JPH02229765A - Sintered body of conductive ceramics and heater - Google Patents
Sintered body of conductive ceramics and heaterInfo
- Publication number
- JPH02229765A JPH02229765A JP1051459A JP5145989A JPH02229765A JP H02229765 A JPH02229765 A JP H02229765A JP 1051459 A JP1051459 A JP 1051459A JP 5145989 A JP5145989 A JP 5145989A JP H02229765 A JPH02229765 A JP H02229765A
- Authority
- JP
- Japan
- Prior art keywords
- sintered body
- conductive
- oxide
- heater
- silicon nitride
- 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.)
- Pending
Links
- 239000000919 ceramic Substances 0.000 title claims abstract description 28
- 229910052581 Si3N4 Inorganic materials 0.000 claims abstract description 16
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 claims abstract description 16
- 229910052804 chromium Inorganic materials 0.000 claims abstract description 7
- 239000004020 conductor Substances 0.000 claims abstract 2
- 150000001875 compounds Chemical class 0.000 claims description 20
- 239000000126 substance Substances 0.000 claims description 10
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical group [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 9
- 239000002131 composite material Chemical class 0.000 claims description 7
- 150000004767 nitrides Chemical class 0.000 claims description 6
- 150000001247 metal acetylides Chemical class 0.000 claims description 5
- 229910052723 transition metal Inorganic materials 0.000 claims description 5
- 230000003647 oxidation Effects 0.000 abstract description 27
- 238000007254 oxidation reaction Methods 0.000 abstract description 27
- 229910052760 oxygen Inorganic materials 0.000 abstract description 11
- 230000000694 effects Effects 0.000 abstract description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 4
- 239000001301 oxygen Substances 0.000 abstract description 4
- 238000009792 diffusion process Methods 0.000 abstract description 2
- 239000000843 powder Substances 0.000 description 19
- 239000012298 atmosphere Substances 0.000 description 11
- 238000005245 sintering Methods 0.000 description 11
- 239000000463 material Substances 0.000 description 9
- 239000002245 particle Substances 0.000 description 8
- 239000000203 mixture Substances 0.000 description 5
- 239000007789 gas Substances 0.000 description 4
- 230000001590 oxidative effect Effects 0.000 description 3
- 229910052761 rare earth metal Inorganic materials 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 230000004584 weight gain Effects 0.000 description 3
- 235000019786 weight gain Nutrition 0.000 description 3
- 229910052684 Cerium Inorganic materials 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 238000001513 hot isostatic pressing Methods 0.000 description 2
- 229910052746 lanthanum Inorganic materials 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 229910052727 yttrium Inorganic materials 0.000 description 2
- 229910003564 SiAlON Inorganic materials 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000009760 electrical discharge machining Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000007731 hot pressing Methods 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- -1 such as N Substances 0.000 description 1
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明は、窒化珪素系セラミックスを母材とし導電性化
合物を含有する導電性セラミックス焼結体およびヒータ
ーにおいて、高温での耐酸化性をＣｒ酸化物の添加によ
り改善した焼結体およびヒーターに関するものである。Detailed Description of the Invention [Field of Industrial Application] The present invention provides a conductive ceramic sintered body and a heater that have a silicon nitride ceramic as a base material and contain a conductive compound, and the oxidation resistance at high temperatures is improved by improving the oxidation resistance at high temperatures. This invention relates to a sintered body and a heater improved by the addition of oxides.
αまたはβＳｉ，Ｎ，を主成分とする窒化珪素、Ｓ ｆ
＠ − ｚ Ａ ｌ ｚ Ｏ ｚ Ｎ ｍ − ｚ
（０ ＜ Ｚ≦４．２）で示されるβサイアロン、Ｍｘ
（ＳＬ，Ａｌ）．（０，Ｎ）．．（ｘ＜２，ＭはＬＬ，
Ｍｇ， ＣＢ， Ｙ ，希土類元素（Ｌａ，Ｃｅ除＜）
〕で示されるαサイアロン、およびこれらの複合した窒
化珪素系のセラミックスは、高温強度および耐酸化性に
優れ、熱膨張係数が小さく耐熱衝撃性が非常に良いため
、近年種々の分野において利用されている。また一方で
、これらは極めて難加工性材料でもあるため、その対策
として放電加工を可能とするために導電性を付与すると
の提案もなされている（特開昭５７−１８８４５３号公
報、特開昭５７−２００２６５号公報、特開昭５９−２
０７８８１号公報、特開昭６０−３３２６５号公報など
）．また、これらをヒーター材として用いるとの提案も
なされている（特開昭６０−６０９８３号公報、特開昭
６２−１４０３８６号公報など）。Silicon nitride containing α or βSi,N, as the main component, S f
@ - z A l z O z N m - z
β-sialon, Mx, denoted by (0 < Z ≦ 4.2)
(SL, Al). (0, N). ．． (x<2, M is LL,
Mg, CB, Y, rare earth elements (excluding La, Ce)
] α-SiAlON and these composite silicon nitride-based ceramics have been used in a variety of fields in recent years because they have excellent high-temperature strength and oxidation resistance, a small coefficient of thermal expansion, and very good thermal shock resistance. There is. On the other hand, these are extremely difficult-to-process materials, and as a countermeasure, it has been proposed to impart electrical conductivity to enable electrical discharge machining (Japanese Unexamined Patent Publication No. 57-188453; Publication No. 57-200265, Japanese Unexamined Patent Publication No. 59-2
07881, JP-A-60-33265, etc.). There have also been proposals to use these as heater materials (JP-A-60-60983, JP-A-62-140386, etc.).
またＴｉＮとＳｉＣを複合添加し高抵抗材における電気
抵抗のバラツキを抑制した焼結体について特願昭６３〜
２３８２８１号として本発明者は提案している。In addition, a patent application has been filed since 1983 regarding a sintered body that suppresses variations in electrical resistance in high-resistance materials by adding a combination of TiN and SiC.
The present inventor has proposed it as No. 238281.
（発明が解決しようとする問題点）
ところが、上記材料は１０００℃以上の温度域では表面
に厚い酸化膜が形成され、それ以上酸化が進行しないの
に対して、約８００〜９００℃で５０時間以上の長時間
保持した場合に酸化量が異常に大きくなり、ふくれ、割
れ等の発生につながることが明らかになった。これはヒ
ーターとして用いる場合、断線に直接結びつき、寿命の
低下につながるものである。(Problem to be Solved by the Invention) However, with the above materials, a thick oxide film is formed on the surface in the temperature range of 1000°C or higher, and oxidation does not proceed any further; It has become clear that when held for a longer period of time, the amount of oxidation becomes abnormally large, leading to the occurrence of blisters, cracks, etc. When used as a heater, this directly leads to disconnection and shortens the service life.
本発明の目的は、上記の８００〜９００℃における酸化
現象を抑制した耐酸化性に優れる導電性セラミックス焼
結体およびヒーターを提供することである。An object of the present invention is to provide a conductive ceramic sintered body and a heater that suppress the above-mentioned oxidation phenomenon at 800 to 900°C and have excellent oxidation resistance.
本発明者は前記の８００〜９００℃における酸化現象を
抑制するために種々検討した結果、Ｃｒ酸化物を添加す
ることにより、上記の酸化現象を抑制できることを見出
し本発明を完成するに至った。As a result of various studies in order to suppress the above-mentioned oxidation phenomenon at 800 to 900°C, the present inventor found that the above-mentioned oxidation phenomenon could be suppressed by adding Cr oxide, and completed the present invention.
本発明において、Ｃｒ酸化物の添加により、８００〜９
００℃の耐酸化性を向上することができるのは以下の理
由によるものと考える。In the present invention, by adding Cr oxide, the
It is believed that the reason why the oxidation resistance at 00°C can be improved is as follows.
すなわち、８００〜９００℃の比較的低温では、１００
０℃以上で形成される厚い酸化膜が形成されておらず、
本系焼結体中の粒界相を通じて大気中の酸素が拡散し、
酸化が進行するものと考えられるが、Ｃｒ酸化物を添加
することにより粒界相中の酸素の拡散が抑制されること
により、酸化が防止されるものと考えられる。That is, at a relatively low temperature of 800 to 900°C, 100
A thick oxide film that is formed at temperatures above 0°C is not formed,
Oxygen in the atmosphere diffuses through the grain boundary phase in this sintered body,
Although it is thought that oxidation progresses, it is thought that oxidation is prevented by suppressing the diffusion of oxygen in the grain boundary phase by adding Cr oxide.
本発明において、Ｃｒ酸化物の添加量は、０．１〜１０
ｗｔ％であり、その理由は０ ． ｌｗｔ％より少ない
とＣｒ酸化物の添加の効果が現われず、また１０ｗｔ％
を越えて添加した場合には、焼結性が低下するからであ
る．より好ましくは０．３〜３ｗｔ％である．Ｃｒ酸化
物としては、化合物として最も安定なＣｒ，Ｏ，を用い
ればよい。また、Ｃｒ酸化物粉末を原料として加える代
りに、焼結中にＣｒ酸化物に変化する化合物、例えばＣ
ｒ（Ｎ Ｏ，），・９Ｈ，Ｏ，ＣｒＣｌ，・６Ｈ，０な
どを用いることも可能である。In the present invention, the amount of Cr oxide added is 0.1 to 10
wt%, and the reason is 0. If it is less than lwt%, the effect of adding Cr oxide will not appear, and if it is less than 10wt%
This is because if it is added in excess of this amount, sinterability will decrease. More preferably, it is 0.3 to 3 wt%. As the Cr oxide, Cr and O, which are the most stable compounds, may be used. Also, instead of adding Cr oxide powder as a raw material, compounds that change to Cr oxide during sintering, such as C
It is also possible to use r(N O, ), .9H,O, CrCl, .6H,0, etc.
また、本発明は従来公知の導電性セラミックス焼結体に
広く遺用が可能である。Furthermore, the present invention can be broadly applied to conventionally known conductive ceramic sintered bodies.
すなわち、母材となる窒化珪素系セラミックスとしては
、
αまたはβＳｔ，Ｎ４を主成分とする窒化珪素焼結体
Ｓｉ．−ＺＡＩＺＯ！Ｎ，−Ｚ（０＜Ｚ≦４．２）で示
されるβサイアロン焼結体、
Ｍｘ（Ｓｉ，ＡＩ），．（０，Ｎ）．［ｘ（２，ＭはＬ
ｉ，Ｍｇ，Ｃａ， Ｙ ，希土類元素（Ｌａ，Ｃｅ除＜
）］で示されるαサイアロン焼結体、
およびこれらの複合した窒化珪素系セラミックス焼結体
のいずれであっても所定の効果を得ることができる。な
お、βサイアロンにあっては、ｚ＜１の場合には常温、
高温強度が優れ、硬さ、靭性も高いものとなるので望ま
しい。That is, as the silicon nitride ceramics serving as the base material, a silicon nitride sintered body Si. -ZAIZO! β-sialon sintered body represented by N,-Z (0<Z≦4.2), Mx(Si,AI), . (0,N). [x(2, M is L
i, Mg, Ca, Y, rare earth elements (excluding La, Ce <
) ], and a composite silicon nitride ceramic sintered body can achieve the desired effect. In addition, for β-sialon, if z<1, at room temperature,
It is desirable because it has excellent high-temperature strength, hardness, and toughness.
また、本系導電性セラミックス焼結体においては、導電
性物質の量を１０〜７０ＶＯ１％とすることが必要であ
る。導電性化合物量が１０ｖｏｌ％未満では導電性を付
与することができず、また７０ｖｏｌ％を越えると窒化
珪素系セラミックスが本来持つ高温強度、耐酸化性が損
なわれるからである。Further, in the present conductive ceramic sintered body, the amount of the conductive substance must be 10 to 70 VO1%. This is because if the amount of the conductive compound is less than 10 vol%, conductivity cannot be imparted, and if it exceeds 70 vol%, the high temperature strength and oxidation resistance inherent to silicon nitride ceramics will be impaired.
導電性物質としては、ＩＶａ，ＶａおよびＶｌａ族の遷
移金属元素の炭化物、窒化物およびこれら化合物から形
成される複化合物の１種または２種以上の導電性化合物
としては、種々のものを選択することが可能であるが、
ＴｉＮを選択した場合には、焼結性、強度、耐酸化性等
の面から好ましい結果が得られる。As the conductive substance, one or more conductive compounds selected from carbides and nitrides of transition metal elements of the IVa, Va and Vla groups, and composite compounds formed from these compounds. It is possible, but
When TiN is selected, favorable results can be obtained in terms of sinterability, strength, oxidation resistance, etc.
また、前記複化合物とは炭窒化物、さらに複窒化物、複
炭化物等を言う。Further, the complex compound refers to carbonitride, double nitride, double carbide, and the like.
導電性セラミックスをヒータｉとして用いる場合に高い
電気抵抗率が必要となる場合もある。この場合には、上
記の導電性物質に加え、ＳｉＣを添加すれば電気抵抗率
のパラツキを抑制しつつ、高い電気抵抗率を得ることが
できる．ＳｉＣ添加によって電気抵抗率のパラツキが抑
制される理由は前記特開昭６３〜２３８２８１号に記載
した通りである．ＳｉＣの添加量は０．１〜５０ｖｏｌ
％とする必要がある．０．１ｖｏｌ％末滴ではその効果
が期待できず、５０ｖｏｌ％を越えると焼結性が低下し
、緻密な焼結体を得ることが困難となるからである．さ
らに望ましいＳｉＣの添加量は３〜３０ｖｏｌ％である
。When using conductive ceramics as the heater i, high electrical resistivity may be required. In this case, by adding SiC in addition to the above-mentioned conductive substances, high electrical resistivity can be obtained while suppressing variations in electrical resistivity. The reason why the variation in electrical resistivity is suppressed by the addition of SiC is as described in the above-mentioned JP-A-63-238281. The amount of SiC added is 0.1 to 50 vol.
It needs to be expressed as %. This is because the effect cannot be expected with powder droplets of 0.1 vol%, and if it exceeds 50 vol%, the sinterability decreases and it becomes difficult to obtain a dense sintered body. A more desirable amount of SiC added is 3 to 30 vol%.
上記の本発明導電性セラミックス焼結体は、次のような
製造方法により得ることができる．すなわちＳｉ，Ｎ４
粉末、Ａｌ，Ｏ，粉末、ＡＩＮ粉末、ＩＩＩａ族元素（
希土類元素を含む）の酸化物粉末，ＭｇＯ粉末等を所定
の窒化珪素および／またはサイアロンとなるように配合
し、これらに対し導電性物質であるＮａ，Ｖａおよび■
ａ族の遷移金属元素の炭化物、窒化物およびこれら化合
物から形成される複化合物の１種または２種以上の粉末
、あるいはさらにＳｉＣ粉末を所定量添加し、さらにＣ
ｒ酸化物粉末（あるいは焼結中にＣｒ酸化物となる物質
）を添加する．そして、混合、成形の後、非酸化性雰囲
気中で焼結する。ここで焼結は常圧焼結、ガス圧焼結、
ＨＩＰ焼結（熱間静水圧プレス）、ホットプレス等の各
種方法を選ぶことができる。焼結の雰囲気は非酸化性雰
囲気で行なうことが好ましく、Ｎ，ガス雰囲気、加圧Ｎ
，ガス雰囲気、減圧Ｎ２ガス雰囲気、Ｎ，を含む不活性
ガス雰囲気等必要に応じ各種の条件で焼結を行なうこと
が可能である。The above-mentioned conductive ceramic sintered body of the present invention can be obtained by the following manufacturing method. That is, Si, N4
powder, Al, O, powder, AIN powder, group IIIa elements (
Oxide powder (including rare earth elements), MgO powder, etc. are blended to form the specified silicon nitride and/or sialon, and conductive substances such as Na, Va, and
Adding a predetermined amount of one or more powders of carbides, nitrides, and composite compounds of group a transition metal elements, or SiC powder, and further adding C
Add r-oxide powder (or a substance that becomes Cr-oxide during sintering). After mixing and shaping, the mixture is sintered in a non-oxidizing atmosphere. Here, sintering is normal pressure sintering, gas pressure sintering,
Various methods such as HIP sintering (hot isostatic pressing) and hot pressing can be selected. The sintering atmosphere is preferably a non-oxidizing atmosphere, such as N, gas atmosphere, pressurized N
The sintering can be carried out under various conditions as required, such as a gas atmosphere, a reduced pressure N2 gas atmosphere, and an inert gas atmosphere containing N.
なお、ＩＶａ、ＶａおよびＶＩａ族の遷移金属元素の炭
化物、窒化物およびこれら化合物から形成される複化合
物は、焼結中にそれぞれそれらの化合物に変化するもの
を原料として用いることもできる．また、焼結後にＨＩ
Ｐ（熱間静水圧プレス）処理によりさらに特性の向上を
図ったり、熱処理を行ない粒界相を結晶化させたりする
ことも可能である。Note that carbides, nitrides, and composite compounds formed from transition metal elements of groups IVa, Va, and VIa, and composite compounds formed from these compounds, can also be used as raw materials that convert into their respective compounds during sintering. Also, after sintering, HI
It is also possible to further improve the properties by P (hot isostatic pressing) treatment, or to crystallize the grain boundary phase by heat treatment.
［実施例］
以下、本発明を実施例に基づいてさらに詳しく説明する
。[Examples] Hereinafter, the present invention will be explained in more detail based on Examples.
実施例Ｉ
Ｓｉ，Ｎ，粉末（粒度０．７μｒｎ，α化率９３％）、
Ｙ，Ｏ，粉末（粒度１μｍ，純度９９．９９％）、ＡＩ
Ｎ粉末（粒度１μｍ）、Ａｔ，Ｏ，粉末（粒度０．５μ
ｍ，純度９９．５％）を用い、Ｚの値が０．４のβサイ
アロンとなるような組成に配合した（ｙ，ｏ，量は６ｗ
ｔ％）。これに対し、ＴｉＮ粉末を２５ｖｏｌ％添加し
たものを原料粉末とし、これにＷ．８４Ｃ，Ｚｒ○，、
ＭＯおよびＣ ｒ＠ Ｏ ｓ （粉末粒径１〜３μｍ）
をそれぞれＩＷｔ％添加した後、混合、成形し、１気圧
窒素雰囲気中で１７２０℃×６時間焼結した。Example I Si, N, powder (particle size 0.7 μrn, gelatinization rate 93%),
Y, O, powder (particle size 1 μm, purity 99.99%), AI
N powder (particle size 1μm), At, O, powder (particle size 0.5μm)
(m, purity 99.5%) was used and blended into a composition such that β-sialon with a Z value of 0.4 (y, o, amount was 6w)
t%). On the other hand, 25 vol% of TiN powder was added as a raw material powder, and W. 84C, Zr○,,
MO and C r@O s (powder particle size 1-3 μm)
After adding IWt% of each, they were mixed, molded, and sintered at 1720° C. for 6 hours in a 1 atm nitrogen atmosphere.
得られた焼結体より３Ｘ４Ｘ ４０ｍの試験片を切り出
し、大気中で８５０℃、１００時間保持の酸化試験を行
ない、酸化増量を調べた。結果を第１図に示す．これよ
りＣｒ，Ｏ，添加により８００〜９００℃での耐酸化性
が著しく改善されることがわかる．
なお、これら焼結体の相対密度はいずれも９８％以上で
あった。A test piece measuring 3×4×40 m was cut out from the obtained sintered body and subjected to an oxidation test held at 850° C. for 100 hours in the atmosphere to examine the oxidation weight gain. The results are shown in Figure 1. This shows that the addition of Cr and O significantly improves the oxidation resistance at 800 to 900°C. Note that the relative densities of these sintered bodies were all 98% or more.
実施例２
実施例１と同様の粉末およびＳｉＣ粉末（粒径０．７Ｉ
Ｌｎ）を用いて，実施例１と同一組成のサイアロンおよ
び２０ｖｏｌ％のＴｉＮ、８ｖ０１％のＳｉＣとなるよ
うな組成に配合した。これにＣｒ，Ｏ，を０．１〜８ｗ
ｔ％添加した。これらを実施例１と同様な条件で焼結し
、得られた焼結体の密度を測定後、これより３Ｘ４Ｘ４
０ｍｍの試験片を切出し、大気中で８５０℃、１５０時
間保持の酸化試験を行ない。酸化増量を測定した。結果
を第１表に示す。Example 2 Powder similar to Example 1 and SiC powder (particle size 0.7I
Ln) was blended into a composition of Sialon having the same composition as in Example 1, 20vol% TiN, and 8vol% SiC. Add 0.1 to 8w of Cr, O,
t% was added. These were sintered under the same conditions as in Example 1, and the density of the obtained sintered body was measured.
A 0 mm test piece was cut out and subjected to an oxidation test held at 850° C. for 150 hours in the atmosphere. Oxidative weight gain was measured. The results are shown in Table 1.
第 １ 表 で耐酸化性向上が達成されることが理解される。Table 1 It is understood that improved oxidation resistance can be achieved.
但し、焼結密度を考慮した場合、０．３〜３ｗｔ％にす
ることが望ましい。However, when considering the sintered density, it is desirable to set the content to 0.3 to 3 wt%.
実施例３
実施例１と同様の粉末およびＴｉＣ，ＺｒＮ（いずれも
粒径１ ．５ μｍ）、およびＭｇＯ（粒径０．５μｍ
）を用い、第２表に示す組成のＳｉ，Ｎ４およびサイア
ロンとなるよう配合し、これらに対し２５ｖｏｌ％の導
電性化合物を添加した。さらにＣｒ，Ｏ，を１ ．５ｗ
ｔ％添加し、混合、成形、焼結を行なった。焼結条件は
表中に示す。これらにつき実施例１と同様に試験片を切
り出し、大気中で８５０℃、１５０時間保持の酸化試験
を行なった。ここでそれぞれＣｒ．Ｏ，を添加していな
いものを比較例として用いた。結果を第２表に示す。Example 3 The same powder as in Example 1, TiC, ZrN (all particle size 1.5 μm), and MgO (particle size 0.5 μm
), Si, N4, and Sialon were blended to have the composition shown in Table 2, and 25 vol% of a conductive compound was added thereto. Furthermore, Cr, O, 1. 5w
t% was added, mixed, molded, and sintered. Sintering conditions are shown in the table. Test pieces were cut out in the same manner as in Example 1, and an oxidation test was conducted at 850° C. for 150 hours in the atmosphere. Here each Cr. A sample to which O was not added was used as a comparative example. The results are shown in Table 2.
？上より、Ｃｒ■Ｏ，添加量が０．１〜８．Ｏｗｔχの
範囲以上より、各種導電性化合物、サイアロン、Ｓｉ，
Ｎ，の種類によらずＣｒ，○，添加により８００〜９０
０℃の耐酸化性が大幅に改善されることがわかる。? From the top, the amount of CrO added is 0.1 to 8. Various conductive compounds, sialon, Si,
Regardless of the type of N, 800 to 90 depending on the addition of Cr, ○.
It can be seen that the oxidation resistance at 0°C is significantly improved.
以上の実施例により、ＳＬ，Ｎ４基セラミックスを母材
としＴｉＮなとの導電性化合物を添加した導電性セラミ
ックス焼結体およびヒーターにおいて、特に問題となる
８００〜９００℃の急激な酸化現象を抑制するためにＣ
ｒ，Ｏ，を添加することが極めて有効であることがわか
る。The above examples suppress the rapid oxidation phenomenon at 800 to 900°C, which is particularly problematic in conductive ceramic sintered bodies and heaters made of SL, N4-based ceramics as a base material and added with conductive compounds such as TiN. C to do
It can be seen that adding r, O, is extremely effective.
本発明により、従来の導電性を有する窒化珪素、サイア
ロン焼結体において問題である８００〜９００℃におけ
る急激な酸化現象を抑制することが可能となった。これ
によりヒーター材、高温用途への本系材料の使用が可能
となり、用途も大幅に広がる。According to the present invention, it has become possible to suppress the rapid oxidation phenomenon at 800 to 900° C., which is a problem in conventional conductive silicon nitride and sialon sintered bodies. This makes it possible to use this material for heater materials and high-temperature applications, greatly expanding the range of applications.
第１図は各種添加元素と酸化増量の関係を示すグラフで
ある。FIG. 1 is a graph showing the relationship between various additive elements and oxidation weight gain.
Claims (1)
．１〜１０ｗｔ％、残部窒化珪素系セラミックスからな
ることを特徴とする導電性セラミックス焼結体。 ２ 窒化珪素系セラミックスがサイアロンである特許請
求の範囲第１項記載の導電性セラミックス焼結体。 ３ 導電性物質がIVａ、ＶａおよびVIａ族の遷移金属元
素の炭化物、窒化物およびこれら化合物から形成される
複化合物の１種または２種以上の導電性化合物である特
許請求の範囲第１項または第２項記載の導電性セラミッ
クス焼結体。 ４ 導電性物質がＴｉＮである特許請求の範囲第１項ま
たは第２項記載の導電性セラミックス焼結体。 ５ 導電性物質がIVａ、ＶａおよびVIａ族の遷移金属元
素の炭化物、窒化物およびこれら化合物から形成される
複化合物の１種または２種以上の導電性化合物が１０〜
７０ｖｏｌ％、ならびに第２の導電性物質としてＳｉＣ
を０．１〜５０ｖｏｌ％、Ｃｒ酸化物が０．１〜１０ｗ
ｔ％、残部窒化珪素系セラミックスからなることを特徴
とする導電性セラミックス焼結体。 ６ 第１の導電性物質がＴｉＮである特許請求の範囲第
５項記載の導電性セラミックス焼結体。 ７ Ｃｒ酸化物の添加量が０．３〜３ｗｔ％であること
を特徴とする特許請求の範囲第１項ないし第６項のいず
れかに記載の導電性セラミックス焼結体。 ８ ＴｉＮが１０〜６０ｖｏｌ％、Ｃｒ酸化物が０．１
〜１０ｗｔ％、残部窒化珪素系セラミックスからなるこ
とを特徴とするヒーター。 ９ ＴｉＮが１０〜４０ｖｏｌ％、ＳｉＣが３〜３０ｖ
ｏｌ％、Ｃｒ酸化物が０．１〜１０ｗｔ％、残部窒化珪
素からなることを特徴とするヒーター。[Claims] 1 The conductive substance is 10 to 70 vol%, and the Cr oxide is 0.
．． A conductive ceramic sintered body comprising 1 to 10 wt% of silicon nitride based ceramics. 2. The conductive ceramic sintered body according to claim 1, wherein the silicon nitride ceramic is Sialon. 3. Claim 1, wherein the conductive substance is one or more conductive compounds of carbides, nitrides, and composite compounds formed from transition metal elements of groups IVa, Va, and VIa, or 2. The conductive ceramic sintered body according to item 2. 4. The conductive ceramic sintered body according to claim 1 or 2, wherein the conductive substance is TiN. 5 The conductive substance is one or more conductive compounds formed from carbides, nitrides, and these compounds of transition metal elements of groups IVa, Va, and VIa.
70 vol% and SiC as the second conductive material
0.1-50vol%, Cr oxide 0.1-10w
A conductive ceramic sintered body characterized in that the balance is silicon nitride ceramic. 6. The conductive ceramic sintered body according to claim 5, wherein the first conductive substance is TiN. 7. The conductive ceramic sintered body according to claim 1, wherein the amount of Cr oxide added is 0.3 to 3 wt%. 8 TiN is 10 to 60 vol%, Cr oxide is 0.1
A heater characterized in that the heater is made of ~10 wt%, the balance being silicon nitride ceramics. 9 TiN is 10-40vol%, SiC is 3-30v
Cr oxide is 0.1 to 10 wt %, and the balance is silicon nitride.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1051459A JPH02229765A (en) | 1989-03-03 | 1989-03-03 | Sintered body of conductive ceramics and heater |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1051459A JPH02229765A (en) | 1989-03-03 | 1989-03-03 | Sintered body of conductive ceramics and heater |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH02229765A true JPH02229765A (en) | 1990-09-12 |
Family
ID=12887519
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP1051459A Pending JPH02229765A (en) | 1989-03-03 | 1989-03-03 | Sintered body of conductive ceramics and heater |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH02229765A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6303055B1 (en) | 1998-01-16 | 2001-10-16 | Kabushiki Kaisha Toyota Chuo Kenkyusho | Composition of a high sensitivity sensor for detecting mechanical quantity |
| JP2003300780A (en) * | 2002-04-04 | 2003-10-21 | Toshiba Corp | Wear resistant member made of silicon nitride and production method therefor |
-
1989
- 1989-03-03 JP JP1051459A patent/JPH02229765A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6303055B1 (en) | 1998-01-16 | 2001-10-16 | Kabushiki Kaisha Toyota Chuo Kenkyusho | Composition of a high sensitivity sensor for detecting mechanical quantity |
| JP2003300780A (en) * | 2002-04-04 | 2003-10-21 | Toshiba Corp | Wear resistant member made of silicon nitride and production method therefor |
| JP4497787B2 (en) * | 2002-04-04 | 2010-07-07 | 株式会社東芝 | Rolling ball |
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