JPH05319910A - Ceramic composite material and its production - Google Patents
Ceramic composite material and its productionInfo
- Publication number
- JPH05319910A JPH05319910A JP4151176A JP15117692A JPH05319910A JP H05319910 A JPH05319910 A JP H05319910A JP 4151176 A JP4151176 A JP 4151176A JP 15117692 A JP15117692 A JP 15117692A JP H05319910 A JPH05319910 A JP H05319910A
- Authority
- JP
- Japan
- Prior art keywords
- average particle
- tic
- composite material
- zro
- less
- 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.)
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Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、特殊構造を有するセラ
ミックス複合材料及びその製造方法に関する。さらに、
詳しくは耐熱性、耐摩耗性、耐熱衝撃性を有する高靱
性、高強度複合セラミックス材料及びその製造方法に関
する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a ceramic composite material having a special structure and a method for producing the same. further,
More specifically, it relates to a high toughness, high strength composite ceramic material having heat resistance, wear resistance, and thermal shock resistance, and a method for producing the same.
【０００２】[0002]
【従来の技術】Ａｌ2 Ｏ3 は、易焼結性で耐熱性、耐蝕
性、電気絶縁性等に優れた特性を有しているため、古く
から工業材料として広範な用途に利用されてきたが、強
度、破壊靱性、耐熱衝撃性が低いという欠点を持ってい
る。そのために、これらの欠点を複合化、例えばＡｌ2
Ｏ3 粒子中に第２相として、ＳｉＣ、Ｓｉ3 Ｎ4 等を分
散することにより改善しようとする試みがなされてきた
が、それらの材料開発の大多数は、第２相としてＳｉ
Ｃ、Ｓｉ3 Ｎ4 等の粒子、ウィスカーを分散したミクロ
ンレベルの複合化が中心であり、その特性改善には限界
があった。 2. Description of the Related Art Al 2 O 3 has been widely used as an industrial material for a long time since it is easy to sinter and has excellent heat resistance, corrosion resistance and electric insulation. However, it has the drawback of low strength, fracture toughness, and thermal shock resistance. To that end, these disadvantages are compounded, for example Al 2
Attempts have been made to improve by dispersing SiC, Si 3 N 4, etc. as a second phase in O 3 particles, but most of the material developments of these have been made as Si as a second phase.
Mostly, the composite of C, Si 3 N 4, etc. particles and whiskers is dispersed at the micron level, and there has been a limit to improving the characteristics.
【０００３】これらの分散粒子、ウィスカーの複合化に
より破壊靱性は、分散粒子がＡｌ2Ｏ3 の粒界に偏在す
るために生じるクラック偏向、あるいはウィスカーの引
き抜き等により改善されている。Fracture toughness is improved by compounding these dispersed particles and whiskers by crack deflection caused by uneven distribution of dispersed particles at the grain boundaries of Al 2 O 3 , or by pulling out whiskers.
【０００４】[0004]
【発明が解決しようとする課題】しかし、このようなク
ラック偏向、あるいはウィスカーの引き抜き等により破
壊靱性を改善するという考えでは、破壊の発生源である
粒界の欠陥には変化がなく、したがって粒界の欠陥は残
存しているため、大幅な強度向上は望めなかった。ま
た、Ａｌ2 Ｏ3 のようなセラミックス焼結体は、異方性
粒子でマトリックスが形成されており、粒子境界で隣接
粒子の熱膨張差により歪が発生し、このために、粒界が
破壊源となり、強度低下になるという欠点を有する。However, in the idea of improving the fracture toughness by such crack deflection or whisker pulling out, there is no change in the defect of the grain boundary, which is the source of the fracture, and therefore the grain boundary is not changed. Since the defects of the field remain, it was not possible to expect a significant improvement in strength. Further, a ceramic sintered body such as Al 2 O 3 has a matrix formed of anisotropic particles, and strain is generated at the grain boundaries due to the difference in thermal expansion between adjacent particles, which causes the grain boundaries to break. It has a drawback that it becomes a source and the strength is reduced.
【０００５】そこで、本発明者等は、上記のような欠点
を改善する目的で、先にＡｌ2 Ｏ3の結晶粒内にＴｉＣ
を分散したＡｌ2 Ｏ3 ／ＴｉＣ複合材料（特開平２−２
２９７５７号公報参照）を提案した。このセラミックス
複合材料は、ＴｉＣ粒子がＡｌ2 Ｏ3 の結晶粒内に分散
した複合化組織を有している点で、室温及び高温でも高
強度を示し、したがって耐磨耗部材、耐熱材料、切削工
具材料等の工業材料に十分に利用し得るものであるが、
更にＡｌ2 Ｏ3 ／ＴｉＣ複合材料にＺｒＯ2 微粒子を分
散することにより、Ａｌ2 Ｏ3 ／ＴｉＣ複合材料の優れ
た特性を損なわず、その上耐熱衝撃性のある高靱性、高
強度のセラミックス複合材料が得られ、また更に低温焼
結が可能であるセラミックス複合材料の製造方法を見出
し、ここに本発明を完成した。Therefore, the inventors of the present invention first aimed to improve the above-mentioned drawbacks by first forming TiC in the Al 2 O 3 crystal grains.
Al 2 O 3 / TiC composite material having dispersed therein (Japanese Patent Laid-Open No. 2-2
No. 29757). This ceramic composite material exhibits high strength even at room temperature and high temperature in that it has a composite structure in which TiC particles are dispersed in Al 2 O 3 crystal grains, and therefore, it has wear resistance members, heat resistant materials, and cutting materials. Although it can be sufficiently used for industrial materials such as tool materials,
By further dispersing ZrO 2 fine particles in the Al 2 O 3 / TiC composite, without compromising the excellent properties of Al 2 O 3 / TiC composite, high toughness thereon a thermal shock resistance, high strength ceramic composite The present invention has been completed by finding a method for producing a ceramic composite material that can obtain a material and can be further sintered at a low temperature.
【０００６】したがって、本発明の目的は、Ａｌ2 Ｏ3
／ＴｉＣ複合材料の有する特性を損なわず、更に耐熱衝
撃性のある高靱性、高強度のセラミックス複合材料を提
供することにある。Therefore, the object of the present invention is to provide Al 2 O 3
Another object of the present invention is to provide a ceramic composite material having high toughness and high strength, which is resistant to thermal shock and does not impair the properties of the / TiC composite material.
【０００７】更に本発明のもう一つの目的は、焼結過程
で緻密に焼結され、かつ低温焼結されて上記特性が得ら
れるセラミックス複合材料の製造方法を提供することに
ある。Still another object of the present invention is to provide a method for producing a ceramic composite material which is densely sintered in a sintering process and is sintered at a low temperature to obtain the above characteristics.
【０００８】[0008]
【課題を解決するための手段】本発明の上記各目的は、
以下の構成要件からなる各発明によってそれぞれ達成さ
れる。 （１）平均粒子径０．２μｍ〜１０μｍの結晶粒子を有
するＡｌ2 Ｏ3 マトリックスの結晶粒内に平均粒子径２
μｍ以下のＴｉＣ微粒子を１〜８体積％分散させたセラ
ミックス中に、平均粒子径２μｍ以下のＺｒＯ2 微粒子
を分散させたことを特徴とするセラミックス複合材料。The respective objects of the present invention are as follows.
The invention is achieved by each invention having the following constituent features. (1) Average particle size 2 within the crystal grains of an Al 2 O 3 matrix having crystal grains with an average particle size of 0.2 μm to 10 μm.
A ceramic composite material, wherein ZrO 2 fine particles having an average particle diameter of 2 μm or less are dispersed in a ceramic in which 1 to 8% by volume of TiC fine particles having an average particle diameter of 2 μm or less are dispersed.
【０００９】（２）安定化剤としてＹ2 Ｏ3 を１〜３ｍ
ｏｌ％含有するＺｒＯ2 １０〜５０体積％、ＴｉＣ １
〜８体積％、残部は平均粒子径５μｍ以下のＡｌ2 Ｏ3
よりなる配合組成を有することを特徴とする前記第１項
記載のセラミックス複合材料。(2) 1 to 3 m of Y 2 O 3 as a stabilizer
ZrO 2 10 to 50% by volume containing ol%, TiC 1
˜8% by volume, the balance being Al 2 O 3 having an average particle size of 5 μm or less
The ceramic composite material according to the above item 1, wherein the composite material has the following composition.
【００１０】（３）未安定化ＺｒＯ2 １０〜３０体積
％、ＴｉＣ １〜８体積％、残部は平均粒子径５μｍ以
下のＡｌ2 Ｏ3 よりなる配合組成を有することを特徴と
する前記第１項記載のセラミックス複合材料。(3) Unstabilized ZrO 2 of 10 to 30% by volume, TiC of 1 to 8% by volume, and the balance of Al 2 O 3 having an average particle size of 5 μm or less. The ceramic composite material according to the item.
【００１１】（４）平均粒子径５μｍ以下のＡｌ2 Ｏ3
と平均粒子径２μｍ以下のＴｉＣ及び平均粒子径２μｍ
以下のＺｒＯ2 を前記第２項又は前記第３項記載の配合
組成で混合し、得られた混合物を成形した後、該成形体
を不活性雰囲気で、１４００℃以上の温度で焼結するこ
とを特徴とするセラミックス複合材料の製造方法。(4) Al 2 O 3 having an average particle size of 5 μm or less
And TiC having an average particle size of 2 μm or less and an average particle size of 2 μm
The following ZrO 2 is mixed with the compounding composition described in the above item 2 or 3, the resulting mixture is molded, and then the molded product is sintered in an inert atmosphere at a temperature of 1400 ° C. or higher. A method for producing a ceramics composite material, comprising:
【００１２】以下、本発明を更に詳しく説明する。本発
明は、平均粒子径０．２μｍ〜１０μｍの結晶粒子を有
するＡｌ2 Ｏ3 マトリックスの結晶粒内に平均粒子径２
μｍ以下のＴｉＣ微粒子を１〜８体積％分散させたセラ
ミックス中に、平均粒子径２μｍ以下のＺｒＯ2 微粒子
を分散させたことを特徴とするもので、このセラミック
ス複合材料の微細組織構造は、Ａｌ2 Ｏ3 結晶粒内にＺ
ｒＯ2 が分散した組織、Ａｌ2 Ｏ3 結晶粒内にＴｉＣ、
ＺｒＯ2 の両者が分散した組織、ＺｒＯ2 結晶粒内にＴ
ｉＣが分散した組織等を含む複合化組織を有するもので
ある。そしてこれによりＡｌ2 Ｏ3 ／ＴｉＣ複合材料の
有する特性を損なわず、更に耐熱衝撃性のある高靱性、
高強度のセラミックス複合材料が得られる。The present invention will be described in more detail below. The present invention has an average particle size of 2 in the crystal grains of an Al 2 O 3 matrix having crystal grains with an average grain size of 0.2 μm to 10 μm.
ZrO 2 fine particles having an average particle diameter of 2 μm or less are dispersed in a ceramic in which 1 to 8% by volume of TiC fine particles of μm or less are dispersed. The fine structure structure of this ceramic composite material is Al. Z in the 2 O 3 crystal grains
A structure in which rO 2 is dispersed, TiC in Al 2 O 3 crystal grains,
A structure in which both ZrO 2 are dispersed, T in the ZrO 2 crystal grains
It has a composite structure including a structure in which iC is dispersed. As a result, the characteristics of the Al 2 O 3 / TiC composite material are not impaired, and the high toughness with thermal shock resistance,
A high-strength ceramic composite material can be obtained.
【００１３】また本発明の製造方法は、平均粒子径５μ
ｍ以下のＡｌ2 Ｏ3 と平均粒子径２μｍ以下のＴｉＣ及
び平均粒子径２μｍ以下のＺｒＯ2 を所定の割合で混合
し、成形した後、焼結することにより緻密で特殊な組織
構造のものが得られ、しかも低温焼結されて上記特性が
得られるセラミックス複合材料が得られる。The manufacturing method of the present invention has an average particle size of 5 μm.
Al 2 O 3 having an average particle diameter of 2 m or less, TiC having an average particle diameter of 2 µm or less and ZrO 2 having an average particle diameter of 2 µm or less are mixed at a predetermined ratio, and the mixture is molded and sintered to obtain a dense and special structure. A ceramics composite material which is obtained and is sintered at a low temperature to obtain the above characteristics can be obtained.
【００１４】本発明によるセラミックス複合材料は、Ａ
ｌ2 Ｏ3 結晶粒内にＴｉＣ微粒子を分散し、ナノオーダ
ーの複合化を行ったセラミックス中に、更にＺｒＯ2 微
粒子を分散して複合化組織を形成することにより、Ｔｉ
Ｃの添加による高靱性化とＺｒＯ2 の添加による相変態
に起因する高靱性化とが互いに阻害することなく作用し
て破壊靱性が向上し、またＡｌ2 Ｏ3 結晶粒内へのＴｉ
Ｃ微粒子、ＺｒＯ2 微粒子の分散により、組織の微細化
と破壊源寸法の減少及びＴｉＣ粒子、ＺｒＯ2粒子によ
る高靱性化により曲げ強度も改善される。The ceramic composite material according to the present invention is
The TiC fine particles are dispersed in the l 2 O 3 crystal grains, and the ZrO 2 fine particles are further dispersed in the nano-ordered composite ceramics to form a composite structure.
The increase in toughness due to the addition of C and the increase in toughness due to the phase transformation due to the addition of ZrO 2 act without interfering with each other to improve the fracture toughness, and Ti in the Al 2 O 3 crystal grains is improved.
The dispersion of C fine particles and ZrO 2 fine particles also improves the bending strength by making the structure finer and reducing the size of the fracture source, and increasing the toughness by TiC particles and ZrO 2 particles.
【００１５】本発明は、マトリックスとしてＡｌ
2 Ｏ3 、分散粒子としてＴｉＣ、ＺｒＯ2の２成分を用
いることが特徴である。そして、この複合焼結体のＡｌ
2 Ｏ3 結晶粒径は、０．２〜１０μｍであり、ＴｉＣ粒
子及びＺｒＯ2 粒子のそれぞれの平均粒径は２μｍ以下
で、好ましくはＡｌ2 Ｏ3 マトリックス中にＴｉＣ粒子
とＺｒＯ2 粒子を均一に分散させた構造のものである。
複合焼結体中のＡｌ2 Ｏ3 マトリックス粒子径を０．２
〜１０μｍとする理由は、強度が大幅に高くなる範囲で
あるためである。The present invention uses Al as a matrix.
The feature is that 2 O 3 and two components of TiC and ZrO 2 are used as dispersed particles. And the Al of this composite sintered body
The 2 O 3 crystal grain size is 0.2 to 10 μm, the average grain size of each of the TiC particles and ZrO 2 particles is 2 μm or less, and preferably the TiC particles and the ZrO 2 particles are uniformly dispersed in the Al 2 O 3 matrix. The structure is dispersed in.
The Al 2 O 3 matrix particle size in the composite sintered body was 0.2
The reason for setting the thickness to 10 μm is that the strength is in a range in which the strength is significantly increased.
【００１６】また焼結前のＡｌ2 Ｏ3 粉末原料として
は、５μｍ以下のＡｌ2 Ｏ3 粒子が好ましく用いられ
が、この理由は、焼結し易いためである。またそれぞれ
の平均粒径が２μｍ以下のＴｉＣ粒子及びＺｒＯ2 粒子
を用いる理由は、Ａｌ2 Ｏ3 マトリックス結晶粒内に取
り込まれ易いこと、そして、材料欠陥となるほどのマイ
クロクラックが発生しない範囲であること等による。ま
た分散粒子であるＴｉＣの添加量を１〜８体積％とする
理由は、複合焼結体の破断時にＺｒＯ2 の相変態が十分
に発現できる組成範囲であることによる。As the Al 2 O 3 powder raw material before sintering, Al 2 O 3 particles having a particle size of 5 μm or less are preferably used, because the reason is that sintering is easy. The reason for using TiC particles and ZrO 2 particles each having an average particle diameter of 2 μm or less is that they are easily incorporated into Al 2 O 3 matrix crystal grains and that microcracks to the extent of material defects are not generated. It depends. Further, the reason why the addition amount of the dispersed particles of TiC is set to 1 to 8% by volume is that the composition range is such that the phase transformation of ZrO 2 can be sufficiently exhibited when the composite sintered body is broken.
【００１７】未安定ＺｒＯ2 の添加量が１０体積％未満
では、本発明の効果が得られず、また３０体積％を越え
ると、ＺｒＯ2 粒子周辺にマイクロクラックが存在する
ようになり、見掛け上高靱性を示すが、これは材質的な
ものではなく、構造的に靱性に寄与しているに過ぎない
のに対して、未安定ＺｒＯ2 粒子１０〜３０体量％添加
の焼結体の研磨面には、単斜相は含まれず、破断時に正
方晶の応力誘起変態の割合が高いものが得られる。If the amount of the unstable ZrO 2 added is less than 10% by volume, the effect of the present invention cannot be obtained, and if it exceeds 30% by volume, microcracks are present around the ZrO 2 particles, apparently. It shows high toughness, but this is not a material but merely contributes to the toughness structurally. On the other hand, polishing of a sintered body containing 10 to 30% by mass of unstable ZrO 2 particles is performed. The surface does not contain a monoclinic phase and a high proportion of tetragonal stress-induced transformation is obtained at break.
【００１８】更に安定化剤としてＹ2 Ｏ3 を１〜３ｍｏ
ｌ％含有することにより部分安定化したＺｒＯ2 の添加
量を１０〜５０容積％とする理由は、この配合組成では
ＺｒＯ2 の応力誘起変態を発現でき、曲げ強度、破壊靱
性を高くすることができるためである。Further, Y 2 O 3 as a stabilizer is added in an amount of 1 to 3 mo.
The reason why the addition amount of partially stabilized ZrO 2 by containing 1% is 10 to 50% by volume is that the composition can express the stress-induced transformation of ZrO 2 and increase the bending strength and fracture toughness. This is because it can be done.
【００１９】またＹ2 Ｏ3 を１〜３ｍｏｌ％と限定した
理由は、３ｍｏｌ％を越えると、準安定状態ではなくな
り、有効な応力誘起変態が得られないためである。本発
明によるマトリックスとしてのＡｌ2 Ｏ3 は、焼結過程
で緻密に焼結され、この粒子内に分散相のＴｉＣ粒子と
ＺｒＯ2 粒子を均一に取り込むことができる。The reason why Y 2 O 3 is limited to 1 to 3 mol% is that if it exceeds 3 mol%, the metastable state is lost and effective stress-induced transformation cannot be obtained. Al 2 O 3 as the matrix according to the present invention is densely sintered in the sintering process, and TiC particles and ZrO 2 particles in the dispersed phase can be uniformly incorporated into the particles.
【００２０】焼結は、不活性雰囲気又は水素雰囲気中で
ホットプレス焼結、常圧焼結あるいは、常圧焼結・ＨＩ
Ｐ（熱間等方圧プレス）により焼結するものである。特
に常圧焼結・ＨＩＰ（熱間等方圧プレス）は、複雑な形
状品を多量に製造できるので好ましい。ＨＩＰ（熱間等
方圧プレス）を用いる時のガス圧は、広範囲に用いられ
るが、特に１０００ｋｇ／ｃｍ2 〜２０００ｋｇ／ｃｍ
2 が好ましい。Sintering is carried out by hot press sintering, atmospheric pressure sintering or atmospheric pressure sintering / HI in an inert atmosphere or a hydrogen atmosphere.
It is sintered by P (hot isostatic pressing). In particular, normal pressure sintering and HIP (hot isostatic pressing) are preferable because a large number of complicated shaped products can be manufactured. The gas pressure when using HIP (hot isostatic press) is widely used, but especially 1000 kg / cm 2 to 2000 kg / cm.
2 is preferred.
【００２１】焼結温度は１４００℃以上が望ましく、更
に望ましくは１４００℃から１６００℃である。不活性
雰囲気としては、ヘリウム、アルゴン、窒素等が用いら
れ、好ましくはアルゴンである。本発明により得られる
セラミックス複合材料は耐熱材料として、切削工具、耐
摩耗部材、耐熱衝撃性を有する構造材料として、特に好
適である。The sintering temperature is preferably 1400 ° C. or higher, more preferably 1400 ° C. to 1600 ° C. As the inert atmosphere, helium, argon, nitrogen or the like is used, preferably argon. The ceramic composite material obtained by the present invention is particularly suitable as a heat resistant material, as a cutting tool, a wear resistant member, and a structural material having thermal shock resistance.
【００２２】[0022]
【作用】本発明によるセラミックス複合材料は、Ａｌ2
Ｏ3 結晶粒内にＴｉＣ微粒子を分散することで、Ａｌ2
Ｏ3 とＴｉＣの熱膨張係数の差により、残留応力が発生
し、これがＴｉＣ微粒子周囲のＡｌ2 Ｏ3 中に引張応力
場を、また隣接するＡｌ2 Ｏ3 同士の粒界に圧縮応力場
を生じさせる。The ceramic composite material according to the present invention is made of Al 2
By dispersing TiC fine particles in O 3 crystal grains, Al 2
Residual stress occurs due to the difference in thermal expansion coefficient between O 3 and TiC, which creates a tensile stress field in Al 2 O 3 around TiC particles and a compressive stress field in the grain boundary between adjacent Al 2 O 3 particles. Give rise to.
【００２３】この応力場及びＴｉＣ微粒子自身によりク
ラックは偏向し、更にＡｌ2 Ｏ3 にＺｒＯ2 が拘束され
ることで、準安定な正方晶を保持したＺｒＯ2 が、クラ
ック先端近傍のプロセスゾーンで相変態、マイクロクラ
ックを生じ、クラック先端の応力集中を緩和させ、また
発生した圧縮応力でクラックの進展を抑制することで、
破壊靱性を向上させようとするものである。The cracks were deflected by the stress field and TiC particles themselves, that ZrO 2 is restrained further Al 2 O 3, ZrO 2 is holding the metastable tetragonal, in the process zone of the crack tip vicinity Phase transformation, micro cracks are generated, stress concentration at the tip of the crack is relaxed, and the compression stress generated suppresses crack development,
It is intended to improve fracture toughness.
【００２４】[0024]
【実施例】以下に本発明を実施例を挙げて更に詳しく説
明するが、本発明は、この実施例に限定されるものでは
ない。EXAMPLES The present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples.
【００２５】実施例 Ａｌ2 Ｏ3 には、住友化学社製α−Ａｌ2 Ｏ3 （ＡＫＰ
−５３、平均粒径０．２μｍ）、ＴｉＣ粉末には、白水
化学社製ＴｉＣ（平均粒径０．２μｍ）、ＺｒＯ2 粉末
には、第一希元素社製未安定ＺｒＯ2 （平均粒径０．４
μｍ）及び東ソー社製部分安定化ＺｒＯ2 （平均粒径
０．３μｍ）を使用した。Example As Al 2 O 3 , α-Al 2 O 3 (AKP manufactured by Sumitomo Chemical Co., Ltd. was used.
-53, average particle size 0.2 μm), TiC powder has TiC (average particle size 0.2 μm) manufactured by Shiramizu Chemical Co., Ltd., and ZrO 2 powder has unstable ZrO 2 (average particle size 0 .4
μm) and partially stabilized ZrO 2 (average particle size 0.3 μm) manufactured by Tosoh Corporation.
【００２６】Ａｌ2 Ｏ3 対して、ＴｉＣを５体積％、未
安定ＺｒＯ2 、又は２ｍｏｌ％のＹ2 Ｏ3 で部分安定化
したＺｒＯ2 を表１に示される割合で添加し、エタノー
ルを分散媒として湿式ボールミルで２４時間混合を行っ
た。これを十分に乾燥した後、乾式ボールミルで解砕混
合を１２時間行って、原料粉末とした。[0026] In contrast Al 2 O 3, the TiC 5% by volume, was added unstabilized ZrO 2, or 2 mol% of Y 2 O 3 partially stabilized the ZrO 2 in the proportions shown in Table 1, dispersed in ethanol Mixing was performed for 24 hours with a wet ball mill as a medium. After it was sufficiently dried, it was crushed and mixed by a dry ball mill for 12 hours to obtain a raw material powder.
【００２７】この原料粉末５０ｇｒを黒鉛ダイスに充填
し、ホットプレス装置（富士電波工業社製）で焼結し
た。ホットプレス条件は、表１に記載の焼結温度まで昇
温させた後、１時間保持した。またプレス圧は３０ＭＰ
ａ、雰囲気ガスにはアルゴンガスを用いた。得られた各
種の焼結体は研削加工してＪｌＳ Ｒ１６０１に準じた
３×４×４０ｍｍの３点曲げ試験片の大きさとした。50 gr of this raw material powder was filled in a graphite die and sintered with a hot press machine (Fuji Denpa Kogyo KK). The hot press conditions were such that the temperature was raised to the sintering temperature shown in Table 1 and maintained for 1 hour. The pressing pressure is 30MP
a, Argon gas was used as the atmosphere gas. The various sintered bodies thus obtained were ground into a size of 3 × 4 × 40 mm three-point bending test piece in accordance with JLSR1601.
【００２８】曲げ強度は、３点曲げ試験法により、荷重
速度０．５ｍｍ／ｍｉｎ、スパン長さ３０ｍｍ、室温で
強度を測定した。破壊靱性は荷重５Ｋｇ重、保持時間１
０秒で、ＩＦ法により測定した。The bending strength was measured by a three-point bending test method at a load rate of 0.5 mm / min, a span length of 30 mm, and room temperature. Fracture toughness is 5 kg load and 1 holding time
It was measured by the IF method at 0 seconds.
【００２９】表１にＡｌ2 Ｏ3 とＴｉＣ、ＺｒＯ2 の組
成配合による曲げ強度、破壊靱性等の特性の変化を示
す。比較のために、Ａｌ2 Ｏ3 単相、Ａｌ2 Ｏ3 ／Ｔｉ
Ｃ複合材料、Ａｌ2 Ｏ3 ／ＴｉＣ／ＺｒＯ2 複合材料の
本発明外のものの特性も示す。Table 1 shows changes in characteristics such as bending strength and fracture toughness due to the composition of Al 2 O 3 , TiC and ZrO 2 . For comparison, Al 2 O 3 single phase, Al 2 O 3 / Ti
The properties of C composite materials, Al 2 O 3 / TiC / ZrO 2 composite materials other than the present invention are also shown.
【００３０】[0030]
【表１】 [Table 1]
【００３１】表１から明らかなように、比較であるＡｌ
2 Ｏ3 ／ＴｉＣ複合材料は、破壊強度はＡｌ2 Ｏ3 単相
よりも大幅に向上するが、破壊靱性の改善は、わずかで
ある。これに対して、Ａｌ2 Ｏ3 ／ＴｉＣ／ＺｒＯ2 複
合材料において、２成分系に未安定化ＺｒＯ2 を添加し
た本発明の系では、ＺｒＯ2 １０〜３０体量％組成の複
合焼結体において曲げ強度、破壊靱性が大幅に改善され
ていることがわかる。また部分安定化ＺｒＯ2 を１０〜
５０体積％添加した本発明の系では、曲げ強度、破壊靱
性は大幅に改善されていることがわかる。As is clear from Table 1, the comparative Al
The 2 O 3 / TiC composite material has a significantly higher fracture strength than the Al 2 O 3 single phase, but the fracture toughness is slightly improved. On the other hand, in the Al 2 O 3 / TiC / ZrO 2 composite material, in the system of the present invention in which the unstabilized ZrO 2 is added to the two-component system, the composite sintered body having a ZrO 2 content of 10 to 30 mass% It can be seen that the flexural strength and fracture toughness are significantly improved. In addition, partially stabilized ZrO 2 is added to 10
It can be seen that the bending strength and fracture toughness are greatly improved in the system of the present invention in which 50% by volume is added.
【００３２】なお、Ｘ線回折により、未安定化ＺｒＯ2
を１０〜３０体積％添加した焼結体の研磨面のＺｒＯ2
は殆ど正方晶で存在し、破断時には、正方晶から単斜相
への応力誘起変態の割合が高い。未安定化ＺｒＯ2 ５体
積％では、応力誘起変態の割合が少なく、したがって破
壊靱性は低く、また未安定化ＺｒＯ2 ４０体積％では、
焼結体中のＺｒＯ2 の約８０％は単斜相で存在してお
り、したがって曲げ強度は低い。By X-ray diffraction, unstabilized ZrO 2
Of ZrO 2 on the polished surface of the sintered body containing 10 to 30% by volume of
Exists in a tetragonal system and has a high rate of stress-induced transformation from the tetragonal system to the monoclinic phase at break. With 5% by volume unstabilized ZrO 2, the proportion of stress-induced transformation is low and therefore the fracture toughness is low, and with 40% by volume unstabilized ZrO 2 ,
About 80% of ZrO 2 in the sintered body exists in a monoclinic phase, and therefore the bending strength is low.
【００３３】部分安定化ＺｒＯ2 を１０〜５０体積％添
加して造られた焼結体の研磨面のＺｒＯ2 は殆ど正方晶
で存在しているが、部分安定化ＺｒＯ2 ５体積％添加し
た焼結体では、破断時の応力誘起変態の割合が少なく、
したがって破壊靱性はあまり改善されないことがわか
る。ZrO 2 on the polished surface of the sintered body prepared by adding 10 to 50% by volume of partially stabilized ZrO 2 is present in almost tetragonal structure, but 5% by volume of partially stabilized ZrO 2 was added. In the sintered body, the ratio of stress-induced transformation at break is small,
Therefore, it is understood that the fracture toughness is not improved so much.
【００３４】[0034]
【発明の効果】以上説明したように本発明のセラミック
ス複合材料は、Ａｌ2 Ｏ3 マトリックス中にＴｉＣ及び
ＺｒＯ2 の２成分を分散していることを特徴とすること
により、Ａｌ2 Ｏ3 単相、Ａｌ2 Ｏ3 ／ＴｉＣ複合材料
の特性を損ねることなく、耐熱衝撃性のある高靱性、高
強度の特性を有し、構造用材料にも応用可能な材料が得
られる。As described above, the ceramic composite material of the present invention is characterized in that two components of TiC and ZrO 2 are dispersed in the Al 2 O 3 matrix, and thus the Al 2 O 3 simple substance is obtained. Phase, the properties of Al 2 O 3 / TiC composite material are not impaired, and the material has high toughness and high strength with thermal shock resistance and is applicable to structural materials.
【００３５】更に従来の複合化セラミックスの焼結温度
は、高温であるのに比較し、本発明の製造方法では、得
られた複合材料は低温焼結で緻密で特殊な組織構造を有
するものが得られ、その結果曲げ強度、破壊靱性等の機
械的特性が大幅に改善される。Further, in comparison with the sintering temperature of the conventional composite ceramics, which is high, in comparison with the manufacturing method of the present invention, the composite material obtained by low temperature sintering has a dense and special microstructure. As a result, mechanical properties such as bending strength and fracture toughness are significantly improved.
Claims (4)
粒子を有するＡｌ2Ｏ3 マトリックスの結晶粒内に平均
粒子径２μｍ以下のＴｉＣ微粒子を１〜８体積％分散さ
せたセラミックス中に、平均粒子径２μｍ以下のＺｒＯ
2 微粒子を分散させたことを特徴とするセラミックス複
合材料。1. A ceramic in which 1 to 8% by volume of TiC fine particles having an average particle diameter of 2 μm or less are dispersed in the crystal grains of an Al 2 O 3 matrix having crystal particles having an average particle diameter of 0.2 μm to 10 μm. ZrO with a particle size of 2 μm or less
Ceramic composite material characterized by containing dispersed 2 particles.
％含有するＺｒＯ2１０〜５０体積％、ＴｉＣ １〜８
体積％、残部は平均粒子径５μｍ以下のＡｌ2 Ｏ3 より
なる配合組成を有することを特徴とする請求項１記載の
セラミックス複合材料。2. A stabilizer containing 1 to 3 mol of Y 2 O 3
% ZrO 2 10-50% by volume, TiC 1-8
The ceramic composite material according to claim 1, wherein the volume% and the balance have a compounding composition of Al 2 O 3 having an average particle diameter of 5 μm or less.
ｉＣ １〜８体積％、残部は平均粒子径５μｍ以下のＡ
ｌ2 Ｏ3 よりなる配合組成を有することを特徴とする請
求項１記載のセラミックス複合材料。3. Unstabilized ZrO 2 10-30% by volume, T
iC 1 to 8% by volume, the balance A having an average particle size of 5 μm or less
The ceramic composite material according to claim 1, which has a compounding composition of 1 2 O 3 .
均粒子径２μｍ以下のＴｉＣ及び平均粒子径２μｍ以下
のＺｒＯ2 を請求項２又は請求項３記載の配合組成で混
合し、得られた混合物を成形した後、該成形体を不活性
雰囲気で、１４００℃以上の温度で焼結することを特徴
とするセラミックス複合材料の製造方法。4. An Al 2 O 3 having an average particle diameter of 5 μm or less, a TiC having an average particle diameter of 2 μm or less and a ZrO 2 having an average particle diameter of 2 μm or less are mixed with the compounding composition according to claim 2 or 3, and thus obtained. A method for producing a ceramic composite material, comprising: molding the mixture, and then sintering the molded body in an inert atmosphere at a temperature of 1400 ° C. or higher.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4151176A JPH05319910A (en) | 1992-05-20 | 1992-05-20 | Ceramic composite material and its production |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4151176A JPH05319910A (en) | 1992-05-20 | 1992-05-20 | Ceramic composite material and its production |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH05319910A true JPH05319910A (en) | 1993-12-03 |
Family
ID=15512969
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP4151176A Pending JPH05319910A (en) | 1992-05-20 | 1992-05-20 | Ceramic composite material and its production |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH05319910A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2008087986A (en) * | 2006-09-29 | 2008-04-17 | Nippon Tungsten Co Ltd | Composite ceramic |
| KR20150027739A (en) * | 2013-08-08 | 2015-03-12 | 니뽄 도쿠슈 도교 가부시키가이샤 | Ceramic composition and cutting tool |
| US20180170811A1 (en) * | 2015-06-17 | 2018-06-21 | National Institute For Materials Science | Oxidation-induced self-healing ceramic composition containing healing activator, method for producing same, use of same, and method for enhancing functionality of oxidation-induced self-healing ceramic composition |
-
1992
- 1992-05-20 JP JP4151176A patent/JPH05319910A/en active Pending
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2008087986A (en) * | 2006-09-29 | 2008-04-17 | Nippon Tungsten Co Ltd | Composite ceramic |
| KR20150027739A (en) * | 2013-08-08 | 2015-03-12 | 니뽄 도쿠슈 도교 가부시키가이샤 | Ceramic composition and cutting tool |
| US9550699B2 (en) | 2013-08-08 | 2017-01-24 | Ngk Spark Plug Co., Ltd. | Ceramic composition and cutting tool |
| US20180170811A1 (en) * | 2015-06-17 | 2018-06-21 | National Institute For Materials Science | Oxidation-induced self-healing ceramic composition containing healing activator, method for producing same, use of same, and method for enhancing functionality of oxidation-induced self-healing ceramic composition |
| US10822277B2 (en) * | 2015-06-17 | 2020-11-03 | National Institute For Materials Science | Oxidation-induced self-healing ceramic composition containing healing activator, method for producing same, use of same, and method for enhancing functionality of oxidation-induced self-healing ceramic compositions |
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