WO2005026076A1 - 窒化珪素結合ＳｉＣ耐火物及びその製造方法 - Google Patents

窒化珪素結合ＳｉＣ耐火物及びその製造方法 Download PDF

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Publication number
WO2005026076A1
WO2005026076A1 PCT/JP2004/010496 JP2004010496W WO2005026076A1 WO 2005026076 A1 WO2005026076 A1 WO 2005026076A1 JP 2004010496 W JP2004010496 W JP 2004010496W WO 2005026076 A1 WO2005026076 A1 WO 2005026076A1
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Prior art keywords
silicon nitride
sic
mass
refractory
bonded sic
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PCT/JP2004/010496
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English (en)
French (fr)
Inventor
Toshiharu Kinoshita
Tsuneo Komiyama
Original Assignee
Ngk Insulators, Ltd.
Ngk Adrec Co., Ltd.
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First worldwide family litigation filed litigation Critical https://patents.darts-ip.com/?family=34308470&utm_source=google_patent&utm_medium=platform_link&utm_campaign=public_patent_search&patent=WO2005026076(A1) "Global patent litigation dataset” by Darts-ip is licensed under a Creative Commons Attribution 4.0 International License.
Application filed by Ngk Insulators, Ltd., Ngk Adrec Co., Ltd. filed Critical Ngk Insulators, Ltd.
Priority to US10/571,073 priority Critical patent/US7494949B2/en
Priority to PL04770889T priority patent/PL1666433T3/pl
Priority to EP04770889A priority patent/EP1666433B1/en
Priority to DE602004032448T priority patent/DE602004032448D1/de
Publication of WO2005026076A1 publication Critical patent/WO2005026076A1/ja

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Definitions

  • the present invention relates to a silicon nitride bonded SiC refractory and a method for producing the same.
  • Silicon carbide (SiC) refractories occupy an industrially important position due to their excellent heat resistance and fire resistance. For example, tiles, ceramics, shelf boards for firing honeycombs, and other firing treatments. It is frequently used for tools and shells.
  • a block-like column that forms a space required for uniform firing of the objects to be fired is a shelf.
  • a plurality of places are placed at the corners of the plate, and the shelf boards and the support columns are alternately stacked in a plurality of stages, and the objects to be fired are placed on the shelf boards stacked in multiple stages for firing.
  • mullite, alumina, and zirconia which can be used at high temperatures (eg, 1200 1600 ° C), have been mainly used as the base material of the shelf boards and columns constituting the shelf assembly. Due to insufficient strength (bending strength and Young's modulus), higher strength oxide bonded SiC refractories and nitride bonded SiC refractories are used depending on the application.
  • a shelf assembly using an oxide-bonded SiC refractory and a nitride-bonded SiC refractory is required to obtain a strength sufficient to withstand external stress generated during use / assembly / disassembly of the shelf. It is necessary to increase the thickness of the struts and increase the weight, and the heat capacity increases as well as the workability decreases. The conductivity was also poor, so it was difficult to achieve a uniform temperature of the fired body.
  • Si-containing materials porous or dense
  • Si as a metal Si phase with high strength and excellent heat resistance, oxidation resistance and thermal conductivity (for example, Si and SiC) Shelf assembly using a metal silicon-silicon carbide composite material [Si-impregnated SiC refractory]) is used.
  • the shelf assembly using Si-impregnated SiC refractories can reduce the thickness and weight of shelf boards and columns, and therefore has a long life span that can contribute to improved workability and energy saving measures.
  • the recycling rate of the shelf board can also be improved.
  • the shelf assembly using Si-impregnated SiC is lower than the upper limit temperature of the Si-impregnated SiC substrate, S1400 ° C.
  • the Si-impregnated SiC substrate S1400 ° C.
  • it can be used at high temperatures of 1400-1600 ° C. It was difficult to do.
  • the present invention has been made in view of the above-described problems of the prior art, and its object is to have heat resistance, thermal shock resistance and oxidation resistance, as well as high strength and resistance.
  • the object is to provide a silicon nitride-bonded SiC refractory having excellent cleaving and thermal conductivity and a method for producing the same.
  • SiC is the main phase
  • Si N and / or Si NO is included as the subphase
  • the bending strength is 150-300 MPa
  • the bulk specific gravity is 2.6-2.9.
  • a silicon nitride bonded SiC refractory is provided.
  • SiC ultrafine powder is uniformly dispersed around the SiC aggregate constituting the main phase.
  • the thermal conductivity is 20—80W / (m * K). ((33)) At least 11 species selected from AAll, CCaa, FFee, TTii, ZZrr, and MMgg were converted to acid oxides. In conversion, 00 .. 11——
  • the largest and largest particle size of SSiiCC aggregate that constitutes the main main phase is 5500——30000 ⁇ mm. .
  • 3300 3700 ⁇ m mm of SSiiCC powder powder is used as the aggregate material.
  • the SSiiCCff fraction end of 00 .. 0055 3300 zz mm is 1100——5500 mass mass 00 // 00
  • the SSiiff fraction end of 00 .. 0055 3300 ⁇ mm is 1100 3300% mass %%
  • 11 kinds of at least selected from AAll, CCaa, FFee, TTii, ZZrr, MMgg This is characterized by the fact that it is equipped with a process that mixes and mixes 00 .. 11—33 mass% by mass in terms of acid oxide conversion.
  • a method of manufacturing and manufacturing SSiiCC refractory refractories is provided. .
  • the forming process is performed in the intrusion forming form. You can stay here and there
  • the present invention is substantially substan- tially under a nitrogen-nitrogen atmosphere.
  • the heat treatment at 11550000 °° CC can be left as you like. .
  • 11335500-- 11550000 °° CC when heat treatment is carried out, the atmosphere of nitrogen-nitrogen atmosphere
  • the concentration of oxygen-oxygen concentration in the atmosphere You can leave it here as it is at 00 .. 0011--22 .. 0000 %%. .
  • the silicon nitride bonded SiC refractory of the present invention has SiC as a main phase and Si N and / or as a sub phase.
  • 3 4 contains Si NO, has a bending strength of 150 MPa or more, and a bulk specific gravity of 2.6 or more.
  • the bending strength is 150 to 300 MPa.
  • the bulk specific gravity is preferably 2.6-2.9. This is because when the bulk specific gravity is low, the number of pores in the refractory increases, the internal surface area of the pores increases, the contact area with oxygen at high temperatures during use increases, and oxidation proceeds. It is easy to do.
  • the SiC aggregate constituting the main phase 1 ⁇ m or less is more preferable around the SiC aggregate constituting the main phase. It is preferable that 0.1 lxm SiC ultra fine powder is uniformly dispersed. This means that when the SiC particles are filled, there will usually be voids in the gaps between the particles, but by dispersing the SiC ultrafine powder below 1 m uniformly, This is because it can be close to the closest packing and the density can be improved. Furthermore, since the amount of the fine pores in question here greatly affects the inner surface area (specific surface area) of the open pores inside the substrate, it has a great influence on the oxidation resistance. By uniformly dispersing ultrafine SiC particles of less than or equal to m around the SiC aggregate, filling the fine pores with SiC can improve the acid resistance.
  • the refractory of the present invention preferably has a Young's modulus of lOOGPa or more, more preferably 100-500 GPa. This is because, for example, when used for shelves and struts that make up a shelves, the shelves and struts against external stresses, especially when assembling the shelves and placing the objects to be fired on the shelves. This is because the stability of the shelf assembly is improved because it is not greatly deformed, and the quality of the ceramic product can be improved because the distortion of the shelf board is small.
  • the refractory according to the present invention has a thermal conductivity of 20 W / (m'K) or more, more preferably 20-80 W / (m * K). High thermal conductivity is preferable because the material to be fired can be soaked and the quality of the material to be fired can be improved.
  • the refractory according to the present invention contains at least one selected from Al, Ca, Fe, Ti, Zr, and Mg in an amount of 0.13% by mass in terms of oxide. From the viewpoints of properties and thermal shock resistance, control of the amount of cristobalite produced, and control of the amount of glass phase.
  • the refractory according to the present invention has a content of alumina (A10) in the raw material composition analyzed by fluorescent X-ray analysis.
  • the content of [Al 2 O 3 + Fe 2 O 3] is preferably 0.5 to 2.0% by mass in terms of oxide.
  • the maximum particle size of the SiC aggregate constituting the main phase is 50 to 300 ⁇ m. This is because when the maximum particle size of the SiC aggregate is less than 50 xm, the microcrack progresses when thermal stress is applied. This is because it shows the function of stopping. On the other hand, in the case of SiC particles of less than 50 xm, the cracks progress to the grain boundaries and immediately abruptly, so the thermal shock resistance decreases. On the other hand, when the maximum particle size of SiC aggregate exceeds 300 / m This is because it is not easy to obtain sufficient thermal shock resistance and strength (bending strength and Young's modulus).
  • the refractory of the present invention preferably contains 60 90 mass% SiC, 10-40 mass% SiN and Z or SiNO. This is because the refractory of the present invention has SiC as an aggregate.
  • Si N and / or Si N 2 O is present as a subphase in the bonding part. If the amount of SiC in the main phase is below the above range, it is difficult to obtain sufficient thermal shock resistance and strength (bending strength and Young's modulus). This is because a sufficient strength is not developed.
  • Si N and / or Si N 0 have the purpose of combining the main phase as a secondary phase to develop strength, but in many cases, the balance with the main phase is lost and sufficient thermal shock resistance and strength (bending strength) are obtained. In addition, when it is difficult to obtain the Young's modulus), sufficient strength is not exhibited.
  • the refractory of the present invention has heat resistance, thermal shock resistance and oxidation resistance, as well as high strength and excellent creep resistance. More specifically, the refractory of the present invention has a temperature (about 1600 ° C) according to the operating temperature of the oxide-bonded SiC refractory and nitride-bonded SiC refractory, and a strength (225— This is a refractory that combines the advantages of conventional refractories.
  • the refractory of the present invention is usually [1] raw material preparation, [2] mixing, [3] squeeze molding, [4] mold release, [5] drying, [6] firing (nitrogen atmosphere firing ([6] -1), oxidation firing ([6] -2), and [7] inspection, etc.
  • the main feature of the method for producing a refractory according to the present invention is as an aggregate. the SiC of xm and 30 70 weight 0/0, and the SiC powder 0.
  • the power of adding Si powder at the time of raw material preparation ([1]) is preferable because Si can be uniformly dispersed around the SiC aggregate.
  • inorganic oxides Al, Ca, Fe, Ti, Zr, Mg
  • the density (denseness) of the obtained refractory can be improved by adding 10-30% by mass of SiC ultrafine powder having a particle size of lxm or less. it can. In conventional blending, the density decreased when the inorganic oxide content was 3% by mass or less, but by adding SiC ultrafine powder, a bulk specific gravity of 2.6 or more can be obtained even if the amount of inorganic oxide is small.
  • the forming step is performed by squeeze forming ([3]).
  • the density of the obtained molded product is improved, so that the strength (bending strength and Young's modulus) of the refractory after firing can be improved.
  • the method for producing a refractory according to the present invention it is preferable that firing is performed at 1350-1500 ° C under a substantially nitrogen atmosphere, and the firing time is set to 1 to 30 hours ([6] -1 ).
  • the firing time is set to 1 to 30 hours ([6] -1 ).
  • Si in the molded body reacts with nitrogen in the atmosphere, and silicon nitride and oxynitride from a small amount of oxygen are generated at the grain boundaries of the SiC particles.
  • SiC aggregate can be combined.
  • the oxygen concentration in the nitrogen atmosphere when the heat treatment is performed at 1350 to 1500 ° C. is more preferably 0.01-2.00%.
  • oxynitrides are formed in the presence of a small amount of oxygen, and SiC grain boundaries can be bonded more firmly. If the nitrogen content in the nitrogen atmosphere is less than 90% by volume, it is not preferable because the nitriding rate is delayed during heat treatment, the non-nitriding phenomenon occurs due to some oxygen, and the raw material is oxidized. .
  • heat treatment is further performed in an air atmosphere at 1300-1500 ° C ([6 ] -2).
  • the oxidation treatment temperature is less than 1300 ° C, the oxide film may not be sufficiently formed and the oxidation resistance may not be exhibited.
  • the oxidation temperature exceeds 1500 ° C. In this case, the oxidation during the formation of the oxide film becomes intense, and bubbles generated by the oxidation are entrained in the oxide film to form a porous oxide film, so that the oxidation resistance may not be exhibited.
  • the refractory does not need to be heat-treated when used at 1300 ° C or higher.
  • Table 1 shows the SiC powder, Si powder, FeO, Al 2 O, dispersion material, and ion-exchanged water shown in Table 1.
  • Raw materials were blended so that the blending ratio (mass%) was obtained (raw material blending [1]).
  • the obtained raw material was put into and mixed in the trommel, and the raw material was uniformly mixed to break up the secondary particles and primary particles of the raw material particles in the slurry (mixing [2]). At this time, the trommel mixing was performed at 100 kg / batch for about 20 hours.
  • the obtained dried molded body was fired in a nitrogen atmosphere at 1450 ° C for 10 hours (firing in a nitrogen atmosphere ([6] _1)).
  • the obtained fired body was subjected to oxidation firing in air atmosphere at 1450 ° C. for 10 hours (oxidation firing ([6] -2)).
  • Example 1 is slightly inferior in strength (bending strength and Young's modulus) and thermal conductivity compared to Comparative Example 1, but the shelf boards and struts constituting the shelf assembly are slightly inferior. It was necessary and sufficient as a substrate. Further, since Example 1 has a higher maximum use temperature compared to Comparative Example 1, it can be applied to a shelf assembly for higher temperature firing. Furthermore, Example 1 is a method of firing in the manufacturing process. Since there was little formation deformation, it was not necessary to grind almost. On the other hand, Comparative Example 1 is difficult to handle because there is only firing deformation in the manufacturing process, so it takes time and effort to correct the deformation, which may increase costs.
  • Example 2 As a result of evaluating the creep resistance of Example 2 and Comparative Example 2, it was found that the creep resistance of Example 2 was much superior to that of Comparative Example 2 as is apparent from the results of FIG. .
  • Example 2 As shown in Table 3, it was confirmed by composition analysis that the content of alumina (A10) was extremely smaller than that in Comparative Example 2. Further, in Example 2, as shown in Table 3, from the results of the qualitative analysis of the crystal phase by XRD, the ⁇ -Si AION (i3 -sialon) and AI O (Corundum) crystal phases present in Comparative Example 2 were analyzed. Although not included, it was confirmed that the ⁇ -Si N crystal phase was larger than that of Comparative Example 2 and had a crystal phase of 1 Si N and Si NO that did not exist in Comparative Example 2.
  • Example 2 since the glass phase does not increase at the interface of the crystal phase by suppressing the amount of alumina (A1 O) to the minimum necessary at the raw material preparation stage, the creep resistance decreases. It is speculated that it can be greatly suppressed.
  • the silicon nitride bonded SiC refractory according to the present invention and the method for producing the same are suitable as a shelf plate and a column constituting a shelf assembly used when firing a fired article (ceramic product) such as a tile, ceramic, or honeycomb. Can be used.

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Abstract

　ＳｉＣを主相とし、副相としてＳｉ3Ｎ4及び／又はＳｉ2Ｎ2Ｏを含むとともに、曲げ強度が１５０～３００ＭＰａで、且つ嵩比重が２．６～２．９である窒化珪素結合ＳｉＣ耐火物である。骨材として３０～３００μｍのＳｉＣ粉末を３０～７０質量％と、０．０５～３０μｍのＳｉＣ粉末を１０～５０質量％と、０．０５～３０μｍのＳｉ粉末を１０～３０質量％に、Ａｌ、Ｃａ、Ｆｅ、Ｔｉ、Ｚｒ、Ｍｇから選択された少なくとも１種類を酸化物換算で０．１～３質量％を混合する工程を備えた窒化珪素結合ＳｉＣ耐火物の製造方法である。この窒化珪素結合ＳｉＣ耐火物及びその製造方法によれば、耐熱性、耐熱衝撃性及び耐酸化性を有するとともに、高強度で且つ耐クリープ性、熱伝導性に優れた耐火物を得ることができる。

Description

明 細 書
窒化珪素結合 SiC耐火物及びその製造方法
技術分野
[0001] 本発明は、窒化珪素結合 SiC耐火物及びその製造方法に関する。
背景技術
[0002] 炭化珪素 (SiC)耐火物は、その優れた耐熱性及び耐火性から工業上重要な位置 を占めており、例えば、タイル、陶磁器、ハニカム等の焼成用棚板、その他の焼成用 治具、サャ等に多用されている。
[0003] 一般に、タイル、陶磁器、ハニカム等の被焼成物 (セラミック製品）を焼成する場合 には、例えば、被焼成物の均一な焼成に必要とされる空間を形成するブロック状の 支柱を棚板の隅に複数箇所載置して、棚板と支柱とを交互に複数段に積み上げな がら、多段に棚組みされた棚板の上に被焼成物を載せて焼成が行われる。
[0004] このような棚組は、従来、手作業によるところが多かったが、近年では、セラミック製 品の焼成、製造ラインにあっても、 自動化、省力化が図られ、棚板や製品の搬送につ いて自動化が進んでいる。
[0005] 上記棚組を構成する棚板及び支柱の基材としては、従来、高温 (例えば、 1200 1600°C)で使用できるムライト質、アルミナ質及びジルコユア質が主に使用されてき たが、強度（曲げ強度及びヤング率）が不十分であるため、より強度の大きい酸化物 結合 SiC耐火物、窒化物結合 SiC耐火物が用途に応じて使用されている。
[0006] しかしながら、酸化物結合 SiC耐火物、窒化物結合 SiC耐火物を用いた棚組は、棚 組の使用 ·組立 ·分解時に生じる外部応力に耐えうるだけの強度を得るため、棚板及 び支柱の肉厚を厚くする必要があり、重量が嵩み、作業性が低下するだけでなぐ熱 容量も大きくなるため、近年の省エネ対策に十分対応することが困難であるだけでな ぐ熱伝導性も悪レ、ため被焼成体の均熱を図るのが困難であった。
[0007] また、上記耐火物として必要な耐酸化性と強度を確保するためには、嵩比重 2. 6 以上が必要であり、通常、酸化物としてアルミナや酸化鉄を 3— 10質量％添加してい この様にアルミナや酸化鉄を 3 10質量％添加した場合、結合部のガラス相が増 して耐火物として必要な耐クリープ性が低下し寿命が短くなる問題があった。更に、 アルミナや酸化鉄は原料調合時の原料の分散効果や、焼結助材的な働きをしている ため、従来の方法ではアルミナや酸化鉄を 3%以下に減量した場合、嵩比重が低下 し、必要な強度が得られない問題があった。
[0008] 以上の点を解消するため、高強度且つ耐熱性、耐酸化性及び熱伝導性に優れた Siを金属 Si相として含む（多孔質又は緻密質)含 Si材料 (例えば、 Siと SiCとを主相と して含有してなる金属珪素-炭化珪素複合材料 [Si含浸 SiC耐火物] )を用いた棚組 が使用されている。
[0009] Si含浸 SiC耐火物を用いた棚組は、棚板及び支柱を薄肉化及び軽量化することが できるため、作業性の向上と省エネ対策に貢献できるだけでなぐ長寿命であるため
、棚板のリサイクル率も向上することができる。
[0010] し力しながら、 Si含浸 SiCを用いた棚組は、基材である Si含浸 SiCの使用上限温度 力 S1400°C未満であるため、例えば、 1400— 1600°Cの高温での使用することが困 難であった。
[0011] 本発明は、上述した従来技術の問題点に鑑みてなされたものであり、その目的とす るところは、耐熱性、耐熱衝撃性及び耐酸化性を有するとともに、高強度で且つ耐ク リーブ性、熱伝導性に優れた窒化珪素結合 SiC耐火物及びその製造方法を提供す ることにある。
発明の開示
[0012] 即ち、本発明によれば、 SiCを主相とし、副相として Si N及び/又は Si N Oを含 むとともに、曲げ強度が 150— 300MPaで、且つ嵩比重が 2. 6— 2. 9である窒化珪 素結合 SiC耐火物が提供される。
[0013] このとき、本発明では、主相を構成する SiC骨材の周辺に、 0. 1— 1 μ mの SiC超 微粉が均一に分散されていることが好ましい。
[0014] また、本発明では、 （1)一（5)の条件をいずれか 1つ以上満たすことが好ましい。
(1)ヤング率が、 100— 500GPaであること。
(2)熱伝導率が、 20— 80W/ (m*K)であること。 ((33)) AAll、、 CCaa、、 FFee、、 TTii、、 ZZrr、、 MMggかからら選選択択さされれたた少少ななくくとともも 11種種類類をを酸酸化化物物換換算算でで 00.. 11——
33質質量量％％含含有有すするるこことと。。
((44))主主相相をを構構成成すするる SSiiCC骨骨材材のの最最大大粒粒子子径径カカ 5500—— 330000 μμ mmででああるるこことと。。
((55)) 6600 9900質質量量％％のの3311〇〇、、 1100 4400質質量量％％のの SSii NN及及びび//又又はは SSii NN OOをを含含むむこことと。。
33 44 22 22
[[00001155]] 更更にに、、本本発発明明にによよれればば、、骨骨材材ととししてて 3300 330000 μμ mmのの SSiiCC粉粉末末をを 3300 7700質質量量％％とと、、 00.. 0055 3300 zz mmのの SSiiCCff分分末末をを 1100—— 5500質質量量00 //00とと、、 00.. 0055 3300 μμ mmのの SSiiff分分末末をを 1100 3300 質質量量％％にに、、 AAll、、 CCaa、、 FFee、、 TTii、、 ZZrr、、 MMggかからら選選択択さされれたた少少ななくくとともも 11種種類類をを酸酸化化物物換換算算 でで 00.. 11—— 33質質量量％％をを混混合合すするる工工程程をを備備ええたたここととをを特特徴徴ととすするる窒窒化化珪珪素素結結合合 SSiiCC耐耐火火 物物のの製製造造方方法法がが提提供供さされれるる。。
[[00001166]] ここののとときき、、本本発発明明のの製製造造方方法法でではは、、成成形形工工程程がが铸铸込込成成形形でで行行わわれれるるここととがが好好ままししいい
[[00001177]] ままたた、、本本発発明明のの製製造造方方法法でではは、、実実質質的的にに窒窒素素雰雰囲囲気気下下でで、、 11335500—— 11550000°°CCににてて熱熱 処処理理すするるここととがが好好ままししいい。。ここののとときき、、 11335500—— 11550000°°CCににてて熱熱処処理理すするるととききのの窒窒素素雰雰囲囲 気気中中のの酸酸素素濃濃度度はは、、 00.. 0011--22.. 0000%%ででああるるここととがが好好ままししいい。。
[[00001188]] 更更にに、、本本発発明明のの製製造造方方法法でではは、、窒窒素素雰雰囲囲気気中中でで熱熱処処理理ししたた後後、、更更にに大大気気雰雰囲囲気気 中中でで、、 11330000—— 11550000°°CCににてて熱熱処処理理すするるこことと力力 SS好好ままししレレ、、。。
図図面面のの簡簡単単なな説説明明
[[00001199]] [[図図 11]]耐耐ククリリーーププ性性のの評評価価試試験験のの結結果果をを示示すす、、経経過過時時間間（（hhrr))にに対対ししててククリリーーププ量量 ((mm
Figure imgf000005_0001
発明を実施するための最良の形態
[0020] 本発明の窒化珪素結合 SiC耐火物は、 SiCを主相とし、副相として Si N及び/又
3 4 は Si N〇を含むとともに、曲げ強度が 150MPa以上で、且つ嵩比重が 2. 6以上で
2 2
あるものである。このとき、曲げ強度は、 150— 300MPaであること力 例えば、棚組 を構成する棚板及び支柱に使用する場合、好適に用レ、ることができるため好ましい。 また、嵩比重は、 2. 6-2. 9であることが好ましい。これは、嵩比重が低値の場合、 耐火物内の気孔が多くなり、気孔の内表面積が増大し、使用中の高温下での酸素と の接触面積が増大することになり、酸化が進行しやすくなるからである。
[0021] このとき、本発明では、主相を構成する SiC骨材の周辺に、 1 μ m以下、より好ましく は、 0. 1一 l x mの SiC超微粉が均一に分散されていることが好ましレ、。これは、 SiC 粒子を充填した場合の粒子の隙間部分には、通常空隙が残ることになるが、： m 以下の SiC超微粉を均一分散することで、 1 μ m以下の空隙部分にも SiCが充填さ れ、最密充填に近づけることができ、密度を向上させることができるからである。更に 、ここで問題にしている微細気孔の存在量は、基材内部の開気孔の内表面積 (比表 面積）に大きく影響するため、耐酸化性への影響も大きい。 SiC骨材周辺に、： m 以下の SiC超微粉を均一に分散させることで、微細気孔を SiCで充填することで、耐 酸ィ匕'性も向上させることができる。
[0022] また、本発明の耐火物は、ヤング率が lOOGPa以上、より好ましくは、 100— 500G Paであることが好ましい。これは、例えば、棚組を構成する棚板及び支柱に使用する 場合、特に、棚組の組立及び棚板に被焼成物を載置したときに、棚板及び支柱が外 部応力に対して大きく変形することがないため、棚組の安定性が向上するとともに、 棚板の歪みが少ないため、セラミック製品の品質を向上することができるからである。
[0023] 更に、本発明の耐火物は、熱伝導率が 20W/ (m'K)以上、より好ましくは、 20— 80W/ (m*K)であることが、高温で加熱された場合、熱伝導が高いと、被焼成物の 均熱化が図られ被焼成物の品質を向上することができるため好ましい。
[0024] ここで、本発明の耐火物は、 Al、 Ca、 Fe、 Ti、 Zr、 Mgから選択された少なくとも 1種 類を酸化物換算で 0. 1 3質量％含有することが、耐酸化特性及び熱衝撃抵抗性、 クリストバライトの生成量の制御、ガラス相量の制御の点から好ましい。特に、本発明 の耐火物は、蛍光 X線分析で組成分析した原料組成中のアルミナ (A1〇）の含有量 力 酸化物換算で 0. 05- 1. 5質量％であり、アルミナ +酸化鉄 [Al O +Fe O ]の 含有量が酸化物換算で 0. 5-2. 0質量％であることが好ましい。
[0025] また、本発明の耐火物は、主相を構成する SiC骨材の最大粒子径が、 50— 300 μ mであることが好ましレ、。これは、 SiC骨材の最大粒子径が 50 x m未満である場合、 熱応力が加わった場合のマイクロクラックの進展は、 50 a m以上の SiC粒子が組織 内に存在するとこの粒子でクラックの進展が止まる働きを示すからである。これに対し て 50 x m未満の SiC粒子の場合、クラックは粒界に進展しやすぐ急激に進行する ため、耐熱衝撃性が低下する。一方、 SiC骨材の最大粒子径が 300 / m超過する場 合、十分な耐熱衝撃性及び強度（曲げ強度及びヤング率）を得ることが容易でない からである。
[0026] 更に、本発明の耐火物は、 60 90質量％の SiC、 10— 40質量％の Si N及び Z 又は Si N〇を含むことが好ましい。これは、本発明の耐火物は骨材として SiCがあり
、結合部に Si N及び/又は Si N Oが副相として存在している。主相の SiCの量が 上記範囲以下では十分な耐熱衝撃性及び強度（曲げ強度及びヤング率)を得ること が難しく、多レ、場合では結合部を構成する副相が少なレ、ために十分な強度が発現し ないからである。また、 Si N及び/又は Si N〇は、副相として主相を結合させ強度 を発現させる目的があるが、多い場合、主相とのバランスが崩れ、十分な耐熱衝撃性 及び強度（曲げ強度及びヤング率)を得ることが難しぐ少ない場合、十分な強度が 発現しない。
[0027] 以上のことから、本発明の耐火物は、耐熱性、耐熱衝撃性及び耐酸化性を有する とともに、高強度で且つ耐クリープ性に優れている。より具体的に説明すると、本発明 の耐火物は、酸化物結合 SiC耐火物、窒化物結合 SiC耐火物の使用温度に準ずる 温度（1600°C程度）と、 Si含浸 SiCに準ずる強度（225— 250MPa程度）を有するも のであり、従来の耐火物の長所を兼ね備えた耐火物である。
[0028] 次に、本発明の窒化珪素結合 SiC耐火物の製造方法について説明する。本発明 の耐火物は、通常、 [1]原料調合、 [2]混合、 [3]铸込成形、 [4]離型、 [5]乾燥、 [6 ]焼成 (窒素雰囲気焼成（[6]-1)、酸化焼成（[6]-2)、 [7]検査といった工程を経て 製造される。ここで、本発明の耐火物の製造方法の主な特徴は、骨材として 30— 30 0 x mの SiCを 30 70質量0 /0と、 0. 05— 30 μ mの SiC粉末を 10 50質量0 /0と、 0 . 05 30 z mの Si粉末を 10— 30質量0 /0に、 Al、 Ca、 Fe、 Ti、 Zr、 Mgから選択され た少なくとも 1種類を酸化物換算で 0. 1— 3質量％を混合する工程（[1] + [2] )を備 えたことにある。無機酸化物が多いと、使用時に結晶粒界中に生成してくるガラス相 の量が増大して、耐火物として必要な耐クリープ性が低下し寿命が短くなつてしまう。
[0029] このとき、本発明の耐火物の製造方法では、原料調合（[1] )時点で Si粉末を添カロ すること力 Siを SiC骨材の周辺に均一に分散させることができるため好ましい。また 、本発明の耐火物の製造方法では、無機酸化物（Al、 Ca、 Fe、 Ti、 Zr、 Mg)の内、 少なくとも、 Al O力 SO. 05—2. 0質量0 /o、 Fe O力 0. 05- 1. 0質量0 /o、 Na O力 0.
1質量％未満であることが好ましい。更に、本発明の耐火物の製造方法では、 l x m 以下の粒子径の SiC超微粉を 10— 30質量％添カ卩することにより、得られた耐火物の 密度 (緻密度）を向上することができる。従来の配合では無機酸化物が 3質量％以下 になると密度が低下していたが、 SiC超微粉を添加することで無機酸化物量が少なく ても 2. 6以上の嵩比重が得られる。
[0030] また、本発明の耐火物の製造方法は、成形工程が铸込成形（[3] )で行われること が好ましい。これにより、本発明の耐火物の製造方法では、得られた成形品の緻密 性が向上するため、焼成後の耐火物の強度（曲げ強度及びヤング率）を向上させる こと力 Sできる。
[0031] 更に、本発明の耐火物の製造方法は、実質的に窒素雰囲気下で、 1350— 1500 °Cにて焼成し、焼成時間は 1一 30hrにすることが好ましい（[6]-1)。これにより、本 発明の耐火物の製造方法は、成形体中の Siと雰囲気中の窒素とが反応し、窒化珪 素と、微量の酸素から酸窒化物とが SiC粒子の粒界に生成され、 SiC骨材を結合さ せることができる。また、 1350— 1500°Cにて熱処理するときの窒素雰囲気中の酸素 濃度は、 0. 01-2. 00%であることがより好ましい。これは、微量の酸素の存在で酸 窒化物が形成され、より強固に SiC粒界を結合させることができるからである。尚、窒 素雰囲気中の窒素の含有割合が 90容量％未満である場合、熱処理時に窒化速度 の遅延や一部の酸素により未窒化現象が生じたり、原料が酸化してしまうため好まし くない。
[0032] 更に、本発明の耐火物の製造方法では、窒素雰囲気中で焼成（[6]_1)した後、更 に大気雰囲気中で 1300— 1500°Cにて熱処理することが好ましい（[6]-2)。
これは、得られた耐火物の表面に強固な酸化被膜を形成させることにより、高温で長 時間使用した場合であっても、酸化劣化が抑制されるため、変形や膨れがほとんど 無ぐ割れ等も生じない、という極めて優れた耐熱衝撃性を発現させることができるか らである。
[0033] このとき、酸化処理温度が 1300°C未満である場合、酸化皮膜が十分に形成されず 、耐酸化性が発揮できない可能性がある。一方、酸化処理温度が 1500°Cを超過し た場合、酸化皮膜形成時の酸化が激しくなり、酸化皮膜中に酸化により発生した気 泡を巻き込み、孔のある酸化皮膜が形成されるため、耐酸化性が発揮できない可能 十生がある。
[0034] 尚、本耐火物は、 1300°C以上で使用する場合、熱処理は無くても良いが、 1300
°c未満で使用する場合、熱処理した方が良い。
[0035] 本発明を実施例に基づいて、更に詳細に説明するが、本発明はこれらの実施例に 限られるものではない。
[0036] (実施例 1)
表 1に示す SiC粉末、 Si粉末、 Fe〇、 Al O、分散材、イオン交換水を表 1に示す
2 3 2 3
配合比 (質量％)になるように、原料調合した (原料調合 [1] )。
[0037] [表 1]
Figure imgf000009_0001
[0038] 得られた原料を、トロンメル内に投入'混合し、原料の均一混合を図り、泥漿内の原 料粒子の二次粒子と一次粒子を解砕した (混合 [2] )。このとき、トロンメル混合は、 1 00kg/バッチで、 20hr程度行った。
[0039] 上記トロンメル混合で得られた泥漿を、石膏型内に注入し、泥漿内の水分を石膏型 に吸収させて、所定厚さを着肉させることにより、成形体を得た (成形 (铸込成形） [3]
) o
[0040] 得られた成形体を、石膏型から取り出し、成形体内の水分を乾燥させた（離型 [4]、 乾燥 [5] )。
[0041] 得られた乾燥成形体を、窒素雰囲気中、 1450°C、 10hrで焼成した（窒素雰囲気 焼成（[6]_1) )。次いで、得られた焼成体を、大気雰囲気中、 1450°C、 10hrで酸化 焼成を行った (酸化焼成（ [6]-2) )。
[0042] 最後に、寸法及び外観キレが検查 (検查 [7] )された耐火物について、曲げ強度、 ヤング率、嵩比重、気孔率、熱伝導率及び研削抵抗の測定を行うとともに、加工性の 評価を行った。その結果を表 2に示す。
[0043] (比較例 1)
従来公知の Si含浸 SiC耐火物（日本ガイシ (株）製 NEWSIC)について、曲げ強 度、ヤング率、嵩比重、気孔率）、熱伝導率、最大使用温度の測定を行うとともに、焼 成変形及びカ卩ェ性の評価を行った。その結果を表 2に示す。
[0044] [表 2]
Figure imgf000010_0001
(考察:実施例 1、比較例 1)
表 2の結果から、実施例 1は、比較例 1と比較して、強度（曲げ強度及びヤング率）と 熱伝導率におレ、てやや劣るが、棚組を構成する棚板及び支柱の基材としては必要 十分であった。また、実施例 1は、比較例 1と比較して、最大使用温度が高いため、よ り高温焼成用の棚組に適用できると考えられる。更に、実施例 1は、製造工程での焼 成変形が少ないため、研削加工をほとんどする必要がなかった。一方、比較例 1は、 製造工程での焼成変形が有るだけでなぐ難カ卩ェ性であるため、変形を修正するの に手間暇がかかり、コスト高になる可能性があった。
[0046] (実施例 2、比較例 2)
表 3に示す化学分析結果による酸化物換算割合を有する窒化珪素結合 SiC耐火 物を 2種類用意し、蛍光 X線分析による組成分析、 XRDによる結晶相の定性分析及 び耐クリープ性の評価試験をそれぞれ行った。その結果を表 3及び図 1に示す。 このうち、一方は、実施例 1と同様の製造方法で得られた窒化珪素結合 SiC耐火物 (実施例 2)であり、もう一方は、従来公知の窒化珪素結合 SiC耐火物（比較例 2)であ る。
[0047] [表 3]
Figure imgf000011_0001
[0048] 尚、耐クリープ性の評価試験は、以下の条件で行った。
•試験温度： 1400°C X 200hr
•試験体开娥： 1 Omm X 2mm X 120mmL
•応力： IMPa •測定個所：試験体の端部及び中央部
[0049] (考察：実施例 2、比較例 2)
実施例 2及び比較例 2について耐クリープ性の評価をした結果、図 1の結果から明 らかなように、実施例 2の耐クリープ性が比較例 2よりも非常に優れていることが判明 した。
また、実施例 2では、表 3に示すように、組成分析においてアルミナ (A1〇）の含有 量が比較例 2よりも極めて少ないことを確認した。更に、実施例 2では、表 3に示すよう に、 XRDによる結晶相の定性分析の結果から、比較例 2に存在する β -Si AION ( i3 -sialon)及び AI O (Corundum)の結晶相を含まない反面、 α—Si Nの結晶相 が比較例 2よりも多めで、比較例 2に存在しない 一 Si N及び Si N Oの結晶相を有 していることを確認した。以上のことから、実施例 2は、原料調合段階で、アルミナ (A1 O )量を必要最小限に抑制することにより、結晶相の界面にガラス相が増すことがな いため、耐クリープ性の低下を大幅に抑制することができると推測される。
産業上の利用可能性
[0050] 本発明の窒化珪素結合 SiC耐火物及びその製造方法は、例えば、タイル、陶磁器 、ハニカム等の被焼成物（セラミック製品）の焼成時に用いる棚組を構成する棚板及 び支柱として好適に用いることができる。

Claims

請求の範囲
[I] SiCを主相とし、副相として Si N及び/又は Si N〇を含むとともに、曲げ強度が 1
50— 300MPaで、且つ嵩比重が 2. 6— 2. 9である窒化珪素結合 SiC耐火物。
[2] 前記主相を構成する SiC骨材の周辺に、 0. 1— 1 μ mの SiC超微粉が均一に分散 されてレ、る請求項 1に記載の窒化珪素結合 SiC耐火物。
[3] ヤング率が、 100— 500GPaである請求項 1又は 2に記載の窒化珪素結合 SiC耐 火物。
[4] 熱伝導率が、 20— 80W/ (m'K)である請求項 1一 3のいずれか 1項に記載の窒 化珪素結合 SiC耐火物。
[5] Al、 Ca、 Fe、 Ti、 Zr、 Mgから選択された少なくとも 1種類を酸化物換算で 0· 1— 3 質量％含有する請求項 1一 4のいずれか 1項に記載の窒化珪素結合 SiC耐火物。
[6] 主相を構成する SiC骨材の最大粒子径カ 50— 300 z mである請求項 1一 5のレ、 ずれか 1項に記載の窒化珪素結合 SiC耐火物。
[7] 60 90質量％の SiC、 10 40質量％の Si N及び/又は Si N Oを含む請求項
1一 6のいずれ力、 1項に記載の窒化珪素結合 SiC耐火物。
[8] 骨材として 30— 300 μ mの SiCf分末を 30— 70質量0 /0と、 0. 05 30 μ mの SiCf分 末を 10一 50質量0 /0と、 0. 05— 30 z mの Sif分末を 10一 30質量0 /0に、 Al、 Ca、 Fe、
Ti、 Zr、 Mgから選択された少なくとも 1種類を酸化物換算で 0. 1 3質量％を混合 する工程を備えた窒化珪素結合 SiC耐火物の製造方法。
[9] 成形工程が、铸込成形で行われる請求項 8に記載の窒化珪素結合 SiC耐火物の 製造方法。
[10] 実質的に窒素雰囲気下で、 1350— 1500°Cにて熱処理する請求項 8又は 9に記 載の窒化珪素結合 SiC耐火物の製造方法。
[I I] 1350— 1500°Cにて熱処理するときの窒素雰囲気中の酸素濃度力 0. 01— 2. 0 0%である請求項 8— 10のいずれ力 1項に記載の窒化珪素結合 SiC耐火物の製造 方法。
[12] 窒素雰囲気中で熱処理した後、更に大気雰囲気中で、 1300— 1500°Cにて熱処 理する請求項 8— 11のいずれか 1項に記載の窒化珪素結合 SiC耐火物の製造方法
96t0請 OOZdf/ェ:) d 9.09Z0/S00Z OAV
PCT/JP2004/010496 2003-09-09 2004-07-23 窒化珪素結合ＳｉＣ耐火物及びその製造方法 WO2005026076A1 (ja)

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US10/571,073 US7494949B2 (en) 2003-09-09 2004-07-23 SiC refractory comprising silicon nitride bond thereto and method for production thereof
PL04770889T PL1666433T3 (pl) 2003-09-09 2004-07-23 Materiał ogniotrwały z SiC zawierający związany z nim azotek krzemu
EP04770889A EP1666433B1 (en) 2003-09-09 2004-07-23 SiC REFRACTORY COMPRISING SILICON NITRIDE BONDED THERETO
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