CN1010816B - Ptc thermister for start of refrigerator compressor and its preparation - Google Patents
Ptc thermister for start of refrigerator compressor and its preparationInfo
- Publication number
- CN1010816B CN1010816B CN 88103610 CN88103610A CN1010816B CN 1010816 B CN1010816 B CN 1010816B CN 88103610 CN88103610 CN 88103610 CN 88103610 A CN88103610 A CN 88103610A CN 1010816 B CN1010816 B CN 1010816B
- Authority
- CN
- China
- Prior art keywords
- semiconductive ceramic
- tio
- ceramic composition
- alms giver
- ptc
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
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- Compositions Of Oxide Ceramics (AREA)
Abstract
The present invention discloses PTC thermistor for the start of a refrigerator compressor and a preparation method, which is characterized in that yttrium (Y) and stibium (Sb) are used as donor adulterant, a main formula is compounded by superfine raw material Ba (TiO) (C2O4) 2.4H2O and BaCO3 + TiO2 sold on the market, the Ba (TiO) (C2O4) 2.4H2O is prepared by chemical (oxalate) liquid phase coprecipitation, and a donor, an accepter, and liquid phase additives are completely added one time simultaneously with the main formula. The invention has the advantages of simple technology, high accuracy of stoichiometric ratio and good comprehensive electrical performance, consistency and repetitiveness of manufactured components.
Description
The present invention relates to a kind of PTC semiconductive ceramic composition and manufacture method thereof.Be particularly related to and a kind ofly be used to make compressor for refrigeration and work PTC semiconductive ceramic composition and the manufacture method thereof of employing thermistor.
As everyone knows, barium titanate [-Base has ptc characteristics (POSitive Temperature COefficient) and is called for short (PTC), and being widely used as various positive temperature coefficient transducers, wherein a kind of common purposes is to be used as motor (as freezer compressor) starter.Motor to the specification requirement of starter is: starting current wants big, and the starting time is suitable, and recovery time is short, and number of starts is many, and is low in energy consumption.Therefore work ptc material of employing and the starter of making thus as motor, comprehensive electrochemical properties preferably be arranged; Promptly low room temperature resistance, high temperature coefficient of resistance, high dielectric strength, short recovery time and low power consumption.
The PTC semiconductive ceramic composition, its performance has quite high sensitiveness to constituent, content and technology.U.S. Pat 4191665 discloses a kind of PTC semiconductive ceramic composition that is used to make motor starter, and its composition is included in principal component BaTiO
3In with the Ca of 5-20mol% displacement Ba, and add the alms giver HO of 0.3-0.9mol% and 0.1～0.18mol% be subjected to main Mn, the liquid additive TiO of＜3mol%
2And SiO
2In the hope of reaching refinement PTC semiconductive ceramic crystal grain, improve high voltage performance, reduce room temperature resistance.But the donor element HO that adds costs an arm and a leg, make PTC semiconductor ceramic material cost increase, and the mutual compensating action of HO and Mn, make the material voltage effects increase, be difficult to guarantee to make the lower power consumption of element, the displacement of Ca easily causes resistance-temperature characteristic to descend, steepness tends towards stability, and dielectric strength descends, and influences useful life, therefore above-mentioned prescription is formed perfect not to the utmost, and still having is worth improved place.
The present invention improves the compositing formula and the technology of preparation PTC semiconductive ceramic for overcoming above-mentioned defective, is more suitable for making motor and works PTC semiconductive ceramic composition of employing thermistor and preparation method thereof to provide a kind of.
Main points of the present invention are, in the PTC semiconductive ceramic composition, select for use cooperative effect preferably rare earth element yttrium (Y) and high volence metal ion antimony (Sb) as donor adulterant, its incorporation is respectively 0.14-0.32mol% and 0.8-0.26mol%, to improve PTC semiconductive ceramic comprehensive electrochemical properties.As everyone knows, Pb can be used as Curie point high temperature phase shift agent in ptc material, so Pb also can introduce in the present invention, addition is 0-0.05mol.On the preparation method, principal component has adopted ultra-fine feed stock (the Ba(TiO) (C of chemical liquid phase coprecipitation preparation
2O
4)
24H
2O) with solid phase synthesis material (BaCO
3+ PbO+TiO
2) (Pb introducing amount is 0～0.05) composite synthetic, both mixing ratios are 0.70-0.95:0.05-0.30mol.
Below just content division of the present invention is as follows:
The present invention can be made up of following component:
A: principal component Ba
1-xPbxTiO
3(x=0-0.05)
B: alms giver's yttrium ten antimony 0.14-0.32mol%+0.08-0.26mol%
C: be subjected to main manganese 0.12-0.4mol%
D: liquid additive Si, Al, Ti, Li 3.0-8.5mol% a kind of or several
In the PTC semiconductive ceramic composition of the present invention, donor adulterant is owing to selecting cooperative effect rare earth element yttrium (Y) and high-valency metal element antimony (Sb) preferably for use, as add Y simultaneously in main formula
2O
3And Sb
2O
3Mixture, can obtain comprehensive electrochemical properties (seeing Table 1) preferably.On incorporation, take to improve the way of its volume, make the withstand voltage properties of element with raising, total incorporation of yttrium and antimony is 0.2-0.4mol%, its preferred incorporation is 0.3-0.4mol%.Be subjected to main manganese can adopt Mn(No
3)
2, and suitably improve its addition, and to reduce the voltage effects of composition material, obtain lower power consumption, being subjected to main mol ratio with alms giver's addition is 0.6～1:1.
Principal component Ba
1-xPbxTiO
3Prior art adopts the commercially available low pure raw material BaCO of tradition
3+ CaCO
3+ PbO+TiO
2Solid phase synthesis process; The superfine powder Ba(TiO that adopts the coprecipitated preparation of single chemistry (oxalates) liquid phase is also arranged) (C
2O
4)
24H
2The O calcination forms.Solid phase synthesis material crystal grain is thick, and purity is low, and the electrical property of element, poor stability behind the sintering are difficult to reach the requirement of high withstand voltage and low-power consumption; The ultra-fine material of liquid phase, active high, element easily takes place to bubble and local stress discharges and causes micro-crack behind the sintering, influences surface quality.The present invention adopts at ultra-fine feed stock Ba(TiO in principal component is synthetic for overcoming above-mentioned defective) (C
2O
4)
24H
2Mix among the O with part solid phase synthesis material BaCO
3+ PbO+TiO
2The preparation method of (Pb=0～0.05) has solved the defective of single material preferably, and the mol ratio of ultra-fine material and solid phase synthesis material is 0.7～0.95:0.05～0.3.Be about to 0.7-0.95 (Ba(TiO) (C
2O
4)
24H
2O)+0.05-0.3 (Ba
1-xPbxTiO
3) (z=0.05-0.3) (x=0～0.05), 0.2 alms giver's mixture (Y+Sb) of～0.4mol%, after a kind of or several mixed grinding refinements of the liquid additive Si, the AL that are subjected to main Mn and 3-8.5mol% of 0.12-0.4mol%, Ti, li, through 1000～1150 ℃ of insulations 1.0-2 hour, calcination ripe material.A, B, C, D can once add simultaneously, also can will add C, D again after A, the B mixing calcination earlier.Be to simplify technology, improve the accuracy of stoichiometric proportion, help micro-additive and fully mix with principal component, complete reaction improves the stability of PTC semiconductor composition, and is repeated and make the comprehensive electrochemical properties of element, and each component is especially once to be added to.
Make and add 5-7Wt% polyvinyl alcohol (PVA) granulation after grog further grinds refinement, with 1000-2000kg/cm
2Moulding sinters porcelain into, and sintered component applies electrode (as chemical sinking nickel electrode, silver-nickel combination electrode, ohmic contact ag paste electrode) through surface treatment (as grinding, ultrasonic cleaning), uses the thermistor chip just make starter motor (freezer compressor).
The present invention, cheap because of adopting, and cooperative effect alms giver's additive yttrium and antimony preferably, and also principal component adopts chemical ultra-fine material and the solid phase synthesis material is composite forms, and each component all once adds.Thereby it is simple to have technology, stoichiometric proportion accuracy height, and it is low to make the element cost, comprehensive electrochemical properties consistency, good reproducibility.Table 2 is the measured value of 2 embodiment of the present invention (example one, example two).
Embodiment one: with (0.95Ba(TiO) (C
2O
4)
24H
2O+0.05(BaCO
3+ TiO
2))+(1.0TiO
2+ 0.16Y
2O
3+ 0.09Sb
2O
3+ 0.18Mn(NO
3)
2+ 2.85SiO
2+ 0.7AL
2O
3) the mol% weighing once adds, mixing and ball milling is 24～36 hours in engine room is arranged, and the oven dry back is with 300～500kg/cm
2Be pressed into piece in advance, in air through 1000～1150 ℃ of insulations 1-2.0 hour, the calcination ripe material, again with the calcination grog through ball milling refinement in 24-30 hour, add the granulation of 5-7Wt% polyvinyl alcohol, through 1000-2000kg/cm
2Be pressed into the circular substrate of φ 15.5 * 3mm, in chamber type electric resistance furnace, sinter porcelain into through 1280-1300 ℃, through grind, the after-applied ohmic contact silver electrode of ultrasonic cleaning.
Embodiment two: compositing formula is (0.82Ba(TiO) (C
2O
4)
24H
2O+0.05(PbO+TiO
2)+0.13(BaCO
3+ TiO
2))+(1.0TiO
2+ 0.08Sb
2O
3+ 0.31Y
2O
3+ 0.31Mn(NO
3)
2+ 3.5SiO
2+ 1.0AL
2O
3+ 0.07LiCO
3) mol%, be pressed into φ 23 * 4.0mm circular substrate by above-mentioned technology, make chip.
Embodiment three: compositing formula (0.072Ba(TiO) (C
2O
4)
24H
2O+0.26(BaCO
3+ TiO
2)+0.02(PbO+TiO))+(1.0TiO
2+ 0.13Sb
2O
3+ 0.2Y
2O
3+ 0.28Mn(NO
3)
2+ 2.5SiO
2+ 0.5AL
2O
3+ 0.1LiCO
3) mol%.
The prepared starter chip of above-mentioned first embodiment generally is applicable to the rotary type refrigerator compressor, and the starter chip that second embodiment is made can be used for reciprocating type freezer compressor, the also alternative electric current Weight type starter that the contact is arranged.
Table 1 alms giver mixes the additive effect contrast
25 ℃ of α m of doping component volume ρ 1g ρ max dielectric strength power consumption recovery time
mol% Ω.Cm %/℃ ρmin V/mm Sec W
Sb
2O
30.33 250-450 32 6.7 430 63 1.7
Y
2O
3
Sb
2O
30.33 500-800 26 5.45 405 78 1.98
Y
2O
30.33 180-260 15 4.8 175 ＞80 ＞2
Annotate: recovery time is for after applying 10 minutes with two times of rated voltages, used time when resistance is reduced to two times of house temperatures.
Two embodiment measured values of table 2
25 ℃ of TC 1g of NO ρ ρ max dielectric strength power consumption recovery time
Ω.Cm ℃ ρmin V/mm t
2RO tRO W
1 280 103 6.53 426 67 1.58
2 135 126 5.56 375 109 2.46
Annotate: tRo, t
2Ro is respectively after element quits work, and its resistance value returns to room temperature resistance value or 2 times of times that room temperature resistance value is used
Claims (8)
1, a kind of PTC semiconductive ceramic composition is included in principal component Ba
(1-x)PbxTiO
3(x=0-0.05) mix the main Mn that is subjected to 0.12-0.4mol% in, 3.0-8.5mol% liquid additive Si, Al, Ti, one kind of Li or several is characterized in that the alms giver adopts the Y of 0.14-0.32mol% and the Sb of 0.08-0.26mol%.
2, by the described PTC semiconductive ceramic composition of claim 1, the total addition level that it is characterized in that alms giver Y and Sb is 0.2-0.4mol%.
3, by the described PTC semiconductive ceramic composition of claim 2, the optimum addition that it is characterized in that alms giver Y and Sb is 0.3-0.4mol%
4, by the described PTC semiconductive ceramic composition of claim 1, it is characterized in that being subjected to the mol ratio of main Mn and alms giver Y and Sb is 0.6-1: 1.
5, by claim 1 or 4 described PTC semiconductive ceramic compositions, it is characterized in that being subjected to main additive is Mn(NO
3)
2
6, by the manufacture method of the described PTC semiconductive ceramic composition of claim 1, comprise Ba(Tio with 0.7-0.95mol) (C
2O
4)
24H
2O, (Ba(0.05-0.3)-xpbx) TiO of 0.05-0.3mol%
3(X=0-0.05), 0.12-0.4mol%'s is subjected to main Mn(NO
3)
2, the alms giver Y of 0.14-0.32mol%+0.08-0.26mol%
2O
3+ Sb
2O
3, 3.0-8.5mol% liquid additive SiO
2, Al
2O
3, LiCO
3, TiO
2A kind of or several mixing and ball milling refinements are tempered refinement through 1000-1150 ℃.
7,, it is characterized in that the alms giver, all once added simultaneously by master, liquid additive with principal component by the manufacture method of the described PTC semiconductive ceramic composition of claim 6.
8, a kind of PTC thermister for start of refrigerator compressor is characterized in that the thermal sensitive ceramics body adopts PTC semiconductive ceramic composition according to claim 1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 88103610 CN1010816B (en) | 1988-06-13 | 1988-06-13 | Ptc thermister for start of refrigerator compressor and its preparation |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 88103610 CN1010816B (en) | 1988-06-13 | 1988-06-13 | Ptc thermister for start of refrigerator compressor and its preparation |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1031150A CN1031150A (en) | 1989-02-15 |
| CN1010816B true CN1010816B (en) | 1990-12-12 |
Family
ID=4832685
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 88103610 Expired CN1010816B (en) | 1988-06-13 | 1988-06-13 | Ptc thermister for start of refrigerator compressor and its preparation |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1010816B (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103360054A (en) * | 2012-03-26 | 2013-10-23 | 常熟市林芝电子有限责任公司 | Thermal sensitive ceramic material, PTC (positive temperature coefficient) thermistor made from thermal sensitive ceramic material for demagnetizing colour TV and manufacturing method of PTC thermistor |
| CN108484159B (en) * | 2018-03-30 | 2021-01-19 | 华南理工大学 | Barium titanate-based NTC/PTC (negative temperature coefficient/positive temperature coefficient) bifunctional ceramic material as well as preparation method and application thereof |
-
1988
- 1988-06-13 CN CN 88103610 patent/CN1010816B/en not_active Expired
Also Published As
| Publication number | Publication date |
|---|---|
| CN1031150A (en) | 1989-02-15 |
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