramic ability two and preparation method thereof, it not only significantly improves the Curie temperature of pottery, realizes the room temperature semiconductor, and environmentally friendly.
For achieving the above object, the present invention also provides a kind of BaTiO
3The preparation method of based PTC thermal sensitive ceramic material comprises the steps:
Step 1: according to mol ratio is (0.9～0.99): (0.005～0.05): (0.005～0.05) takes by weighing BaCO
3, Bi
2O
3, and K
2CO
3, mix the back and form mixture A, then, take by weighing TiO
2, with TiO
2Is to mix at 1: 1 to form mixture B with mixture A according to mol ratio;
Step 2: get mixture B, zirconium ballstone respectively, and deionized water, be the back ball milling of mixing in 1: 1: 2.5 10 hours according to mass ratio, then, 100 ℃ of oven dry, subsequently, be passed to 1000～1230 ℃ of insulations in high-temperature electric resistance furnace inherence 2 hours, form and close material in advance, standby;
Step 3: in mixture B is 1mol, gets the Nb of 0.1～0.75mol% respectively according to molar content
2O
5, 0.1～0.55mol% Y
2O
3, 0.15～0.2mol% Mn (NO
3)
2Sb with 0.1～0.65mol%
2O
3As auxiliary material, then, auxiliary material is added into closing in advance in the material that step 2 obtains, mix the back and form full batching;
Step 4: getting full batching, zirconium ballstone that step 3 obtains respectively, and deionized water, is to carry out ball milling, oven dry, granulation successively after mixing at 1: 1: 2.5 according to mass ratio, forms the granulation material, sieves then;
Step 5: the granulation material after step 4 sieved is pressed into sample under the pressure of 120MPa, then, be placed on the zirconium white is to move into high-temperature electric resistance furnace in the aluminum oxide saggar of backing plate, make and be the pure nitrogen gas atmosphere in the electric furnace, and heat up with 3 ℃/min, when reaching 120 ℃, 450 ℃ respectively, temperature respectively is incubated 30 minutes, insulation is 2～3 hours when temperature rises to 1300～1340 ℃, afterwards, with 5 ℃/min cooling, when temperature is reduced to 1100 ℃～900 ℃, the adjusting electric furnace makes and presents air atmosphere in it, and be incubated 1.5～3.5 hours, subsequently, cool to room temperature with the furnace:
Step 6; Behind the sample that cleaning step five sinters,,, promptly make BaTiO 500 ℃ of sintering 10 minutes at the even electrode coated slurry of tow sides
3The based PTC thermal sensitive ceramic material sample.
As the preferred embodiments of the present invention, in the step 4, adopted wet ball grinding 10 hours, behind the ball milling, 100 ℃ of oven dry;
As the preferred embodiments of the present invention, in the step 4, form the oven dry material after full batching, zirconium ballstone and deionized water mixing, ball milling, the oven dry, then, be that 4～8% tackiness agent is added in the oven dry material and carries out granulation, 4～8% of binder constitutes oven dry material with concentration;
As the preferred embodiments of the present invention, described tackiness agent is selected from polyvinyl alcohol water solution.
For achieving the above object, the present invention also provides a kind of BaTiO
3Based PTC thermal sensitive ceramic material, major ingredient are TiO
2, BaCO
3, Bi
2O
3, and K
2CO
3, its mol ratio is 1: (0.9～0.99): (0.005～0.05): (0.005～0.05), dressing are Nb
2O
5, Y
2O
3, Mn (NO
3)
2And Sb
2O
3, wherein, according to molar content meter, Nb
2O
5Account for 0.1～0.75% of major ingredient, Y
2O
3Account for 0.1～0.55% of major ingredient, Mn (NO
3)
2Account for 0.15～0.2% of major ingredient, Sb
2O
3Account for 0.1～0.65% of major ingredient.
BaTiO of the present invention
3Based PTC thermal sensitive ceramic material and preparation method thereof has the following advantages at least: add Bi
2O
3And K
2CO
3, improved BaTiO
3The Curie temperature of base positive temperature coefficient resistor ceramic is up to 185 ℃, and liftdrag is 1.9 * 10
3～4.3 * 10
3, room temperature resistivity ρ
RTBe 96～197 Ω cm; The control sintering atmosphere reaches the low room temperature resistivity and the good PTC effect of ceramics sample; In addition, the raw material and the processing condition of the present invention's employing realize the good reproducibility of material property easily.
[description of drawings]
Fig. 1 is the electronic scanning Electronic Speculum figure of thermal sensitive ceramic material of the present invention;
Fig. 2 is the PTC performance map of thermal sensitive ceramic material of the present invention.
[embodiment]
Embodiment one:
Step 1: according to mol ratio is to take by weighing BaCO at 0.96: 0.002: 0.002
3, Bi
2O
3, and K
2CO
3, mix the back and form mixture A, then, take by weighing TiO
2, with TiO
2Is to mix at 1: 1 to form mixture B with mixture A according to mol ratio;
Step 2: according to mass ratio is to take by weighing the mixture B that step 1 obtains at 1: 1: 2.5, and zirconium ballstone and deionized water, it is positioned over ball milling moves in the baking oven in the ball grinder after 10 hours, 100 ℃ of oven dry, then, be passed in the high-temperature electric resistance furnace and be incubated 2 hours, form and close material in advance at 1100 ℃, standby;
Step 3: with major ingredient mixture B is 1mol, takes by weighing the Nb that accounts for major ingredient 0.3mol% according to molar content
2O
5, account for the Y of major ingredient 0.2mol%
2O
3, account for the Mn (NO of major ingredient 0.02mol%
3)
2, and the Sb that accounts for major ingredient 0.2mol%
2O
3, then, with above-mentioned Nb
2O
5, Y
2O
3, Mn (NO
3)
2, and Sb
2O
3Be added into closing in advance in the material that step 2 obtains, mix the back and form full batching;
Step 4: get full batching and zirconium ballstone and deionized water that step 3 obtains, be positioned over the interior ball milling of ball mill 12 hours, form the ball milling material, wherein, full batching: the zirconium ballstone: the mass ratio of deionized water is 1: 1: 2.5;
Step 5: the ball milling material that step 4 is obtained moves in the baking oven, 100 ℃ of oven dry, forming the oven dry material, then, is that 4% polyvinyl alcohol water solution as tackiness agent is added in the oven dry material and carries out granulation with concentration, form the granulation material, then, the granulation material is crossed 60 mesh sieves, wherein, according to the quality meter, 8% of binder constitutes oven dry material;
Step 6: the granulation material that step 5 is obtained moves in the metal mould, with pressing machine the granulation material is pressed under the pressure of 120Mpa
The disk sample;
Step 7: it is in the aluminum oxide saggar of backing plate that the sample that step 6 is obtained is placed on the zirconium white, space 2mm between the sample;
Step 8: moving into sintering in the high-temperature electric resistance furnace, in the atmosphere of pure nitrogen gas, is that 3 ℃/min heats up with heat-up rate, insulation is 30 minutes when temperature reaches 120 ℃, and insulation is 30 minutes when temperature reaches 450 ℃, and insulation is 2 hours when temperature reaches 1330 ℃, afterwards, with 5 ℃/min cooling, when temperature is reduced to 1000 ℃, regulate high-temperature electric resistance furnace, make and be air atmosphere in the stove, and be incubated 2.5 hours, subsequently, cool to room temperature with the furnace;
Step 9: after the surface-conditioning of the sample that step 8 is sintered, evenly apply the ohmic contact aluminum electrode slurry,, promptly make BaTiO 500 ℃ of sintering 10 minutes at tow sides
3The based PTC thermal sensitive ceramic material sample.
Embodiment two
Step 1: according to mol ratio is to take by weighing BaCO at 0.98: 0.001: 0.001
3, Bi
2O
3, and K
2CO
3, mix the back and form mixture A, then, take by weighing TiO
2, with TiO
2Is to mix at 1: 1 to form mixture B with mixture A according to mol ratio;
Step 2: according to mass ratio is to take by weighing mixture B and zirconium ballstone and the deionized water that step 1 obtains at 1: 1: 2.5, it is positioned over ball milling moves in the baking oven in the ball grinder after 10 hours, 100 ℃ of oven dry, then, be passed in the high-temperature electric resistance furnace 1200 ℃ of insulations 2 hours, form and close material in advance, standby;
Step 3: with major ingredient mixture B is 1mol, takes by weighing the Nb that accounts for major ingredient 0.15mol% according to molar content
2O
5, 0.1mol% Y
2O
3, 0.025mol% Mn (NO
3)
2, and the Sb of 0.1mol%
2O
3, then, with above-mentioned Nb
2O
5, Y
2O
3, Mn (NO
3)
2, and Sb
2O
3Be added into closing in advance in the material that step 2 obtains, mix the back and form full batching;
Step 4: get full batching and zirconium ballstone and deionized water that step 3 obtains, be positioned over the interior ball milling of ball mill 12 hours, form the ball milling material, wherein, full batching: the zirconium ballstone: the mass ratio of deionized water is 1: 1: 2.5;
Step 5: the ball milling material that step 4 is obtained moves in the baking oven, 100 ℃ of oven dry, forming the oven dry material, then, is that 4.5% polyvinyl alcohol water solution as tackiness agent is added in the oven dry material and carries out granulation with concentration, form the granulation material, then, the granulation material is crossed 60 mesh sieves, wherein, according to the quality meter, 7.5% of binder constitutes oven dry material;
Step 6: the granulation material that step 5 is obtained moves in the metal mould, with pressing machine the granulation material is pressed under the pressure of 120Mpa
The disk sample;
Step 7: it is in the aluminum oxide saggar of backing plate that the sample that step 6 is obtained is placed on the zirconium white, space 2mm between the sample;
Step 8: moving into sintering in the high-temperature electric resistance furnace, in the atmosphere of pure nitrogen gas, is that 3 ℃/min heats up with heat-up rate, insulation is 30 minutes when temperature reaches 120 ℃, and insulation is 30 minutes when temperature reaches 450 ℃, and insulation is 3 hours when temperature reaches 1330 ℃, afterwards, with 5 ℃/min cooling, when temperature reaches 1100 ℃, regulate high-temperature electric resistance furnace, make and be air atmosphere in the stove, and be incubated 2 hours, subsequently, cool to room temperature with the furnace;
Step 9: after the surface-conditioning of the sample that step 8 is sintered, evenly apply the ohmic contact aluminum electrode slurry,, promptly make BaTiO 500 ℃ of sintering 10 minutes at tow sides
3The based PTC thermal sensitive ceramic material sample.
Embodiment three
Step 1: according to mol ratio is to take by weighing BaCO at 0.99: 0.005: 0.005
3, Bi
2O
3, and K
2CO
3, mix the back and form mixture A, then, take by weighing TiO
2, with TiO
2Is to mix at 1: 1 to form mixture B with mixture A according to mol ratio;
Step 2: according to mass ratio is to take by weighing mixture B and zirconium ballstone and the deionized water that step 1 obtains at 1: 1: 2.5, it is positioned over ball milling moves in the baking oven in the ball grinder after 10 hours, 100 ℃ of oven dry, then, be passed in the high-temperature electric resistance furnace 1230 ℃ of insulations 2 hours, form and close material in advance, standby;
Step 3: with major ingredient mixture B is 1mol, takes by weighing the Nb that accounts for major ingredient 0.1mol% according to molar content
2O
5, 0.05mol% Y
2O
3, 0.02mol% Mn (NO
3)
2, and the Sb of 0.15mol%
2O
3, then, with above-mentioned Nb
2O
5, Y
2O
3, Mn (NO
3)
2, and Sb
2O
3Be added into closing in advance in the material that step 2 obtains, mix the back and form full batching;
Step 4: get full batching, zirconium ballstone that step 3 obtains, and deionized water, be positioned over the interior ball milling of ball mill 12 hours, form the ball milling material, wherein, full batching: the zirconium ballstone: the mass ratio of deionized water is 1: 1: 2.5;
Step 5: the ball milling material that step 4 is obtained moves in the baking oven, 100 ℃ of oven dry, forming the oven dry material, then, is that 5% polyvinyl alcohol water solution as tackiness agent is added in the oven dry material and carries out granulation with concentration, form the granulation material, then, the granulation material is crossed 60 mesh sieves, wherein, according to the quality meter, 7% of binder constitutes oven dry material;
Step 6: the granulation material that step 5 is obtained moves in the metal mould, with pressing machine the granulation material is pressed under the pressure of 120Mpa
The disk sample;
Step 7: it is in the aluminum oxide saggar of backing plate that the sample that step 6 is obtained is placed on the zirconium white, space 2mm between the sample;
Step 8: moving into sintering in the high-temperature electric resistance furnace, in the atmosphere of pure nitrogen gas, is that 3 ℃/min heats up with heat-up rate, insulation is 30 minutes when temperature reaches 120 ℃, and insulation is 30 minutes when temperature reaches 450 ℃, and insulation is 2 hours when temperature reaches 1340 ℃, afterwards, with 5 ℃/min cooling, when temperature is reduced to 1140 ℃, regulate high-temperature electric resistance furnace, make and be air atmosphere in the stove, and be incubated 2 hours, subsequently, cool to room temperature with the furnace;
Step 9: after the surface-conditioning of the sample that step 8 is sintered, evenly apply the ohmic contact aluminum electrode slurry,, promptly make BaTiO 500 ℃ of sintering 10 minutes at tow sides
3The based PTC thermal sensitive ceramic material sample.
Embodiment four
Step 1: according to mol ratio is to take by weighing BaCO at 0.95: 0.04: 0.01
3, Bi
2O
3, and K
2CO
3, mix the back and form mixture A, then, take by weighing TiO
2, with TiO
2Is to mix at 1: 1 to form mixture B with mixture A according to mol ratio;
Step 2: according to mass ratio is to take by weighing mixture B and zirconium ballstone and the deionized water that step 1 obtains at 1: 1: 2.5, it is positioned over ball milling moves in the baking oven in the ball grinder after 10 hours, 100 ℃ of oven dry, then, be passed in the high-temperature electric resistance furnace 1170 ℃ of insulations 2 hours, form and close material in advance, standby;
Step 3: with major ingredient mixture B is 1mol, takes by weighing the Nb that accounts for major ingredient 0.3mol% according to molar content
2O
5, 0.25mol% Y
2O
3, 0.05mol% Mn (NO
3)
2, and the Sb of 0.35mol%
2O
3, then, with above-mentioned Nb
2O
5, Y
2O
3, Mn (NO
3)
2, and Sb
2O
3Be added into closing in advance in the material that step 2 obtains, mix the back and form full batching;
Step 4: get full batching, zirconium ballstone that step 3 obtains, and deionized water, be positioned over the interior ball milling of ball mill 12 hours, form the ball milling material, wherein, full batching: the zirconium ballstone: the mass ratio of deionized water is 1: 1: 2.5;
Step 5: the ball milling material that step 4 is obtained moves in the baking oven, 100 ℃ of oven dry, forming the oven dry material, then, is that 5.5% polyvinyl alcohol water solution as tackiness agent is added in the oven dry material and carries out granulation with concentration, form the granulation material, then, the granulation material is crossed 60 mesh sieves, wherein, according to the quality meter, 6.5% of binder constitutes oven dry material;
Step 6: the granulation material that step 5 is obtained moves in the metal mould, with pressing machine the granulation material is pressed under the pressure of 120Mpa
The disk sample;
Step 7: it is in the aluminum oxide saggar of backing plate that the sample that step 6 is obtained is placed on the zirconium white, space 2mm between the sample;
Step 8: moving into sintering in the high-temperature electric resistance furnace, in the atmosphere of pure nitrogen gas, is that 3 ℃/min heats up with heat-up rate, insulation is 30 minutes when temperature reaches 120 ℃, and insulation is 30 minutes when temperature reaches 450 ℃, and insulation is 2 hours when temperature reaches 1300 ℃, afterwards, with 5 ℃/min cooling, when temperature reaches 980 ℃, regulate high-temperature electric resistance furnace, make and be air atmosphere in the stove, and be incubated 1.5 hours, subsequently, cool to room temperature with the furnace;
Step 9: after the surface-conditioning of the sample that step 8 is sintered, evenly apply the ohmic contact aluminum electrode slurry,, promptly make BaTiO 500 ℃ of sintering 10 minutes at tow sides
3The based PTC thermal sensitive ceramic material sample.
Embodiment five
Step 1: according to mol ratio is to take by weighing BaCO at 0.94: 0.03: 0.03
3, Bi
2O
3, and K
2CO
3, mix the back and form mixture A, then, take by weighing TiO
2, with TiO
2Is to mix at 1: 1 to form mixture B with mixture A according to mol ratio;
Step 2: according to mass ratio is to take by weighing mixture B and zirconium ballstone and the deionized water that step 1 obtains at 1: 1: 2.5, it is positioned over ball milling moves in the baking oven in the ball grinder after 10 hours, 100 ℃ of oven dry, then, be passed in the high-temperature electric resistance furnace 1180 ℃ of insulations 2 hours, form and close material in advance, standby;
Step 3: with major ingredient mixture B is 1mol, takes by weighing the Nb that accounts for major ingredient 0.28mol% according to molar content
2O
5, 0.32mol% Y
2O
3, 0.04mol% Mn (NO
3)
2, and the Sb of 0.28mol%
2O
3, then, with above-mentioned Nb
2O
5, Y
2O
3, Mn (NO
3)
2, and Sb
2O
3Be added into closing in advance in the material that step 2 obtains, mix the back and form full batching;
Step 4: get full batching, zirconium ballstone that step 3 obtains, and deionized water, be positioned over the interior ball milling of ball mill 12 hours, form the ball milling material, wherein, full batching: the zirconium ballstone: the mass ratio of deionized water is 1: 1: 2.5;
Step 5: the ball milling material that step 4 is obtained moves in the baking oven, 100 ℃ of oven dry, forming the oven dry material, then, is that 5% polyvinyl alcohol water solution as tackiness agent is added in the oven dry material and carries out granulation with concentration, form the granulation material, then, the granulation material is crossed 60 mesh sieves, wherein, according to the quality meter, 6% of binder constitutes oven dry material;
Step 6: the granulation material that step 5 is obtained moves in the metal mould, with pressing machine the granulation material is pressed under the pressure of 120Mpa
The disk sample;
Step 7: it is in the aluminum oxide saggar of backing plate that the sample that step 6 is obtained is placed on the zirconium white, space 2mm between the sample;
Step 8: moving into sintering in the high-temperature electric resistance furnace, in the atmosphere of pure nitrogen gas, is that 3 ℃/min heats up with heat-up rate, insulation is 30 minutes when temperature reaches 120 ℃, and insulation is 30 minutes when temperature reaches 450 ℃, and insulation is 2 hours when temperature reaches 1315 ℃, afterwards, with 5 ℃/min cooling, when temperature reaches 1080 ℃, regulate high-temperature electric resistance furnace, make and be air atmosphere in the stove, and be incubated 2 hours, subsequently, cool to room temperature with the furnace;
Step 9: after the surface-conditioning of the sample that step 8 is sintered, evenly apply the ohmic contact aluminum electrode slurry,, promptly make BaTiO 500 ℃ of sintering 10 minutes at tow sides
3The based PTC thermal sensitive ceramic material sample.
Embodiment six
Step 1: according to mol ratio is to take by weighing BaCO at 0.93: 0.025: 0.045
3, Bi
2O
3, and K
2CO
3, mix the back and form mixture A, then, take by weighing TiO
2, with TiO
2Is to mix at 1: 1 to form mixture B with mixture A according to mol ratio;
Step 2: according to mass ratio is to take by weighing mixture B and zirconium ballstone and the deionized water that step 1 obtains at 1: 1: 2.5, it is positioned over ball milling moves in the baking oven in the ball grinder after 10 hours, 100 ℃ of oven dry, then, be passed in the high-temperature electric resistance furnace 1200 ℃ of insulations 2 hours, form and close material in advance, standby;
Step 3: with major ingredient mixture B is 1mol, takes by weighing the Nb that accounts for major ingredient 0.5mol% according to molar content
2O
5, 0.2mol% Y
2O
3, 0.02mol% Mn (NO
3)
2, and the Sb of 0.25mol%
2O
3, then, with above-mentioned Nb
2O
5, Y
2O
3, Mn (NO
3)
2, and Sb
2O
3Be added into closing in advance in the material that step 2 obtains, mix the back and form full batching;
Step 4: get full batching, zirconium ballstone that step 3 obtains, and deionized water, be positioned over the interior ball milling of ball mill 12 hours, form the ball milling material, wherein, full batching: the zirconium ballstone: the mass ratio of deionized water is 1: 1: 2.5;
Step 5: the ball milling material that step 4 is obtained moves in the baking oven, 100 ℃ of oven dry, forming the oven dry material, then, is that 5.5% polyvinyl alcohol water solution as tackiness agent is added in the oven dry material and carries out granulation with concentration, form the granulation material, then, the granulation material is crossed 60 mesh sieves, wherein, according to the quality meter, 5% of binder constitutes oven dry material;
Step 6: the granulation material that step 5 is obtained moves in the metal mould, with pressing machine the granulation material is pressed under the pressure of 120Mpa
The disk sample;
Step 7: it is in the aluminum oxide saggar of backing plate that the sample that step 6 is obtained is placed on the zirconium white, space 2mm between the sample;
Step 8: moving into sintering in the high-temperature electric resistance furnace, in the atmosphere of pure nitrogen gas, is that 3 ℃/min heats up with heat-up rate, insulation is 30 minutes when temperature reaches 120 ℃, and insulation is 30 minutes when temperature reaches 450 ℃, and insulation is 2 hours when temperature reaches 1315 ℃, afterwards, with 5 ℃/min cooling, when temperature reaches 1000 ℃, regulate high-temperature electric resistance furnace, make and be air atmosphere in the stove, and be incubated 3.5 hours, subsequently, cool to room temperature with the furnace;
Step 9: after the surface-conditioning of the sample that step 8 is sintered, evenly apply the ohmic contact aluminum electrode slurry,, promptly make BaTiO 500 ℃ of sintering 10 minutes at tow sides
3The based PTC thermal sensitive ceramic material sample.
Embodiment seven
Step 1: according to mol ratio is to take by weighing BaCO at 0.9: 0.05: 0.05
3, Bi
2O
3, and K
2CO
3, mix the back and form mixture A, then, take by weighing TiO
2, with TiO
2Is to mix at 1: 1 to form mixture B with mixture A according to mol ratio;
Step 2: according to mass ratio is to take by weighing mixture B and zirconium ballstone and the deionized water that step 1 obtains at 1: 1: 2.5, it is positioned over ball milling moves in the baking oven in the ball grinder after 10 hours, 100 ℃ of oven dry, then, be passed in the high-temperature electric resistance furnace 1000 ℃ of insulations 2 hours, form and close material in advance, standby;
Step 3: with major ingredient mixture B is 1mol, takes by weighing the Nb that accounts for major ingredient 0.75mol% according to molar content
2O
5, 0.5mol% Y
2O
3, 0.15mol% Mn (NO
3)
2, and the Sb of 0.55mol%
2O
3, then, with above-mentioned Nb
2O
5, Y
2O
3, Mn (NO
3)
2, and Sb
2O
3Be added into closing in advance in the material that step 2 obtains, mix the back and form full batching;
Step 4: get full batching, zirconium ballstone that step 3 obtains, and deionized water, be positioned over the interior ball milling of ball mill 12 hours, form the ball milling material, wherein, full batching: the zirconium ballstone: the mass ratio of deionized water is 1: 1: 2.5;
Step 5: the ball milling material that step 4 is obtained moves in the baking oven, 100 ℃ of oven dry, forming the oven dry material, then, is that 7% polyvinyl alcohol water solution as tackiness agent is added in the oven dry material and carries out granulation with concentration, form the granulation material, then, the granulation material is crossed 60 mesh sieves, wherein, according to the quality meter, 4.5% of binder constitutes oven dry material;
Step 6: the granulation material that step 5 is obtained moves in the metal mould, with pressing machine the granulation material is pressed under the pressure of 120Mpa
The disk sample;
Step 7: it is in the aluminum oxide saggar of backing plate that the sample that step 6 is obtained is placed on the zirconium white, space 2mm between the sample;
Step 8: moving into sintering in the high-temperature electric resistance furnace, in the atmosphere of pure nitrogen gas, is that 3 ℃/min heats up with heat-up rate, insulation is 30 minutes when temperature reaches 120 ℃, and insulation is 30 minutes when temperature reaches 450 ℃, and insulation is 2 hours when temperature reaches 1300 ℃, afterwards, with 5 ℃/min cooling, when temperature reaches 900 ℃, regulate high-temperature electric resistance furnace, make and be air atmosphere in the stove, and be incubated 1.5 hours, subsequently, cool to room temperature with the furnace;
Step 9: after the surface-conditioning of the sample that step 8 is sintered, evenly apply the ohmic contact aluminum electrode slurry,, promptly make BaTiO 500 ℃ of sintering 10 minutes at tow sides
3The based PTC thermal sensitive ceramic material sample.
Embodiment eight
Step 1: according to mol ratio is to take by weighing BaCO at 0.92: 0.04: 0.04
3, Bi
2O
3, and K
2CO
3, mix the back and form mixture A, then, take by weighing TiO
2, with TiO
2Is to mix at 1: 1 to form mixture B with mixture A according to mol ratio;
Step 2: according to mass ratio is to take by weighing mixture B and zirconium ballstone and the deionized water that step 1 obtains at 1: 1: 2.5, it is positioned over ball milling moves in the baking oven in the ball grinder after 10 hours, 100 ℃ of oven dry, then, be passed in the high-temperature electric resistance furnace 1130 ℃ of insulations 2 hours, form and close material in advance, standby;
Step 3: with major ingredient mixture B is 1mol, takes by weighing the Nb that accounts for major ingredient 0.65mol% according to molar content
2O
5, 0.55mol% Y
2O
3, 0.2mol% Mn (NO
3)
2, and the Sb of 0.65mol%
2O
3, then, with above-mentioned Nb
2O
5, Y
2O
3, Mn (NO
3)
2, and Sb
2O
3Be added into closing in advance in the material that step 2 obtains, mix the back and form full batching;
Step 4: get full batching, zirconium ballstone that step 3 obtains, and deionized water, be positioned over the interior ball milling of ball mill 12 hours, form the ball milling material, wherein, full batching: the zirconium ballstone: the mass ratio of deionized water is 1: 1: 2.5;
Step 5: the ball milling material that step 4 is obtained moves in the baking oven, 100 ℃ of oven dry, forming the oven dry material, then, is that 8% polyvinyl alcohol water solution as tackiness agent is added in the oven dry material and carries out granulation with concentration, form the granulation material, then, the granulation material is crossed 60 mesh sieves, wherein, according to the quality meter, 4% of binder constitutes oven dry material;
Step 6: the granulation material that step 5 is obtained moves in the metal mould, with pressing machine the granulation material is pressed under the pressure of 120Mpa
The disk sample;
Step 7: it is in the aluminum oxide saggar of backing plate that the sample that step 6 is obtained is placed on the zirconium white, space 2mm between the sample;
Step 8: moving into sintering in the high-temperature electric resistance furnace, in the atmosphere of pure nitrogen gas, is that 3 ℃/min heats up with heat-up rate, insulation is 30 minutes when temperature reaches 120 ℃, and insulation is 30 minutes when temperature reaches 450 ℃, and insulation is 2 hours when temperature reaches 1310 ℃, afterwards, with 5 ℃/min cooling, when temperature reaches 1000 ℃, regulate high-temperature electric resistance furnace, make and be air atmosphere in the stove, and be incubated 2 hours, subsequently, cool to room temperature with the furnace;
Step 9: after the surface-conditioning of the sample that step 8 is sintered, evenly apply the ohmic contact aluminum electrode slurry,, promptly make BaTiO 500 ℃ of sintering 10 minutes at tow sides
3The based PTC thermal sensitive ceramic material sample.
After testing, the performance perameter of ceramics sample of the present invention is as follows:
| Room temperature resistivity (ρ RT)/Ω·cm | Curie temperature (Tc)/℃ | Liftdrag [lg (ρ max/ρ min)] | |
| Embodiment one | ?126 | ??171 | ??3.2×10 3 |
| Room temperature resistivity (ρ RT)/Ω·cm | Curie temperature (Tc)/℃ | Liftdrag [lg (ρ max/ρ min)] | |
| Embodiment two | ?102 | ??152 | ??2.8×10 3 |
| Embodiment three | ?96 | ??143 | ??2.3×10 3 |
| Embodiment four | ?123 | ??175 | ??3.6×10 3 |
| Embodiment five | ?138 | ??168 | ??2.9×10 3 |
| Embodiment six | ?152 | ??163 | ??4.3×10 3 |
| Embodiment seven | ?197 | ??185 | ??1.9×10 3 |
| Embodiment eight | ?110 | ??178 | ??3.5×10 3 |
The above only is one embodiment of the present invention, it or not whole or unique embodiment, the conversion of any equivalence that those of ordinary skills take technical solution of the present invention by reading specification sheets of the present invention is claim of the present invention and contains.
Claims (5)
1.BaTiO
3The preparation method of based PTC thermal sensitive ceramic material is characterized in that: may further comprise the steps:
Step 1: according to mol ratio is (0.9～0.99): (0.005～0.05): (0.005～0.05) takes by weighing BaCO
3, Bi
2O
3, and K
2CO
3, mix the back and form mixture A, then, take by weighing TiO
2, with TiO
2Is to mix at 1: 1 to form mixture B with mixture A according to mol ratio;
Step 2: get mixture B, zirconium ballstone respectively, and deionized water, according to mass ratio be carry out ball milling, oven dry successively after mixing at 1: 1: 2.5 after, be passed in the high-temperature electric resistance furnace to form in 2 hours and close material in advance 1000～1230 ℃ of insulations, standby;
Step 3: in mixture B is 1mol, gets the Nb of 0.1～0.75mol% respectively according to molar content
2O
5, 0.1～0.55mol% Y
2O
3, 0.15～0.2mol% Mn (NO
3)
2Sb with 0.1～0.65mol%
2O
3As auxiliary material, then, auxiliary material is added into closing in advance in the material that step 2 obtains, mix the back and form full batching;
Step 4: getting full batching, zirconium ballstone that step 3 obtains respectively, and deionized water, is to carry out ball milling, oven dry, granulation successively after mixing at 1: 1: 2.5 according to mass ratio, forms the granulation material, sieves then;
Step 5: the granulation material after step 4 sieved is pressed into sample under the pressure of 120MPa, then, be placed on the zirconium white is to move into high-temperature electric resistance furnace in the aluminum oxide saggar of backing plate, be under the condition of pure nitrogen gas atmosphere in electric furnace, heat up with 3 ℃/min, when reaching 120 ℃, 450 ℃ respectively, temperature respectively is incubated 30 minutes, insulation is 2～3 hours when temperature rises to 1300～1340 ℃, afterwards, with 5 ℃/min cooling, when temperature reaches 1100 ℃～900 ℃, the adjusting electric furnace makes and is air atmosphere in it, and be incubated 1.5～3.5 hours, subsequently, cool to room temperature with the furnace;
Step 6; Behind the sample that cleaning step five sinters,,, promptly make BaTiO 500 ℃ of sintering 10 minutes at the even electrode coated slurry of tow sides
3The based PTC thermal sensitive ceramic material sample.
2. BaTiO as claimed in claim 1
3The preparation method of based PTC thermal sensitive ceramic material is characterized in that: in the step 4, the ball milling time is 10 hours, behind the ball milling, 100 ℃ of oven dry.
3. BaTiO as claimed in claim 1
3The preparation method of based PTC thermal sensitive ceramic material, it is characterized in that: in the step 4, form the oven dry material after full batching, zirconium ballstone and deionized water mixing, ball milling, the oven dry, then, with mass concentration is that 4～8% tackiness agent is added in the oven dry material and carries out granulation, 4～8% of binder constitutes oven dry material.
4. BaTiO as claimed in claim 3
3The preparation method of based PTC thermal sensitive ceramic material is characterized in that: described tackiness agent is selected from polyvinyl alcohol water solution.
5. the BaTiO for preparing according to any one preparation method in the claim 1 to 4
3Based PTC thermal sensitive ceramic material is characterized in that: major ingredient is for being TiO
2, BaCO
3, Bi
2O
3, and K
2CO
3, its mol ratio is 1: (0.9～0.99): (0.005～0.05): (0.005～0.05), dressing are Nb
2O
5, Y
2O
3, Mn (NO
3)
2And Sb
2O
3, wherein, according to molar content meter, Nb
2O
5Account for 0.1～0.75% of major ingredient, Y
2O
3Account for 0.1～0.55% of major ingredient, Mn (NO
3)
2Account for 0.15～0.2% of major ingredient, Sb
2O
3Account for 0.1～0.65% of major ingredient.
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| CN102503414A (en) * | 2011-11-09 | 2012-06-20 | 中南大学 | High-Curie temperature (Tc) lead-free positive temperature coefficient (PTC) thermal sensitive ceramic material |
| CN103011835A (en) * | 2012-11-28 | 2013-04-03 | 大连大友高技术陶瓷有限公司 | Production process of high-compactness compound ceramic ball bearing rolling element |
| CN103030406A (en) * | 2013-01-02 | 2013-04-10 | 桂林理工大学 | Ptc ceramic sintering method |
| CN104609853A (en) * | 2015-01-28 | 2015-05-13 | 陕西科技大学 | BaTiO3 based lead-free PTC thermistor ceramic material added with SiO2 and having high Curie point and preparation method thereof |
| CN108147809A (en) * | 2018-02-06 | 2018-06-12 | 北京元六鸿远电子科技股份有限公司 | Low temperature sintering barium-titanium series microwave dielectric material and preparation method |
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| CN104609853A (en) * | 2015-01-28 | 2015-05-13 | 陕西科技大学 | BaTiO3 based lead-free PTC thermistor ceramic material added with SiO2 and having high Curie point and preparation method thereof |
| CN108164252A (en) * | 2017-12-12 | 2018-06-15 | 孝感华工高理电子有限公司 | A kind of PTC raw powder's production technologies |
| CN108147809A (en) * | 2018-02-06 | 2018-06-12 | 北京元六鸿远电子科技股份有限公司 | Low temperature sintering barium-titanium series microwave dielectric material and preparation method |
| CN108147809B (en) * | 2018-02-06 | 2022-07-12 | 北京元六鸿远电子科技股份有限公司 | Medium-low temperature sintered barium-titanium series microwave dielectric material and preparation method thereof |
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