JPS63268202A - Dielectric porcelain having varistor characteristic and manufacture thereof - Google Patents
Dielectric porcelain having varistor characteristic and manufacture thereofInfo
- Publication number
- JPS63268202A JPS63268202A JP62102543A JP10254387A JPS63268202A JP S63268202 A JPS63268202 A JP S63268202A JP 62102543 A JP62102543 A JP 62102543A JP 10254387 A JP10254387 A JP 10254387A JP S63268202 A JPS63268202 A JP S63268202A
- Authority
- JP
- Japan
- Prior art keywords
- porcelain
- varistor
- semiconductor
- dielectric
- ions
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 229910052573 porcelain Inorganic materials 0.000 title claims abstract description 20
- 238000004519 manufacturing process Methods 0.000 title claims description 8
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 10
- 150000004706 metal oxides Chemical class 0.000 claims abstract description 10
- 239000004065 semiconductor Substances 0.000 claims abstract description 9
- 238000000034 method Methods 0.000 claims abstract description 6
- 229910001415 sodium ion Inorganic materials 0.000 claims abstract description 6
- 239000013078 crystal Substances 0.000 claims abstract description 5
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 claims abstract description 3
- 239000000463 material Substances 0.000 claims abstract description 3
- 150000001875 compounds Chemical class 0.000 claims abstract 4
- 239000000919 ceramic Substances 0.000 claims description 8
- 238000005245 sintering Methods 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims 1
- 239000000843 powder Substances 0.000 abstract description 7
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 abstract description 4
- 239000000203 mixture Substances 0.000 abstract description 4
- 239000004372 Polyvinyl alcohol Substances 0.000 abstract description 2
- 229920002451 polyvinyl alcohol Polymers 0.000 abstract description 2
- 238000005476 soldering Methods 0.000 abstract description 2
- LEDMRZGFZIAGGB-UHFFFAOYSA-L strontium carbonate Chemical compound [Sr+2].[O-]C([O-])=O LEDMRZGFZIAGGB-UHFFFAOYSA-L 0.000 abstract description 2
- 229910000018 strontium carbonate Inorganic materials 0.000 abstract description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 abstract 2
- ZKATWMILCYLAPD-UHFFFAOYSA-N niobium pentoxide Chemical compound O=[Nb](=O)O[Nb](=O)=O ZKATWMILCYLAPD-UHFFFAOYSA-N 0.000 abstract 2
- 229910002370 SrTiO3 Inorganic materials 0.000 abstract 1
- 229910052681 coesite Inorganic materials 0.000 abstract 1
- 229910052906 cristobalite Inorganic materials 0.000 abstract 1
- 239000008187 granular material Substances 0.000 abstract 1
- 150000003839 salts Chemical class 0.000 abstract 1
- 239000000377 silicon dioxide Substances 0.000 abstract 1
- 235000012239 silicon dioxide Nutrition 0.000 abstract 1
- 229910052682 stishovite Inorganic materials 0.000 abstract 1
- 229910052905 tridymite Inorganic materials 0.000 abstract 1
- 229910000679 solder Inorganic materials 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 3
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 2
- WMWLMWRWZQELOS-UHFFFAOYSA-N bismuth(iii) oxide Chemical compound O=[Bi]O[Bi]=O WMWLMWRWZQELOS-UHFFFAOYSA-N 0.000 description 2
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 2
- 230000035939 shock Effects 0.000 description 2
- 229910052709 silver Inorganic materials 0.000 description 2
- 239000004332 silver Substances 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 229910010293 ceramic material Inorganic materials 0.000 description 1
- BERDEBHAJNAUOM-UHFFFAOYSA-N copper(I) oxide Inorganic materials [Cu]O[Cu] BERDEBHAJNAUOM-UHFFFAOYSA-N 0.000 description 1
- KRFJLUBVMFXRPN-UHFFFAOYSA-N cuprous oxide Chemical compound [O-2].[Cu+].[Cu+] KRFJLUBVMFXRPN-UHFFFAOYSA-N 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000012776 electronic material Substances 0.000 description 1
- 230000005496 eutectics Effects 0.000 description 1
- 238000005469 granulation Methods 0.000 description 1
- 230000003179 granulation Effects 0.000 description 1
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum oxide Inorganic materials [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 description 1
- 229910052745 lead Inorganic materials 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- 150000003891 oxalate salts Chemical class 0.000 description 1
- KTUFCUMIWABKDW-UHFFFAOYSA-N oxo(oxolanthaniooxy)lanthanum Chemical compound O=[La]O[La]=O KTUFCUMIWABKDW-UHFFFAOYSA-N 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
Landscapes
- Compositions Of Oxide Ceramics (AREA)
- Ceramic Capacitors (AREA)
- Thermistors And Varistors (AREA)
- Inorganic Insulating Materials (AREA)
Abstract
Description
【発明の詳細な説明】
[産業上の利用分野]
この発明は、誘電体としての特性と共にバリスタとして
の電圧非直線特性を備えた磁器とその製造方法に関する
。DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a porcelain having characteristics as a dielectric and voltage nonlinear characteristics as a varistor, and a method for manufacturing the same.
[従来の技術]
5rTiOa系の焼結体からなる磁器は、典型的な粒界
利用型の電子材料用セラミクスであり、見かけ上の高い
誘電率と共に、電圧非直線特性、いわゆるバリスタ特性
を有している。[Prior Art] Porcelain made of a 5rTiOa-based sintered body is a typical ceramic for electronic materials that utilizes grain boundaries, and has an apparent high dielectric constant as well as voltage nonlinear characteristics, so-called varistor characteristics. ing.
従来用いられていたこれらの磁器は、5rT103系磁
器材料にBi20a、Cu2O、’PbO。These porcelains conventionally used include 5rT103-based porcelain materials with Bi20a, Cu2O, and 'PbO.
ZnO等の微量な金属酸化物を添加して混合したものを
、焼結させたものである。この磁器は結晶粒界に上記金
属酸化物が析出し、N型半導体磁器としての構造を呈し
ている。It is made by sintering a mixture to which a trace amount of metal oxide such as ZnO is added. This porcelain has the structure of N-type semiconductor porcelain, with the metal oxide precipitated at the grain boundaries.
[発明が解決しようとする問題点]
し2カ)し、上記の静電容量を有するバリスタは、誘電
損失(tanδ)が大きく、また熱衝撃に対して弱く、
半田付けの際に結晶板にクラックが生じゃずいという欠
点がある。これは結晶粒界に拡散した金属或はそれらの
酸化物が上記金属酸化物の層と異質な第二の層を形成す
ること力(原因と考えられる。[Problems to be solved by the invention] 2) The varistor having the above-mentioned capacitance has a large dielectric loss (tan δ) and is weak against thermal shock.
The drawback is that cracks may form on the crystal plate during soldering. This is thought to be caused by the fact that the metals or their oxides diffused into the grain boundaries form a second layer that is different from the metal oxide layer.
この発明は上記従来の問題点を解決し、大きな静電容量
と低いバリスタ電圧が得られながら、熱衝撃に強い磁器
とその製造方法を提供することを目的とする。It is an object of the present invention to solve the above-mentioned conventional problems and to provide a porcelain that is resistant to thermal shock while providing a large capacitance and a low varistor voltage, and a method for manufacturing the same.
[問題を解決するための手段]
即ち、第一の発明しこよる静電容量を有するバリスタ特
性を有する誘電体磁器は、微量の金属酸化物を添加して
半導体化させた5rTiCh系磁器結晶の粒界付近に、
Naイオンを拡散させたものである。[Means for solving the problem] That is, the dielectric ceramic having varistor characteristics with high capacitance according to the first invention is made of a 5rTiCh ceramic crystal made into a semiconductor by adding a trace amount of metal oxide. Near the grain boundaries,
It is made by diffusing Na ions.
また、第二の発明し乙よる上記誘電体磁器の製造方法は
、微量の金属酸化物が添加された5rTiOq 系磁
器材料を焼結させて得られた焼結体の表面;こ、Naの
化合物を塗布し、熱処理するものである。In addition, the method for manufacturing dielectric ceramic according to the second invention (B) includes the surface of a sintered body obtained by sintering a 5rTiOq-based ceramic material to which a trace amount of metal oxide is added; is applied and heat treated.
[実 施 例] 次に、この発明の具体的な実施例について説明する。[Example] Next, specific embodiments of the present invention will be described.
(S r+−×1Vh) (T j、 I−YM’Y
) 03’ (但し、M=、Ca、Mg、Pb、Ba、
M’ =Sn、Z「)のXおよびYがそれぞれ第1表の
第一成分の各欄の値になるように純度99.0%以」−
のSrCO3、TiO2および上記M、、M’の炭酸塩
、シュウ酸塩、硝酸塩若しくは酸化物をそれぞれ秤量配
合した。そして、これをボールミルにより20時間攪拌
し、乾燥した後、粉砕した。さら 5に、粉砕後の粉末
を1200℃で3時間焼成し、再び粉砕した。これによ
り、第一成分が得られる。(S r+-×1Vh) (T j, I-YM'Y
) 03' (However, M=, Ca, Mg, Pb, Ba,
The purity is 99.0% or more so that M' = Sn, Z's X and Y are respectively the values in each column of the first component in Table 1.
SrCO3, TiO2, and carbonates, oxalates, nitrates, or oxides of the above M, , M' were weighed and blended, respectively. Then, this was stirred for 20 hours using a ball mill, dried, and then ground. Furthermore, the powder after pulverization was calcined at 1200° C. for 3 hours and pulverized again. This yields the first component.
この第一成分の100モル部(一定)に対し、純度99
.0%以上のNbp○5、T a205、N d203
、Dyp03、Y20q、La2O3、Ce0qから選
択された一種以上の金属酸化物(第二成分)の粉末と、
純度99.0%以上のS i 02、A l 203、
MnO2から選択された1種以上の金属酸化物(第四成
分)の粉末とを、それぞれ第1衷ζこ示す比率になるよ
うに秤量した。Purity 99% for 100 mole parts (constant) of this first component
.. 0% or more Nbp○5, T a205, N d203
, Dyp03, Y20q, La2O3, and Ce0q powder of one or more metal oxides (second component);
S i 02, A l 203 with a purity of 99.0% or more,
Powder of one or more metal oxides (fourth component) selected from MnO2 were weighed so as to have the ratios shown in the following.
次にこれらの粉末をボールミルにより20時間攪拌し、
混合した。さらに有機結合材として上記混合物に対して
10〜15重量%のポリビニルアルコールを混入し、造
粒した後、約10.OO,kg/cm2の圧力で直径1
3mm、厚さ1.2…1nの円板に加圧成型した。これ
らの円板をN2・ガス(95容積%)とH2ガス(5容
積%)とからなる還元雰囲気し乙於て、約1400℃の
温度で3時間焼成し、直径10mm、厚ざQ、8mmの
半導体磁器を得た。Next, these powders were stirred for 20 hours using a ball mill.
Mixed. Further, 10 to 15% by weight of polyvinyl alcohol is mixed into the above mixture as an organic binder, and after granulation, about 10% by weight is added. Diameter 1 at a pressure of OO, kg/cm2
It was press-molded into a disk with a diameter of 3 mm and a thickness of 1.2...1 nm. These discs were fired in a reducing atmosphere consisting of N2 gas (95% by volume) and H2 gas (5% by volume) at a temperature of about 1400°C for 3 hours to give a diameter of 10 mm, thickness Q, and 8 mm. of semiconductor porcelain was obtained.
次にこの磁器の表面にNaのフッ化物あるいは酸化物を
1.0m、g/ cm2の割合で塗布し、大気中におい
て、800〜1250°Cの温度で30分間熱処理し、
Naイオンを半導体磁器の中に拡散させた。Next, Na fluoride or oxide was applied to the surface of this porcelain at a rate of 1.0 m and g/cm2, and heat treated in the air at a temperature of 800 to 1250°C for 30 minutes.
Na ions were diffused into the semiconductor porcelain.
次に上記磁器の特性を調べるために、第1図で示すよう
に、磁器1の両主面に公知の銀ベーストを塗布し、これ
を800℃の温度で焼き付け、直径約7闘の銀電極2.
2を形成し、バリスタを構成した。そして、このバリス
タについて、バリスタ電圧V1、非直線係数α、バリス
タ電圧■1の温度変化率へv1、静電容量C及び誘電損
失tanδをそれぞれ測定し、さらにハンダ耐熱性の試
験を実施した。その結果を第2表に示す。Next, in order to investigate the characteristics of the above porcelain, as shown in Fig. 1, a known silver base coat was applied to both main surfaces of the porcelain 1, and this was baked at a temperature of 800 degrees Celsius, and silver electrodes with a diameter of about 7 cm were applied. 2.
2 to form a varistor. Then, for this varistor, the varistor voltage V1, the nonlinear coefficient α, the temperature change rate v1 of the varistor voltage 1, the capacitance C, and the dielectric loss tan δ were measured, and a solder heat resistance test was conducted. The results are shown in Table 2.
バリスタ電圧■1は第2図に示す回路を使用して測定し
た。即ち直流定電流電源EにバリスタVRを接続し、ま
た直流定電流電源Eとバ刀スタVRとの間に電流計Aを
接続し、゛バリスタ電圧に並列に電圧計Vを接続した。Varistor voltage (1) was measured using the circuit shown in FIG. That is, a varistor VR was connected to a DC constant current power source E, an ammeter A was connected between the DC constant current power source E and the batten VR, and a voltmeter V was connected in parallel to the varistor voltage.
そして、バリスタVRた゛けを20°Cの温度に保たれ
た恒温槽Cに収納してバリスタVR+に1mへの電ン禿
■1 を?克し、その時の電圧を測定してバリスタ電圧
V1 とした。Then, store the varistor VR+ in a thermostatic chamber C maintained at a temperature of 20°C, and apply an electric current to 1m to the varistor VR+. The voltage at that time was measured and defined as the varistor voltage V1.
非直線係数αは上記第2図の装置を使用し、バリスタ電
圧V1の他にバリスタVRに10m Aの電流1+nを
冶じた時の印加電圧V+pを測・定し次式により求めた
。The nonlinear coefficient α was determined by using the apparatus shown in FIG. 2, and by measuring the applied voltage V+p when a current 1+n of 10 mA was applied to the varistor VR in addition to the varistor voltage V1, and using the following equation.
log (l[]/11) 1m度変化率八
■1は第2図の装置に於て、恒温槽C内の温度を一40
°C〜+125℃の範囲で変化させ、各温度T(℃)に
おいてバリスタVRに1mへの電流を流した時のバリス
タ電圧VTを測定し、これが20℃のときのV1ζこ対
しどの程度変化したかを次式で求めた。なお、6衷には
前記温度範囲に於ける上記へV1の最大値を示した。log (l[]/11) 1m degree change rate 8 ■ 1 is the temperature in the thermostatic chamber C in the apparatus shown in Figure 2 at -40
We measured the varistor voltage VT when a current of 1 m was passed through the varistor VR at each temperature T (°C) by changing it in the range of °C to +125 °C, and how much did this change from V1ζ at 20 °C? was calculated using the following formula. In addition, the maximum value of V1 above in the above temperature range is shown on the 6th side.
ハンダ耐熱試験は、上記バリスタを80°Cの温度で2
分間予熱した後、これを270℃の共晶ハンダに3秒間
浸漬し、クラックの有無を目視検査するすることで行っ
た。In the solder heat resistance test, the above varistor was tested at a temperature of 80°C.
After preheating for a minute, it was immersed in eutectic solder at 270° C. for 3 seconds and visually inspected for the presence of cracks.
なお、第1表及び第2表において、試料番号28以降は
本実施例に対する比較例である。第1表の各欄に示す通
り、これら比較例では、上記実施例で使用したNaFに
代えて、Bi2O3、CuO5P I) O等を使用し
た。In addition, in Tables 1 and 2, sample numbers 28 and later are comparative examples with respect to the present example. As shown in each column of Table 1, in these comparative examples, Bi2O3, CuO5P I) O, etc. were used in place of NaF used in the above examples.
衷 1
衷 2
以上の結果が示すように、上記各衷において試料N00
1〜27で示すこの発明の実施例によるバリスタは、試
料NO,2B以降の比較例と同等或はそれ以下のバリス
タ電圧V1が得られ、かつバリスタ電圧■1の温度変化
率へV1、静電容量C5誘電損失tanδ及びハンダ耐
熱性では顕著な特性の改善が認められる。Back 1 Back 2 As the above results show, sample N00
The varistors according to the embodiments of the present invention shown in 1 to 27 can obtain varistor voltages V1 that are equal to or lower than those of the comparative examples after Samples No. Remarkable improvements in characteristics are observed in the capacitance C5 dielectric loss tan δ and solder heat resistance.
[発明の効果]
以上のことから、この発明による磁器を用いて構成され
たバリスタは、従来のものと同等或はそれ以下のバリス
タ電圧V1が得られながら、バリスタ電圧V1の温度変
化率△V1、静電容量C5誘電損失tanδ及びハンダ
耐熱性について、より優れた特性が得られる。[Effects of the Invention] From the above, the varistor constructed using the porcelain according to the present invention can obtain a varistor voltage V1 equal to or lower than that of the conventional one, while reducing the temperature change rate ΔV1 of the varistor voltage V1. , better characteristics can be obtained in terms of capacitance C5 dielectric loss tan δ and solder heat resistance.
第1図はこの発明の実施例に於て試験に供したバリスタ
の構造を示す半断面斜視図、第2図は同バリスタの電気
特性試験を行った装置の回路図である。FIG. 1 is a half-sectional perspective view showing the structure of a varistor tested in an embodiment of the present invention, and FIG. 2 is a circuit diagram of an apparatus in which the electrical characteristics of the varistor were tested.
Claims (5)
TiO_3系焼結体からなるバリスタ特性を有する誘電
体磁器に於て、磁器結晶の粒界付近にNaイオンを拡散
させたことを特徴とするバリスタ特性を有する誘電体磁
器。(1) Sr made into a semiconductor by adding a small amount of metal oxide
A dielectric porcelain having varistor characteristics made of a TiO_3-based sintered body and having Na ions diffused near the grain boundaries of the ceramic crystal.
厚さの層状に拡散している特許請求の範囲第1項記載の
誘電体磁器。(2) The dielectric ceramic according to claim 1, wherein Na ions are diffused in a layer with a thickness of about 100 Å near the grain boundaries of crystal grains.
rTiO_3系磁器材料を焼結させてバリスタ特性を有
する半導体磁器を製造する方法に於て、焼結体の表面に
Naの化合物を塗布し、熱処理することを特徴とするバ
リスタ特性を有する誘電体磁器の製造方法。(3) S made into a semiconductor by adding a trace amount of metal oxide
A dielectric porcelain having varistor characteristics, which is a method of manufacturing semiconductor porcelain having varistor characteristics by sintering rTiO_3-based porcelain material, which comprises applying a Na compound to the surface of the sintered body and heat-treating it. manufacturing method.
範囲第3項に記載の誘電体磁器の製造方法。(4) The method for manufacturing dielectric ceramics according to claim 3, wherein the Na compound is a fluoride of these.
〜1200℃である特許請求の範囲第3項または第4項
記載の誘電体磁器の製造方法。(5) The heat treatment temperature after applying the Na compound is 800℃.
The method for manufacturing dielectric ceramic according to claim 3 or 4, wherein the temperature is 1200°C.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP62102543A JPS63268202A (en) | 1987-04-25 | 1987-04-25 | Dielectric porcelain having varistor characteristic and manufacture thereof |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP62102543A JPS63268202A (en) | 1987-04-25 | 1987-04-25 | Dielectric porcelain having varistor characteristic and manufacture thereof |
Publications (2)
Publication Number | Publication Date |
---|---|
JPS63268202A true JPS63268202A (en) | 1988-11-04 |
JPH0435884B2 JPH0435884B2 (en) | 1992-06-12 |
Family
ID=14330165
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP62102543A Granted JPS63268202A (en) | 1987-04-25 | 1987-04-25 | Dielectric porcelain having varistor characteristic and manufacture thereof |
Country Status (1)
Country | Link |
---|---|
JP (1) | JPS63268202A (en) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
KR100295282B1 (en) * | 1998-07-29 | 2001-07-12 | 박호군 | Fabrication method of the low-breakdown voltage disk and chip varistor |
Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS5727001A (en) * | 1980-07-25 | 1982-02-13 | Tdk Electronics Co Ltd | Voltage nonlinear resistance element |
JPS58135604A (en) * | 1982-02-08 | 1983-08-12 | 太陽誘電株式会社 | Voltage nonlinear porcelain composition |
-
1987
- 1987-04-25 JP JP62102543A patent/JPS63268202A/en active Granted
Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS5727001A (en) * | 1980-07-25 | 1982-02-13 | Tdk Electronics Co Ltd | Voltage nonlinear resistance element |
JPS58135604A (en) * | 1982-02-08 | 1983-08-12 | 太陽誘電株式会社 | Voltage nonlinear porcelain composition |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
KR100295282B1 (en) * | 1998-07-29 | 2001-07-12 | 박호군 | Fabrication method of the low-breakdown voltage disk and chip varistor |
Also Published As
Publication number | Publication date |
---|---|
JPH0435884B2 (en) | 1992-06-12 |
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