CN101101812A - Positive temperature coefficient strontium titanate pressure sensitive resistor and its production process - Google Patents
Positive temperature coefficient strontium titanate pressure sensitive resistor and its production process Download PDFInfo
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- CN101101812A CN101101812A CNA2006100286023A CN200610028602A CN101101812A CN 101101812 A CN101101812 A CN 101101812A CN A2006100286023 A CNA2006100286023 A CN A2006100286023A CN 200610028602 A CN200610028602 A CN 200610028602A CN 101101812 A CN101101812 A CN 101101812A
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- strontium titanate
- temperature coefficient
- pressure sensitive
- sensitive resistor
- positive temperature
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Abstract
The invention is concerned with a kind of SrTiO3 piezo-resistor with direct proportion to temperature and its preparation method. It is made of 100 share of Sr (1-x-y) BaxCayTiO3, 0.01 to 5.00 share of semi-conducting property modifying additive, 0.01 to 5.0 share of property modifying additive and 0.001 to 3.00 share of sinter auxiliary agent. The preparation method relates to the confect of barium strontium calcium titanate, the preparation of resistor, and so on. Compared with the existing technology, this invention has good consistency of pressure, small rate of change changing ratio, high coincidence rate of users, and so on. The direct proportion to temperature can effectively protect the electronical equipment, such as electrical micro-machine, when the piezo-press of has small and positive change with the raised temperature.
Description
Technical field
The present invention relates to inorganic non-metallic composite function ceramics field of new, particularly positive temperature coefficient strontium titanate pressure sensitive resistor and preparation method thereof.
Background technology
Strontium titanate pressure-sensitive resistor is with SrTiO
3Be main material, add Nb
2O
5, Sm
2O
3Deng metal oxide and rare earth oxide, adopt electronic ceramic process to make, be used for the garden sheet wire type varistor and the annular voltage-sensitive resistor that is used for the de-noising of electrical micro-machine arc extinguishing of overvoltage protection.
SrTiO
3Varistor has big dielectric constant and good nonlinear characteristic, and the low pressure sensitive voltage and the voltage range of broad have electric capacity-pressure-sensitive dual-use function concurrently.When no abnormal overvoltage, it plays capacitor, but filtering High-frequency Interference, when transient overvoltage occurs, it absorbs overvoltage as piezo-resistance, and particularly its voltage temperature coefficient is littler than ZnO varistor, and can reach on the occasion of, its capacitance temperature stability is better than conventional ceramic capacitor again, therefore in the low-voltage field especially aspect the de-noising of electrical micro-machine arc extinguishing application prospect very wide.
Temperature characterisitic is the important performance indexes of varistor, normally represents with the variation of temperature coefficient with pressure sensitive voltage, for SrTiO
3Piezo-resistance, voltage temperature coefficient K is shown below:
In the formula (1) (E10)
50(E10)
25Pressure sensitive voltage value when representing 50 ℃ and 25 ℃ respectively.
The absolute value of k value is the smaller the better.The k value be on the occasion of the time, the ability that piezo-resistance is born electrical surge and static power significantly improves, the job stability and the reliability of element are further improved.In the world from the eighties, at first by PANASONIC, TDK, the SrTiO that releases one after another of company of TAIYO YUDAN and field, village company
3Varistor, and commercialization.Domesticly begin one's study from the late nineteen eighties; release commodity in the nineties initial stage; the unit for electrical property parameters of product satisfies user's requirement at that time substantially; but the temperature characterisitic of product is relatively poor; general temperature coefficient is a negative value, and also promptly with the rising of ambient temperature, the pressure sensitive voltage of sample can reduce; finally cause the nonlinear characteristic variation, the protection effect of electrical micro-machine and other electronic equipment or device is weakened until losing protective effect.
The eighties in 20th century, Japanese SrTiO
3The voltage temperature coefficient of varistor is approximately-0.5%/℃, nineteen ninety Japan TAIYO YUDAN and the product standard of TDK in be defined as-0.3%/℃, actual product is-0.15%/℃, the SrTiO of the Japanese TDK that saw from the market by 2002
3The voltage temperature coefficient of piezo-resistance is+0.05%/℃, on the occasion of.
When domestic nineteen ninety-five is produced typing in Guangzhou temperature coefficient be-0.35%/℃, through development and improvement for many years, still-0.3%/℃～fluctuate in-0.35%/℃ scope.
Summary of the invention
Purpose of the present invention is exactly to provide excellent especially positive temperature coefficient strontium titanate pressure sensitive resistor of a kind of technology stability and adaptability and preparation method thereof for the weak point that overcomes above-mentioned prior art existence.
Purpose of the present invention can be achieved through the following technical solutions: a kind of positive temperature coefficient strontium titanate pressure sensitive resistor is characterized in that this resistor is made by the raw material of following component and content (molar part, together following): Sr
(1-x-y)Ba
xCa
yTiO
3100 parts, 0.01～5.00 part of semiconducting additive, 0.01～5.00 part of property-modifying additive, 0.001～3.00 part of sintering aid.
Described Sr
(1-x-y)Ba
xCa
yTiO
3, x+y≤1, x=0.1～0.8, y=0.1～0.8.
Described semiconducting additive comprises Nb
2O
5, Ta
2O
5, WO
3High valence ion at least a, add Y simultaneously
2O
3, Sm
2O
3, Pr
6O
11, Nd
2O
3, Eu
2O
3Rare-earth oxide at least a.
Described property-modifying additive comprises Sb
2O
3, MnCO
3, Cr
2O
3, CuO's is at least a.
Described sintering aid comprises SiO
2
When above-mentioned principal component was defined as 100mol%, other additive was for adding composition, so total quantity is greater than 100mol%.Above-mentioned second composition is in the 0.01-5.0mol%, and the 3rd composition is 0.01-5.0mol%, and four-component is 0.001-3.0mol%
A kind of preparation method of positive temperature coefficient strontium titanate pressure sensitive resistor is characterized in that, this preparation method comprises following processing step:
(1) preparation of barium strontium titanate calcium
Take by weighing a certain amount of SrCO
3, BaCO
3, CaCO
3And TiO
2Ball milling mixes 10～40h or stirring ball-milling 2～8h in ball mill, discharging, and 100 ℃～150 ℃ baking 4～15h sieve, pack in the high temperature saggar according to certain limiting the quantity of, compacting a little enters calcining in the high temperature furnace, calcining heat 1100-1350 ℃, be incubated 1-10 hour, the warehouse-in of coming out of the stove is stand-by.
(2) preparation of resistor
Take by weighing 100 parts of barium strontium titanate calcium, add 0.01～5.00 part of semiconducting additive, 0.01～5.0 part of property-modifying additive, 0.001～3.00 part of sintering aid, ball milling mixes 10～40h or stirring ball-milling 1～10h, makes slurry, mist projection granulating, compression molding is got rid of adhesive under 600 ℃～1200 ℃ temperature, burn till in 1200 ℃～1500 ℃ high temperature reduction atmosphere, heat treatment in 600～1200 ℃ of scopes, printed silver electrode afterwards, 500～800 ℃ of silver ink firing temperature are measured sorting again.
Described resistor comprises garden sheet wire type piezo-resistance, ring varistor, lamination type piezoresistor and cast, column type piezo-resistance.
Compared with prior art, characteristics of the present invention are: prescription system is selected two or more alms givers and is subjected to main oxide to carry out compound interpolation, the suitable proportioning of while property-modifying additive and sintering aid, make its technology stability of this material and adaptability excellent especially, be more suitable in industrialization and commercialization, be fit to the equipment of selecting for use commercially pure raw material and general industry to use, and do not need high-purity material and high end equipment, make the manufacturing cost of product significantly reduce, the market competitiveness improves.
Description of drawings
Fig. 1 is side three electrode SrTiO of the present invention
3The schematic diagram of annular voltage-sensitive resistor;
Fig. 2 is plane three electrode SrTiO of the present invention
3The schematic diagram of annular voltage-sensitive resistor;
Fig. 3 is plane five electrode SrTiO of the present invention
3The schematic diagram of annular voltage-sensitive resistor.
Embodiment
Embodiment 1
Select technical pure or chemical pure SrCO for use
3, BaCO
3, CaCO
3And TiO
2Raw material, take by weighing by table 1 formula rate, in the ball mill mixing and ball milling 10-30 hour, or adopted the agitating ball mill mixing and ball milling 4-6 hour, discharging, 100-150 ℃ of oven dry 8-15 hour, the back of sieving is packed in the high temperature saggar compacting a little into according to certain limiting the quantity of, enter calcining in the high temperature furnace, temperature 1100-1350 ℃, be incubated 1-10 hour, the warehouse-in of coming out of the stove is stand-by.It is as shown in table 1 from the content of SrO to measure each sample middle reaches respectively.
The formula rate of synthesis material is as shown in table 1
Different sequence number synthesis materials in the table 1 add the additive of the second～the four-component of same ratio respectively, each additive component is the chemical pure raw material, batching, ball milling 10-40 hour or stirring ball-milling 1-10 hour, make slurry, mist projection granulating, compression molding, under 600 ℃～1200 ℃ temperature, get rid of adhesive, in 1200 ℃～1500 ℃ high temperature reduction atmosphere, burn till heat treatment in 600～1200 ℃ of scopes.Printed silver electrode afterwards, 500～800 ℃ of silver ink firing temperature.The electrical property of sample and the measurement of temperature coefficient and result of calculation are as shown in table 2.
The relation of the prescription of table 1 synthesis material and calcining heat and free SrO content
| Sequence number | SrCO 3 BaCO 3 CaCO 3(mol％) | TiO 2 (mol％) | Calcining heat ℃ | SrO％ |
| ZST-6 | 0.80 0.10 0.10 | 1.0 | 1200 1250 1300 | 0.22 0.18 0.15 |
| ZST-7 | 0.10 0.80 0.10 | 1.0 | 1200 1250 1300 | 0.28 0.25 0.25 |
| ZST-8 | 0.10 0.10 0.80 | 1.0 | 1200 1250 1300 | 0.20 0.22 0.22 |
| ZST-9 | 0.20 0.60 0.20 | 1.0 | 1200 1250 1300 | 0.15 0.13 0.11 |
| ZST-10 | 0.60 0.30 0.10 | 1.0 | 1200 1250 1300 | 0.27 0.20 0.25 |
| ZST-11 | 0.70 0.10 0.20 | 1.0 | 1200 1250 1300 | 0.23 0.18 0.16 |
Table 2 unit for electrical property parameters
| The ST item number | E10 | α | C(nF) | tgδ | Temperature coefficient %/℃ |
| ZST-6 | 8.5 | 5.5 | 28 | 0.25 | 0.13 |
| ZST-7 | 7.8 | 3.0 | 35 | 0.35 | 0.15 |
| ZST-8 | 6.5 | 5.5 | 30 | 0.24 | -0.12 |
| ZST-9 | 8.2 | 4.5 | 25 | 0.26 | 0.22 |
| ZST-10 | 9.5 | 5.6 | 25 | 0.36 | -0.28 |
| ZST-11 | 6.2 | 4.5 | 36 | 0.33 | 0.18 |
Embodiment 2
According to the data result of table 1 and table 2, selecting ZST-6 is major ingredient prescription, fixedly Sm, the content of Mn and Si is constant, the content that changes Nb is from 0.00～5.00mol%, prepares sample and measures its electrical property, alpha value calculated and temperature coefficient as identical process conditions as described in the embodiment 1.The result is as shown in table 3.
Table 3 additive formulations is to Effect on Performance (different content of Nb)
| The ZSV item number | Nb | Sm | Mn | Si | E10 | α | Temperature coefficient %/℃ |
| ZSV-1 | 0.00 | 1.5 | 0.1 | 0.1 | Not semiconducting | ||
| ZSV-2 | 0.01 | ＞100 | ＜1.0 | ||||
| ZSV-3 | 0.10 | 78 | 1.5 | ||||
| ZSV-4 | 1.50 | 8.5 | 4.5 | +0.35 | |||
| ZSV-5 | 3.00 | 7.8 | 4.5 | +0.31 | |||
| ZSV-6 | 4.00 | 6.8 | 5.0 | +0.23 | |||
| ZSV-7 | 5.00 | 8.0 | 5.5 | -0.42 | |||
Embodiment 3
Fix N b, the content of Mn and Si is constant, and the content that changes Sm is from 0.00～5.00mol%, prepares sample and measures its electrical property, alpha value calculated as identical process conditions as described in the embodiment 1.Prepared sample as described in the embodiment 1 is also measured its electrical property, alpha value calculated and temperature coefficient.The result is as shown in table 4:
Table 4 additive formulations is to Effect on Performance (different content of Sm)
| Item number | Nb | Sm | Mn | Si | E10 | α | Temperature coefficient %/℃ |
| ZSV-8 | 1.5 | 0.00 | 0.1 | 0.1 | 65 | 1.3 | |
| ZSV-9 | 0.01 | 32 | 1.5 | ||||
| ZSV-10 | 0.10 | 29 | 2.1 | ||||
| ZSV-11 | 1.50 | 9.5 | 2.5 | +0.16 |
| ZSV-12 | 3.00 | 8.6 | 3.4 | +0.30 | |||
| ZSV-13 | 4.00 | 8.5 | 3.0 | +0.25 | |||
| ZSV-14 | 5.00 | 9.0 | 4.0 | -0.23 |
Embodiment 4
Fix N b, the content of Sm and Si is constant, and the content that changes Mn is from 0.00～5.00mol%, prepares sample and measures its electrical property, alpha value calculated and temperature coefficient as identical process conditions as described in the embodiment 1.The result is as shown in table 5.
Table 5 additive formulations is to Effect on Performance (different content of Mn)
| Item number | Nb | Sm | Mn | Si | E10 | α | Temperature coefficient %/℃ |
| ZSV-15 | 1.5 | 1.5 | 0.00 | 0.1 | 45 | 1.0 | |
| ZSV-16 | 0.01 | 33 | 1.5 | ||||
| ZSV-17 | 0.10 | 9.8 | 2.8 | +0.18 | |||
| ZSV-18 | 1.50 | 6.8 | 2.5 | +0.23 | |||
| ZSV-19 | 3.00 | 7.5 | 2.8 | +0.35 | |||
| ZSV-20 | 4.00 | 6.5 | 3.4 | -0.31 | |||
| ZSV-21 | 5.00 | 7.7 | 3.0 | +0.28 |
Embodiment 5
Fix N b, Sm, the content of Mn is constant, and the content that changes Si is from 0.00～3.00mol%, prepares sample and measures its electrical property, alpha value calculated and temperature coefficient as identical process conditions as described in the embodiment 1.The result is as shown in table 6.
Table 6 additive formulations is to Effect on Performance (different content of Si)
| Item number | Nb | Sm | Mn | Si | E10 | α | Temperature coefficient %/℃ |
| ZSV-22 | 1.5 | 1.5 | 0.1 | 0.00 | 52 | 2.0 | |
| ZSV-23 | 0.01 | 45 | 1.8 | ||||
| ZSV-24 | 0.10 | 15 | 2.3 | +0.19 | |||
| ZSV-25 | 1.00 | 5.8 | 2.5 | +0.26 | |||
| ZSV-26 | 1.50 | 6.8 | 3.3 | -0.35 | |||
| ZSV-27 | 2.00 | 5.5 | 4.5 | +0.13 | |||
| ZSV-28 | 3.00 | 4.5 | 3.8 | -0.28 |
Claims (7)
1. a positive temperature coefficient strontium titanate pressure sensitive resistor is characterized in that, this resistor is made by the raw material of following component and content (molar part, together following): Sr
(1-x-y)Ba
xCa
yTiO
3100 parts, 0.01～5.00 part of semiconducting additive, 0.01～5.00 part of property-modifying additive, 0.001～3.00 part of sintering aid.
2. a kind of positive temperature coefficient strontium titanate pressure sensitive resistor according to claim 1 is characterized in that, described Sr
(1-x-y)Ba
xCa
yTiO
3, x+y≤1, x=0.1～0.8, y=0.1～0.8.
3. a kind of positive temperature coefficient strontium titanate pressure sensitive resistor according to claim 1 is characterized in that, described semiconducting additive comprises Nb
2O
5, Ta
2O
5, WO
3High valence ion at least a, add Y simultaneously
2O
3, Sm
2O
3, Pr
6O
11, Nd
2O
3, Eu
2O
3Rare-earth oxide at least a.
4. a kind of positive temperature coefficient strontium titanate pressure sensitive resistor according to claim 1 is characterized in that described property-modifying additive comprises Sb
2O
3, MnCO
3, Cr
2O
3, CuO's is at least a.
5. a kind of positive temperature coefficient strontium titanate pressure sensitive resistor according to claim 1 is characterized in that described sintering aid comprises SiO
2
6. the preparation method of a positive temperature coefficient strontium titanate pressure sensitive resistor is characterized in that, this preparation method comprises following processing step:
(1) preparation of barium strontium titanate calcium
Take by weighing a certain amount of SrCO
3, BaCO
3, CaCO
3And TiO
2Ball milling mixes 10～40h or stirring ball-milling 2～8h in ball mill, discharging, and 100 ℃～150 ℃ baking 4～15h sieve, pack in the high temperature saggar according to certain limiting the quantity of, compacting a little enters calcining in the high temperature furnace, calcining heat 1100-1350 ℃, be incubated 1-10 hour, the warehouse-in of coming out of the stove is stand-by.
(2) preparation of resistor
Take by weighing 100 parts of barium strontium titanate calcium, add 0.01～5.00 part of semiconducting additive, 0.01～5.0 part of property-modifying additive, 0.001～3.00 part of sintering aid, ball milling mixes 10～40h or stirring ball-milling 1～10h, makes slurry, mist projection granulating, compression molding is got rid of adhesive under 600 ℃～1200 ℃ temperature, burn till in 1200 ℃～1500 ℃ high temperature reduction atmosphere, heat treatment in 600～1200 ℃ of scopes, printed silver electrode afterwards, 500～800 ℃ of silver ink firing temperature are measured sorting again.
7. the preparation method of a kind of positive temperature coefficient strontium titanate pressure sensitive resistor according to claim 6 is characterized in that, described resistor comprises garden sheet wire type piezo-resistance, ring varistor, lamination type piezoresistor and cast, column type piezo-resistance.
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|---|---|---|---|
| CNA2006100286023A CN101101812A (en) | 2006-07-04 | 2006-07-04 | Positive temperature coefficient strontium titanate pressure sensitive resistor and its production process |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA2006100286023A CN101101812A (en) | 2006-07-04 | 2006-07-04 | Positive temperature coefficient strontium titanate pressure sensitive resistor and its production process |
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| Publication Number | Publication Date |
|---|---|
| CN101101812A true CN101101812A (en) | 2008-01-09 |
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|---|---|---|---|
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102260075A (en) * | 2011-05-26 | 2011-11-30 | 中国科学院上海硅酸盐研究所 | Barium strontium calcium titanate pyroelectric ceramic material and preparation method thereof |
| CN103319172A (en) * | 2013-06-14 | 2013-09-25 | 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 |
| CN103319171A (en) * | 2013-06-14 | 2013-09-25 | 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 |
| CN105384436A (en) * | 2015-11-10 | 2016-03-09 | 江苏科技大学 | Titanium-rich barium strontium titanate-based dielectric medium ceramic material and preparation method thereof |
| 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 |
-
2006
- 2006-07-04 CN CNA2006100286023A patent/CN101101812A/en active Pending
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102260075A (en) * | 2011-05-26 | 2011-11-30 | 中国科学院上海硅酸盐研究所 | Barium strontium calcium titanate pyroelectric ceramic material and preparation method thereof |
| CN102260075B (en) * | 2011-05-26 | 2013-10-16 | 中国科学院上海硅酸盐研究所 | Barium strontium calcium titanate pyroelectric ceramic material and preparation method thereof |
| CN103319172A (en) * | 2013-06-14 | 2013-09-25 | 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 |
| CN103319171A (en) * | 2013-06-14 | 2013-09-25 | 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 |
| 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 |
| CN105384436A (en) * | 2015-11-10 | 2016-03-09 | 江苏科技大学 | Titanium-rich barium strontium titanate-based dielectric medium ceramic material and preparation method thereof |
| 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 |
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