JP2012076940A - SiC TOOL MATERIAL FOR FIRING - Google Patents
SiC TOOL MATERIAL FOR FIRING Download PDFInfo
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- 239000000463 material Substances 0.000 title claims abstract description 49
- 238000010304 firing Methods 0.000 title claims abstract description 23
- 239000013078 crystal Substances 0.000 claims abstract description 50
- 239000000203 mixture Substances 0.000 claims abstract description 34
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 42
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 24
- 239000002245 particle Substances 0.000 claims description 7
- 239000000758 substrate Substances 0.000 abstract description 23
- 230000003078 antioxidant effect Effects 0.000 abstract description 17
- 230000035939 shock Effects 0.000 abstract description 14
- 238000000576 coating method Methods 0.000 abstract description 11
- 239000011248 coating agent Substances 0.000 abstract description 10
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 101
- 229910010271 silicon carbide Inorganic materials 0.000 description 99
- 238000007254 oxidation reaction Methods 0.000 description 18
- 230000003647 oxidation Effects 0.000 description 17
- 239000000155 melt Substances 0.000 description 12
- 238000010438 heat treatment Methods 0.000 description 11
- 239000000919 ceramic Substances 0.000 description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 10
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 9
- 239000001301 oxygen Substances 0.000 description 9
- 229910052760 oxygen Inorganic materials 0.000 description 9
- 238000011156 evaluation Methods 0.000 description 8
- 239000012298 atmosphere Substances 0.000 description 6
- 230000000694 effects Effects 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- 239000007789 gas Substances 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 229910021486 amorphous silicon dioxide Inorganic materials 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 238000005452 bending Methods 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 229910003465 moissanite Inorganic materials 0.000 description 3
- 239000003963 antioxidant agent Substances 0.000 description 2
- 238000005336 cracking Methods 0.000 description 2
- 239000011268 mixed slurry Substances 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 230000003064 anti-oxidating effect Effects 0.000 description 1
- 239000012300 argon atmosphere Substances 0.000 description 1
- 229910002113 barium titanate Inorganic materials 0.000 description 1
- JRPBQTZRNDNNOP-UHFFFAOYSA-N barium titanate Chemical compound [Ba+2].[Ba+2].[O-][Ti]([O-])([O-])[O-] JRPBQTZRNDNNOP-UHFFFAOYSA-N 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 239000003985 ceramic capacitor Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 230000003628 erosive effect Effects 0.000 description 1
- 239000008240 homogeneous mixture Substances 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 229910052575 non-oxide ceramic Inorganic materials 0.000 description 1
- 239000011225 non-oxide ceramic Substances 0.000 description 1
- -1 or alternatively Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 125000006850 spacer group Chemical group 0.000 description 1
- 238000004611 spectroscopical analysis Methods 0.000 description 1
- 238000005728 strengthening Methods 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 229910000859 α-Fe Inorganic materials 0.000 description 1
Abstract
Description
本発明は、積層セラミックスコンデンサ（multiple-layerceramic capacitor；以下、ＭＬＣＣという）やフェライト等のセラミック電子部品の焼成や熱処理工程において使用される道具材であって、多孔質ＳｉＣ基材を用いたＳｉＣ焼成用道具材に関する。 The present invention is a tool material used in firing and heat treatment processes of ceramic electronic components such as multilayer ceramic capacitors (hereinafter referred to as MLCC) and ferrite, and SiC firing using a porous SiC substrate. It relates to tool materials.
電子部品用セラミックスの焼成や熱処理は、一般に、１０００〜１４００℃の温度範囲で行われる。このため、その焼成用道具材としては、Ａｌ2Ｏ3−ＳｉＯ2質、Ａｌ2Ｏ3−ＳｉＯ2−ＭｇＯ質、ＭｇＯ−Ａｌ2Ｏ3−ＺｒＯ2質、ＳｉＣ質等の耐熱性に優れたセラミックスが用いられている。これらの中でも、特に、ＳｉＣ質セラミックスは、耐熱強度及び耐クリープ性に優れており、好適な材料である。 The firing and heat treatment of the ceramic for electronic parts is generally performed in a temperature range of 1000 to 1400 ° C. For this reason, it is excellent in heat resistance such as Al 2 O 3 —SiO 2 quality, Al 2 O 3 —SiO 2 —MgO quality, MgO—Al 2 O 3 —ZrO 2 quality, SiC quality, etc. Ceramics are used. Among these, SiC ceramics are particularly suitable materials because of their excellent heat resistance and creep resistance.
一方、代表的なセラミック電子部品であるＭＬＣＣの焼成においては、電極材を酸化させることなく、その主成分である酸化物のチタン酸バリウムを焼成する必要がある。
したがって、炉内雰囲気中の酸素分圧は重要な要素であるが、ＳｉＣ質セラミックスの焼成用道具材を用いた場合、ＳｉＣの酸化反応により、炉内の酸素分圧が変動することがある。
On the other hand, in firing MLCC, which is a typical ceramic electronic component, it is necessary to fire barium titanate, which is the main component, without oxidizing the electrode material.
Therefore, the oxygen partial pressure in the furnace atmosphere is an important factor, but when a SiC ceramic firing tool material is used, the oxygen partial pressure in the furnace may fluctuate due to the oxidation reaction of SiC.
このため、セラミック電子部品の焼成時に、道具材のＳｉＣの酸化に伴うセラミック電子部品の特性が劣化することを防ぐ目的で、道具材を構成するＳｉＣ質構造体（基材）の表面又は内部のＳｉＣ結晶表面に酸化物等による酸化防止被膜を形成することが、従来から知られている。
例えば、特許文献１に、ＳｉＣ焼結多孔体の開気孔の内面を前記多孔体に対して０．１〜０．６重量％のアルカリ土類金属、Ａｌ2Ｏ3、ＳｉＯ2等を含むガラス被膜で覆うことが記載されている。
また、特許文献２には、多孔質ＳｉＣ基材を酸素濃度２％以上の酸素雰囲気下、１４００〜１５００℃で焼成してＳｉＣ結晶表面にＳｉＯ2層を形成する方法が記載されている。
For this reason, at the time of firing the ceramic electronic component, in order to prevent the characteristics of the ceramic electronic component from being deteriorated due to the oxidation of SiC of the tool material, the surface or the inside of the SiC structure (base material) constituting the tool material It is conventionally known to form an anti-oxidation film made of oxide or the like on the surface of SiC crystal.
For example, Patent Document 1 discloses a glass containing 0.1 to 0.6% by weight of an alkaline earth metal, Al 2 O 3 , SiO 2 or the like on the inner surface of an open pore of a SiC sintered porous body with respect to the porous body. Covering with a coating is described.
Patent Document 2 describes a method in which a porous SiC substrate is baked at 1400 to 1500 ° C. in an oxygen atmosphere having an oxygen concentration of 2% or more to form a SiO 2 layer on the SiC crystal surface.
さらに、特許文献３には、非酸化物セラミックス基体表面に、ＳｉＣ又はＴｉＯ2を含むＡｌ2Ｏ3層を形成し、かつ、前記基体と酸化物層との界面に、所定量のＡｌ2Ｏ3とＹ2Ｏ3とＳｉＯ2との反応によって得られる層を形成することにより、整合性のある界面となり、強度特性及び耐酸化性、耐食性が向上することが記載されている。 Further, in Patent Document 3, an Al 2 O 3 layer containing SiC or TiO 2 is formed on the surface of a non-oxide ceramic substrate, and a predetermined amount of Al 2 O is formed at the interface between the substrate and the oxide layer. It is described that by forming a layer obtained by the reaction of 3 with Y 2 O 3 and SiO 2 , a consistent interface is formed, and strength characteristics, oxidation resistance, and corrosion resistance are improved.
ところで、ＭＬＣＣを焼成する雰囲気は、通常、酸素分圧が１×１０-9ａｔｍ程度であり、これは、水蒸気を導入して、水の解離によって生じる酸素によって制御している。このような雰囲気下においては、酸化防止被膜で覆われたＳｉＣの酸化速度は、該酸化防止被膜を通過する水分子の量に左右される。 By the way, the atmosphere for firing MLCC is usually an oxygen partial pressure of about 1 × 10 −9 atm, which is controlled by oxygen generated by dissociating water by introducing water vapor. Under such an atmosphere, the oxidation rate of SiC covered with the antioxidant coating depends on the amount of water molecules passing through the antioxidant coating.
上記特許文献１，２に記載されているようなガラス被膜やＳｉＯ2層は、ＳｉＣ結晶の表面を均一に覆うことはできるものの、水分子が通過しやすい。しかも、これらの被膜は、ＳｉＣ質基材との熱膨張係数の差が大きく、また、密着性に劣ることから、繰り返しの熱履歴によって、割れやＳｉＣ質基材表面からの剥離を生じやすく、十分な酸化防止効果が得られなかった。 Although the glass coating and the SiO 2 layer described in Patent Documents 1 and 2 can uniformly cover the surface of the SiC crystal, water molecules easily pass through. Moreover, these coatings have a large difference in thermal expansion coefficient with the SiC base material, and are poor in adhesion, so that repeated thermal history tends to cause cracks and peeling from the surface of the SiC base material. A sufficient antioxidant effect could not be obtained.
また、上記特許文献３に記載されているような混合酸化物は、これにより形成される層自体は、水分子等のガスの透過抑制効果に優れているものの、ＳｉＣとの濡れ性に劣るため、ＳｉＣ質基材を構成するＳｉＣ結晶表面すべてを覆うことは困難である。さらに、前記混合酸化物による層は、前記ガラス被膜と同様に、割れや剥離を生じやすく、十分な酸化防止効果を得られるとは言えないものであった。 Moreover, although the mixed oxide as described in the above-mentioned Patent Document 3 is excellent in the permeation suppressing effect of gas such as water molecules, the layer itself formed is inferior in wettability with SiC. It is difficult to cover the entire surface of the SiC crystal constituting the SiC substrate. Further, the layer made of the mixed oxide, like the glass film, is easily cracked and peeled off, and it cannot be said that a sufficient antioxidant effect can be obtained.
したがって、ＳｉＣ質基材に対して、より高い酸化防止効果を付与するためには、ＳｉＣとの密着性に優れた膜でＳｉＣ結晶表面全体を覆う必要がある。
また、近年、セラミック電子部品の焼成においては、ローラーハースキルン等による高速焼成のニーズが高く、このため、焼成用道具材の耐熱衝撃性の向上も求められている。
Therefore, in order to give a higher antioxidant effect to the SiC substrate, it is necessary to cover the entire SiC crystal surface with a film having excellent adhesion to SiC.
In recent years, there is a high need for high-speed firing by roller hearth kiln or the like in firing of ceramic electronic components, and therefore, improvement of thermal shock resistance of firing tool materials is also required.
本発明は、上記技術的課題を解決するためになされたものであり、ＳｉＣ基材に対する密着性に優れ、より高い酸化防止効果を付与することができる被膜を備え、かつ、優れた耐熱衝撃性を有するＳｉＣ焼成用道具材を提供することを目的とするものである。 The present invention has been made to solve the above technical problem, and has a coating film that has excellent adhesion to a SiC substrate and can impart a higher antioxidant effect, and has excellent thermal shock resistance. It aims at providing the tool material for SiC baking which has this.
本発明に係るＳｉＣ焼成用道具材は、多孔質ＳｉＣ基材と、前記基材のＳｉＣ結晶表面に形成される酸化物膜とからなり、前記酸化物膜の組成は、ＳｉＯ2が６５重量％以上９０重量％以下、残部がＡｌ2Ｏ3及びＹ2Ｏ3であり、かつ、前記Ａｌ2Ｏ3及びＹ2Ｏ3の重量組成比が２０：８０〜６０：４０であることを特徴とする。
上記のような組成からなる酸化物膜により、被膜のＳｉＣ基材に対する密着性が向上し、かつ、酸化防止効果が向上するとともに、耐熱衝撃性にも優れたＳｉＣ焼成用道具材を得ることができる。
The SiC firing tool material according to the present invention comprises a porous SiC substrate and an oxide film formed on the SiC crystal surface of the substrate, and the composition of the oxide film is 65% by weight of SiO 2. 90 wt% or less, the balance being Al 2 O 3 and Y 2 O 3 , and the weight composition ratio of the Al 2 O 3 and Y 2 O 3 being 20:80 to 60:40 To do.
With the oxide film having the above composition, it is possible to improve the adhesion of the coating to the SiC substrate, improve the antioxidant effect, and obtain an SiC baking tool material excellent in thermal shock resistance. it can.
前記ＳｉＯ2は結晶粒子を含み、前記結晶粒子の結晶粒径が１μｍ以上１０μｍ以下であるが好ましい。
結晶粒径を上記範囲内とすることにより、ＳｉＣ結晶表面の凹凸が十分に形成され、前記酸化物膜の割れや剥離の抑制効果を高めることができる。
なお、本発明でいう結晶粒径は、該酸化物膜組織の顕微鏡写真から、ＳｉＯ2結晶粒子の長径ａと、これと垂直な方向における径ｂとをそれぞれ測定し、両径の平均値（ａ＋ｂ）／２を求めたものである。
The SiO 2 contains crystal particles, and the crystal particle size of the crystal particles is preferably 1 μm or more and 10 μm or less.
By setting the crystal grain size within the above range, the unevenness of the SiC crystal surface is sufficiently formed, and the effect of suppressing cracking and peeling of the oxide film can be enhanced.
The crystal grain size referred to in the present invention is determined by measuring the major axis “a” of the SiO 2 crystal grain and the diameter “b” in the direction perpendicular thereto from the micrograph of the oxide film structure. a + b) / 2.
また、前記酸化物膜の厚さは１μｍ以上２００μｍ以下であることが好ましい。
上記範囲内の厚さの酸化物膜によれば、ＳｉＣ基材との熱膨張係数の差に起因する酸化物膜の割れや剥離を効果的に防止することができ、優れた酸化防止効果が得られる。
The oxide film preferably has a thickness of 1 μm to 200 μm.
According to the oxide film having a thickness within the above range, the oxide film can be effectively prevented from cracking or peeling due to the difference in thermal expansion coefficient from the SiC base material, and an excellent antioxidant effect can be obtained. can get.
本発明によれば、ＳｉＣ焼成用道具材において、特定組成からなる酸化物膜によって、ＳｉＣ基材に対する密着性を向上させ、かつ、従来よりも優れた酸化防止効果を付与することができ、さらに、耐熱衝撃性の向上を図ることができる。
したがって、本発明に係るＳｉＣ焼成用道具材は、ＭＬＣＣ等のセラミック電子部品の製造に好適に適用することができ、特に、ローラーハースキルン等による高速焼成にも好適であり、製造効率の向上にも寄与し得るものである。
According to the present invention, in the SiC firing tool material, the oxide film having a specific composition can improve the adhesion to the SiC base material, and can impart an antioxidant effect superior to conventional ones, The thermal shock resistance can be improved.
Therefore, the SiC firing tool material according to the present invention can be suitably applied to the production of ceramic electronic components such as MLCCs, and is particularly suitable for high-speed firing by roller hearth kiln, etc., to improve production efficiency. Can also contribute.
以下、本発明をより詳細に説明する。
本発明に係るＳｉＣ焼成用道具材は、多孔質ＳｉＣ基材と、前記基材のＳｉＣ結晶表面に形成される酸化物膜とからなるものである。そして、前記酸化物膜の組成は、ＳｉＯ2が６５重量％以上９０重量％以下、残部がＡｌ2Ｏ3及びＹ2Ｏ3であり、かつ、前記Ａｌ2Ｏ3及びＹ2Ｏ3の重量組成比が２０：８０〜６０：４０であることを特徴としている。
ＳｉＣ焼成用道具材において、多孔質ＳｉＣ基材に、上記のような組成からなる酸化物膜を形成することにより、被膜のＳｉＣ基材に対する密着性が向上し、かつ、酸化防止効果を向上させることができる。さらに、耐熱衝撃性の向上も図ることができる。
Hereinafter, the present invention will be described in more detail.
The SiC firing tool material according to the present invention comprises a porous SiC base material and an oxide film formed on the SiC crystal surface of the base material. The composition of the oxide film is that SiO 2 is 65 wt% or more and 90 wt% or less, the balance is Al 2 O 3 and Y 2 O 3 , and the weight of the Al 2 O 3 and Y 2 O 3 The composition ratio is 20:80 to 60:40.
In the SiC firing tool material, by forming an oxide film having the above composition on the porous SiC base material, the adhesion of the coating to the SiC base material is improved and the antioxidant effect is improved. be able to. Furthermore, the thermal shock resistance can be improved.
本発明に係るＳｉＣ焼成用道具材おいては、ＳｉＣ基材として多孔質体を用いる。
多孔質体とすることにより、ＳｉＣ結晶表面の表面積が大きくなり、ＳｉＣ結晶表面の一部を酸化させてＳｉＯ2として酸化物層の密着性を向上させることができ、また、凹凸を生じさせやすくなり、物理的に密着性を向上させる効果も得られる。
In the SiC baking tool material according to the present invention, a porous body is used as the SiC base material.
By making the porous body, the surface area of the SiC crystal surface is increased, and a part of the SiC crystal surface can be oxidized to improve the adhesion of the oxide layer as SiO 2 , and unevenness is easily generated. Thus, an effect of physically improving the adhesion can be obtained.
なお、前記多孔質ＳｉＣ基材は、見掛け気孔率が１５％以上５０％以下、炭化ケイ素含有量が９０重量％以上であることが好ましい。
上記範囲の見掛け気孔率及び炭化ケイ素含有量であれば、酸化物層の密着性を保持しつつ、十分な耐熱強度を有する道具材を構成することができる。
The porous SiC substrate preferably has an apparent porosity of 15% to 50% and a silicon carbide content of 90% by weight or more.
When the apparent porosity and silicon carbide content are in the above ranges, a tool material having sufficient heat resistance strength can be configured while maintaining the adhesion of the oxide layer.
上記のような多孔質ＳｉＣ基材は、その製造方法は特に限定されるものではなく、公知の方法により製造することができる。例えば、炭化ケイ素粉末原料に、水、有機バインダ等を添加して混合したものを成形して多孔質成形体とし、これを１６００〜２４００℃で焼成することにより、多孔質焼結体として得ることができる。 The production method of the porous SiC substrate as described above is not particularly limited, and can be produced by a known method. For example, a silicon carbide powder raw material added with water, an organic binder, and the like is mixed to form a porous molded body, which is fired at 1600 to 2400 ° C. to obtain a porous sintered body. Can do.
前記多孔質ＳｉＣ基材のＳｉＣ結晶表面に形成される酸化物膜の組成成分は、ＳｉＯ2、Ａｌ2Ｏ3及びＹ2Ｏ3である。
前記酸化物膜は、Ｙ2Ｏ3とＡｌ2Ｏ3の混合物、又は、Ｙ2Ｏ3とＡｌ2Ｏ3とＳｉＯ2の混合物を多孔質ＳｉＣ基材に含浸又は塗布した後、ＳｉＣが酸化する雰囲気下で、１４００℃以上の温度で熱処理して前記混合物又はその一部を溶融させることにより、ＳｉＣ結晶表面に形成することができる。
このとき、ＳｉＣ結晶表面には、前記混合物の溶融物の層を通して酸素や水蒸気が供給されるとともに、ＳｉＣの酸化によって生じるＳｉＯ2が存在するため、前記溶融物は、ＳｉＣ結晶表面と濡れやすい状態となり、ＳｉＣ結晶表面全体を覆うことができる。
そして、前記溶融物の層を通してなされるＳｉＣ結晶表面への酸素や水蒸気の供給が継続されると、ＳｉＣの酸化は進行し、生じたＳｉＯ2は前記溶融物の中に溶け込むため、ＳｉＣ結晶表面は酸化により生じた非晶質のＳｉＯ2のみで覆われることはない。この非晶質のＳｉＯ2は前記溶融物の中に溶け込んだ状態で存在するか、あるいはまた、前記溶融物の中に新たな結晶として析出する。
Composition components of the oxide film formed on the SiC crystal surface of the porous SiC base material are SiO 2 , Al 2 O 3, and Y 2 O 3 .
The oxide film is a mixture of Y 2 O 3 and Al 2 O 3, or, after impregnating or coating a mixture of Y 2 O 3 and Al 2 O 3 and SiO 2 in the porous SiC substrate, SiC oxidation In the atmosphere, the heat treatment is performed at a temperature of 1400 ° C. or higher to melt the mixture or a part of the mixture, thereby forming the SiC crystal surface.
At this time, the surface of the SiC crystal is supplied with oxygen and water vapor through the melt layer of the mixture, and SiO 2 generated by the oxidation of SiC is present, so that the melt is easily wetted with the surface of the SiC crystal. Thus, the entire surface of the SiC crystal can be covered.
Then, when the supply of oxygen or water vapor to the SiC crystal surface made through the melt layer is continued, the oxidation of SiC proceeds, and the generated SiO 2 dissolves into the melt, so that the SiC crystal surface Is not covered only with amorphous SiO 2 produced by oxidation. This amorphous SiO 2 exists in a state of being dissolved in the melt, or alternatively, precipitates as new crystals in the melt.
ＳｉＣ結晶表面は、結晶方位、結晶欠陥及び不純物等の分布によって、酸化しやすさの部分差が生じ、酸化しやすい部分が選択的に酸化される。酸化により生じたＳｉＯ2は、上述したように前記溶融物の中に溶け込んでいき、その部分での酸化が継続して進行する。このため、ＳｉＣ結晶表面の酸化しやすい部分は、酸化しにくい部分に比べて、ＳｉＣの浸食（減少）の度合いが大きく、結果として、ＳｉＣ結晶表面に凹凸が形成される。
上述した酸化物膜形成のための熱処理の終了後、この凹凸は、アンカー効果によってＳｉＣと酸化物膜との結合を物理的に強め、密着性を向上させる効果を奏する。
なお、本発明において、酸化物膜が形成されるＳｉＣ結晶表面とは、ＳｉＣ基材中に存在するすべてのＳｉＣ結晶の表面を意味するものではなく、ＳｉＣ基材の外表面及び内部の気孔連通部のＳｉＣ結晶の表面である。
The SiC crystal surface has a partial difference in easiness of oxidation due to the distribution of crystal orientation, crystal defects, impurities, and the like, and a portion that is easily oxidized is selectively oxidized. As described above, the SiO 2 produced by the oxidation dissolves into the melt, and the oxidation at that portion continues. For this reason, the portion of the SiC crystal surface that is easily oxidized has a higher degree of SiC erosion (reduction) than the portion that is difficult to oxidize, and as a result, irregularities are formed on the surface of the SiC crystal.
After the heat treatment for forming the oxide film described above is completed, the unevenness has an effect of physically strengthening the bond between SiC and the oxide film by the anchor effect and improving the adhesion.
In the present invention, the SiC crystal surface on which the oxide film is formed does not mean the surface of all SiC crystals present in the SiC base material, but the outer surface and internal pore communication of the SiC base material. It is the surface of the part SiC crystal.
前記酸化物膜の組成のうち、ＳｉＯ2の含有量は６５重量％以上９０重量％以下とする。このＳｉＯ2の含有量は、上述したように、基材のＳｉＣの酸化により生じるＳｉＯ2と、含浸又は塗布等を行う混合物由来のものとの合計である。
前記含有量が６５重量％未満の場合は、ＳｉＣの酸化により生じるＳｉＯ2の量が不十分であり、ＳｉＣ結晶表面に十分な凹凸が生じず、ＳｉＣ基材と酸化物膜との密着性が十分に得られない。
一方、前記含有量が９０重量％を超える場合は、酸化物膜中で、通常クリストバライトとして生成するＳｉＯ2の量が多くなり、ＳｉＯ2とＳｉＣの熱膨張係数の差から、酸化物膜に割れが生じやすくなり、酸化防止効果が低減する。
ＳｉＯ2の含有量は、より好ましくは、７０重量％以上８５重量％以下である。
Of the composition of the oxide film, the content of SiO 2 is 65 wt% or more and 90 wt% or less. Content of SiO 2, as described above, a SiO 2 produced by the oxidation of SiC substrates, the sum of those derived from mixtures of performing impregnation or coating.
When the content is less than 65% by weight, the amount of SiO 2 generated by the oxidation of SiC is insufficient, the surface of the SiC crystal is not sufficiently uneven, and the adhesion between the SiC substrate and the oxide film is low. Not enough.
On the other hand, when the content exceeds 90% by weight, the amount of SiO 2 that is usually generated as cristobalite in the oxide film increases, and the oxide film cracks due to the difference in thermal expansion coefficient between SiO 2 and SiC. Is likely to occur, and the antioxidant effect is reduced.
The content of SiO 2 is more preferably 70% by weight or more and 85% by weight or less.
前記酸化物膜中のＳｉＯ2の含有量が上記範囲内であっても、該道具材製造時の熱処理方法、条件等によっては、ＳｉＣの酸化速度が大きく、前記混合物が溶融する前にＳｉＣ結晶表面全面に非晶質のＳｉＯ2が生成し、その上に、前記混合物の溶融物による膜が形成される場合がある。このような場合には、酸化物膜の割れや剥離が生じやすく、酸化防止効果が十分に得られないおそれがある。
したがって、前記酸化物膜中のＳｉＯ2は、結晶及び非晶質が混在したものであることが好ましい。
ＳｉＯ2の結晶を含み、粒子状の形態で存在していることは、ＳｉＣの酸化により生じたＳｉＯ2が前記溶融物に溶け込んでいることを意味する。このような状態の酸化物膜は、ＳｉＣ結晶表面が浸食されて、凹凸が十分に形成されており、ＳｉＣ基材と酸化物膜との優れた密着性を得ることができる。
Even if the content of SiO 2 in the oxide film is within the above range, depending on the heat treatment method, conditions, and the like at the time of manufacturing the tool material, the oxidation rate of SiC is large, and before the mixture melts, the SiC crystal In some cases, amorphous SiO 2 is formed on the entire surface, and a film made of a melt of the mixture is formed thereon. In such a case, the oxide film is likely to be cracked or peeled off, and there is a possibility that the antioxidant effect cannot be sufficiently obtained.
Accordingly, the SiO 2 in the oxide film is preferably a mixture of crystal and amorphous.
The presence of SiO 2 crystals in the form of particles means that SiO 2 produced by the oxidation of SiC is dissolved in the melt. In the oxide film in such a state, the surface of the SiC crystal is eroded and the unevenness is sufficiently formed, and excellent adhesion between the SiC substrate and the oxide film can be obtained.
Ｙ2Ｏ3とＡｌ2Ｏ3とＳｉＯ2との混合物による酸化物膜においては、全体が均質に溶融する組成は温度によって異なるが、前記酸化物膜中のＡｌ2Ｏ3及びＹ2Ｏ3の重量組成比は、２０：８０〜６０：４０とする。
前記重量組成比が上記範囲外の場合は、酸化物膜形成のための熱処理時に、均質な混合物としての溶融物を生じにくく、その結果、ＳｉＣ結晶表面に凹凸が形成されず、ＳｉＣ基材と酸化物膜の密着性を高めることが困難となる。
前記Ａｌ2Ｏ3及びＹ2Ｏ3の重量組成比は、より好ましくは、２５：７５〜５０：５０である。
In an oxide film made of a mixture of Y 2 O 3 , Al 2 O 3, and SiO 2 , the composition that melts uniformly as a whole varies depending on the temperature, but Al 2 O 3 and Y 2 O 3 in the oxide film are different. The weight composition ratio is set to 20:80 to 60:40.
When the weight composition ratio is out of the above range, it is difficult to form a melt as a homogeneous mixture during the heat treatment for forming the oxide film, and as a result, unevenness is not formed on the surface of the SiC crystal. It becomes difficult to improve the adhesion of the oxide film.
The weight composition ratio of the Al 2 O 3 and Y 2 O 3 is more preferably 25:75 to 50:50.
なお、酸化物膜の重量組成は、以下のような方法により求めることができる。
まず、道具材試料を粉砕して酸化熱処理し、ＳｉＣ基材を完全にＳｉＯ2にする。この時に発生するＣＯ2ガスの発生量からＳｉＣ重量を算出する。
そして、酸化熱処理後の試料について、ＩＰＳ発光分光分析等の化学分析を行い、得られた分析値から上記において算出したＳｉＣの寄与分を差し引くことにより、酸化物膜中のＳｉＯ2、Ｙ2Ｏ3及びＡｌ2Ｏ3の各重量組成を算出する。
The weight composition of the oxide film can be obtained by the following method.
First, the tool material sample is pulverized and subjected to an oxidation heat treatment to completely change the SiC base material to SiO 2 . The SiC weight is calculated from the amount of CO 2 gas generated at this time.
Then, the sample after the oxidation heat treatment is subjected to chemical analysis such as IPS emission spectroscopic analysis, and by subtracting the SiC contribution calculated above from the obtained analysis value, the SiO 2 and Y 2 O in the oxide film are subtracted. 3 and the weight composition of Al 2 O 3 are calculated.
また、前記ＳｉＯ2の結晶は、結晶粒径が１μｍ以上１０μｍ以下であることが好ましい。
前記結晶粒径が１μｍ未満の場合、ＳｉＣ結晶表面の凹凸が小さく、ＳｉＣ基材と酸化物膜の物理的な結合が弱く、前記酸化物膜が剥離しやすくなる。
一方、前記結晶粒径が１０μｍを超える場合、ＳｉＯ2の変態による体積変化により、酸化物膜が割れやすくなる。
The SiO 2 crystal preferably has a crystal grain size of 1 μm or more and 10 μm or less.
When the crystal grain size is less than 1 μm, the unevenness of the SiC crystal surface is small, the physical bond between the SiC substrate and the oxide film is weak, and the oxide film is easily peeled off.
On the other hand, when the crystal grain size exceeds 10 μm, the oxide film is easily cracked due to the volume change due to the transformation of SiO 2 .
また、前記酸化物膜の厚さは、１μｍ以上２００μｍ以下であることが好ましい。
前記厚さが１μｍ未満の場合は、薄すぎて、ＳｉＣ基材が露出するおそれがあり、該酸化物膜による酸化防止効果が十分に得られない。
一方、前記厚さが２００μｍを超える場合は、厚すぎて、ＳｉＣ基材との熱膨張係数の差により、該酸化物膜に割れや剥離が生じるおそれがある。
前記酸化物膜の厚さは、より好ましくは、１０μｍ以上１００μｍ以下である。
The thickness of the oxide film is preferably 1 μm or more and 200 μm or less.
When the thickness is less than 1 μm, the SiC base material may be exposed because it is too thin, and the antioxidant effect by the oxide film cannot be sufficiently obtained.
On the other hand, when the thickness exceeds 200 μm, it is too thick and the oxide film may be cracked or peeled off due to the difference in thermal expansion coefficient from the SiC base material.
The thickness of the oxide film is more preferably 10 μm or more and 100 μm or less.
ＳｉＣは、一般的な焼成用道具材の材料として用いられているＡｌ2Ｏ3−ＳｉＯ2質に比べて、熱膨張係数が小さいため、急速な温度変化による熱衝撃破壊に対する抵抗が大きいが、本発明によれば、ＳｉＣ基材の耐熱衝撃性をより向上させることができる。
ここで、熱衝撃破壊に対する抵抗性を表す指標である熱衝撃破壊係数Ｒは、Ｒ＝Ｓ（１−ν）／Ｅα（ここで、Ｓ：強度、ν：ポアソン比、Ｅ：弾性率、α：熱膨張係数）の式で表すことができる。この式から、耐熱衝撃性の向上には、強度Ｓが大きいことが好ましいと考えられる。
後述の実施例にも示すように、本発明に係るＳｉＣ焼成用道具材は、ＳｉＣ基材に所定の酸化物膜が形成されていることにより、ＳｉＣ焼結体のみよりも、曲げ強度も大きく、耐熱衝撃性にも優れているものである。
SiC has a low thermal expansion coefficient compared to Al 2 O 3 —SiO 2 used as a material for general firing tool materials, and thus has a high resistance to thermal shock destruction due to rapid temperature changes. According to the present invention, the thermal shock resistance of the SiC substrate can be further improved.
Here, the thermal shock fracture coefficient R, which is an index representing the resistance to thermal shock fracture, is R = S (1-ν) / Eα (where S: strength, ν: Poisson's ratio, E: elastic modulus, α : Thermal expansion coefficient). From this formula, it is considered that a high strength S is preferable for improving the thermal shock resistance.
As shown also in the examples described later, the SiC firing tool material according to the present invention has a higher bending strength than the SiC sintered body alone, because a predetermined oxide film is formed on the SiC base material. It also has excellent thermal shock resistance.
以下、本発明を実施例に基づきさらに具体的に説明するが、本発明は下記の実施例により制限されるものではない。
（試験１）
ＳｉＯ2、Ｙ2Ｏ3及びＡｌ2Ｏ3の各粉末を所定量ずつ混合し、これに水を加えてボールミルで混合粉砕し、混合スラリーを調製した。
このスラリーを２５０ｍｍ×２５０ｍｍ×厚さ１ｍｍの見掛け気孔率約２２％の多孔質ＳｉＣ基材に含浸させた後、乾燥して水分を除去した。
これをガスバーナ炉中、１５００℃で熱処理したものを評価用試料とした。
ただし、比較例７，８においては、アルゴン雰囲気下、１５００℃で熱処理した。
また、比較例９は、ＳｉＣ基材に混合スラリーを含浸させずに、ガスバーナ炉中、１５００℃で熱処理し、ＳｉＣ基材表面にＳｉＯ2膜を形成した試料である。
EXAMPLES Hereinafter, although this invention is demonstrated more concretely based on an Example, this invention is not restrict | limited by the following Example.
(Test 1)
A predetermined amount of each powder of SiO 2 , Y 2 O 3 and Al 2 O 3 was mixed, water was added thereto, and the mixture was pulverized and mixed with a ball mill to prepare a mixed slurry.
The slurry was impregnated into a porous SiC substrate having an apparent porosity of about 22%, 250 mm × 250 mm × thickness 1 mm, and then dried to remove moisture.
This was heat-treated at 1500 ° C. in a gas burner furnace as an evaluation sample.
However, in Comparative Examples 7 and 8, heat treatment was performed at 1500 ° C. in an argon atmosphere.
Comparative Example 9 is a sample in which a SiC base material was heat-treated at 1500 ° C. in a gas burner furnace without impregnating the SiC base material with the mixed slurry to form a SiO 2 film on the surface of the SiC base material.
これらの各評価用試料について、以下のような各種評価を行った。これらの結果を表１にまとめて示す。
上述したような化学分析により、酸化物膜中のＳｉＯ2、Ｙ2Ｏ3及びＡｌ2Ｏ3の重量組成を求めた。なお、前記重量組成においては、ＳｉＯ2、Ｙ2Ｏ3及びＡｌ2Ｏ3以外の微量成分は無視し、前記３成分の合計が１００％となるように算出した。ただし、表１においては、末桁の四捨五入により、１００％未満又は１００％を超える表示となっている場合もある。
また、各評価用試料を、水蒸気が含まれ、かつ、酸素分圧が１０-9ＭＰａの雰囲気下、１２５０℃で１０時間熱処理した。これを試料毎に５回行い、熱処理前後の試料の重量を測定し、熱処理１回（１０時間）当たりの平均重量変化率を求め、この値により酸化防止効果の評価を行った。
Each of these evaluation samples was subjected to the following various evaluations. These results are summarized in Table 1.
By chemical analysis as described above, the weight composition of SiO 2 , Y 2 O 3 and Al 2 O 3 in the oxide film was determined. In the weight composition, the trace components other than SiO 2 , Y 2 O 3 and Al 2 O 3 were ignored, and the total of the three components was calculated to be 100%. However, in Table 1, it may be displayed as less than 100% or more than 100% by rounding off the last digit.
Each evaluation sample was heat-treated at 1250 ° C. for 10 hours in an atmosphere containing water vapor and an oxygen partial pressure of 10 −9 MPa. This was performed five times for each sample, the weight of the sample before and after the heat treatment was measured, the average weight change rate per one heat treatment (10 hours) was determined, and the antioxidant effect was evaluated based on this value.
表１に示した結果から、酸化物膜中のＳｉＯ2が６５重量％以上９０重量％以下、残部がＡｌ2Ｏ3及びＹ2Ｏ3であり、かつ、前記Ａｌ2Ｏ3及びＹ2Ｏ3の重量組成比が２０：８０〜６０：４０である場合（実施例１〜１３）、酸化による重量増加率が低減され、酸化防止効果が向上していることが認められた。 From the results shown in Table 1, SiO 2 in the oxide film is 65 wt% or more and 90 wt% or less, the balance is Al 2 O 3 and Y 2 O 3 , and the Al 2 O 3 and Y 2 O When the weight composition ratio of 3 was 20:80 to 60:40 (Examples 1 to 13), it was recognized that the rate of weight increase due to oxidation was reduced and the antioxidant effect was improved.
（試験２）
試験１と同様にして作製し、酸化物膜の重量組成を求めた表２に示す各評価用試料について、酸化物膜中のＳｉＯ2の結晶粒径、試料の曲げ強さ及び弾性率を測定した。
また、以下のようにして、酸化物膜の耐熱衝撃性評価を行った。まず、各評価用試料を１０枚ずつ多段積みした。このとき、試料１枚毎に荷重としてＺｒＯ2粉２５０ｇを各試料の縁から１０ｍｍよりも内側に積載し、１０ｍｍ×１０ｍｍ×１０ｍｍのスペーサを４隅に配置して、その上の試料を４点で支持するようにした。このようにして多段積みした各試料を、６００℃で保持した電気炉内に、常温で入炉して１時間保持した後、炉出しし、酸化物膜の割れの発生枚数により、耐熱衝撃性を評価した。
これらの評価結果をまとめて表２に示す。
なお、比較例１２は、ＳｉＣ基材のみで酸化物膜で覆われていない試料である。
(Test 2)
For each sample for evaluation shown in Table 2, which was prepared in the same manner as in Test 1 and the weight composition of the oxide film was determined, the crystal grain size of SiO 2 in the oxide film, the bending strength and elastic modulus of the sample were measured. did.
Moreover, the thermal shock resistance evaluation of the oxide film was performed as follows. First, 10 samples for each evaluation were stacked in multiple stages. At this time, 250 g of ZrO 2 powder is loaded as a load for each sample, and 10 mm × 10 mm × 10 mm spacers are arranged at four corners from the edge of each sample, and four samples are placed thereon. To support. Each sample stacked in this manner is placed in an electric furnace maintained at 600 ° C. and held at room temperature for 1 hour, and then removed from the furnace. Evaluated.
These evaluation results are summarized in Table 2.
In addition, the comparative example 12 is a sample which is not covered only with the SiC base material with the oxide film.
表２に示す結果から分かるように、ＳｉＣ基材表面の酸化物膜中のＳｉＯ2の結晶粒径が１μｍ以上１０μｍ以下である場合（実施例１４〜１６）、酸化物膜による酸化防止効果が向上し、かつ、曲げ強度が大きく、耐熱衝撃性にも優れていることが認められた。 As can be seen from the results shown in Table 2, when the crystal grain size of SiO 2 in the oxide film on the surface of the SiC substrate is 1 μm or more and 10 μm or less (Examples 14 to 16), the oxide film has an antioxidant effect. It was confirmed that the bending strength was high and the thermal shock resistance was excellent.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2017206394A (en) * | 2016-05-16 | 2017-11-24 | 日本電気硝子株式会社 | Refractory, method for manufacturing refractory, and apparatus and method for manufacturing glass article |
| CN108530084A (en) * | 2018-05-31 | 2018-09-14 | 深圳市商德先进陶瓷股份有限公司 | Porous ceramics and preparation method thereof, air-bearing and application |
| JP2019011238A (en) * | 2017-06-30 | 2019-01-24 | クアーズテック株式会社 | Tool material for firing |
| JP2019014636A (en) * | 2017-07-10 | 2019-01-31 | 三井金属鉱業株式会社 | Silicon carbide sintered body substrate and electronic component sintering tool including the same |
Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH07206556A (en) * | 1994-01-17 | 1995-08-08 | Tokai Konetsu Kogyo Co Ltd | Coating material for refractory and method for application |
| JP2001213666A (en) * | 2000-01-28 | 2001-08-07 | Mitsui Mining & Smelting Co Ltd | Material for making electronic part by sintering |
| JP2001322875A (en) * | 2000-05-10 | 2001-11-20 | Mitsui Mining & Smelting Co Ltd | Implement for calcination of electronic parts |
| JP2003239087A (en) * | 2001-12-19 | 2003-08-27 | United Technol Corp <Utc> | Article comprising material containing silicon |
| JP2004238215A (en) * | 2003-02-03 | 2004-08-26 | National Institute For Materials Science | Silicon carbide sintered member having non-reactive thermally sprayed film and method of manufacturing the same |
| JP2006117472A (en) * | 2004-10-21 | 2006-05-11 | Toshiba Ceramics Co Ltd | Silicon carbide tool material for firing and its manufacturing method |
| JP2008137860A (en) * | 2006-12-04 | 2008-06-19 | Covalent Materials Corp | Ceramics burning tool material for electronic components |
| JP2009029686A (en) * | 2007-03-28 | 2009-02-12 | Kyocera Corp | Corrosion-resistant member, its production method, and its treatment apparatus |
| JP2012513946A (en) * | 2008-12-24 | 2012-06-21 | スネクマ・プロピュルシオン・ソリド | Environmental barrier for heat-resistant substrates containing silicon |
-
2010
- 2010-09-30 JP JP2010221410A patent/JP5465143B2/en active Active
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH07206556A (en) * | 1994-01-17 | 1995-08-08 | Tokai Konetsu Kogyo Co Ltd | Coating material for refractory and method for application |
| JP2001213666A (en) * | 2000-01-28 | 2001-08-07 | Mitsui Mining & Smelting Co Ltd | Material for making electronic part by sintering |
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| JP2003239087A (en) * | 2001-12-19 | 2003-08-27 | United Technol Corp <Utc> | Article comprising material containing silicon |
| JP2004238215A (en) * | 2003-02-03 | 2004-08-26 | National Institute For Materials Science | Silicon carbide sintered member having non-reactive thermally sprayed film and method of manufacturing the same |
| JP2006117472A (en) * | 2004-10-21 | 2006-05-11 | Toshiba Ceramics Co Ltd | Silicon carbide tool material for firing and its manufacturing method |
| JP2008137860A (en) * | 2006-12-04 | 2008-06-19 | Covalent Materials Corp | Ceramics burning tool material for electronic components |
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| JP2019011238A (en) * | 2017-06-30 | 2019-01-24 | クアーズテック株式会社 | Tool material for firing |
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