JPH0222162A - Sintered material of ceramic and production thereof - Google Patents
Sintered material of ceramic and production thereofInfo
- Publication number
- JPH0222162A JPH0222162A JP63171029A JP17102988A JPH0222162A JP H0222162 A JPH0222162 A JP H0222162A JP 63171029 A JP63171029 A JP 63171029A JP 17102988 A JP17102988 A JP 17102988A JP H0222162 A JPH0222162 A JP H0222162A
- Authority
- JP
- Japan
- Prior art keywords
- sintering
- ceramic
- temperature
- surface layer
- raw material
- 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
- 239000000919 ceramic Substances 0.000 title claims abstract description 33
- 238000004519 manufacturing process Methods 0.000 title claims description 12
- 239000000463 material Substances 0.000 title abstract description 3
- 238000005245 sintering Methods 0.000 claims abstract description 51
- 239000002344 surface layer Substances 0.000 claims abstract description 14
- 239000000203 mixture Substances 0.000 claims abstract description 13
- 239000002994 raw material Substances 0.000 claims abstract description 13
- 238000010438 heat treatment Methods 0.000 claims abstract description 7
- 238000000465 moulding Methods 0.000 claims abstract description 6
- 239000000126 substance Substances 0.000 claims abstract description 4
- 230000035939 shock Effects 0.000 abstract description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 14
- 229910052782 aluminium Inorganic materials 0.000 description 13
- 238000000034 method Methods 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 4
- 230000006866 deterioration Effects 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 229910010271 silicon carbide Inorganic materials 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- 229910052580 B4C Inorganic materials 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- INAHAJYZKVIDIZ-UHFFFAOYSA-N boron carbide Chemical compound B12B3B4C32B41 INAHAJYZKVIDIZ-UHFFFAOYSA-N 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 238000005304 joining Methods 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 239000011265 semifinished product Substances 0.000 description 2
- 230000008016 vaporization Effects 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 229910052582 BN Inorganic materials 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- JXOOCQBAIRXOGG-UHFFFAOYSA-N [B].[B].[B].[B].[B].[B].[B].[B].[B].[B].[B].[B].[Al] Chemical compound [B].[B].[B].[B].[B].[B].[B].[B].[B].[B].[B].[B].[Al] JXOOCQBAIRXOGG-UHFFFAOYSA-N 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 150000001573 beryllium compounds Chemical class 0.000 description 1
- FFBGYFUYJVKRNV-UHFFFAOYSA-N boranylidynephosphane Chemical compound P#B FFBGYFUYJVKRNV-UHFFFAOYSA-N 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 238000005219 brazing Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000002612 dispersion medium Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 239000012770 industrial material Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000010680 novolac-type phenolic resin Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 230000000171 quenching effect Effects 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 229910000679 solder Inorganic materials 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 238000009834 vaporization Methods 0.000 description 1
Landscapes
- Compositions Of Oxide Ceramics (AREA)
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明は、セラミックス焼結体およびその製造法に関す
るものである。DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a ceramic sintered body and a method for manufacturing the same.
一般に、工業用材料としてのセラミックスは、高温にお
ける強度を確保するためになるべく緻密な組織のものが
好ましいとされ、製造に当たっても、なるべく緻密な焼
結体が得られるように、原材料、焼結助剤、成形条件、
焼結条件等の選択が行われる。In general, it is said that ceramics as industrial materials should preferably have as dense a structure as possible in order to ensure strength at high temperatures. agent, molding conditions,
Selection of sintering conditions, etc. is made.
比較的低密度のセラミックスも一部の用途においては使
用可能であり、また好まれる場合もあるが、そのような
ものは、それに応じた製造法によって全体が低密度のも
のに作られる。いずれにせよ、全体が単一化学組成の一
つのセラミックス焼結体においては密度も一様のものが
普通であり、高密度部分と低密度部分とが混在するよう
なものは、従来作られていない。Relatively low-density ceramics can be used and may be preferred in some applications, but such can be made to have a low overall density by corresponding manufacturing methods. In any case, a single ceramic sintered body with a single chemical composition as a whole usually has a uniform density, and those with a mixture of high-density and low-density areas have not been produced conventionally. do not have.
しかしながら、セラミックスを金属と接合する場合、あ
るいはセラミックス同士を接合する場合、緻密な高強度
セラミックスは、接着剤となるろう材、活性金属等が表
面によくなじまず、したがって高い接合強度を得ること
ができないという問題があった。However, when joining ceramics to metals or joining ceramics to each other, dense high-strength ceramics do not allow the brazing filler metal, active metal, etc. that serve as adhesives to blend well with the surface, making it difficult to obtain high joint strength. The problem was that I couldn't do it.
また、使用状態においてセラミックスの周辺に急激な温
度変化が生じた場合、当然、セラミックス表層部の温度
変化が芯部よりも大きく且つ急速であるから、表層部に
おいて亀裂や劣化が生じ易いが、そのような傾向は、緻
密な高強度セラミックスにおいて特に顕著である。In addition, when a sudden temperature change occurs around the ceramic during use, the temperature change in the surface layer of the ceramic is naturally larger and more rapid than in the core, so cracks and deterioration are likely to occur in the surface layer. This tendency is particularly noticeable in dense high-strength ceramics.
本発明の目的は、高強度を達成するためにセラミックス
を緻密化した場合に生じる上述のような問題点を解決し
、高強度でありながら接合が容易で耐熱衝撃性にもすぐ
ｔ；セラミックスを提供することにある。The purpose of the present invention is to solve the above-mentioned problems that occur when ceramics are densified to achieve high strength, and to create a ceramic that has high strength, is easy to bond, and has excellent thermal shock resistance. It is about providing.
上記目的を達成することに成功した本発明は、全体が実
質的に同一化学組成のセラミックス焼結体からなりその
全部または一部において表層部の密度が芯部の密度より
も低いことを特徴とするセラミックス焼結体、およびそ
の製造法として、セラミックス焼結原料と焼結助剤との
混合物を成形し、得られた成形体を焼結原料の焼結温度
以上の温度に加熱してセラミックス焼結体を製造するに
当たり、成形体をその焼結開始前に減圧下焼結温度以下
の温度に加熱することにより成形体表層部にある焼結助
剤の一部を気化させて除き、その後、常圧下に加熱して
焼結を進めることを特徴とするセラミックス製造法を提
供するものである。The present invention, which has succeeded in achieving the above object, is characterized in that the entire body is made of a ceramic sintered body having substantially the same chemical composition, and the density of the surface layer is lower than the density of the core in all or part of the body. The ceramic sintered body and its manufacturing method include molding a mixture of a ceramic sintering raw material and a sintering aid, and heating the resulting molded body to a temperature higher than the sintering temperature of the sintering raw material. In producing the compact, before the start of sintering, the compact is heated to a temperature below the sintering temperature under reduced pressure to vaporize and remove a portion of the sintering aid on the surface of the compact, and then, The present invention provides a method for manufacturing ceramics characterized by proceeding with sintering by heating under normal pressure.
上記本発明の製造法により表層部のみが低密度のセラミ
ックス焼結体を製造する場合は、従来のセラミックス製
造法と異なり焼結助剤の一部を焼結開始前に気化させて
除くので、焼結助剤としては、少なくとも一部に、減圧
下焼結温度以下の温度において分解しまたは蒸発して気
化するもの（以下、気化性焼結助剤という）を用いる必
要がある。使用可能な気化性焼結助剤の例としては、た
とえば炭化ケイ素質セラミックスを製造する場合、リン
化ホウ素、アルミニウム、ホウ化アルミニウム、ベリリ
ウム化合物などがある。炭化ケイ素質セラミックスを製
造するに当たり気化性焼結助剤と併用可能な非気化性焼
結助剤としては、炭素、ホウ素、炭化ホウ素、窒化ホウ
素などがある。When manufacturing a ceramic sintered body with a low density only in the surface layer by the manufacturing method of the present invention, unlike conventional ceramic manufacturing methods, a part of the sintering aid is vaporized and removed before sintering starts. It is necessary to use at least a portion of the sintering aid that decomposes or evaporates into vapor at a temperature below the sintering temperature under reduced pressure (hereinafter referred to as a volatile sintering aid). Examples of vaporizable sintering aids that can be used include boron phosphide, aluminum, aluminum boride, and beryllium compounds when producing silicon carbide ceramics. Examples of non-volatile sintering aids that can be used in combination with volatile sintering aids in producing silicon carbide ceramics include carbon, boron, boron carbide, and boron nitride.
上述のような気化性焼結助剤を少なくとも一部に用いる
ことを除けば、焼結原料の選択、成形条件等に制限はな
い。There are no restrictions on the selection of sintering raw materials, molding conditions, etc., except that the above-mentioned volatile sintering aid is used at least in part.
焼結助剤を混入した焼結原料からなる成形体は、焼結に
先立って、減圧下に焼結温度以下の温度に加熱する。た
とえば、炭化ケイ素質セラミックスを製造する場合にお
いて気化性焼結助剤としてアルミニウムを用いたときは
、１０−２＋＋ｍＨｇ程度の真空状態にして約１３００
°Ｃに昇温する。アルミニウムの蒸気圧は１２８４℃で
Ｉ ＩＩｆｆｉｎｇであるから、この加熱により、成形
体表面からアルミニウムが活発に蒸発する。このとき焼
結はまだ起こっていないので、成形体芯部で気化したア
ルミニウムも成形体表面に向かって拡散するが、表面か
らのアルミニウムの離脱が急速なため、表面に近い部分
はどアルミニウムの少ない状態が形成される。この部分
的焼結助剤除去工程の温度、真空度、処理時間等の処理
条件は、用いた気化性焼結助剤の気化特性や量、表層部
と芯部について意図する密度差などに応じて、実験的に
選定する（温度に関しては、焼結開始温度まで上げてお
き、そのまま焼結工程に移行することも可能である。）
。この後、常圧に戻し、温度を約２０００℃に上げ、焼
結を開始させる。表層部は、焼結助剤が少ないため芯部
はとには焼結が進まない。したがって、焼結が終わった
とき、表層部は芯部よりも低密度である。Prior to sintering, the molded body made of a sintering raw material mixed with a sintering aid is heated under reduced pressure to a temperature below the sintering temperature. For example, when aluminum is used as a volatile sintering aid in the production of silicon carbide ceramics, approximately 1300
Increase temperature to °C. Since the vapor pressure of aluminum is I IIffing at 1284° C., aluminum is actively evaporated from the surface of the compact due to this heating. At this time, sintering has not yet occurred, so the aluminum vaporized in the core of the compact also diffuses toward the surface of the compact, but because aluminum is rapidly separated from the surface, there is little aluminum near the surface. A state is formed. The processing conditions such as temperature, degree of vacuum, and processing time for this partial sintering aid removal process depend on the vaporization characteristics and amount of the volatile sintering aid used, the intended density difference between the surface layer and the core, etc. (Regarding the temperature, it is also possible to raise it to the sintering starting temperature and then proceed to the sintering process.)
. Thereafter, the pressure is returned to normal, the temperature is raised to about 2000°C, and sintering is started. Since there is less sintering aid in the surface layer, sintering does not progress as much as in the core. Therefore, when sintering is finished, the surface layer has a lower density than the core.
上記製造法の部分的焼結助剤除去工程において、気化し
た焼結助剤の離脱を妨げ得るシールド材（たとえば鉄、
ニッケル等の金属板、アルミナ、シリカ等の微粉末）で
成形体表面の一部を覆うと、その箇所だけは、表層部も
芯部と同じ量の焼結助剤を含有したまま焼結処理される
から、緻密な表層部になる。このようにして、表層部の
中でも所望の箇所だけを低密度のものとすることもでき
る。In the partial sintering aid removal step of the above manufacturing method, a shielding material (e.g. iron,
When a part of the surface of the compact is covered with a metal plate such as nickel (metal plate such as nickel, fine powder such as alumina, silica, etc.), the surface layer can be sintered while containing the same amount of sintering aid as the core. Because of this, the surface layer becomes dense. In this way, it is also possible to make only desired portions of the surface layer have a low density.
実施例１
平均粒径０．５μｍのアルミニウム粉末（気化性焼結助
剤）１．０％、ノボラック型フェノール樹脂３．０％、
平均粒径０．４μｍの炭化ホウ素粉末０．５％、残部が
平均粒径０．５μｍの炭化ケイ素粉末からなる原料混合
物を、アセトンを分散媒として湿式ボールミルで混合し
てから乾燥し、粉砕した。得られた原料混合物粉末を、
単軸プレスを用いて、１ 、５１ ｏｎ／ａｍ”の圧力
で径３０ｍｍ×厚さｌＯｍ＋＋＋の円盤状に成形した。Example 1 1.0% aluminum powder (volatile sintering aid) with an average particle size of 0.5 μm, 3.0% novolac type phenolic resin,
A raw material mixture consisting of 0.5% boron carbide powder with an average particle size of 0.4 μm and the balance consisting of silicon carbide powder with an average particle size of 0.5 μm was mixed in a wet ball mill using acetone as a dispersion medium, then dried and pulverized. . The obtained raw material mixture powder is
Using a uniaxial press, it was molded into a disk shape with a diameter of 30 mm and a thickness of 1 Om+++ at a pressure of 1.51 on/am''.
得られた成形体をアルゴンガス中で加熱して３０℃／Ｆ
ｉｒの割合で昇温し、１３００°Ｃで１０−”ｍｎ［１
ｇの真空状態にして３時間保持することによりアルミニ
ウムの一部を除去し、その後、３００°Ｏ／Ｈｒで昇温
し、２０００°Ｃで焼結させた。The obtained molded body was heated in argon gas to 30°C/F.
The temperature was increased at a rate of ir, and at 1300°C it was
A part of the aluminum was removed by holding the vacuum state for 3 hours, and then the temperature was raised at 300° O/Hr and sintered at 2000°C.
実施例２
実施例１の場合と同様にして得られた原料混合物の成形
体を、アルゴンガス中で３００°Ｏ／Ｈｒで昇温し、１
４００°Ｃで１０−３ｍｍ［１ｇにして３時間保持する
ことによりアルミニウムの一部を除去し、その後、３０
０℃／Ｈｒで昇温し、２０００°Ｃで焼結させた。Example 2 A molded body of the raw material mixture obtained in the same manner as in Example 1 was heated at 300° O/Hr in argon gas, and 1
Part of the aluminum was removed by holding at 400°C for 3 hours at 10-3 mm [1 g;
The temperature was raised at 0°C/Hr and sintered at 2000°C.
上記２例による製品について表面から芯部にかけての密
度の変化を調べた結果を第１図に示す。また、分析用半
製品（アルミニウムの一部を除去する工程までの処理を
した、未焼結のもの）について表面から芯部にかけての
アルミニウム含有率の変化を調べた結果を第２図に示す
。FIG. 1 shows the results of examining changes in density from the surface to the core of the products according to the above two examples. In addition, FIG. 2 shows the results of examining changes in aluminum content from the surface to the core of semi-finished products for analysis (unsintered products that have been processed up to the step of removing part of the aluminum).
また、実施例２の製品を銀ロウ箔（厚さ３μｍ）および
チタン箔（厚さ１μｍ）でステンレス鋼板（ＳＵＳ３ｏ
ｔ）と１０００°Ｃで溶融結合させたところ、結合強度
は６ｋｇ／ａｍ”であった。同じ原料からアルミニウム
の一部を気化させることなく製造した全体が緻密な対照
例焼結体は、同様の結合試験において１ 、２ ｋｇ／
ｍｓ＋２の結合強度を示した。さらに、実施例２の製品
の耐熱衝撃性を水中急冷法（加熱状態から瞬時に水中に
投入し、製品強度の劣化の有無を調べる）で試験したと
ころ、ΔＴ（劣化が起こる加熱温度と水温の差）は３５
０℃であり、対照例焼結体のそれは２５０°Ｃであった
。In addition, the product of Example 2 was coated with a stainless steel plate (SUS3O) using silver solder foil (3 μm thick) and titanium foil (1 μm thick).
When the bonding strength was 6 kg/am'' at 1000°C, the control sintered body was manufactured from the same raw material without vaporizing part of the aluminum, and was entirely dense. In a binding test of 1,2 kg/
A binding strength of ms+2 was shown. Furthermore, when the thermal shock resistance of the product of Example 2 was tested using the underwater quenching method (instantly put into water from a heated state to check for deterioration in product strength), it was found that ΔT (the difference between the heating temperature at which deterioration occurs and the water temperature) difference) is 35
0°C, and that of the control sintered body was 250°C.
上述のように、本発明によるセラミックス焼結体は表面
だけが低密度で、微細な気孔を有するものものであるか
ら、全体としては優れｔ；強度を有するにもかかわらず
、強力な接合が可能であり、また耐熱衝撃性にも優れた
ものである。本発明の製造法によれば、この不均一構造
のセラミックス焼結体を単一の原料混合物から、また複
雑な成形法を採用する必要もなく、容易に製造すること
ができる。As mentioned above, the ceramic sintered body according to the present invention has a low density only on the surface and has fine pores, so it has excellent overall strength; strong bonding is possible even though it has strength. It also has excellent thermal shock resistance. According to the manufacturing method of the present invention, a ceramic sintered body having a non-uniform structure can be easily manufactured from a single raw material mixture and without the need to employ a complicated molding method.
第１図は実施例による製品の表面から芯部にかけての密
度の変化を示すグラフ、第２図は分析用半製品の表面か
ら芯部にかけてのアルミニウム含有率の変化を示すグラ
フである。FIG. 1 is a graph showing the change in density from the surface to the core of the product according to the example, and FIG. 2 is a graph showing the change in aluminum content from the surface to the core of the semi-finished product for analysis.
Claims (2)
らなり、その全部または一部において、表層部の密度が
芯部の密度よりも低いことを特徴とするセラミックス焼
結体。(1) A ceramic sintered body made entirely of ceramic having substantially the same chemical composition, and characterized in that the density of the surface layer is lower than the density of the core in all or part of the body.
形し、得られた成形体を焼結原料の焼結温度以上の温度
に加熱してセラミックス焼結体を製造するに当たり、成
形体をその焼結開始前に減圧下焼結温度以下の温度に加
熱することにより成形体表層部にある焼結助剤の一部を
気化させて除き、その後、常圧下に加熱して焼結を進め
ることを特徴とする請求項１記載のセラミックス焼結体
の製造法。(2) When producing a ceramic sintered body by molding a mixture of a ceramic sintering raw material and a sintering aid and heating the resulting molded body to a temperature higher than the sintering temperature of the sintering raw material, the molded body Before the start of sintering, a part of the sintering aid on the surface layer of the compact is vaporized and removed by heating it to a temperature below the sintering temperature under reduced pressure, and then heated under normal pressure to start sintering. 2. The method for producing a ceramic sintered body according to claim 1, further comprising the steps of:
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63171029A JP2732256B2 (en) | 1988-07-11 | 1988-07-11 | Ceramic sintered body and method for producing the same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63171029A JP2732256B2 (en) | 1988-07-11 | 1988-07-11 | Ceramic sintered body and method for producing the same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0222162A true JPH0222162A (en) | 1990-01-25 |
| JP2732256B2 JP2732256B2 (en) | 1998-03-25 |
Family
ID=15915766
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP63171029A Expired - Fee Related JP2732256B2 (en) | 1988-07-11 | 1988-07-11 | Ceramic sintered body and method for producing the same |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2732256B2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0246324U (en) * | 1988-09-22 | 1990-03-29 |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5815802A (en) * | 1981-07-18 | 1983-01-29 | 住友電気工業株式会社 | ceramic spikes |
-
1988
- 1988-07-11 JP JP63171029A patent/JP2732256B2/en not_active Expired - Fee Related
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5815802A (en) * | 1981-07-18 | 1983-01-29 | 住友電気工業株式会社 | ceramic spikes |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0246324U (en) * | 1988-09-22 | 1990-03-29 |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2732256B2 (en) | 1998-03-25 |
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