CN101565305B - High-temperature lead-free PTC material and production process thereof - Google Patents

High-temperature lead-free PTC material and production process thereof Download PDF

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CN101565305B
CN101565305B CN200910106240.9A CN200910106240A CN101565305B CN 101565305 B CN101565305 B CN 101565305B CN 200910106240 A CN200910106240 A CN 200910106240A CN 101565305 B CN101565305 B CN 101565305B
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郜长福
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Shenzhen Jinke Special Materials Co ltd
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Abstract

The invention provides a high-temperature lead-free PTC material and production process thereof, belonging to the thermal sensitive ceramic processing materials technical field, mainly comprising main raw materials, semi-conductivity agents, dopant and sintering additive, characterized in that: the main materials comprise barium carbonate, strontium carbonate, calcium carbonate, sodium carbonate, bismuth oxide and titanium dioxide; the semi-conductivity agents are at least two kinds of compounds selected from columbium oxide, yttrium oxide, lanthana, antimonic oxide and tantalum oxide and themol percentage of the addition amount of the semi-conductivity agents is 0.005-5.0% mol accounting for the total amount of the materials; the mol ratios of the components to the semi-conductivity agents are (BaXSrYCaZ)1-m (Bi1/2Na1/2)mTinO3+aE1; the main raw materials and the trace raw materials are subjected to twice blending, the first mixture is subjected to wet grinding and then drying in a 120 DEG C dry box after leaving from the jar and being pressed and then the first mixture performs the pre-synthesis in the crucible after insulating for 2 hours at 1100 DEG C and then quadric blending is performed and water is added into the mixture to wet grind the mixture for 24 and then the mixture is dried and granulated and dry-pressed to form the billets and the billets are sintered at high temperature for 1 hour in 1300 DEG C nitrogen oven to form porcelain.

Description

High-temperature lead-free PTC material and production technique
Technical field:
The present invention relates to a kind of high-temperature lead-free PTC material and production technique, it belongs to thermal sensitive ceramics work material technical field.
Background technology:
The fabricating technology that present Curie temperature is higher than 120 ℃ ptc material all is to improve its microtexture by the doping lead element, improve its macroscopic property, and it toxic of lead element is well-known, leaded PTCR from preparation, use recycling use and all have plumbous harm.Unleaded BaTiO 3The research that base PTC pottery improves Curie temperature is a popular domain in recent years.At present domestic and international research to non-plumbum ferroelectric body and piezoelectrics has obtained certain achievement, and BaTiO 3The lead-free high-temperature ptc material research of series seldom.The key of high-temperature lead-free PTC is to seek lead-free high-curie temperature soluble solids in order to adjusting the Curie temperature of compound ptc material, with the ptc material that solves present high-curie temperature because of leaded pollution to environment and harm that the mankind are caused.
Existing high-temperature lead-free PTC material generally adopts solid-phase synthesis with Bi 2O 3, Na 2CO 3, TiO 2Three kinds of raw materials are pre-mixed and grind synthetic (Bi 1/2Na 1/2) TiO 3(being called for short BNT) powder, BaCO 3, TiO 2Mixed grinding synthesizes BaTiO 3Then powder is mixed together two kinds of synthetic powders and other additive grinding, granulation, moulding, sintering, electrode and prepares finished product.Use this doping techniques and technique, cause easily material component skew, cause that product performance are unstable, production poor repeatability, Curie temperature drift or make the material can not semiconductor.
Summary of the invention:
The object of the present invention is to provide that a kind of processability is stable, the PTC effect is strong, withstand voltage level is higher, the high-temperature lead-free PTC material that the production reproducibility is strong and production technique.
The present invention is achieved in that
A kind of high-temperature lead-free PTC material, it comprises main raw material, semiconductor agent, doping agent and sintering aid, it is characterized in that described main raw material is barium carbonate BaCO 3, Strontium carbonate powder SrCO 3, calcium carbonate CaCO 3, yellow soda ash Na 2CO 3, bismuth oxide Bi 2O 3With titanium dioxide TiO 2The semiconductor agent is niobium oxides Nb 2O 5, yttrium oxide Y 2O 3, lanthanum trioxide La 2O 3, weisspiessglanz Sb 2O 3With tantalum oxide Ta 2O 5In at least two kinds, the molar percentage that the addition of described semiconductor agent accounts for total amount of material is 0.05～5.0%mol; The mole proportioning of the various compositions of described main raw material and semiconductor agent is:
(Ba XSr YCa Z) 1-m(Bi 1/2Na 1/2) mTi nO 3+ aE 1X=0.5～1.0 wherein; Y=0.10～0.20; Z=0.05～0.10; M=0.05～0.20; N=1.0～1.10; A=0.0005～0.050;
E 1Be the semiconductor agent;
Described doping agent is manganese oxide MnO 2, addition accounts for 0.10～0.20%mol of total amount of material; Described sintering aid comprises aluminium oxide Al 2O 3, silicon oxide sio 2And additive, described additive comprises magnesium oxide MgO, silicon nitride Si 3N 4, at least a among boron nitride BN and the cupric oxide CuO, the molar percentage that addition accounts for total amount of material is 5～10%mol, described sintering aid and the additive proportional quantity in total material is:
(Ba XSr YCa Z) 1-m(Bi 1/2Na 1/2) mTi nO 3+aE 1+bE 2+cE 3。X=0.5～1.0 wherein; Y=0.10～0.20; Z=0.05～0.10; M=0.05～0.20; N=1.0～1.10; A=0.0005～0.050; B=0.0010～0.0020; C=0.05～0.10;
E 1Be semiconductor agent, E 2Be doping agent, E 3Be sintering aid.
Described semiconductor agent is niobium oxides Nb 2O 5, yttrium oxide Y 2O 3, lanthanum trioxide La 2O 3, weisspiessglanz Sb 2O 3With tantalum oxide Ta 2O 5In at least two kinds, the molar percentage that addition accounts for total amount of material is 0.05～5.0%mol, wherein the concrete shared molar percentage of each composition is Nb 2O 5: 0.01～0.10%mol, Y 2O 3: 0.15～0.25%mol, La 2O 3: 0.05～0.15%mol, Sb 2O 3: 0.10～0.20%mol, Ta 2O 5: 0.10～0.20%mol.
Described sintering aid comprises aluminium oxide Al 2O 3, silicon oxide sio 2And additive, described additive comprises magnesium oxide MgO, silicon nitride Si 3N 4, at least a among boron nitride (BN) and the cupric oxide CuO, the molar percentage that addition accounts for total amount of material is 5～10%mol, wherein the concrete shared molar percentage of each composition is Al 2O 3: 2.5～5.0%mol, SiO 2: 2.5～4.5%mol, MgO:0.20～0.30%mol, Si 3N 4: 0.10～0.20%mol, BN:0.10～0.20%mol, CuO:0.10～0.20%mol.
Described main raw material is barium carbonate BaCO 3, Strontium carbonate powder SrCO 3, calcium carbonate CaCO 3, yellow soda ash Na 2CO 3, bismuth oxide Bi 2O 3With titanium dioxide TiO 2The semiconductor agent is niobium oxides Nb 2O 5, yttrium oxide Y 2O 3Doping agent is manganese oxide MnO 2, sintering aid is aluminium oxide Al 2O 3And silicon oxide sio 2, the additive of sintering aid is magnesium oxide MgO; The mole proportioning of described each composition is: (Ba XSr YCa Z) 1-m(Bi 1/2Na 1/2) mTi nO 3+ aE 1+ bE 2+ cE 3, X=0.82 wherein; Y=0.10; Z=0.08; M=0.10; N=1.08; E 1Be semiconductor agent: Nb 2O 5Add-on 0.0005mol, Y 2O 3Add-on 0.0020mol; E 2Be doping agent: MnO 2Add-on is 0.0010mol; E3-sintering aid: Al 2O 3Add-on is 0.05mol; SiO 2Add-on 0.04mol; MgO add-on 0.0020mol.
Processing step of the present invention is as follows:
At first prepare required starting material, main raw material is barium carbonate BaCO 3, Strontium carbonate powder SrCO 3, calcium carbonate CaCO 3, yellow soda ash Na 2CO 3, bismuth oxide Bi 2O 3, titanium dioxide TiO 2The semiconductor element is the rare earth microelement of trivalent or pentavalent, and must jointly add with two or more semiconductor agent, and the selected semiconductor agent of using is niobium oxides Nb 2O 5, yttrium oxide Y 2O 3, lanthanum trioxide La 2O 3, weisspiessglanz Sb 2O 3, tantalum oxide Ta 2O 5In at least two kinds, addition accounts for 0.05～5.0%mol of total amount of material, the molar percentage of concrete various compositions is Nb 2O 5: 0.01～0.10%mol, Y 2O 3: 0.15～0.25%mol, La 2O 3: 0.05～0.15%mol, Sb 2O 3: 0.10～0.20%mol, Ta 2O 5: 0.10～0.20%mol;
Select needed doping agent, described doping agent is manganese oxide MnO 2, addition accounts for 0.10～0.20%mol of total amount of material;
Select sintering aid, sintering aid comprises aluminium oxide Al 2O 3, silicon oxide sio 2, and add micro-magnesium oxide MgO, silicon nitride Si 3N 4, at least a among boron nitride BN and the cupric oxide CuO, its addition accounts for total amount of material 5～10%mol, the molar percentage of concrete various compositions is Al 2O 3: 2.5～5.0%mol, SiO 2: 2.5～4.5%mol, MgO:0.20～0.30%mol, Si 3N 4: 0.10～0.20%mol, BN:0.10～0.20%mol, CuO:0.10～0.20%mol;
At first carry out the batching first time:
Primary batching system forms: (Ba XSr YCa Z) 1-m(Bi 1/2Na 1/2) mTi nO 3+ aE 1, X=0.5～1.0 wherein; Y=0.10～0.20; Z=0.05～0.10; M=0.05～0.20; N=1.0～1.10; A=0.0005～0.050; E 1-semiconductor agent; Adopt BaCO 3, SrCO 3, CaCO 3, Bi 2O 3, Na 2CO 3, TiO 2Main raw material and semiconductor agent Primary batching system, wet grinding mixed 20～24 hours, and it is synthetic to carry out the pre-burning reaction after the press filtration oven dry, 1100 ℃～1150 ℃ of synthesis temperatures, generated time 2～3 hours;
And then carry out second batch:
The mole proportioning of second batch is: (Ba XSr YCa Z) 1-m(Bi 1/2Na 1/2) mTi nO 3+ aE 1+ bE 2+ cE 3X=0.5～1.0 wherein; Y=0.10～0.20; Z=0.05～0.10; M=0.05～0.20; N=1.0～1.10; A=0.0005～0.050; B=0.0010～0.0020; C=0.05～0.10; E 1-semiconductor agent, E 2-doping agent, E 3-sintering aid; Sintering aid, doping agent add when second batch, mix 20～24h with the synthetic material wet grinding, prepare finished product through granulation, moulding, sintering, electrode.
Selection process step of the present invention is as follows:
Semiconductor agent Y 2O 3When Primary batching system, add;
Described Primary batching system forms: (Ba XSr YCa Z) 1-m(Bi 1/2Na 1/2) mTi nO 3+ a 1E 1, X=0.5～1.0 wherein; Y=0.10～0.20; Z=0.05～0.10; M=0.05～0.20; N=1.0～1.10; a 1=0.00025～0.025; E 1-semiconductor agent; Adopt BaCO 3, SrCO 3, CaCO 3, Bi 2O 3, Na 2CO 3, TiO 2Main raw material and semiconductor agent Y 2O 3Primary batching system, wet grinding mixes 20～24h, and it is synthetic to carry out the pre-burning reaction after the press filtration oven dry, 1100 ℃～1150 ℃ of synthesis temperatures, generated time 2h～3h;
Then carry out second batch: semiconductor agent Nb 2O 5Add when the second batch with doping agent, sintering aid;
Second batch forms: (Ba XSr YCa Z) 1-m(Bi 1/2Na 1/2) mTi nO 3+ a 1E 1+ a 2E 1+ bE 2+ cE 3X=0.5～1.0 wherein; Y=0.10～0.20; Z=0.05～0.10; M=0.05～0.20; N=1.0～1.10; a 1=0.00025～0.025; a 2=0.00025～0.025; A=a 1+ a 2B=0.0010～0.0020; C=0.05～0.10; E 1-semiconductor agent, E 2-doping agent, E 3-sintering aid, semiconductor agent Nb 2O 5With doping agent MnO 2, sintering aid adds when second batch, mixes 20～24h with the synthetic material wet grinding, prepares finished product through granulation, moulding, sintering, electrode.
Another selection process step of the present invention is as follows:
Semiconductor agent Nb 2O 5And Y 2O 3And doping agent MnO 2When Primary batching system, add;
Described Primary batching system forms: (Ba XSr YCa Z) 1-m(Bi 1/2Na 1/2) mTi nO 3+ aE 1+ bE 2, X=0.5～1.0 wherein; Y=0.10～0.20; Z=0.05～0.10; M=0.05～0.20; N=1.0～1.10; A=0.0005～0.050; B=0.0010～0.0020; E 1-semiconductor agent, E 2-doping agent; Adopt BaCO 3, SrCO 3, CaCO 3, Bi 2O 3, Na 2CO 3, TiO 2Main raw material and semiconductor agent Nb 2O 5And Y 2O 3And doping agent MnO 2Primary batching system, wet grinding mixed 20～24 hours, and it is synthetic to carry out the pre-burning reaction after the press filtration oven dry, 1100 ℃～1150 ℃ of synthesis temperatures, generated time 2～3 hours;
Then carry out second batch: sintering aid Al 2O 3,, SiO 2Add when the second batch with MgO;
Second batch forms: (Ba XSr YCa Z) 1-m(Bi 1/2Na 1/2) mTi nO 3+ aE 1+ bE 2+ cE 3X=0.5～1.0 wherein; Y=0.10～0.20; Z=0.05～0.10; M=0.05～0.20; N=1.0～1.10; A=0.0005～0.050; B=0.0010～0.0020; C=0.05～0.10; E 1-semiconductor agent, E 2-doping agent, E 3-sintering aid, sintering aid adds when second batch, mixes 20～24h with the synthetic material wet grinding, prepares finished product through granulation, moulding, sintering, electrode.
The present invention adopts BaCO by optimizing doping techniques and formulating reasonable process 3, SrCO 3, CaCO 3, Bi 2O 3, Na 2CO 3, TiO 2At least two kinds among main raw material and semiconductor element nb, Y, La, Sb, the Ta are carried out Primary batching system, and wet grinding mixes, and it is synthetic to carry out the pre-burning reaction.Doped element Mn and sintering aid Al, Si and Mg, Si (Si 3N 4), at least a element among B, the Cu adds when second batch, with the synthetic material mixed grinding, but afterwards stable through granulation, moulding, sintering, electrode processability, the PTC effect is strong, withstand voltage level is higher, the high-temperature lead-free PTC product that the production reproducibility is strong.Solved the poor technical barrier of high-temperature lead-free PTC production reproducibility, laid the foundation for realizing the industrialization of high-temperature lead-free PTC achievement.
The unit for electrical property parameters of new type high temperature lead-free PTC material of the present invention:
Curie temperature Tc:120 ℃～250 ℃;
Side reaction coefficient: 6%～20%;
β liftdrag: 〉=3;
Proof voltage: 〉=150V/mm.
Description of drawings:
Fig. 1 is the resistance-temperature characteristics curve of the embodiment of the invention 1 sample;
Fig. 2 is the resistance-temperature characteristics curve of the embodiment of the invention 2 samples;
Fig. 3 is the resistance-temperature characteristics curve of the embodiment of the invention 3 samples.
Embodiment:
Embodiment 1: the semiconductor agent is added when Primary batching system simultaneously, and doping agent, sintering aid add in second batch simultaneously;
In the present embodiment, starting material form: (Ba XSr YCa Z) 1-m(Bi 1/2Na 1/2) mTi nO 3+ aE 1+ bE 2+ cE 3X=0.82 wherein; Y=0.10; Z=0.08; M=0.10; N=1.08; E 1-semiconductor agent: Nb 2O 5Add-on 0.0005mol, Y 2O 3Add-on 0.0020mol; E 2-doping agent: MnO 2Add-on 0.0010mol; E3-sintering aid: Al 2O 3Add-on 0.05mol; SiO 2Add-on 0.04mol; MgO add-on 0.0020mol.
The various raw materials of present embodiment calculate according to above-mentioned mole proportioning, and the weight that takes by weighing each main raw material is: BaCO 3: 145.64g, SrCO 3: 13.29g, CaCO 3: 7.21g, Bi 2O 3: 11.65g, Na 2CO 3: 2.65g, TiO 2: 86.29g, the semiconductor agent is Nb 2O 5: 0.1329g, Y 2O 3: 0.4517g.
Prepare burden for the first time: the form of eight kinds of above-mentioned raw materials with compound added in the ball grinder, make grinding medium with alcohol, compound wet-milling 24h; Go out to put into 120 ℃ of loft drier after the tank pressure filter and dry, behind the crucible of packing into 1100 ℃ of lower insulation 2h pre-synthesis.
Add doping agent and sintering aid, i.e. MnO during second batch 2: 0.08694g, Al 2O 3: 5.0980g, SiO 2: 2.4032g, MgO:0.08062g, add water wet-milling 24h post-drying, add an amount of binding agent PVA mixing granulation, dry-pressing formed 24mm*15mm*2.5mm base sheet, the base sheet is put into 1300 ℃ of nitrogen furnace high temperature sintering 1h become porcelain, then to becoming ceramics to carry out oxidizing thermal treatment, abrasive disc cleans clean rear top electrode test performance.
The properties of sample parameter is as follows: resistance value: 106 Ω, and Curie temperature Tc:160.6 ℃, side reaction coefficient: 9.99, β liftdrag: 2.791E+3, proof voltage:＞150V/mm, its R-T curve is seen Fig. 1.
Embodiment 2:
Semiconductor agent Y 2O 3When Primary batching system, add semiconductor agent Nb 2O 5With doping agent MnO 2And sintering aid adds when second batch.
Primary batching system takes by weighing raw material: BaCO 3: 145.64g, SrCO 3: 13.29g, CaCO 3: 7.21g, Bi 2O 3: 11.65g, Na 2CO 3: 2.65g, TiO 2: 86.29g, Y 2O 3: 0.4517g, these seven kinds of raw materials are pressed in the form adding ball grinder of composition and ratio with compound, make grinding medium with alcohol, compound wet-milling 24h; Go out to put into 120 ℃ of loft drier after the tank pressure filter and dry, behind the crucible of packing into 1100 ℃ of lower insulation 2h pre-synthesis.
Add Nb during second batch 2O 5: 0.1329g, MnO 2: 0.08694g, Al 2O 3: 5.0980g, SiO 2: 2.4032g, MgO:0.08062g, add water wet-milling 24h post-drying, add an amount of binding agent PVA mixing granulation, dry-pressing formed 24mm*15mm*2.5mm base sheet, the base sheet is put into 1300 ℃ of nitrogen furnace high temperature sintering 1h become porcelain, then to becoming ceramics to carry out oxidizing thermal treatment, abrasive disc cleans clean rear top electrode test performance.
The properties of sample parameter is as follows: resistance value: 6252 Ω, and Curie temperature Tc:159.1 ℃, side reaction coefficient: 6.58, β liftdrag: 7.117E+2, proof voltage:＞150V/mm, its R-T curve is seen Fig. 2.
Other parts of present embodiment are identical with embodiment 1.
Embodiment 3:
Semiconductor agent Nb 2O 5And Y 2O 3And doping agent MnO 2Add when Primary batching system, sintering aid adds when second batch;
Primary batching system takes by weighing raw material: BaCO 3: 145.64g, SrCO 3: 13.29g, CaCO 3: 7.21g, Bi 2O 3: 11.65g, Na 2CO 3: 2.65g, TiO 2: 86.29g, Nb 2O 5: 0.1329g, Y 2O 3: 0.4517g, MnO 2: 0.08694g, these nine kinds of raw materials are pressed in the form adding ball grinder of composition and ratio with compound, make grinding medium with alcohol, compound wet-milling 24 hours; Go out to put into 120 ℃ of loft drier after the tank pressure filter and dry, behind the crucible of packing in 2 hours pre-synthesis of 1100 ℃ of lower insulations.
Add Al during second batch 2O 3: 5.0980g, SiO 2: 2.4032g, MgO:0.08062g, add water wet-milling 24h post-drying, add again an amount of binding agent PVA mixing granulation, dry-pressing formed is 24mm*15mm*2.5mm base sheet, the base sheet is put into 1300 ℃ of nitrogen furnace high temperature sintering 1h become porcelain, then to becoming ceramics to carry out oxidizing thermal treatment, abrasive disc cleans clean rear top electrode test performance.
The properties of sample parameter is as follows: resistance value: 4910 Ω, and Curie temperature Tc:152.2 ℃, side reaction coefficient: 6.87, β liftdrag: 8.748E+2, proof voltage:＞150V/mm, the R-T curve is seen Fig. 3.
Other parts of present embodiment are identical with embodiment 1.

Claims (7)

1. high-temperature lead-free PTC material, it comprises main raw material, semiconductor agent, doping agent and sintering aid, described main raw material is barium carbonate BaCO 3, Strontium carbonate powder SrCO 3, calcium carbonate CaCO 3, yellow soda ash Na 2CO 3, bismuth oxide Bi 2O 3With titanium dioxide TiO 2The semiconductor agent is niobium oxides Nb 2O 5, yttrium oxide Y 2O 3, lanthanum trioxide La 2O 3, weisspiessglanz Sb 2O 3With tantalum oxide Ta 2O 5In at least two kinds, the molar percentage that the addition of described semiconductor agent accounts for total amount of material is 0.05～5.0%mol; The mole proportioning of the various compositions of described main raw material and semiconductor agent is:
(Ba XSr YCa Z) 1-m(Bi 1/2Na 1/2) mTi nO 3+ aE 1X=0.5～1.0 wherein; Y=0.10～0.20; Z=0.05～0.10; M=0.05～0.20; N=1.0～1.10; A=0.0005～0.050; E 1Be the semiconductor agent;
It is characterized in that described doping agent is manganese oxide MnO 2, addition accounts for 0.10～0.20%mol of total amount of material; Described sintering aid comprises aluminium oxide Al 2O 3, silicon oxide sio 2And additive, described additive comprises magnesium oxide MgO, silicon nitride Si 3N 4, at least a among boron nitride BN and the cupric oxide CuO, the molar percentage that addition accounts for total amount of material is 5～10%mol, described sintering aid and the additive proportional quantity in total material is: (Ba XSr YCa Z) 1-m(Bi 1/2Na 1/2) mTi nO 3+ aE 1+ bE 2+ cE 3, X=0.5～1.0 wherein; Y=0.10～0.20; Z=0.05～0.10; M=0.05～0.20; N=1.0～1.10; A=0.0005～0.050; B=0.0010～0.0020; C=0.05～0.10;
E 1Be semiconductor agent, E 2Be doping agent, E 3Be sintering aid.
2. high-temperature lead-free PTC material as described in claim 1 is characterized in that described semiconductor agent is niobium oxides Nb 2O 5, yttrium oxide Y 2O 3, lanthanum trioxide La 2O 3, weisspiessglanz Sb 2O 3With tantalum oxide Ta 2O 5In at least two kinds, the molar percentage that addition accounts for total amount of material is 0.05～5.0%mol, wherein the concrete shared molar percentage of each composition is Nb 2O 5: 0.01～0.10%mol, Y 2O 3: 0.15～0.25%mol, La 2O 3: 0.05～0.15%mol, Sb 2O 3: 0.10～0.20%mol, Ta 2O 5: 0.10～0.20%mol.
3. high-temperature lead-free PTC material as described in claim 1 is characterized in that described sintering aid comprises aluminium oxide Al 2O 3, silicon oxide sio 2And additive, described additive comprises magnesium oxide MgO, silicon nitride Si 3N 4, at least a among boron nitride (BN) and the cupric oxide CuO, the molar percentage that addition accounts for total amount of material is 5～10%mol, wherein the concrete shared molar percentage of each composition is Al 2O 3: 2.5～5.0%mol, SiO 2: 2.5～4.5%mol, MgO:0.20～0.30%mol, Si 3N 4: 0.10～0.20%mol, BN:0.10～0.20%mol, CuO:0.10～0.20%mol.
4. high-temperature lead-free PTC material as described in claim 1 is characterized in that described main raw material is barium carbonate BaCO 3, Strontium carbonate powder SrCO 3, calcium carbonate CaCO 3, yellow soda ash Na 2CO 3, bismuth oxide Bi 2O 3With titanium dioxide TiO 2The semiconductor agent is niobium oxides Nb 2O 5, yttrium oxide Y 2O 3Doping agent is manganese oxide MnO 2, sintering aid is aluminium oxide Al 2O 3And silicon oxide sio 2, the additive of sintering aid is magnesium oxide MgO; The mole proportioning of described each composition is: (Ba XSr YCa Z) 1-m(Bi 1/2Na 1/2) mTi nO 3+ aE 1+ bE 2+ cE 3, X=0.82 wherein; Y=0.10; Z=0.08; M=0.10; N=1.08; E 1Be semiconductor agent: Nb 2O 5Add-on 0.0005mol, Y 2O 3Add-on 0.0020mol; E 2Be doping agent: MnO 2Add-on is 0.0010mol; E3-sintering aid: Al 2O 3Add-on is 0.05mol; SiO 2Add-on 0.04mol; MgO add-on 0.0020mol.
5. the production technique of the high-temperature lead-free PTC material described in the claim 1, its feature exists
Comprise following technique in it:
At first prepare required starting material, main raw material is barium carbonate BaCO 3, Strontium carbonate powder SrCO 3, calcium carbonate CaCO 3, yellow soda ash Na 2CO 3, bismuth oxide Bi 2O 3, titanium dioxide TiO 2The semiconductor element is the rare earth microelement of trivalent or pentavalent, and must jointly add with two or more semiconductor agent, and the selected semiconductor agent of using is niobium oxides Nb 2O 5, yttrium oxide Y 2O 3, lanthanum trioxide La 2O 3, weisspiessglanz Sb 2O 3, tantalum oxide Ta 2O 5In at least two kinds, addition accounts for 0.05～5.0%mol of total amount of material, the molar percentage of concrete various compositions is Nb 2O 5: 0.01～0.10%mol, Y 2O 3: 0.15～0.25%mol, La 2O 3: 0.05～0.15%mol, Sb 2O 3: 0.10～0.20%mol, Ta 2O 5: 0.10～0.20%mol; Select needed doping agent, described doping agent is manganese oxide MnO 2, addition accounts for 0.10～0.20%mol of total amount of material;
Select sintering aid, sintering aid comprises aluminium oxide Al 2O 3, silicon oxide sio 2, and add micro-magnesium oxide MgO, silicon nitride Si 3N 4, at least a among boron nitride BN and the cupric oxide CuO, its addition accounts for total amount of material 5～10%mol, the molar percentage of concrete various compositions is Al 2O 3: 2.5～5.0%mol, SiO 2: 2.5～4.5%mol, MgO:0.20～0.30%mol, Si 3N 4: 0.10～0.20%mol, BN:0.10～0.20%mol, CuO:0.10～0.20%mol;
At first carry out the batching first time:
Primary batching system forms: (Ba XSr YCa Z) 1-m(Bi 1/2Na 1/2) mTi nO 3+ aE 1, X=0.5～1.0 wherein; Y=0.10～0.20; Z=0.05～0.10; M=0.05～0.20; N=1.0～1.10; A=0.0005～0.050; E 1-semiconductor agent; Adopt BaCO 3, SrCO 3, CaCO 3, Bi 2O 3, Na 2CO 3, TiO 2Main raw material and semiconductor agent Primary batching system, wet grinding mixed 20～24 hours, and it is synthetic to carry out the pre-burning reaction after the press filtration oven dry, 1100 ℃～1150 ℃ of synthesis temperatures, generated time 2～3 hours;
And then carry out second batch:
The mole proportioning of second batch is: (Ba XSr YCa Z) 1-m(Bi 1/2Na 1/2) mTi nO 3+ aE 1+ bE 2+ cE 3, X=0.5～1.0 wherein; Y=0.10～0.20; Z=0.05～0.10; M=0.05～0.20; N=1.0～1.10; A=0.0005～0.050; B=0.0010～0.0020; C=0.05～0.10; E 1-semiconductor agent, E 2-doping agent, E 3-sintering aid; Sintering aid, doping agent add when second batch, mix 20～24h with the synthetic material wet grinding, prepare finished product through granulation, moulding, sintering, electrode.
6. the production technique of high-temperature lead-free PTC material as described in claim 1 is characterized in that it comprises following technique:
Semiconductor agent Y 2O 3When Primary batching system, add;
Described Primary batching system forms: (Ba XSr YCa Z) 1-m(Bi 1/2Na 1/2) mTi nO 3+ a 1E 1, X=0.5～1.0 wherein; Y=0.10～0.20; Z=0.05～0.10; M=0.05～0.20; N=1.0～1.10; a 1=0.00025～0.025; E 1-semiconductor agent; Adopt BaCO 3, SrCO 3, CaCO 3, Bi 2O 3, Na 2CO 3, TiO 2Main raw material and semiconductor agent Y 2O 3Primary batching system, wet grinding mixes 20～24h, and it is synthetic to carry out the pre-burning reaction after the press filtration oven dry, 1100 ℃～1150 ℃ of synthesis temperatures, generated time 2h～3h;
Then carry out second batch: semiconductor agent Nb 2O 5Add when the second batch with doping agent, sintering aid;
Second batch forms: (Ba XSr YCa Z) 1-m(Bi 1/2Na 1/2) mTi nO 3+ a 1E 1+ a 2E 1+ bE 2+ cE 3, X=0.5～1.0 wherein; Y=0.10～0.20; Z=0.05～0.10; M=0.05～0.20; N=1.0～1.10; a 1=0.00025～0.025; a 2=0.00025～0.025; A=a 1+ a 2
B=0.0010～0.0020; C=0.05～0.10; E 1-semiconductor agent, E 2-doping agent, E 3-sintering aid, semiconductor agent Nb 2O 5With doping agent MnO 2, sintering aid adds when second batch, mixes 20～24h with the synthetic material wet grinding, prepares finished product through granulation, moulding, sintering, electrode.
7. the production technique of high-temperature lead-free PTC material as described in claim 1 is characterized in that it comprises following technique:
Semiconductor agent Nb 2O 5And Y 2O 3And doping agent MnO 2When Primary batching system, add;
Described Primary batching system forms: (Ba XSr YCa Z) 1-m(Bi 1/2Na 1/2) mTi nO 3+ aE 1+ bE 2, X=0.5～1.0 wherein; Y=0.10～0.20; Z=0.05～0.10; M=0.05～0.20; N=1.0～1.10; A=0.0005～0.050; B=0.0010～0.0020; E 1-semiconductor agent, E 2-doping agent; Adopt BaCO 3, SrCO 3, CaCO 3, Bi 2O 3, Na 2CO 3, TiO 2Main raw material and semiconductor agent Nb 2O 5And Y 2O 3And doping agent MnO 2Primary batching system, wet grinding mixed 20～24 hours, and it is synthetic to carry out the pre-burning reaction after the press filtration oven dry, 1100 ℃～1150 ℃ of synthesis temperatures, generated time 2～3 hours;
Then carry out second batch: sintering aid Al 2O 3,, SiO 2Add when the second batch with MgO;
Second batch forms: (Ba XSr YCa Z) 1-m(Bi 1/2Na 1/2) mTi nO 3+ aE 1+ bE 2+ cE 3, X=0.5～1.0 wherein; Y=0.10～0.20; Z=0.05～0.10; M=0.05～0.20; N=1.0～1.10; A=0.0005～0.050; B=0.0010～0.0020; C=0.05～0.10; E 1-semiconductor agent, E 2-doping agent, E 3-sintering aid, sintering aid adds when second batch, mixes 20～24h with the synthetic material wet grinding, prepares finished product through granulation, moulding, sintering, electrode.
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