JP6041719B2 - Heat treatment member made of zirconia sintered body - Google Patents
Heat treatment member made of zirconia sintered body Download PDFInfo
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本発明は耐食性と耐久性に優れたジルコニア質焼結体からなる熱処理用部材に関する。なお、本発明におけるジルコニア質焼結体からなる熱処理用部材とは、圧電体や誘電体などの電子部品材料の熱処理に使用するセッター、容器及び治具類など、及び各種電気炉用炉心管及び各種機器用の保護管などである。 The present invention relates to a heat treatment member comprising a zirconia sintered body having excellent corrosion resistance and durability. In the present invention, the heat treatment member comprising a zirconia sintered body refers to setters, containers, jigs and the like used for heat treatment of electronic component materials such as piezoelectric bodies and dielectrics, and various furnace core tubes for electric furnaces. Protective tubes for various devices.
電子部品材料である圧電体、誘電体及び磁性体などは、その熱処理の際に、被焼成体の蒸発成分を極力少なくして組成変動を抑制するため耐食性に優れたセラミックス焼結体を使用してきた。中でも鉛を含有する圧電体や誘電体などの電子部品材料の焼成工程には、鉛に対する耐食性が高い緻密質のジルコニア質が採用されてきた。しかしながら、近年、その発展が目覚ましい情報端末（パソコン、携帯電話、携帯情報端末など）や情報家電（複写機、プリンター、音響機器、映像機器など）に搭載される高機能な電子部品材料は、精密な組成制御が必要不可欠なため、焼成に使用する熱処理用部材として従来よりも耐食性に優れていることは勿論のこと、繰り返し使用しても耐食性が著しく低下せずに長期間使用できるジルコニア質が要求されている。 Piezoelectric bodies, dielectric bodies, and magnetic bodies, which are electronic component materials, use ceramic sintered bodies with excellent corrosion resistance in order to suppress composition fluctuations by minimizing the evaporation components of the body to be fired during heat treatment. It was. In particular, dense zirconia having high corrosion resistance against lead has been employed in the firing process of electronic component materials such as piezoelectrics and dielectrics containing lead. However, in recent years, high-performance electronic component materials installed in information terminals (PCs, mobile phones, portable information terminals, etc.) and information appliances (copiers, printers, audio equipment, video equipment, etc.) that have made remarkable progress Since it is indispensable to control the composition, the zirconia material that can be used for a long period of time without remarkably reducing the corrosion resistance even if it is repeatedly used is of course superior in corrosion resistance as a heat treatment member used for firing. It is requested.
特許文献１には、鉛含有化合物に対する反応を防止した立方晶ジルコニアを主結晶相とするジルコニア焼結体が開示されている。そして助剤として加えたＣａをＣａ３ＺｒＳｉＯ９結晶としてジルコニア結晶粒界に析出させることにより、ジルコニア結晶と鉛含有化合物との反応を極めて低くできるとしている。しかしながら、ジルコニア結晶と鉛含有化合物との反応を抑制できても、Ｓｉを含有するＣａ３ＺｒＳｉＯ９結晶と鉛が容易に反応するため、結果的にジルコニア焼結体全体としての耐食性が低下するという問題があり、高機能な電子部品材料の熱処理の用途で十分満足できる特性を有するものでは無かった。しかも、助剤として添加しているＣａＯは、一般的にはジルコニアの安定化剤でもあり、特許文献１における安定化剤はＹ２Ｏ３とＣａＯの２種類を併用していることになるが、Ｙ２Ｏ３とＣａＯのジルコニアへの固溶形態が異なるため、ジルコニア結晶相の安定性が低下し、耐久性に劣るという問題があった。 Patent Document 1 discloses a zirconia sintered body having cubic zirconia that prevents reaction to a lead-containing compound as a main crystal phase. The reaction between the zirconia crystals and the lead-containing compound can be made extremely low by precipitating Ca added as an auxiliary agent as Ca 3 ZrSiO 9 crystals at the zirconia grain boundaries. However, even if the reaction between the zirconia crystal and the lead-containing compound can be suppressed, the Ca 3 ZrSiO 9 crystal containing Si easily reacts with lead, resulting in a decrease in the corrosion resistance of the entire zirconia sintered body. There was a problem, and it did not have sufficiently satisfactory characteristics for heat treatment of highly functional electronic component materials. In addition, CaO added as an auxiliary agent is also a zirconia stabilizer, and the stabilizer in Patent Document 1 uses two types of Y 2 O 3 and CaO in combination. , Y 2 O 3 and CaO have different solid solution forms in zirconia, so that there is a problem that stability of the zirconia crystal phase is lowered and durability is inferior.
またジルコニア質焼結体にＡｌ２Ｏ３を含有させて特性向上を図る技術は数多く提案されており、例えば特許文献２には、ジルコニア結晶相、焼結体の組成及び平均結晶粒径を制御して得た、耐久性及び耐食性に優れたジルコニア製熱処理用部材が開示されている。そして、含有させる特定量のＡｌ２Ｏ３が、ジルコニアの焼結性向上や粒界強化に寄与することにより、耐熱衝撃抵抗性や耐久性向上に効果があるとしている。しかし、この技術は従来の電子部品材料に使用できる程度の耐食性は有するが、ジルコニアよりも鉛に対する耐食性が劣るＡｌ２Ｏ３を含有しているため、精密な組成制御が必要不可欠な高機能の電子部品材料に対する耐食性は十分では無かった。またＣａＯを安定化剤とするジルコニア質においては、Ａｌ２Ｏ３とＣａＯが反応してジルコニア結晶粒界に低融点化合物やガラス相を形成し、これがジルコニア結晶粒界に偏析して、耐食性や耐久性を低下させるという問題があった。しかも、低融点化合物やガラス相とジルコニア結晶粒子との熱膨張差等の影響により、焼成時の冷却過程で低融点化合物やガラス相にクラックが生じ、ジルコニア結晶粒界が脆くなってジルコニア結晶粒子の脱粒が発生しやすくなること、及び脱粒したジルコニア結晶粒子が被焼成体に混入・付着したり、脱粒で部材表面に凹凸が生じ、被焼成体表面にこの凹凸が転写されて被焼成体の歩留まりが著しく悪化するという問題もあり、特に製品厚みの薄い電子部品材料の熱処理の用途では全く使用できなかった。 Further, many techniques for improving characteristics by incorporating Al 2 O 3 into a zirconia sintered body have been proposed. For example, Patent Document 2 controls the zirconia crystal phase, the composition of the sintered body, and the average crystal grain size. A heat-treating member made of zirconia having excellent durability and corrosion resistance is disclosed. And the specific amount of Al 2 O 3 to be contained is said to be effective in improving thermal shock resistance and durability by contributing to improvement in sinterability and grain boundary strengthening of zirconia. However, although this technology has corrosion resistance to the extent that it can be used for conventional electronic component materials, it contains Al 2 O 3 which is inferior in corrosion resistance to lead compared to zirconia. Corrosion resistance to electronic component materials was not sufficient. In addition, in zirconia having CaO as a stabilizer, Al 2 O 3 and CaO react to form a low melting point compound or glass phase at the zirconia crystal grain boundary, which segregates at the zirconia crystal grain boundary, resulting in corrosion resistance and There was a problem of reducing durability. In addition, due to the effects of the low melting point compound and the difference in thermal expansion between the glass phase and zirconia crystal particles, cracks occur in the low melting point compound and glass phase during the cooling process during firing, and the zirconia crystal grain boundaries become brittle and the zirconia crystal particles Degranulation is likely to occur, and degranulated zirconia crystal particles are mixed and adhered to the body to be fired, or unevenness occurs on the surface of the member due to grain removal, and the unevenness is transferred to the surface of the body to be fired. There is also a problem that the yield is remarkably deteriorated. In particular, it cannot be used at all for heat treatment of electronic component materials having a thin product thickness.
本発明は、ＣａＯを安定化剤とする従来のジルコニア質焼結体よりも優れた耐食性と耐久性を有するジルコニア質焼結体よりなる熱処理用部材の提供を目的とする。
なお、本発明でいう優れた耐食性とは、被焼成体と接触しているジルコニア質焼結体側への被焼成体成分（鉛など）の浸透量が極めて少ないこと、及びジルコニア質焼結体中の成分が被焼成体へ浸透したり、被焼成体成分と反応しないことを意味する。また、優れた耐久性とは、長期間にわたって繰り返し使用した際でも耐食性が著しく低下せず、ジルコニア質焼結体に変形、クラック、割れなどが生じないことを意味する。
An object of the present invention is to provide a heat treatment member comprising a zirconia sintered body having corrosion resistance and durability superior to those of a conventional zirconia sintered body using CaO as a stabilizer.
The excellent corrosion resistance as used in the present invention means that the amount of the component of the body to be fired (such as lead) penetrating into the zirconia sintered body in contact with the body to be fired is extremely small, and in the zirconia sintered body. Means that it does not penetrate into the fired body or react with the fired body component. Further, excellent durability means that the corrosion resistance does not remarkably decrease even when used repeatedly for a long period of time, and the zirconia sintered body is not deformed, cracked, cracked or the like.
本発明者らは鋭意研究を重ねた結果、上記課題が次の発明（１）により解決できることを見出した。
（１）次の（ａ）〜（ｆ）の要件を満たすことを特徴とするジルコニア質焼結体からなる熱処理用部材。
（ａ）ＺｒＯ２／ＣａＯ（モル比）が、９０／１０〜８０／２０
（ｂ）ＣａＯ／ＭｇＯ（モル比）が、９９／１〜９５／５
（ｃ）Ａｌ２Ｏ３量が、０．２０重量％以下
（ｄ）不純物量が、０．１０重量％以下
（ｅ）かさ密度が、５．２ｇ／ｃｍ３以上
（ｆ）平均結晶粒径が、１０〜４０μｍ
As a result of intensive studies, the present inventors have found that the above problem can be solved by the following invention (1).
(1) A heat treatment member comprising a zirconia sintered body, characterized by satisfying the following requirements (a) to (f).
(A) ZrO 2 / CaO (molar ratio), 90 / 10-80 / 20
(B) CaO / MgO (molar ratio) is 99/1 to 95/5.
(C) Al 2 O 3 amount is 0.20 wt% or less (d) Impurity amount is 0.10 wt% or less (e) Bulk density is 5.2 g / cm 3 or more (f) Average crystal grain size 10 to 40 μm
本発明によれば、ＣａＯを安定化剤とする従来のジルコニア質焼結体よりも優れた耐食性と耐久性を有するジルコニア質焼結体よりなる熱処理用部材を提供できる。
この熱処理用部材は、特にＰｂＯを含有する被焼成体に対しては、ジルコニア質焼結体側へのＰｂＯの浸透量が極めて少なく、ジルコニア質焼結体中の成分が被焼成体へ浸透したり、被焼成体成分と反応することの無い優れた耐食性を有する。また、長期間にわたって繰り返し使用した際でも耐食性が著しく低下せず、変形、クラック及び割れなどが生じない優れた耐久性を有する。
ADVANTAGE OF THE INVENTION According to this invention, the member for heat processing consisting of the zirconia sintered compact which has the corrosion resistance and durability superior to the conventional zirconia sintered compact which uses CaO as a stabilizer can be provided.
This heat treatment member has a very small amount of PbO penetrating into the zirconia sintered body, particularly for the body to be fired containing PbO, and the components in the zirconia sintered body penetrate into the body to be fired. It has excellent corrosion resistance that does not react with the component to be fired. Further, even when used repeatedly over a long period of time, the corrosion resistance is not significantly lowered, and it has excellent durability that does not cause deformation, cracks, cracks and the like.
以下、上記本発明について詳しく説明する。
（ａ）ＺｒＯ２／ＣａＯ（モル比）が９０／１０〜８０／２０である点
本発明に係るジルコニア質焼結体は、ＺｒＯ２／ＣａＯ（モル比）を９０／１０〜８０／２０とする。好ましくは８８／１２〜８２／１８である。
ＣａＯの割合が９０／１０未満の場合、ジルコニア結晶相として単斜晶系ジルコニアが増加し、加熱・冷却した時にジルコニア結晶相の相転移に伴う体積膨張によって変形やクラックが発生し、耐久性が低下する。しかも発生したクラックに被焼成体成分が浸透して耐食性も低下する。
なお、本発明におけるジルコニア結晶相は、立方晶系ジルコニアが９５容積％以上となり、正方晶系ジルコニアの許容含有量は３容積％以下、単斜晶系ジルコニアの許容含有量は２容積％以下である。これらの割合は、定法に従って、焼結体表面を鏡面にした試料を用い、Ｘ線回折法により、回折角２７〜３３°と、７２〜７５．５°の走査範囲で測定することにより容易に求めることができる。
Hereinafter, the present invention will be described in detail.
(A) a zirconia sintered body which ZrO 2 / CaO (molar ratio) according to the present invention that it is 90 / 10-80 / 20, ZrO 2 / CaO (molar ratio) and 90 / 10-80 / 20 To do. Preferably it is 88 / 12-82 / 18.
When the proportion of CaO is less than 90/10, monoclinic zirconia increases as the zirconia crystal phase, and deformation and cracks occur due to volume expansion accompanying the phase transition of the zirconia crystal phase when heated and cooled, resulting in durability. descend. And the to-be-fired body component osmose | permeates the crack which generate | occur | produced, and corrosion resistance also falls.
The zirconia crystal phase in the present invention is 95% by volume or more of cubic zirconia, the allowable content of tetragonal zirconia is 3% by volume or less, and the allowable content of monoclinic zirconia is 2% by volume or less. is there. These ratios can be easily determined by measuring in a scanning range of diffraction angles 27 to 33 ° and 72 to 75.5 ° by an X-ray diffraction method using a sample having a sintered body surface as a mirror surface according to a conventional method. Can be sought.
一方、ＣａＯの割合が８０／２０を越える場合、ジルコニアに固溶できなかった余剰のＣａＯがジルコニア質焼結体中で第２相を形成して被焼成体と反応し、耐食性や耐久性が低下するため好ましくない。本発明におけるジルコニア質焼結体の結晶相はＺｒＯ２とＣａＯの化合物単相からなり、これ以外の結晶相は存在しない。仮に第２相が存在すれば、耐食性が低下することになる。
なお、本発明でいう第２相が存在しない状態とは、下記条件のＸ線回折測定において、ＺｒＯ２とＣａＯの化合物以外の回折ピークが検出されないレベルのことを言う。また、測定には、焼結体を鏡面加工仕上げした試料を用いる。
・Ｘ線源：ＣｕＫα
・出力：４０ｋＶ／４０ｍＡ
・発散スリット：１°
・散乱スリット：１°
・受光スリット：０．１５ｍｍ
・スキャンスピード：３．０°／ｍｉｎ
・走査軸：２θ／θ
・走査範囲：１０〜７０°
・モノクロ受光スリット：０．８ｍｍ
・カウンタ：シンチレーションカウンタ
・モノクロメーター：自動モノクロメーター
On the other hand, when the proportion of CaO exceeds 80/20, excess CaO that could not be dissolved in zirconia forms a second phase in the zirconia sintered body and reacts with the object to be fired, resulting in corrosion resistance and durability. Since it falls, it is not preferable. The crystal phase of the zirconia sintered body in the present invention is composed of a single phase of a compound of ZrO 2 and CaO, and no other crystal phase exists. If the second phase is present, the corrosion resistance is lowered.
The state where the second phase does not exist in the present invention refers to a level at which diffraction peaks other than the compounds of ZrO 2 and CaO are not detected in the X-ray diffraction measurement under the following conditions. Moreover, the sample which carried out the mirror surface finishing of the sintered compact is used for a measurement.
・ X-ray source: CuKα
・ Output: 40kV / 40mA
・ Divergent slit: 1 °
・ Scatter slit: 1 °
・ Reception slit: 0.15mm
・ Scanning speed: 3.0 ° / min
・ Scanning axis: 2θ / θ
・ Scanning range: 10 ~ 70 °
・ Monochrome light receiving slit: 0.8mm
・ Counter: Scintillation counter ・ Monochrome meter: Automatic monochromator
（ｂ）ＣａＯ／ＭｇＯ（モル比）が９９／１〜９５／５である点
本発明に係るジルコニア質焼結体は、ＣａＯ／ＭｇＯ（モル比）を９９／１〜９５／５とする。好ましくは９８／２〜９６／４である。
従来のＺｒＯ２−ＣａＯ系又はＺｒＯ２−Ｙ２Ｏ３系の熱処理用部材では、アルカリ土類金属酸化物に属するＭｇＯは不純物として扱われ、その量は極力少ない方が良いとされていた。これに対し、本発明ではＣａＯに対して特定割合のＭｇＯを意図的に含有させる。その結果、本発明では、ＭｇＯがジルコニアの安定化剤として働く上に、ＣａＯと混入したＡｌ２Ｏ３との反応を抑制する機能を発揮するので、耐食性や耐久性の低下を非常に効果的に抑制することができる。
ＭｇＯの割合が９９／１未満の場合には、ＭｇＯの添加効果が低下するため、耐食性や耐久性の低下をきたす。一方、ＭｇＯの割合が９５／５を越えると、耐熱衝撃抵抗性が低下して短期間でクラックや割れが発生し、耐久性の低下をきたす。
(B) The point whose CaO / MgO (molar ratio) is 99/1 to 95/5 The zirconia sintered body according to the present invention has a CaO / MgO (molar ratio) of 99/1 to 95/5. Preferably it is 98/2-96/4.
In a conventional ZrO 2 —CaO-based or ZrO 2 —Y 2 O 3 -based heat treatment member, MgO belonging to an alkaline earth metal oxide is treated as an impurity, and the amount thereof should be as small as possible. On the other hand, in the present invention, a specific ratio of MgO is intentionally included with respect to CaO. As a result, in the present invention, MgO works as a zirconia stabilizer and also exhibits a function of suppressing the reaction between CaO and mixed Al 2 O 3 , so that it is very effective in reducing corrosion resistance and durability. Can be suppressed.
When the ratio of MgO is less than 99/1, the effect of adding MgO is reduced, so that corrosion resistance and durability are reduced. On the other hand, when the ratio of MgO exceeds 95/5, the thermal shock resistance decreases, cracks and cracks occur in a short period of time, and the durability decreases.
（ｃ）Ａｌ２Ｏ３量が０．２０重量％以下である点
前述したように、ＣａＯを安定化剤とするジルコニア質において、多量のＡｌ２Ｏ３が共存すると耐食性や耐久性が低下する。したがって、本発明ではＡｌ２Ｏ３量を０．２０重量％以下とする。好ましくは０．１５重量％以下、より好ましくは０．１０重量％以下である。０．２０重量％を越えると耐食性や耐久性が低下する。
Ａｌ２Ｏ３量を少なくするには、Ａｌ２Ｏ３量の少ない原料を選択したり、Ａｌ２Ｏ３の混入を抑制できるような製造方法を採用する。しかし、使用原料や製造工程（特に原料処理工程と焼成工程）から混入するＡｌ２Ｏ３を完全になくすことは不可能であり、０．０２重量％程度が下限である。
そこで本発明では、特定量のＭｇＯを含有させることによりＡｌ２Ｏ３とＣａＯの反応を抑制し、低融点化合物やガラス相が生成しないようにして、より確実に耐食性及び耐久性の低下を防止することにした。なお、本発明では、Ａｌ２Ｏ３量が非常に少ないため、従来技術のようなジルコニア結晶粒子の脱粒は発生しない。
(C) The amount of Al 2 O 3 is 0.20% by weight or less As described above, in a zirconia having CaO as a stabilizer, if a large amount of Al 2 O 3 coexists, corrosion resistance and durability are lowered. . Therefore, in the present invention, the amount of Al 2 O 3 is set to 0.20% by weight or less. Preferably it is 0.15 weight% or less, More preferably, it is 0.10 weight% or less. If it exceeds 0.20% by weight, the corrosion resistance and durability deteriorate.
To reduce the amount of Al 2 O 3 is to select a small feed of the amount of Al 2 O 3, to adopt a production method as can suppress the contamination of the Al 2 O 3. However, it is impossible to completely eliminate Al 2 O 3 mixed from the raw materials used and the manufacturing steps (particularly the raw material treatment step and the firing step), and the lower limit is about 0.02% by weight.
Therefore, in the present invention, by containing a specific amount of MgO, the reaction between Al 2 O 3 and CaO is suppressed, and a low melting point compound and a glass phase are not generated, thereby more reliably preventing a decrease in corrosion resistance and durability. Decided to do. In the present invention, since the amount of Al 2 O 3 is very small, zirconia crystal grains do not fall apart as in the prior art.
（ｄ）不純物量が０．１０重量％以下である点
本発明に係るジルコニア質焼結体の不純物量は０．１０重量％以下とする。
本発明における不純物とは入荷原料や製造工程から混入する成分であり、主にＳｉＯ２、Ｆｅ２Ｏ３、ＴｉＯ２、Ｋ２Ｏ、Ｎａ２Ｏ等である。これらの不純物の合計量が０．１０重量％を越えると、ジルコニア結晶粒界にガラス相が多く形成され、このガラス相が被焼成体と反応して、耐食性や耐久性が低下する。なお、現状の原料及び製造工程では、不純物量を０．０２重量％程度以下とすることは難しい。不純物の中でも特にＳｉＯ２は有害成分である。何故ならばＳｉＯ２やＳｉ化合物は被焼成体と容易に反応して耐食性を低下させたり、ジルコニア結晶粒界にガラス相を多く形成して耐食性や耐久性を著しく低下させたりするからである。そのため、ＳｉＯ２量は０．０３重量％以下とすることが好ましい。なお、現状の原料及び製造工程では、ＳｉＯ２量を０．０１重量％程度以下とすることは難しい。
(D) The amount of impurities is 0.10 wt% or less The amount of impurities in the zirconia sintered body according to the present invention is 0.10 wt% or less.
The impurities in the present invention is a component to be mixed from the stock material and manufacturing processes are primarily SiO 2, Fe 2 O 3, TiO 2, K 2 O, Na 2 O or the like. When the total amount of these impurities exceeds 0.10% by weight, a lot of glass phase is formed at the zirconia crystal grain boundary, and this glass phase reacts with the body to be fired, resulting in a decrease in corrosion resistance and durability. In the current raw materials and manufacturing processes, it is difficult to reduce the impurity amount to about 0.02% by weight or less. Among impurities, especially SiO 2 is a harmful component. This is because SiO 2 and Si compounds easily react with the object to be fired to lower the corrosion resistance, or form a large amount of glass phase at the zirconia crystal grain boundaries to significantly reduce the corrosion resistance and durability. Therefore, the amount of SiO 2 is preferably 0.03% by weight or less. In the current raw material and manufacturing process, it is difficult to reduce the SiO 2 amount to about 0.01% by weight or less.
（ｅ）かさ密度が５．２ｇ／ｃｍ３以上である点
本発明に係るジルコニア質焼結体のかさ密度は５．２ｇ／ｃｍ３以上とする。好ましくは５．３ｇ／ｃｍ３以上である。かさ密度が５．２ｇ／ｃｍ３未満の場合、焼結体中の気孔が増加し、この気孔に被焼成体成分が浸透して、耐食性や耐久性が低下する。かさ密度の上限は、技術上の制約から５．６ｇ／ｃｍ３程度である。なお、本発明におけるかさ密度はアルキメデス法で測定したものである。
(E) The bulk density is 5.2 g / cm 3 or more The bulk density of the zirconia sintered body according to the present invention is 5.2 g / cm 3 or more. Preferably it is 5.3 g / cm 3 or more. When the bulk density is less than 5.2 g / cm 3 , pores in the sintered body increase, and the fired body component penetrates into the pores, resulting in a decrease in corrosion resistance and durability. The upper limit of the bulk density is about 5.6 g / cm 3 due to technical restrictions. The bulk density in the present invention is measured by Archimedes method.
（ｆ）平均結晶粒径が１０〜４０μｍである点
本発明に係るジルコニア質焼結体の平均結晶粒径は１０〜４０μｍとする。好ましくは１５〜３５μｍである。平均結晶粒径が１０μｍ未満の場合、ジルコニア結晶粒界面積が増加し、この増加した粒界に被焼成体成分が浸透して耐食性や耐久性が低下する。また、平均結晶粒径が４０μｍを越えると、耐食性の低下は来たさないが、耐熱衝撃抵抗性の低下をきたす。
本発明における平均結晶粒径は、焼結体表面を鏡面まで研磨加工し、得られた鏡面に熱エッチング又は化学エッチングを施した後、走査電子顕微鏡で観察して、インターセプト法により１０点測定した平均値とする。算出式は下記のとおりである。
Ｄ＝１．５×Ｌ／ｎ
〔Ｄ：平均結晶粒径（μｍ）、Ｌ：測定長さ（μｍ）、ｎ：長さＬ当たりの結晶粒子数〕
(F) The point where an average crystal grain diameter is 10-40 micrometers The average crystal grain diameter of the zirconia sintered compact concerning this invention shall be 10-40 micrometers. Preferably it is 15-35 micrometers. When the average crystal grain size is less than 10 μm, the zirconia crystal grain interfacial area increases, and the fired body component penetrates into the increased grain boundary, thereby reducing the corrosion resistance and durability. On the other hand, when the average crystal grain size exceeds 40 μm, the corrosion resistance does not decrease, but the thermal shock resistance decreases.
The average crystal grain size in the present invention was measured at 10 points by the intercept method after polishing the surface of the sintered body to a mirror surface, subjecting the obtained mirror surface to thermal etching or chemical etching, and then observing with a scanning electron microscope. Average value. 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 length L]
本発明の熱処理用部材は種々の方法で作製できるが、その一例を下記に示す。
ジルコニア原料粉末は純度が９９．９重量％以上、平均粒子径が１０μｍ以下のものを用いる。純度が９９．９重量％未満の場合、原料粉末中に含まれる不純物量が多いため、焼結体中の不純物量も多くなり、耐食性や耐久性が低下する。また平均粒子径が１０μｍを超えると、焼結性が低下してかさ密度が低下する。平均粒子径の下限は０．５μｍ程度である。
安定化剤であるＣａＯ及びＭｇＯ原料粉末は純度が９９．９重量％以上、平均粒子径が５μｍ以下のものを用いる。純度が９９．９重量％未満の場合、原料粉末中に含まれる不純物量が多いため、焼結体中の不純物量も多くなり、耐食性や耐久性が低下する。また、平均粒子径が５μｍを越えると、ＣａＯ及びＭｇＯ原料粉末が粗いためにジルコニア原料粉末との混合・分散が不十分となり、焼結体中に単斜晶系ジルコニアが多くなる。平均粒子径の下限は０．５μｍ程度である。
Although the member for heat processing of this invention can be produced with various methods, the example is shown below.
A zirconia raw material powder having a purity of 99.9% by weight or more and an average particle size of 10 μm or less is used. When the purity is less than 99.9% by weight, since the amount of impurities contained in the raw material powder is large, the amount of impurities in the sintered body is also increased, and the corrosion resistance and durability are lowered. On the other hand, when the average particle diameter exceeds 10 μm, the sinterability is lowered and the bulk density is lowered. The lower limit of the average particle diameter is about 0.5 μm.
As the stabilizer, CaO and MgO raw material powders having a purity of 99.9% by weight or more and an average particle diameter of 5 μm or less are used. When the purity is less than 99.9% by weight, since the amount of impurities contained in the raw material powder is large, the amount of impurities in the sintered body is also increased, and the corrosion resistance and durability are lowered. On the other hand, if the average particle diameter exceeds 5 μm, the CaO and MgO raw material powder is coarse, so that mixing and dispersion with the zirconia raw material powder becomes insufficient, and monoclinic zirconia increases in the sintered body. The lower limit of the average particle diameter is about 0.5 μm.
また、ＣａＯ及びＭｇＯは炭酸塩、水酸化物等の化合物の形態で添加しても良い。その場合、予めジルコニア原料粉末と化合物原料粉末を、所定量の安定化剤量となるように水を溶媒として湿式混合し、乾燥後、１０００〜１４００℃の温度範囲で合成する。ＣａＯ及びＭｇＯの炭酸塩、水酸化物等の化合物原料粉末は、不純物量０．１重量％以下、平均粒子径５μｍ以下のものを使用する。原料粉末の不純物量が多いとジルコニア焼結体中の不純物量が増加する。また原料粉末の平均粒子径が５μｍを越えるとジルコニア原料粉末との混合・分散が不十分となる。平均粒子径の下限は０．５μｍ程度である。なお、酸化物であるＣａＯやＭｇＯを用いる場合は上記の合成工程を省略しても良い。
また、各原料粉末に含まれるＡｌ２Ｏ３量は０．０５重量％以下とする。好ましくは０．０３重量％以下である。これは、ジルコニア質焼結体中のＡｌ２Ｏ３量を０．２０重量％以下にするためである。
CaO and MgO may be added in the form of a compound such as carbonate or hydroxide. In that case, the zirconia raw material powder and the compound raw material powder are wet-mixed in advance using water as a solvent so as to have a predetermined amount of stabilizer, dried, and then synthesized in a temperature range of 1000 to 1400 ° C. Compound raw material powders such as carbonates and hydroxides of CaO and MgO are those having an impurity amount of 0.1% by weight or less and an average particle size of 5 μm or less. When the amount of impurities in the raw material powder is large, the amount of impurities in the zirconia sintered body increases. If the average particle diameter of the raw material powder exceeds 5 μm, mixing and dispersion with the zirconia raw material powder will be insufficient. The lower limit of the average particle diameter is about 0.5 μm. In addition, when using CaO and MgO which are oxides, you may abbreviate | omit said synthetic | combination process.
The amount of Al 2 O 3 contained in each raw material powder is 0.05% by weight or less. Preferably it is 0.03 weight% or less. This is to reduce the amount of Al 2 O 3 in the zirconia sintered body to 0.20% by weight or less.
以上の原料粉末を所定の組成になるように配合し、公知のポットミル、アトリッションミル等の粉砕機により、水又は有機溶媒を用いて湿式で粉砕・混合・分散の原料処理を行う。この時、粉砕機の内張材及びアームなどの部材や、粉砕機に充填するボールからの摩耗粉の混入を防止するため、該部材及びボールには耐摩耗性に優れたセラミックス材料を使用する。このように、原料処理工程からの摩耗紛の混入を防止することにより、ジルコニア質焼結体中のＡｌ２Ｏ３量だけでなく不純物量も制御することができる。 The above raw material powders are blended so as to have a predetermined composition, and raw material processing such as pulverization, mixing, and dispersion is performed in a wet manner using water or an organic solvent by a known pulverizer such as a pot mill or an attrition mill. At this time, a ceramic material having excellent wear resistance is used for the member and the ball in order to prevent contamination of wear powder from the lining material and arm of the pulverizer and the ball filled in the pulverizer. . Thus, by preventing the mixing of wear powder from the raw material processing step, not only the amount of Al 2 O 3 in the zirconia sintered body but also the amount of impurities can be controlled.
粉砕・混合・分散処理により得られた処理粉体の平均粒子径は１．５μｍ以下とする。該平均粒子径が１．５μｍを越えると、処理粉体中に粒子径の大きい粗い粉体が多く含まれるため、成形性が低下して成形体内部に多くの気孔が存在することになり、焼結体のかさ密度が低下する。処理粉体の平均粒子径の下限は０．５μｍ程度である。
なお、上記本発明における原料粉末及び処理粉体の平均粒子径とは、一次粒子が凝集した二次粒子の粒子径の平均値のことであり、レーザー回折式粒度分布測定装置で測定できる。
The average particle diameter of the treated powder obtained by pulverization / mixing / dispersion treatment is 1.5 μm or less. When the average particle diameter exceeds 1.5 μm, the processed powder contains many coarse powders having a large particle diameter, so that the moldability is reduced and there are many pores inside the molded body. The bulk density of the sintered body decreases. The lower limit of the average particle diameter of the treated powder is about 0.5 μm.
In addition, the average particle diameter of the raw material powder and the treated powder in the present invention is an average value of the particle diameter of the secondary particles in which the primary particles are aggregated, and can be measured with a laser diffraction particle size distribution measuring apparatus.
成形方法としてプレス成形、ラバープレス成形等の方法を採用する場合には、粉砕・混合・分散スラリーへ必要により公知の成形助剤（例えばアクリル系樹脂、ＰＶＡ等）を添加し、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、この成形用粉体を金型やゴム型などに充填して成形する。また、鋳込み成形法を採用する場合には、粉砕・混合・分散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、アクリル系樹脂等）を添加し、石膏型又は樹脂型を用いて排泥鋳込法、充填鋳込法、加圧鋳込法により成形する。また、押出成形法を採用する場合は、得られた粉砕・混合・分散スラリーを乾燥し整粒して、押出成形用バインダー（カルボキシルメチルセルロース、ワックスエマルジョン等の公知のバインダーが使用できる）と水又は有機溶媒を添加して混合し、土練して成形用坏土とする。この成形用坏土を用いて、公知の押出成形機により所定の形状になるように押出成形する。 When adopting a method such as press molding or rubber press molding as a molding method, a known molding aid (for example, acrylic resin, PVA, etc.) is added to the pulverized / mixed / dispersed slurry as necessary, and a spray dryer or the like is added. A molding powder is produced by drying by a known method, and the molding powder is filled into a mold or a rubber mold and molded. In addition, when adopting the casting method, a known binder (for example, wax emulsion, acrylic resin, etc.) is added to the pulverized / mixed / dispersed slurry as required, and the waste mud is cast using a gypsum mold or a resin mold. Molding is performed by the method of filling, casting and pressure casting. In addition, when an extrusion molding method is employed, the obtained pulverized / mixed / dispersed slurry is dried and sized, and an extrusion molding binder (known binders such as carboxymethyl cellulose and wax emulsion can be used) and water or An organic solvent is added and mixed, and then kneaded to form a molding clay. Using this molding clay, it is extruded to a predetermined shape by a known extruder.
以上のようにして得た成形体を、大気中、焼成温度１５５０〜１７５０℃で焼成する。焼成温度が１５５０℃未満の場合、平均結晶粒径やかさ密度の低下をきたし、耐食性や耐久性が低下する。焼成温度が１７５０℃を越えると、焼結体の平均結晶粒径が４０μｍを越えて耐久性が低下する。また、焼成工程でのＡｌ２Ｏ３や不純物の混入を避けるため、焼成に使用する敷き板などの道具は高純度ジルコニア質のものを使用する。 The molded body obtained as described above is fired at a firing temperature of 1550 to 1750 ° C. in the air. When the firing temperature is less than 1550 ° C., the average crystal grain size and bulk density are lowered, and the corrosion resistance and durability are lowered. When the firing temperature exceeds 1750 ° C., the average crystal grain size of the sintered body exceeds 40 μm and the durability is lowered. In order to avoid contamination of as Al 2 O 3 and impurities in the firing step, a tool such as laying plate for use in baking uses a high purity zirconia.
以下、実施例及び比較例を挙げて本発明を更に具体的に説明するが、本発明はこれらの実施例により何ら限定されるものではない。 EXAMPLES Hereinafter, although an Example and a comparative example are given and this invention is demonstrated further more concretely, this invention is not limited at all by these Examples.
実施例１〜８、比較例１〜１０
比較例６と１０以外は、純度９９．９重量％、平均粒子径４μｍのジルコニア原料粉末と、不純物量０．３重量％、平均粒子径３μｍのＣａＣＯ３粉末及びＭｇＣＯ３粉末を使用し、ジルコニア質焼結体からなる熱処理用部材を作製した。比較例６と１０については純度９９．０重量％、平均粒子径７μｍの不純物の多いジルコニア原料粉末を使用した。
なお、これらの原料粉末のＡｌ２Ｏ３含有量は０．０３重量％以下であった。
Examples 1-8, Comparative Examples 1-10
Except for Comparative Examples 6 and 10, a zirconia raw material powder having a purity of 99.9% by weight and an average particle diameter of 4 μm, and CaCO 3 powder and MgCO 3 powder having an impurity amount of 0.3% by weight and an average particle diameter of 3 μm were used. A heat-treating member made of a sintered material was produced. For Comparative Examples 6 and 10, zirconia raw material powder having a purity of 99.0% by weight and an average particle diameter of 7 μm and containing many impurities was used.
Note that the Al 2 O 3 content of these material powders was 0.03 wt% or less.
合成後に表１に示す含有量（モル比）となるように、上記ジルコニア、ＣａＣＯ３及びＭｇＣＯ３原料粉末を、水を溶媒として湿式混合し、９０℃で乾燥した後、１３５０℃で３時間熱処理して合成原料を作製した。次いで、耐摩耗性ジルコニア質のポットミルとボールを使用し、このポットミルにボールを投入し、水を溶媒とした湿式で前記合成原料の粉砕・混合・分散処理を行った。得られた処理粉体について、レーザー回折式粒度分布測定装置（マイクロトラックＭＴ３３００ＥＸ、日機装社製）を用いて測定した平均粒子径を表１に示す。次いで、分散処理後のスラリーにＰＶＡ系バインダーを１重量％添加し、スプレードライヤーで乾燥して成形用粉体を得た。得られた成形用粉体を、金型を用いて１ｔｏｎ／ｃｍ２の圧力でプレス成形した。この成形体を高純度ジルコニア製敷き板の上に載せ、大気中、１５３０〜１７７０℃で焼成し、板状焼結体を作製した。なお、比較例１０は、アルミナ製敷き板を用いて焼成することによりＡｌ２Ｏ３量を多くした例である。 After the synthesis, the above zirconia, CaCO 3 and MgCO 3 raw material powders are wet-mixed using water as a solvent and dried at 90 ° C., followed by heat treatment at 1350 ° C. for 3 hours so that the content (molar ratio) shown in Table 1 is obtained. Thus, a synthetic raw material was produced. Next, a wear-resistant zirconia pot mill and balls were used. The balls were put into the pot mill, and the synthetic raw materials were pulverized, mixed, and dispersed in a wet process using water as a solvent. Table 1 shows the average particle diameter of the obtained treated powder measured using a laser diffraction particle size distribution measuring apparatus (Microtrac MT3300EX, manufactured by Nikkiso Co., Ltd.). Next, 1% by weight of a PVA binder was added to the slurry after the dispersion treatment and dried with a spray dryer to obtain a molding powder. The obtained molding powder was press-molded at a pressure of 1 ton / cm 2 using a mold. This molded body was placed on a high-purity zirconia laying board and fired at 1530 to 1770 ° C. in the atmosphere to produce a plate-like sintered body. In Comparative Example 10 is an example in which a lot of the amount of Al 2 O 3 by firing using an alumina laying plate.
上記実施例及び比較例の各板状焼結体について、以下のようにして特性を調べた。
なお、耐食性試験及び耐久性試験において、セラミックス製の重しを載せて応力を掛けたのは、被焼成体（ＰｂＯ又はＰＺＴ）との反応を促進させるためである。
＜耐食性＞
耐食性試験の被焼成体にはＰｂＯ（酸化鉛）を用いた。市販のＰｂＯ粉末（純度９９％以上）を金型プレス成形で直径１０ｍｍ、厚さ１ｍｍに成形し、このＰｂＯ成形体を、各板状焼結体サンプル（１５ｍｍ×１５ｍｍ×３ｍｍ）の上に載せ、更にＰｂＯ成形体にセラミックス製の重しを載せて１ｋＰａの応力を掛け、８７０℃で２０時間保持する操作を２０サイクル行った。操作前後のサンプル重量を測定し、下記式により重量増加率（％）を算出した。結果を表１に示す。
重量増加率（％）＝〔（操作後重量−操作前重量）／操作前重量〕×１００
About each plate-shaped sintered compact of the said Example and a comparative example, the characteristic was investigated as follows.
In the corrosion resistance test and the durability test, the stress was applied by applying a ceramic weight in order to promote the reaction with the object to be fired (PbO or PZT).
<Corrosion resistance>
PbO (lead oxide) was used as the body to be fired in the corrosion resistance test. Commercially available PbO powder (purity 99% or more) was molded by die press molding to a diameter of 10 mm and a thickness of 1 mm, and this PbO compact was placed on each plate-shaped sintered body sample (15 mm × 15 mm × 3 mm). Further, an operation of placing a ceramic weight on the PbO molded body, applying a stress of 1 kPa, and holding at 870 ° C. for 20 hours was performed 20 cycles. The sample weight before and after the operation was measured, and the weight increase rate (%) was calculated by the following formula. The results are shown in Table 1.
Weight increase rate (%) = [(weight after operation−weight before operation) / weight before operation] × 100
＜耐久性＞
耐久性試験には、電子部品材料の成分の一つであるＰＺＴ（チタン酸ジルコン酸鉛）を用いた。市販のＰＺＴ粉末（純度：９９％以上）を直径１０ｍｍ、厚さ１ｍｍに成形し、このＰＺＴ成形体を、各板状焼結体サンプル（１５ｍｍ×１５ｍｍ×３ｍｍ）の上に載せ、更にＰＺＴ成形体にセラミックス製の重しを載せて１ｋＰａの応力を掛け、１３００℃で５時間保持する操作を２０サイクルまで行い、サイクル毎に板状焼結体サンプルの変形、クラック及び割れの発生の有無を調べた。変形、クラック、割れが発生したサイクル数を表１に示す。なお、実施例１〜８の「２０＜」は、２０サイクルでも変形、クラック、割れが発生しなかったことを示す。
<Durability>
For the durability test, PZT (lead zirconate titanate), which is one of the components of the electronic component material, was used. A commercially available PZT powder (purity: 99% or more) is molded to a diameter of 10 mm and a thickness of 1 mm, and this PZT molded body is placed on each plate-like sintered body sample (15 mm × 15 mm × 3 mm), and further PZT molded Place a ceramic weight on the body, apply a stress of 1 kPa and hold at 1300 ° C. for 5 hours up to 20 cycles, and check whether the plate-like sintered body sample is deformed, cracked or cracked every cycle. Examined. Table 1 shows the number of cycles in which deformation, cracks and cracks occurred. In addition, “20 <” in Examples 1 to 8 indicates that no deformation, cracking or cracking occurred even in 20 cycles.
表１の耐食性試験結果から判るように、実施例１〜８は重量増加率が２．７重量％以下と優れた耐食性を示し、高機能な電子部品材料の熱処理用部材として使用可能である。
これに対し、比較例では、比較例５と９を除いて、重量増加率が３．０重量％を越え、耐食性に劣るため、高機能な電子部品材料の熱処理用部材としては使用できない。
また、表１の耐久性試験結果から判るように、実施例１〜８は、２０サイクルの繰り返し試験でも、板状焼結体に変形、クラック、割れは生じず、優れた耐久性を示し、高機能な電子部品材料の熱処理用部材として使用可能である。
これに対し、比較例１〜１０は、２０サイクルに到達する前に変形、クラック、割れが発生し耐久性に劣るため、高機能な電子部品材料の熱処理用部材としては使用できない。
As can be seen from the results of the corrosion resistance test in Table 1, Examples 1 to 8 show excellent corrosion resistance with a weight increase rate of 2.7% by weight or less, and can be used as heat-treating members for highly functional electronic component materials.
On the other hand, in Comparative Examples, except for Comparative Examples 5 and 9, the weight increase rate exceeds 3.0% by weight and the corrosion resistance is poor, so it cannot be used as a heat-treating member for highly functional electronic component materials.
In addition, as can be seen from the durability test results in Table 1, Examples 1 to 8 show excellent durability without deformation, cracks, or cracks in the plate-like sintered body even in a 20-cycle repeated test. It can be used as a heat treatment member for highly functional electronic component materials.
On the other hand, Comparative Examples 1 to 10 cannot be used as a heat-treating member for a highly functional electronic component material because deformation, cracking and cracking occur before reaching 20 cycles and the durability is poor.
実施例に比べて比較例１〜１０の特性が劣る理由は以下のとおりである。
比較例１はＡｌ２Ｏ３量が規定範囲を超えているため、Ａｌ２Ｏ３とＣａＯが反応してジルコニア結晶粒界に偏析した低融点化合物やガラス相の影響で耐食性や耐久性が劣るものであった。
比較例２はＺｒＯ２／ＣａＯモル比が規定範囲未満のため、立方晶系ジルコニア量が減少し、耐食性や耐久性に劣るものであった。
比較例３はＺｒＯ２／ＣａＯモル比が規定範囲を超えているため、ジルコニア結晶に固溶できなかった余剰のＣａＯによる第２相が存在し、耐食性や耐久性に劣るものであった。
比較例４はＣａＯ／ＭｇＯモル比が規定範囲未満のため、ＭｇＯ添加効果が得られず、耐食性や耐久性に劣るものであった。
比較例５はＣａＯ／ＭｇＯモル比が規定範囲を超えているため、耐熱衝撃抵抗性が低下し、耐久性に劣るものであった。
比較例６は純度の低いジルコニア原料粉末を使用したため、ジルコニア質焼結体の不純物量が規定範囲を越え、耐食性や耐久性に劣るものであった。
比較例７は処理粉体の平均粒子径が１．５μｍを越え、かさ密度が規定範囲未満のため、耐食性や耐久性に劣るものであった。
比較例８は焼成温度が低いため、かさ密度及び平均結晶粒径が規定範囲未満となり、耐食性に劣るものであった。
比較例９は焼成温度が高いため、平均結晶粒径が規定範囲を超え、耐熱衝撃性が低下して耐久性に劣るものであった。
比較例１０はＡｌ２Ｏ３量と不純物量の両方が規定範囲を超えているため、耐食性や耐久性に劣るものであった。
The reason why the characteristics of Comparative Examples 1 to 10 are inferior to those of Examples is as follows.
In Comparative Example 1, since the amount of Al 2 O 3 exceeds the specified range, corrosion resistance and durability are inferior due to the influence of the low melting point compound and glass phase segregated at the zirconia crystal grain boundary due to the reaction of Al 2 O 3 and CaO. It was a thing.
In Comparative Example 2, since the ZrO 2 / CaO molar ratio was less than the specified range, the amount of cubic zirconia was reduced, and the corrosion resistance and durability were inferior.
In Comparative Example 3, since the ZrO 2 / CaO molar ratio exceeded the specified range, there was a second phase of excess CaO that could not be dissolved in the zirconia crystal, and the corrosion resistance and durability were inferior.
In Comparative Example 4, since the CaO / MgO molar ratio was less than the specified range, the effect of adding MgO was not obtained, and the corrosion resistance and durability were inferior.
In Comparative Example 5, since the CaO / MgO molar ratio exceeded the specified range, the thermal shock resistance decreased and the durability was inferior.
In Comparative Example 6, since a low-purity zirconia raw material powder was used, the amount of impurities in the zirconia sintered body exceeded the specified range, and the corrosion resistance and durability were inferior.
Comparative Example 7 was inferior in corrosion resistance and durability because the average particle diameter of the treated powder exceeded 1.5 μm and the bulk density was less than the specified range.
In Comparative Example 8, since the firing temperature was low, the bulk density and the average crystal grain size were less than the specified ranges, and the corrosion resistance was inferior.
In Comparative Example 9, since the firing temperature was high, the average crystal grain size exceeded the specified range, the thermal shock resistance was lowered, and the durability was inferior.
Comparative Example 10 was inferior in corrosion resistance and durability because both the Al 2 O 3 amount and the impurity amount exceeded the specified range.
Claims (1)
（ａ）ＺｒＯ２／ＣａＯ（モル比）が、９０／１０〜８０／２０
（ｂ）ＣａＯ／ＭｇＯ（モル比）が、９９／１〜９５／５
（ｃ）Ａｌ２Ｏ３量が、０．２０重量％以下
（ｄ）不純物量が、０．１０重量％以下
（ｅ）かさ密度が、５．２ｇ／ｃｍ３以上
（ｆ）平均結晶粒径が、１０〜４０μｍ A heat-treating member comprising a zirconia sintered body, characterized by satisfying the following requirements (a) to (f):
(A) ZrO 2 / CaO (molar ratio), 90 / 10-80 / 20
(B) CaO / MgO (molar ratio) is 99/1 to 95/5.
(C) Al 2 O 3 amount is 0.20 wt% or less (d) Impurity amount is 0.10 wt% or less (e) Bulk density is 5.2 g / cm 3 or more (f) Average crystal grain size 10 to 40 μm
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