CN1175434C - Voltage nonlinear resistance and its manufacturing method - Google Patents

Voltage nonlinear resistance and its manufacturing method Download PDF

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CN1175434C
CN1175434C CNB001309986A CN00130998A CN1175434C CN 1175434 C CN1175434 C CN 1175434C CN B001309986 A CNB001309986 A CN B001309986A CN 00130998 A CN00130998 A CN 00130998A CN 1175434 C CN1175434 C CN 1175434C
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accessory ingredient
ceramic composition
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CN1292557A (en
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佐藤茂树
史
野村武史
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TDK Corp
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Abstract

The present invention relates to a voltage nonlinear resistor where thermal shock resistance is superior, moreover transverse rupture strength is high and control of varistor voltage is easy, and a manufacturing method of the resistor. This voltage nonlinear resistor is composed of a ceramic composition, which contains strontium titanate as the main component, and carbon content in the ceramic composition after baking is at most 410 ppm. It is preferable that the content of carbon in the ceramic composition after baking be at least 120 ppm. It is also preferable that the content of carbon in the ceramic composition after degreasing be at most 2,100 ppm.

Description

Voltage non-linear resistor and manufacture method thereof
The invention relates to voltage non-linear resistor and manufacture method thereof, say so about heat shock resistance characteristic good and bending strength height in more detail, control the voltage non-linear resistor and the manufacture method thereof of nonlinear resistance voltage easily.
Typical example as voltage non-linear resistor has nonlinear resistance.Overvoltage or noise etc. for example take place in the electric equipment such as motor and use in order to absorb or to remove in nonlinear resistance.In the public clear 55-49404 communique of spy, disclose with SrTiO 3Be the nonlinear resistance of principal component, this nonlinear resistance not only has the nonlinear resistance function, and has capacitor function, and therefore can be absorbed in well has glow discharge, arc discharge, abnormal voltage and the noise etc. of causing danger in the electric equipment.In addition, in No. 2944697 communique of patent, the means as the temperature dependency of controlling nonlinear resistance voltage have proposed SrTiO 3-BaTiO 3-CaTiO 3The nonlinear resistance of system.
, such SrTiO 3Perhaps SrTiO 3-BaTiO 3-CaTiO 3Be nonlinear resistance, general use as the noise parts that produce between rotor that is used to absorb DC motor and the brush.Therefore, general, the nonlinear resistance of these systems has annular shape, utilizes solder to carry out the electrode of nonlinear resistance and being connected of rotor.When this solder operation, produce big thermal shock for nonlinear resistance in annular shape.In addition, cooperate the height outputization of motor, the nonlinear resistance of annular shape also is in the tendency that becomes big, follows this, wishes to improve the resistance to sudden heating of nonlinear resistance.
The present invention finishes in view of such reality, and purpose is to provide heat shock resistance characteristic good and bending strength height, controls the voltage non-linear resistor and the manufacture method thereof of nonlinear resistance voltage easily.
In order to achieve the above object, the feature of the voltage non-linear resistor of relevant the 1st viewpoint of the present invention is that to contain the ceramic composition formation that strontium titanates is a principal component, the carbon content in the ceramic composition behind the sintering is below the 410ppm, preferably below the 300ppm.
The feature of the voltage non-linear resistor of relevant the 2nd viewpoint of the present invention is, making carbon content in the ceramic composition behind the sintering is that 410ppm is following, preferably 300ppm selects the composition of substance and/or degreasing condition followingly and constitutes.
If carbon content is too much, when the bending strength of voltage non-linear resistor reduces, be in the tendency that the heat shock resistance characteristic reduces, this is bad.
Carbon content in the ceramic composition behind the preferred sintering is more than the 120ppm and then preferably more than the 200ppm.If carbon content is very few, just be in the tendency that is difficult to control nonlinear resistance voltage, this is bad.
In the present invention,, have no particular limits, but best above-mentioned ceramic composition contains as containing the ceramic composition that strontium titanates is a principal component:
With composition formula (Sr (1-x-y)Ba xCa y) mTiO 2+mPrincipal components representative, x=0.1～0.9, y=0.01～0.5, x+y＜1,0.98≤m≤1.02,
The 1st accessory ingredient that comprises the oxide that is selected from least a kind the 1st element in Nb, Ta and the rare earth element composition group,
The 2nd accessory ingredient that comprises the oxide that is selected from least a kind the 2nd element in Mn, Co, Ni, Cu, Zn and the V composition group, and
Comprise the 3rd accessory ingredient of the oxide of any the 3rd element at least among Si and the Al.
When above-mentioned principal component is defined as 100mol%, with above-mentioned the 1st accessory ingredient is 0.01～3mol%, 0.5～2.0mol% preferably, above-mentioned the 2nd accessory ingredient be 0.005～3mol%, preferably 0.02～0.5mol% (but, when representing above-mentioned the 2nd element with M, be the mol number when representing its oxide with MO) scope, be included in the above-mentioned ceramic composition.
When above-mentioned principal component is defined as 100 quality %, be 0.005～1 quality %, the scope of 0.02～0.1 quality % preferably, be included in the above-mentioned ceramic composition with above-mentioned the 3rd accessory ingredient.
X in above-mentioned composition formula less than 0.1 or y less than 0.1 o'clock, the temperature characterisitic of nonlinear resistance voltage becomes negative characteristic, its result, along with temperature rises, nonlinear resistance voltage reduces, and is in the tendency that causes short circuit phenomenon, this is bad.In addition, if x surpasses 0.9, just be in the tendency that can not show nonlinear resistance voltage, this also is bad.In addition, if y surpasses 0.5, just be in the tendency that can not show nonlinear resistance property, this also is bad.
So-called nonlinear resistance voltage is meant nonlinear resistive element added the voltage that slowly increases, the applied voltage the during electric current of the 10mA that for example flows.In addition, when so-called nonlinear resistance property is meant nonlinear resistive element is added slowly the voltage that increases, the phenomenon that the electric current that flows through in element non-linearly increases.
As the oxide that is selected from least a kind the 1st element in Nb, Ta and the rare earth element composition group, can enumerate Nb 2O 5, Ta 2O 5, Y 2O 3, La 2O 3, CeO 4, Pr 6O 11, Nd 2O 3, Sm 2O 3, Eu 2O 3, Gd 2O 3, Tb 4O 7, Dy 2O 3, Ho 2O 3, Er 2O 3, Tm 2O 3, Yb 2O 3, Lu 2O 3These oxides are included in the composition with the scope of above-mentioned mol%, therefore help the semiconductor transformation of composition.
As the 2nd accessory ingredient, for example can enumerate MnO, Co 3O 4, NiO, Cu 2O, ZnO, V 2O 5Deng.These oxides are the oxides that help the nonlinear characteristic of nonlinear resistance voltage and nonlinear resistance.If the content of these oxides is very few, nonlinear resistance voltage and nonlinear characteristic just are in the tendency of deterioration significantly.If too much, because insulating, nonlinear resistance property is deterioration significantly.But, for example at V 2O 5Occasion, be converted into VO 5/2Obtain the molal quantity of the 2nd accessory ingredient.
As the 3rd accessory ingredient, can enumerate SiO 2, Al 2O 3These oxides are the crystalline additives that help composition.If the content of the 3rd accessory ingredient is very few, the density of sintered body will reduce, and is in the tendency that can not get full intensity, if too much, nonlinear resistance property just is in the tendency of deterioration significantly.
Preferably, above-mentioned composition also contains the 4th accessory ingredient of the oxide that is selected from the 4th element more than at least a kind in Li, Na, K and the Rb composition group.
When above-mentioned principal component was defined as 100 quality %, above-mentioned the 4th accessory ingredient was better with less than 0.1 quality %, and preferably the scope with 0.05～0.5 quality % contains.
As the 4th accessory ingredient, for example can enumerate Li 2O, Na 2O, K 2O, RbO.These oxides are the oxides that help the non linear coefficient of nonlinear resistance.If the content of these oxides is very few, just be in nonlinear resistance non-linear system number improve the little tendency of effect.If too much, because insulating, nonlinear resistance property is deterioration significantly.
Voltage non-linear resistor composition of the present invention is to constitute by containing the ceramic composition of strontium titanates as principal component, and the carbon content in the ceramic composition after the degreasing is below the 2100ppm.If the carbon content in the ceramic composition after the degreasing surpasses 2100ppm, carbon content in the ceramic composition behind the sintering just is difficult to be controlled at below the 410ppm, when the bending strength of voltage non-linear resistor reduced, the heat shock resistance characteristic was in the tendency of reduction, and this is bad.
In the case, the carbon content in the ceramic composition after the degreasing is preferably more than the 180ppm.Carbon content in the ceramic composition after degreasing is during less than 180ppm, and the carbon content in the ceramic composition behind the sintering just is difficult to be controlled at more than the 120ppm, and nonlinear resistance voltage just is in unmanageable tendency, and this is bad.
The feature of the manufacture method of voltage non-linear resistor of the present invention is, carbon content in the ceramic composition behind the skimming processes is become below the 2100ppm, preferably become 180ppm is above, 2100ppm selects substance composition and/or skimming processes condition followingly.As above-mentioned skimming processes condition, skimming processes is preferably under the reducing atmosphere, under the neutral atmosphere, carry out under any atmosphere under the carbon dioxide atmosphere.Preferably preferably contain any of amorphous carbon, graphite, carbide, organic compound in the ceramic composition before skimming processes.
Voltage non-linear resistor of the present invention can be suitable as the nonlinear resistive element that is used for noise absorption, voltage protection and use.
The present invention can provide heat shock resistance characteristic good and bending strength height, control the voltage non-linear resistor and the manufacture method thereof of nonlinear resistance voltage easily.
Below, explain the present invention according to embodiment.
Fig. 1 is the sectional drawing of the nonlinear resistance of the embodiment of the invention.
Fig. 2 is used to measure the nonlinear resistance voltage of nonlinear resistance of the embodiment of the invention and the circuit diagram of non linear coefficient.
Fig. 3 is the curve chart of the relation that reoxidizes temperature and nonlinear resistance voltage in the nonlinear resistance of the expression embodiment of the invention.
Embodiment 1
As raw material, weighing SrCO 3, BaCO 3, CaCO 3, TiO 2, Nb 2O 5, SiO 2, fit in (the Sr that consists of that finally obtains 0.35Ba 0.35Ca 0.3) TiO 3+ Nb 2O 5(1.5mol%)+MnO (0.02mol%)+SiO 2(0.1 quality %).Moreover, Nb 2O 5With the mol% of MnO be with (Sr 0.35Ba 0.35Ca 0.3) TiO 3Mol% when being defined as 100mol%, SiO 2Quality % be with (Sr 0.35Ba 0.35Ca 0.3) TiO 3Quality % when being defined as 100 quality %.
Then, use ball mill that this raw material mixing after 10～20 hours, is dewatered and drying.After this, this raw material carries out false sintering at 1150～1250 ℃, after the coarse crushing,, dewaters and drying after 10～20 hours with the ball mill mixing again.Then, in this raw material, add the polyvinyl alcohol (PVA) of 1 quality % as binding agent.Its result, the carbon content in the raw material is 2820ppm.Then, this raw material is compressed into capable press forming with the shaping of about 196Mpa, obtain outer discoid preform through 12.5mm, internal diameter 8mm, thick 1mm.
Then, carry out the degreasing of preform.Shown in the table 1 described as follows, Yi Bian continue to flow at the flow that makes air with 2L/min, Yi Bian under 600 ℃, 12 hours condition, carry out degreasing.Carbon content in the preform after the degreasing is 448ppm.Then, as shown in table 2, at N 2(97 volume %)+H 2Under the reducing atmosphere of (3 volume %), 1380 ℃ with this preform sintering 2 hours, obtain the semiconductor sintered body.As shown in table 2, the carbon content in the sintered body behind sintering is 122ppm.
Carry out the processing that reoxidizes of this sintered body then.As shown in table 2, reoxidize treatment conditions (in oxidizing atmosphere) in air, be 900 ℃ and 4 hours.The carbon containing ratio that reoxidizes the sintered body after the processing is 111ppm.The mensuration of carbon content is behind the sample after weighing 0.2g pulverizes with agate mortar, to use analysis of carbon and sulfur device (the hole field makes made EMIA520) to carry out.
Then,, as shown in Figure 1, stick with paste, toast at 600 ℃ and form silver electrode 4, finish nonlinear resistance 6 at the surface coated silver of sintered body 2 in order to investigate the characteristic of the sintered body that obtains like this.
Then, measure nonlinear resistance voltage V10, non linear coefficient α 10, heat shock resistance characteristic (heat-resistant quality) and the bending strength of this nonlinear resistance 6.As shown in Figure 2, nonlinear resistance 6 is connected on the direct current constant voltage power supply 8, when acting on two interelectrode voltages of nonlinear resistance 6,, obtain nonlinear resistance voltage V10 by reading out in the electric current that flows through on the nonlinear resistance 6 at galvanometer 12 with potentiometer 10 mensuration.Specifically, when the electric current that flows through is 10mA, utilize potentiometer 10 to read to act on the interelectrode voltage of nonlinear resistance 6 on nonlinear resistance 6, with this value as nonlinear resistance voltage V10.
Obtain non linear coefficient α 10 by following mathematical expression (1).
α10＝log(I 10/I 1)/log(V10/V1)＝1/log(V10/V1)……(1)
V10 means on nonlinear resistance shown in Figure 26 and flows through I 10Nonlinear resistance voltage during the electric current of=10mA, V1 mean on nonlinear resistance shown in Figure 26 and flow through I 1Nonlinear resistance voltage during the electric current of=1mA.This non linear coefficient α 10 is big more, and nonlinear resistance property is good more.
The heat shock resistance characteristic is carried out as shown below.That is, the nonlinear resistance 6 shown in the Fig. 1 after electrode formed, along with soft solder together be heated to 380 ℃ flatiron contact the solder of simulating.After this solder is handled, clean solder flux, checking has flawless.Prepare to form on 20 each elements the nonlinear resistive element of the electrode of 5 utmost points,, carry out the solder of 5 utmost points, add up to and carry out the solder of 100 utmost points, represent the 100 extremely middle numbers of poles that crackle takes place with percentage to each sample.
And, with above-mentioned same condition under make sample according to the clavate of JIS-R1601, this sample is carried out test according to JIS-R1601, obtain bending strength.
The result who measures comes together in the table 3.
Table 1
Add carbon amount substance Addition (weight %) Carbon content (ppm) before the degreasing The degreasing condition Carbon content after the degreasing (ppm)
T1 (℃-time) Atmosphere
Reference example 1 PVA 0.5 980 800-12h Air-2L/min *190
PVA 0.5 980 800-12h Air-2L/min *190
PVA 0.5 980 800-12h Air-2L/min *190
PVA 0.5 980 800-12h Air-2L/min *190
PVA 0.5 980 800-12h Air-2L/min *190
Embodiment 1 PVA 1 2820 600-12h Air-2L/min 448
Embodiment 2 PVA 1 2820 600-2h Air-2L/min 605
Embodiment 3 PVA 1.5 6450 600-2h Air-2L/min 829
PVA 1.5 6450 600-2h Air-2L/min 829
PVA 1.5 6450 600-2h Air-2L/min 829
PVA 1.5 6450 600-2h Air-2L/min 829
PVA 1.5 6450 600-2h Air-2L/min 829
PVA 1.5 6450 600-2h Air-2L/min 829
Embodiment 4 PVA 1.5 6450 600-2h N 2-2L/min 1916
Embodiment 5 PVA 1.5 6450 600-2h Co 2-2L/min 2078
Embodiment 6 PVA 3.2 13800 600-2h Air-2L/min 1308
Comparative example 1 PVA 3.2 13800 600-2h N 2-2L/min *2799
Comparative example 2 PVA 3.2 13800 600-2h Co 2-2L/min *3083
Embodiment 7 PVA 6 25800 600-2h Air-2L/min 1788
Comparative example 3 PVA 10 43100 600-2h Air-2L/min *2374
Embodiment 8 PVA (1.5 weight %)+C 0.1 8120 600-2h Air-2L/min 1357
Comparative example 4 PVA (1.5 weight %)+C 1 15420 600-2h Air-2L/min *5447
Comparative example 5 PVA (1.5 weight %)+C 2 26580 600-2h Air-2L/min *7701
Embodiment 9 C 0.01 114 600-2h Air-2L/min 32
Embodiment 10 C 0.1 1085 600-2h Air-2L/min 1470
Comparative example 6 C 2 20259 600-2h Air-2L/min *14730
Comparative example 7 C 5 30445 600-2h Air-2L/min *23443
Embodiment 11 PVA (1.5 weight %)+SiC 0.1 7870 600-2h Air-2L/min 1856
Embodiment 12 PVA (1.5 weight %)+TiC 0.1 7060 600-2h Air-2L/min 1742
Embodiment 13 PVA 1 2820 600-12h Air-2L/min 431
Table 2
Sintering condition Carbon content behind the sintering (ppm) Reoxidize condition Reoxidize back carbon content (ppm)
T2 (℃-time) Atmosphere T3 (℃-time) Atmosphere
Reference example 1 1380-2h H 2-3％ *110 800-4h Air 103
1380-2h H 2-3％ *110 850-4h Air 98
1380-2h H 2-3％ *110 900-4h Air 82
1380-2h H 2-3％ *110 950-4h Air 80
1380-2h H 2-3％ *110 1000-4h Air 77
Embodiment 1 1380-2h H 2-3％ 122 900-4h Air 111
Embodiment 2 1380-2h H 2-3％ 205 900-4h Air 164
Embodiment 3 1380-2h H 2-3％ 268 800-4h Air 263
1380-2h H 2-3％ 268 850-4h Air 257
1380-2h H 2-3％ 268 900-4h Air 251
1380-2h H 2-3％ 268 950-4h Air 239
1380-2h H 2-3％ 268 1000-4h Air 245
1380-2h H 2-3％ 268 1050-4h Air 232
Embodiment 4 1380-2h H 2-3％ 363 900-4h Air 338
Embodiment 5 1380-2h H 2-3％ 363 900-4h Air 342
Embodiment 6 1380-2h H 2-3％ 329 900-4h Air 315
Comparative example 1 1380-2h H 2-3％ *465 900-4h Air 455
Comparative example 2 1380-2h H 2-3％ *471 900-4h Air 462
Embodiment 7 1380-2h H 2-3％ 402 900-4h Air 399
Comparative example 3 1380-2h H 2-3％ *445 900-4h Air 428
Embodiment 8 1380-2h H 2-3％ 391 900-4h Air 387
Comparative example 4 1380-2h H 2-3％ *493 900-4h Air 493
Comparative example 5 1380-2h H 2-3％ *505 900-4h Air 499
Embodiment 9 1380-2h H 2-3％ 31 900-4h Air 30
Embodiment 10 1380-2h H 2-3％ 371 900-4h Air 304
Comparative example 6 1380-2h H 2-3％ *490 900-4h Air 481
Comparative example 7 1380-2h H 2-3％ *502 900-4h Air 449
Embodiment 11 1380-2h H 2-3％ 367 900-4h Air 363
Embodiment 12 1380-2h H 2-3％ 351 900-4h Air 351
Embodiment 13 1380-2h H 2-3％ 134 900-4h Air 110
Table 3
Reoxidize condition T3 (℃-time) V10 (V) α10 Heat-resisting (%) Bending strength MPa
Reference example 1 800-4h 47.1 1.8 10 225.6
850-4h 12.3 3.8 3 225.6
900-4h 17.8 3.9 4 210.8
950-4h 33.2 4.3 2 220.6
1000-4h 89 4.1 5 216.7
Embodiment 1 900-4h 11.4 3.2 3 227.5
Embodiment 2 900-4h 12.2 2.9 5 223.6
Embodiment 3 800-4h 6.2 2 8 216.7
850-4h 8.5 2.7 4 212.8
900-4h 10.4 3.3 4 201.0
950-4h 13.2 3.6 5 215.7
1000-4h 17.2 3.8 6 210.8
1050-4h 24.2 4.1 4 223.6
Embodiment 4 900-4h 9.8 2.7 8 201.0
Embodiment 5 900-4h 10.4 2.8 13 213.8
Embodiment 6 900-4h 10.5 2.8 16 205.0
Comparative example 1 900-4h 7.2 2.5 *45 176.5
Comparative example 2 900-4h 6.54 2.4 *60 168.7
Embodiment 7 900-4h 8.3 2.5 28 175.5
Comparative example 3 900-4h 7.2 2.3 *70 176.5
Embodiment 8 900-4h 7.6 2.6 17 202.0
Comparative example 4 900-4h 9.1 2.7 *50 *131.4
Comparative example 5 900-4h 10.6 3.1 *76 *109.8
Embodiment 9 900-4h 9.4 2.7 24 215.7
Embodiment 10 900-4h 7.32 2.8 28 206.9
Comparative example 6 900-4h 13.3 3.3 *88 *100.0
Comparative example 7 900-4h 15.6 3.3 *100 *107.9
Embodiment 11 900-4h 8.8 2.9 25 191.2
Embodiment 12 900-4h 9.9 2.8 20 207.9
Embodiment 13 900-4h 19.3 4.1 2 222.6
In table 1～3, * represents the numerical value beyond the preferable range of the present invention.
Embodiment 2
Except carrying out in the same manner with embodiment 1 the degreasing condition implementing under the condition of 600 ℃ and 2 hours, make the nonlinear resistance sample, carry out identical test.The results are shown in table 1～3.
Embodiment 3
The polyvinyl alcohol (PVA) that adds 1.5 quality % is as binding agent, and the carbon content in the raw material is 6450ppm, at CO 2Atmosphere down in, the condition of 600 ℃ and 2 hours implements degreasing, in addition, carries out in the same manner with embodiment 1, makes the nonlinear resistance sample, carries out identical test.But in embodiment 3, as shown in table 2, the condition that reoxidizes changes between 800 ℃～1050 ℃, makes several samples.The results are shown among table 1～3 and Fig. 3.In the present embodiment, as shown in Figure 3, can confirm, exist with ... the temperature that reoxidizes, nonlinear resistance voltage V10 can be controlled to rough directly proportional relation.Nonlinear resistance voltage V10 changes with purposes, exists with ... the temperature that reoxidizes, and nonlinear resistance voltage V10 can be controlled to rough directly proportional relation, is the key factor as characteristic that nonlinear resistance requires.In addition, in the present embodiment, have to make and result from the advantage that the fluctuation of nonlinear resistance voltage V10 of the condition of reoxidizing reduces.
Reference example 1
The polyvinyl alcohol (PVA) that adds 0.5 quality % is as binding agent, and the carbon content in the raw material is 980ppm, implements degreasing in the condition of 800 ℃ and 12 hours, in addition, carries out in the same manner with embodiment 1, makes the nonlinear resistance sample, carries out identical test.But in reference example 1, as shown in table 2, the condition of reoxidizing is changed between 800 ℃～1000 ℃, make several samples.The results are shown among table 1～3 and Fig. 3.In reference example 1, as shown in Figure 3, can confirm that exist with ... the increase that reoxidizes temperature, nonlinear resistance voltage V10 increases significantly.Can confirm that promptly reference example 1 is compared with embodiment 3, the control of nonlinear resistance voltage is difficult.
Embodiment 4
The polyvinyl alcohol (PVA) that adds 1.5 quality % is as binding agent, and the carbon content in the raw material is 6450ppm, at N 2Implement degreasing under the condition of under atmosphere is enclosed 600 ℃ and 2 hours, in addition, carry out in the same manner, make the nonlinear resistance sample, carry out identical test with embodiment 1.The results are shown in table 1～3.
Embodiment 5
The polyvinyl alcohol (PVA) that adds 1.5 quality % is as binding agent, and the carbon content in the raw material is 6450ppm, at CO 2Atmosphere encloses down, implement degreasing under the condition of 600 ℃ and 2 hours, in addition, carries out in the same manner with embodiment 1, makes the nonlinear resistance sample, carries out identical test.The results are shown in table 1～3.
Embodiment 6
The polyvinyl alcohol (PVA) that adds 3.2 quality % is as binding agent, and the carbon content in the raw material is 13800ppm, implements degreasing under the condition of 600 ℃ and 2 hours, in addition, carry out in the same manner with embodiment 1, make the nonlinear resistance sample, carry out identical test.The results are shown in table 1～3.
Comparative example 1
The polyvinyl alcohol (PVA) that adds 3.2 quality % is as binding agent, and the carbon content in the raw material is 13800ppm, at N 2Implement degreasing under the condition of under atmosphere is enclosed 600 ℃ and 2 hours, in addition, carry out in the same manner, make the nonlinear resistance sample, carry out identical test with embodiment 1.The results are shown in table 1～3.Shown in table 1～3, the carbon content of observing after the degreasing is more than 2100ppm, and the carbon content behind the sintering is also many than 410ppm, the heat shock resistance deterioration in characteristics.
Comparative example 2
The polyvinyl alcohol (PVA) that adds 3.2 quality % is as binding agent, and the carbon content in the raw material is 13800ppm, at CO 2Implement degreasing under the condition of under the atmosphere 600 ℃ and 2 hours, in addition, carry out in the same manner, make the nonlinear resistance sample, carry out identical test with embodiment 1.The results are shown in table 1～3.Shown in table 1～3, the carbon content of observing after the degreasing is more than 2100ppm, and the carbon content behind the sintering is also many than 410ppm, the heat shock resistance deterioration in characteristics.
Embodiment 7
The polyvinyl alcohol (PVA) that adds 6 quality % is as binding agent, and the carbon content in the raw material is 25800ppm, implements degreasing under the condition of 600 ℃ and 2 hours, in addition, carries out in the same manner with embodiment 1, makes the nonlinear resistance sample, carries out identical test.The results are shown in table 1～3.
Comparative example 3
The polyvinyl alcohol (PVA) that adds 10 quality % is as binding agent, and the carbon content in the raw material is 43100ppm, implements degreasing under the condition of 600 ℃ and 2 hours, in addition, carries out in the same manner with embodiment 1, makes the nonlinear resistance sample, carries out identical test.The results are shown in table 1～3.Shown in table 1～3, the carbon content of observing after the degreasing is more than 2100ppm, and the carbon content behind the sintering is also many than 410ppm, the heat shock resistance deterioration in characteristics.
Embodiment 8
The polyvinyl alcohol (PVA) that adds 1.5 quality % is as binding agent, simultaneously, add the amorphous state shape carbon of 0.1 quality %, carbon content in the raw material is 8120ppm, under the condition of 600 ℃ and 2 hours, implement degreasing, in addition, carry out in the same manner with embodiment 1, make the nonlinear resistance sample, carry out identical test.The results are shown in table 1～3.
Comparative example 4
The polyvinyl alcohol (PVA) that adds 1.5 quality % is as binding agent, simultaneously, add the amorphous state shape carbon of 1 quality %, carbon content in the raw material is 15420ppm, under the condition of 600 ℃ and 2 hours, implement degreasing, in addition, carry out in the same manner with embodiment 1, make the nonlinear resistance sample, carry out identical test.The results are shown in table 1～3.Shown in table 1～3, the carbon content of observing after the degreasing is more than 2100ppm, and the carbon content behind the sintering is also many than 410ppm, heat shock resistance characteristic and bending strength deterioration.
Comparative example 5
The polyvinyl alcohol (PVA) that adds 1.5 quality % is as binding agent, simultaneously, add the amorphous state shape carbon of 2 quality %, carbon content in the raw material is 26580ppm, under the condition of 600 ℃ and 2 hours, implement degreasing, in addition, carry out in the same manner with embodiment 1, make the nonlinear resistance sample, carry out identical test.The results are shown in table 1～3.Shown in table 1～3, the carbon content of observing after the degreasing is more than 2100ppm, and the carbon content behind the sintering is also many than 410ppm, heat shock resistance characteristic and bending strength deterioration.
Embodiment 9
For raw material, do not add PVA, add the amorphous state shape carbon of 0.01 quality %, carbon content in the raw material is 114ppm, implements degreasing under the condition of 600 ℃ and 2 hours, in addition, carry out in the same manner with embodiment 1, make the nonlinear resistance sample, carry out identical test.The results are shown in table 1～3.
Embodiment 10
For raw material, do not add PVA, add the amorphous state shape carbon of 0.1 quality %, carbon content in the raw material is 1085ppm, implements degreasing under the condition of 600 ℃ and 2 hours, in addition, carry out in the same manner with embodiment 1, make the nonlinear resistance sample, carry out identical test.The results are shown in table 1～3.
Comparative example 6
For raw material, do not add PVA, add the amorphous state shape carbon of 2 quality %, carbon content in the raw material is 20259ppm, implements degreasing under the condition of 600 ℃ and 2 hours, in addition, carry out in the same manner with embodiment 1, make the nonlinear resistance sample, carry out identical test.The results are shown in table 1～3.Shown in table 1～3, the carbon content of observing after the degreasing is more than 2100ppm, and the carbon content behind the sintering is also many than 410ppm, heat shock resistance characteristic and bending strength deterioration.
Comparative example 7
For raw material, do not add PVA, add the amorphous state shape carbon of 5 quality %, carbon content in the raw material is 30445ppm, implements degreasing under the condition of 600 ℃ and 2 hours, in addition, carry out in the same manner with embodiment 1, make the nonlinear resistance sample, carry out identical test.The results are shown in table 1～3.Shown in table 1～3, the carbon content of observing after the degreasing is more than 2100ppm, and the carbon content behind the sintering is also many than 410ppm, heat shock resistance characteristic and bending strength deterioration.
Embodiment 11
The polyvinyl alcohol (PVA) that adds 1.5 quality % is as binding agent, simultaneously, add the SiC of 0.1 quality %, carbon content in the raw material is 7870ppm, under the condition of 600 ℃ and 2 hours, implement degreasing, in addition, carry out in the same manner with embodiment 1, make the nonlinear resistance sample, carry out identical test.The results are shown in table 1～3.
Embodiment 12
The polyvinyl alcohol (PVA) that adds 1.5 quality % is as binding agent, simultaneously, add the TiC of 0.1 quality %, carbon content in the raw material is 7060ppm, under the condition of 600 ℃ and 2 hours, implement degreasing, in addition, carry out in the same manner with embodiment 1, make the nonlinear resistance sample, carry out identical test.The results are shown in table 1～3.
Embodiment 13
As raw material, weighing SrCO 3, BaCO 3, CaCO 3, TiO 2, Nb 2O 5, Li 2O, SiO 2, fit in (the Sr that consists of that finally obtains 0.35Ba 0.35Ca 0.3) TiO 3+ Nb 2O 5(0.42mol%)+MnO (0.014mol%)+Li 2O (0.1 quality %)+SiO 2(0.1 quality %) in addition, carries out in the same manner with embodiment 1, makes the nonlinear resistance sample, carries out identical test.The results are shown in table 1～3.
Estimate
Shown in table 1～3, the nonlinear resistance factor alpha 10 of nonlinear resistance sample of the present invention is more than 2, and the fraction defective of expression heat shock resistance characteristic is below 30%, and bending strength is more than the 166.7MPa, can confirm to have good characteristic as nonlinear resistance.In addition, as shown in Figure 3, reference example 1 is compared with embodiment 3, can confirm as follows.That is, the carbon content in the ceramic composition after the degreasing is more than the 180ppm, and the carbon content in the ceramic composition behind the sintering is more than the 120ppm, controls the nonlinear resistance voltage that is caused by the temperature that reoxidizes processing easily.
Fig. 1 is the sectional drawing of the nonlinear resistance of the embodiment of the invention.
Fig. 2 is used to measure the nonlinear resistance voltage of nonlinear resistance of the embodiment of the invention and the circuit diagram of non linear coefficient.
Fig. 3 be the expression embodiment of the invention nonlinear resistance in the curve chart that reoxidizes temperature and nonlinear resistance voltage relationship.
Symbol among the figure: 2-sintered body, 4-electrode, 6-nonlinear capacitor,
8-direct current constant voltage power supply, 10-potentiometer, 12-galvanometer.

Claims (10)

1. voltage non-linear resistor is characterized in that, constitutes by containing the ceramic composition of strontium titanates as principal component, and the carbon content in the ceramic composition behind the sintering is below the 410ppm, and wherein, described ceramic composition contains:
With composition formula (Sr (1-x-y)Ba xCa y) mTiO 2+mPrincipal components expression, x=0.1～0.9, y=0.01～0.5, x+y＜1,0.98≤m≤1.02 and
Comprise the 1st element that is selected from Nb, Ta and the rare earth element at least a kind oxide the 1st accessory ingredient and
The 2nd accessory ingredient that comprises the oxide of the 2nd element that is selected among Mn, Co, Ni, Cu, Zn and the V at least a kind, and
The 3rd accessory ingredient that comprises the oxide of the 3rd at least a among Si and Al element;
When above-mentioned principal component is 100mol%, in the above-mentioned ceramic composition, contain above-mentioned the 1st accessory ingredient in the scope of 0.01～3mol%, scope at 0.005～3mol% contains above-mentioned the 2nd accessory ingredient, wherein, when representing above-mentioned the 2nd element, be the mol number when representing its oxide with MO with M;
When above-mentioned principal component is 100 quality %, contain above-mentioned the 3rd accessory ingredient in the scope of 0.005～1 quality %.
2. the described voltage non-linear resistor of claim 1 is characterized in that, the carbon content in the ceramic composition behind the sintering is more than the 120ppm.
3. the described voltage non-linear resistor of claim 1 is characterized in that, also contains the 4th accessory ingredient, and this accessory ingredient comprises the oxide that is selected from the 4th element more than at least a kind among Li, Na, k and the Rb;
When above-mentioned principal component is 100 quality %, in the scope of less than 0.1 quality %, contain above-mentioned the 4th accessory ingredient.
4. the voltage non-linear resistor composition is characterized in that, constitutes by containing the ceramic composition of strontium titanates as principal component, and the carbon content in the ceramic composition after the degreasing is below the 2100ppm, and wherein, described ceramic composition contains:
With composition formula (Sr (1-x-y)Ba xCa y) mTiO 2+mPrincipal components expression, x=0.1～0.9, y=0.01～0.5, x+y＜1,0.98≤m≤1.02 and
Comprise the 1st element that is selected from Nb, Ta and the rare earth element at least a kind oxide the 1st accessory ingredient and
The 2nd accessory ingredient that comprises the oxide of the 2nd element that is selected among Mn, Co, Ni, Cu, Zn and the V at least a kind, and
The 3rd accessory ingredient that comprises the oxide of the 3rd at least a among Si and Al element;
When above-mentioned principal component is 100mol%, in the above-mentioned ceramic composition, contain above-mentioned the 1st accessory ingredient in the scope of 0.01～3mol%, scope at 0.005～3mol% contains above-mentioned the 2nd accessory ingredient, wherein, when representing above-mentioned the 2nd element, be the mol number when representing its oxide with MO with M;
When above-mentioned principal component is 100 quality %, contain above-mentioned the 3rd accessory ingredient in the scope of 0.005～1 quality %.
5. the described voltage non-linear resistor composition of claim 4 is characterized in that the carbon content in the ceramic composition after the degreasing is more than the 180ppm.
6. voltage non-linear resistor is characterized in that, selects the composition and/or the degreasing condition of substance, and making the carbon content in the ceramic composition behind the sintering is below the 410ppm, and wherein, described ceramic composition contains:
With composition formula (Sr (1-x-y)Ba xCa y) mTiO 2+mPrincipal components expression, x=0.1～0.9, y=0.01～0.5, x+y＜1,0.98≤m≤1.02 and
Comprise the 1st element that is selected from Nb, Ta and the rare earth element at least a kind oxide the 1st accessory ingredient and
The 2nd accessory ingredient that comprises the oxide of the 2nd element that is selected among Mn, Co, Ni, Cu, Zn and the V at least a kind, and
The 3rd accessory ingredient that comprises the oxide of the 3rd at least a among Si and Al element;
When above-mentioned principal component is 100mol%, in the above-mentioned ceramic composition, contain above-mentioned the 1st accessory ingredient in the scope of 0.01～3mol%, scope at 0.005～3mol% contains above-mentioned the 2nd accessory ingredient, wherein, when representing above-mentioned the 2nd element, be the mol number when representing its oxide with MO with M;
When above-mentioned principal component is 100 quality %, contain above-mentioned the 3rd accessory ingredient in the scope of 0.005～1 quality %.
7. the manufacture method of voltage non-linear resistor is characterized in that, selects the composition and/or the degreasing process condition of substance, and making the carbon content in the ceramic composition behind the degreasing process is below the 2100ppm, and wherein, described ceramic composition contains:
With composition formula (Sr (1-x-y)Ba xCa y) mTiO 2+mPrincipal components expression, x=0.1～0.9, y=0.01～0.5, x+y＜1,0.98≤m≤1.02 and
Comprise the 1st element that is selected from Nb, Ta and the rare earth element at least a kind oxide the 1st accessory ingredient and
The 2nd accessory ingredient that comprises the oxide of the 2nd element that is selected among Mn, Co, Ni, Cu, Zn and the V at least a kind, and
The 3rd accessory ingredient that comprises the oxide of the 3rd at least a among Si and Al element;
When above-mentioned principal component is 100mol%, in the above-mentioned ceramic composition, contain above-mentioned the 1st accessory ingredient in the scope of 0.01～3mol%, scope at 0.005～3mol% contains above-mentioned the 2nd accessory ingredient, wherein, when representing above-mentioned the 2nd element, be the mol number when representing its oxide with MO with M;
When above-mentioned principal component is 100 quality %, contain above-mentioned the 3rd accessory ingredient in the scope of 0.005～1 quality %.
8. the manufacture method of the described voltage non-linear resistor of claim 7 is characterized in that, selects the composition and/or the degreasing process condition of substance, and making the carbon content in the ceramic composition behind the degreasing process is more than the 180ppm.
9. the manufacture method of claim 7 or 8 described voltage non-linear resistors is characterized in that, as above-mentioned degreasing process condition, carries out under degreasing process any environment in reproducibility environment, neutral environment, carbon dioxide environment.
10. the manufacture method of claim 7 or 8 described voltage non-linear resistors is characterized in that, contains in amorphous carbon, graphite, carbide, the organic compound any in the ceramic composition before degreasing process.
CNB001309986A 1999-10-04 2000-10-03 Voltage nonlinear resistance and its manufacturing method Expired - Fee Related CN1175434C (en)

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