JPS5836976A - High tenacity zirconia sintered body - Google Patents

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】 本発明はＺｒ０１とＡｌｓへ等よりなる高靭性ジルコニ
ア焼結体に関する。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a high toughness zirconia sintered body made of Zr01, Als, etc.

従来セライック材料の最大の短所は抗折力の弱さであり
、若しこれが改善され＼ば、切削工具や人工骨材や、ま
た社内燃機関の部品等に使用して大１１す効果があげら
れるため、多くの研究者がζＯ間ＩＮＫ取り組んできた
０例えば、Ｙ。The biggest drawback of conventional Ceric materials is their low transverse rupture strength, but if this could be improved, they could be used for cutting tools, artificial aggregates, and parts for in-house combustion engines, etc., and would be highly effective. Many researchers have been working on INK between ζ0 and Y, for example.

Ｃａ＊Ｍｇ等の酸化物で部分安定化したＺｒＯｓが特開
昭１１−　＃（１７ｔＪ号「ジル：２：Ｍ−ア質切削工
具材」として開示され、正方晶系と等軸重系の含量が４
０〜り！重量−であることが報告されている。ZrOs partially stabilized with oxides such as Ca*Mg has been disclosed in Japanese Patent Application Laid-open No. 11-17-17 ``Zir:2:M-A quality cutting tool material'', and the content of tetragonal system and equiaxed heavy system. is 4
0~ri! It is reported that the weight is -.

またＺｒＯＣｌｇとｙｃｔｓｏ拠金物を共沈させ、その
粉末を仮焼してＹｊ　ｏｓで安定化したＺｒ０ｍの微粉
末を焼結すれば高強度のＺｒ０１焼結体の得られること
が米国に於いて発行されたセラ書ツクプリティン１２７
４年！ｊ巻の７／７真においてＪ、　８゜Ｒｅｅｄによ
シ発表せられている。然し、これらは何れも強度の面で
満足なものではなく、更に一段と強度を増加すれば大い
に利用範囲を拡大できると考えられる。これを達成する
方法を昭和１４年を月７３日出願の高靭性ジルコニア焼
結体として出願した。In addition, it was published in the United States that a high-strength Zr01 sintered body can be obtained by co-precipitating ZrOClg and yctso metal, calcining the powder, and sintering fine Zr0m powder stabilized with Yjos. Sera Book Tsukupritin 127
4 years! It was announced by J, 8゜Reed in 7/7 of volume J. However, none of these are satisfactory in terms of strength, and it is thought that the range of use can be greatly expanded if the strength is further increased. A method for achieving this was filed as a high-toughness zirconia sintered body on May 73, 1945.

つまり、ＡＩ！ＯａがＺｒ０ｇに同情・分散することに
よって正方晶のＺｒ０１が単斜晶に転移する温度を下げ
、Ｚｒ０１の粒成長を抑制し、これが正方晶Ｚｒ０ｚの
含有量を高め、かつＺｒＯｓ粒界での滑り抵抗を増加し
、硬度を増し高温強度を約−倍にも高めることができる
ことを見いだしている。In other words, AI! By sympathizing and dispersing Oa with Zr0g, the temperature at which tetragonal Zr01 transforms to monoclinic is lowered, and the grain growth of Zr01 is suppressed, which increases the content of tetragonal Zr0z and prevents slipping at ZrOs grain boundaries. It has been found that resistance can be increased, hardness can be increased, and high temperature strength can be increased by about - times.

しかし、前出願においては各成分は湿式混合法によって
混合されたが、各成分の分散り完全でなく、その為に局
部的に組織的不均一を生じたり、マイクロポアを生じて
いた。However, in the previous application, each component was mixed by a wet mixing method, but each component was not completely dispersed, resulting in local structural non-uniformity and micropores.

そヒでＺｒ０ｚ　を安定化剤ｅ　Ａｌｔｏｓの各成分を
より理想的に分散させる為に共沈法によって原料を得、
焼成テストを行った。その結果微粒、均一な組織を有し
、マイクロポアの＃徽とんどない焼結体が得られ、強度
も約１ｚｏｈ／■２と従来のセラｔツクスでは考えられ
ない高強度を示すことを見いだし、本発明を完成した。In order to more ideally disperse each component of Zr0z as a stabilizer e Altos, raw materials were obtained by coprecipitation method.
A firing test was conducted. As a result, a sintered body with fine grains, a uniform structure, and almost no micropores was obtained, and the strength was approximately 1 ZOH/2, which is unimaginable with conventional ceramics. and completed the present invention.

、その要−旨は特許請求範囲の通）のものである。こ＼
でＡｌ５Ｏａの含有量はａｔ重量ｔｓ（以下「重量」を
省く）以下では添加効果が乏しく、４ｏチ以上では靭性
あるＺｒ０１の含有量を低め、強度、靭性共に不満足と
なる。, the gist of which is contained in the claims. child\
If the content of Al5Oa is less than at weight ts (hereinafter "weight" is omitted), the addition effect will be poor, and if it is more than 4o, the content of Zr01, which has toughness, will be lowered, resulting in unsatisfactory strength and toughness.

また、Ｚｒ０１の結晶相は正方晶系と立方晶系との合量
の比率が１０４以上必要で、これ以下でれ靭性が低く、
マた正方晶系と立方晶系の比率が１８３以上であること
が必要で、これ以下では靭性が不足である。また焼結体
の平均結晶粒径ｌｉＪμ以下であることが必要でＪμを
超えると正方晶系が挙斜晶系に変〕靭性を低下する。In addition, the crystal phase of Zr01 needs to have a total ratio of tetragonal and cubic crystals of 104 or more, and if it is less than this, the shear toughness is low.
It is necessary that the ratio of tetragonal system to cubic system is 183 or more, and if it is less than this, the toughness is insufficient. It is also necessary that the average crystal grain size of the sintered body is not more than li Jμ; if it exceeds Jμ, the tetragonal system changes to the orthoclinic system, and the toughness decreases.

また許容できる不純物は８１０ｓでＪ−迄、Ｆｅａｒｓ
またはＴｉ１ｌで幻−迄、合計でＪ−迄で、これ以上で
あると焼結性が紡げられ靭性が乏しいものとなる。また
、Ｚｒ０１はその一部以上全部迄ＨｆＯ，によって置換
しても全く同様の特性を示す。Also, allowable impurities are 810s up to J-, Fears
Or, if Ti1l is up to phantom, and the total is up to J-, if it is more than this, the sinterability will be poor and the toughness will be poor. Further, even if Zr01 is partially or completely replaced with HfO, it exhibits exactly the same characteristics.

以下実施例にょシーそう具体的に説明する。Examples will be explained in detail below.

実施例Ｉ 得られる粉末の組成が第１表の割合にな本ように純度タ
ンＰ−のオキシ塩化ジルコニウム（但し、ＺｒＯＨ酸化
物成分中にＪ−７−のＨｆ０ｍ分を含む）のｌ七ル優溶
液に安定化剤としてり寅デーの塩化イツトリウム、塩化
！グネシクム、塩化カルシウムを加え、２灯］の塩化ア
ル建ニウムを加え均一に混合した後、共沈にょ夛混合水
酸化物を得、これを脱水乾燥しｔｏｏｚで仮焼して平均
粒径コク０大の一次粒子粉末を得た。峡粉末ｔ−／、ｊ
ｔｏｎ／ｄで加圧成形し、電気炉にて大気中で１ｕｏｏ
−ｉｔｚｏｃの温度で１時間焼成した。Example I The composition of the powder obtained was as shown in Table 1, and the composition of the powder was as follows. Yttrium chloride, chloride, used as a stabilizer in a good solution! After adding gnesicum and calcium chloride, and adding aluminum chloride (2 lamps) and mixing uniformly, a co-precipitated hydroxide mixture was obtained, which was dehydrated and dried and calcined in a tooz to reduce the average particle size to 0. A large primary particle powder was obtained. gorge powder t-/,j
Pressure molded at ton/d and 1uoo in air in an electric furnace.
-itzoc temperature for 1 hour.

焼成後焼結体を参Ｘ　Ｉ　Ｘ　Ｊｊｍに研胎し第１表に
示す緒特性を測定した。なお、結晶粒径はいずれも平均
Ｊμ以下であったが、焼成温度を第１表に示す以上に高
くすると３２以上に大きく成長し強度は低下した。ｊｌ
ｌｌ／表よシ明らかなように共沈によＦ）　Ａ１ｍ０ａ
を添加することによって正方晶から単斜晶への転移が抑
制され、残留する正方晶が増加して強度および靭性が改
善されていることがわかる。第１表の試料中よシ数種を
選択して硬度および高温抗折力ｔ１１定し、第２表およ
び第１図に示した。これよシ判るようにＡｌ５Ｏｎの、
増加と共に硬度は増加し４０−を配合したム３参ではは
とんどＡｌ５Ｏｓ単昧の磁器と同勢の硬１ｉｔｔ−示し
、また高温強度も同時に比較測定した市販品の部分安定
化ジルコニアＪＲ（米国スーニング社製）に比べて著し
く向上している。After firing, the sintered bodies were ground to a standard temperature and the properties shown in Table 1 were measured. The crystal grain sizes were all below the average Jμ, but when the firing temperature was increased above that shown in Table 1, they grew to 32 or more and the strength decreased. jl
ll/As is clear from the table, due to coprecipitation F) A1m0a
It can be seen that by adding , the transition from tetragonal to monoclinic is suppressed, the remaining tetragonal is increased, and the strength and toughness are improved. The hardness and high-temperature transverse rupture strength t11 of several selected samples from Table 1 were determined and shown in Table 2 and FIG. As you can see, Al5On's
As the hardness increases, the hardness increases, and the hardness of Mu3-3 mixed with 40- is almost the same as that of porcelain containing only Al5Os, and the high-temperature strength was also compared and measured at the same time as the commercially available partially stabilized zirconia JR ( This is a significant improvement compared to the product manufactured by Sooning Co., Ltd. in the United States.

第２表 注ｌ）各種物性の一定法 （１）曲げ強度はＪＩａ　Ｂ亭ｉｏ＃によＣａ１ｌ定、
１本の平均値を示す。Table 2 Note l) Fixed method for various physical properties (1) Bending strength is determined by Cal1l according to JIaBio#,
The average value for one line is shown.

（Ｊ）破壊靭性はムＳＴＭスペシャルテクニカルパプリ
ケーシ璽ンＡ＃１０Ｋ準じ て、中−■、厚さ！■、長さコ！−の 試片に深さくｌ　ｊ　ｍ、巾Ｑ／ｊｗの切欠きを入れ、
スパンコク腸の三点曲げ切欠 き法によって測定した。Ｉｌ定値は各３本の平均値であ
る。(J) Fracture toughness is medium-■, thickness according to Mu STM Special Technical Published Case A#10K! ■、Length! - Make a notch with a depth l j m and a width Q/jw in the specimen,
It was measured by the three-point bending notch method of spankoku intestines. The Il constant value is the average value of each three lines.

（Ｊ）硬［ｔｉＯツクウエルスーパーフイツシャル硬度
針にて荷重＃ｊ−にて一定し た。(J) Hardness [constant at load #j- with a TiO Tsukwell Super Physical Hardness needle.

に）結晶系唸還学電機製ガイガーフレックｘＲＡＤ−ｒ
ＡＩＩを用い、Ｘ線回折法によシ行った。ｔず、　／１
１１ダイヤモンドペーストで鏡両研磨した試片をＸ線 回折し、単斜晶ＺｒＯ虐の［／　／　／］面と〔１１７
１面の積分強度！ｍと、正方晶Ｚｒ０ａの［／／／］面
と立方晶Ｚｒ０ｍの（／／／）面の積分強度の和Ｉｔ＋
Ｉｃ。2) Crystalline Geigerfleck xRAD-r made by Gakuen Gakudenki
This was carried out using X-ray diffraction method using AII. tzu, /1
11 X-ray diffraction of a specimen mirror-polished with diamond paste shows that the [/ / /] plane of monoclinic ZrO and [117
Integrated intensity of one surface! m and the sum of the integrated intensities of the [///] plane of tetragonal Zr0a and the (///) plane of cubic Zr0m It+
Ic.

比から、単斜晶Ｚｒ０１の量を決定した。From the ratio, the amount of monoclinic Zr01 was determined.

ついで焼結体をＪＪＩメツシュ全通迄 粉砕し、同条件でＸ線回折し、再度単 斜晶ＺｒＯ麿と立方晶ｚｒへの積分強ｆ　Ｉ’ｍおよび
Ｉ’ｅを求めた。この際、焼結体中の残留正方晶ＺｒＯ
ｘは粉砕によって機械的応力を受け、すべて単斜晶Ｚｒ
０１に変態すると考えられるので、 Ｉ’ｃ　／　（Ｉ’ｍ　＋　Ｉ’ｃ　）から立方晶Ｚｒ
ＯＨ量が決定され、ついで正方晶Ｚｒ０重量も決定した
。The sintered body was then crushed to a JJI mesh and subjected to X-ray diffraction under the same conditions, and the integral intensities f I'm and I'e of monoclinic ZrO and cubic Zr were determined again. At this time, residual tetragonal ZrO in the sintered body
x is subjected to mechanical stress due to crushing, and all monoclinic Zr
Since it is considered that the transformation to 01 occurs, cubic Zr
The OH amount was determined and then the tetragonal Zr0 weight was also determined.

注コ）試料番号でＲの添字を有するものは比較例である
。Note: Sample numbers with the suffix R are comparative examples.

【図面の簡単な説明】[Brief explanation of the drawing]

鮪１図は実施例Ｉの試料と比較市販品の高温強度を表す
グラフ、ＡＲは比較のための市販品でコーニング社製部
分安定化ジル；ニアである。Figure 1 is a graph showing the high-temperature strength of the sample of Example I and a comparative commercial product, and AR is a commercial product for comparison, Partially Stabilized Zil;Nia manufactured by Corning.

Claims (1)

【特許請求の範囲】[Claims] （１）　　下ｆｆ１Ａ成分′ｆｒ４Ｉ０〜デ灯重量−１
ＩＩＩＳＢ成分ｔ−４１−４０重量−と、場合によシＣ
成分を含有することもある焼結体で、全焼結体の平均結
晶粒径がＳμ以下である仁とｔ％徴と−する高靭性ジル
コニア焼結体。 Ａ　成分：　ＹｍＯｓ　ｔ　ＣａＯｔ　ｈｌｈｉＫ）等
の安定化剤を會むＺｒＯｓで、２０重量−以上が正方晶
系または立方晶系で占められ、正方 晶系と立方晶系の比がｌ：３以上で あるＺｒ０ｓ Ｂ成分：　Ａｌｔｏｓ Ｃ成分：１重量−以下の５ｉｏｎ　＊　”重量−以下の
Ｆｅ５Ｏａまた紘０．２重量−以下のＴｉ０ｍ　を合計
で全体の１重量−以下０）　特許請求の範囲ＩＩ／項に
おいてＺｒ０ｍ　ｍ安定化剤、　Ａ１１０ｍの各成分紘
、各成分Ｏ水Ｓ性塩を、所定の開会にして水溶液の状態
で均一混合された後、共沈させて得られた原料を用いる
ことｔ特徴とする高靭性ジルコニア焼結体・ （Ｊ）　　％許錆求の範囲第７項においてＺｒ０１の一
部または全部をＨｆへで置換した高靭性ジルコニア焼結
体。(1) Lower ff1A component'fr4I0~de lamp weight -1
IIISB component t-41-40 wt- and optionally C
A high-toughness zirconia sintered body which may contain a component and whose average crystal grain size of the entire sintered body is Sμ or less. A component: ZrOs with a stabilizer such as YmOs t CaOt hlhiK), in which more than 20% by weight is occupied by the tetragonal or cubic system, and the ratio of the tetragonal system to the cubic system is 1:3 or more. A certain Zr0s B component: Altos C component: 1 weight - less than 5 ion * "weight - less than 5 ion *" weight - less than 0.2 weight - less than 0.0 m; total of 1 weight - less than 0) Claims II/Claim In this method, the Zr0mm stabilizer, each component of A110m, and each component O, S, and S salt are uniformly mixed in an aqueous solution state in a predetermined manner, and then the raw materials obtained by coprecipitation are used. (J) A high toughness zirconia sintered body in which part or all of Zr01 is replaced with Hf in the desired range of % allowable rust.