JP4043425B2 - Zirconia heat treatment material - Google Patents
Zirconia heat treatment material Download PDFInfo
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- JP4043425B2 JP4043425B2 JP2003315007A JP2003315007A JP4043425B2 JP 4043425 B2 JP4043425 B2 JP 4043425B2 JP 2003315007 A JP2003315007 A JP 2003315007A JP 2003315007 A JP2003315007 A JP 2003315007A JP 4043425 B2 JP4043425 B2 JP 4043425B2
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- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 title claims description 98
- 238000010438 heat treatment Methods 0.000 title claims description 21
- 239000000463 material Substances 0.000 title description 7
- 239000003381 stabilizer Substances 0.000 claims description 25
- 239000013078 crystal Substances 0.000 claims description 16
- 239000010987 cubic zirconia Substances 0.000 claims description 10
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 7
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 7
- 229910052760 oxygen Inorganic materials 0.000 claims description 6
- 238000012545 processing Methods 0.000 claims description 2
- 230000007797 corrosion Effects 0.000 description 19
- 238000005260 corrosion Methods 0.000 description 19
- 239000000843 powder Substances 0.000 description 14
- 239000002245 particle Substances 0.000 description 11
- 238000000034 method Methods 0.000 description 10
- 238000010304 firing Methods 0.000 description 8
- 238000000465 moulding Methods 0.000 description 8
- 238000001816 cooling Methods 0.000 description 6
- 238000005259 measurement Methods 0.000 description 5
- 239000004372 Polyvinyl alcohol Substances 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- 239000011268 mixed slurry Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 229920002451 polyvinyl alcohol Polymers 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
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- 238000012360 testing method Methods 0.000 description 3
- 239000004925 Acrylic resin Substances 0.000 description 2
- 229920000178 Acrylic resin Polymers 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 238000005266 casting Methods 0.000 description 2
- 229910010293 ceramic material Inorganic materials 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 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 description 2
- 238000005336 cracking Methods 0.000 description 2
- 239000003989 dielectric material Substances 0.000 description 2
- 239000000839 emulsion Substances 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 230000008020 evaporation Effects 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 239000000696 magnetic material Substances 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 230000001681 protective effect Effects 0.000 description 2
- 229910001404 rare earth metal oxide Inorganic materials 0.000 description 2
- 239000007921 spray Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 238000012935 Averaging Methods 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000007580 dry-mixing Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000012776 electronic material Substances 0.000 description 1
- 230000003628 erosive effect Effects 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 229910052602 gypsum Inorganic materials 0.000 description 1
- 239000010440 gypsum Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 229920000609 methyl cellulose Polymers 0.000 description 1
- 239000001923 methylcellulose Substances 0.000 description 1
- 235000010981 methylcellulose Nutrition 0.000 description 1
- 239000004570 mortar (masonry) Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- -1 oxygen ions Chemical class 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
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- 230000035939 shock Effects 0.000 description 1
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- 238000007669 thermal treatment Methods 0.000 description 1
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- Compositions Of Oxide Ceramics (AREA)
- Furnace Charging Or Discharging (AREA)
Description
本発明は耐久性及び耐食性にすぐれたジルコニア製熱処理用部材に関する。なお、本発明でいう熱処理用部材とは、圧電体、誘電体、磁性体などの電子部品材料、蛍光体及びセラミック材料のための熱処理用容器およびセッター、単結晶育成用ルツボ、金属溶解用ルツボ、各種電気炉用炉心管及び各種機器の保護管などである。 The present invention relates to a heat treatment member made of zirconia having excellent durability and corrosion resistance. The heat treatment member referred to in the present invention is an electronic component material such as a piezoelectric material, a dielectric material, or a magnetic material, a heat treatment container and setter for phosphor and ceramic material, a crucible for growing a single crystal, and a crucible for melting metal. And various types of furnace core tubes for electric furnaces and protective tubes for various devices.
電子部品材料である圧電体、あるいは誘電体や磁性体の焼成は、被焼成成分の蒸発成分を極力少なくして組成の変動を少なくする焼成方法がとられている。圧電体、誘電体や磁性体の焼成の場合、被焼成体からの蒸発成分が熱処理用部材と反応し、被焼成体と部材が引っ付いたり、部材が腐食により短期間で使用できなくなるなどの問題があり、被焼成体の電気特性の低下が起こったりするため、圧電体や誘電体の組成成分に対する耐食性が高いジルコニアが使用されており、特許文献１にはジルコニア製焼成用セッターが開示されている。しかしながら、この特許公報に開示されているジルコニア製焼成セッターは立方晶系ジルコニアとすることにより耐食性にすぐれるとしているが、ただ単に立方晶系ジルコニアというだけでは耐食性だけは向上するものの、加熱・冷却の繰り返しによる寿命がすぐれているとは言えず、最近の急速な電子材料部品の発展に伴う、より高機能化された電子部品材料の焼成にはいまだ十分満足できる特性を有するものとは言えない。 As a method of firing a piezoelectric material, or a dielectric or magnetic material, which is an electronic component material, a firing method is adopted in which the evaporation component of the component to be fired is reduced as much as possible to reduce the composition variation. In the case of firing a piezoelectric, dielectric or magnetic body, the evaporation component from the fired body reacts with the heat treatment member, causing the fired body and the member to be stuck, or the member to be used in a short period of time due to corrosion. Therefore, zirconia having high corrosion resistance against the compositional components of the piezoelectric body and the dielectric is used, and Patent Document 1 discloses a zirconia firing setter. Yes. However, although the zirconia calcined setter disclosed in this patent publication is said to be excellent in corrosion resistance by using cubic zirconia, only the corrosion resistance is improved by simply using cubic zirconia, but heating / cooling It cannot be said that it has a long life due to the repetition of the above, and it cannot be said that it still has satisfactory characteristics for firing more sophisticated electronic component materials with the recent rapid development of electronic material components. .
本発明の目的は、耐久性及び耐食性にすぐれたジルコニア製熱処理用部材を提供する点にある。
なお、本発明で示す耐久性とは加熱・冷却によるクラックや割れの発生がなく、また、変形もほとんど発生しないことである。
An object of the present invention is to provide a zirconia heat treatment member having excellent durability and corrosion resistance.
The durability shown in the present invention means that cracks and cracks do not occur due to heating and cooling, and that almost no deformation occurs.
本発明者らは前記のような現状を鑑みて鋭意研究を重ねてきた結果、熱処理用部材としてのジルコニア質焼結体が耐食性および耐久性であるための要件としては、結晶相が立方晶系ジルコニアのみからなるという条件だけでは不十分であり、結晶相が立方晶系ジルコニアであることに加え、焼結体密度、平均結晶粒径が特定の条件を満足しているとともに、１００〜３００℃における内部摩擦挙動が重要であることを見出した。すなわち、結晶相が立方晶系ジルコニアのみからなるジルコニア質焼結体であっても、ジルコニア中に固溶する安定化剤の均一性および焼成温度などによっても内部摩擦ピーク強度は大きく影響を受け、焼結体中の酸素イオンの拡散に起因する１００〜３００℃における内部摩擦ピーク強度が高ければ耐食性および耐久性が低くなることが分かってきた。そこで本発明者らはジルコニア質焼結体をすぐれた耐食性および耐久性を有する熱処理用部材とするため、ある特定の結晶相からなり、その焼結体の組成及び結晶粒径、さらには内部摩擦ピーク強度を制御することの必要性に着目し、本発明を完成するに至った。 As a result of intensive studies in view of the present situation as described above, the inventors of the present invention, as a requirement for the zirconia sintered body as a heat treatment member to have corrosion resistance and durability, have a crystal phase of cubic system. The condition that it consists only of zirconia is not sufficient. In addition to the fact that the crystal phase is cubic zirconia, the sintered body density and the average crystal grain size satisfy specific conditions, and the temperature is 100 to 300 ° C. It was found that the internal friction behavior in is important. That is, even if the crystal phase is a zirconia sintered body consisting only of cubic zirconia, the internal friction peak strength is greatly influenced by the uniformity of the stabilizer solid-solved in zirconia and the firing temperature, It has been found that the higher the internal friction peak strength at 100 to 300 ° C. due to the diffusion of oxygen ions in the sintered body, the lower the corrosion resistance and durability. In order to make the zirconia sintered body a heat-treating member having excellent corrosion resistance and durability, the inventors of the present invention are composed of a specific crystal phase, the composition and crystal grain size of the sintered body, and further internal friction. Focusing on the necessity of controlling the peak intensity, the present invention has been completed.
即ち、本発明の第１は、（ａ）立方晶系ジルコニアからなるジルコニア質焼結体であって、（ｂ）気孔率が２％以下であり、（ｃ）平均結晶粒径が５〜３０μｍであって、（ｄ）ＳｉＯ ２ 、Ｎａ ２ ＯおよびＫ ２ Ｏの合計量が０．３重量％以下であって、（ｅ）１００〜３００℃における内部摩擦ピーク強度が２５×１０−３以下であることを特徴とするジルコニア製熱処理用部材に関する。
本発明の第２は、（ｆ）Ｙ２Ｏ３およびＣａＯよりなる群から選ばれた少なくとも１種の安定化剤がジルコニアに対し８〜２０ｍｏｌ％含有するものである請求項１記載のジルコニア製熱処理用部材に関する。
本発明の第３は、（ｇ）Ａｌ ２ Ｏ ３ 含有量が１重量％以下であることを特徴とする請求項１または２記載のジルコニア製熱処理用部材に関する。
That is, the first of the present invention is (a) a zirconia sintered body made of cubic zirconia, (b) having a porosity of 2% or less, and (c) an average crystal grain size of 5 to 30 μm. (D) The total amount of SiO 2 , Na 2 O and K 2 O is 0.3% by weight or less, and (e) the internal friction peak strength at 100 to 300 ° C. is 25 × 10 −3 or less. The present invention relates to a member for heat treatment made of zirconia.
The second of the present invention is (f) wherein at least one stabilizer selected from the group consisting of Y 2 O 3 and CaO is contained in an amount of 8 to 20 mol% based on zirconia. The present invention relates to a heat treatment member.
The third invention relates to zirconia thermal treatment member according to claim 1 or 2, wherein it is (g) Al 2 O 3 content is less than 1 wt%.
以下に詳細な本発明について説明する。
（ａ）立方晶系ジルコニアからなるジルコニア質焼結体である点
本発明において、ジルコニア質焼結体は立方晶系ジルコニアからなることが必要である。焼結体に単斜晶系ジルコニアが多く含有されていると加熱・冷却の繰り返しにより、クラックが発生し、割れや剥離が起こり耐久性に劣るので好ましくない。本発明における単斜晶系ジルコニアの許容できる含有量は５容積％以下までである。
なお、本発明では、単斜晶系ジルコニア（Ｍ）の存在および含有量については下記の方法でＸ線回折により求める。
即ち、焼結体を乳鉢等を用い、指頭に粒子の存在を感じない程度まで粉砕し、Ｘ線回折により、回折角２７〜３４度の範囲で測定し、単斜晶系ジルコニアの有無および含有量を下記式より求める。
(A) Point that is a zirconia sintered body made of cubic zirconia In the present invention, the zirconia sintered body needs to be made of cubic zirconia. If the sintered body contains a large amount of monoclinic zirconia, cracking occurs due to repeated heating and cooling, and cracking and peeling occur, resulting in poor durability. The acceptable content of monoclinic zirconia in the present invention is up to 5% by volume.
In the present invention, the presence and content of monoclinic zirconia (M) are determined by X-ray diffraction by the following method.
That is, using a mortar or the like, the sintered body was pulverized to such an extent that the presence of particles on the fingertips was not felt, measured by X-ray diffraction in a diffraction angle range of 27 to 34 degrees, and presence or absence of monoclinic zirconia The amount is obtained from the following formula.
（ｂ）気孔率が２％以下である点
本発明においては気孔率は２％以下、好ましくは１％以下であることが必要である。気孔率が２％を超える場合には耐食性の低下が起こるので好ましくない。下限は０％である。なお、気孔率とは焼結体に含有されている空隙の量を指し、その測定はＪＩＳ Ｒ １６３４に準拠して行う。
(B) The porosity is 2% or less In the present invention, the porosity needs to be 2% or less, preferably 1% or less. When the porosity exceeds 2%, the corrosion resistance is lowered, which is not preferable. The lower limit is 0%. The porosity means the amount of voids contained in the sintered body, and the measurement is performed according to JIS R 1634.
（ｃ）平均結晶粒径が５〜３０μｍである点
本発明においては平均結晶粒径は５〜３０μｍ、好ましくは８〜２５μｍである。平均結晶粒径が５μｍ未満の場合は、耐食性の低下や繰り返しの使用による変形が起こるので好ましくない。一方、３０μｍを超える場合には耐熱衝撃抵抗性の低下が起こるので好ましくない。
平均結晶粒径の測定は、焼結体を鏡面仕上げし、熱エッチングを施し、走査電子顕微鏡により観察してインターセプト法により１０点測定した平均値とする。算出式は下記の通りである。
Ｄ＝１．５×Ｌ／ｎ
Ｄ：平均結晶粒径（μｍ）
Ｌ：測定長さ（μｍ）
ｎ：測定長さあたりの結晶粒子数
(C) The point that the average crystal grain size is 5 to 30 μm In the present invention, the average crystal grain size is 5 to 30 μm, preferably 8 to 25 μm. When the average crystal grain size is less than 5 μm, the corrosion resistance is lowered and deformation due to repeated use occurs. On the other hand, when it exceeds 30 μm, the thermal shock resistance is lowered, which is not preferable.
The average grain size is measured by averaging the sintered body with a mirror finish, applying thermal etching, observing with a scanning electron microscope, and measuring 10 points by the intercept method. The calculation formula is as follows.
D = 1.5 × L / n
D: Average crystal grain size (μm)
L: Measurement length (μm)
n: Number of crystal grains per measurement length
（ｄ）ＳｉＯ２、Ｎａ２ＯおよびＫ２Ｏの合計量が０．３重量％以下である点
本発明においては、ＳｉＯ２、Ｎａ２ＯおよびＫ２Ｏの合計量が０．３重量％以下、好ましくは０．２重量％以下、より好ましくは０．１重量％以下であることが必要である。
ＳｉＯ２、Ｎａ２ＯおよびＫ２Ｏの合計量が０．３重量％を越える場合には、ジルコニア結晶粒界にガラス相および第２相として層あるいは固まりとなって存在しやすくなり、耐食性の低下だけでなく、加熱・冷却による変形の原因となるため好ましくない。とりわけ、ＳｉＯ２含有量は０．１重量％以下、より好ましくは０．０５重量％以下であることが好ましい。なお、ＳｉＯ２含有量は下限値は０．０３重量％程度である。
(D) The total amount of SiO 2 , Na 2 O and K 2 O is 0.3 wt% or less In the present invention, the total amount of SiO 2 , Na 2 O and K 2 O is 0.3 wt% In the following, it is necessary that it is preferably 0.2% by weight or less, more preferably 0.1% by weight or less.
When the total amount of SiO 2 , Na 2 O and K 2 O exceeds 0.3% by weight, it tends to exist as a glass phase and a second phase as a glass phase and a second phase at the zirconia crystal grain boundary, and corrosion resistance This is not preferable because it causes not only a reduction but also deformation due to heating and cooling. In particular, the SiO 2 content is preferably 0.1% by weight or less, more preferably 0.05% by weight or less. The lower limit of the SiO 2 content is about 0.03% by weight.
（ｅ）１００〜３００℃における内部摩擦ピーク強度が２５×１０−３以下である点
本発明においては、１００〜３００℃における内部摩擦ピーク強度は２５×１０−３以下、より好ましくは２０×１０−３以下である。内部摩擦ピーク強度が２５×１０−３を超える場合には耐食性だけでなく、加熱・冷却により立方晶系ジルコニアが正方晶系ジルコニアに変態し、さらにこの正方晶系ジルコニアが単斜晶系ジルコニアに変態して、焼結体中のクラックや割れを引き起こすので好ましくない。
なお、本発明における内部摩擦の測定は、ＪＩＳ Ｒ １６４２−１に準拠してねじり振子法により行った。なお、測定に用いる試料は７×２×８０ｍｍの板状のものである。
(E) The point that the internal friction peak strength at 100 to 300 ° C. is 25 × 10 −3 or less In the present invention, the internal friction peak strength at 100 to 300 ° C. is 25 × 10 −3 or less, more preferably 20 × 10. -3 or less. When the internal friction peak strength exceeds 25 × 10 −3 , not only corrosion resistance but also cubic zirconia is transformed into tetragonal zirconia by heating and cooling, and this tetragonal zirconia is transformed into monoclinic zirconia. It is not preferable because it transforms and causes cracks and cracks in the sintered body.
In addition, the measurement of the internal friction in this invention was performed by the torsion pendulum method based on JISR1642-1. The sample used for the measurement is a 7 × 2 × 80 mm plate.
（ｆ）ジルコニアと安定化剤の合計量を１００ｍｏｌ％としたとき、Ｙ２Ｏ３およびＣａＯよりなる群から選ばれた少なくとも１種の安定化剤が８〜２０ｍｏｌ％含有されている点
本発明においては、ジルコニアと安定化剤の合計量を１００ｍｏｌ％としたとき、Ｙ２Ｏ３およびＣａＯよりなる群から選ばれた少なくとも１種の安定化剤が８〜２０ｍｏｌ％、好ましくは１０ｍｏｌ％を超え１６ｍｏｌ％以下含有されていることが必要である。通常、ＺｒＯ２原料中に少量含有することのあるＨｆＯ２が混入していても良く、このＨｆＯ２量を含めたＺｒＯ２とＨｆＯ２の合計量をＺｒＯ２量とする。安定化剤の含有量が８ｍｏｌ％未満の場合は焼結体中の単斜晶系ジルコニア量が増加し、耐久性および耐食性の低下をきたすため好ましくない。一方、安定化剤の含有量が２０ｍｏｌ％を越える場合にはジルコニアに固溶する安定化剤が多くなりすぎ、ジルコニア結晶粒界に第２相の生成などが起こり、耐食性および耐久性の低下が起こるので好ましくない。なお、ＨｆＯ２は、通常ジルコニア中に１〜３重量％程度含有されている。
また、安定化剤のうち、３０重量％までは、ＭｇＯおよび他の希土類酸化物（Ｙ２Ｏ３以外の希土類酸化物）の１種または２種以上で置換したものも用いることができる。
When a 100 mol% of the total amount of (f) zirconia and stabilizing agent, Y 2 O 3 and at least one stabilizing agent selected from the group consisting of CaO present invention that are contained 8～20Mol% in, when the total amount of zirconia and stabilizing agent and 100 mol%, of at least one stabilizing agent selected from the group consisting of Y 2 O 3 and CaO are 8～20Mol%, preferably more than 10 mol% It is necessary to contain 16 mol% or less. Usually, HfO 2 that may contain minor amounts to ZrO 2 in the raw material may also be mixed to the total amount of ZrO 2 and HfO 2, including the HfO 2 amount and ZrO 2 amount. When the content of the stabilizer is less than 8 mol%, the amount of monoclinic zirconia in the sintered body increases, resulting in a decrease in durability and corrosion resistance. On the other hand, when the content of the stabilizer exceeds 20 mol%, the amount of the stabilizer dissolved in zirconia is excessive, and the formation of the second phase occurs at the zirconia grain boundaries, resulting in a decrease in corrosion resistance and durability. Since it happens, it is not preferable. HfO 2 is usually contained in zirconia in an amount of about 1 to 3% by weight.
Of the stabilizers, up to 30% by weight can be used substituted with one or more of MgO and other rare earth oxides (rare earth oxides other than Y 2 O 3 ).
（ｇ）不純物であるＡｌ ２ Ｏ ３ の含有量は１重量％以下まで許容できる点。
不純物であるＡｌ２Ｏ３の含有量は１重量％以下まで許容できる。Ａｌ２Ｏ３はジルコニアの焼結性向上に効果がある反面、耐食性低下の原因となる。Ａｌ２Ｏ３含有量が１重量％を越える場合には耐食性の低下が起こるので好ましくない。通常の精製手段による下限値は０．０５重量％程度である。
(G) The content of Al 2 O 3 which is an impurity is acceptable up to 1% by weight or less.
The content of Al 2 O 3 that is an impurity is acceptable up to 1% by weight or less. Al 2 O 3 is effective in improving the sinterability of zirconia, but causes a decrease in corrosion resistance. If the Al 2 O 3 content exceeds 1% by weight, the corrosion resistance is lowered, which is not preferable. The lower limit of the usual purification means is about 0.05% by weight.
また、ジルコニア、安定化剤およびＡｌ２Ｏ３以外の不純物は、０．５重量％以下、好ましくは０．３重量％以下、より好ましくは０．０５重量％以下である。 Moreover, zirconia, impurities other than stabilizers and Al 2 O 3 is 0.5 wt% or less, preferably 0.3 wt% or less, more preferably 0.05 wt% or less.
本発明のジルコニア製熱処理用部材の製造方法について説明する。
ジルコニアおよび安定化剤であるＹ２Ｏ３およびＣａＯ原料粉体は、いずれも純度９９．５％以上、平均粒子径が５μｍ以下であることが好ましい。安定化剤として用いるＹ２Ｏ３およびＣａＯは炭酸塩、水酸化物等の化合物の形態で添加しても良いが、その場合は予めジルコニアと所定量の安定化剤量となるように化合物を乾式混合もしくは湿式混合し、乾燥後、１０００〜１４００℃で合成することが好ましい。酸化物を用いる場合には合成を行っても、省略しても良い。
なお、本発明における合成とは、ジルコニア原料粉体と安定化剤とを混合した粉体を焼成温度より低い温度で処理することを言う。この処理を行う目的、効果はジルコニアと安定化剤とをあらかじめ焼成前に反応させておくことによりジルコニアに固溶する安定化剤を均質化する。使用する安定化剤が炭酸塩あるいは水酸化物のような形態の場合には、この処理により酸化物の形に変え、最終的には得られる焼結体の緻密性を向上させる。しかしながら、この合成工程を省略しても問題がない場合には、当然のことながら省略することができる。
The manufacturing method of the member for heat processing made from zirconia of this invention is demonstrated.
It is preferable that the zirconia and the Y 2 O 3 and CaO raw material powders that are stabilizers have a purity of 99.5% or more and an average particle diameter of 5 μm or less. Y 2 O 3 and CaO used as stabilizers may be added in the form of compounds such as carbonates, hydroxides, etc. In this case, the compounds are preliminarily added to zirconia and a predetermined amount of stabilizer. It is preferable to synthesize at 1000 to 1400 ° C. after dry mixing or wet mixing and drying. When an oxide is used, it may be synthesized or omitted.
The synthesis in the present invention means that a powder obtained by mixing a zirconia raw material powder and a stabilizer is treated at a temperature lower than the firing temperature. The purpose and effect of this treatment are to homogenize the stabilizer that is dissolved in zirconia by reacting zirconia and the stabilizer in advance before firing. When the stabilizer to be used is in the form of carbonate or hydroxide, it is changed to the form of oxide by this treatment, and finally the denseness of the obtained sintered body is improved. However, if there is no problem even if this synthesis step is omitted, it can be omitted as a matter of course.
具体的には、ジルコニアおよび安定化剤、もしくは合成粉体を溶媒として水または有機溶媒を用いてポットミル、アトリッションミル等の粉砕機により粉砕・分散・混合する。得られた粉体の平均粒子径（Ｄ）は０．８μｍ以下、好ましくは０．５μｍ以下であることが必要である。さらに、平均粒子径（Ｄ）と比表面積から求まる粒子径（Ｂ）との比：Ｄ／Ｂすなわち（平均粒子径）／（比表面積から求まる粒子径）が６以下、好ましくは５以下であることが好ましい。平均粒子径およびＤ／Ｂが上記の範囲外の場合は、得られたジルコニア焼結体に固溶する安定化剤の均一性が低下し、立方晶系ジルコニアのみからなる焼結体であっても内部摩擦ピーク強度が高くなって耐食性および耐久性の低下につながるので好ましくない。 Specifically, the mixture is pulverized, dispersed, and mixed by a pulverizer such as a pot mill or an attrition mill using zirconia and a stabilizer or synthetic powder as a solvent and water or an organic solvent. The average particle diameter (D) of the obtained powder needs to be 0.8 μm or less, preferably 0.5 μm or less. Further, the ratio of the average particle diameter (D) to the particle diameter (B) determined from the specific surface area: D / B, that is, (average particle diameter) / (particle diameter determined from the specific surface area) is 6 or less, preferably 5 or less. It is preferable. When the average particle diameter and D / B are out of the above ranges, the uniformity of the stabilizer that dissolves in the obtained zirconia sintered body is lowered, and the sintered body is composed only of cubic zirconia. However, it is not preferable because the internal friction peak strength is increased and the corrosion resistance and durability are lowered.
成形方法として、プレス成形やラバープレス成形等の方法を採用する場合には、粉砕・分散・混合スラリーに必要により公知の成型助剤（例えばワックスエマルジョン、ＰＶＡ、アクリル樹脂等）を加え、スプレードライヤー等の公知の方法で乾燥させて成形用粉体を作製し、これを用いて成型する。また、鋳込成形法を採用する場合には、粉砕・分散・混合スラリーに必要により公知のバインダー（例えばワックスエマルジョン、アクリル樹脂等）を加え、石膏型あるいは樹脂型を用いて坏泥鋳込、充填鋳込あるいは加圧鋳込法により成形する。さらに、押出成形法を用いる場合には、粉砕・分散・混合スラリーを乾燥させ、整粒し、混合機を用いて水、バインダー（例えばメチルセルロース等）を混合して坏土を作製し、押出成形する。 When a method such as press molding or rubber press molding is adopted as a molding method, a known molding aid (for example, wax emulsion, PVA, acrylic resin, etc.) is added to the pulverized / dispersed / mixed slurry as necessary, and a spray dryer is used. A powder for molding is produced by drying by a known method such as the above, and molded using this. In addition, when adopting a casting method, a known binder (for example, wax emulsion, acrylic resin, etc.) is added to the pulverized / dispersed / mixed slurry as necessary, and a gypsum mold or a resin mold is used to cast the mud. Molded by filling or pressure casting. Furthermore, when using the extrusion molding method, the pulverized / dispersed / mixed slurry is dried, sized, mixed with water and a binder (for example, methyl cellulose) using a mixer to produce a clay, and extruded. To do.
以上のようにして得た成形体を１５００〜１７５０℃、好ましくは１５５０〜１７００℃で焼成することによってジルコニア製熱処理用部材を得る。 The molded body obtained as described above is fired at 1500 to 1750 ° C., preferably 1550 to 1700 ° C., to obtain a zirconia heat treatment member.
本発明のジルコニア製熱処理用部材は耐久性および耐食性にすぐれている。そのため、本発明のジルコニア製熱処理用部材は、圧電体、誘電体および磁性体などの電子部品材料、蛍光体およびセラミック材料の熱処理用容器およびセッター、単結晶育成用ルツボ、金属溶解用ルツボ、各種電気炉用炉心管および各種機器用の保護管などの用途において有用である。 The heat-treating member made of zirconia of the present invention is excellent in durability and corrosion resistance. Therefore, the heat treatment member made of zirconia of the present invention includes electronic parts materials such as piezoelectric bodies, dielectric bodies and magnetic bodies, heat treatment containers and setters for phosphors and ceramic materials, crucibles for growing single crystals, crucibles for melting metals, It is useful in applications such as electric furnace core tubes and protective tubes for various devices.
以下に実施例を挙げて本発明を説明するが、本発明はこれより何ら限定されるものでない。 Hereinafter, the present invention will be described with reference to examples, but the present invention is not limited thereto.
実施例１〜６、比較例１〜５
純度９９．５％、平均粒子径３．５μｍであるジルコニア粉体と、安定化剤としての純度９９．８％、平均粒子径０．５μｍのＹ２Ｏ３および純度９９．０％、平均粒子径５μｍのＣａＣＯ３粉体とを用いた。安定化剤としてＹ２Ｏ３を用いる場合は、表１に示す所定量のＹ２Ｏ３量になるように配合し、アトリッションミルで湿式で粉砕・分散・混合し、スラリーを作製した。安定化剤としてＣａＯを用いる場合は、表１に示す所定量のＣａＯ量になるような量のＣａＣＯ３粉体を湿式で混合、乾燥し、１３００℃で合成し、得られた合成粉体を安定化剤としてＹ２Ｏ３を用いる場合と同様にして粉砕・分散し、スラリーを作製した。得られたスラリーに粉体に対してポリビニルアルコール（ＰＶＡ）を２重量％添加し、スプレードライヤー乾燥を施して成形用粉体とした。得られた成形用粉体を金型を用いて１ｔｏｎｆ／ｃｍ２の圧力によりプレス成形し、１４５０〜１８００℃で焼成して、１５０ｍｍ角で厚さ２ｍｍの板状熱処理用セッターを作製した。得られた焼結体特性を表２に示す。
得られた熱処理用セッターの上に市販のＰＺＴ粉体を直径２５ｍｍ、厚さ５ｍｍに成形した成形体を載せ、さらに成形体に１ｋＰａの応力をかけた状態で１３００℃、５時間保持し、７００℃まで１００℃／ｈで冷却後、炉外に取り出すテストを５サイクル行い、セッターの割れの有無により耐久性の評価をした。また、上記耐久性テストで割れなかったセッターについてはテスト後の焼結体断面を鏡面仕上げし、ＥＤＸにより浸食深さを測定した。
Examples 1-6, Comparative Examples 1-5
Zirconia powder having a purity of 99.5% and an average particle diameter of 3.5 μm, a purity of 99.8% as a stabilizer, Y 2 O 3 having an average particle diameter of 0.5 μm, and a purity of 99.0% and an average particle CaCO 3 powder having a diameter of 5 μm was used. When Y 2 O 3 was used as a stabilizer, it was blended so as to have a predetermined amount of Y 2 O 3 as shown in Table 1, and was pulverized, dispersed, and mixed wet by an attrition mill to prepare a slurry. . When CaO is used as a stabilizer, an amount of CaCO 3 powder of a predetermined amount shown in Table 1 is wet mixed, dried, synthesized at 1300 ° C., and the resulting synthetic powder is obtained. The slurry was pulverized and dispersed in the same manner as in the case of using Y 2 O 3 as a stabilizer. To the obtained slurry, 2% by weight of polyvinyl alcohol (PVA) was added to the powder, followed by spray dryer drying to obtain a molding powder. The obtained molding powder was press-molded with a mold at a pressure of 1 tonf / cm 2 and fired at 1450 to 1800 ° C. to produce a plate heat treatment setter having a 150 mm square and a thickness of 2 mm. The obtained sintered body characteristics are shown in Table 2.
A molded product obtained by molding a commercially available PZT powder with a diameter of 25 mm and a thickness of 5 mm is placed on the setter for heat treatment, and further maintained at 1300 ° C. for 5 hours with a stress of 1 kPa applied to the molded product. After cooling to 100 ° C./h at 100 ° C./h, a test for taking out the outside of the furnace was conducted for 5 cycles, and durability was evaluated by the presence or absence of setter cracks. Moreover, about the setter which was not cracked by the said durability test, the sintered compact cross section after the test was mirror-finished and the erosion depth was measured by EDX.
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