CN101402524B - Low-resistance, high-overpressure resistance barium titanate based ceramic thermal resistance and method of manufacturing the same - Google Patents
Low-resistance, high-overpressure resistance barium titanate based ceramic thermal resistance and method of manufacturing the same Download PDFInfo
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- CN101402524B CN101402524B CN2008102350682A CN200810235068A CN101402524B CN 101402524 B CN101402524 B CN 101402524B CN 2008102350682 A CN2008102350682 A CN 2008102350682A CN 200810235068 A CN200810235068 A CN 200810235068A CN 101402524 B CN101402524 B CN 101402524B
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Abstract
The invention relates to a barium-titanate-based ceramic thermistor with a low resistance and high withstand voltage and a method for preparing the same. The method comprises the following steps: based on a quarternary system of BaTiO3-SrTiO3-CaTiO3-PbTiO3 and a crystal boundary adjustment phase (Ba2TiSi2O8, SiO2 and Li2O), doping two donor elements yttrium (Y) and niobium (Nb) and two acceptor elements manganese (Mn) and copper (Cu) through non-homogeneous precipitation to form composite micro powders with high reactivity, and sintering the composite micro powders into ceramic, wherein the Ba2TiSi2O8 in the crystal boundary adjustment phase is formed by pre-sintering the SiO2, BaCO3 and TiO2 according to a certain proportion, and the non-homogeneous precipitation is performed in a ballmill or a mixing mill under the condition that the pH value is between 8.5 and 12. The low resistance high-pressure resistant barium-titanate-based ceramic thermistor has the advantages of even distribution of the donor and the acceptor elements, low ceramic sintering temperature, low resistivity, high withstand voltage, short process flow, and suitability for large-scale production.
Description
One, technical field
The invention belongs to ceramic material and device manufacturing technology field, particularly a kind of low-resistance, high-overpressure resistance barium titanate based ceramic thermal resistance and preparation method thereof.
Two, background technology
Barium titanate-based positive temperature coefficient resistance (Positive Temperature coefficient Resistance is called for short PTCR) ceramic material is a kind of Ferro-Electric Semiconductor material.Because the PTCR pottery has temperature sensitive, straight control, characteristics such as energy-conservation and safe, with and " switch " function automatically such as distinctive temperature-sensitive, current limliting, time-delay, be widely used in every field such as communication, space flight and aviation, semiconductor lighting, auto industry, household electrical appliance.
Along with an urgent demand to the big electric current of PTCR element, miniaturization, low-resistance barium titanate based ceramic technology of preparing arouses attention.Chinese patent CN1137679A discloses the manufacture method of the thermistor that a kind of powder semiconductor ceramic material with positive temperature coefficient constitutes, pottery mainly consist of BaTiO
3, SrTiO
3And PbTiO
3, adopt two alms giver's antimony (Sb) and niobiums (Nb) and mixed by main manganese (Mn), make the thermistor of room temperature resistivity by regulation and control batching and system of heat treatment process less than 3.0 Ω cm, the withstand voltage 150V/mm of being higher than.To the twentieth century end, the electricalresistivity of barium titanate-based PTC R pottery has reached 8 Ω cm, but because the resistivity of material is low, resistance-temperature characteristic is worsened, and the proof voltage intensity decreases is subjected to the restriction of working voltage and is difficult to obtain use.Chinese patent CN1247842A discloses a kind of ceramic material of the PTC of being used for thermistor and has formed and the preparation method, the room temperature resistivity of thermistor is 5 Ω cm, it is 60V/mm that static state can be born voltage, and the related ceramic major constituent of this patent is 30～97 moles of %BaTiO
3, 1～50 mole of %PbTiO3,1～30 mole of %SrTiO
3With 1～25 mole of %CaTiO
3, and doped chemical Sm (0.1～0.3 mole of %), Mn (0.01～0.03 mole of %) and Si (0～2.0 mole of %), simultaneously, in heat treatment process, need to adopt special atmosphere system, higher temperature (1400 ℃) and longer reaction time.
Up to the present, reduce the room temperature resistivity of barium titanate based ceramic thermal resistance and the difficult problem that its withstand voltage properties of raising is still the present technique field.Simultaneously, the traditional preparation process technological process of thermistor is long, the sintering temperature height, and properties of product instability, its key technology are how to adopt better simply manufacturing process and technology to realize that ceramic material is formed, effective regulation and control of microstructure.
Three, summary of the invention
Technical problem: the present invention adopts better simply preparation technology, and a kind of low-resistivity, high withstand voltage barium titanate based ceramic thermal resistance material and preparation method thereof are provided.
Technical scheme: the present invention is achieved through the following technical solutions:
A kind of low-resistance, high-overpressure resistance barium titanate based ceramic thermal resistance contain: BaTiO
3-SrTiO
3-CaTiO
3-PbTiO
3Quaternary system, crystal boundary are regulated mutually and additive:
Described BaTiO
3-SrTiO
3-CaTiO
3-PbTiO
3Quaternary is a principal component, per 100 moles of described BaTiO
3-SrTiO
3-CaTiO
3-PbTiO
3Consisting of of quaternary system principal component:
60～90 moles of BaTiO
3,
5～18 moles of SrTiO
3,
1～15 mole of CaTiO
3,
Surplus is PbTiO
3
Described crystal boundary is regulated: Ba
2TiSi
2O
8, nanometer SiO
2And Li
2O, three's molal quantity are respectively 0.1～1%, 1.5～2.5% and 0.09～0.12% of above-mentioned quaternary system principal component total mole number;
Described additive is: containing in the manganese compound Cu element in the Mn element and copper-containing compound, the amount of substance sum is 0.05～0.08% Mn+Cu of above-mentioned quaternary system principal component total mole number; And containing in the yttrium compound Y element and to contain Nb element in the niobium compound, the amount of substance sum is 0.2～0.5% Y+Nb of above-mentioned quaternary system principal component total mole number.
The method for preparing above-mentioned low-resistance, high-overpressure resistance barium titanate based ceramic thermal resistance, step is:
A. quaternary system is prepared burden: get BaTiO
3, SrTiO
3, CaCO
3Form the quaternary system base stock with PbO, make consisting of of per 100 moles of described quaternary system base stocks: 60～90 moles of BaTiO
3, 5～18 moles of SrTiO
3, 1～15 mole of CaCO
3, surplus is PbO; Get TiO again
2Add in the described quaternary system base stock, quaternary system batching, add TiO
2Molal quantity be CaCO in the described quaternary system base stock
3With PbO molal quantity sum;
B. Muffle furnace pyroreaction: with SiO
2, BaCO
3And TiO
2Powder is SiO by mole ratio
2: BaCO
3: TiO
2=2:2:1 mixes, SiO
2, BaCO
3And TiO
2Molal quantity account for 0.2～2%, 0.2～2% and 0.1～1% of the total mole number of quaternary system base stock described in the step a respectively, in Muffle furnace, carry out pyroreaction, be reflected at and carried out under 1150 ℃ 10 hours, generate Ba
2TiSi
2O
8, ball milling 10 hours is to the following powder of 3 μ m then;
C. the preparation of solid-phase powder material: the quaternary system batching that step a is obtained, the Ba that step b obtains
2TiSi
2O
8Powder mixes, and adds nanometer SiO again
2And Li
2CO
3, described nanometer SiO
2And Li
2CO
3Addition be respectively 1.5～2.5% and 0.09～0.12% of the total mole number of quaternary system base stock described in the step a, obtain solid-phase powder material;
D. the preparation of soluble metal saline solution: get and contain the manganese soluble metallic salt, the cupric soluble metallic salt, contain the yttrium soluble metallic salt and contain the niobium soluble metallic salt and mix, and be dissolved in water, the addition of each component meets the following conditions: containing Mn in the manganese soluble metallic salt and the molal quantity sum of the Cu in the cupric soluble metallic salt is 0.05～0.08% of the total mole number of quaternary system base stock described in the step a, contain in the yttrium soluble metallic salt Y and with the molal quantity sum that contains the Nb in the niobium soluble metallic salt be 0.2～0.5% of the total mole number of quaternary system base stock described in the step a;
E. non-homogeneous phase deposition reaction: the mixing soluble metal saline solution that the solid-phase powder material that obtains with step c is solid phase, obtain with steps d is a liquid phase, in ball mill or mixer, adopt ammoniacal liquor regulator solution pH value between 8.5～12, carry out the non-homogeneous phase deposition reaction, react after 10～24 hours, make the high reaction activity composite granule of particle diameter below 2 μ m after filtration;
F. back procedure of processing: in the above-mentioned high reaction activity composite granule that makes, add mass percent concentration and be 5% polyvinyl alcohol water solution and carry out mist projection granulating, the addition of described polyvinyl alcohol water solution is a powder total weight 12%, make powder particles be distributed in 50～180 mu m ranges after the granulation, water content is 0.18～0.28%, flow angle is 25～35 °; After then the powder after the granulation being packed into mould, make blank forming; Again blank is carried out sintering, obtain containing BaTiO
3-SrTiO
3-CaTiO
3-PbTiO
3Quaternary system, crystal boundary are regulated mutually and the composite material of additive, carry out abrasive disc processing and top electrode at last, make ceramic thermal resistance.
Wherein, among the preparation process d, described contain manganese soluble metallic salt, cupric soluble metallic salt, contain the yttrium soluble metallic salt and contain the niobium soluble metallic salt be respectively manganese nitrate, copper nitrate, yttrium nitrate and niobium chloride.
Wherein, among the preparation process f, described sintering step carries out in tunnel cave, step for 1. by room temperature with per hour 200～250 ℃ be warming up to 950 ℃, be incubated 40～60 minutes; 2. with per hour 700 ℃ be warming up to 1310 ℃ from 950 ℃, be incubated 40～60 minutes; 3. with per hour 100～120 ℃ be cooled to 1120 ℃ at a slow speed from 1310 ℃, naturally cool to then below 200 ℃ and come out of the stove.
Beneficial effect: the invention provides a kind of low-resistivity, high withstand voltage barium titanate based ceramic thermal resistance and preparation method thereof.Compared with the prior art, the present invention has following beneficial effect:
Barium titanate based ceramic thermal resistance product disclosed by the invention mixes the Ca of high level in principal crystalline phase, can reach the purpose that stops crystal grain-growth, make product obtain the compact tissue structure, improve the high voltage withstanding performance of final resistance product, improve the flatness of resistance product resistance temperature (R-T) curve bottom; An amount of simultaneously Ba that adds
2TiSi
2O
8, nanometer SiO
2And Li
2O regulates phase as the crystal boundary in the reaction system, can reduce the resistivity of resistance product; Could produce good technique effect after four kinds of composition combinations of quaternary system are collaborative; There are the collaborative problem of combination too in the donor element that mixes (Y and Nb), recipient element (Mn and Cu): the one, and collaborative between collaborative, the recipient element between donor element, the 2nd, the combination of executing between the recipient element is collaborative.
The preparation method of barium titanate based ceramic thermal resistance product disclosed by the invention is at BaTiO
3-SrTiO
3-CaTiO
3-PbTiO
3Quaternary system is regulated (Ba mutually with crystal boundary
2TiSi
2O
8, SiO
2And Li
2O) on the basis, mix two donor element yttriums (Y) and niobium (Nb), two recipient element manganese (Mn) and copper (Cu) by non-homogeneous phase deposition, the non-homogeneous phase deposition method that is adopted makes and executes recipient element and evenly distribute, and formation has the composite granule of high reaction activity; Adopt non-homogeneous phase deposition also can make the unification of traditional batch mixing and grinding process, shortened technological process, can improve raw material availability simultaneously and pollute with reducing.In addition, at firing process, adopt cooling at a slow speed, fully the oxidation crystal boundary obtains thicker crystal boundary potential barrier.
Four, description of drawings
Fig. 1 is thermistor resistance-warm curve chart.
Wherein, PTC01, PTC02, PTC03 are respectively the resistance-warm curve of the low-resistance that makes among the embodiment 1 to 3, high withstand voltage ceramic thermal resistance.PTC04, PTC05 are the resistance-warm curve of the ceramic thermal resistance of prior art example 1,2 acquisitions of prior art example.
Five, embodiment
Following description is to specify of the present invention, should not regard limitation of the invention as.
Embodiment 1
A kind of low-resistance, high-overpressure resistance barium titanate based ceramic thermal resistance contain: BaTiO
3-SrTiO
3-CaTiO
3-PbTiO
3Quaternary system, crystal boundary are regulated mutually and additive: described BaTiO
3-SrTiO
3-CaTiO
3-PbTiO
3Quaternary is a principal component, contains in per 100 moles of these quaternary system principal components: 60 moles of BaTiO
3, 18 moles of SrTiO
3, 15 moles of CaTiO
3With 7 moles of PbTiO
3Described crystal boundary is regulated: Ba
2TiSi
2O
8, nanometer SiO
2And Li
2O, three's molal quantity are respectively 0.5%, 1.5% and 0.09% of above-mentioned quaternary system principal component total mole number; Described additive is: containing in the manganese compound Cu element in the Mn element and copper-containing compound, the amount of substance sum is 0.07% Mn+Cu of above-mentioned quaternary system principal component total mole number; And containing in the yttrium compound Y element and to contain Nb element in the niobium compound, the amount of substance sum is 0.25% Y+Nb of above-mentioned quaternary system principal component total mole number.
The step for preparing above-mentioned low-resistance, high-overpressure resistance barium titanate based ceramic thermal resistance is:
Step a, quaternary system batching: get BaTiO
3, SrTiO
3, CaCO
3Form the quaternary system base stock with PbO, make consisting of of per 100 moles of described quaternary system base stocks: 60 moles of BaTiO
3, 18 moles of SrTiO
3, 15 moles of CaCO
3, 7 moles of PbO; Get TiO again
2Add in the described quaternary system base stock, quaternary system batching, add TiO
2Molal quantity be CaCO in the described quaternary system base stock
3With PbO molal quantity sum;
Step b, Muffle furnace pyroreaction: mix SiO
2, BaCO
3And TiO
2Powder, SiO
2, BaCO
3And TiO
2Molal quantity be respectively 1%, 1% and 0.5% of the total mole number of quaternary system base stock described in the step a, in Muffle furnace, carry out pyroreaction, be reflected at and carried out under 1150 ℃ 10 hours, generate Ba
2TiSi
2O
8, ball milling 10 hours is to the following powder of 3 μ m then;
Step c, the preparation of solid-phase powder material: the quaternary system batching that step a is obtained, the Ba that step b obtains
2TiSi
2O
8Powder mixes, and adds nanometer SiO again
2And Li
2CO
3, described nanometer SiO
2And Li
2CO
3Addition be respectively 1.5% and 0.09% of the total mole number of quaternary system base stock described in the step a, obtain solid-phase powder material
Steps d, the preparation of soluble metal saline solution: get manganese nitrate, copper nitrate, yttrium nitrate and niobium chloride and mix, and be dissolved in water, the addition of each component meets the following conditions: Mn in the manganese nitrate and the molal quantity sum of the Cu in the copper nitrate are 0.07% of the total mole number of quaternary system base stock described in the step a, and Y in the yttrium nitrate and the molal quantity sum of the Nb in the niobium chloride are 0.25% of the total mole number of quaternary system base stock described in the step a;
Step e, non-homogeneous phase deposition reaction: the mixing soluble metal saline solution that the solid-phase powder material that obtains with step c is solid phase, obtain with steps d is a liquid phase, in ball mill or mixer, adopt ammoniacal liquor regulator solution pH value between 8.5～12, carry out the non-homogeneous phase deposition reaction, react after 10～24 hours, make the high reaction activity composite granule of particle diameter below 2 μ m after filtration;
Step f, back procedure of processing: in the above-mentioned high reaction activity composite granule that makes, add mass percent concentration and be 5% polyvinyl alcohol water solution and carry out mist projection granulating, the addition of described polyvinyl alcohol water solution is a powder total weight 12%, make powder particles be distributed in 50～180 mu m ranges after the granulation, water content is 0.18～0.28%, flow angle is 25～35 °; After then the powder after the granulation being packed into mould, make blank forming; Again blank is carried out sintering, abrasive disc processing and top electrode, make ceramic thermal resistance.Wherein, sintering step carries out in tunnel cave, step for 1. by room temperature with per hour 200～250 ℃ be warming up to 950 ℃, be incubated 40～60 minutes; 2. with per hour 700 ℃ be warming up to 1310 ℃ from 950 ℃, be incubated 40～60 minutes; 3. with per hour 100～120 ℃ be cooled to 1120 ℃ at a slow speed from 1310 ℃, naturally cool to then below 200 ℃ and come out of the stove.
A kind of low-resistance, high-overpressure resistance barium titanate based ceramic thermal resistance contain: BaTiO
3-SrTiO
3-CaTiO
3-PbTiO
3Quaternary system, crystal boundary are regulated mutually and additive: described BaTiO
3-SrTiO
3-CaTiO
3-PbTiO
3Quaternary is a principal component, contains in per 100 moles of these quaternary system principal components: 75 moles of BaTiO
3, 11 moles of SrTiO
3, 8 moles of CaTiO
3With 6 moles of PbTiO
3Described crystal boundary is regulated: Ba
2TiSi
2O
8, nanometer SiO
2And Li
2O, three's molal quantity are respectively 0.1%, 2% and 0.1% of above-mentioned quaternary system principal component total mole number; Described additive is: containing in the manganese compound Cu element in the Mn element and copper-containing compound, the amount of substance sum is 0.08% Mn+Cu of above-mentioned quaternary system principal component total mole number; And containing in the yttrium compound Y element and to contain Nb element in the niobium compound, the amount of substance sum is 0.5% Y+Nb of above-mentioned quaternary system principal component total mole number.
The step for preparing above-mentioned low-resistance, high-overpressure resistance barium titanate based ceramic thermal resistance is:
Step a, quaternary system batching: get BaTiO
3, SrTiO
3, CaCO
3Form the quaternary system base stock with PbO, make consisting of of per 100 moles of described quaternary system base stocks: 75 moles of BaTiO
3, 11 moles of SrTiO
3, 8 moles of CaCO
3, 6 moles of PbO; Get TiO again
2Add in the described quaternary system base stock, quaternary system batching, add TiO
2Molal quantity be CaCO in the described quaternary system base stock
3With PbO molal quantity sum;
Step b, Muffle furnace pyroreaction: mix SiO
2, BaCO
3And TiO
2Powder, SiO
2, BaCO
3And TiO
2Molal quantity be respectively 0.2%, 0.2% and 0.1% of the total mole number of quaternary system base stock described in the step a, in Muffle furnace, carry out pyroreaction, be reflected at and carried out under 1150 ℃ 10 hours, generate Ba
2TiSi
2O
8, ball milling 10 hours is to the following powder of 3 μ m then;
Step c, the preparation of solid-phase powder material: the quaternary system batching that step a is obtained, the Ba that step b obtains
2TiSi
2O
8Powder mixes, and adds nanometer SiO again
2And Li
2CO
3, described nanometer SiO
2And Li
2CO
3Addition be respectively 2% and 0.1% of the total mole number of quaternary system base stock described in the step a, obtain solid-phase powder material;
Steps d, the preparation of soluble metal saline solution: get manganese nitrate, copper nitrate, yttrium nitrate and niobium chloride and mix, and be dissolved in water, the addition of each component meets the following conditions: Mn in the manganese nitrate and the molal quantity sum of the Cu in the copper nitrate are 0.08% of the total mole number of quaternary system base stock described in the step a, and Y in the yttrium nitrate and the molal quantity sum of the Nb in the niobium chloride are 0.5% of the total mole number of quaternary system base stock described in the step a;
Step e, non-homogeneous phase deposition reaction: the mixing soluble metal saline solution that the solid-phase powder material that obtains with step c is solid phase, obtain with steps d is a liquid phase, in ball mill or mixer, adopt ammoniacal liquor regulator solution pH value between 8.5～12, carry out the non-homogeneous phase deposition reaction, react after 10～24 hours, make the high reaction activity composite granule of particle diameter below 2 μ m after filtration;
Step f, back procedure of processing: in the above-mentioned high reaction activity composite granule that makes, add mass percent concentration and be 5% polyvinyl alcohol water solution and carry out mist projection granulating, the addition of described polyvinyl alcohol water solution is a powder total weight 12%, make powder particles be distributed in 50～180 mu m ranges after the granulation, water content is 0.18～0.28%, flow angle is 25～35 °; After then the powder after the granulation being packed into mould, make blank forming; Again blank is carried out sintering, abrasive disc processing and top electrode, make ceramic thermal resistance.Wherein, sintering step carries out in tunnel cave, step for 1. by room temperature with per hour 200～250 ℃ be warming up to 950 ℃, be incubated 40～60 minutes; 2. with per hour 700 ℃ be warming up to 1310 ℃ from 950 ℃, be incubated 40～60 minutes; 3. with per hour 100～120 ℃ be cooled to 1120 ℃ at a slow speed from 1310 ℃, naturally cool to then below 200 ℃ and come out of the stove.
A kind of low-resistance, high-overpressure resistance barium titanate based ceramic thermal resistance contain: BaTiO
3-SrTiO
3-CaTiO
3-PbTiO
3Quaternary system, crystal boundary are regulated mutually and additive: described BaTiO
3-SrTiO
3-CaTiO
3-PbTiO
3Quaternary is a principal component, contains in per 100 moles of these quaternary system principal components: 90 moles of BaTiO
3, 5 moles of SrTiO
3, 1 mole of CaTiO
3With 4 moles of PbTiO
3Described crystal boundary is regulated: Ba
2TiSi
2O
8, nanometer SiO
2And Li
2O, three's molal quantity are respectively 1%, 2.5% and 0.12% of above-mentioned quaternary system principal component total mole number; Described additive is: containing in the manganese compound Cu element in the Mn element and copper-containing compound, the amount of substance sum is 0.05% Mn+Cu of above-mentioned quaternary system principal component total mole number; And containing in the yttrium compound Y element and to contain Nb element in the niobium compound, the amount of substance sum is 0.4% Y+Nb of above-mentioned quaternary system principal component total mole number.
The step for preparing above-mentioned low-resistance, high-overpressure resistance barium titanate based ceramic thermal resistance is:
Step a, quaternary system batching: get BaTiO
3, SrTiO
3, CaCO
3Form the quaternary system base stock with PbO, make consisting of of per 100 moles of described quaternary system base stocks: 90 moles of BaTiO
3, 5 moles of SrTiO
3, 1 mole of CaCO
3, 4 moles of PbO; Get TiO again
2Add in the described quaternary system base stock, quaternary system batching, add TiO
2Molal quantity be CaCO in the described quaternary system base stock
3With PbO molal quantity sum;
Step b, Muffle furnace pyroreaction: mix SiO
2, BaCO
3And TiO
2Powder, SiO
2, BaCO
3And TiO
2Molal quantity be respectively 2%, 2% and 1% of the total mole number of quaternary system base stock described in the step a, in Muffle furnace, carry out pyroreaction, be reflected at and carried out under 1150 ℃ 10 hours, generate Ba
2TiSi
2O
8, ball milling 10 hours is to the following powder of 3 μ m then
Step c, the preparation of solid-phase powder material: the quaternary system batching that step a is obtained, the Ba that step b obtains
2TiSi
2O
8Powder mixes, and adds nanometer SiO again
2And Li
2CO
3, described nanometer SiO
2And Li
2CO
3Addition be respectively 2.5% and 0.12% of the total mole number of quaternary system base stock described in the step a, obtain solid-phase powder material;
Steps d, the preparation of soluble metal saline solution: get manganese nitrate, copper nitrate, yttrium nitrate and niobium chloride and mix, and be dissolved in water, the addition of each component meets the following conditions: Mn in the manganese nitrate and the molal quantity sum of the Cu in the copper nitrate are 0.05% of the total mole number of quaternary system base stock described in the step a, and Y in the yttrium nitrate and the molal quantity sum of the Nb in the niobium chloride are 0.4% of the total mole number of quaternary system base stock described in the step a;
Step e, non-homogeneous phase deposition reaction: the mixing soluble metal saline solution that the solid-phase powder material that obtains with step c is solid phase, obtain with steps d is a liquid phase, in ball mill or mixer, adopt ammoniacal liquor regulator solution pH value between 8.5～12, carry out the non-homogeneous phase deposition reaction, react after 10～24 hours, make the high reaction activity composite granule of particle diameter below 2 μ m after filtration;
Step f, back procedure of processing: in the above-mentioned high reaction activity composite granule that makes, add mass percent concentration and be 5% polyvinyl alcohol water solution and carry out mist projection granulating, the addition of described polyvinyl alcohol water solution is a powder total weight 12%, make powder particles be distributed in 50～180 mu m ranges after the granulation, water content is 0.18～0.28%, flow angle is 25～35 °; After then the powder after the granulation being packed into mould, make blank forming; Again blank is carried out sintering, abrasive disc processing and top electrode, make ceramic thermal resistance.Wherein, sintering step carries out in tunnel cave, step for 1. by room temperature with per hour 200～250 ℃ be warming up to 950 ℃, be incubated 40～60 minutes; 2. with per hour 700 ℃ be warming up to 1310 ℃ from 950 ℃, be incubated 40～60 minutes; 3. with per hour 100～120 ℃ be cooled to 1120 ℃ at a slow speed from 1310 ℃, naturally cool to then below 200 ℃ and come out of the stove.
Embodiment 4
Present embodiment is contrast test embodiment.
Following table is that embodiment 1 to embodiment 3 prepared barium titanate based ceramic thermal resistance is formed:
Following table is embodiment 1 to embodiment 3 a prepared barium titanate based ceramic thermal resistance unit for electrical property parameters:
| Sample number into spectrum | Curie point (℃) | Room temperature resistance value rate (ρ 25, Ω cm) | Withstand voltage (VBD, Ω/mm) | Index is than (VBD/ ρ 25) | Remarks |
| 1 | 93 | 8 | 315 | 39.4 | Embodiment 1 |
| 2 | 98 | 7 | 305 | 43.5 | |
| 3 | 95 | 8 | 312 | 39.0 | |
For comparing test, two prior art examples are provided in addition, its unit for electrical property parameters is compared with the unit for electrical property parameters of thermistor of the present invention, to show that the present invention is than the superior part of prior art.
Two kinds of composed as follows as the barium titanate based ceramic thermal resistance of prior art example:
The unit for electrical property parameters of these two kinds of existing barium titanate based ceramic thermal resistances is as follows:
| Sample number into spectrum | Curie point (℃) | Room temperature resistance value rate (ρ 25, Ω cm) | Withstand voltage (VBD, Ω/mm) | Index is than (VBD/ ρ 25) | Remarks |
| ?4 | 99 | 30 | 160 | 5.3 | Prior art example 1 |
| ?5 | 115 | 40 | 250 | 6.25 | Prior art example 2 |
More than the data of the unit for electrical property parameters of each thermistor contrast as can be known in the table: the embodiment sample that the present invention relates to has low room temperature resistivity, high withstand voltage and high target ratio, and the room temperature resistivity of comparative sample, withstand voltage and index are than the performance index that then are starkly lower than the foregoing description product.
Simultaneously, accompanying drawing 1 is thermistor resistance-warm curve chart.Wherein, PTC01, PTC02, PTC03 are respectively the resistance-warm curve of the low-resistance that makes among the embodiment 1 to 3, high withstand voltage ceramic thermal resistance.PTC04, PTC05 are the resistance-warm curve of the ceramic thermal resistance of prior art example 1,2 acquisitions of prior art example.As can be seen from this figure: the embodiment sample that the present invention relates to has low-resistance, high thermo-resistive effect, and the room temperature resistivity of comparative sample is higher, thermo-resistive effect obviously descends, and has negative temperature coefficient feature in the greenhouse to Curie-point temperature.
Claims (4)
1. a low-resistance, high-overpressure resistance barium titanate based ceramic thermal resistance is characterized in that containing: BaTiO
3-SrTiO
3-CaTiO
3-PbTiO
3Quaternary system, crystal boundary are regulated mutually and additive:
Described BaTiO
3-SrTiO
3-CaTiO
3-PbTiO
3Quaternary is a principal component, per 100 moles of BaTiO
3-SrTiO
3-CaTiO
3-PbTiO
3Consisting of of quaternary system principal component:
60～90 moles of BaTiO
3,
5～18 moles of SrTiO
3,
1～15 mole of CaTiO
3,
Surplus is PbTiO
3
Described crystal boundary is regulated: Ba
2TiSi
2O
8, nanometer SiO
2And Li
2O, three's molal quantity are respectively 0.1～1%, 1.5～2.5% and 0.09～0.12% of above-mentioned quaternary system principal component total mole number;
Described additive is: containing in the manganese compound Cu element in the Mn element and copper-containing compound, the amount of substance sum is 0.05～0.08% Mn+Cu of above-mentioned quaternary system principal component total mole number; And containing in the yttrium compound Y element and to contain Nb element in the niobium compound, the amount of substance sum is 0.2～0.5% Y+Nb of above-mentioned quaternary system principal component total mole number.
2. method for preparing the described low-resistance of claim 1, high-overpressure resistance barium titanate based ceramic thermal resistance is characterized in that step is:
A. quaternary system is prepared burden: get BaTiO
3, SrTiO
3, CaCO
3Form the quaternary system base stock with PbO, make consisting of of per 100 moles of described quaternary system base stocks: 60～90 moles of BaTiO
3, 5～18 moles of SrTiO
3, 1～15 mole of CaCO
3, surplus is PbO; Get TiO again
2Add in the described quaternary system base stock, quaternary system batching, add TiO
2Molal quantity be CaCO in the described quaternary system base stock
3With PbO molal quantity sum;
B. Muffle furnace pyroreaction: with SiO
2, BaCO
3And TiO
2Powder is SiO by mole ratio
2: BaCO
3: TiO
2=2:2:1 mixes, SiO
2, BaCO
3And TiO
2Molal quantity account for 0.2～2%, 0.2～2% and 0.1～1% of the total mole number of quaternary system base stock described in the step a respectively, in Muffle furnace, carry out pyroreaction, be reflected at and carried out under 1150 ℃ 10 hours, generate Ba
2TiSi
2O
8, ball milling 10 hours is to the following powder of 3 μ m then;
C. the preparation of solid-phase powder material: the quaternary system batching that step a is obtained, the Ba that step b obtains
2TiSi
2O
8Powder mixes, and adds nanometer SiO again
2And Li
2CO
3, described nanometer SiO
2And Li
2CO
3Addition be respectively 1.5～2.5% and 0.09～0.12% of the total mole number of quaternary system base stock described in the step a, obtain solid-phase powder material;
D. the preparation of soluble metal saline solution: get and contain the manganese soluble metallic salt, the cupric soluble metallic salt, contain the yttrium soluble metallic salt and contain the niobium soluble metallic salt and mix, and be dissolved in water, the addition of each component meets the following conditions: containing Mn in the manganese soluble metallic salt and the molal quantity sum of the Cu in the cupric soluble metallic salt is 0.05～0.08% of the total mole number of quaternary system base stock described in the step a, contain in the yttrium soluble metallic salt Y and with the molal quantity sum that contains the Nb in the niobium soluble metallic salt be 0.2～0.5% of the total mole number of quaternary system base stock described in the step a;
E. non-homogeneous phase deposition reaction: the mixing soluble metal saline solution that the solid-phase powder material that obtains with step c is solid phase, obtain with steps d is a liquid phase, in ball mill or mixer, adopt ammoniacal liquor regulator solution pH value between 8.5～12, carry out the non-homogeneous phase deposition reaction, react after 10～24 hours, make the high reaction activity composite granule of particle diameter below 2 μ m after filtration;
F. back procedure of processing: in the above-mentioned high reaction activity composite granule that makes, add mass percent concentration and be 5% polyvinyl alcohol water solution and carry out mist projection granulating, the addition of described polyvinyl alcohol water solution is a powder total weight 12%, make powder particles be distributed in 50～180 mu m ranges after the granulation, water content is 0.18～0.28%, flow angle is 25～35 °; After then the powder after the granulation being packed into mould, make blank forming; Again blank is carried out sintering, obtain containing BaTiO3-SrTiO3-CaTiO
3-PbTiO
3Quaternary system, crystal boundary are regulated mutually and the composite material of additive, carry out abrasive disc processing and top electrode at last, make ceramic thermal resistance.
3. according to the described method for preparing low-resistance, high-overpressure resistance barium titanate based ceramic thermal resistance of claim 2, it is characterized in that in the steps d, described contain manganese soluble metallic salt, cupric soluble metallic salt, contain the yttrium soluble metallic salt and contain the niobium soluble metallic salt be respectively manganese nitrate, copper nitrate, yttrium nitrate and niobium chloride.
4. according to the described method for preparing low-resistance, high-overpressure resistance barium titanate based ceramic thermal resistance of claim 2, it is characterized in that among the step f, described sintering step carries out in tunnel cave, step for 1. by room temperature with per hour 200～250 ℃ be warming up to 950 ℃, be incubated 40～60 minutes; 2. with per hour 700 ℃ be warming up to 1310 ℃ from 950 ℃, be incubated 40～60 minutes; 3. with per hour 100～120 ℃ be cooled to 1120 ℃ at a slow speed from 1310 ℃, naturally cool to then below 200 ℃ and come out of the stove.
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| CN103319172B (en) * | 2013-06-14 | 2014-10-15 | 广东风华高新科技股份有限公司 | Annular piezoresistor ceramic and preparation method thereof, and annular piezoresistor and preparation method thereof |
| CN104761260B (en) * | 2015-03-18 | 2017-01-25 | 中国科学院福建物质结构研究所 | Preparation method of (Ba＜x＞Ca＜1-x＞)(Ti＜y＞M＜1-y＞)O3 system piezoelectric ceramic material |
| CN105472792A (en) * | 2015-11-25 | 2016-04-06 | 浙江哈亿曼电子科技有限公司 | PTC thermal sensitive ceramic heating sheet manufacturing technology |
| CN106495171A (en) * | 2016-11-14 | 2017-03-15 | 东北大学 | A kind of LaxBa2‑xTiSi2O8Amorphous and preparation method thereof |
| CN107607216A (en) * | 2017-09-25 | 2018-01-19 | 南京航伽电子科技有限公司 | A kind of temperature transmitter with good compensation performance |
| CN113793716B (en) * | 2021-11-17 | 2022-02-25 | 西安宏星电子浆料科技股份有限公司 | Low-voltage coefficient resistance paste |
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