JPS63260869A - Silicon carbide whisker reinforced composite material - Google Patents
Silicon carbide whisker reinforced composite materialInfo
- Publication number
- JPS63260869A JPS63260869A JP62156633A JP15663387A JPS63260869A JP S63260869 A JPS63260869 A JP S63260869A JP 62156633 A JP62156633 A JP 62156633A JP 15663387 A JP15663387 A JP 15663387A JP S63260869 A JPS63260869 A JP S63260869A
- Authority
- JP
- Japan
- Prior art keywords
- sialon
- weight
- sintered body
- silicon carbide
- composite 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
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 title claims description 19
- 229910010271 silicon carbide Inorganic materials 0.000 title claims description 16
- 239000011208 reinforced composite material Substances 0.000 title claims description 5
- 239000000919 ceramic Substances 0.000 claims description 16
- 239000000203 mixture Substances 0.000 claims description 16
- 239000011521 glass Substances 0.000 claims description 12
- 239000002131 composite material Substances 0.000 claims description 10
- 229910052757 nitrogen Inorganic materials 0.000 claims description 9
- 229910052710 silicon Inorganic materials 0.000 claims description 9
- 229910052760 oxygen Inorganic materials 0.000 claims description 7
- 229910052761 rare earth metal Inorganic materials 0.000 claims description 7
- 239000012535 impurity Substances 0.000 claims description 6
- 229910052782 aluminium Inorganic materials 0.000 claims description 5
- 229910052727 yttrium Inorganic materials 0.000 claims description 4
- 150000002910 rare earth metals Chemical class 0.000 claims description 3
- 229910052726 zirconium Inorganic materials 0.000 claims description 3
- 229910052791 calcium Inorganic materials 0.000 claims description 2
- 229910052749 magnesium Inorganic materials 0.000 claims description 2
- 229910052744 lithium Inorganic materials 0.000 claims 1
- 238000005245 sintering Methods 0.000 description 20
- 239000000843 powder Substances 0.000 description 15
- 239000000463 material Substances 0.000 description 10
- 150000001875 compounds Chemical class 0.000 description 8
- 229910052581 Si3N4 Inorganic materials 0.000 description 7
- 239000002245 particle Substances 0.000 description 7
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 7
- 239000007789 gas Substances 0.000 description 6
- 238000000034 method Methods 0.000 description 5
- 238000002441 X-ray diffraction Methods 0.000 description 4
- 239000006104 solid solution Substances 0.000 description 4
- RKTYLMNFRDHKIL-UHFFFAOYSA-N copper;5,10,15,20-tetraphenylporphyrin-22,24-diide Chemical compound [Cu+2].C1=CC(C(=C2C=CC([N-]2)=C(C=2C=CC=CC=2)C=2C=CC(N=2)=C(C=2C=CC=CC=2)C2=CC=C3[N-]2)C=2C=CC=CC=2)=NC1=C3C1=CC=CC=C1 RKTYLMNFRDHKIL-UHFFFAOYSA-N 0.000 description 3
- 238000005260 corrosion Methods 0.000 description 3
- 230000007797 corrosion Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000007496 glass forming Methods 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 229910001873 dinitrogen Inorganic materials 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229910001018 Cast iron Inorganic materials 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 235000008375 Decussocarpus nagi Nutrition 0.000 description 1
- 244000309456 Decussocarpus nagi Species 0.000 description 1
- 229910003564 SiAlON Inorganic materials 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000005539 carbonized material Substances 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 229910010293 ceramic material Inorganic materials 0.000 description 1
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 description 1
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 239000013022 formulation composition Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 238000007731 hot pressing Methods 0.000 description 1
- 229910000816 inconels 718 Inorganic materials 0.000 description 1
- 238000007373 indentation Methods 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 238000011002 quantification Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 239000012779 reinforcing material Substances 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
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）
本発明は炭化珪素ウィスカーを用いて強化した窒化珪素
系複合材料に関し、特に高ニッケル、鋳鉄、銅、アルミ
ニウム、チタン等の難切削材料についても高速切削をな
し得る切削工具材料又はセラミックパルプ等の自動車エ
ンジン部材及びその他の耐摩耗性、耐食性、耐熱性部材
等に広く有用な複合材料に関するものである。Detailed Description of the Invention (Industrial Field of Application) The present invention relates to silicon nitride-based composite materials reinforced using silicon carbide whiskers, and particularly to difficult-to-cut materials such as high nickel, cast iron, copper, aluminum, and titanium. The present invention relates to cutting tool materials capable of high-speed cutting or composite materials such as ceramic pulp that are widely useful for automobile engine parts and other wear-resistant, corrosion-resistant, and heat-resistant parts.
（従来の技術）
窒化珪素を主成分とする窒化珪素（ｓｌｓＮａ）系セラ
ミックスは、強度、耐酸化性、耐摩耗性、耐熱衝撃性、
耐食性等の特性に優れているので、工ンジン部品等の構
造材料や切削工具材料として実用化が始まっている。(Prior art) Silicon nitride (slsNa)-based ceramics whose main component is silicon nitride have excellent strength, oxidation resistance, abrasion resistance, thermal shock resistance,
Because it has excellent properties such as corrosion resistance, it has begun to be put to practical use as a structural material for engine parts and as a material for cutting tools.
しかしこのような優れた特徴を持っているにもかかわら
ず、金属と比較すると品質安定性や均質性に乏しく、信
頼性の向上や高特性という視点から、窒化珪素セラミッ
クスに於いても一層の高靭性化が望まれている。その為
特公昭５８−５１９１１、特公昭６０−５５５１６、特
公昭６０−５５４６９、特開昭５９−１０２８６２、特
開昭６０−２００８．５５、特開昭６０−２４６２６８
、特開昭１−２９１４６３等のように炭化珪素（ＳｉＣ
）ウィスカーを強化材として用い、複合化する試みが行
われているが、いまだ十分に実用化し得るまでには至っ
ておらず、なお一層の高靭性化が期待されている。However, despite having these excellent characteristics, compared to metals, they lack quality stability and homogeneity, and from the perspective of improving reliability and high properties, even higher quality silicon nitride ceramics are being developed. Toughness is desired. Therefore, JP 58-51911, JP 60-55516, JP 60-55469, JP 59-102862, JP 60-2008.55, JP 60-246268
, JP-A No. 1-291463, etc., silicon carbide (SiC)
) Attempts have been made to make composites using whiskers as reinforcing materials, but they have not yet been fully put into practical use, and further improvements in toughness are expected.
又、さらにＳｉＣウィスカーの異方性によって、難焼結
性を示す窒化珪素系複合材料は、加圧焼結が可能でも常
圧焼結およびガス圧焼結（１００気圧以下）によっては
得ることが出来なかった。Furthermore, due to the anisotropy of SiC whiskers, silicon nitride-based composite materials that exhibit difficult sintering properties cannot be obtained by normal pressure sintering or gas pressure sintering (below 100 atmospheres) even if pressure sintering is possible. I could not do it.
（発明が解決しようとする問題点）
本発明は上記の如き実情に鑑み、窒化珪素系セラミック
スの中でも特に耐酸化性や金属との反応性に於いて安定
なサイアロン基セラミック焼結体にＳｉＣウィスカーと
Ｚｒ 酸化物およびまたはＺｒ酸窒化物を複合化させる
ことによって、従来得ることが出来なかった靭性と信頼
性に優れた特性を有し、又常圧焼結およびガス圧焼結が
可能な炭化珪素ウィスカー強化複合材料を目的とするも
のである。(Problems to be Solved by the Invention) In view of the above-mentioned circumstances, the present invention incorporates SiC whiskers into a sialon-based ceramic sintered body, which is particularly stable among silicon nitride ceramics in terms of oxidation resistance and reactivity with metals. By combining Zr oxide and/or Zr oxynitride, it has excellent toughness and reliability properties that could not be obtained conventionally, and it also has a carbonized material that can be sintered under normal pressure and gas pressure. It is aimed at silicon whisker reinforced composite materials.
（問題点を解決するための手段）
本発明は上記の目的を達成するために種々検討の結果な
されたもので、Ｚｒ 酸化物およびまたはＺｒ酸窒化物
が靭性を改善しまた常圧焼結およびガス圧焼結を可能に
し得るという知見と、サイアロン基セラミックとしであ
る特定の組成式のものが好ましいこと、及び焼結助剤等
の構成するガラス相に関する知見から生み出されたもの
である。(Means for Solving the Problems) The present invention has been made as a result of various studies to achieve the above object. This was created based on the knowledge that gas pressure sintering is possible, the preference for a certain compositional formula as a sialon-based ceramic, and the knowledge regarding the glass phase of the sintering aid.
本発明の概要を述べれば以下のとおりである。The outline of the present invention is as follows.
量チ、残部サイアロン基セラミックを主成分とするもの
からなり、前記サイアロン基セラミックは組成式Ｓｉ、
−ｇｌＡ１ｇ１０２Ｎ、 ＋ｇ （但しＯ（Ｚ≦１
）で表わされるβ−サイアロンもしくは該β−サイアロ
ンと組成式Ｍｘ（Ｓｉ、Ａ１）、、 （ＯｗＮ）ｔｓ
（但しＭはＬｉ 。The remaining portion consists of a sialon-based ceramic as a main component, and the sialon-based ceramic has a composition formula of Si,
-glA1g102N, +g (However, O(Z≦1
) or the β-sialon and the composition formula Mx (Si, A1), (OwN)ts
(However, M is Li.
Ｃａ 、 Ｊ 、 Ｙおよび稀土類元素から選ばれた単
独または混合物からな？）、０＜ｘ≦２）で表わされる
α−サイアロン（結晶構造的にはα−８ｉ、！ｌ、のＳ
１位置にＡ１を、Ｎ位置に０が置換され固溶されると同
時に格子間に他の元素が浸入固溶されている。Is it selected from Ca, J, Y and rare earth elements alone or in a mixture? ), 0<x≦2)
A1 is substituted at the 1 position and 0 is substituted at the N position to form a solid solution, and at the same time, other elements enter the interstitial space and form a solid solution.
コノ浸入固溶元素としてＬｉ 、 Ｈａ 、 Ｃａ 、
Ｍｇ 、 Ｙ及び稀土類元素が挙げられる。）から成
るα、β複合サイアロンで構成される。又、このサイア
ロン基セラミックには１〜２５重量−のＺｒ 、 Ｓｉ
。Solid solution elements such as Li, Ha, Ca,
Mention may be made of Mg, Y and rare earth elements. ) is composed of α and β composite sialons. In addition, this sialon-based ceramic contains 1 to 25% by weight of Zr, Si
.
Ａｌ 、 Ｏ、Ｎ と不可避不純物又はそれにＹ 、
Ｍｇ。Al, O, N and inevitable impurities or Y,
Mg.
Ｃａ及び希土類金属の１種以上から成るガラス相な含ん
でいる。It contains a glass phase consisting of one or more of Ca and rare earth metals.
本発明で用いられるＳｉＣウィスカーはそれ自体常温か
ら高温まで硬度や強度が高く、焼結後もウィスカーの形
状のまま残存し、組織内で分散していることによってセ
ラミックスの高温強度を向上し、破壊靭性な大きクシ、
かつ硬くするものであるＯ
ここに用いられるＳｉＣウィスカーとしては平均直径０
．２〜５μ贋、平均長さ５〜１００μｍ、アスペクト比
５−５００のもので、Ａｌ１ Ｃａｅ Ｍｇ ＊Ｎｉ
、 Ｆｅ 、 Ｍｎ 、 Ｃｏ 、 Ｃｒ等のカチオン
不純物や、５１０８含有量が１．０重量−以下のくびれ
や枝分れ及び面欠陥等が少ないひげ状結晶を用いること
が高靭性の緻密体を得る上で好ましい。The SiC whiskers used in the present invention have high hardness and strength from room temperature to high temperatures, remain in the whisker shape even after sintering, and are dispersed within the structure, improving the high-temperature strength of ceramics and causing fracture. Tough big comb,
The SiC whiskers used here have an average diameter of 0.
．． 2-5 μm fake, average length 5-100 μm, aspect ratio 5-500, Al1 Cae Mg *Ni
, Fe, Mn, Co, Cr, and other cationic impurities, and whisker-like crystals with a 5108 content of 1.0 wt. preferred above.
このＳｉＣウィスカーを５〜４５重量％とする理由は、
５重量慢よシ少ない場合にはセラミック材料における靭
性の向上が不十分で、逆に４５重量％を超える場合はウ
ィスカーの異方性によって均一分散性や焼結性が低下す
るので上記５〜４５重量−を好ましい範囲とし、更に好
ましくは１０〜５０重量％、最も好ましくは１５〜２５
重量％の範囲とするものである。The reason why this SiC whisker is set at 5 to 45% by weight is as follows.
If the weight is less than 5%, the toughness of the ceramic material will not be improved sufficiently, and if it exceeds 45% by weight, the uniform dispersibility and sinterability will decrease due to the anisotropy of the whiskers. The weight is in a preferred range, more preferably 10 to 50% by weight, most preferably 15 to 25% by weight.
% by weight.
Ｚｒ酸化物およびまたはＺｒ 酸窒化物の作用は常圧焼
結及びガス圧焼結を可能とする一方、焼結時に一旦ガラ
ス相：：固溶したｚｒがガラス相とＳｉＣウィスカーの
界面に於て両者の濡れ性を改善し、両者のよシ強固な結
合を可能にすることによって、ＳｉＣウィスカーの持つ
本来の特性が十分に発揮できるように作用して靭性な向
上することにある。The action of Zr oxide and/or Zr oxynitride enables normal pressure sintering and gas pressure sintering, while at the time of sintering, Zr, which is once dissolved in the glass phase, forms a solid solution at the interface between the glass phase and the SiC whiskers. By improving the wettability of the two and enabling a stronger bond between the two, the original characteristics of the SiC whiskers can be fully exhibited and the toughness can be improved.
ここでＺｒ 酸化物やＺｒ 酸窒化物は特に限定されな
いが、例えばＺｒＯ！（単斜晶、正方晶、立方晶又はそ
れらの共存体）やＡＳ’ｌ’Ｍカード凪２０−６８４の
ＺｒＯにＸ線回折の結果がかなりよく一致するようなＺ
ｒ 酸化物またはＺｒ 酸窒化物が適用される。Here, Zr oxide and Zr oxynitride are not particularly limited, but for example, ZrO! (monoclinic, tetragonal, cubic, or coexistence thereof) or ZrO whose X-ray diffraction results match fairly well with ZrO of AS'l'M card Nagi 20-684.
r oxide or Zr oxynitride is applied.
またガラス相に固溶したＺｒ は焼結後に一部がガラス
相中に残るものの、大半はその時の配合組成（：よって
とシ得る結晶相で、ガラス相より再析出し、前記のＺｒ
酸化物およびまたはＺｒ酸窒化物として焼結体中に存在
する。In addition, although some of the Zr dissolved in the glass phase remains in the glass phase after sintering, most of the Zr remains in the glass phase after sintering, but most of the Zr remains in the blended composition at that time (i.e., the resulting crystalline phase is reprecipitated from the glass phase, and the aforementioned Zr
It is present in the sintered body as an oxide and/or Zr oxynitride.
従って例えば焼結体中にＺｒＯ，として存在する場合で
も、配合組成によって単斜晶、正方晶、立方晶又はそれ
らの共存体として存在することが可能であり、又その結
晶系に違いがあってもすべて焼結時におけるＺｒ の作
用効果が同じであるので、・′同様に高強度、高靭性の
焼結体となシ得る。Therefore, for example, even if it exists as ZrO in a sintered body, it can exist as monoclinic, tetragonal, cubic, or a coexistence of these depending on the composition, and there are differences in the crystal system. Since the effect of Zr during sintering is the same in all cases, a sintered body with high strength and high toughness can be obtained in the same manner as in case .
７、ｒ 酸化物およびまたはＺｒ酸窒化物をＺｒ換算
で６〜２０重−ａ ％とする理由は、３重ｆｆｌ慢未満
では靭性の改善効果が十分でなく、又２０重量％を越え
ると焼結体の硬度や熱伝導率や靭性や耐酸化性が低下し
好ましくないからである。7. The reason why the content of r oxide and/or Zr oxynitride is 6 to 20 wt-a% in terms of Zr is that if it is less than 3 times thick, the toughness improvement effect is not sufficient, and if it exceeds 20 wt%, sintering will occur. This is because the hardness, thermal conductivity, toughness, and oxidation resistance of the compact decrease, which is undesirable.
サイアロン基セラミックはＳｉ、 Ｎ４． Ａ１．０．
及びＡＩＮのセラミックスの固溶体であるが、本発明で
は組成式ｓｔ、 −２ＡｌｚＯｚｌｉ、−ｓｇ（但し０
（ｚ≦１）で表わされるβ−サイアロンと、その格子
中に金属が固溶した組成式Ｍｘ（Ｓｉ＋Ａｌ）ｔ＊ （
０，Ｎ）ｓｓ （但しＱ（Ｘ≦２）で表わされるα−サ
イアロンとによって構成される。The sialon-based ceramic is Si, N4. A1.0.
and AIN, but in the present invention, the composition formula st, -2AlzOzli, -sg (however, 0
β-sialon expressed as (z≦1) and the compositional formula Mx (Si+Al)t* (
0, N)ss (where Q (X≦2)).
一般に前者のβサイアロンは靭性は高いが硬度は低く、
後者のαサイアロンは比較的靭性は低いが硬度は高い特
徴がある。In general, the former β-sialon has high toughness but low hardness.
The latter α-sialon is characterized by relatively low toughness but high hardness.
本発明では前者のβ−サイアロンを主体とするかまたは
、か＼るβ−サイアロンと後者のα−サイアロンとを複
合させたものであシ、α−サイアロンとβ−サイアロン
とを複合する場合の比率は特に限定するものではないが
、高硬度高靭性材料を必要とするときはα−サイアロン
の比率は全サイアロン量に対して１０〜３０％の範囲が
望ましいＯ
本発明で特定されたβ−サイアロンの組成式の２値をＱ
（Ｚ≦１とする理由は、ｚ〉１の場合に機械的強度や
靭性が低下するため、各種の高温構造部材や切削工具材
料として必要な機械的特性を満足することができなくな
るためである。In the present invention, the former β-sialon is mainly used, or the latter β-sialon is combined with the latter α-sialon. Although the ratio is not particularly limited, when a high hardness and high toughness material is required, the ratio of α-sialon is preferably in the range of 10 to 30% with respect to the total amount of sialon. The two values of the composition formula of Sialon are Q
(The reason for setting Z≦1 is that when z>1, the mechanical strength and toughness decrease, making it impossible to satisfy the mechanical properties required for various high-temperature structural members and cutting tool materials. .
又、α−サイアロンの組成式のＸ値を０く工≦２とする
理由紘、これが通常得られるα−サイアロンであるため
である。Further, the reason why the X value in the compositional formula of α-sialon is set to 0≦2 is that this is α-sialon that is normally obtained.
次に前記サイアロン基セラミックに含まれる１〜２５重
量％の訃、 Ｓｉ 、 Ａｌ 、 Ｏ、Ｎ と不可避
不純物又はそれにＹｅ Ｍｇ ｅ Ｃａ及び希土類金属
の１種以上を含むガラス相は、これが１重量−よシ少な
い場合はサイアロンの焼結が十分達成できないため、所
望の密度の焼結体を得ることができず、又、２５！！量
チより多い場合は、靭性や高温強度の劣化を来すため、
高温材料や切削工具材料等には好ましくないからである
。Next, the glass phase containing 1 to 25% by weight of Si, Al, O, N and unavoidable impurities or one or more of Ye Mg e Ca and rare earth metals contained in the sialon-based ceramic is 1 wt. If the density is too low, sufficient sintering of Sialon cannot be achieved, and a sintered body with the desired density cannot be obtained. ! If the amount is more than 1, the toughness and high-temperature strength will deteriorate.
This is because it is not preferable for high temperature materials, cutting tool materials, etc.
又、本発明の焼結体は出発原料として用いるＳｉ、Ｎ４
粉末の純度や配合組成の比率によって、Ｓｉ、 Ｎ！Ｏ
、Ｓｉ、 ＯＮ、 、 Ｙ、 ０．・Ｓ’＊ ”ａ ＊
５Ｙ１０ｓ・５Ａｌ、０． 。Moreover, the sintered body of the present invention is made of Si, N4 used as starting materials.
Depending on the purity of the powder and the ratio of the composition, Si, N! O
, Si, ON, , Y, 0.・S'* ”a *
5Y10s・5Al, 0. .
１０Ｙ、 Ｏ，−９ＳｉＯ，−８ｉ、 Ｎ、 ｔ ４Ｙ
、 ０．−８ｉｎ、 ・Ｓｉ、 Ｎ、 、 ＹＳｉＯ
，Ｎ。10Y, O, -9SiO, -8i, N, t 4Y
, 0. -8in, ・Si, N, , YSiO
,N.
Ｍｇ、 ５ｉｎ４． Ｍｇ５ｉＮ、等の化合物が微量に
生成し、焼結体中に存在する場合があるが、特に特性に
悪い影響を及ぼさない範囲で存在してもさしつかえない
。なお又、上記のようなガラス生成化合物の添加は、特
に常圧焼結法やガス圧焼結法を採用する際に有効である
。Mg, 5in4. A small amount of compounds such as Mg5iN may be generated and present in the sintered body, but there is no problem with their presence within a range that does not particularly adversely affect the properties. Furthermore, the addition of the glass-forming compound as described above is particularly effective when employing an atmospheric pressure sintering method or a gas pressure sintering method.
以下本発明の実施例について説明する。 Examples of the present invention will be described below.
実施例１：
α率９０％で平均粒径０．６μｍのＳｉ、Ｎ、 粉末
に平均粒径１μ贋のα−Ａ１． Ｏ，粉末とＳｉＣウィ
スカー（ＡＲＣＯケミカル社製ＳＣ−９）及び平均粒径
０．６μｍの単斜晶ＺｒＯ！を第１表に示すような割合
に配合し、エタノール中で４時間均一に分散混合した、
後、乾燥し、造粒して素地粉末を得た。Example 1: Si and N powders with an α rate of 90% and an average particle size of 0.6 μm were mixed with a counterfeit α-A1 powder with an average particle size of 1 μm. O, powder, SiC whiskers (SC-9 manufactured by ARCO Chemical), and monoclinic ZrO with an average particle size of 0.6 μm! were mixed in the proportions shown in Table 1 and uniformly dispersed and mixed in ethanol for 4 hours.
Thereafter, it was dried and granulated to obtain a base powder.
次にこの素地粉末を黒鉛型中で表中に示すような焼結温
度で各６０分間２ａｏｋｇ／ｅｘ” の圧力でホット
プレスし緻密に焼結した焼結体を得た。Next, this base powder was hot pressed in a graphite mold at the sintering temperature shown in the table for 60 minutes at a pressure of 2 aokg/ex" to obtain a densely sintered body.
得られた焼結体は４Ｘ３Ｘ４０ｍの寸法に研摩加工した
後、ＪＩＳ−Ｒ１６０１によシ抗折強度、又荷重３０＃
でビッカース硬度及びインデンテインヨンマイクロフジ
クテヤー法によシ破壊靭性値を測定した。焼結体組成の
うちＺｒ％とｓｉｃ ウィスカーはＸ線回折や化学分
析やカーボン定量を行うことによシ、殆んど配合組成の
ままであることを確認した。The obtained sintered body was polished to a size of 4 x 3 x 40 m, and then tested for flexural strength and load of 30# according to JIS-R1601.
The Vickers hardness and fracture toughness were measured by the indentation microfujikteyer method. It was confirmed through X-ray diffraction, chemical analysis, and carbon quantification that Zr% and SIC whiskers in the sintered body composition remained almost the same.
又β−サイアロンの２値はＸ線回折によりβ−サイアロ
ンの格子定数から求めた。得られた結果は第１表に示す
とおシである。Further, the binary values of β-sialon were determined from the lattice constant of β-sialon by X-ray diffraction. The results obtained are shown in Table 1.
なお、同表には得られた焼結体を５ＮＧＮ４５２のチッ
プ形状（−研摩加工して切削性能を評価した結果を併記
した。The same table also shows the results of evaluating the cutting performance of the obtained sintered body by polishing it into a 5NGN452 chip shape.
切削テストは下記条件に於いて行い、被剛材ブロックの
２００Ｘ５０ｍの面を長手方向にフライス切削し、刃先
が欠損するまでの衝撃回数を測定結果１０点の平均値で
求めた。The cutting test was conducted under the following conditions, where a 200 x 50 m surface of a rigid block was milled in the longitudinal direction, and the number of impacts until the cutting edge broke was determined by the average value of the 10 measurement results.
切削条件
被削材 インコネル７１８
切削速度 ２００ ｒｓ ／ ｍｉｎ送 ＃）
０．２ ｇｗ ／ ｔＱｏｔｈ切シ込み １．５Ｍ
これらの結果から本発明範囲内でＳｉＣウィスカーとＺ
ｒＯ，を含有させたＱ ＜ｚ≦１ のβ−サイアロン基
複合焼結体は靭性に優れており、又それを用いて作った
切削工具の耐欠損性は大きく改善されることが判った。Cutting conditions Work material Inconel 718 Cutting speed 200 rs / min feed #)
0.2 gw / tQoth cutting depth 1.5M From these results, within the scope of the present invention, SiC whiskers and Z
It has been found that the β-sialon group composite sintered body containing rO, with Q<z≦1, has excellent toughness, and the fracture resistance of cutting tools made using it is greatly improved.
実施例２：
平均粒径０．５μｍのＡＩＮ及び平均粒径２μ躊以下の
Ｙｅ ０＊ ＊ Ｍｇ０ｅ ＣａＯ＊ ］）ｙ、 ｏ、
ｅ ＣｅＯ２をＺｒ 、 Ｓｉ 。Example 2: AIN with an average particle size of 0.5 μm and Ye 0* * Mg0e CaO* ]) y, o, with an average particle size of 2 μm or less
e CeO2 with Zr and Si.
Ａ’ｌ 、 Ｏ、Ｎ と不可避不純物以外のガラス生
成化合物として加える以外は実施例１と同様にして第２
表に示す様な割合に配合した素地粉末を得た後、１７５
０℃、２ ’ Ｏ＃／ｅ１Ｍ” の条件で各６０分間
ホットプレスして緻密な焼結体を得た。得られた焼結体
は実施例１と同様にして評価した。A second sample was prepared in the same manner as in Example 1, except that A'l, O, N and other glass-forming compounds were added as glass-forming compounds other than unavoidable impurities.
After obtaining the base powder mixed in the proportions shown in the table, 175
A dense sintered body was obtained by hot pressing for 60 minutes each at 0°C and 2'O#/e1M''.The obtained sintered body was evaluated in the same manner as in Example 1.
得られた結果は第２表に示すとおシである。The results obtained are shown in Table 2.
この結果からｚｒ 、 Ｓｉ 、 Ａｌ 、 Ｏ、Ｎ
と不可避不純物及び添加したＹｅ Ｍｇ 、 Ｃａ及
び希土類の１種以上で構成されるガラス相を１〜２５重
量％含むβ−サイアロン基複合焼結体は優れた強度と靭
性な有した焼結体であることが判った。From this result, zr, Si, Al, O, N
A β-sialon group composite sintered body containing 1 to 25% by weight of a glass phase consisting of 1 to 25% by weight of a glass phase composed of 1 to 25% by weight of unavoidable impurities and one or more of added Ye, Mg, Ca, and rare earth elements is a sintered body with excellent strength and toughness. I found out something.
又特にこれを用いた切削工具は耐欠損性に優れ、工具寿
命と信頼性の向上が大巾に改善できることが判った〇
一方サイアロン生成化合物としてＡ１ 化合物を含まな
い窒化珪素セラミック焼結体は、サイアロン基セラミッ
ク焼結体に比べ切削性能が劣ることが判った〇
実施例３：
実施例１及び実施例２と同様にして第３表に示すような
割合で配合した素地粉末を焼結した後、Ｘ線回折によシ
焼結体組成の同定を行った。In addition, it was found that cutting tools using this material have excellent fracture resistance, and that tool life and reliability can be greatly improved.On the other hand, silicon nitride ceramic sintered bodies that do not contain A1 compound as a sialon-forming compound are It was found that the cutting performance was inferior to that of the sialon-based ceramic sintered body. Example 3: In the same manner as in Examples 1 and 2, base powders mixed in the proportions shown in Table 3 were sintered. Thereafter, the composition of the sintered body was identified by X-ray diffraction.
その結果を第６表に示しである。この結果から添加した
Ｚ ｒｏ、は配合組成によってＺｒＯ，や７．ｒＯまた
はＺｒの酸窒化物と思われるＺｒ化合物として焼結体中
に存在していることが判った。又焼結体中にＺｒＯ，と
して存在する場合でも配合組成によって単斜晶、正方晶
、立方晶又はそれらの共存体として存在するが、すべて
同様に高強度、高靭性な焼結体となることが判った。The results are shown in Table 6. From this result, the added Zro may be ZrO, or 7.5% depending on the formulation composition. It was found that a Zr compound, which is thought to be an oxynitride of rO or Zr, was present in the sintered body. In addition, even when ZrO is present in the sintered body, it may exist as monoclinic, tetragonal, cubic, or a coexistence of these depending on the composition, but all of them result in a sintered body with the same high strength and high toughness. It turns out.
ここではβ−サイアロンとともにα−サイアロンを共存
させたものも用い得ることが示されている。It has been shown here that a mixture of α-sialon and β-sialon can also be used.
実施例４：
添加するＺｒＯ，を平均粒径０．８−のＹ、 Ｏ，共沈
ＺｒＯ，粉末とする以外は実施例１と同様にして第４表
に示すような割合に配合し、得られた素地粉末を実施例
２と同様にして焼結し、機械的特性を評価した。又Ｙ、
０．を全く固溶していないＺｒＯ，を用いた場合の結果
を併せて第４表に示した。Example 4: The compositions were mixed in the same manner as in Example 1 except that the ZrO to be added was a powder of Y, O, and co-precipitated ZrO with an average particle size of 0.8, and the proportions shown in Table 4 were blended. The resulting base powder was sintered in the same manner as in Example 2, and its mechanical properties were evaluated. Y again,
0. Table 4 also shows the results when using ZrO in which ZrO was not dissolved at all.
この結果から添加するＺｒＯ，の形態が変わっても同様
に高強度、高靭性な焼結体が得られることが判った。From this result, it was found that a sintered body with high strength and high toughness can be obtained even if the form of ZrO added is changed.
実施例５：
出発原料としてＳｉ、Ｎ４粉末に代えて予め所望の２値
に合成された平均直径０．８μｍのβ−サイアロン粉末
を用いる以外は実施例２と同様にして第５表に示すよう
な割合に配合し、得られた素地粉末を焼結し機械的特性
を評価した。その結果を第５表に示す。この結果からＯ
＜２≦１の範囲のβ−サイアロン粉末を出発物質として
使用した場合も高強度、高靭性な焼結体が得られること
が判った。Example 5: The same procedure as in Example 2 was carried out as shown in Table 5, except that β-SiAlON powder with an average diameter of 0.8 μm synthesized in advance into a desired binary value was used instead of Si and N4 powders as the starting raw material. The resulting base powder was sintered and its mechanical properties were evaluated. The results are shown in Table 5. From this result O
It has been found that a sintered body with high strength and high toughness can also be obtained when β-sialon powder in the range of <2≦1 is used as a starting material.
実施例６：
平均粒径２μｍ以下の各種Ｚｒ化合物を用いる以外は、
実施例２と同様にして第６表に示すような割合で配合し
た素地粉末をタテ５０謂ヨコ５０ＷＩＭ厚さ７期の寸法
に成形圧Ｌ５ｔｏｎ／ｄでプレス成形した後、１７５０
℃１気圧の窒素ガス雰囲気中で２時間焼結し、１次焼結
体を得た。次にこの焼結体を１７５０℃、７０気圧の加
圧窒素ガス雰囲気中で２時間再焼結し、緻密な２次焼結
体を得た。このようにして得られた焼結体を実施例１と
同様な評価を行い、その結果を第６表に示した。Example 6: Except for using various Zr compounds with an average particle size of 2 μm or less,
In the same manner as in Example 2, the base powder blended in the proportions shown in Table 6 was press-molded to a size of 50 mm vertically, 50 mm horizontally, and 7 mm thick at a molding pressure of L5 ton/d.
Sintering was carried out for 2 hours in a nitrogen gas atmosphere at 1 atm at °C to obtain a primary sintered body. Next, this sintered body was re-sintered at 1750° C. in a pressurized nitrogen gas atmosphere of 70 atmospheres for 2 hours to obtain a dense secondary sintered body. The sintered body thus obtained was evaluated in the same manner as in Example 1, and the results are shown in Table 6.
この結果からＺｒＯ，を添加したものだけが常圧及びガ
ス圧焼結法に於いても本発明の範囲内の組成を有した焼
結体は優れた機械的特性を有していることが判った。From this result, it was found that sintered bodies containing ZrO and having a composition within the range of the present invention have excellent mechanical properties even in normal pressure and gas pressure sintering methods. Ta.
又本発明の複合材料を用いて切削工具を作り、実施例１
と同様にして切削テストを行った結果についても第６表
に示すとおシで本発明による焼結体は切削工具として欠
損するまでの衝撃回数が大きいことが判った。In addition, a cutting tool was made using the composite material of the present invention, and Example 1
The results of a cutting test conducted in the same manner as above are also shown in Table 6, and it was found that the sintered body according to the present invention required a large number of impacts before being damaged as a cutting tool.
（発明の効果２
本発明の複合材料は前記実施例の内容から明らかなとお
シ、抗折強度、破壊靭性及びビッカース硬度などの焼結
体特性に優れているので、切削工具、自動車用エンジン
部材、耐摩耗部材、耐食性部材、耐熱性部材等々に広く
利用することが可能である。(Effect of the invention 2) The composite material of the present invention has excellent sintered properties such as strength, bending strength, fracture toughness, and Vickers hardness, which is clear from the contents of the above examples, so it can be used in cutting tools, automobile engine parts, etc. It can be widely used for wear-resistant members, corrosion-resistant members, heat-resistant members, etc.
Claims (3)
よびまたはＺｒ酸窒化物をＺｒ換算にて３〜２０重量％
、残部サイアロン基セラミックを主成分とするものから
なり、前記サイアロン基セラミックは組成式Ｓｉ＿６＿
−＿ｚＡｌ＿ｚＯ＿ｚＮ＿６＿−＿ｚ（但し０＜ｚ≦１
）で表わされるβ−サイアロンもしくは該β−サイアロ
ンと組成式Ｍ＿ｘ（Ｓｉ、Ａｌ）＿１＿２（Ｏ、Ｎ）＿
１＿６（但しＭはＬｉ、Ｃａ、Ｍｇ、Ｙおよび稀土類元
素から選ばれた単独または混合物からなり０＜ｘ≦２）
で表わされるα−サイアロンとからなるα、β複合サイ
アロンから選択され、かつ１〜２５重量％のＺｒ、Ｓｉ
、Ａｌ、Ｏ、Ｎと不可避不純物又はそれにＹ、Ｍｇ、Ｃ
ａ及び希土類金属の１種以上を含むガラス相で主として
構成されていることを特徴とする炭化珪素ウィスカー強
化複合材料(1) 5 to 45% by weight of SiC whiskers, 3 to 20% by weight of Zr oxide and/or Zr oxynitride in terms of Zr
, the remainder is mainly composed of sialon-based ceramic, and the sialon-based ceramic has the composition formula Si_6_
−_zAl_zO_zN_6_-_z (however, 0<z≦1
) or the β-sialon and the compositional formula M_x(Si, Al)_1_2(O,N)_
1_6 (However, M is selected from Li, Ca, Mg, Y, and rare earth elements alone or in a mixture 0<x≦2)
selected from α, β composite sialon consisting of α-sialon represented by 1 to 25% by weight of Zr, Si
, Al, O, N and inevitable impurities or Y, Mg, C
A silicon carbide whisker-reinforced composite material characterized in that it is mainly composed of a glass phase containing one or more of a and rare earth metals.
およびまたはＺｒ酸窒化物Ｚｒ換算で７〜２０重量％と
することを特徴とする特許請求の範囲第１項記載の炭化
珪素ウィスカー強化複合材料(2) The silicon carbide whisker reinforced composite material according to claim 1, characterized in that the SiC whisker is 10 to 30% by weight, and the Zr oxide and/or Zr oxynitride is 7 to 20% by weight in terms of Zr.
およびまたはＺｒ酸窒化物をＺｒ換算で７〜１５重量％
とすることを特徴とする特許請求の範囲第１項記載の炭
化珪素ウィスカー強化複合材料(3) 15-25% by weight of SiC whiskers, 7-15% by weight of Zr oxide and/or Zr oxynitride in terms of Zr
A silicon carbide whisker-reinforced composite material according to claim 1, characterized in that:
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62156633A JPS63260869A (en) | 1986-08-18 | 1987-06-25 | Silicon carbide whisker reinforced composite material |
| US07/086,455 US4946807A (en) | 1986-08-18 | 1987-08-18 | Composite ceramic material reinforced with silicon carbide whiskers |
Applications Claiming Priority (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP19158586 | 1986-08-18 | ||
| JP61-191585 | 1986-08-18 | ||
| JP61-233230 | 1986-10-02 | ||
| JP61-291633 | 1986-12-09 | ||
| JP62156633A JPS63260869A (en) | 1986-08-18 | 1987-06-25 | Silicon carbide whisker reinforced composite material |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS63260869A true JPS63260869A (en) | 1988-10-27 |
| JPH0535697B2 JPH0535697B2 (en) | 1993-05-27 |
Family
ID=26484325
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP62156633A Granted JPS63260869A (en) | 1986-08-18 | 1987-06-25 | Silicon carbide whisker reinforced composite material |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS63260869A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4866013A (en) * | 1986-05-28 | 1989-09-12 | Anseau Michael R | Process for making an improved ceramic material |
| WO2006068220A1 (en) * | 2004-12-22 | 2006-06-29 | Ngk Spark Plug Co., Ltd. | Sialon insert and cutting tool equipped therewith |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH072234U (en) * | 1993-06-17 | 1995-01-13 | 公子 大野 | Powdered detergent in a box |
-
1987
- 1987-06-25 JP JP62156633A patent/JPS63260869A/en active Granted
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4866013A (en) * | 1986-05-28 | 1989-09-12 | Anseau Michael R | Process for making an improved ceramic material |
| WO2006068220A1 (en) * | 2004-12-22 | 2006-06-29 | Ngk Spark Plug Co., Ltd. | Sialon insert and cutting tool equipped therewith |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0535697B2 (en) | 1993-05-27 |
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