JPH01224264A - Production of zirconia-reinforced alumina ceramics - Google Patents
Production of zirconia-reinforced alumina ceramicsInfo
- Publication number
- JPH01224264A JPH01224264A JP63049271A JP4927188A JPH01224264A JP H01224264 A JPH01224264 A JP H01224264A JP 63049271 A JP63049271 A JP 63049271A JP 4927188 A JP4927188 A JP 4927188A JP H01224264 A JPH01224264 A JP H01224264A
- Authority
- JP
- Japan
- Prior art keywords
- zirconia
- crystal
- oxide
- crystals
- reinforced alumina
- 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.)
- Pending
Links
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 title claims abstract description 38
- 239000000919 ceramic Substances 0.000 title claims description 27
- 238000004519 manufacturing process Methods 0.000 title claims description 8
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims abstract description 90
- 239000013078 crystal Substances 0.000 claims abstract description 29
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims abstract description 21
- 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 17
- 239000000395 magnesium oxide Substances 0.000 claims abstract description 15
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229910001404 rare earth metal oxide Inorganic materials 0.000 claims abstract description 9
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims abstract description 8
- 238000002156 mixing Methods 0.000 claims abstract description 6
- 239000010987 cubic zirconia Substances 0.000 claims abstract description 4
- 238000010298 pulverizing process Methods 0.000 claims abstract description 4
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims abstract description 3
- 229910001928 zirconium oxide Inorganic materials 0.000 claims abstract description 3
- 238000010304 firing Methods 0.000 claims description 4
- 238000000465 moulding Methods 0.000 claims description 2
- 239000000203 mixture Substances 0.000 abstract description 7
- 239000000463 material Substances 0.000 abstract description 3
- 238000001354 calcination Methods 0.000 abstract 1
- 238000002845 discoloration Methods 0.000 abstract 1
- 239000000843 powder Substances 0.000 description 17
- 235000012245 magnesium oxide Nutrition 0.000 description 11
- 238000000034 method Methods 0.000 description 8
- 239000002245 particle Substances 0.000 description 8
- 239000003381 stabilizer Substances 0.000 description 8
- 239000000126 substance Substances 0.000 description 8
- 238000005452 bending Methods 0.000 description 6
- 229960000869 magnesium oxide Drugs 0.000 description 6
- 230000000694 effects Effects 0.000 description 5
- 230000007423 decrease Effects 0.000 description 4
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 4
- 239000001095 magnesium carbonate Substances 0.000 description 4
- 229910000021 magnesium carbonate Inorganic materials 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 2
- 239000004372 Polyvinyl alcohol Substances 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 239000011362 coarse particle Substances 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000000227 grinding Methods 0.000 description 2
- UHNWOJJPXCYKCG-UHFFFAOYSA-L magnesium oxalate Chemical compound [Mg+2].[O-]C(=O)C([O-])=O UHNWOJJPXCYKCG-UHFFFAOYSA-L 0.000 description 2
- 229920002451 polyvinyl alcohol Polymers 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 238000005245 sintering Methods 0.000 description 2
- 229910003320 CeOx Inorganic materials 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 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
- 230000008859 change Effects 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 239000010432 diamond Substances 0.000 description 1
- 229910003460 diamond Inorganic materials 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 229910052735 hafnium Inorganic materials 0.000 description 1
- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical compound [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 150000004677 hydrates Chemical class 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- UEGPKNKPLBYCNK-UHFFFAOYSA-L magnesium acetate Chemical compound [Mg+2].CC([O-])=O.CC([O-])=O UEGPKNKPLBYCNK-UHFFFAOYSA-L 0.000 description 1
- 239000011654 magnesium acetate Substances 0.000 description 1
- 235000011285 magnesium acetate Nutrition 0.000 description 1
- 229940069446 magnesium acetate Drugs 0.000 description 1
- 239000004337 magnesium citrate Substances 0.000 description 1
- 229960005336 magnesium citrate Drugs 0.000 description 1
- 235000002538 magnesium citrate Nutrition 0.000 description 1
- 150000002681 magnesium compounds Chemical class 0.000 description 1
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 1
- 239000000347 magnesium hydroxide Substances 0.000 description 1
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 1
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 1
- 229960003390 magnesium sulfate Drugs 0.000 description 1
- 235000019341 magnesium sulphate Nutrition 0.000 description 1
- 229940091250 magnesium supplement Drugs 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000011029 spinel Substances 0.000 description 1
- 229910052596 spinel Inorganic materials 0.000 description 1
- 238000001694 spray drying Methods 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- PLSARIKBYIPYPF-UHFFFAOYSA-H trimagnesium dicitrate Chemical compound [Mg+2].[Mg+2].[Mg+2].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O.[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O PLSARIKBYIPYPF-UHFFFAOYSA-H 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Abstract
Description
【発明の詳細な説明】
（産業上の利用分野）
本発明は機械的強度、破壊靭性等に優れたジルコニア強
化アルミナセラミックスの製造法に関する。DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to a method for producing zirconia-reinforced alumina ceramics having excellent mechanical strength, fracture toughness, and the like.
（従来の技術）
アルミナセラミックスは一般的なセラミックスより機械
的強度、耐薬品性、耐摩耗性に優れ、比較的安価なため
９機械部材として広く使用されている。しかし近年用途
が拡大するとともに、より過酷な条件で使用されるよう
になり、よし高性能のアルミナセラミックスが必ｌ！に
なってきた。アルミナセラミックスの高性能化法の一つ
にアルミナセラミックス中にジルコニアを分散して機械
的強度、破壊靭性等を向上させる方法がある（ジルコニ
ア強化アルミナセラミックス）。。(Prior Art) Alumina ceramics have better mechanical strength, chemical resistance, and wear resistance than general ceramics, and are relatively inexpensive, so they are widely used as mechanical parts. However, as its applications have expanded in recent years, it has come to be used under harsher conditions, making high-performance alumina ceramics a must! It has become. One method for improving the performance of alumina ceramics is to disperse zirconia in alumina ceramics to improve mechanical strength, fracture toughness, etc. (zirconia-reinforced alumina ceramics). .
このようなジルコニア強化アルミナセラミックスはよく
知られており、以下の２種類に大別できる。Such zirconia-reinforced alumina ceramics are well known and can be broadly classified into the following two types.
（１）特公昭５９−２５７４８号公報に示されるように
焼結温度域から室温に冷却する過程でジルコニアを正方
晶から単斜晶に相転移させ、その際発生するマイクロク
ラックにより靭性を向上させたもの。(1) As shown in Japanese Patent Publication No. 59-25748, zirconia undergoes a phase transition from tetragonal to monoclinic in the process of cooling from the sintering temperature range to room temperature, and the toughness is improved by the microcracks generated at this time. Something.
（２）米国特許第４３１６９６４号明細書に示されるよ
うに室温においては準安定相である正方晶ジルコニアを
、結晶粒径を約０．５μｍ以下ＫＬ＆す、安定化剤を用
いるなどの方法で焼結体中に安定して存在させることに
より靭性を向上させたもの。(2) As shown in U.S. Pat. No. 4,316,964, tetragonal zirconia, which is a metastable phase at room temperature, is sintered by reducing the crystal grain size to about 0.5 μm or less, using a stabilizer, etc. Improved toughness by stably existing in the structure.
このうち（１）のものは、靭性は向上するが９強度はさ
ほど改善されず、ジルコニアの添加量が多すぎると逆に
靭性及び強度が低下するという欠点が生じる。Among these, (1) improves toughness but does not significantly improve strength, and has the disadvantage that if too much zirconia is added, toughness and strength decrease.
これに対しく２）のものは、靭性が向上すると共に強度
も向上するという優れたものである。（２）の方法にお
いて、ジルコニアの結晶粒径を０．５μｍ以下に制御し
て正方晶ジルコニアを安定に存在させることの困難さか
ら、安定化剤を添加して正方晶ジルコニアを安定化させ
ることが多く行なわれている。この安定化剤としてはＭ
ｇＯ，Ｃａｂ、 ＹｘＯｓ。On the other hand, the material 2) is superior in that both toughness and strength are improved. In method (2), it is difficult to control the crystal grain size of zirconia to 0.5 μm or less and make tetragonal zirconia stably exist, so a stabilizer is added to stabilize the tetragonal zirconia. is being done a lot. As this stabilizer, M
gO, Cab, YxOs.
Ｃｅｎｔｓ Ｌａ５ｈｓ ＊ Ｅｒａ’ｓなどが公知で
ある。Cents La5hs*Era's and the like are known.
Ｃｅｎｔを安定化剤として用いた正方晶ジルコニアセラ
ミックスは、特開昭６０−１０８３６７号公報などに示
され、化学的耐食性、高温耐久性に優れることが知られ
ており、ｉた正方晶ジルコニアセラミックスを用いたジ
ルコニア強化アルミナセラミックスは、米国特許第４３
１６９４号明細書に示される。Tetragonal zirconia ceramics using Cent as a stabilizer are disclosed in JP-A-60-108367, etc., and are known to have excellent chemical corrosion resistance and high-temperature durability. The zirconia-reinforced alumina ceramics used are disclosed in U.S. Patent No. 43.
No. 1694.
（発明が解決しようとする課題）
ＣｅＯ２を安定化剤とした正方晶ジルコニアセラミック
スを用いて得られたジルコニア強化アルミナセラミック
スは、 ＹｘＯｓを安定化剤としたジルコニア強化アル
ミナセラミックスに比較して、化学的耐食性、高温耐久
性に優れるが９反面機械的強度などの特性はばらつきが
大きく、平均値も低いという欠点があった。(Problems to be Solved by the Invention) Zirconia-reinforced alumina ceramics obtained using tetragonal zirconia ceramics using CeO2 as a stabilizer have a chemically Although it has excellent corrosion resistance and high-temperature durability, it has the disadvantage that properties such as mechanical strength vary widely and the average value is low.
また、焼成して得られた焼結体は１表面と内部とでは色
調が異なり、研削加工等によって焼結体内部が露出する
場合には、著しく外観を害し、商品価値を大きく低下さ
せるものであった。この傾向ｔｆ、 安定化剤トＬ テ
Ｙ＊Ｏｓ 、 Ｇｄ５Ｏｓ 、 ＹｂｚＯｓの一種以上
とＣｅｎｔに用い九ジルコニア強化アルミナセラミック
スにおいても同様であっ九。In addition, the sintered body obtained by firing has a different color tone between the surface and the inside, and if the inside of the sintered body is exposed due to grinding, etc., the appearance will be significantly damaged and the product value will be greatly reduced. there were. This tendency is also the same in zirconia-reinforced alumina ceramics when one or more of Y*Os, Gd5Os, and YbzOs is used as a stabilizer.
本発明は焼結体の機械的強度などの特性を高め。The present invention improves the mechanical strength and other properties of the sintered body.
ばらつきを小さくシ、さらに焼結体の着色や色むらをな
くしたジルコニア強化アルミナセラミックスの製造法を
提供することを目的とするものである。It is an object of the present invention to provide a method for manufacturing zirconia-reinforced alumina ceramics that reduces variations and eliminates coloring and color unevenness of sintered bodies.
（課題を解決するための手段）
本発明者らは、上記の欠点について添加物等を変え走り
して焼結体の性能について調査研究を進め＆Ｍ来、 Ｃ
ａｂ冨を安定化剤とし九正方晶ジルコニアを用いたジル
コニア強化アルミナセラミックスが着色する原因は、焼
成温度域ではＣｅ’十がある程度Ｃｅ３＋とじて存在す
るが、冷却過程でＣｅ３＋が室温で安定なＣｅ’＋に変
わるとき、焼結体の内部まで酸素が十分に拡散せず、Ｃ
ｅ′が残存するためと考え、またこの正方晶ジルコニア
を用いたジルコニア強化アルミナセラミックスにおける
色むらの原因も同様であるものと考えた。ここでＣｅ’
＋とＣｅ３＋はｚ「０．を安定化させる能力が異なり、
その結果強度などの焼結体特性も異なったものとなるた
め色むらが発生した場合、焼結体特性がばらつき易くな
るということをつきとめた。(Means for Solving the Problems) The present inventors have conducted research and research on the performance of sintered bodies by changing additives, etc. to address the above-mentioned drawbacks.
The reason why zirconia-reinforced alumina ceramics using nine-tetragonal zirconia with ab-rich as a stabilizer is colored is that in the firing temperature range, Ce'+ exists to some extent as Ce3+, but during the cooling process, Ce3+ is converted into Ce3+, which is stable at room temperature. ' When it changes to +, oxygen does not diffuse sufficiently into the inside of the sintered body, and C
It was thought that this was because e' remained, and that the same was the cause of color unevenness in zirconia-reinforced alumina ceramics using this tetragonal zirconia. Here Ce'
+ and Ce3+ differ in their ability to stabilize z'0.
As a result, the properties of the sintered bodies, such as strength, differed, so it was found that when color unevenness occurs, the properties of the sintered bodies tend to vary.
そこで本発明者らは、さらに研究を進めた結果主として
Ｃｅ０ｚなどの希土類酸化物を安定化剤とする正方晶ジ
ルコニアを用いたジルコニア強化アルミナにマグネシア
を適量添加し、混合、粉砕。Therefore, the present inventors conducted further research and, as a result, added an appropriate amount of magnesia to zirconia-reinforced alumina using tetragonal zirconia using a rare earth oxide such as CeOz as a stabilizer, mixed it, and pulverized it.
成形、焼成すると色むらをなくすことができ、その結果
機械的強度などの特性に優れ、焼結体特性のばらつきを
小さくすることができることを確認した。It was confirmed that when molded and fired, color unevenness can be eliminated, resulting in excellent properties such as mechanical strength, and variations in the properties of the sintered body can be reduced.
本発明は希土類酸化物１．５〜１５モル慢及び酸化ジル
コニウム８５〜９８．５モルチを混合後１１００〜１５
００℃で熱処理してジルコニア成分とし、ついでジルコ
ニア成分１０〜４０重量％。In the present invention, after mixing 1.5 to 15 mol of rare earth oxide and 85 to 98.5 mol of zirconium oxide, 1100 to 15
Heat treated at 00°C to obtain a zirconia component, and then 10 to 40% by weight of the zirconia component.
酸化アルミニウム５５〜８９．８重量％及び酸化マグネ
シウムα２〜５１量慢を混合、粉砕、成形後１５００〜
１７００℃の温度で焼成するジルコニア強化アルミナセ
ラミックスの製造法に関する。After mixing 55 to 89.8% by weight of aluminum oxide and 2 to 51% of magnesium oxide, pulverizing and molding, the
This invention relates to a method for producing zirconia-reinforced alumina ceramics that is fired at a temperature of 1700°C.
本発明における希土類酸化物とは正方晶ジルコニアを安
定化する効果をもつ希土類酸化物を示す。The rare earth oxide in the present invention refers to a rare earth oxide that has the effect of stabilizing tetragonal zirconia.
特に少なくともＣｅＯｘを含み、必要に応じて他にＹ２
ｏｓ、ＧｄｚＯｓｓ ＹｂｔＯｓ＊ ＮｄｔＯｍｔ Ｓ
ｍｔＯｓの１種以上を含むことが好ましい。In particular, it contains at least CeOx, and if necessary, Y2
os, GdzOss YbtOs* NdtOmt S
It is preferable that one or more types of mtOs are included.
本発明においてジルコニア成分中の希土類酸化物の含有
量は１．５〜１５モルチ、好ましくはＣｅＯｓのみ添加
する場合は５〜１５モルｓ、 ＣｅＯｓとＹｚ Ｏｓ。In the present invention, the content of the rare earth oxide in the zirconia component is 1.5 to 15 mols, preferably 5 to 15 mols when only CeOs is added, and CeOs and YzOs.
Ｇｄｘ Ｏｓ 、 Ｙｂｚ Ｏｓ、 Ｎｄｓ Ｏｓ 、
８ｍ＊ Ｏｓの１種以上を添加する場合はＣｅＯ□が
１〜１〇七ルチ、 Ｙ、０．。Gdx Os, Ybz Os, Nds Os,
8m* When one or more types of Os are added, CeO□ is 1 to 107 ruti, Y, 0. .
Ｇｄｘ Ｏｓ 、Ｙｘ Ｏｓ 、 Ｎ４０ｓ 、 ８ｍ
ｓ Ｏｓの１種以上が０、５〜５モルチの範囲とされ、
この範囲から外れると焼結体の機械的強度か低くなる。Gdx Os, Yx Os, N40s, 8m
One or more types of sOs is in the range of 0.5 to 5 molti,
Outside this range, the mechanical strength of the sintered body decreases.
熱処理温度は１１００〜１５００℃の範囲とされ、１１
００℃未満であると処理の効果が小さく成形体の嵩密度
の低下、焼結しにくくなる等の欠点が生じ、また１５０
０℃を越えるとその後の工程における粉砕が困難となる
。The heat treatment temperature is in the range of 1100 to 1500°C, and 11
If the temperature is less than 150°C, the effect of the treatment will be small, resulting in disadvantages such as a decrease in the bulk density of the molded product and difficulty in sintering.
If the temperature exceeds 0°C, pulverization in subsequent steps becomes difficult.
ジルコニア成分は、平均粒径を２μｍ以下、望ましくは
０．８μｍ以下に粉砕した後酸化アルミニウム及び酸化
マグネシウムと混合すれば、焼結体の機械的強度が向上
し、かつ安定するので好ましい。The zirconia component is preferably pulverized to an average particle size of 2 μm or less, preferably 0.8 μm or less, and then mixed with aluminum oxide and magnesium oxide, since the mechanical strength of the sintered body is improved and stabilized.
本発明における希土類酸化物を含有するジルコニア成分
の量は１０〜４０重量係の範囲、アルミナの量は５５〜
８９．８重量％の範囲とされ、ジルコニア成分の量が１
０１［’ｊ＊％未満で、アルミナの量が８９．８重量％
を越えるとジルコニア添加による強度、靭性の改善効果
は小さくジルコニア成分が４０重量％を越えアルミナの
量が５０重量％未満であると９価格が高くなり、アルミ
ナセラミックスの長所が失われる。In the present invention, the amount of zirconia component containing rare earth oxide is in the range of 10 to 40% by weight, and the amount of alumina is in the range of 55 to 40% by weight.
The range is 89.8% by weight, and the amount of zirconia component is 1
01['j*%, the amount of alumina is 89.8% by weight
If the amount exceeds 40% by weight, the strength and toughness improvement effect due to the addition of zirconia will be small, and if the zirconia component exceeds 40% by weight and the amount of alumina is less than 50% by weight, the price will become high and the advantages of alumina ceramics will be lost.
またマグネシアの量は０．２〜５重量％の範囲とされ、
０．２重量％未満であると色むらの発生及び特性のばら
つきを抑制する効果が劣り、５重量％を越えると機械的
強度及び破壊靭性が低下する。In addition, the amount of magnesia is in the range of 0.2 to 5% by weight,
If it is less than 0.2% by weight, the effect of suppressing the occurrence of color unevenness and variations in properties will be poor, and if it exceeds 5% by weight, mechanical strength and fracture toughness will decrease.
本発明において酸化マグネシウムとは加熱して酸化マグ
ネシウムとなるマグネシウム化合物を示し、酸化マグネ
シウム、酢酸マグネシウム、硫酸マグネシウム、はう酸
マグネシウム、炭酸マグネシウム、塩基性炭酸マグネシ
ウム、くえん酸マグネシウム、水酸化マグネシウム、硝
酸マグネシウム、しゆう酸マグネシウム等及びこれらの
水和物が用いられる。In the present invention, magnesium oxide refers to a magnesium compound that becomes magnesium oxide when heated, including magnesium oxide, magnesium acetate, magnesium sulfate, magnesium oxalate, magnesium carbonate, basic magnesium carbonate, magnesium citrate, magnesium hydroxide, and nitric acid. Magnesium, magnesium oxalate, etc. and hydrates thereof are used.
本発明においてジルコニア成分粉、酸化アルミニウム粉
及び酸化マグネシウムを所定量混合、粉砕するが、これ
は例えばボールミル、アトライター等を用いて平均粒径
を２μｍ以下、好ましくは０．８μｍ以下に粉砕する。In the present invention, a predetermined amount of zirconia component powder, aluminum oxide powder, and magnesium oxide are mixed and pulverized using, for example, a ball mill, an attritor, etc., to an average particle size of 2 μm or less, preferably 0.8 μm or less.
焼成温度は１５００〜１７００℃の範囲とされ。The firing temperature is in the range of 1500 to 1700°C.
１５００℃未満であるとセラミックスが焼結せず。If the temperature is less than 1500°C, the ceramic will not sinter.
また１７００℃を越えると成形物に変形等が生じる。Moreover, if the temperature exceeds 1700°C, deformation etc. will occur in the molded product.
本発明におけるジルコニア強化アルミナセラミックス（
焼結体）の結晶相は、主としてα−アルミナ結晶及び正
方晶ジルコニア結晶を含み、この他に必要に応じ単斜晶
ジルコニア結晶及び／又は立方晶ジルコニア結晶が少量
含まれる場合があり。Zirconia-reinforced alumina ceramics in the present invention (
The crystal phase of the sintered body mainly contains α-alumina crystals and tetragonal zirconia crystals, and may also contain a small amount of monoclinic zirconia crystals and/or cubic zirconia crystals as required.
もし単斜晶ジルコニア結晶及び／又は立方晶ジルコニア
結晶が含まれる場合、全ジルコニア結晶中の８０モルチ
以上が正方晶ジルコニア結晶であることが好ましい。さ
らに上記の他に少量であればスピネルなどのマグネシア
化合物が含まれていても差し支えない。If monoclinic zirconia crystals and/or cubic zirconia crystals are included, it is preferred that 80 moles or more of all zirconia crystals be tetragonal zirconia crystals. Furthermore, in addition to the above, a small amount of magnesia compounds such as spinel may be included.
なお、正方晶ジルコニア結晶中にはジルコニウムと性質
が類似で分離が困難なハフニウムを含有してもよい。Note that the tetragonal zirconia crystal may contain hafnium, which has similar properties to zirconium and is difficult to separate.
（実施例） 以下本発明の詳細な説明する。(Example) The present invention will be explained in detail below.
実施例ｌ
Ｚｒ０ｚ粉（第−希元素製、ＥＰグレード、純度９９．
５慢）、 Ｙ冨Ｏｓ粉（信越化学展、純度９９．９−）
及びＣｅ ０２粉（信越化学制、９９．９％）を第１表
に示す配合割合に秤量し、ボールミルで平均粒径１．０
μｍ以下になるまで湿式粉砕、混合し九。次に乾燥した
後大気中１４００℃で１時間熱処理した。これをボール
ミルで平均粒径０．７μｍ以下になるまで湿式粉砕し、
乾燥してジルコニア成分（中間原料粉）を得た。Example 1 Zr0z powder (manufactured by Dai-Kisen, EP grade, purity 99.
5), Y Tomi Os powder (Shin-Etsu Chemical Exhibition, purity 99.9-)
and Ce 02 powder (Shin-Etsu Chemical, 99.9%) were weighed in the proportions shown in Table 1, and the average particle size was 1.0 using a ball mill.
Wet grind and mix until it becomes less than μm.9. Next, after drying, it was heat-treated at 1400° C. for 1 hour in the air. This was wet-pulverized in a ball mill until the average particle size was 0.7 μm or less.
It was dried to obtain a zirconia component (intermediate raw material powder).
この中間原料粉に酸化アルミニウム粉（住友化学裂、商
品名ＡＥＳ−１２．純度９９．９％）、及び塩基性炭酸
マグネシウム（和光純薬工業製、試薬特級）を酸化物換
算で第１表に示す配合割合に秤量し、ボールミルで平均
粒径０．６μｍ以下になるまで湿式粉砕、混合した。得
られた泥漿にポリビニルアルコール（ＰＶＡ）及びワッ
クス（中京油脂製、商品名マクセロンＭ）を添加し、噴
霧乾燥法で造粒して成形粉を得た。さらにこの成形粉を
１．２トン／ａｎ”の圧力で加圧成形後、電気炉を用い
大気中で第１表に示す温度で２時間焼成して焼結体を得
た。To this intermediate raw material powder, aluminum oxide powder (Sumitomo Chemical Co., Ltd., trade name AES-12, purity 99.9%) and basic magnesium carbonate (Wako Pure Chemical Industries, Ltd., reagent special grade) were added as shown in Table 1 in terms of oxides. The mixtures were weighed in the indicated proportions, wet-pulverized and mixed in a ball mill until the average particle size was 0.6 μm or less. Polyvinyl alcohol (PVA) and wax (manufactured by Chukyo Yushi Co., Ltd., trade name: Maxelon M) were added to the obtained slurry, and the mixture was granulated by a spray drying method to obtain a molded powder. Further, this molded powder was press-molded at a pressure of 1.2 tons/an'' and then fired in the air at the temperature shown in Table 1 for 2 hours using an electric furnace to obtain a sintered body.
次に得られた焼結体を切断し、ついで表面を研磨（φＳ
ＯＯダイヤモンド砥石）して３Ｘ４Ｘ４０−寸法の試料
を得た。得られた各試料を用いて。Next, the obtained sintered body is cut and the surface is polished (φS
OO diamond grinding wheel) to obtain a sample with dimensions of 3X4X40-. Using each sample obtained.
ＪＩＳ Ｒ１６０１−１９８１に基き０曲げ強度を測定
し、切断面の色を観察し念。その結果を第１表に示す。Measure the zero bending strength based on JIS R1601-1981 and observe the color of the cut surface. The results are shown in Table 1.
なお曲げ強度の値は試料数１０本の値である。The bending strength values are based on 10 samples.
一方曲げ強度測定用試料に幅０．１ ａｍ及び深さ０．
７−のノツチ金入れ、ノツチドビーム法（８ＥＮＢ法）
Ｋより破壊靭性（ＫＩＯ）を測定した。その結−果を第
１表に示す。On the other hand, the sample for bending strength measurement had a width of 0.1 am and a depth of 0.1 am.
7- Notch insert, notched beam method (8ENB method)
Fracture toughness (KIO) was measured from K. The results are shown in Table 1.
第１表から明らかなように１本発明になるジルコニア強
化アルミナセラミックスは９曲げ強度。As is clear from Table 1, the zirconia-reinforced alumina ceramic according to the present invention has a bending strength of 9.
破壊靭性に優れ、かつこれらの特性のばらつきが小さく
９色むらのないことがわかる。It can be seen that the fracture toughness is excellent, and the variations in these properties are small and there is no unevenness in the nine colors.
実施例２ ＺｒＯ２粉（第−希元素製、ｓｐｚグレード）。Example 2 ZrO2 powder (manufactured by Dai-ki Elements, spz grade).
Ｃｅ０ｚ粉（信越化学展、純度９９．９ Ｔｏ ） 、
ＹｚＯａ（信越化学展、純度９９．９チ） 、 Ｇｄ
３０ｓ粉（信越化学友、純度９９．９１）及びＹｂ２０
ｓ粉（信越化学友、純度９９．９ ％ ）を第２表に示
す配合割合に秤量し、以下実施例１と同様の工程を経て
中間原料粉を得た。Ce0z powder (Shin-Etsu Chemical Exhibition, purity 99.9 To),
YzOa (Shin-Etsu Chemical Exhibition, purity 99.9%), Gd
30s powder (Shin-Etsu Kagakuyu, purity 99.91) and Yb20
S powder (manufactured by Shin-Etsu Kagakuyu Co., Ltd., purity 99.9%) was weighed in the proportion shown in Table 2, and the same steps as in Example 1 were carried out to obtain an intermediate raw material powder.
この中間原料粉に酸化アルミニウム粉（住友化字型、商
品名ＡＥＳ−１２．純度９９．９チ）及び塩基性炭酸マ
グネシウム（和光純薬工業製、試薬特級）を酸化物換算
で第２表に示す配合割合に秤量し。To this intermediate raw material powder, aluminum oxide powder (Sumitomo type, trade name AES-12, purity 99.9%) and basic magnesium carbonate (manufactured by Wako Pure Chemical Industries, reagent special grade) are added as shown in Table 2 in terms of oxides. Weigh the mixture according to the proportion shown.
以下実施例１と同様の工程を経て焼結体を得た。Thereafter, a sintered body was obtained through the same steps as in Example 1.
得られた焼結体について実施例１と同様の方法で曲げ強
度、破壊靭性及び切断面の色を観察した。The bending strength, fracture toughness, and color of the cut surface of the obtained sintered body were observed in the same manner as in Example 1.
その結果を合わせてｗｃ２表に示す。The results are shown in table wc2.
第２表から明らかなように９本発明になるジルコニア強
化アルミナセラミックスは１曲げ強度。As is clear from Table 2, the zirconia-reinforced alumina ceramic according to the present invention has a bending strength of 1.
破壊靭性に優れ、かつこれらの特性のばらつきが小さく
１色むらのないことがわかる。It can be seen that the fracture toughness is excellent, and the variation in these properties is small and there is no uniform color.
次に本発明になるジルコニア強化アルミナセラミックス
をＸ線マイクロアナライザー（ＸＭＡ）で調べたところ
、マグネシアはジルコニアとは独立に存在することが判
明した。Next, when the zirconia-reinforced alumina ceramic of the present invention was examined using an X-ray microanalyzer (XMA), it was found that magnesia exists independently of zirconia.
また本発明になるジルコニア強化アルミナセラミックス
の組織を走査型電子顕微鏡で任意の１０ケ所で観察し、
その中から粒径の大きな粒子を１０個選び、その平均粒
径を粗大粒子径として。In addition, the structure of the zirconia-reinforced alumina ceramic according to the present invention was observed at 10 arbitrary locations using a scanning electron microscope.
Select 10 particles with large particle sizes from among them, and use their average particle size as the coarse particle size.
これとマグネシア添加量との関係を求めた。この関係を
第１図に示す。第１図から、マグネシアの添加により粗
大粒子径はさほど変化しないことが明らかである。The relationship between this and the amount of magnesia added was determined. This relationship is shown in FIG. From FIG. 1, it is clear that the addition of magnesia does not significantly change the coarse particle size.
（発明の効果）
本発明の製造法によって得られるジルコニア強化アルミ
ナセラミックスは１機械的強度、靭程に優れ、ばらつき
が小さく２色むらがないことから。(Effects of the Invention) The zirconia-reinforced alumina ceramics obtained by the production method of the present invention have excellent mechanical strength and toughness, and have small variations and no color unevenness.
一般機械部品、耐摩耗部品、大型構造体など幅広い用途
があり、これまでアルミナセラミックスでは使用できな
かった過酷な条件下でも使用に耐える効果を持つジルコ
ニア強化アルミナセラミックスである。It is a zirconia-reinforced alumina ceramic that can be used in a wide range of applications, including general mechanical parts, wear-resistant parts, and large structures, and can withstand use under harsh conditions where alumina ceramics could not previously be used.
Claims (3)
ウム８５〜９８．５モルーを混合後１１００〜１５００
℃で熱処理してジルコニア成分とし，ついでジルコニア
成分１０〜４０重量％，酸化アルミニウム５５〜８９．
８重量％及び酸化マグネシウム０．２〜５重量％を混合
，粉砕，成形後１５００〜１７００℃の温度で焼成する
ことを特徴とするジルコニア強化アルミナセラミックス
の製造法。1. 1100-1500 after mixing 1.5-15 mol% of rare earth oxide and 85-98.5 mol% of zirconium oxide
The zirconia component is heat-treated at 10°C, and then the zirconia component is 10 to 40% by weight, and the aluminum oxide is 55 to 89% by weight.
A method for producing zirconia-reinforced alumina ceramics, which comprises mixing 8% by weight of magnesium oxide and 0.2 to 5% by weight of magnesium oxide, pulverizing, molding, and then firing at a temperature of 1500 to 1700°C.
としてα−アルミナ結晶及び正方晶ジルコニア結晶を含
む結晶相である請求項１記載のジルコニア強化アルミナ
セラミックスの製造法。2. 2. The method for producing zirconia-reinforced alumina ceramics according to claim 1, wherein the crystalline phase of the zirconia-reinforced alumina ceramics is a crystal phase mainly containing α-alumina crystals and tetragonal zirconia crystals.
としてα−アルミナ結晶及び正方晶ジルコニア結晶であ
り、他に単斜晶ジルコニア結晶及び／又は立方晶ジルコ
ニア結晶を含み，かつ全ジルコニア結晶中の８０モル％
以上が正方晶ジルコニア結晶である請求項１記載のジル
コニア強化アルミナセラミックスの製造法。3. The crystal phase of zirconia-reinforced alumina ceramics is mainly α-alumina crystals and tetragonal zirconia crystals, and also contains monoclinic zirconia crystals and/or cubic zirconia crystals, and accounts for 80 mol% of the total zirconia crystals.
The method for producing a zirconia-reinforced alumina ceramic according to claim 1, wherein the above is a tetragonal zirconia crystal.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63049271A JPH01224264A (en) | 1988-03-02 | 1988-03-02 | Production of zirconia-reinforced alumina ceramics |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63049271A JPH01224264A (en) | 1988-03-02 | 1988-03-02 | Production of zirconia-reinforced alumina ceramics |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH01224264A true JPH01224264A (en) | 1989-09-07 |
Family
ID=12826177
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP63049271A Pending JPH01224264A (en) | 1988-03-02 | 1988-03-02 | Production of zirconia-reinforced alumina ceramics |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH01224264A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2016132577A (en) * | 2015-01-16 | 2016-07-25 | 三井金属鉱業株式会社 | Alumina-zirconia sintered body |
-
1988
- 1988-03-02 JP JP63049271A patent/JPH01224264A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2016132577A (en) * | 2015-01-16 | 2016-07-25 | 三井金属鉱業株式会社 | Alumina-zirconia sintered body |
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