JPH0244066A - Silicon nitride sintered body - Google Patents
Silicon nitride sintered bodyInfo
- Publication number
- JPH0244066A JPH0244066A JP1087807A JP8780789A JPH0244066A JP H0244066 A JPH0244066 A JP H0244066A JP 1087807 A JP1087807 A JP 1087807A JP 8780789 A JP8780789 A JP 8780789A JP H0244066 A JPH0244066 A JP H0244066A
- Authority
- JP
- Japan
- Prior art keywords
- silicon nitride
- sintered body
- strength
- less
- sintering
- 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
- 229910052581 Si3N4 Inorganic materials 0.000 title claims description 70
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 title claims description 30
- 239000013078 crystal Substances 0.000 claims description 32
- 239000002245 particle Substances 0.000 claims description 15
- 238000002441 X-ray diffraction Methods 0.000 claims description 10
- 239000011575 calcium Chemical group 0.000 claims description 7
- 239000011777 magnesium Chemical group 0.000 claims description 7
- 229910052727 yttrium Inorganic materials 0.000 claims description 7
- 229910052791 calcium Inorganic materials 0.000 claims description 6
- 229910052749 magnesium Inorganic materials 0.000 claims description 6
- 229910052744 lithium Inorganic materials 0.000 claims description 4
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical group [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 3
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical group [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 3
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical group [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 3
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 claims description 3
- 238000005245 sintering Methods 0.000 description 24
- 230000000052 comparative effect Effects 0.000 description 23
- 239000012071 phase Substances 0.000 description 20
- 239000000203 mixture Substances 0.000 description 18
- 239000000843 powder Substances 0.000 description 18
- 239000002994 raw material Substances 0.000 description 16
- 230000003647 oxidation Effects 0.000 description 15
- 238000007254 oxidation reaction Methods 0.000 description 15
- 238000013001 point bending Methods 0.000 description 15
- 230000007423 decrease Effects 0.000 description 13
- 238000000034 method Methods 0.000 description 12
- 239000000463 material Substances 0.000 description 11
- 239000000470 constituent Substances 0.000 description 9
- 239000011521 glass Substances 0.000 description 8
- 239000007858 starting material Substances 0.000 description 8
- 239000006104 solid solution Substances 0.000 description 7
- 238000007656 fracture toughness test Methods 0.000 description 6
- 238000001272 pressureless sintering Methods 0.000 description 6
- 239000007789 gas Substances 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- 230000000694 effects Effects 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 239000011812 mixed powder Substances 0.000 description 4
- 238000000465 moulding Methods 0.000 description 4
- 239000007791 liquid phase Substances 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- BYFGZMCJNACEKR-UHFFFAOYSA-N aluminium(i) oxide Chemical compound [Al]O[Al] BYFGZMCJNACEKR-UHFFFAOYSA-N 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000003779 heat-resistant material Substances 0.000 description 2
- 238000007731 hot pressing Methods 0.000 description 2
- 238000003825 pressing Methods 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 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
- 229910052786 argon Inorganic materials 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 238000011088 calibration curve Methods 0.000 description 1
- 238000005467 ceramic manufacturing process Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 238000000280 densification Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 238000007373 indentation Methods 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 230000001404 mediated effect Effects 0.000 description 1
- 150000001247 metal acetylides Chemical class 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- 229910052575 non-oxide ceramic Inorganic materials 0.000 description 1
- 239000011225 non-oxide ceramic Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 229910021332 silicide Inorganic materials 0.000 description 1
- 238000007569 slipcasting Methods 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229910001845 yogo sapphire Inorganic materials 0.000 description 1
Landscapes
- Ceramic Products (AREA)
Abstract
(57)【要約】本公報は電子出願前の出願データであるた
め要約のデータは記録されません。(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明は、高温構造用材料等として用いることができる
、高強度、高靭性であり、かつ耐酸化性に優れた窒化珪
素質焼結体に関するものである。[Detailed Description of the Invention] [Industrial Application Field] The present invention provides a silicon nitride sintered body that has high strength, high toughness, and excellent oxidation resistance and can be used as a material for high-temperature structures. It is related to.
窒化珪素（Ｓｉ３Ｎ、）の焼結体は、高温強度、耐熱衝
撃性、耐食性が優れているために、ガスタービン部材、
熱交換器材料、高温用ベアリングあるいは製鋼用高温ロ
ール材等の耐熱構造用材料に使用されている。Sintered bodies of silicon nitride (Si3N) have excellent high-temperature strength, thermal shock resistance, and corrosion resistance, so they are used in gas turbine components,
It is used in heat-resistant structural materials such as heat exchanger materials, high-temperature bearings, and high-temperature roll materials for steel manufacturing.
しかしながら、５Ｌ３Ｎ４は単独では焼結が困難なため
に、通常ＭｇＯ，ＭｇＡｊ’２０４、Ａｆｆｚ０３、Ｙ
２Ｏ３等の酸化物を焼結助剤として添加し、焼結してい
る。これらの焼結助剤を用いた焼結は、焼結時に生ずる
液相を媒介とした液相焼結によるものと考えられている
。多（の場合、焼結後液相はガラス相として焼結体中に
残存し、高温強度、耐クリープ性などの高温特性を低下
させる。However, since it is difficult to sinter 5L3N4 alone, it is usually used in MgO, MgAj'204, Affz03, Y
Oxides such as 2O3 are added as sintering aids for sintering. Sintering using these sintering aids is thought to be based on liquid phase sintering mediated by the liquid phase generated during sintering. In the case of a polycarbonate, the liquid phase remains in the sintered body as a glass phase after sintering, reducing high-temperature properties such as high-temperature strength and creep resistance.
一方、Ｓｉａ、Ｎ＋に種々の元素が固溶したもの（一般
にサイアロンと呼ばれるもの）は、高温特性に優れ、高
温構造用材料として注目されている。On the other hand, Sia and N+ in which various elements are dissolved in solid solution (generally referred to as Sialon) have excellent high-temperature properties and are attracting attention as materials for high-temperature structures.
例えば、α−５ｉ３Ｎ４構造で、Ｓｉ位置にＡ１が、Ｎ
位置にＯが置換し、更に格子間位置に他の元素（Ｌ ｉ
、 Ｍｇ、 Ｃａ、 Ｙ等）が侵入型として固溶した、
一般式Ｍ、 （Ｓ ｉ、 Ａｌ） ＋２ （０゜Ｎ）
１６ （ｏ＜ｘ≦２、ＭはＬｉ、 Ｍｇ、 Ｃａ、 Ｙ
等のうちの少なくとも１種）で表されるα −８１３Ｎ
４（一般にα−サイアロンと呼ばれる）、あるいはβ−
５ｉ３Ｎ＋構造で、Ｓｉ位置にＡｌが、Ｎ位置にＯが固
溶し、一般式５ｉａ−ｙＡｌｙＯ，Ｎ、□ （０＜ｙ≦
４．２）で表されるβ’ −５１３Ｎ１（一般にβ−サ
イアロンと呼ばれる）が注目されている。For example, in the α-5i3N4 structure, A1 is at the Si position and N
O is substituted at the position, and another element (L i
, Mg, Ca, Y, etc.) are dissolved as an interstitial type,
General formula M, (S i, Al) +2 (0°N)
16 (o<x≦2, M is Li, Mg, Ca, Y
α −813N represented by at least one of the following)
4 (commonly called α-Sialon), or β-
In the 5i3N+ structure, Al is in solid solution at the Si position and O is in solid solution at the N position, and the general formula 5ia-yAlyO,N, □ (0<y≦
4.2) β'-513N1 (generally called β-sialon) is attracting attention.
しかしながら、これらのＳｉ、Ｎ４は、α５ｉａＮ４ま
たはβ’−８ｉ３Ｎ、のみからなる場合には、室温強度
が他の５ｉａＮ＋質焼結体よりも劣り、また靭性も低い
という欠点を有している。また、α’−８ｉ３Ｎ、とβ
’−８ｉ３Ｎ。However, when these Si and N4 are composed only of α5iaN4 or β'-8i3N, they have the disadvantage that the room temperature strength is inferior to other 5iaN+ sintered bodies, and the toughness is also low. Also, α'-8i3N, and β
'-8i3N.
とを混合した焼結体も以下のように開発されいてる。A sintered body that is a mixture of and has also been developed as follows.
Ｊ、Ｍａｔｅｒｉａｌｓ Ｓｃｉ、 １４ （１９７
９） Ｐ ｌ ７４９では、Ｓ １３ Ｎ４ Ｙ２０
３ Ａｌ２Ｏの混合粉末を焼結することによって、α
’ ５１３Ｎ４の単相あるいはα’−３ｉｓＮ４と
β’ −８ｉ３Ｎ４との混合相からなる焼結体が得られ
ることを報告している。また、特開昭５８−１８５４８
４号では、α’−８ｉａＮ＋とβ’−８ｉ＋Ｎ＋粉末を
原料として、α’−８ｉ、Ｎ＋とβ’ ３１３Ｎ４
との混合相からなる焼結体を得ている。しかし、この２
例の焼結体とも、室温強度、高温強度が低い。J. Materials Sci., 14 (197
9) In P l 749, S 13 N4 Y20
3 By sintering the mixed powder of Al2O, α
It has been reported that a sintered body consisting of a single phase of '513N4 or a mixed phase of α'-3isN4 and β'-8i3N4 can be obtained. Also, JP-A-58-18548
In No. 4, using α'-8iaN+ and β'-8i+N+ powder as raw materials, α'-8i, N+ and β' 313N4
A sintered body consisting of a mixed phase with However, these two
Both of the example sintered bodies have low room temperature strength and high temperature strength.
更に、特開昭５９−１８２２７６号では、５１３Ｎ４−
Ａｌ２Ｏ−Ｙ２Ｏ２−ＡＣ０８系の混合粉末を焼結する
ことによりα’−８ｉ、Ｎ、とβ−８ｉ３Ｎ＋ とから
なる焼結体を得ている。この例では、α’−８ｉ３Ｎ４
の存在比率が０．０５〜０゜７、その結晶粒の大きさが
長径方向で４０μｍ以下からなる焼結体は高温強度が改
善されるとしているが、１２００℃以上での高温強度は
不充分である。Furthermore, in JP-A-59-182276, 513N4-
By sintering the Al2O-Y2O2-AC08-based mixed powder, a sintered body consisting of α'-8i, N, and β-8i3N+ was obtained. In this example, α'-8i3N4
It is said that a sintered body with an abundance ratio of 0.05 to 0°7 and a crystal grain size of 40 μm or less in the long axis direction has improved high temperature strength, but high temperature strength at 1200°C or higher is insufficient. It is.
〔第１発明の説明〕
本第１発明（請求項（１）に記載の発明）は、上記従来
技術の欠点に鑑み、α’−窒化珪素とβ’窒化珪素との
存在比率及び結晶粒の粒径について検討を重ねた結果な
されたものであり、室温、高温ともに高い強度を有し、
しかも高い靭性、優れた耐酸化性を有する窒化珪素質焼
結体を提供しようとするものである。[Description of the first invention] In view of the above-mentioned drawbacks of the prior art, the first invention (the invention according to claim (1)) improves the abundance ratio of α'-silicon nitride and β' silicon nitride and the crystal grain size. This was achieved after repeated studies regarding the particle size, and it has high strength at both room and high temperatures.
Furthermore, the present invention aims to provide a silicon nitride sintered body having high toughness and excellent oxidation resistance.
本第１発明は、α゛ −窒化珪素とβ°−窒化珪素とか
らなる窒化珪素質焼結体であってＸ線回折によるピーク
強度比における存在比率は、α’窒化珪素０．０５〜０
．５０、β’−窒化珪素０．９５〜０．５０であり、α
’ −窒化珪素は、結晶粒の平均粒径が２．０μｍ以下
であり、β″ −窒化珪素は、結晶粒の平均粒径が長径
方向において５．０μｍ以下、短径方向において１．０
μｍ以下であることを特徴とする窒化珪素質焼結体であ
る。The first invention is a silicon nitride sintered body consisting of α゛-silicon nitride and β°-silicon nitride, and the abundance ratio in the peak intensity ratio determined by X-ray diffraction is 0.05 to 0.
．． 50, β'-silicon nitride 0.95 to 0.50, α
'-Silicon nitride has a crystal grain with an average grain size of 2.0 μm or less, and β″-silicon nitride has a crystal grain with an average grain size of 5.0 μm or less in the major axis direction and 1.0 μm or less in the minor axis direction.
It is a silicon nitride sintered body characterized by having a diameter of μm or less.
本第１発明によれば、室温でも高温でも高い強度を有し
、かつ高靭性で優れた耐酸化性を有する窒化珪素質焼結
体を提供することができる。According to the first invention, it is possible to provide a silicon nitride sintered body that has high strength both at room temperature and high temperature, and has high toughness and excellent oxidation resistance.
すなわち、本第１発明の焼結体は、靭性を損なわず、室
温、高温での強度が格段に高いものである。強度につい
ては、従来の窒化珪素質焼結体の最高レベルのものに比
しても大きな向上が得られている。しかも、１３００°
Ｃのような高温になると従来の物では室温時に較べて急
激に強度が低下してしまうが、本第１発明のものでは、
その低下が極めて少なく安定している。また、破壊靭性
についても、従来の焼結体に比して大きな靭性値を有す
る。更に、高温における耐酸化性も従来の焼結体に比し
て極めて優れている。このように、本第１発明の焼結体
は、強度と靭性と耐酸化性の各面において従来技術では
達し得なかった優れた特性を有し、しかも高温でもその
特性が安定しており、特に高温で使用する耐熱性材料等
として有用である。That is, the sintered body of the first invention has significantly high strength at room temperature and high temperature without impairing toughness. In terms of strength, a significant improvement has been achieved compared to the highest level of conventional silicon nitride sintered bodies. Moreover, 1300°
At high temperatures such as C, the strength of conventional products decreases rapidly compared to that at room temperature, but with the product of the first invention,
The decrease is extremely small and stable. Also, regarding fracture toughness, it has a greater toughness value than conventional sintered bodies. Furthermore, the oxidation resistance at high temperatures is also extremely superior to that of conventional sintered bodies. As described above, the sintered body of the first invention has excellent properties in terms of strength, toughness, and oxidation resistance that could not be achieved with conventional technology, and its properties are stable even at high temperatures. It is particularly useful as a heat-resistant material used at high temperatures.
本第１発明にかかる焼結体が上記効果を奏する理由は十
分解明されていないが、以下のようなものであると考え
られる。The reason why the sintered body according to the first invention has the above effects is not fully elucidated, but it is thought to be as follows.
（１）柱状のβ’ −窒化珪素の結晶粒の隙間が等軸状
の微細なα゛ −窒化珪素の結晶粒で埋められているた
め、高温での粒界すベリが生じにくい組織になっている
こと、及び（２）α’−窒化珪素およびβ’ −窒化珪
素の結晶粒が非常に微細であるため、内部欠損が著しく
小さくなり、また、結晶粒界に存在するガラス相が分散
して、その相対的な量が減少すること、などによる。(1) The gaps between columnar β'-silicon nitride crystal grains are filled with equiaxed fine α'-silicon nitride grains, resulting in a structure that is less likely to cause grain boundary burrs at high temperatures. (2) Since the crystal grains of α'-silicon nitride and β'-silicon nitride are extremely fine, internal defects are significantly reduced, and the glass phase existing at the grain boundaries is dispersed. and their relative amount decreases, etc.
また、上記により、結晶粒界の間に存在するガラス相の
量が少なくなり、従って、結晶粒同士の接触面積の割合
が大きくなっており、このことも上記効果に寄与してい
ると考えられる。Additionally, as a result of the above, the amount of glass phase existing between grain boundaries decreases, and therefore the proportion of contact area between grains increases, which is thought to also contribute to the above effect. .
〔第２発明の説明〕
本第２発明（請求項（３）に記載の発明）は、上記従来
技術の欠点に鑑み、α’ −窒化珪素とβ。[Description of the Second Invention] In view of the drawbacks of the above-mentioned prior art, the present second invention (invention according to claim (3)) combines α'-silicon nitride and β.
窒化珪素との存在比率及び組成について検討を重ねた結
果なされたものであり、室温、高温ともに高い強度を有
し、しかも高い靭性、優れた耐酸化性を有する窒化珪素
質焼結体を提供しようとするものである。This was achieved after repeated studies on the proportion and composition of silicon nitride, and we aim to provide a silicon nitride sintered body that has high strength at both room and high temperatures, as well as high toughness and excellent oxidation resistance. That is.
本第２発明は、α’ −窒化珪素とβ’ −窒化珪素と
からなる窒化珪素質焼結体であって、Ｘ線回折によるピ
ーク強度比における存在比率は、α’−窒化珪素０．０
５〜０．５０、β’ −窒化珪素０．９５〜０．５０で
あり、α’ −窒化珪素は、Ｍ、 （Ｓｉ、ＡＡ）、
□（０，Ｎ）、６（Ｍは、リチウム、マグネシウム、カ
ルシウム、イツトリウムのうちの少なくとも１種である
。０＜ｘ≦０．３）で表されるものであり、β’ −窒
化珪素は、５ｉ８−ｙＡｊ！ｙＯ７Ｎ８□ （０〈ｙ≦
１．０）で表されるものであることを特徴とする窒化珪
素質焼結体である。The second invention is a silicon nitride sintered body consisting of α'-silicon nitride and β'-silicon nitride, and the abundance ratio in the peak intensity ratio determined by X-ray diffraction is 0.0 of α'-silicon nitride.
5 to 0.50, β'-silicon nitride 0.95 to 0.50, and α'-silicon nitride is M, (Si, AA),
□ (0, N), 6 (M is at least one of lithium, magnesium, calcium, and yttrium. 0<x≦0.3), and β'-silicon nitride is ,5i8-yAj! yO7N8□ (0〈y≦
1.0) is a silicon nitride-based sintered body.
本第２発明によれば、室温でも高温でも高い強度を有し
、かつ高靭性で優れた耐酸化性を有する窒化珪素質焼結
体を提供することができる。According to the second invention, it is possible to provide a silicon nitride sintered body that has high strength both at room temperature and high temperature, and has high toughness and excellent oxidation resistance.
すなわち、本第２発明の焼結体は、本第１発明と同様に
、強度と靭性と耐酸化性の各面において従来技術では達
し得なかった優れた特性を有し、しかも高温でもその特
性が安定しており、特に高温で使用する耐熱性材料等と
して有用である。That is, like the first invention, the sintered body of the second invention has excellent properties in terms of strength, toughness, and oxidation resistance that could not be achieved with the conventional technology, and moreover, the sintered body has excellent properties even at high temperatures. is stable and is particularly useful as a heat-resistant material used at high temperatures.
本第２発明にかかる焼結体が上記効果を奏する理由は十
分解明されていないが、本第１発明と同様に、
（１）柱状のβ’ −窒化珪素の結晶粒の隙間が等軸状
の微細なα゛ −窒化珪素の結晶粒で埋められているた
め、高温での粒界すベリが生じにくい組織になっている
こと、（２）α’−窒化珪素およびβ’−窒化珪素の結
晶粒が非常に微細であるため、内部欠損が著しく小さく
なり、また、結晶粒界に存在するガラス相が分散して、
その相対的量が減少すること、および（３ン組成の限定
により、結晶粒界のガラス相の絶対量が少な（なること
、などによると考えられる。The reason why the sintered body according to the second invention achieves the above effects is not fully elucidated, but similarly to the first invention, (1) the gaps between the columnar β'-silicon nitride crystal grains are equiaxed; (2) The microstructure of α'-silicon nitride and β'-silicon nitride is filled with fine grains of α'-silicon nitride, making it difficult for grain boundary burrs to occur at high temperatures. Because the crystal grains are extremely fine, internal defects are significantly reduced, and the glass phase present at the grain boundaries is dispersed,
This is thought to be due to the fact that the relative amount of the glass phase decreases, and that the absolute amount of the glass phase at the grain boundaries decreases due to the limitation of the 3-layer composition.
また、上記により、結晶粒界の間に存在するガラス相の
量が少なくなり、従って、結晶粒同士の接触面積の割合
が大きくなっており、このことも上記の効果に寄与して
いると考えられる。In addition, as a result of the above, the amount of glass phase existing between grain boundaries is reduced, and therefore the proportion of contact area between crystal grains is increased, which is thought to also contribute to the above effect. It will be done.
〔第１発明および第２発明のその他の発明の説明〕以下
、本第１発明および本第２発明をより具体的にしたその
他の発明について説明する。[Description of other inventions of the first invention and the second invention] Hereinafter, other inventions that make the first invention and the second invention more specific will be described.
本発明の窒化珪素（Ｓ ｉ３ Ｎ４ ）質焼結体は、α
’ −窒化珪素とβ’ −窒化珪素とを構成相とし、か
つそれぞれの結晶粒を非常に微細にするか、あるいはα
’−窒化珪素とβ°−窒化珪素とを特定の組成にしたも
のである。The silicon nitride (S i3 N4 ) sintered body of the present invention has α
' -silicon nitride and β' -silicon nitride are the constituent phases, and the crystal grains of each are made very fine, or α
'-silicon nitride and β°-silicon nitride in a specific composition.
本発明において、α’−窒化珪素（Ｓｉ３Ｎ＜）とは、
α−３１３Ｎ４構造で、Ｓｉ位置にＡ１が、Ｎ位置に０
が置換し、更に格子間位置に他の元素（リチウム（Ｌｉ
）、マグネシウム（Ｍｇ）、カルシウム（Ｃａ）、イツ
トリウム（Ｙ）等のう。In the present invention, α'-silicon nitride (Si3N<) is
α-313N4 structure, A1 at Si position and 0 at N position
is substituted, and furthermore, another element (lithium (Li
), magnesium (Mg), calcium (Ca), yttrium (Y), etc.
ちの少なくとも１種）が侵入型に固溶した、一般式Ｍｘ
（Ｓ １１ Ａ Ｉ−） ＋□（ｏ、Ｎ）、、（Ｍ
はＬｉ。General formula Mx in which at least one type of
(S 11 A I-) +□(o, N),, (M
is Li.
Ｍｇ、Ｃａ、Ｙ等のうちの少なくとも１種である。At least one of Mg, Ca, Y, etc.
０＜ｘ≦２）で示されるものであり、α−サイアロンと
呼ばれるものである。0<x≦2), and is called α-sialon.
また、β’−３ｉ３Ｎ４とは、β−８ｉ３Ｎ４構造で、
Ｓｉ位置にＡＩが、Ｎ位置にＯが固溶したもので、一般
式Ｓ １ａ−ｙ Ａｌｙ ｏ、 Ｎ８−Ｆ （０＜ｙ
≦４．２）で示されるものであり、β−サイアロンと呼
ばれるものである。In addition, β'-3i3N4 has a β-8i3N4 structure,
A solid solution of AI at the Si position and O at the N position, with the general formula S 1a-y Aly o, N8-F (0<y
≦4.2) and is called β-sialon.
また、上記α’−８ｉ３Ｎ、とβ’−８ｉ３Ｎ。Also, the above α'-8i3N and β'-8i3N.
の一般式において、Ｏ＜ｘ≦０．３、Ｑ＜ｙ≦１．０の
範囲内が更に望ましい。この範囲内であれば、結晶粒の
粒界のガラス相が少なくなり、高温での焼結体の強度が
向上する。In the general formula, it is more desirable that O<x≦0.3 and Q<y≦1.0. Within this range, the glass phase at the grain boundaries of crystal grains will be reduced, and the strength of the sintered body at high temperatures will be improved.
α−３ｉａＮ４
比率は、Ｘ線回折ピークの強度比による割合で、α’−
８ｉ３Ｎ＋が０．０５〜０．５０、残部（０，９５〜０
．５０）がβ ５１３Ｎ＋ となるようにする。α’
−８ｉ、Ｎ、の存在比率が０．０５未満あるいは０．５
０を越える場合には、焼結体の靭性が低下し、また十分
な強度向上が達成できない。なお、更に望ましくは、α
−３ｉａＮ４の存在比率が０．０７〜０．３５であれば
、より高い強度が得られる。本発明では、存在比率をＸ
線回折ピークの強度比より求めており、回折ピークの最
大強度と次に大きい強度とを合計してα”、β’のそれ
ぞれの合計を比較した。α-3iaN4 ratio is the ratio based on the intensity ratio of X-ray diffraction peaks,
8i3N+ is 0.05-0.50, the rest (0.95-0
．． 50) becomes β 513N+. α'
-8i, N, abundance ratio is less than 0.05 or 0.5
If it exceeds 0, the toughness of the sintered body decreases and sufficient strength improvement cannot be achieved. Furthermore, more preferably, α
If the abundance ratio of -3iaN4 is 0.07 to 0.35, higher strength can be obtained. In the present invention, the abundance ratio is
It was determined from the intensity ratio of the line diffraction peaks, and the maximum intensity and the next highest intensity of the diffraction peaks were summed and the respective sums of α'' and β' were compared.
α’−８ｉ３Ｎ＋の結晶粒の大きさは、その平均粒径が
２．０μｍ以下とするのが望ましい。また、β’−８ｉ
ｓＮ＋の結晶粒の大きさは、その平均粒径が、長径方向
において５．０μｍ以下、短径方向において１．０μｍ
以下とするのが望ましい。これは、α−３ｉａＮ４とβ
’ ５ｔ３１’Ｌの結晶粒の両方あるいはいずれか
一方の結晶粒が上記範囲を越えると、強度の向上が得ら
れないためである。なお、より高い強度が得られるのは
、α−３ｉａＮ４の結晶粒の平均粒径が１．０μｍ以下
、β’−８ｉ３Ｎ＋の結晶粒の平均粒径が長径方向にお
いて２．５μｍ以下、短径方向において０．５μｍ以下
の範囲である。また、長径方向は短径方向に対して２以
上とするのがよい。２未満の場合には、結晶粒が等軸状
になり、強度及び靭性が低下しやすくなる。As for the size of the α'-8i3N+ crystal grains, it is desirable that the average grain size is 2.0 μm or less. Also, β'-8i
The average grain size of sN+ is 5.0 μm or less in the major axis direction and 1.0 μm in the minor axis direction.
The following is desirable. This is α-3iaN4 and β
This is because if both or one of the crystal grains of '5t31'L exceeds the above range, no improvement in strength can be obtained. In addition, higher strength can be obtained when the average grain size of α-3iaN4 crystal grains is 1.0 μm or less, the average grain size of β'-8i3N+ crystal grains is 2.5 μm or less in the major axis direction, and when the average grain size of β'-8i3N+ crystal grains is 2.5 μm or less in the major axis direction. It is in the range of 0.5 μm or less. Further, it is preferable that the length in the major axis direction is two or more with respect to the minor axis direction. If it is less than 2, the crystal grains become equiaxed and strength and toughness tend to decrease.
次に、本発明にがかる５ｉａＮ４質焼結体を製造する方
法としては、α’−８ｉ３Ｎ４原料とβ。Next, as a method for producing a 5iaN4 sintered body according to the present invention, α'-8i3N4 raw material and β.
Ｓｉ３Ｎ４原料とを混合し、高温度において加熱、焼結
する方法がある。There is a method of mixing Si3N4 raw materials, heating and sintering at high temperature.
上記において、α’−３ｉ３Ｎ、原料としては、焼結体
中においてα−３ｉａＮ４の状態となる原料であり、こ
れにはα’−８ｉ３Ｎ＜自体及び加熱焼結時の反応によ
りα−３ｉａＮ４を生成する混合物がある。それ故、α
’−８ｉ、Ｎ、原料としては、この一方または双方を用
いる。反応してα’−８ｉ３Ｎ、を形成する混合物とし
ては、例えば、Ｙを固溶したα−３ｉａＮ４を形成する
場合、３１３ Ｎ４ Ａｌ２Ｎ Ｙ２０３ 、Ｓ
１ ａＮ４−ＡＩＮ−Ａｌ２Ｏ２Ｙ２０３ 、Ｓ １８
Ｎ４Ａ １２０３ Ｙ２０３ ＹＮ等の混合物が
挙げられる。In the above, α'-3i3N, as a raw material, is a raw material that becomes α-3iaN4 in the sintered body, and includes α'-8i3N< itself and the reaction that produces α-3iaN4 during heating and sintering. There is a mixture that Therefore, α
'-8i, N, one or both of these are used as raw materials. As a mixture that reacts to form α'-8i3N, for example, when forming α-3iaN4 in which Y is dissolved as a solid solution, 313 N4 Al2N Y203, S
1 aN4-AIN-Al2O2Y203, S 18
Examples include mixtures such as N4A 1203 Y203 YN.
また、β’−８ｉ３Ｎ＋原料としては、焼結体中におい
てβ’−８ｉ３Ｎ＋の状態となる原料であり、これには
β’−８ｉ３Ｎｔ自体及び加熱焼結時の反応によりβ’
−８ｉ３Ｎ、を生成する混合物がある。それ故、β’−
８ｉ３Ｎ、原料としては、この一方または双方を用いる
。反応してβ。In addition, the β'-8i3N+ raw material is a raw material that becomes β'-8i3N+ in the sintered body, and this includes β'-8i3Nt itself and β'
There is a mixture that produces -8i3N. Therefore, β'−
8i3N, one or both of these are used as raw materials. React and β.
５ｉ３Ｎｌを形成する混合物としては、５ｉ３Ｎｔ−Ａ
１２０３ 、Ｓ １３Ｎｔ −ＡｎＮ−ＡＬ０３ 、Ｓ
ｉ３Ｎ＜ −Ａｌｚ ０３−８ ｉ０２等の混合物が
挙げられる。As a mixture forming 5i3Nl, 5i3Nt-A
1203 , S 13Nt -AnN-AL03 , S
Examples include mixtures such as i3N<-Alz 03-8 i02.
また、α’ −８ｉ３Ｎ、原料のうちの加熱焼結時の
反応によりα’−８ｉ３Ｎ、を生成する混合物において
、混合物の配合割合を制御することによりα’ ８
１３Ｎ４を生成させると同時にβ’−３ｉａＮｔ も生
成させることができる。例えば、Ｙが固溶したα−３ｉ
ａＮ４とβ’−８ｉ３Ｎ。In addition, in a mixture that produces α'-8i3N and α'-8i3N through a reaction during heating and sintering among the raw materials, α'8
β'-3iaNt can also be generated at the same time as 13N4 is generated. For example, α-3i in which Y is dissolved as a solid solution
aN4 and β'-8i3N.
とを同時に形成させようとする場合、５ｉａＮ４に対す
るＹ２０ｓ Ａ Ｉ Ｎ、 Ｙ２０３ Ａ １２
Ｎ−Ａｌ２Ｏ３、あるいはＹＮ−ＡＡ２０３−Ｙ２０３
の配合割合を制御することにより、α’ −８ｉ３Ｎ４
とβ’−８ｉ、Ｎ４とを同時に生成させることができる
。これは、Ｙ、Ａｌ、ＯがＳｉ３Ｎ＜に固溶してα’−
３ｉ３Ｎ＜を形成すると同時にＡＩ、Ｏが５１３ｆ’Ｌ
に固溶してβ’−８ｉ３Ｎ。If you want to form them at the same time, Y20s A I N for 5iaN4, Y203 A 12
N-Al2O3 or YN-AA203-Y203
By controlling the blending ratio of α'-8i3N4
, β'-8i, and N4 can be generated simultaneously. This is because Y, Al, and O are dissolved in Si3N< and α'-
At the same time as forming 3i3N<, AI and O are 513f'L
β'-8i3N in solid solution.
を形成するためである。この場合、同じ混合物であって
も焼結温度、焼結時間によってαｌ ３ｉ。This is to form a In this case, even if the mixture is the same, αl 3i depends on the sintering temperature and sintering time.
Ｎ４とβ’−８ｉ３Ｎ４との生成割合が異なるため、焼
結条件を制御することにより所望の生成割合の焼結体を
得ることができる。Since the production ratios of N4 and β'-8i3N4 are different, a sintered body with a desired production ratio can be obtained by controlling the sintering conditions.
なお、α Ｓ １３Ｎ４、β’−５ｉａＮ１の組成が
２種以上のもの（前記α’−５ｉ３Ｎ１゜β’−８ｉａ
Ｎ４の一般式におけるｘ、 ｙが２種以上のもの）か
らなる焼結体を得る場合には、粒度分布の広いα’
５１３Ｎ４原料粉末、β’Ｓｉ３Ｎ＜原料粉末を用い
るか、あるいは組成の異なる２種以上のα’−８ｉ、Ｎ
、粉末、β゛Ｓｉ３Ｎ、Ｓｉ３Ｎ、粉末い。In addition, those with two or more compositions of α S 13N4 and β'-5iaN1 (the above α'-5i3N1゜β'-8ia
When obtaining a sintered body consisting of two or more types of x and y in the general formula of N4, α' with a wide particle size distribution is used.
513N4 raw material powder, β'Si3N < raw material powder, or two or more types of α'-8i, N with different compositions
, powder, β゛Si3N, Si3N, powder.
次に、α’−８ｉ３Ｎ４原料とβ’ ８１３Ｎ４原
料との混合粉末を成形し、加熱焼結する工程は、通常の
非酸化物セラミックスの製造工程を用いることができる
。この成形法としては、金型プレス、ラバープレス、押
し出し、スリップキャスト、射出成形等を用いることが
できる。また、焼結は、Ｎ２ガス、アルゴンガス等の不
活性ガス雰囲気、あるいは真空中等の非酸化性雰囲気中
で加熱焼結するのが望ましい。焼結方法としては、常圧
焼結法、ガス圧焼結法、熱間静水圧焼結（ＨＩ Ｐ）法
、ホットプレス法等を用いることができる。また、焼結
温度は１６５０〜１９００°Ｃが望ましい。焼結温度が
１６５０℃より低いと十分に緻密化が進行せず、１９０
０°Ｃを越えると粒成長が著しくなり、十分な強度が得
られない。Next, the process of molding the mixed powder of the α'-8i3N4 raw material and the β' 813N4 raw material and heating and sintering it can use a normal non-oxide ceramic manufacturing process. As this molding method, mold pressing, rubber pressing, extrusion, slip casting, injection molding, etc. can be used. Further, the sintering is preferably carried out by heating in an inert gas atmosphere such as N2 gas or argon gas, or a non-oxidizing atmosphere such as vacuum. As the sintering method, a normal pressure sintering method, a gas pressure sintering method, a hot isostatic pressure sintering (HIP) method, a hot press method, etc. can be used. Moreover, the sintering temperature is preferably 1650 to 1900°C. If the sintering temperature is lower than 1650°C, densification will not proceed sufficiently, and the
If the temperature exceeds 0°C, grain growth becomes significant and sufficient strength cannot be obtained.
しかして、α’−８ｉ３Ｎ４原料とβ’ ５ｔ３Ｎ
４原料との混合割合、焼結条件等を制御して、焼結体中
のα’−５ｉ３Ｎ４とβ’−３ｉ３Ｎ４との存在比率、
および結晶粒の大きさ、あるいは組成が前記範囲内とな
るようにする。Therefore, α'-8i3N4 raw material and β' 5t3N
By controlling the mixing ratio with the four raw materials, sintering conditions, etc., the abundance ratio of α'-5i3N4 and β'-3i3N4 in the sintered body,
And the size or composition of crystal grains should be within the above range.
本発明の窒化珪素質焼結体は、高靭性であり、高温にお
いて高強度及び耐酸化性が優れているためガスタービン
部材、熱交換器材料等の耐熱構造用材料等として利用す
ることができる。The silicon nitride sintered body of the present invention has high toughness, high strength at high temperatures, and excellent oxidation resistance, so it can be used as a heat-resistant structural material such as gas turbine components and heat exchanger materials. .
本発明の窒化珪素質焼結体には、用途に応じて各種耐熱
性物質、例えば酸化物、窒化物、炭化物、ケイ素化物、
ホウ素化物、硫化物などを第３成分として添加してもよ
い。The silicon nitride sintered body of the present invention may contain various heat-resistant substances, such as oxides, nitrides, carbides, silicides,
A boronide, sulfide, etc. may be added as a third component.
以下、本発明の詳細な説明する。 The present invention will be explained in detail below.
実施例Ｉ
出発原料として、平均粒径０．５μｍ以下のＳｉ３Ｎ、
（α率９５％以上）粉末、平均粒径０．５μｍ以下の高
純度（９９，９％）Ｙ２０３粉末、及び平均粒径０．５
．ｃｚｍ以下の高純度（９９，９％） Ａｊ２Ｎ粉末を
用いて、これを成形し、ホットプレス法により第１表に
示すような構成相、結晶粒を有するα’ ８１３Ｎ
４ とβ’−８ｉ３Ｎ、とからなる焼結体を製造した。Example I As a starting material, Si3N with an average particle size of 0.5 μm or less,
(α rate 95% or more) powder, high purity (99.9%) Y203 powder with an average particle size of 0.5 μm or less, and an average particle size of 0.5
．． Using Aj2N powder with high purity (99.9%) of czm or less, it is molded and hot pressed to form α' 813N having the constituent phases and crystal grains shown in Table 1.
A sintered body consisting of 4 and β'-8i3N was produced.
なお、ホットプレスは１６５０〜１９００°Ｃ１圧力２
００〜３００ｋｇ／ｃｉ、０゜５〜１０時間の条件で行
った。In addition, hot press is 1650-1900°C1 pressure2
The test was carried out under the conditions of 00 to 300 kg/ci and 0° for 5 to 10 hours.
また、比較のため、第１表中の比較例に示すように焼結
体中のα’−８ｉ３Ｎ、の存在比率、あるいはα’
８１３ Ｎ４ 、β’−８ｉ３Ｎ、の結晶粒の平均粒径
が本第１発明の範囲をはずれるものも上記と同様にして
製造した。In addition, for comparison, as shown in the comparative example in Table 1, the abundance ratio of α'-8i3N in the sintered body or α'
813N4 and β'-8i3N crystal grains whose average grain size was outside the range of the first invention were also produced in the same manner as above.
得られた各焼結体から３Ｘ４Ｘ４０ｍｍの曲げ試験片を
切り出し、ＪＩＳＲ−１６０１に準じた４点曲げ試験及
び圧痕法（ビッカース硬度計、荷重２０ｋｇ）により破
壊靭性（Ｋｌ。）の測定を実施した。その結果を第１表
に示す。なお、第１表中のα’−８ｉ３Ｎ４の存在比率
は、焼結体のＸ線回折ピークの強度比より求めた値であ
り、α’−８ｉ、Ｎ、とβ’−８ｉ３Ｎ４との存在比率
の合計を１とした場合のα’−８ｉ３Ｎ、の存在比率で
ある（以降の表についても同様である。）。なお、第１
図及び第２図に試料Ｎ０１４．１２の焼結体のＸ線回折
チャートを示す。存在比率の求め方は、第１図において
α’型の強度の高い上位２個のピークａｌｓａ２の合計
とβ゛型の強度の高い上位２個のピークｂ１、ｂ２の合
計とを比較した。A bending test piece of 3 x 4 x 40 mm was cut out from each of the obtained sintered bodies, and the fracture toughness (Kl.) was measured by a 4-point bending test according to JISR-1601 and an indentation method (Vickers hardness tester, load 20 kg). The results are shown in Table 1. The abundance ratio of α'-8i3N4 in Table 1 is a value determined from the intensity ratio of the X-ray diffraction peaks of the sintered body, and the abundance ratio of α'-8i,N and β'-8i3N4. This is the abundance ratio of α'-8i3N when the sum of 1 is taken as 1 (the same applies to the following tables). In addition, the first
The X-ray diffraction chart of the sintered body of sample N014.12 is shown in the figure and FIG. The abundance ratio was determined by comparing the sum of the top two peaks alsa2 with the highest α'-type intensity in FIG. 1 with the sum of the top two peaks b1 and b2 with the highest β′-type intensity in FIG.
第１表より明らかなように、比較例では、室温での強度
が最高で９３ ｋｇ／ ｍｍ２、Ｋ ｔｃ値が最高で６
、６ Ｍ Ｐ ａ ｍ””であるのに対して、本実施例
のものでは、室温での強度がいずれも１００ｋｇ／Ｍ２
以上であり、しかもＫＩＣ値も７ＭＰａｍ”を越えてい
る。しかも、室温から１３００℃での強度の低下は、比
較例では２１〜２５ｋｇ／ｍｍ２であるのに対して、本
実施例では、１０〜１７ｋｇ／ｍｍ２と非常に小さい。As is clear from Table 1, in the comparative example, the maximum strength at room temperature was 93 kg/mm2, and the maximum K tc value was 6.
, 6 M P a m"", whereas in this example, the strength at room temperature is 100 kg/M2.
Moreover, the KIC value also exceeds 7 MPam''.Moreover, the decrease in strength from room temperature to 1300°C is 21 to 25 kg/mm2 in the comparative example, whereas in the present example, the decrease in strength is 10 to 10 kg/mm2. Very small at 17kg/mm2.
また、本実施例中には１３００℃の高温での強度が１０
０ ｋｇ／ ｍ１１２を越えるものがあり、従来では達
成し得なかった高温での４点曲げ強度が１００ ｋｇ／
ｍｍ２を本実施例では達成し得る。In addition, in this example, the strength at a high temperature of 1300°C was 10
There are some that exceed 0 kg/m112, and the four-point bending strength at high temperatures, which was previously unachievable, is 100 kg/m.
mm2 can be achieved in this example.
次に、第１表の試料Ｎα３．６．９．１２、Ｃ１゜Ｃ４
、Ｃ６の７種類の試料に対して高温酸化試験を行った。Next, sample Nα3.6.9.12, C1°C4 in Table 1
, C6 samples were subjected to high temperature oxidation tests.
この高温酸化試験は、試料を静止大気中１２００℃また
は１３００℃で１００時間酸化し、その後試料の重量変
化を測定し、更にＪＩＳＲ１６０１に準じた４点曲げ試
験を行った。その結果を第２表に示す。In this high-temperature oxidation test, the sample was oxidized at 1200° C. or 1300° C. for 100 hours in a still atmosphere, and then the weight change of the sample was measured, and a 4-point bending test according to JISR1601 was conducted. The results are shown in Table 2.
第 ２ 表
第２表より明らかなように、本実施例では、比較例に比
して重量増加及び４点曲げ強度の低下が非常に少なく、
耐酸化性に優れていることが分る。Table 2 As is clear from Table 2, in this example, the increase in weight and the decrease in 4-point bending strength were very small compared to the comparative example.
It can be seen that it has excellent oxidation resistance.
このように、本実施例のものは、靭性と強度（特に高温
強度）と耐酸化性の各面において従来のものに比して優
れていることが分る。Thus, it can be seen that the material of this example is superior to the conventional material in terms of toughness, strength (especially high-temperature strength), and oxidation resistance.
実施例２
実施例１と同様な出発原料を用いて、これを成形し、常
圧焼結法により第３表に示すような構成相、結晶粒を有
するα ５１３Ｎ４とβ’−８ｉ、Ｎ、とからなる焼
結体を製造した。なお、常圧焼結は、Ｎ２中、１７５０
〜１９００°Ｃ，１〜６時間の条件で行った。Example 2 Using the same starting material as in Example 1, it was molded and subjected to pressureless sintering to produce α513N4, β'-8i, N, having constituent phases and crystal grains as shown in Table 3. A sintered body consisting of Note that pressureless sintering is performed at 1750 ml in N2.
The test was carried out at ~1900°C for 1 to 6 hours.
また、比較のため、第３表中の比較例に示すように、焼
結体中のα’−８ｉ３Ｎ、の存在比率、あ°るいはα
Ｓ １ 、Ｎ４ 、β’ ８１３Ｎ４の結晶粒の
平均粒径が本第１発明の範囲をはずれるものも上記と同
様に製造した。For comparison, as shown in the comparative example in Table 3, the abundance ratio of α'-8i3N in the sintered body or α
Crystal grains of S 1 , N4, and β' 813N4 whose average grain sizes were outside the range of the first invention were also produced in the same manner as above.
得られた各焼結体について実施例１と同様にして４点曲
げ試験及び破壊靭性の測定を実施した。A four-point bending test and fracture toughness measurements were performed on each of the obtained sintered bodies in the same manner as in Example 1.
その結果を第３表に示す。The results are shown in Table 3.
第３表より明らかなように、比較例では、室温での強度
が最高で８０ｋｇ／ｍｍ２、ＫＩＣが最高で６゜６ＭＰ
ａｍ”であるのに対して、本実施例のものでは、室温で
の強度が８３ｋｇ／ｆｆ１ｍ２以上と高く、またＫＩＣ
も７ＭＰａｍ””以上と高いものである。As is clear from Table 3, in the comparative example, the maximum strength at room temperature was 80 kg/mm2, and the maximum KIC was 6°6MP.
am'', whereas the one in this example has a high strength of 83 kg/ff1m2 or more at room temperature, and the KIC
It is also high, at 7 MPam or more.
また、本実施例のものは、１２００℃、１３００℃の高
温での強度が比較例のものよりもｌＯ〜２０ＭＰａｍ”
”高く、高温での安定性に優れていることが分る。In addition, the strength of this example at high temperatures of 1200°C and 1300°C is 10 to 20 MPam higher than that of the comparative example.
``It can be seen that it has excellent stability at high temperatures.
次に、第３表の試料Ｎ（Ｌｉ２．１７．２０．２２、Ｉ
！、０．Ｎ、、、０．５≦ｙ≦３．０）の混合粉末、あ
るいは上記混合粉末に必要に応じて平均粒径し５μｍ以
下のＳｉ３Ｎ＜粉末（α比率９５％以上）、平均粒径０
．１μｍ以下のＹ２Ｏ３粉末、：たは平均粒径０．７μ
ｍ以下のＡｎＮ粉末の少な・とも１種を添加・混合した
粉末を成形し、ホップレス法によって第５表に示すよう
な構成相、糸晶粒を有するα’−８ｉａＮｔとβ’−８
ｉ３ｒとからなる焼結体を製造した。なおホットプレ２
は１６００〜１９００℃、圧力２００〜３００ト／ｃｍ
２．０．２５〜４．０時間の範囲で行った。Next, sample N (Li2.17.20.22, I
! ,0. 0.5≦y≦3.0), or Si3N<powder with an average particle size of 5 μm or less (α ratio 95% or more), an average particle size of 0 to the above mixed powder as necessary.
．． Y2O3 powder of 1 μm or less: or average particle size of 0.7 μm
α'-8iaNt and β'-8 having constituent phases and filament grains as shown in Table 5 are formed by molding the powder to which at least one type of AnN powder of m or less is added and mixed, and by the hopless method.
A sintered body consisting of i3r was manufactured. In addition, hot play 2
is 1600~1900℃, pressure 200~300t/cm
2. It was carried out in the range of 0.25 to 4.0 hours.
得られた焼結体について、実施例１と同様に点曲げ試験
および破壊靭性の測定を行った。そ【結果を第５表に示
す。The obtained sintered body was subjected to a point bending test and fracture toughness measurement in the same manner as in Example 1. [The results are shown in Table 5.
第５表から明らかなように、比較例では室温の強度が最
高９５ ｋｇ／ ｍｍ２、Ｋ Ｉｃ値が最高で６゜ＭＰ
ａｍ”であるのに対して、本実施例のもでは、室温での
強度がいずれも１１０ ｋｇ／ｍｍ２上であり、しかも
ＫＩＣ値７．１ ＭＰ ａｍ”以上ある。また、１３０
０°Ｃでの４点曲げ強度がｌ第
表
Ｃ７、Ｃ９、Ｃ１ｌの７種類の試料に対して実施例Ｉと
同様に高温酸化試験を行った。その結果を第４表に示す
。As is clear from Table 5, in the comparative example, the maximum strength at room temperature is 95 kg/mm2, and the maximum K Ic value is 6°MP.
am'', whereas in the present example, the strength at room temperature is all 110 kg/mm2 or higher, and the KIC value is 7.1 MP am'' or higher. Also, 130
A high-temperature oxidation test was conducted in the same manner as in Example I on seven types of samples having four-point bending strengths at 0° C. shown in Table C7, C9, and C11. The results are shown in Table 4.
第４表より明らかなように、本実施例では、比較例に比
して重量増加及び４点曲げ強度の低下が非常に少なく、
耐酸化性に優れていることが分る。As is clear from Table 4, in this example, the increase in weight and the decrease in 4-point bending strength were very small compared to the comparative example.
It can be seen that it has excellent oxidation resistance.
実施例３
平均粒径０．５μｍ以下の種々の組成のα”−８ｉｓｒ
ｔＬ粉末（Ｙｘ （Ｓ ｉ、 Ａｊ’）１゜（０，Ｎ
）１６．０．３≦Ｘ≦０．６）、平均粒径０バμｍ以下
の種々の組成のβ’−８ｉ３Ｎ４粉末（Ｓｉａ−ｙＡＯ
ｋｇ／ｍｍ２を超える例が多数あり、従来では達成し得
なかった高温での４点曲げ強度が１００ｋｇ／ｍｍ２以
上を本実施例では達成し得ることが分かる。Example 3 α''-8 isr of various compositions with an average particle size of 0.5 μm or less
tL powder (Yx (S i, Aj') 1° (0, N
)16.0.3≦X≦0.6), β'-8i3N4 powder (Sia-yAO
There are many examples in which the strength exceeds 100 kg/mm2, and it can be seen that the present example can achieve a four-point bending strength of 100 kg/mm2 or more at high temperatures, which could not be achieved conventionally.
実施例４
実施例３と同様な出発原料を用いて、これを成形し、常
圧焼結法により第６表に示すような構成相、結晶粒を有
するα’−８ｉ３Ｎ、とβ°−８１３Ｎ４ とからなる
焼結体を製造した。なお、常圧焼結は、Ｎ２中、１７５
０〜１９００°Ｃ，１〜６時間の条件で行った。Example 4 Using the same starting material as in Example 3, it was molded and subjected to pressureless sintering to produce α'-8i3N and β°-813N4 having constituent phases and crystal grains as shown in Table 6. A sintered body consisting of Note that pressureless sintering is performed in N2 at 175
The test was conducted at 0 to 1900°C for 1 to 6 hours.
また、比較のため、第６表中の比較例に示すように、焼
結体中のα’−８ｉ、Ｎ、の存在比率、あるいはα
Ｓ ｌ ３ Ｎ＋ 、β’−８ｉ３Ｎ、の結晶粒の平均
粒径か本第１発明の範囲をはずれるものも上記と同様に
製造した。For comparison, as shown in the comparative example in Table 6, the abundance ratio of α'-8i, N, or α
Crystal grains of S l 3 N+ and β'-8i3N whose average grain diameters were outside the range of the first invention were also produced in the same manner as above.
得られた各焼結体について実施例１と同様にして４点曲
げ試験及び破壊靭性の測定を実施した。A four-point bending test and fracture toughness measurements were performed on each of the obtained sintered bodies in the same manner as in Example 1.
その結果を第６表に示す。The results are shown in Table 6.
第６表より明らかなように、比較例では、室温での強度
が最高で７５ ｋｇ／ ｍｍ２、Ｋ ＋ｃが最高で６゜
６ＭＰａｍ”であるのに対して、本実施例のものでは、
室温での強度が８５ｋｇ／ｍｍ２以上と高く、またに、
。も７ＭＰａｍ“７以上と高いものである。As is clear from Table 6, in the comparative example, the maximum strength at room temperature is 75 kg/mm2, and the maximum K + c is 6°6 MPam, whereas in the present example,
It has high strength at room temperature of 85 kg/mm2 or more, and
. It is also high, at 7 MPam"7 or more.
また、本実施例のものは、１２００°Ｃ，１３０００Ｃ
の高温での強度が比較例のものよりも１０〜２０ ｋｇ
／ ｍｍ ’高く、高温での安定性に優れていること
が分る。In addition, in this example, 1200°C, 13000C
The strength at high temperature is 10 to 20 kg higher than that of the comparative example.
/ mm' and is found to have excellent stability at high temperatures.
実施例５
出発原料として平均粒径０．５μｍ以下のＹを固溶した
ａ’ Ｓ ｉ ３ Ｎ４粉末、平均粒径０．５μｍ
以下のβ”−８ｉ３Ｎ、粉末を用いて実施例１と同様な
条件でホットプレス法により、第７表に示すような構成
相、結晶粒を有するα’−３ｉ、Ｎ。Example 5 As a starting material, a' Si 3 N4 powder containing Y with an average particle size of 0.5 μm or less, an average particle size of 0.5 μm
α'-3i,N having the constituent phases and crystal grains shown in Table 7 was obtained by hot pressing the following β''-8i3N powder under the same conditions as in Example 1.
とβ’ ５１３Ｎ−とからなる焼結体を製造した。A sintered body consisting of and β' 513N- was produced.
また実施例１と同様にして４点曲げ強度、破壊靭性の測
定を実施した。その結果を第７表に示す。In addition, the four-point bending strength and fracture toughness were measured in the same manner as in Example 1. The results are shown in Table 7.
第７表から明らかなように、比較例では室温での強度が
最高で９３ｋｇ／ｍｍ２であるのに対して、本実施例の
ものでは、室温で強度が１０９ ｋｇ／ｍｍ２以上と高
く、またＫＩＣも７．１ＭＰａｍ”以上と高い。さらに
、本実施例のものは、１２００°Ｃ１■３００°Ｃでの
強度が比較例よりも非常に高く安定性に優れていること
が分かる。As is clear from Table 7, the strength at room temperature of the comparative example is 93 kg/mm2 at maximum, while the strength of this example is as high as 109 kg/mm2 or more at room temperature. Furthermore, it can be seen that the strength of this example is much higher than that of the comparative example at 1200°C and 300°C, indicating that it has excellent stability.
実施例６
実施例５と同様な出発原料を用いて、これを成形し、常
圧焼結法により第８表に示すような構成相、結晶粒を有
するα’−５ｉ３Ｎ＋とβ″ −８ｉ３Ｎ、とからなる
焼結体を製造した。なお、常圧焼結は、Ｎ２中、１７５
０〜１９００°Ｃ，１〜６時間の条件で行った。Example 6 Using the same starting material as in Example 5, it was molded and subjected to pressureless sintering to produce α′-5i3N+ and β″-8i3N, each having the constituent phases and crystal grains shown in Table 8. A sintered body consisting of
The test was conducted at 0 to 1900°C for 1 to 6 hours.
また、比較のため、第８表中の比較例に示すように、焼
結体中のα’ ８１３Ｎ＋の存在比率、あるいはα
Ｓ ｌ ａ Ｎ＜ 、β’−５ｉ３Ｎ１の結晶粒の
平均粒径が本第１発明の範囲をはずれるものも上記と同
様に製造した。For comparison, as shown in the comparative example in Table 8, the abundance ratio of α' 813N+ in the sintered body or α
S la N<, β'-5i3N1 crystal grains whose average grain size was outside the range of the first invention were also produced in the same manner as above.
得られた各焼結体について実施例１と同様にして４点曲
げ試験及び破壊靭性の測定を実施した。A four-point bending test and fracture toughness measurements were performed on each of the obtained sintered bodies in the same manner as in Example 1.
その結果を第８表に示す。The results are shown in Table 8.
第８表からも明らかなように、比較例では室温での強度
が最高で７５ｋｇ／ｍｍ２であるのに対して、本実施例
のものでは、室温で強度が８５ ｋｇ／ｍｍ２以上と高
く、またＫＩＣも７．０ＭＰａｍ”以上と高い。さらに
、本実施例のものは、１２００°Ｃ１１３００°Ｃでの
強度が比較例に比して高く、高温での安定性に優れてい
る。As is clear from Table 8, the comparative example has a maximum strength of 75 kg/mm2 at room temperature, while the material of this example has a high strength of 85 kg/mm2 or more at room temperature. The KIC is also high at 7.0 MPam'' or more.Furthermore, the strength of this example at 1200°C and 11300°C is higher than that of the comparative example, and it has excellent stability at high temperatures.
実施例７
出発原料として平均粒径０．５μｍ以下のＹを固溶した
α’−３ｉ３Ｎ＋粉末、平均粒径０．５μｍ以下のＳｉ
３Ｎ＋粉末（α率９５％以上）を用いてこれを成形し、
ホットプレス法により第９表に示すような構成相、結晶
粒を有するαｌ ３ｉ３Ｎ４とβ’−８ｉ、Ｎ、と
からなる焼結体を製造した。なおホットプレスは１６５
０〜１９００°Ｃ１圧力２００〜３００ｋｇ、 ０．５
〜１０時間の条件で行った。Example 7 α'-3i3N+ powder containing Y with an average particle size of 0.5 μm or less and Si with an average particle size of 0.5 μm or less as starting materials
Molding this using 3N+ powder (α rate of 95% or more),
A sintered body consisting of αl 3i3N4, β′-8i, and N having the constituent phases and crystal grains shown in Table 9 was produced by a hot pressing method. In addition, hot press is 165
0~1900°C1 pressure 200~300kg, 0.5
The test was carried out under conditions of ~10 hours.
また、比較のため、第９表中の比較例に示すように焼結
体中のα’−８ｉ、Ｎ、の存在比率、あるいはα ５
１ａｆ’Ｌ、β’−８ｉｘＮ＋の組成が本第２発明の範
囲をはずれるものも上記と同様にして製造した。In addition, for comparison, as shown in the comparative example in Table 9, the abundance ratio of α'-8i, N, or α 5
A sample whose composition of 1af'L and β'-8ixN+ was outside the scope of the second invention was also produced in the same manner as above.
得られた各焼結体について、実施例１と同様にして４点
曲げ試験及び破壊靭性の測定を実施した。A four-point bending test and a fracture toughness measurement were performed on each of the obtained sintered bodies in the same manner as in Example 1.
その結果を第９表に示す。なお、第９表中のＸ、ｙはそ
れぞれα Ｓ ｌ ３ Ｎ＋であるＹ、（Ｓｉ。The results are shown in Table 9. Note that X and y in Table 9 are Y and (Si), respectively, which are α S l 3 N+.
Ａｎ）、。（０，Ｎ） 、、のＸ、β’−８ｉ３Ｎ＋で
あるＳ １６−ｙ Ａ’（２０，Ｎｇ□のｙである。ま
た、ｙの値はＸ線回折ｙによって得られた回折図形から
格子定数を計算し、ｙ値に換算して求めた。Ｘの値は、
実施例１と同じ出発原料をホットプレスによって長時間
焼結し、はぼ系を平衡に達成せしめた後、急冷して得た
試料の中からαｌ ３ｉ３Ｎ４とβ’−３ｉ３Ｎ、
との混合、およびαＳｉ３Ｎ４のみからなる試料を選び
、Ｘ線回折法によってα’ ５ｔａＮｔの格子定数
を求め、出発原料中のＹの量をＸに換算して、α’ −
３ｉ３Ｎ４の格子定数とＸの関係を求めて、検量線を作
り、これに従ってＸの値を求めた（以降の表についても
同様である）。An),. (0, N), , is S 16-y A' (20, Ng□, which is The constant was calculated and converted to a y value.The value of X is
αl 3i3N4, β'-3i3N,
A sample consisting only of αSi3N4 was selected, the lattice constant of α' 5taNt was determined by X-ray diffraction method, the amount of Y in the starting material was converted to X, and α' -
The relationship between the lattice constant of 3i3N4 and X was determined, a calibration curve was created, and the value of X was determined according to this (the same applies to the following tables).
また、第９表中のα ５１３Ｎｌの存在比率は、焼結
体のＸ線回折ピークの強度比より求めた値であり、α’
５１３Ｎ４とβ’ ５１３Ｎ＜との存在比率
の合計を１とした場合のα Ｓ １３Ｎ４の存在比率
である。Furthermore, the abundance ratio of α 513Nl in Table 9 is a value determined from the intensity ratio of the X-ray diffraction peaks of the sintered body, and α'
This is the abundance ratio of α S 13N4 when the sum of the abundance ratios of 513N4 and β'513N< is 1.
第９表より明らかなように、比較例では、室温での強度
が最高で９０ｋｇ／ｍｍ２、ＫＩｏ値が最高で６．６Ｍ
Ｐａｍ”であるのに対して、本実施例のものでは、室温
での強度がいずれも１００ｋｇ／ｍｍ２以上であり、し
かもＫｔｃ値も７ＭＰａｍ”を越えている。しかも、室
温から１３００°Ｃでの強度の低下は、比較例では２５
〜２９ｋｇ／ｍｍ２であるのに対して、本実施例では、
９〜１８ ｋｇ／ ｆｆ１ｌｌ＋２と非常に小さい。ま
た、本実施例中には１３００°Ｃの高温での強度が１０
０ｋｇ／ｍｍ２を越えるものが多数あり、従来では達成
し得なかった高温での４点曲げ強度が１００ｋｇ／ｍｍ
２を本実施例では達成し得る。As is clear from Table 9, in the comparative example, the maximum strength at room temperature was 90 kg/mm2, and the maximum KIo value was 6.6 M.
Pam'', whereas in this example, the strength at room temperature is all 100 kg/mm2 or more, and the Ktc value also exceeds 7 MPam''. Moreover, the decrease in strength from room temperature to 1300°C was 25% in the comparative example.
~29kg/mm2, whereas in this example,
Very small at 9-18 kg/ff1ll+2. In addition, in this example, the strength at a high temperature of 1300°C was 10
There are many products that exceed 0 kg/mm2, and the four-point bending strength at high temperatures, which was previously unachievable, is 100 kg/mm.
2 can be achieved in this embodiment.
実施例８
実施例Ｉと同様な出発原料を用いて、これを成形し、常
圧焼結法により第１Ｏ表に示すような構成相、結晶粒を
有するα’−８ｉａＮ＋とβ’５ｉ３Ｎ１とからなる焼
結体を製造した。なお、常圧焼結は、Ｎ２中、１７５０
〜１９００°Ｃ，，１〜６時間の条件で行った。Example 8 Using the same starting material as in Example I, it was molded and pressureless sintered to form α'-8iaN+ and β'5i3N1 having constituent phases and crystal grains as shown in Table 1O. A sintered body was manufactured. Note that pressureless sintering is performed at 1750 ml in N2.
The test was carried out at ~1900°C for 1 to 6 hours.
また、比較のため、第１０表中の比較例に示すように、
焼結体中のα’ −８ｉ３Ｎ＋の存在比率、あるいは
α Ｓ １３ Ｎ＋ 、β’ ３１３Ｎ４の組成が
本第２発明の範囲をはずれるものも上記と同様に製造し
た。In addition, for comparison, as shown in the comparative example in Table 10,
A sintered body in which the abundance ratio of α'-8i3N+ or the composition of α S 13 N+ and β' 313N4 was outside the scope of the second invention was also produced in the same manner as above.
得られた各焼結体について実施例１と同様にして４点曲
げ試験及び破壊靭性の測定を実施した。A four-point bending test and fracture toughness measurements were performed on each of the obtained sintered bodies in the same manner as in Example 1.
その結果を第１０表に示す。The results are shown in Table 10.
第１Ｏ表より明らかなように、比較例では、室温での強
度が最高で７５ｋｇ、／ｍｍ２、Ｋ＋ｃが最高で６．６
ＭＰａｍ”であるのに対して、本実施例のものでは、室
温での強度が８５ｋｇ／ｍｍ２以上と高く、またＫＩＣ
も７ＭＰａｍ”以上と高いものである。また、本実施例
のものは、■２００°ＣＸ１３００°Ｃの高温での強度
が比較例のものよりもかなり高く、高温での安定性に優
れていることが分る。As is clear from Table 1O, in the comparative example, the maximum strength at room temperature is 75 kg, /mm2, and the maximum K+c is 6.6.
MPam'', whereas the one in this example has a high strength of 85 kg/mm2 or more at room temperature, and
In addition, the strength of this example at high temperatures of 200°C x 1300°C is significantly higher than that of the comparative example, and it has excellent stability at high temperatures. I understand.
第１図および第２図は、実施例１における焼結体のＸ線
回折チャートである。1 and 2 are X-ray diffraction charts of the sintered body in Example 1.
Claims (3)
珪素質焼結体であって、Ｘ線回折によるピーク強度比に
おける存在比率は、α’−窒化珪素０．０５〜０．５０
、β’−窒化珪素０．９５〜０．５０であり、α’−窒
化珪素は、結晶粒の平均粒径が２．０μｍ以下であり、
β’−窒化珪素は、結晶粒の平均粒径が長径方向におい
て５．０μｍ以下、短径方向において１．０μｍ以下で
あることを特徴とする窒化珪素質焼結体。(1) A silicon nitride sintered body consisting of α'-silicon nitride and β'-silicon nitride, the abundance ratio of α'-silicon nitride in the peak intensity ratio determined by X-ray diffraction is 0.05 to 0. 50
, β'-silicon nitride is 0.95 to 0.50, and α'-silicon nitride has an average grain size of 2.0 μm or less,
β'-silicon nitride is a silicon nitride sintered body characterized in that the average grain size of crystal grains is 5.0 μm or less in the major axis direction and 1.0 μm or less in the minor axis direction.
、α’−窒化珪素は、結晶粒の平均粒径が１．０μｍ以
下であり、β’−窒化珪素は、結晶粒の平均粒径が長径
方向において２．５μｍ以下、短径方向において０．５
μｍ以下であることを特徴とする窒化珪素質焼結体。(2) In the silicon nitride sintered body according to claim (1), the α'-silicon nitride has a crystal grain with an average grain size of 1.0 μm or less, and the β'-silicon nitride has a crystal grain of 1.0 μm or less. The average particle diameter is 2.5 μm or less in the major axis direction and 0.5 μm or less in the minor axis direction.
A silicon nitride sintered body characterized by having a particle size of μm or less.
珪素質焼結体であって、Ｘ線回折によるピーク強度比に
おける存在比率は、α’−窒化珪素０．０５〜０．５０
、β’−窒化珪素０．９５〜０．５０であり、α’−窒
化珪素は、Ｍ＿ｘ（Ｓｉ，Ａｌ）＿１＿２（Ｏ，Ｎ）＿
１＿６（Ｍは、リチウム、マグネシウム、カルシウム、
イットリウムのうちの少なくとも１種である。 ０＜ｘ≦０．３）で表されるものであり、β’−窒化珪
素は、Ｓｉ＿６＿−＿ｙＡｌ＿ｙＯ＿ｙＮ＿８＿−＿ｙ
（０＜ｙ≦１．０）で表されるものであることを特徴と
する窒化珪素質焼結体。(3) A silicon nitride sintered body consisting of α'-silicon nitride and β'-silicon nitride, in which the abundance ratio in the peak intensity ratio determined by X-ray diffraction is 0.05 to 0. 50
, β'-silicon nitride is 0.95 to 0.50, and α'-silicon nitride is M_x(Si,Al)_1_2(O,N)_
1_6 (M is lithium, magnesium, calcium,
At least one type of yttrium. 0<x≦0.3), and β'-silicon nitride is Si_6_-_yAl_yO_yN_8_-_y
A silicon nitride sintered body characterized by being represented by (0<y≦1.0).
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1087807A JP2736386B2 (en) | 1988-04-07 | 1989-04-06 | Silicon nitride sintered body |
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP8672188 | 1988-04-07 | ||
| JP63-86721 | 1988-04-07 | ||
| JP1087807A JP2736386B2 (en) | 1988-04-07 | 1989-04-06 | Silicon nitride sintered body |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0244066A true JPH0244066A (en) | 1990-02-14 |
| JP2736386B2 JP2736386B2 (en) | 1998-04-02 |
Family
ID=26427811
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP1087807A Expired - Fee Related JP2736386B2 (en) | 1988-04-07 | 1989-04-06 | Silicon nitride sintered body |
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| Country | Link |
|---|---|
| JP (1) | JP2736386B2 (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH04125950A (en) * | 1990-09-18 | 1992-04-27 | Ngk Insulators Ltd | Ceramic package |
| US5275772A (en) * | 1991-05-22 | 1994-01-04 | Sumitomo Electric Industries, Ltd. | Silicon nitride sintered body and process for producing the same |
| US5275986A (en) * | 1991-11-25 | 1994-01-04 | Sumitomo Electric Industries, Ltd. | Silicon nitride sintered body |
| WO2014092021A1 (en) * | 2012-12-14 | 2014-06-19 | 株式会社東芝 | Silicon nitride sintered body and sliding member using same |
| JP2020180346A (en) * | 2019-04-25 | 2020-11-05 | 日本製鉄株式会社 | Method for manufacturing ceramic laminate, and ceramic laminate manufactured thereby |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS59199581A (en) * | 1983-04-26 | 1984-11-12 | 三菱マテリアル株式会社 | Abrasion resistant sialon base ceramics |
-
1989
- 1989-04-06 JP JP1087807A patent/JP2736386B2/en not_active Expired - Fee Related
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS59199581A (en) * | 1983-04-26 | 1984-11-12 | 三菱マテリアル株式会社 | Abrasion resistant sialon base ceramics |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH04125950A (en) * | 1990-09-18 | 1992-04-27 | Ngk Insulators Ltd | Ceramic package |
| US5275772A (en) * | 1991-05-22 | 1994-01-04 | Sumitomo Electric Industries, Ltd. | Silicon nitride sintered body and process for producing the same |
| US5275986A (en) * | 1991-11-25 | 1994-01-04 | Sumitomo Electric Industries, Ltd. | Silicon nitride sintered body |
| WO2014092021A1 (en) * | 2012-12-14 | 2014-06-19 | 株式会社東芝 | Silicon nitride sintered body and sliding member using same |
| JPWO2014092021A1 (en) * | 2012-12-14 | 2017-01-12 | 株式会社東芝 | Silicon nitride sintered body and sliding member using the same |
| JP2020180346A (en) * | 2019-04-25 | 2020-11-05 | 日本製鉄株式会社 | Method for manufacturing ceramic laminate, and ceramic laminate manufactured thereby |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2736386B2 (en) | 1998-04-02 |
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