TW464885B - Voltage nonlinear resistor and manufacturing method thereof - Google Patents

Abstract

The present invention provide 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

464885 V. Description of the invention (l) The technical field to which the invention belongs: The present invention relates to voltage non-linear resistors and detailed descriptions, and it is related to the resistance to shock resistance. The method of making 2 is more bang ^ ^ 7 " It is quite excellent in shock characteristics And, it has a very high resistance to ruggedness, and the varistor voltage is easy to control. 'Controlled voltage non-linear resistors and their know-how: As voltage non-linear resistors and # &#Main ^? Tf3. The varistor system is used for receiving and removing electronic devices such as motors.

J and, etc. are used. Yu Te Gazhao No. 55_494〇4: Lu Qi Titanium lithium is a varistor with lithium as the main component. This varistor not only has the function of a varistor, but also has the function of a capacitor. It can smoothly absorb glow discharge that may occur in electronic equipment. , Arc discharge, abnormal voltage and clutter. In Japanese Patent No. 2944697, a strontium titanate-barium titanate-calcium titanate-based varistor is proposed as a technique for controlling the temperature dependence of the varistor voltage. Problems to be solved by the invention:

However, 'such a titanate gill or a lithium titanate-barium titanate-calcium titanate varistor' is generally used as a component to absorb clutter. This clutter is generated by the rotor of a DC motor and Between the brushes. Therefore, in general, these series of rheostats are ring-shaped, and the electrodes of the rheostat and the rotor are connected by welding. During this welding operation, a large thermal shock is generated for the ring-shaped varistor element. In addition, the shape of the ring-shaped varistor with a high output f-force ratio of the combined motor tends to increase, and the thermal shock resistance of the varistor is expected to be improved accordingly.

4 6 4 8 8 5 ----------- Case_dragon .. 89120360_year i? Month rule day _ revised look __ V. Description of the invention (2) In view of this fact, the Department of the present invention The purpose is to provide a voltage non-linear resistor with excellent thermal shock resistance characteristics, high bending strength, and easy control of the varistor voltage, and a method for manufacturing the same. Means for solving the problem: In order to achieve the above-mentioned object, the voltage non-linear resistor according to the first aspect of the present invention is characterized in that it is composed of a ceramic tincture composition containing osmium titanate as a main component, The carbon content in the ceramic composition is 410 ppm or less, and is preferably 300 ppjn or less. The voltage non-linear resistor according to the second aspect of the present invention is to properly select the composition of the additive and / or the carbon content in the ceramic composition after firing can be 40 ppm or less, and preferably 300 ppm. Degreasing conditions. If the content of carbon is too large, the thermal shock resistance tends to decrease as the flexural strength of the voltage non-linear resistor decreases, which is not desirable. It is preferable that the carbon content in the ceramic composition after firing is 120 pp melon or more and 200 ppm or more. If the carbon content is too small, the varistor voltage tends to be difficult to control, so it is not good. In the present invention, "as a ceramic composition containing osmium titanate as a main component" is not particularly limited, but it is preferable that the aforementioned ceramic composition includes: This composition is based on a composition formula (Sr (bu " 邙 & / \) 1 ^ 102 + „1 to represent, where x = 0.09, 0.9, y = 0.05, 0.5, x + y < i, 〇, 98 ^ ms 1. 0 2 main components; ~ The first sub-component containing at least one oxide of the first element selected from the group consisting of sharp, group, and rare-earth elements; the first sub-component containing manganese, cobalt, nickel, copper, zinc, and vanadium Come in groups

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464885 Five 'invention description (3) __ Add a second sub-component of the second element oxide; and at least one of the third sub-component of the third element oxide's component: 0 before = component as 1 〇. In the case of Mole%, it is divided into the aforementioned first pair (Toou Mole%, preferably 0.5 ~ 2.0 Mole%: The aforementioned second pair means that the former Γth price is 5 Mole% ( In the form of "in the number of μ", _ indicates the case of the mole of the oxide when it is included in the ceramic composition, and the β component is to be regarded as 100 f% by weight. = (^ 005)% by mass' preferably in the range of 〇02 ~ 〇1% by mass and it is contained in the ceramic composition described above. Then x in Κίίϊ is less than °, 1 or y is less than 0 · In the case of 1, rise and variable resistance: The Γ characteristic is a negative characteristic. As a result, the temperature is ignored. Ί Because there is a tendency to cause a short circuit phenomenon, the θ center is 4 ^, and the right χ exceeds 0 · 9, then There is a "special": "Thinking" that cannot see the voltage of the varistor. And if 'y exceeds 0.5', the tendency to change the characteristics of the theft cannot be seen. Applying a gradually increasing voltage to 70, such as an applied voltage when a current of 10 milliamperes flows. And the so-called varistor characteristic refers to applying a gradually increasing voltage to In the case of one variable resistance, the current flowing through the element may increase non-linearly. I is an oxide of the first element of a hafnium species, which is a group formed of niobium, lithium, and rare earth elements. Examples can be as follows: pentoxide, niobium, tantalum pentoxide, yttrium oxide, lanthanum oxide, hafnium tetroxide, eleven

Page 6 464885 Fifth, invented coffee '-------- oxidized difin (prg〇ii), oxidized trioxide, osmium oxide, oxidized trioxide: ": Second test, fourth test, Trioxide secondary pin, trioxide-dihalide: ^ dioxin, oxidized record, dysprosium oxide, H bromide, etc. These emulsions are included in the above-mentioned mole% range and are included in the semiconductorization of a group of components. Examples of the second component that can help are as follows:-Manganese oxide, tetraoxide, cuprous oxide, oxidizing agent, pentoxide, etc. These ΐΐίί: the varistor ... and the non-linear characteristics of the oxygen: Properties: Ϊ: If the content of the substance is too small, the varistor voltage and the non-linear characteristics will tend to deteriorate. If too much, the Λ resistance Λ characteristics will obviously deteriorate. But the Mohr number of the second sub-component; In the case of 2 3 (dioxinium oxide), it is necessary to convert it to V05,2 and calculate it as the third auxiliary component. Examples include the following: Stone dioxide is an additive that contributes to the crystallinity of the composition. The third pair tends to have a sufficient density and the density will decrease. 'The characteristics of the varistor will be obvious. The composition further includes: the fourth sub-component containing at least one 4-membered oxide selected from the group consisting of lithium, sodium, and potassium. ㈣ to 7 In the case where the above-mentioned Jth element contains 100% by mass of the essential ingredient, in the aforementioned fourth pair of K = ΐ is less than 0.1% by mass, and ° · 5 ~ .. 5 is better: Within the range and included in the aforementioned ceramic composition. Better 464885 V. Description of the invention (5) As the fourth sub-component, it can be phased & τ & Li, Sodium Oxide, M ^ ^ $ Dioxide is an emulsified product that contributes to the non-linear coefficient of the rheostat. If the content of these oxides is too low, it will be non-post-generational age. ® · @ 的 于: Euphorization and subsequent fruiting tend to decrease. If it is too much, the characteristics of the varistor will be significantly degraded due to the inferiority of the inferiority. There is ί:! ΊΓ = ίVoltage non-linear resistor The composition is composed of a ceramic composition containing a content, and the carbon content of the degreased ceramic 1 is 2100 ppm or less. If the carbon content in the degreased ceramic composition exceeds 2100 ppm, it will be difficult to control the carbon content in the burnt-out ceramic composition to less than 410 ppm. , The thermal shock resistance tends to decrease, so it is not ideal. In this case, 'the carbon content in the ceramic composition after degreasing is preferably 180 ppm or more. The broken content in the ceramic composition after degreasing If it is less than 180 ppm, it will be difficult to control the carbon content in the ceramic composition after firing to 120 ppm or more, and the varistor voltage tends to be difficult to control, so it is not ideal. The method for manufacturing a voltage non-linear resistor according to the present invention is characterized in that the composition and the composition of the additives are selected so that the breaking content of the ceramic composition after the degreasing process is 2100 ppm or less, preferably 180 ppm or more and 2100 ppm or less. / Or degreasing engineering conditions. As the aforementioned degreasing process item #, the degreasing process is preferably performed under any of a reducing environment, a neutral environment, and a carbon dioxide gas environment. Preferably, the ceramic composition before the degreasing process includes amorphous carbon, graphite, carbide,

2030-346 (/-PFptd p. 8

5. Description of the invention (6) Any one of organic compounds. Regarding this "voltage non-linear resistor body", in order to protect the clutter absorption voltage, a varistor element can be appropriately used. Effects and Effects of the Invention: The present invention can provide a transformer voltage which is excellent in thermal shock resistance and has a high degree. An easy-to-control voltage non-linear resistor ^ its manufacturing method.… Embodiments of the invention: The present invention will be described in detail based on the embodiments. FIG. 1 is a profiler of a rheostat according to an embodiment of the present invention. The circuit diagram of the varistor voltage and the non-linear coefficient of the varistor of the embodiment of the present invention is shown in Fig. 6. The old, the third, and the third are the variable resistances. Graph of the relationship between the degree of resistance and the variable resistive voltage. Example 1: In order to make the final composition TiTiO3 + Nb205 (1 5 簟 mutual less, m λ ^ 0.35t5a0, 35La0.3 ; Cao Ermao Mo) (0.02 mol%) + Si〇2 (0.1 titanium oxide, five gills as raw materials gill carbonate, barium carbonate, calcium carbonate, dioxa niobium, silicon dioxide, etc. are weighed And deploy. Furthermore, Oxygen And Mole% of manganese monoxide are based on titanic acid ^^^^ 5 soil.) Add 3 # as Mole% in the case of 100 Mole%, and the mass% of monoxide will be presented. The quality of the rigid case ^ ° .35Ba ° .35Ca ") is called 100. Second, use a ball mill to mix this raw material for 10 to 20 hours, then add ^ 1648 8 5

5. Description of the invention (7) Dehydrate and dry. Thereafter, this raw material was preliminarily calcined at 11 50 to 1 250 ° C, and after coarsely pulverized, it was mixed again using a ball mill for 10 to 20 hours and then dehydrated and dried. Next, 1% by mass of polyvinyl alcohol (pvA) was added as a binder to this raw material. As a result, the carbon content in the raw material was 28Oppm. Next, this raw material was subjected to voluntary molding with a molding pressure of about 1,96 million Pa to obtain a disc-shaped preform having an outer diameter of 12.5 mm, an inner diameter of 8 mm, and a thickness of 1 millimeter.

Thereafter, the preform is degreased. As shown in Table 1 below, the degreasing system was performed under conditions of 600 ° C and 12 hours while continuously flowing air at a flow rate of 2 liters / minute. The carbon content in the degreased preform was 448 ppm. Next, 'as shown in Table 2, this preform was subjected to a reducing atmosphere of gas (97 vol%) + hydrogen (3 vol%)', and was baked at 138 ° C for 2 hours to obtain a semiconductor. Sintered body. As shown in Table 2, the carbon content of the sintered body after firing was 122 ppm. Thereafter, a reoxidation treatment of this sintered body is performed. The conditions of the reoxidation treatment are shown in Table 2 under the conditions of air (in an oxidizing environment), 900 t: and 4 hours. The carbon content of the sintered body after the reoxidation treatment was 11 lPpm. In addition, the carbon content was measured by weighing 0.2 g of the ground sample of the magazine spider, and then using a carbon-sulfur analyzer (EMIA520 manufactured by Horiba, Ltd.). 1 Secondly, in order to study the characteristics of the sintered body thus obtained, as shown in FIG. I, a silver solder paste is coated on the surface of the sintered body 2 and the silver electrode 4 is formed by fusion plating in 60 ° C to complete Varistor 6. Next, measure the varistor voltage V1 () and nonlinear coefficient of this varistor 6

2030-3460 (^? '〇1 (1 Section 10 胄 464685) V. Description of the invention (8) ----- 1 j Thermal shock characteristics (financial thermal characteristics) and flexural strength. Furthermore, the varistor voltage VI 0, As shown in FIG. 2, the varistor 6 is connected to a DC constant voltage power supply 8, and the voltage between the two poles of the varistor 6 is measured with a voltmeter 10, and the current flowing through the varistor 2 is read by an ammeter F is obtained by adding 6 to the current. Specifically, the current flowing through the varistor 6 is 10 milliamps, and 'the voltage across the electrodes of the varistor 6 is read by a voltmeter, and this value is used as the varistor. The voltage νι〇β non-linear coefficient α 丨 〇 can be obtained by the following mathematical formula (1). [Number 1]

α 10 = l〇g (Ii〇 / I,) / log (V10 / V1) = l / log (V10 / V1) ---- (1) Furthermore, 'V1 0 means, as shown in Figure 2 The varistor 6 makes the varistor voltage when Ii () = 1-10 milliamps of current flows; and V1 means that 1 ^ is not as obvious as the varistor 6 of FIG. 2 when the current of L = 1 milliamps flows Rheostat electric Li. The larger the non-linear coefficient α 1 〇, the more excellent the varistor characteristics.

The thermal shock resistance is implemented as follows. That is, for the varistor 6 shown in Fig. 1 after the electrode formation, it will be 38 °.匚 Hot soldering iron and solder are connected together for simulated soldering. After the soldering process, the stripping flux was inspected for cracks. 5 pieces of varistor element specimens each forming a 5-pole electrode were prepared. 20 such specimens were prepared, and a total of 100 poles of 5 poles were welded to each specimen. A total of 100 poles were welded, and cracks occurred in the 100 poles. The pole bran is expressed as a percentage. The flexural strength is obtained by using the same conditions as above.

464885 V. Description of the invention (9) Obtained in accordance with JIS-R1 601 in accordance with JIS-R1601. The measurement results are summarized and shown in Table 3.

2030-3460-PF-pld Page 12 46 48 8 5 V. Description of the invention (10) [Table 1] Added carbon content, added strength, degreasing conditions before degreasing, and substances added after degreasing (heavy carbon content 4 (ppm) T1 rc-time) Environmental carbon content (PPm) Reference Example 1 Polyvinyl alcohol 0.5 980 800-12 hours air-2 official minutes * 190 Polyvinyl alcohol 0.5 980 800-12 hours air-2 public minutes minute 190 Polyvinyl alcohol 0.5 980 800-12 small 8 ^ air-2 min / min 190 polyvinyl alcohol 0.5 9g 0 800-12 hours air-2 liter / min 氺 190 polyvinyl alcohol 0.5 980 800-12 small 4 air-2 liter / min * 190 Example 1 Polyvinyl alcohol 1 2820 600-12 hours air-2 minutes # 448 Example 2 Polyvinyl alcohol 1 2820 600-2 hours air-2 official minutes 605 Example 3 Polyvinyl alcohol 1.5 6450 600- 2 hours air-2 liters ^ min 829 polyhexenol 1.5 6450 600-2 small empty tr2 liter system | 829 polyhexenol 1.5 6450 600-2 hours air-2 hr min 829 polyvinyl alcohol 1.5 6450 600-2 Koito air * 2 Gongju minutes 829 polyvinyl alcohol 1.5 6450 600-2 Kochi air * 2 bulletin minutes 829 polyvinyl alcohol 1.5 6450 600-2 small volume of air * 2 liters per minute 829 Example 4 Polyvinyl alcohol 1.5 6450 600-2 small 4 Air gas-2 Gen_ 1916 Example 5 Polyvinyl alcohol 1.5 6450 600-2 Small ai 2078 Example 6 Polyvinyl alcohol 3.2 13800 600-2 small 'air * 2 liter fenbell 1380 Comparative Example 1 Polyvinyl alcohol 3.2 13800 600-2 hours Nitrogen-2 Sulfur 2799 Comparative example 2 Polyvinyl alcohol 3.2 13800 600-2 hours * 3083 Example 7 Polyvinyl alcohol 6 25800 600-2 hours air 2 book minutes 1788 Comparative example 3 Polyvinyl alcohol 10 43100 600-2 hours air 2 min. 2 minutes 氺 2374 Example 8 Polyvinyl alcohol (1.5% by weight ) + Carbon 0.1 8120 600-2 small 4 air 2 male well Fenzhong 1357 Comparative Example 4 polyvinyl alcohol (1.5% by weight) + broken 1 15420 600-2 hours air-2 public training 5447 Comparative Example 5 polyvinyl alcohol (1.5% by weight) + carbon 2 26580 600-2 hours air-2 liters * 7701 Example 9 0.01 114 600 ~ 2 hours empty tr2 published minutes 32 Example 10 carbon 0.1 1085 600-2 small 'air · 2 Gongju Min. 1470 Comparative Example 6 Break 2 20 259 600-2 hours Air-2 minutes Min. 14730 Comparative Example 7 Carbon 5 30 445 600- 2 hours air-2 ffV minutes 氺 23443 solid example 11 polyethylene (1 * 5 weight 0.1 7870 600-2 small 'air 2 minutes 1856 implementation, example 12 polyvinyl alcohol (1.5 weight t%) + Broken 0.1 7060 600-2 hours air-2 liter fenbell 1742 Example 13 Polyvinyl alcohol 1 2820 600-12 hours air · 2 liter 7 minutes 431 2030-346-: ??. ΡΗ Page 13 5. Description of the invention ( 11) [Table 2] 1 ί Carbon content after roasting (ppm) Reoxidation Carbon content (PPm) after reoxidation! Τ2 (° C — time) Environment Τ3 (0C — time) Environmental Reference Example 1 1380- 2 hours argon-3% 氺 110 800-4 hours air 103 1380-2 hours hydrogen-3% 氺 110 850-4 hours air 98 1380-2 hours argon-3 ° /. * 110 900-4 hours air 82 1380-2 hours hydrogen-3% 氺 110 950-4 hours air 80 1380-2 hours hydrogen-3% 氺 110 1000-4 hours air 77 Example 1 1380-2 hours hydrogen-3 % 122 900-4 hours of air 111 Example 2 1380-2 hours of argon-3% 205 900-4 hours of air 164 Example 3 1380-2 hours of hydrogen-3% 268 800-4 hours of air 263 1380-2 hours of argon Gas-3% 268 850-4 hours of air 257 1380-2 hours of hydrogen-3% 268 900-4 hours of air 251 1380-2 hours of hydrogen-3% 268 950-4 hours of air 239 1380-2 hours of hydrogen-3% 268 1000-4 hours air 245 1380-2 hours hydrogen-3% 268 1050-4 hours Γ air 232 Example 4 1380-2 hours hydrogen-3% 363 900-4 hours air 338 Example 5 1380-2 hours hydrogen-3 % 363 900-4 hours of air 342 Example 6 1380-2 hours of hydrogen-3% 329 900-4 hours of air 315 Comparative example 1 1380-2 hours of hydrogen-3% 氺 465 900-4 hours of air 455 Comparative example 2 1380- 2 hours hydrogen-3% * 471 900-4 hours air 462 Example 7 1380-2 hours argon-3% 402 900-4 hours air 399 Comparative example 3 1380-2 hours hydrogen-3% 氺445 900-4 hours of air 428 Example 8 1380-2 hours of hydrogen-3% 391 900-4 hours of air 387 Comparative Example 4 1380-2 hours of hydrogen-3% 氺 493 9004 hours of air 493 Comparative example 5 1380-2 hours of hydrogen -3% 505 900 4 hours air 499 Example 9 1380-2 hours argon-3% 31 900-4 hours air 30 Example 10 1380-2 hours hydrogen-3% 371 900-4 hours air 304: Comparison Example 6 1380-2 hours hydrogen-3% * 490 900-4 hours air 481 Comparative Example 7 1380-2 hours hydrogen-3% -3502 900-4 hours air 449 Example 11 1380-2 hours hydrogen-3% 367 900 -4 hours of air 363 Gui Example 12 1380-2 hours of hydrogen-3% 351 900-4 hours of air 351 Example 13 1380-2 hours of hydrogen-3% 134 0-4 hours of air 110 2030-346 (i-PF -piii Page 14 464885 V. Description of the invention (12) [Table 3] Reoxidation conditions V10 α10 Heat and flexural strength T3 (° C_time) (V) (%) Milli-Pascal Reference Example 1 800-4 hours 47.1 1.8 10 225.6 850-4 hours 12.3 3.8 3 225.6 900-4 hours 17.8 3.9 4 210.8 950-4 hours 33.2 4.3 2 220.6 1000-4 hours 89 4.1 5 216.7 Example 1 900-4 Time 11.4 3.2 3 227.5 Example 2 900-4 hours 12.2 2.9 5 223.6 Example 3 800-4 hours 6.2 2 8 216.7 850-4 hours 8.5 2.7 4 212.8 900-4 hours 10.4 3.3 4 201.0 950-4 hours 13.2 3.6 5 215.7 1000-4 hours 17.2 3.8 6 210.8 1050-4 hours 24.2 4.1 4 223.6 Example 4 900-4 hours 9.8 2.7 8 201.0 Example 5 900-4 hours 10.4 2.8 13 213.8 Example 6 900-4 hours 10.5 2.8 16 205.0 Comparative Example 1 900 · 4 hours 7.2 2.5 氺 45 176.5 Comparative Example 2 900-4 hours 6.54 2.4 氺 60 168.7 Example 7 900 ~ 4 hours 8.3 2.5 28 175.5 Comparative Example 3 900-4 hours 7.2 2.3 氺 70 176.5 Example 8 900 ~ 4 hours 7.6 2.6 17 202,0 Comparative Example 4 900-4 hours 9.1 2.7 氺 50 氺 131.4 Comparative Example 5 900-4 hours 10.6 3.1 氺 76 * 109.8 Example 9 9004 hours 9.4 2.7 24 215.7 Example 10 900- 4 hours 7.32 2.8 28 206.9 Comparative Example 6 900-4 hours 13.3 3.3 * 88 氺 100.0 Comparative Example 7 900-4 hours 15.6 3.3 * 100 * 107.9 Example 11 900 ~ 4 hours 8.8 2.9 25 191.2 Example 12 900-4 hours 9.9 2.8 20 207.9 Example 13 900-4 hours 19.3 4.1 2 222.6 2030-34 6,0-PF-ptd Page 15

氺 indicates a deviation from the preferred range of the present invention. Fifth, the description of the invention (13) and ′ are the values in Tables 1 to 3. Example 2: Except for the implementation of the conditions other than the implementation of the 'experiment'. The results are shown in Table 3! ... samples to perform the same test. Example 3: The carbon content in Additive 1 was 645: 〇 卿 'ethidium alcohol (PV :) as a raw material for the binder'. (3) The condition of hours is as follows: the varistor sample is made under the same conditions as in the environment, and the remaining sound is the same as that in Example 1. As shown in Table 2, #oxidized strip II is the same test. However, in the examples, the emulsification conditions were varied from 80 0 ° to 1 flRn h to change to 2 and various samples were prepared. As a result, as shown in Fig. 3, it can be confirmed that M 3 = 3. For the case where J = electricity = which is slightly proportional, this can be attributed to the re-oxidation condition, but for this implementation it is small and has this-advantage. Double Resistance ™ Voltage Variation Reduction Reference Example 1: 1 What is the point of adding u mass% of polyvinyl alcohol? 8〇PPm, the same as in Example 1 except that 800 ×: and carbon content in the raw material for 12 hours were the same as in Example 1:

464885

The same test. However, for Reference Example i, it is changed between 800 X: ~ 1,000, as shown in Figure 3 and Figure 3. For reference example] Increase in reoxidation temperature, varistor lightning For reference example 1, it is difficult to compare with example 3. Example 4: As shown in Table 2, the re-hybridization condition was to prepare various samples. The results are shown in the table. As shown in FIG. 3 ', it can be confirmed that the dependence on the pressure v 1 0 significantly increases. That is, 'the amount of polyethylene which can confirm the control of the varistor voltage is 1/0, 0,650 ppm, except that the carbon content in the raw material as a gas binder is used as a degreasing condition * at 600 ° under the environment C and two-hour condition samples were performed in the same manner as in Example 1 to make a rheostat. Example 5: The test results are shown in Table 3. Adding 5 mass% of the polymerization amount is 645Oppm, except for-alcohol as a binder, the condition of carbon content in the raw material is used as a degreasing strip and the gas environment is 600 ° C and 2 small as a rheostat sample, who = 1, The rest are the same as in Example 丨, Example 6: Sample test. The results are shown in Table 3. Adding 3.2% by mass of polyethylene strip was 13800 ppm, except for 6%. Except for the carbon content in the raw material as a binder, the rest were tested in the same manner as the degreasing conditions under the conditions of 2 hours and 2 hours. The result is shown in Figure 5. A varistor sample was made to perform the comparison shown in Figure 1 and * d. 'Adding 3.2% by mass of poly, the carbon content in the raw materials and the conditions for 2 hours amounted to 1 38 00 ppm, and the scopolamine was reduced as a bond in the nitrogen ring $ π ^ ^ long * brother to 600.

464885 V. Description of the invention (15) Except for the degreasing conditions, the rest are the same as in Example 丨, and a variable resistance sample is made for the same test. The results are shown in Table 3. As shown in Table 3, the carbon content after degreasing is more than 2100 ppm, and the carbon content after calcination is more than 41 Ορριη. Deterioration of thermal shock resistance can be observed. Comparative Example 2: Polyvinyl alcohol was added as a binder in an amount of 3_2% by mass, and the amount in the raw material was 13800 PPffl, except for the degreasing conditions of the strips at 600 and 9:00 in a carbon dioxide gas environment, and the rest All are the same as those in the implementation of ㈣. The results are shown in Table 3. As shown in Table 3, the carbon content after degreasing is more than 2 ΙΟρρπι, and 妗 carbon. Degradation of thermal shock characteristics was observed. Example 7: Adding 6% by mass of polyethylene glycol as a binder, the starting material was 2, except 600. . The conditions of 2 hours were used as the degreasing conditions. The rest were the same as those in Example 1. A varistor sample was made, and a "test" was performed. The results are shown in Table 3. Inquiry Comparative Example 3: Except for the carbon content in the amount ==, the rest are the same as in Example i and are shown in Tables 1 to 2. As shown in the table, the carbon content of the carbon is more than 21,000 ppm, and the carbon content after firing is more than ’, and the deterioration of the thermal shock resistance is observed. PPm also Example 8:

V. Description of the invention (16) With the addition of 1.5% by mass of 0.1% by mass of amorphous fracture: Alcohol as a binder, the carbon content of your raw materials added at 600 t and 2 hours is 81 20ppm, except for the example 1 is the same, making the varistor H is outside the conditions of the moon, the rest are shown in the implementation table 3. ° sample to perform the same test. The results are as Comparative Example 4: With the addition of 1.5 mass of a # 1 mass% of amorphous carbon, the original. Material; 作为 2 as a binder '-add 60 (TC and 2 hours conditions: is: J: the amount is 1 5420,' except the same as 1, make a rheostat test description, the rest of the white and only examples ^^ 10 Π ^ Samples are subjected to the same test. The results are shown in Tables 1 to d. As shown in Tables 1 to 3, the initial carbon content is greater than 2100 ppm, and The carbon content after firing was more than μ ^ Λ,, 2, ^ than 41 〇ΡΠΠ1, and the degradation of thermal shock resistance and flexural strength was observed. Comparative Example 5:

Jt added 1.5 mass% of polyvinyl alcohol as a binder 'and added 2 substances together. Amount of amorphous carbon, the carbon content in the raw material is 2658 0ppm 'except that the conditions of 60 ° C and 2 hours are used as the degreasing conditions, the rest are the same as in Example 1, and a varistor sample is made to perform the same The results are shown in Table 3. As shown in Table 3, the carbon content after degreasing is more than 210,01)? 11], and the carbon content after baking is more than 41,0 ppm, and heat resistance can be observed. Deterioration of impact characteristics and flexural strength. Example 9: To the raw material 'without the addition of polyvinyl alcohol', 0.01% by mass of amorphous carbon was added. The carbon content in the raw material was 114 ppm, except for 600. (: And 2 hours

2030-346 (/-PF'ptii Page 19 V. Explanation of the invention (π) The conditions are the same as in Example 1 except that the degreasing conditions are the same as in Example 1. Samples of varistor were made for the same test. The results are shown in Table 1 ~ This is shown in Example 10. Example 10: For the raw materials, no polyvinyl alcohol was added, and 0.1% by mass of amorphous carbon was added. The carbon content in the raw materials was 1.085 ppra, except that the conditions of 600 ° C and 2 hours were used as Except for the degreasing conditions, the rest are the same as in Example 1. A varistor sample was made to perform the same test. The results are shown in Table 3. Comparative Example 6:

Regarding the raw materials, no polyvinyl alcohol was added, and 2% by mass of the amorphous carbon was added. The carbon content in the raw materials was 20,259 ppm. The conditions were the same as those for degreasing except for the conditions of 600 ° C and 2 hours as the degreasing conditions. Example 1 was the same, and a varistor sample was made to perform the same test. The results are shown in Table 3. As shown in Tables 1 to 3, the carbon content after degreasing was more than siooppm, and the carbon content after firing was more than 41 Oppm. Deterioration of thermal shock resistance and flexural strength was observed. Comparative Example 7: As for raw materials, no polyvinyl alcohol was added, and 5% by mass of amorphous carbon was added. 'The carbon content in the raw materials was 30445 ppm' except that the conditions of 600 ° C and 2 hours were used as degreasing conditions. In the same manner as in Example 1, a varistor sample was prepared to perform the same test. The results are shown in Table 3 ^ As shown in Tables 1 to 3, 'The carbon content after degreasing is more than 2100ρρπι, and the carbon content after firing is more than 41 Oppm. Deterioration of thermal shock resistance and flexural strength can be observed. . Example 11:

2030 * 346 (i-PF.ptd Page 20 ^ 6488〇 Five, description of the invention (18) With the addition of 1.5% by mass of polyvinyl alcohol as a binder, together with 0.1% by mass of carbonized stone Xi ' The carbon content in the raw material was 7870 ppm. The conditions were the same as in Example 1 except that the conditions of 60 ° C and 2 hours were used as the degreasing conditions. A varistor sample was made for the same test. The results are shown in Tables 1 to 3. Example 12 2: With the addition of 1.5% by mass of polyvinylacetate as a binder, the carbon content in the 0.1% by mass of the obstructing titanium 'raw material was 70.6 ppm, except for 600. The conditions of 1 and 2 hours were the same as those in Example 1 except that the conditions of degreasing were the same. The varistor samples were made for the same test. The results are shown in Tables 1 to 3. Example 13: In order to obtain the final result The composition is titanic acid (Sr,

Ti03 + Nb205 (0.42 mol%) + MnO (〇, 〇14 mol%) ° · 3 ^ =, except for argon sulfonium = acid (Crane, barium carbonate, acid inhibitor, osmium dioxide, Except for Sinioni oxide, lithium oxide, silicon dioxide, etc., which were weighed and formulated, the rest were the same as those in the example (phase = j) as a rheostat sample, and the same test was performed. The results are shown in Table 3. Evaluation: Department / Second 23: Π: The device sample has good characteristics under non-linearity, with an anti-f strength of ==. Also, as shown in FIG.

9) Confirm the following. That is, it can be confirmed that the carbon content in the degreased ceramic-Kouxiang is 180 ppm or more, and the carbon content in the ceramic composition after firing is 120 ppm or more, and the varistor is caused by the temperature of the reoxidation treatment. The voltage becomes easy to control. Brief description of the drawings: FIG. 1 is a partial plan view of a varistor according to an embodiment of the present invention. Fig. 2 is a circuit diagram for measuring a varistor voltage and a nonlinear coefficient of a varistor according to an embodiment of the present invention. Fig. 3 is a top-line diagram showing the relationship between the reoxidation temperature and the varistor voltage of the varistor according to the embodiment of the present invention. [Explanation of symbols] 2 --- Sintered body 4--Electrode 6--Rheological resistor 8--DC constant voltage power supply 10--Voltmeter 12--Ammeter

2030-346li-FF-! ≫ td Page 22

Claims (1)

s 0 8 8 § Case No. ⑽fin_ <? „Yan Youyue-6. Application for patent scope 1. A voltage non-linear resistor characterized by using a ceramic composition containing strontium titanate as the main component The carbon content in the ceramic composition after firing is 410 ρριη or less. 2. The voltage non-linear resistor as described in item 1 of the scope of the patent application, wherein the carbon content in the ceramic composition after firing is 120 ppm. 3. The voltage non-linear resistor according to item 1 or 2 of the scope of the patent application, wherein the aforementioned ceramic composition includes: represented by a composition formula (Sr (卜 x_y) BaxCay) JiOw, where X = 0 . 0.9, y = 〇, 〇 〇 0.5, x + y < l, 0.98SmSl. 〇2 main components; contains at least one of the group consisting of sharp, group and rare earth elements to select The second subcomponent of the first element oxide; the second subcomponent of the second element oxide containing at least one selected from the group consisting of manganese, cobalt, nickel, copper, zinc, and vanadium ; And the third component contained in the hair and the inscription: before The main ingredient is taken as the case of 00 mole% in the foregoing case: and included in the aforementioned research combination: the middle ingredient is in the range of om]% by mass and the === in the third pair. I withered in the description Ceramic composition 464385 ___Case No. 89120360_ Year Article ___ 6. Application for Patent Scope 4. The voltage non-linear resistor as described in item 3 of the scope of application for patent, which further includes: containing a chain, nano, god and rice The fourth sub-component of at least one or more oxides of the fourth element selected by forming a group; when the aforementioned main component is taken as 100% by mass, the aforementioned fourth sub-component is less than 0, 1 mass! ^ Is included in the aforementioned ceramic composition. 5. A composition for a voltage non-linear resistor, which is characterized by using a ceramics composition containing acid crane as a main component, and the carbon content in the degreased ceramic composition is 2100 ppm or less. 6. The composition for a voltage non-linear resistor according to item 5 of the scope of the patent application, wherein the carbon content in the degreased ceramic composition is 180 ppm or more. 7-A voltage non-linear resistor, in order to make the carbon content in the ceramic composition after firing be 410 ppm or less, the composition of the additives and / or degreasing conditions are selected. 8. A method for manufacturing a voltage non-linear resistor, characterized in that the composition of the additives and / or the degreasing process are selected so that the breaking content of the ceramic composition after the degreasing process is 2 ppm or less. condition. 9. The method for manufacturing a voltage non-linear resistor according to item 8 of the scope of the patent application, wherein the composition of the additive and / or the degreasing process is selected so that the carbon content in the ceramic composition after the degreasing process is 180 ppm or more. condition. 1 0. Voltage non-linear resistance as described in item 8 or 9 of the scope of patent application 4 6 4 i A: _Case No. 89120360_year month __ VI. Manufacturing method of the scope of patent application, which is used as the aforementioned degreasing project Conditions, the degreasing project is carried out in any of a reducing environment, a neutral environment, and a carbon dioxide gas environment. 11. The method for manufacturing a voltage non-linear resistor according to item 8 or 9 of the scope of the patent application, wherein the ceramics before the degreasing process and the composition include amorphous composites, graphite, carbides, and organic compounds. Either. 2030-3460-PF2.ptc Page 25