JPH02157157A - Zirconia sintered body having superior corrosion resistance and hot water resistrance - Google Patents
Zirconia sintered body having superior corrosion resistance and hot water resistranceInfo
- Publication number
- JPH02157157A JPH02157157A JP63311961A JP31196188A JPH02157157A JP H02157157 A JPH02157157 A JP H02157157A JP 63311961 A JP63311961 A JP 63311961A JP 31196188 A JP31196188 A JP 31196188A JP H02157157 A JPH02157157 A JP H02157157A
- Authority
- JP
- Japan
- Prior art keywords
- zirconia
- hot water
- sintered body
- corrosion resistance
- partially stabilized
- 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
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 title claims abstract description 48
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title abstract description 16
- 230000007797 corrosion Effects 0.000 title abstract description 10
- 238000005260 corrosion Methods 0.000 title abstract description 10
- 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 claims abstract description 15
- 229910002077 partially stabilized zirconia Inorganic materials 0.000 claims abstract description 12
- 239000003381 stabilizer Substances 0.000 claims abstract description 6
- 239000013078 crystal Substances 0.000 claims description 27
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 abstract description 6
- 229910052593 corundum Inorganic materials 0.000 abstract description 5
- 229910001845 yogo sapphire Inorganic materials 0.000 abstract description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 abstract 4
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 abstract 2
- 229910052681 coesite Inorganic materials 0.000 abstract 2
- 229910052906 cristobalite Inorganic materials 0.000 abstract 2
- 239000000377 silicon dioxide Substances 0.000 abstract 2
- 235000012239 silicon dioxide Nutrition 0.000 abstract 2
- 229910052682 stishovite Inorganic materials 0.000 abstract 2
- 229910052905 tridymite Inorganic materials 0.000 abstract 2
- 230000007704 transition Effects 0.000 description 13
- 230000006866 deterioration Effects 0.000 description 11
- 238000005452 bending Methods 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 7
- 230000000694 effects Effects 0.000 description 6
- 238000000034 method Methods 0.000 description 4
- 239000000843 powder Substances 0.000 description 3
- 239000002253 acid Substances 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 239000000919 ceramic Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000005245 sintering Methods 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- OBOSXEWFRARQPU-UHFFFAOYSA-N 2-n,2-n-dimethylpyridine-2,5-diamine Chemical compound CN(C)C1=CC=C(N)C=N1 OBOSXEWFRARQPU-UHFFFAOYSA-N 0.000 description 1
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 1
- 241000219112 Cucumis Species 0.000 description 1
- 235000015510 Cucumis melo subsp melo Nutrition 0.000 description 1
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 1
- 241000277269 Oncorhynchus masou Species 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- FJJCIZWZNKZHII-UHFFFAOYSA-N [4,6-bis(cyanoamino)-1,3,5-triazin-2-yl]cyanamide Chemical compound N#CNC1=NC(NC#N)=NC(NC#N)=N1 FJJCIZWZNKZHII-UHFFFAOYSA-N 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 239000001110 calcium chloride Substances 0.000 description 1
- 229910001628 calcium chloride Inorganic materials 0.000 description 1
- 235000019402 calcium peroxide Nutrition 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
- 238000010586 diagram Methods 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 230000003601 intercostal effect Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000011812 mixed powder Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- CMOAHYOGLLEOGO-UHFFFAOYSA-N oxozirconium;dihydrochloride Chemical compound Cl.Cl.[Zr]=O CMOAHYOGLLEOGO-UHFFFAOYSA-N 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
Landscapes
- Compositions Of Oxide Ceramics (AREA)
Abstract
Description
【発明の詳細な説明】
［産業上の利用分野］
本発明は高強度であって耐食性および熱安定性に優れ、
かつ長時間熱水中に保持しても経時劣化の少ない、すな
わち耐熱水性に優れたジルコニア焼結体に関するもので
ある。[Detailed description of the invention] [Industrial application field] The present invention has high strength, excellent corrosion resistance and thermal stability,
The present invention also relates to a zirconia sintered body that exhibits little deterioration over time even when kept in hot water for a long time, that is, has excellent hot water resistance.
［従来の技術］
従来から高強度セラミックス飼料の１つとして、ジルコ
ニアにＹ２Ｏ３を添加した部分安定化ジルコニアか知ら
れている。しかしながら、この部分安定化ジルコニアは
熱的に不安定であり、大気中２００〜２５０℃で長時間
保持すると結晶の正方晶が単斜晶に相転移し、このため
機械的強度や靭性か低下するという問題かある。[Prior Art] Partially stabilized zirconia, which is obtained by adding Y2O3 to zirconia, has been known as one of the high-strength ceramic feeds. However, this partially stabilized zirconia is thermally unstable, and when kept in the atmosphere at 200-250°C for a long time, the tetragonal crystal phase transitions to monoclinic crystal, resulting in a decrease in mechanical strength and toughness. There is a problem.
これと同様のことか酸、アルカリ水溶液または熱水中に
おいても生しるが、特に１７０〜２００°Ｃの熱水中で
は相転移か促進されることか知られている。A similar phenomenon occurs in acid, alkaline aqueous solutions, or hot water, but it is known that the phase transition is particularly accelerated in hot water at 170 to 200°C.
近年、この温度範囲における劣化（低温劣化）を防くた
めに、Ｙ２Ｏ３添加量の増加したあるいは安定化剤をＹ
２Ｏ３からＣｅＯ２に変更した部分安定化ジルコニアか
研究されている（１９８３年窯業基礎討論会ＩＡ６．１
０項）。そして、Ｙ２０３の他にＣａＯ２およびＡ ｌ
２０３の両者を含む耐熱安定性に優れた部分安定化ジ
ルコニアが得られている（特開昭６ｌ−２１９７５Ｇ
）。しかしなから、Ｙ２Ｏ３含有量を増加したものやＣ
ｅＯ２系部分安定化ジルコニアを安定化剤として用いた
ものは、機械的強度が低い。また、Ｙ２Ｏ３のほかＣｅ
０９およびＡｌ２Ｏ３を併用するものは、多量のＣｅＯ
２を添加しないと効果が発揮されない。この他、Ｙ２Ｏ
３系部分安定化ジルコニアにＡ １２０３．Ｍｇ０．Ｓ
ｉ○２およびＣａＯの４成分を添加して低温劣化を抑
制したものも知られているか（特開昭５９−１１１９７
０ ） 、これも劣化を防ぐには十分てなく、機械的強
度も低いことや添加剤の種類か多いこともあり、経済的
でない。In recent years, in order to prevent deterioration in this temperature range (low-temperature deterioration), the amount of Y2O3 added has increased or stabilizers have been added to Y.
Partially stabilized zirconia in which CeO2 is used instead of 2O3 is being researched (1983 Ceramics Basics Conference IA6.1)
0 terms). In addition to Y203, CaO2 and Al
Partially stabilized zirconia containing both No. 203 and excellent heat resistance stability has been obtained (Japanese Patent Application Laid-Open No. 61-21975G).
). However, there are some products with increased Y2O3 content and C
Those using eO2-based partially stabilized zirconia as a stabilizer have low mechanical strength. In addition to Y2O3, Ce
When 09 and Al2O3 are used together, a large amount of CeO
If 2 is not added, the effect will not be exhibited. In addition, Y2O
A 1203. for 3-system partially stabilized zirconia. Mg0. S
Is there any known product that suppresses low-temperature deterioration by adding the four components i○2 and CaO?
0), this is also not economical because it is not sufficient to prevent deterioration, has low mechanical strength, and requires many types of additives.
以上述べてきたように、Ｙ２Ｏ３によって部分安定化し
たジルコニアには、優れた耐食性耐熱安定性および耐熱
水性を示し、かつ高い機械的強度を有するものかないの
が現状である。As described above, at present, there is no zirconia partially stabilized by Y2O3 that exhibits excellent corrosion resistance, heat stability, and hot water resistance, and has high mechanical strength.
［発明か解決しようとする課題］
本発明はこのような背景および状況において、優れた耐
食性、耐熱安定性および耐熱水性を示し、かつ高い機械
的強度を有するＹ２Ｏ３系部分安定化ジルコニアを提供
することにある。[Problems to be Solved by the Invention] In view of the above background and circumstances, the present invention provides a partially stabilized Y2O3-based zirconia that exhibits excellent corrosion resistance, heat-resistant stability, and hot water resistance, and has high mechanical strength. It is in.
［課題を解決するための手段および作用］本発明は、安
定化剤としてＹ２０．を２５〜５ ｍｏ１％含む主とし
て正方晶からなる部分安定化ジルコニア、ＡＩ２０３
０．０５〜６０ｗｔ％およびＣａＯ０，０１〜０．４ｗ
ｔ％からなり、５ｉｎ２含有量は０．０５ｗｔ％未満で
あり、平均結晶粒径か０．３μｍ以下であるジルコニア
焼結体、を要旨とするものである。[Means and effects for solving the problems] The present invention uses Y20. AI203, partially stabilized zirconia mainly consisting of tetragonal crystals containing 25 to 5 mo1% of
0.05-60wt% and CaO0.01-0.4w
t%, the 5in2 content is less than 0.05wt%, and the average crystal grain size is 0.3 μm or less.
以下、本発明をさらに詳細に説明する。The present invention will be explained in more detail below.
本発明における部分安定化ジルコニアは、十分な機械的
強度および靭性をもたせるために、主として正方晶から
なるものでなければならない。とくに正方晶 ７０％以
上のものが望ましい。この他の結晶相として、単斜晶や
立方晶か含まれていてもかまわない。The partially stabilized zirconia in the present invention must be mainly composed of tetragonal crystals in order to have sufficient mechanical strength and toughness. In particular, it is desirable to have 70% or more tetragonal crystals. Other crystal phases may include monoclinic or cubic.
Ｙ２Ｏ３は、正方晶のジルコニアを室温まで保持するた
めに必要な安定化剤であるか、２．５ｍｏ１％より少な
いと焼結体の熱安定性および耐熱水性を十分には向上さ
せることかできす、いっぽう、５ｍｏ１％より多いと結
晶か立方晶からなるジルコニアとなって機械的強度か低
下する。Y2O3 is a necessary stabilizer to keep tetragonal zirconia up to room temperature, or if it is less than 2.5 mo1%, it can sufficiently improve the thermal stability and hot water resistance of the sintered body. On the other hand, if the amount is more than 5 mo1%, zirconia will be made of crystals or cubic crystals, resulting in a decrease in mechanical strength.
Ａ１□０３は、正方晶のジルコニアが単斜晶に転移する
温度を下げ、ジルコニアの粒成長を抑制し、かつジルコ
ニア粒界での滑り抵抗を増加させて高温強度を高める作
用があるが、０．０５ｖｔ９ｇより少ないとこの添加効
果が十分でなく、６０ｗｔ％より多いと靭性の高い上記
ジルコニアの含有量を低めることとなって機械的強度、
靭性共に十分な焼結体とすることができない。しかし、
その含有量が５ｗｔ％以上になると耐食性、耐熱安定性
および耐熱水性に差のないことから、０．０５〜５ｗＬ
％でよい。A1□03 has the effect of lowering the temperature at which tetragonal zirconia transforms to monoclinic, suppressing zirconia grain growth, and increasing the slip resistance at zirconia grain boundaries to increase high-temperature strength. If it is less than .05vt9g, the effect of this addition will not be sufficient, and if it is more than 60wt%, the content of zirconia, which has high toughness, will be lowered and the mechanical strength will be reduced.
It is not possible to form a sintered body with sufficient toughness. but,
When the content is 5 wt% or more, there is no difference in corrosion resistance, heat resistance stability, and hot water resistance, so 0.05 to 5 wL
% is fine.
ＣａＯは、正方晶ジルコニアを得るための安定化剤とし
ても、または焼結助剤としても知られている。Ｙ２Ｏ３
と併用する場合は、Ｙ２Ｏ３系ジルコニア焼結体の焼結
助剤として寄与することとなる。０．０１．ｗｔ％より
少ないと添加効果は見られず、０．４ｗｔ％より多くな
るとジルコニアの粒成長か促進され、平均結晶粒径０．
３μｍ以下の焼結体とするのが困難になる。CaO is also known as a stabilizer for obtaining tetragonal zirconia or as a sintering aid. Y2O3
When used in combination with Y2O3-based zirconia sintered body, it contributes as a sintering aid for Y2O3-based zirconia sintered body. 0.01. If it is less than 0.4 wt%, no effect is observed, and if it is more than 0.4 wt%, grain growth of zirconia is promoted, and the average crystal grain size is 0.4 wt%.
It becomes difficult to form a sintered body with a diameter of 3 μm or less.
５ｉｎ２は、ジルコニア中に０．０５ｗｔ％以上含まれ
ると、Ａｌ２Ｏ３と共にジルコニア粒界にガラス相を形
成して熱安定性および耐食性を低下させる。When 5in2 is contained in zirconia in an amount of 0.05 wt% or more, it forms a glass phase together with Al2O3 at the zirconia grain boundaries, reducing thermal stability and corrosion resistance.
平均結晶粒径か０．３μｍをこえると、ＡＩ。０３やＣ
ａＯを含有させても熱安定性および耐熱水性が向上しな
いので好ましくない。When the average crystal grain size exceeds 0.3 μm, AI occurs. 03 and C
Even if aO is contained, thermal stability and hot water resistance are not improved, so it is not preferable.
本発明の焼結体は、例えば、所定量の原料の混合粉末を
ラバープレス法、射出成形法、金形成形法、押出成形法
などの周知の方法で成形して所望の成形体を作り、この
成形体を加熱炉に入れ、１３００〜１５００°Ｃて焼成
して製造することかできる。The sintered body of the present invention can be produced by forming a desired molded body by molding a predetermined amount of mixed powder of raw materials by a well-known method such as a rubber press method, an injection molding method, a metal molding method, or an extrusion molding method. This molded body can be placed in a heating furnace and fired at 1300 to 1500°C to produce the molded body.
［発明の効果］
以上の説明から明らかなように、本発明のジルコニア焼
結体は、従来のＹ２Ｏ３系部分安定化ンルコニア焼結体
が不安定とされる温度に長肋間さらされてもほとんど劣
化することなく、上記の従来の焼結体を激しく劣化させ
る酸、アルカリ、熱水などの中においても高い安定性と
機械的強度を示すため、その実用上の価値は大なるもの
かある。[Effects of the Invention] As is clear from the above explanation, the zirconia sintered body of the present invention hardly deteriorates even when exposed to long intercostal temperatures at which conventional Y2O3-based partially stabilized luconia sintered bodies are considered unstable. It has great practical value because it exhibits high stability and mechanical strength even in acids, alkalis, hot water, etc., which severely deteriorate the conventional sintered bodies, without causing any damage.
［実施例］ 以下、実施例により本発明の詳細な説明する。[Example] Hereinafter, the present invention will be explained in detail with reference to Examples.
製造例
第１表（本発明刊）および第２表（比較刊）に示す組成
の部分安定化ジルコニア焼結体を以下のようにして作製
した。ずなイっち、ます、純度９９．９ｗｔ％のオキシ
塩化ジルコニウム。Production Example Partially stabilized zirconia sintered bodies having the compositions shown in Table 1 (published by the present invention) and Table 2 (published by the comparative publication) were produced as follows. Zunaichi, Masu, zirconium oxychloride with a purity of 99.9wt%.
塩化イツトリウムおよび塩化カルシウムからなる水溶液
の加水分解によって得られたジルコニアゾル溶液を凝縮
させて沈澱をえ、これを脱水・乾燥し、９００°Ｃで仮
焼して部分安定化シルコア粉末を得た。この粉末の比表
面積は、１５ｒｒ？／ｇてあった。この粉末に純度９９
．９ ｗ ｔ％のＡｌ２０．および純度９９．９ｗｔ％
の５１０２を加え、湿式混合後、乾燥させたちのを−，
３ｔｏｎ／ ｃｎＹの圧力で等方向に成型し、１４００
〜１５５０°Ｃで大気中２時間焼成した。A zirconia sol solution obtained by hydrolysis of an aqueous solution consisting of yttrium chloride and calcium chloride was condensed to form a precipitate, which was dehydrated and dried and calcined at 900°C to obtain a partially stabilized silcore powder. The specific surface area of this powder is 15rr? /g was there. This powder has a purity of 99
．． 9 wt% Al20. and purity 99.9wt%
5102 was added, and after wet mixing, the mixture was dried.
Molded in the same direction with a pressure of 3 tons/cnY, 1400
It was baked at ~1550°C for 2 hours in the air.
こうして得た焼結体を３Ｘ４Ｘ４０ｍｍに切断し、研磨
し、加工したものを試験片とした。The thus obtained sintered body was cut into 3×4×40 mm, polished, and processed to give test pieces.
焼結体における単斜晶および正方晶の割合を第′３表お
よび第４表の試験前の欄に示す。The proportions of monoclinic and tetragonal crystals in the sintered bodies are shown in the pre-test columns of Tables 3 and 4.
試験例 ］
熱劣化試験を、オートクレーブを用いて１７０ ’Ｃの
熱水中に２４時間保持する方法で行った。そして、試験
前と試験後の焼結体表面の結晶（１１および曲げ強度を
測定した。結晶相の定Ｈ１ｌｌｉ定は、Ｘ線回折測定法
により行った。すなわち、ｌｌｉ斜晶の（１１１）面と
（１１■）面の積分強度ＩＭと、正方晶の（１］、 １
． ）面の積分強度１１゛、立方晶の（１１］、 ）面
の積分強度ＩＣから単斜晶量か次のように求まる。Test Example] A thermal deterioration test was conducted by holding the sample in hot water at 170'C for 24 hours using an autoclave. Then, the crystal (11) and bending strength on the surface of the sintered body before and after the test were measured. and the integrated intensity IM of the (11■) plane, and the (1], 1 of the tetragonal crystal.
．． The integrated intensity of the ) plane is 11゛, the integrated intensity of the cubic crystal is (11], and the monoclinic content is determined from the integrated intensity IC of the ) plane as follows.
＋１１斜晶量（％）−
ｆｌＭ ／ （ＩＭ ＋ＩＴ ＋ Ｉｃ ） ］ Ｘ１
００次に、焼結体を微粉砕し、Ｘ線回折にょる単斜晶お
よび立方晶の積分強度ＩＭ’ およびＩｃ′がら立方品
量か次のように求まる。+11 Clinic crystal content (%) - flM / (IM +IT + Ic) ] X1
Next, the sintered body is finely pulverized, and the cubic mass is determined from the integrated intensities IM' and Ic' of monoclinic and cubic crystals as determined by X-ray diffraction as follows.
立方品量（％）＝
ＮＣ’ ／ （ＩＭ’ ＋ＩＣ’ ） ｌ Ｘ１００」
二記の微粉砕によって正方晶はすべて単斜晶に相転移し
たとみなぜるので、正方晶は以下のように求まる。Cubic quantity (%) = NC' / (IM' + IC') l X100
It is assumed that all the tetragonal crystals undergo a phase transition to monoclinic crystals due to the fine pulverization described in Section 2, so the tetragonal crystals can be determined as follows.
正方晶量（％）＝
ＯＯ−（上記ｑ１斜晶瓜＋上記正方晶凰）試験結果を第
３表および第４表に示す。Amount of tetragonal crystals (%) = OO- (the above q1 crystalline melon + the above tetragonal crystal) The test results are shown in Tables 3 and 4.
これらの表において、本発明制である試料Ｎｏ、１〜１
２は、試験後においても相転移が小さく、曲げ強度にも
劣化は認められず、これに対し、Ｙ２Ｏ３が２ｍｏ１％
である比較４４ Ｎ ｏ 。In these tables, sample Nos. 1 to 1 according to the present invention
2 had a small phase transition even after the test, and no deterioration was observed in bending strength. In contrast, Y2O3 was 2mol1%
Comparison 44 No.
］は、試験後において相転移が進んでおり、曲げ強度に
も劣化が見られる。逆にＹ２Ｏ３か６ｍｏ１％のもの（
比較祠Ｎｏ、１２）は、試験後において相転移は生じて
いないが、曲げ強度が低く、実用的でない。], the phase transition has progressed after the test, and deterioration in bending strength is also observed. On the contrary, Y2O3 or 6mo1% (
Comparative shrine No. 12) did not undergo a phase transition after the test, but had low bending strength and was not practical.
Ａｌ２Ｏ３およびＣａＯのいずれの含有量も小さずぎる
もの（比較４Ａ Ｎｏ、２） 、ＣａＯ含有量の小さす
きるもの（比較月Ｎｏ、３Ｎｏ、６） 、ＡＩ。０３含
有量の小さすぎるもの（比較）ｊＡ’Ｎｏ、４．１０．
１１）は相転移が進んでおり、曲げ強度にも劣化が認め
られる。Those in which the contents of both Al2O3 and CaO are too small (Comparison 4A No. 2), those in which the CaO content is too small (Comparison Month No. 3, No. 6), AI. 03 content is too small (comparison)jA'No, 4.10.
In No. 11), the phase transition has progressed, and deterioration in bending strength is also observed.
また、ＣａＯが０．４ｗｔ％より多く含まれるもの（比
較祠Ｎ０１７）あるいは１５５０℃で焼成したもの（比
較月Ｎｏ、５）は粒成長が進み、０．３１ｔｍをこえて
いるため、相転移が大きく進む。５ｉｎ２か０．０５ｗ
ｔ％以上含まれる試料（比較４４Ｎｏ 、 ８ 、 ９
）も相転移が進んでいる。In addition, in those containing more than 0.4 wt% of CaO (comparative shrine No. 017) or those fired at 1550°C (comparative month No. 5), grain growth progresses and the grain size exceeds 0.31 tm, so phase transition occurs. Go big. 5in2 or 0.05w
Samples containing t% or more (Comparison No. 44, No. 8, No. 9)
) is also undergoing a phase transition.
以上のことから本発明によるジルコニア焼結体は優れた
耐熱水性を有することが分る。From the above, it can be seen that the zirconia sintered body according to the present invention has excellent hot water resistance.
試験例 ２
製造例の第１表および第２表にそれぞれ示した本発明４
月の試料Ｎｏ、３．６，１０．１．１および比較祠の試
料Ｎｏ、１．２，３．４を用いて、２５０℃における熱
エージング試験を行った。その結果を第１図に示す。Test Example 2 Invention 4 shown in Table 1 and Table 2 of Manufacturing Examples, respectively
A heat aging test was conducted at 250° C. using Moon sample No. 3.6, 10.1.1 and comparative shrine sample No. 1.2, 3.4. The results are shown in FIG.
この図より比較祠Ｎｏ、］、、２．３および４は、いず
れも時間と共に相転移か大きく進む。From this figure, the phase transition of comparative shrines Nos. 2, 2, 3 and 4 significantly progresses over time.
これに対し、本発明祠Ｎｏ、３．６．１０および１１は
、いずれも相転移か小さいことか分る。On the other hand, it can be seen that the present invention shrines No. 3, 6, 10, and 11 all have small phase transitions.
従って、本発明の焼結体は優れた耐熱性を有していると
言える。Therefore, it can be said that the sintered body of the present invention has excellent heat resistance.
試験例 ３
試験例２と同じ試料を用いて１００℃、３０ｗｔ％Ｈ，
Ｓｏ４に対する耐食性試験をつぎのようにして行った。Test Example 3 Using the same sample as Test Example 2, 100°C, 30wt%H,
A corrosion resistance test for So4 was conducted as follows.
すなわち、試料を３０ｗｔ％Ｈ，Ｓｏ、溶液中に３０日
間浸漬した後、試料表面の単斜晶量および曲げ強度をｆ
ｌｌｌｌ定した。That is, after immersing the sample in a 30 wt% H, So solution for 30 days, the amount of monoclinic crystals and bending strength on the sample surface were determined by f.
lllll determined.
試験結果を第５表に示す。この表より比較材Ｎｏ、］、
、２．３および４は、いずれも相転移が大きく進むこと
か分る。これに対し、本発明祠Ｎｏ、３．６．１０およ
び１］は、いずれも相転移か小さく、曲げ強度にも劣化
は認められない。従って本発明の焼結体は耐食性に優れ
ていることか分る。The test results are shown in Table 5. From this table, comparative material No.],
, 2.3 and 4, it can be seen that the phase transition progresses greatly. On the other hand, in the present invention shrines No. 3.6.10 and 1], the phase transition was small, and no deterioration was observed in the bending strength. Therefore, it can be seen that the sintered body of the present invention has excellent corrosion resistance.
第１図は、 試験例２における熱劣化試験の時 間と単斜晶の量との関係を示した図である。 Figure 1 shows During the thermal deterioration test in Test Example 2 FIG. 4 is a diagram showing the relationship between the monoclinic crystal content and the amount of monoclinic crystals.
Claims (1)
％含む主として正方晶からなる部分安定化ジルコニア，
Ａｌ＿２Ｏ＿３０．０５〜６０ｗｔ％およびＣａＯ０．
０１〜０．４ｗｔ％からなり、ＳｉＯ＿２含有量は０．
０５ｗｔ％未満であり、平均結晶粒径が０．３μｍ以下
であることを特徴とする、ジルコニア焼結体。(1) 2.5-5 mol of Y_2O_3 as a stabilizer
Partially stabilized zirconia consisting mainly of tetragonal crystals containing %
Al_2O_30.05-60wt% and CaO0.
01 to 0.4 wt%, and the SiO_2 content is 0.01 to 0.4 wt%.
A zirconia sintered body, characterized in that the amount thereof is less than 0.05 wt% and the average crystal grain size is 0.3 μm or less.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63311961A JP2762495B2 (en) | 1988-12-12 | 1988-12-12 | Zirconia sintered body with excellent corrosion resistance and hot water resistance |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63311961A JP2762495B2 (en) | 1988-12-12 | 1988-12-12 | Zirconia sintered body with excellent corrosion resistance and hot water resistance |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH02157157A true JPH02157157A (en) | 1990-06-15 |
| JP2762495B2 JP2762495B2 (en) | 1998-06-04 |
Family
ID=18023521
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP63311961A Expired - Fee Related JP2762495B2 (en) | 1988-12-12 | 1988-12-12 | Zirconia sintered body with excellent corrosion resistance and hot water resistance |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2762495B2 (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2012528782A (en) * | 2009-06-03 | 2012-11-15 | サン−ゴバン サントル ド レシェルシュ エ デテュド ユーロペアン | Sintered products based on alumina and zirconia |
| US8425809B2 (en) | 2008-10-15 | 2013-04-23 | Loughborough University | Deformable granule production |
| WO2023190119A1 (en) * | 2022-03-31 | 2023-10-05 | 第一稀元素化学工業株式会社 | Zirconia powder, sintered zirconia object, and method for producing sintered zirconia object |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS59111976A (en) * | 1982-12-14 | 1984-06-28 | 松下電器産業株式会社 | Zirconia ceramics |
| JPS6126562A (en) * | 1984-07-18 | 1986-02-05 | 東ソー株式会社 | Zirconia sintered body |
| JPS6212662A (en) * | 1985-07-08 | 1987-01-21 | 株式会社ノリタケカンパニーリミテド | High toughness zirconia base sintered body |
-
1988
- 1988-12-12 JP JP63311961A patent/JP2762495B2/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS59111976A (en) * | 1982-12-14 | 1984-06-28 | 松下電器産業株式会社 | Zirconia ceramics |
| JPS6126562A (en) * | 1984-07-18 | 1986-02-05 | 東ソー株式会社 | Zirconia sintered body |
| JPS6212662A (en) * | 1985-07-08 | 1987-01-21 | 株式会社ノリタケカンパニーリミテド | High toughness zirconia base sintered body |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8425809B2 (en) | 2008-10-15 | 2013-04-23 | Loughborough University | Deformable granule production |
| JP2012528782A (en) * | 2009-06-03 | 2012-11-15 | サン−ゴバン サントル ド レシェルシュ エ デテュド ユーロペアン | Sintered products based on alumina and zirconia |
| WO2023190119A1 (en) * | 2022-03-31 | 2023-10-05 | 第一稀元素化学工業株式会社 | Zirconia powder, sintered zirconia object, and method for producing sintered zirconia object |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2762495B2 (en) | 1998-06-04 |
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