JPH0431360A - Highly acid-resistant high-strength zirconia ceramics and production thereof - Google Patents
Highly acid-resistant high-strength zirconia ceramics and production thereofInfo
- Publication number
- JPH0431360A JPH0431360A JP2134445A JP13444590A JPH0431360A JP H0431360 A JPH0431360 A JP H0431360A JP 2134445 A JP2134445 A JP 2134445A JP 13444590 A JP13444590 A JP 13444590A JP H0431360 A JPH0431360 A JP H0431360A
- Authority
- JP
- Japan
- Prior art keywords
- zro2
- range
- based component
- magnesium
- powder
- 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
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 title claims abstract description 117
- 239000002253 acid Substances 0.000 title claims abstract description 43
- 239000000919 ceramic Substances 0.000 title claims abstract description 34
- 238000004519 manufacturing process Methods 0.000 title claims description 4
- 239000000843 powder Substances 0.000 claims abstract description 34
- 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 18
- 239000011777 magnesium Substances 0.000 claims abstract description 16
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims abstract description 15
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 15
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 14
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 14
- 239000006104 solid solution Substances 0.000 claims abstract description 11
- 239000008240 homogeneous mixture Substances 0.000 claims abstract description 6
- 238000010304 firing Methods 0.000 claims description 5
- 239000013078 crystal Substances 0.000 abstract description 10
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 abstract description 8
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 abstract description 8
- 238000005245 sintering Methods 0.000 abstract description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 abstract description 2
- 229910052593 corundum Inorganic materials 0.000 abstract description 2
- 229910001845 yogo sapphire Inorganic materials 0.000 abstract description 2
- 238000005452 bending Methods 0.000 description 23
- 238000000034 method Methods 0.000 description 12
- 238000012360 testing method Methods 0.000 description 9
- 239000007858 starting material Substances 0.000 description 6
- 238000002156 mixing Methods 0.000 description 5
- 150000003839 salts Chemical class 0.000 description 5
- 239000007864 aqueous solution Substances 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 230000007062 hydrolysis Effects 0.000 description 3
- 238000006460 hydrolysis reaction Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 229910002077 partially stabilized zirconia Inorganic materials 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 239000003381 stabilizer Substances 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- BYFGZMCJNACEKR-UHFFFAOYSA-N aluminium(i) oxide Chemical compound [Al]O[Al] BYFGZMCJNACEKR-UHFFFAOYSA-N 0.000 description 2
- 238000001354 calcination Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000011812 mixed powder Substances 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 230000003746 surface roughness Effects 0.000 description 2
- 230000007704 transition Effects 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 230000007423 decrease Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 229910003460 diamond Inorganic materials 0.000 description 1
- 239000010432 diamond Substances 0.000 description 1
- 230000003203 everyday effect Effects 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000013001 point bending Methods 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 230000004580 weight loss Effects 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）
本発明は高耐酸性の高強度ジルコニアセラミックスおよ
びその製造方法に関する。DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to a highly acid-resistant, high-strength zirconia ceramic and a method for producing the same.
（従来技術）
安定化剤としてＹ２Ｏ３を１．５〜５■０１％含有する
ジルコニアセラミックスは部分安定化ジルコニアセラミ
ックス（ＰＳｚ）ト称され、高強度のジルコニアセラミ
ックスとして機械構造材料としての用途開発がなされて
いる。しかしながら、上記した部分安定化ジルコニアセ
ラミックスはかならずしも十分な曲げ強度を備えていな
いため、本出願人は特開昭６４−３０７１号公報に示さ
れているように高強度ジルコニアセラミックスを提供し
ている。(Prior art) Zirconia ceramics containing 1.5 to 5% of Y2O3 as a stabilizer are called partially stabilized zirconia ceramics (PSz), and have been developed for use as mechanical structural materials as high-strength zirconia ceramics. ing. However, the partially stabilized zirconia ceramics described above do not necessarily have sufficient bending strength, so the applicant has provided high-strength zirconia ceramics as disclosed in Japanese Patent Application Laid-Open No. 64-3071.
当該ジルコニアセラミックスはＺｒ０ａＪ Ｍ ｔｌＥ
中に安定化剤としてｙ２ｏ、およびＣｅＯ２を含有す
るとともに、焼結助剤としてアルミニウム系成分およヒ
ｖグネシウム系成分を含有することを特徴とする特ので
ある。The zirconia ceramic is Zr0aJ M tlE
It is characterized in that it contains y2o and CeO2 as stabilizers, as well as an aluminum-based component and a magnesium-based component as sintering aids.
（発明が解決しようとする課１ｉ）
上記した組成のジルコニアセラミックスは曲げ強度に優
れたものであり、かつ耐酸性にも優れている。しかしな
がら、高濃度の酸や加熱された酸に対してはさらに高い
耐酸性が要求される。(Issue 1i to be Solved by the Invention) Zirconia ceramics having the above composition have excellent bending strength and acid resistance. However, even higher acid resistance is required for highly concentrated acids and heated acids.
本発明者は、部分安定化ジルコニアセラミックス焼結体
においては結晶相のうち正方晶の格子面間距離（定数ｄ
）と耐酸性が密接な関係にあることを見いだした。また
、安定化剤としてＣｅＯ２を添加すれば正方晶の格子定
数は大きくなって耐酸性は向上するものの曲げ強度８０
ｋｇ ／■２以下であり、満足できるものは得られない
ことを見いだした。The present inventor has discovered that in a partially stabilized zirconia ceramic sintered body, the distance between tetragonal lattice planes (constant d
) and acid resistance are closely related. In addition, if CeO2 is added as a stabilizer, the lattice constant of the tetragonal crystal will increase and the acid resistance will improve, but the bending strength will be 80.
kg/■2 or less, and it was found that a satisfactory result could not be obtained.
従って、本発明の目的はかかる問題に対処することにあ
る。It is therefore an object of the present invention to address such problems.
（課題を解決するための手段）
本発明の第１の発明は、Ｙ２Ｏ３が１，５〜５ｍｏｌ％
の範囲で固溶する第１のＺｒＯ２粉末と、ＣｅＯ２が７
〜２０ＩｌＯＩ％の範囲で固溶する第２のＺｒ０ｚ粉末
と、アルミニウム系成分およびマグネシウム系成分との
均一混合物の焼結体であり、同均一混合物が第１のＺｒ
Ｏ２をＳＯ〜９０ｗｔ％、第２のＺｒＯ２を９〜４９ｗ
ｔＬ アルミニウム系成分およびマグネシウム系成分
をＡｌ２Ｏ，およびＭｇＯ換算で１〜３０マｔ％含有し
ていることを特徴とする高耐酸性の高強度ジルコニアセ
ラミックスにある。(Means for Solving the Problems) The first invention of the present invention provides Y2O3 in an amount of 1.5 to 5 mol%.
The first ZrO2 powder is dissolved in solid solution in the range of 7
It is a sintered body of a homogeneous mixture of a second Zr0z powder in solid solution in the range of ~20 IlOI%, an aluminum-based component and a magnesium-based component, and the same homogeneous mixture is the first Zr0z powder.
O2 is SO~90wt%, second ZrO2 is 9~49w
tL A highly acid-resistant, high-strength zirconia ceramic characterized by containing an aluminum component and a magnesium component in an amount of 1 to 30 mat% in terms of Al2O and MgO.
また、第２の発明はかかるジルコニアセラミックスにお
いて、焼結体の正方品（１１１）面の格子定数ｄが２．
９６０〜２．９６５人の範囲にあることを特徴とするも
のである。さらにまた、第３の発明はかかるジルコニア
セラミックスの製造方法であり、焼結体の焼成温度が１
２００〜１３５０℃の範囲であることを特徴とするもの
である。Further, in the second invention, in the zirconia ceramic, the lattice constant d of the square (111) plane of the sintered body is 2.
It is characterized by being in the range of 960 to 2.965 people. Furthermore, the third invention is a method for manufacturing such zirconia ceramics, in which the firing temperature of the sintered body is 1.
It is characterized by a temperature range of 200 to 1350°C.
しかして、本発明に係るジルコニアセラミックスの原料
である第１のＺｒ０ａ粉末、第２のＺｒＯ２粉末は下記
の方法にて得られる。The first Zr0a powder and the second ZrO2 powder, which are the raw materials for the zirconia ceramics according to the present invention, can be obtained by the following method.
（１）Ｙ、Ｃｅの水溶性塩とＺｒＯ２粉末とを湿式混合
し乾燥した後仮焼する方法。(1) A method in which water-soluble salts of Y and Ce and ZrO2 powder are wet mixed, dried, and then calcined.
（２）Ｙ、、ＣｅとＺｒとの混合塩水溶液を加水分解し
得られた混合物を仮焼する方法＠
これらの方法により得られた第１のＺｒＯ２粉末と、第
２のＺｒＯ２粉末と、アルミニウム系成分およびマグネ
シウム系成分とは湿式法または乾式法で均一に混合され
、成形用の原料に供される。アルミニウム系成分および
マグネシウム系成分はＡ１２０ｉ粉末、ＭｇＯ粉末であ
ってもよく、また上記両成分の混合塩水溶液の加水分解
を仮焼して得られる混合粉末であってもよく、さらにま
た上記両成分の混合粉末であってもよい。これらのセラ
ミ・ツクス原料は粉末の状態で、または予備成形体の状
態でホ、）アイソスタティックプレス、ホ・ットブレス
等１こて加圧焼成されて焼結体となる。(2) A method of hydrolyzing a mixed salt aqueous solution of Y, Ce and Zr and calcining the resulting mixture @ The first ZrO2 powder obtained by these methods, the second ZrO2 powder, and aluminum The system component and the magnesium component are uniformly mixed by a wet method or a dry method and used as a raw material for molding. The aluminum-based component and the magnesium-based component may be A120i powder or MgO powder, or may be a mixed powder obtained by calcining the hydrolysis of a mixed salt aqueous solution of both of the above components. It may be a mixed powder of. These ceramic/tux raw materials are fired in the powder state or in the preformed state into a sintered body by pressurizing and firing with one trowel such as isostatic press or hot press.
（発明の作用・効果）
ジルコニアセラミックスにおいて、Ｙａｋｓのみの焼結
体は曲げ強度９０ｋｇｆ／■２以上の特性を得られるが
、正方晶（１１１）面の格子定数ｄが２．９５５人程度
で耐酸性が悪く、またＣｅ０ｇのみを含む焼結体は正方
晶（１１１）面の格子定数ｄが２．９５５Å以上で耐酸
性に優れているものの、曲げ強度が８０ｋｇｆ／■２程
度と低い。このことから、Ｙ２Ｏ３を固溶した第１のＺ
ｒＯ２粉末とＣｅＯ２を固溶した第２のＺｒＯ２粉末を
混合することにより、これらの相乗効果にて曲げ強度８
０ｋｇ ｆ／■２以上でかつ耐酸性が５＋＋＠／ｃ＋ａ
”以下の高耐酸性の高強度ジルコニアセラミックスとな
る。(Operations and Effects of the Invention) In zirconia ceramics, a sintered body made only of Yaks can have a bending strength of 90 kgf/■2 or more, but the lattice constant d of the tetragonal (111) plane is about 2.955, making it difficult to resist acid. Furthermore, although the sintered body containing only Ce0g has a lattice constant d of the tetragonal (111) plane of 2.955 Å or more and is excellent in acid resistance, its bending strength is as low as about 80 kgf/2. From this, it can be seen that the first Z containing Y2O3 as a solid solution
By mixing the rO2 powder and the second ZrO2 powder containing CeO2 as a solid solution, the bending strength is increased to 8 due to the synergistic effect of these powders.
0kg f/■2 or more and acid resistance 5++@/c+a
``The following highly acid-resistant, high-strength zirconia ceramics are produced.
第１図は焼結体であるジルコニアセラミックスにおける
第１のＺｒＯ２中に固溶しているＺｒ０２（ｍｏ１％）
と曲げ強度および耐酸性との関係を示すグラフ、第２図
は第２のＺｒＯ２中に固溶しているＣｅ０２（ｌｏ１％
）と曲げ強度および耐酸性との関係を示すグラフ、第３
図はｙ２ｏ、を３ｍｏ１％含む第１のＺｒＯ２，ＣｅＯ
２を１２ｍｏ１％含む第２のＺｒ（ｈの混合割合（ｗｔ
％）と曲げ強度および耐酸性との関係を示すグラフ（白
印）、第４図はアルミニウム系成分およびマグネシウム
系成分（ｗｔ％）と曲げ強度および耐酸性との関係を示
すグラフである。Figure 1 shows Zr02 (mo1%) dissolved in the first ZrO2 in zirconia ceramics, which is a sintered body.
Figure 2 is a graph showing the relationship between bending strength and acid resistance.
), Graph showing the relationship between bending strength and acid resistance, 3rd
The figure shows the first ZrO2,CeO containing 3mol1% of y2o.
The second Zr containing 12 mo1% of 2 (mixing ratio of h (wt
%) and bending strength and acid resistance (white marks), and FIG. 4 is a graph showing the relationship between aluminum-based components and magnesium-based components (wt%) and bending strength and acid resistance.
これらのグラフを参照すれば、曲げ強度が８０ｋｇｆ／
■２以上でかつ耐酸性が５ｍｇ／ｃｍ２以下の高耐酸性
の高強度ジルコニアセラミックスを得るには第１のＺｒ
Ｏ２中に固溶するｙ２ｏ、は１．５〜５ｍｏｌ％の範囲
でかつ第２のＺｒＯ２中に固溶するＣｅＯ２は７〜２０
■Ｏ１％の範囲であることが好ましく、また第１のＺｒ
０ａ、第２のＺｒＯ２およびアルミニウム、マグネシウ
ム両成分の混合量は５０〜９０ｗｔ％、ｉｏ〜５０ｗｔ
％、１〜３０萱ｔ％の範囲であることが好ましい。一方
、耐酸性に関しては耐酸性に優れたジルコニアセラミッ
クスにおける正方晶（１１１）面の格子定数ｄは第５図
のグラフに示すように２．９６０〜２．９６５人の範囲
にある。Referring to these graphs, the bending strength is 80kgf/
■To obtain highly acid-resistant and high-strength zirconia ceramics with an acid resistance of 2 or more and an acid resistance of 5 mg/cm2 or less, the first Zr
The amount of y2o dissolved in O2 is in the range of 1.5 to 5 mol%, and the amount of CeO2 dissolved in the second ZrO2 is in the range of 7 to 20.
(2) It is preferable that the O is in the range of 1%, and the first Zr
0a, the mixing amount of the second ZrO2 and both aluminum and magnesium components is 50 to 90 wt%, io to 50 wt%
%, preferably in the range of 1 to 30 t%. On the other hand, regarding acid resistance, the lattice constant d of the tetragonal (111) plane in zirconia ceramics, which has excellent acid resistance, is in the range of 2.960 to 2.965 as shown in the graph of FIG.
なお、第３図の黒用で示すグラフはＹ２Ｏ３およびＣｅ
ｎ２をそれぞれＺｒ０ｅに固溶させることなく、両成分
を同時にＺｒＯ２に添加した場合のグラフであり。The graph shown in black in Figure 3 is for Y2O3 and Ce.
This is a graph when both components are added to ZrO2 at the same time without each n2 being solid-dissolved in Zr0e.
Ｙ２Ｏ３およびＣｅ０ｚをそれぞれｚｒｏｚに固溶させ
た場合の日用で示すグラフと比較すれば、これらをそれ
ぞれ固溶させた場合曲げ強度および耐酸性に対する効果
が高いことがわかる。これは、以下の理由によるものと
推測される。Comparison with the graph for everyday use in which Y2O3 and Ce0z are each dissolved in zroz shows that the effect on bending strength and acid resistance is high when these are dissolved in each. This is presumed to be due to the following reasons.
前者の場合には、Ｚｒ０ｚ粉末内にＹ２（ｈまたはＣｅ
Ｏ２が予め固溶していないため、焼成後焼結体中のＹ２
Ｏ５とＣｓ０２の分布が不均一になり、焼結体中に単斜
晶、立方晶が発生して強度が低くなるとともに。In the former case, Y2 (h or Ce
Since O2 is not dissolved in solid solution in advance, Y2 in the sintered body after firing
The distribution of O5 and Cs02 becomes uneven, monoclinic crystals and cubic crystals occur in the sintered body, and the strength decreases.
Ｙ２Ｏ３とＣｅＯ２の含有量が少ない部分より優先的に
劣化して耐酸性が悪い、これに対して、後者の場合には
ＺｒＯ２粉末内にＹ２Ｏ，またはＣｅｄｅが予め固溶し
ているため、焼成後焼結体中のＹ＊ＯｓとＣｅＯｓの分
布が均一で焼結体中に単斜晶および立方晶がほとんど発
生しないため１曲げ強度が太き（かつ耐酸性にも優れて
いる。In contrast, in the latter case, Y2O or Cede is preliminarily dissolved in the ZrO2 powder, so that it deteriorates preferentially than the part with a low content of Y2O3 and CeO2, so that the acid resistance is poor. Since the distribution of Y*Os and CeOs in the sintered body is uniform and almost no monoclinic crystals or cubic crystals are generated in the sintered body, the 1 bending strength is high (and the acid resistance is also excellent).
（実施例１）
（１）原料の調合
ＺｒとＹとの混合塩水溶液から加水分解により得られた
Ｚｒ０２−Ｙ２０２共沈物を９００℃にて仮焼し、粒径
１μ璽以下の第１のＺｒＯ２粉末を得た。また、Ｚｒ、
Ｃｅとの混合塩水溶液から加水分解法により得られたＺ
ｒＯ＊−Ｃｅ０．２共沈物を９００℃にて仮焼した後粉
砕して、粒径ｌμ■以下の第２のＺｒＯ２を得た。これ
ら両ＺｒＯ２粉末にＡ１ａＯａ粉末を添加してボットミ
ルで解砕混合し、噴霧乾燥して出発原料とした。(Example 1) (1) Preparation of raw materials A Zr02-Y202 coprecipitate obtained by hydrolysis from a mixed salt aqueous solution of Zr and Y was calcined at 900°C, and the first ZrO2 powder was obtained. Also, Zr,
Z obtained by hydrolysis method from mixed salt aqueous solution with Ce
The rO*-Ce0.2 coprecipitate was calcined at 900°C and then pulverized to obtain second ZrO2 having a particle size of 1μ or less. A1aOa powder was added to both ZrO2 powders, crushed and mixed in a bot mill, and spray-dried to obtain starting materials.
（２）試料の調製
各種の出発原料を２０（１ｋｇ ／霞２の圧力で予備成
形し、これらの予備成形物をラバープレス法にてｇｔｏ
ｎ／ｅ１１２の圧力で成形して６０■Ｘ８０■の方形で
厚さ８■の各種の角板を得た。これらの角板を１１５０
〜１４００℃で５時間常圧焼結法、等方加圧焼結法（Ｉ
ＩＩＰ・・・圧力２ｔｏｎ／ｃ＋ｎ’）にて焼成し、試
料とした。(2) Preparation of samples Various starting materials were preformed at a pressure of 20 (1 kg/haze 2), and these preforms were subjected to GTO using a rubber press method.
Various rectangular plates measuring 60 cm x 80 cm and having a thickness of 8 cm were obtained by molding at a pressure of n/e112. These square plates are 1150
Normal pressure sintering method at ~1400℃ for 5 hours, isostatic pressure sintering method (I
IIP...The sample was fired at a pressure of 2 ton/c+n').
（３）試験
曲げ強度試験： ＪＩＳ−Ｒ１６０１
４点曲げ強さの試験法に基づ＜（ｋｇｆ／■２）、但し
試料は４謹Ｘ４０■の長方形で厚さ３■、クロスヘプト
スピード０．５■／■Ｉｎｓ 上部スパンｌＯ■、下
部スパン３０■。(3) Test bending strength test: Based on JIS-R1601 4-point bending strength test method < (kgf/■2), however, the sample is a rectangle of 4cm x 40cm, thickness 3cm, crosshepto speed 0 .5■/■Ins Upper span lO■, lower span 30■.
耐酸性：
試料およびＨａｔ％［ＩＣ１溶液を密封容器に入れ、１
５０℃で２００時間放置したときの重量を測定し、単位
面積当りの重量減（１ｇ／ｃ＋ｎ２）を算出した。但し
試料は１５■Ｘ１５−の方形で厚さ３■、その全表面を
表面粗度Ｒｍａｘｇ１． Ｏμ■に仕上げたもの。Acid resistance: Sample and Hat% [IC1 solution was placed in a sealed container,
The weight when left at 50° C. for 200 hours was measured, and the weight loss per unit area (1 g/c+n2) was calculated. However, the sample is a 15cm x 15cm square with a thickness of 3cm, and its entire surface has a surface roughness of Rmaxg1. Finished in Oμ■.
熱劣化試験：
特開昭６０−３５０号公報に開示された［セラミックス
の試験方法」に基づき、試料をオートクレーブ内の熱水
中（熱水温度２５０℃、オートクレーブ内蒸気圧約３９
ｋｇ／ ３ｔ）で５０時間熱処理し、下記の方法により
試料中における正方晶および立方晶の単斜晶への転移率
（％）を算出する。Thermal deterioration test: Based on the "Testing method for ceramics" disclosed in JP-A-60-350, the sample was placed in hot water in an autoclave (hot water temperature 250°C, steam pressure inside the autoclave approx. 39°C).
kg/3t) for 50 hours, and the transition rate (%) of tetragonal and cubic crystals to monoclinic crystals in the sample is calculated by the following method.
試料を予めダイヤモンドヘッドにて鏡面研磨してＸ線回
折し、単斜晶の（１１１）面、立方晶の（１１１）面お
よび正方晶の（１１１）面の回折ピークの積分強度ＩＭ
、 ＩＴ、 ＩＣ）から正方晶および立方晶の量（Ｖｓ
）ＶｓＩＩ（ｌＴ＋Ｉｃ）／（［Ｍ＋ＩＴ＋ＩＣ） ニ
テ算出する。また、熱処理後の試料をＸ線回折に付して
上記と同様に正方晶および立方晶の量（ｖｌ）を算出し
、これらＶ、、Ｖｔから転移率（駕）
転移率（％）ｌｌ（ｖＩ−ｖｌ）／ｖＩＸ Ｚｏ。The sample was mirror-polished with a diamond head in advance and subjected to X-ray diffraction, and the integrated intensity IM of the diffraction peaks of the monoclinic (111) plane, the cubic (111) plane, and the tetragonal (111) plane was obtained.
, IT, IC) to the amount of tetragonal and cubic crystals (Vs
)VsII(IT+Ic)/([M+IT+IC)]. In addition, the heat-treated sample was subjected to X-ray diffraction, the amount of tetragonal and cubic crystals (vl) was calculated in the same manner as above, and from these V, , Vt, the transition rate (%) ll ( vI-vl)/vIX Zo.
にて算出する。但し試料は１５■Ｘ１５諺の方形で厚さ
３−１全表面を表面粗度Ｒ■ａｘｍ１． Ｏμ■に仕上
げたもの。Calculated by. However, the sample is a 15×15 square with a thickness of 3-1 and a surface roughness of R×axm1. Finished in Oμ■.
（４）試験結果
各試料の試験結果および試料の正方晶（１１１）面の格
子定数ｄの値を第１表に示すとともに、第１のＺｒＯ２
中に固溶しているＹ２Ｏ３（曹ｏｆ％）と曲げ強度およ
び耐酸性との関係を第１図に、箪２のＺｒＯ２中に固溶
しているＣｏｏｓ（冒ｏ１％）と曲げ強度および耐酸性
との関係を第２図に、第１、第２のＺｒ０ｔの混合割合
（ｗｔ％）と曲げ強度および耐酸性との関係を第３図に
、アルミニウムおよびマグネシウム両成分（ｗｔ％）と
曲げ強度および耐酸性との関係を第４図に、格子定数ｄ
と耐酸性との関係を第５図にそれぞれ示す。(4) Test results The test results of each sample and the value of the lattice constant d of the tetragonal (111) plane of the sample are shown in Table 1, and the first ZrO2
Figure 1 shows the relationship between Y2O3 (solute of %) dissolved in ZrO2 and bending strength and acid resistance. Figure 2 shows the relationship between the mixing ratio (wt%) of the first and second Zr0t and bending strength and acid resistance, and the relationship between the aluminum and magnesium components (wt%) and bending strength. Figure 4 shows the relationship between strength and acid resistance, and the lattice constant d
FIG. 5 shows the relationship between and acid resistance.
第１図のグラフは試験Ｎａ５．Ｎｏ１０〜ＮＱ１４に基
づくもの、第２図のグラフは試験Ｎｎ ５．Ｎｎ １５
〜ＮＱ １９ｉ：基づくもの、第３図の日中のグラフは
試験ＮＱＩ〜ＮＱ９に基づくもの、第４図のグラフは試
験ＮＱ４．Ｎα２０゜ＮＧ２２〜Ｎｃｉ２Ｓに基づ（も
のであり、これらのグラフおよび第１表から曲げ強度お
よび耐酸性に優れたジルコニアセラミックスは下記の組
成のものであることが明かである。The graph in Figure 1 shows the test Na5. Based on No. 10 to NQ14, the graph in Figure 2 is based on Test Nn 5. Nn 15
~NQ 19i: Based on, the intraday graph in Figure 3 is based on exams NQI to NQ9, and the graph in Figure 4 is based on exam NQ4. It is clear from these graphs and Table 1 that zirconia ceramics with excellent bending strength and acid resistance have the following composition.
すなわち、かかるジルコニアセラミックスは第１のＺｒ
Ｏ２中に固溶するＹ２Ｏ３が１．５〜５ｍｏｌ％、箪２
のＺｒＯ２中に固溶するＣｅＯ２が７〜２０ｍｏ１％、
第１のＺｒＯ２が５０〜９０１ｔ％、アルミニウム系成
分およびマグネシウム系成分が＾１２０．および１１１
ｇ０換算で１〜３０ｗｔ％の範囲にある。That is, such zirconia ceramics contain the first Zr
1.5 to 5 mol% of Y2O3 dissolved in O2, Kan 2
CeO2 dissolved in solid solution in ZrO2 is 7 to 20 mo1%,
The first ZrO2 is 50 to 901 t%, and the aluminum-based component and magnesium-based component are ^120. and 111
It is in the range of 1 to 30 wt% in terms of g0.
なお、第３図の黒用で示すグラフはｙ２ｏａ粉末とＣｅ
ｄｅ粉末とを共にＺｒＯ２粉末に添加し、これにＡＩｅ
Ｏｓ粉末およびＭｇＯ粉末を添加してポットミルで解砕
混合し、噴霧乾燥して出発原料とした点を除き、日中に
対応するＮＯのものと同条件で試料の調製および試験を
行った場合の比較例の結果である。かかる比較例におい
ては、日中で示す本実施例に比較して曲げ強度、耐酸性
共に著しく低いことがわかる。The graph shown in black in Figure 3 is for y2oa powder and Ce.
de powder together with ZrO2 powder, and add AIe to this.
Samples were prepared and tested under the same conditions as the corresponding NO samples during the day, except that Os powder and MgO powder were added, crushed and mixed in a pot mill, and spray-dried to serve as the starting material. These are the results of a comparative example. It can be seen that in this comparative example, both the bending strength and acid resistance are significantly lower than in the present example shown in daylight.
第５図のグラフは各試料における格子定数ｄと耐酸性と
の関係を示すもので、耐酸性の良好なジルコニアセラミ
ックスにおいては格子定数ｄが２．９６０〜２．９６５
人の範囲にあり、上記した特定のものでかかる範囲の格
子定数ｄを備えたジルコニアセラミックスが特に高耐酸
性の高強度ジルコニアセラミックスということができる
。また、かかるジルコニアセラミックスは成形物を１２
００〜１３５０℃の範囲の温度で焼成することにより得
られる。The graph in Figure 5 shows the relationship between the lattice constant d and acid resistance for each sample. Zirconia ceramics with good acid resistance have a lattice constant d of 2.960 to 2.965.
Zirconia ceramics having a lattice constant d within the human range, and the specific ones mentioned above, can be said to be particularly highly acid-resistant and high-strength zirconia ceramics. In addition, such zirconia ceramics can be used to form molded products at 12
It is obtained by firing at a temperature in the range of 00 to 1350°C.
（実施例２）
Ｚｒ０２粉末とＹ（ＮＯｓｈとをボットミルにて混合し
たものを９００℃にて仮焼後粉砕して５粒径１μ璽以下
の第１のＺｒＯ２粉末を得た。また、ＺｒＯ２粉末とＣ
ｅ（ＮＯｓ）ｓとをボットミルにて混合したものを９０
０℃にて仮焼後粉砕して、粒径１μ璽以下の第２のＺｒ
Ｏ２粉末を得た、これらの両ＺｒＯ２粉末にＡｌ２Ｏ３
粉末およびＭｇＯ粉末を添加してボットミルで解砕混合
し、噴霧乾燥して出発原料とした。各種の出発原料を用
いて実施例１と同様に試料を調製しかつ同様の試験を行
い、第２表に示す結果を得た。(Example 2) A mixture of Zr02 powder and Y (NOsh) in a bot mill was calcined at 900°C and then crushed to obtain a first Zr02 powder with a particle size of 1 μm or less. and C
e(NOs)s mixed in a bot mill with 90
Calcined at 0°C and then crushed to produce a second Zr with a particle size of 1 μm or less.
Al2O3 was added to both ZrO2 powders to obtain O2 powders.
The powder and MgO powder were added, crushed and mixed in a bot mill, and spray-dried to obtain a starting material. Samples were prepared in the same manner as in Example 1 using various starting materials, and the same tests were conducted to obtain the results shown in Table 2.
（実施例３）
アルミニウム系成分、マグネシウム系成分を含む化合物
としてＡＩ（ＯＨ）ｓ、 ＡｌＣｌ５． ＡＩ （ＮＯ
ｓ）ｓ、 ｋｌｇ（Ｈ）２ＭｇＣ］ｚ、 Ｍｇ（Ｎｏｗ
）２を用いた点を除き、実施例１と同様に出発原料の調
合、試料の調製および試験を行い、第３表の結果を得た
。(Example 3) AI(OH)s, AlCl5. AI (NO
s)s, klg(H)2MgC]z, Mg(Now
) 2 was used, the starting materials were mixed, samples were prepared and tested in the same manner as in Example 1, and the results shown in Table 3 were obtained.
（以下余白）(Margin below)
第１図は第１のＺｒＯ２中に固溶しているＹ２Ｏ２（Ｍ
ｏ２Ｓ＞と曲げ強度および耐酸性との関係を示すグラフ
、第２図は第２のＺｒ０ｅ中に固溶しているＣｅｎ２（
１０１％）と曲げ強度および耐酸性との関係を示すグラ
フ、第３図は第１．第２のＺｒＯ２の混合割合（ｗｔ％
）と曲げ強度および耐酸性との関係を示すグラフ、第４
図はアルミニウムおよびマグネシウム両成分と曲げ強度
および耐酸性との関係を示すグラフ、第５図は格子定数
と耐酸性との関係を示すグラフである。Figure 1 shows Y2O2 (M
Figure 2 is a graph showing the relationship between o2S>, bending strength, and acid resistance.
101%), bending strength, and acid resistance. Mixing ratio of second ZrO2 (wt%
), Graph showing the relationship between bending strength and acid resistance, 4th
The figure is a graph showing the relationship between aluminum and magnesium components, bending strength and acid resistance, and FIG. 5 is a graph showing the relationship between lattice constant and acid resistance.
Claims (3)
する第１のＺｒＯ＿２粉末と、ＣｅＯ＿２が７〜２０ｍ
ｏｌ％の範囲で固溶する第２のＺｒＯ＿２粉末と、アル
ミニウム系成分およびマグネシウム系成分との均一混合
物の焼結体であり、同均一混合物が第１のＺｒＯ＿２を
５０〜９０ｗｔ％、第２のＺｒＯ＿２を９〜４９ｗｔ％
、アルミニウム系成分およびマグネシウム系成分をＡｌ
＿２Ｏ＿３およびＭｇＯ換算で１〜３０ｗｔ％含有して
いることを特徴とする高耐酸性の高強度ジルコニアセラ
ミックス。(1) First ZrO_2 powder in which Y_2O_3 is dissolved in the range of 1.5 to 5 mol% and CeO_2 is 7 to 20 m
It is a sintered body of a homogeneous mixture of a second ZrO_2 powder dissolved in a solid solution in the range of 1.5 ol% and an aluminum-based component and a magnesium-based component. 9 to 49 wt% ZrO_2
, the aluminum-based component and the magnesium-based component are
A highly acid-resistant, high-strength zirconia ceramic characterized by containing _2O_3 and 1 to 30 wt% in terms of MgO.
、焼結体の正方晶（１１１）面の格子定数ｄが２．９６
０〜２．９６５Åの範囲にあることを特徴とする高耐酸
性の高強度ジルコニアセラミックス。(2) In the zirconia ceramic described in item 1, the lattice constant d of the tetragonal (111) plane of the sintered body is 2.96.
A highly acid-resistant and high-strength zirconia ceramic characterized by having a thickness in the range of 0 to 2.965 Å.
法であり、焼結体の焼成温度が１２００〜１３５０℃の
範囲であることを特徴とする高耐酸性の高強度ジルコニ
アセラミックスの製造方法。(3) The method for producing zirconia ceramics according to item 1, which is characterized in that the firing temperature of the sintered body is in the range of 1200 to 1350°C.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2134445A JPH0431360A (en) | 1990-05-24 | 1990-05-24 | Highly acid-resistant high-strength zirconia ceramics and production thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2134445A JPH0431360A (en) | 1990-05-24 | 1990-05-24 | Highly acid-resistant high-strength zirconia ceramics and production thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH0431360A true JPH0431360A (en) | 1992-02-03 |
Family
ID=15128522
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2134445A Pending JPH0431360A (en) | 1990-05-24 | 1990-05-24 | Highly acid-resistant high-strength zirconia ceramics and production thereof |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0431360A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5411583A (en) * | 1993-11-15 | 1995-05-02 | E. I. Du Pont De Nemours And Company | HF-resistant ceramics and use thereof |
| US7399722B2 (en) | 2003-09-10 | 2008-07-15 | Kyocera Corporation | Alumina/zirconia ceramics and method of producing the same |
-
1990
- 1990-05-24 JP JP2134445A patent/JPH0431360A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5411583A (en) * | 1993-11-15 | 1995-05-02 | E. I. Du Pont De Nemours And Company | HF-resistant ceramics and use thereof |
| US7399722B2 (en) | 2003-09-10 | 2008-07-15 | Kyocera Corporation | Alumina/zirconia ceramics and method of producing the same |
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