JPH0797259A - Zirconia refractory - Google Patents
Zirconia refractoryInfo
- Publication number
- JPH0797259A JPH0797259A JP5239486A JP23948693A JPH0797259A JP H0797259 A JPH0797259 A JP H0797259A JP 5239486 A JP5239486 A JP 5239486A JP 23948693 A JP23948693 A JP 23948693A JP H0797259 A JPH0797259 A JP H0797259A
- Authority
- JP
- Japan
- Prior art keywords
- zirconia
- stabilized
- weight
- unstabilized
- refractory
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 title claims abstract description 114
- 239000000203 mixture Substances 0.000 claims abstract description 22
- RUDFQVOCFDJEEF-UHFFFAOYSA-N yttrium(III) oxide Inorganic materials [O-2].[O-2].[O-2].[Y+3].[Y+3] RUDFQVOCFDJEEF-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000011819 refractory material Substances 0.000 claims description 19
- 238000010438 heat treatment Methods 0.000 abstract description 28
- 238000001816 cooling Methods 0.000 abstract description 17
- 239000002245 particle Substances 0.000 abstract description 12
- 230000035939 shock Effects 0.000 abstract description 7
- 238000005245 sintering Methods 0.000 abstract description 6
- 239000011230 binding agent Substances 0.000 abstract description 4
- 229920002134 Carboxymethyl cellulose Polymers 0.000 abstract description 3
- 239000001768 carboxy methyl cellulose Substances 0.000 abstract description 3
- 235000010948 carboxy methyl cellulose Nutrition 0.000 abstract description 3
- 239000008112 carboxymethyl-cellulose Substances 0.000 abstract description 3
- 229920003171 Poly (ethylene oxide) Polymers 0.000 abstract description 2
- 239000004372 Polyvinyl alcohol Substances 0.000 abstract description 2
- 229920002451 polyvinyl alcohol Polymers 0.000 abstract description 2
- 230000008859 change Effects 0.000 description 15
- 229910002076 stabilized zirconia Inorganic materials 0.000 description 11
- 239000000463 material Substances 0.000 description 10
- 238000000034 method Methods 0.000 description 6
- 238000013329 compounding Methods 0.000 description 5
- 230000008602 contraction Effects 0.000 description 5
- 238000010304 firing Methods 0.000 description 5
- 238000000465 moulding Methods 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- 230000006641 stabilisation Effects 0.000 description 5
- 238000011105 stabilization Methods 0.000 description 5
- RKTYLMNFRDHKIL-UHFFFAOYSA-N copper;5,10,15,20-tetraphenylporphyrin-22,24-diide Chemical compound [Cu+2].C1=CC(C(=C2C=CC([N-]2)=C(C=2C=CC=CC=2)C=2C=CC(N=2)=C(C=2C=CC=CC=2)C2=CC=C3[N-]2)C=2C=CC=CC=2)=NC1=C3C1=CC=CC=C1 RKTYLMNFRDHKIL-UHFFFAOYSA-N 0.000 description 4
- 238000009826 distribution Methods 0.000 description 4
- 230000009466 transformation Effects 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 3
- 239000010419 fine particle Substances 0.000 description 3
- 230000001965 increasing effect Effects 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 229910001233 yttria-stabilized zirconia Inorganic materials 0.000 description 3
- 239000011362 coarse particle Substances 0.000 description 2
- 230000006378 damage Effects 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 238000005338 heat storage Methods 0.000 description 2
- 229910002077 partially stabilized zirconia Inorganic materials 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000003381 stabilizer Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 238000007088 Archimedes method Methods 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 229920000609 methyl cellulose Polymers 0.000 description 1
- 239000001923 methylcellulose Substances 0.000 description 1
- 235000010981 methylcellulose Nutrition 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 239000006104 solid solution Substances 0.000 description 1
Landscapes
- Compositions Of Oxide Ceramics (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明はジルコニア質耐火物に関
するもので、たとえば、加熱冷却を繰り返す高温熱交換
器の体積及び形状の安定性を要求される蓄熱体用部材と
して適した、部分安定化ジルコニア質耐火物に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a zirconia refractory material, for example, a partially stabilized material suitable as a member for a heat storage body which requires stability of volume and shape of a high temperature heat exchanger that repeats heating and cooling. Regarding zirconia refractories.
【０００２】[0002]
【従来の技術】ジルコニア単体は、１１００℃付近で単
斜晶から正方晶への相変態に伴う不規則熱膨張収縮を起
こすことが知られている。耐火物等その製造において、
このようなジルコニア単体を原料として焼成工程を必要
とする成形体を得ようとする場合には、その焼成工程中
において、特に冷却時における正方晶から単斜晶への変
態に伴う大きな体積膨張により組織破壊を起こすため、
成形体が得られにくい。そして安定化または部分安定化
ジルコニアを原料とするか、またはさらにＣａＯ、Ｍｇ
Ｏ、Ｙ2 Ｏ3 等の酸化物を安定化剤として共に加える事
により高温においてこれら酸化物を固溶させ、部分的あ
るいは全体的に立方晶の結晶構造をもつ部分安定化また
は安定化ジルコニアとして成形体を得るのが一般的であ
る。2. Description of the Related Art It is known that a simple substance of zirconia causes irregular thermal expansion and contraction accompanying a phase transformation from monoclinic to tetragonal at around 1100 ° C. In the manufacture of refractories, etc.,
When trying to obtain a molded body that requires a firing step using such a zirconia simple substance as a raw material, during the firing step, due to a large volume expansion due to the transformation from tetragonal to monoclinic during cooling. To cause tissue destruction,
It is difficult to obtain a molded product. Then, using stabilized or partially stabilized zirconia as a raw material, or further CaO, Mg
Oxides such as O 2 and Y 2 O 3 are added together as stabilizers to form a solid solution of these oxides at high temperature to form a partially stabilized or stabilized zirconia partially or wholly having a cubic crystal structure. Generally, a molded body is obtained.
【０００３】また、加熱冷却を繰り返す使用条件に対し
ては耐熱衝撃性が必要とされるが、ジルコニア、特に安
定化された正方晶系のジルコニアは熱膨張係数が大き
く、耐熱衝撃性が低い。これに対しある程度気孔率を上
昇させることにより耐熱衝撃性を向上させる方法がある
が、その場合でも１８００℃以上の高温の熱処理を受け
る場合には非常に緻密な材料組織である以外は、焼結に
より体積の収縮が起こる。Although thermal shock resistance is required for repeated use of heating and cooling, zirconia, particularly stabilized tetragonal zirconia, has a large thermal expansion coefficient and low thermal shock resistance. On the other hand, there is a method of improving the thermal shock resistance by increasing the porosity to some extent, but even in that case, when it is subjected to a high temperature heat treatment of 1800 ° C. or higher, it has a very dense material structure, and it is sintered. Causes volume contraction.
【０００４】[0004]
【発明が解決しようとする課題】本発明は、高温までの
加熱冷却を繰り返すような使用条件においても、体積安
定性、耐熱衝撃性に優れたジルコニア質耐火物の提供を
課題とする。SUMMARY OF THE INVENTION It is an object of the present invention to provide a zirconia-based refractory having excellent volume stability and thermal shock resistance even under use conditions in which heating and cooling to high temperatures are repeated.
【０００５】[0005]
【課題を解決するための手段】本発明のジルコニア質耐
火物は、イットリアにより安定化または部分的に安定化
されたジルコニア（以下、安定化ジルコニアともいう）
と未安定化ジルコニアとの組成物であって、未安定化ジ
ルコニアの組成比が７重量％〜２０重量％の割合であ
り、かつ１８００℃以上の温度での焼成体であることを
特徴とする。The zirconia-based refractory material of the present invention is zirconia stabilized or partially stabilized by yttria (hereinafter also referred to as stabilized zirconia).
And a non-stabilized zirconia, wherein the composition ratio of the non-stabilized zirconia is 7% by weight to 20% by weight, and the composition is a fired product at a temperature of 1800 ° C. or higher. .
【０００６】また、本発明のジルコニア質耐火物は、イ
ットリアにより安定化または部分的に安定化されたジル
コニアと未安定化ジルコニアとの組成物であって、未安
定化ジルコニアの組成比が７重量％〜２０重量％の割合
であると共に、１８００℃以上の温度での焼成体で、か
つ２０％〜２７％の見掛け気孔率を有するものであるこ
とを特徴とする。The zirconia-based refractory material of the present invention is a composition of zirconia stabilized or partially stabilized by yttria and unstabilized zirconia, and the composition ratio of unstabilized zirconia is 7% by weight. % To 20% by weight, and is a fired body at a temperature of 1800 ° C. or higher and has an apparent porosity of 20% to 27%.
【０００７】安定化ジルコニアは、イットリアによる安
定化率が８０％〜１００％、好ましくは９０％〜１００
％のものである。安定化率が８０％より低いと加熱冷却
操作に際して、組織破壊が生じ好ましくない。このよう
な安定化ジルコニアは耐火物とされるにあたり、粒径が
５ｍｍ以下、好ましくは３ｍｍ以下の粒子を使用して形
成されるとよい。粒径が５ｍｍを越えると１８００℃で
も焼結が進みにくく、本発明の目的を達成するべき安定
な材料組織が得られない。Stabilized zirconia has a stabilization rate by yttria of 80% to 100%, preferably 90% to 100.
%belongs to. When the stabilization rate is lower than 80%, tissue destruction occurs during heating / cooling operation, which is not preferable. When such a stabilized zirconia is used as a refractory material, it is preferable to use particles having a particle size of 5 mm or less, preferably 3 mm or less. If the particle size exceeds 5 mm, sintering is difficult to proceed even at 1800 ° C., and a stable material structure for achieving the object of the present invention cannot be obtained.
【０００８】未安定化ジルコニア（安定化率０％）は、
ジルコニア全体において７重量％〜２０重量％、好まし
くは使用する未安定化ジルコニアの粒径に応じた最適な
組成比を有する。未安定化ジルコニアの組成比が７重量
％より少ないと、組織全体の焼結収縮が未安定化ジルコ
ニアの膨張よりも大きいため、加熱冷却を繰り返す毎に
耐火物の体積は収縮し、また未安定化ジルコニアの組成
比が２０重量％よりも多い場合には、逆に膨張が収縮を
上回るため加熱冷却を繰り返す毎に耐火物の体積は膨張
するので、体積の安定性は得られない。Unstabilized zirconia (stabilization rate 0%) is
The total zirconia content is 7% by weight to 20% by weight, and preferably has an optimum composition ratio according to the particle size of the unstabilized zirconia used. When the composition ratio of unstabilized zirconia is less than 7% by weight, the sintering shrinkage of the entire structure is larger than the expansion of unstabilized zirconia, so the volume of the refractory material shrinks each time heating and cooling are repeated, and In the case where the composition ratio of the zirconia oxide is more than 20% by weight, on the contrary, the expansion exceeds the contraction, so that the volume of the refractory material expands every time heating and cooling are repeated, so that the volume stability cannot be obtained.
【０００９】また、未安定化ジルコニアは耐火物とされ
るにあたり、粒径が０．０００１ｍｍ〜０．５ｍｍ、好
ましくは０．００１ｍｍ〜０．３ｍｍのものを使用して
形成されるとよい。粒径が０．０００１ｍｍよりも小さ
い場合は、焼成過程或いは熱処理を受けたときに、未安
定化ジルコニアが、安定化ジルコニアから安定化剤であ
るイットリアを引き抜きそれ自身が安定化してしまうた
め好ましくなく、また、０．５ｍｍを越えると冷却時の
膨張が大きくなりすぎ、材料組織を大幅に破壊してしま
うためである。When the unstabilized zirconia is used as a refractory material, it is preferable that the unstabilized zirconia has a particle size of 0.0001 mm to 0.5 mm, preferably 0.001 mm to 0.3 mm. If the particle size is smaller than 0.0001 mm, unstabilized zirconia pulls out yttria which is a stabilizer from the stabilized zirconia and stabilizes itself when the firing process or the heat treatment is performed, which is not preferable. Also, if it exceeds 0.5 mm, the expansion during cooling becomes too large and the material structure is largely destroyed.
【００１０】また、耐火物とされるにあたり、未安定化
ジルコニアと安定化ジルコニアからなる耐火材料に対し
て、結合剤として、例えばカルボキシメチルセルロー
ス、メチルセルロース、ポリエチレンオキサイド、ポリ
ビニルアルコール等の１種、またはそれらの混合物と水
との混合物、または水溶液が添加される。混合物、また
は水溶液における結合剤の割合は２重量％〜１０重量％
とするとよく、これらの混合物、または水溶液を耐火材
料１００重量部に対して２重量部〜６重量部、好ましく
は３重量部〜５重量部の割合で添加し、タイヤミキサ
ー、万能ミキサー等耐火物の混練に一般的に用いられる
混練器にて混練される。In addition, in the case of being made into a refractory, one kind of binder such as carboxymethyl cellulose, methyl cellulose, polyethylene oxide, polyvinyl alcohol, or the like is used for the refractory material composed of unstabilized zirconia and stabilized zirconia. And a mixture of water and an aqueous solution are added. The proportion of the binder in the mixture or the aqueous solution is 2% by weight to 10% by weight.
It is advisable to add these mixtures or aqueous solutions at a ratio of 2 parts by weight to 6 parts by weight, preferably 3 parts by weight to 5 parts by weight, relative to 100 parts by weight of the refractory material. It is kneaded by a kneader generally used for kneading.
【００１１】次いで、一軸プレスで成形圧力２００ｋｇ
／ｃｍ2 〜５００ｋｇ／ｃｍ2 で成形された後、１００
℃以上で乾燥され、更に１８００℃以上で焼成して目的
とするジルコニア質耐火物を得ることができる。焼成温
度を１８００℃以上とするのは、本発明の目的を達成す
るべく安定した材料組織にまで焼結させるためである。Then, the molding pressure is 200 kg with a uniaxial press.
/ Cm 2 to 500 kg / cm 2 and then 100
The desired zirconia-based refractory material can be obtained by drying at a temperature of 1800C or higher and firing at 1800C or higher. The firing temperature is set to 1800 ° C. or higher in order to sinter to a stable material structure to achieve the object of the present invention.
【００１２】このような成形方法により得られた耐火物
における見掛け気孔率は、アルキメデス法等により測定
されるが、成形圧力を調節することにより制御しうる。
本発明においては、成形圧力を２００ｋｇ／ｃｍ2 〜５
００ｋｇ／ｃｍ2 とそれほど高くしないことにより、見
掛気孔率を２０％〜２７％と比較的高くでき、耐熱衝撃
性を高めるのに有効に働く。また、１８００℃以上の加
熱冷却の前後における体積が安定しているということ
は、物理的材料組織もその前後において変化しないこと
に他ならない。これはジルコニア耐火物の材料組織内部
で以下のような機構が起こることにより達成されると推
定される。即ち、昇温・高温保持過程においては焼結に
より体積の収縮が起こり、冷却過程においては１１００
〜９００℃付近で未安定化ジルコニアが正方晶から単斜
晶へ相変態することにより体積の膨張が起こる。この収
縮と膨張が連続して発生することにより、結果的に加熱
冷却の前後において成形体の体積の増減はなくなり体積
の安定性を得ることができるものである。The apparent porosity of the refractory obtained by such a molding method is measured by the Archimedes method or the like, but can be controlled by adjusting the molding pressure.
In the present invention, the molding pressure is 200 kg / cm 2 to 5
By not increasing the pressure so high as 00 kg / cm 2 , the apparent porosity can be relatively increased to 20% to 27%, and it works effectively for enhancing the thermal shock resistance. Further, the stable volume before and after heating and cooling at 1800 ° C. or higher means that the physical material structure does not change before and after that. It is presumed that this is achieved by the following mechanism occurring inside the material structure of the zirconia refractory. That is, volume contraction occurs due to sintering in the temperature rising / high temperature holding process, and 1100 in the cooling process.
Around ˜900 ° C., unstabilized zirconia undergoes phase transformation from tetragonal to monoclinic, causing volume expansion. Since the contraction and expansion occur continuously, the volume of the molded body does not increase or decrease before and after heating and cooling, and the volume stability can be obtained.
【００１３】[0013]
【作用】本発明のジルコニア質耐火物は、室温から１８
００℃以上の高温までの加熱冷却処理に対して、焼結に
よる収縮と相変態による膨張とを示す両成分からなるこ
とにより、加熱冷却処理を受ける毎にそれらの作用を順
次発生させることができ、加熱冷却の前後において体積
の安定性に優れたジルコニア質耐火物とすることができ
る。The zirconia-based refractory material of the present invention has a temperature range from room temperature to 18
Since it is composed of both components exhibiting shrinkage due to sintering and expansion due to phase transformation in response to heat-cooling treatment up to a high temperature of 00 ° C or higher, these effects can be sequentially generated every time the heat-cooling treatment is performed. A zirconia-based refractory having excellent volume stability before and after heating and cooling can be obtained.
【００１４】また、本発明のジルコニア質耐火物におけ
る見掛気孔率を２０％〜２７％と比較的高くすることに
より、体積の安定性に優れると共に耐熱衝撃性の高いジ
ルコニア質耐火物とできる。By making the apparent porosity of the zirconia-based refractory of the present invention relatively high at 20% to 27%, a zirconia-based refractory having excellent volume stability and high thermal shock resistance can be obtained.
【００１５】[0015]
【実施例１】安定化率が９８％のイットリア安定化ジル
コニアに対し、安定化率が０％の未安定化ジルコニアを
混合したものを原料として、表１に示す割合でジルコニ
ア質耐火物を作成した。Example 1 A zirconia-based refractory material was prepared at a ratio shown in Table 1 using a material obtained by mixing yttria-stabilized zirconia having a stabilization rate of 98% with unstabilized zirconia having a stabilization rate of 0%. did.
【００１６】原料の粒度配合は、通常の耐火物と同様に
粗粒部、細粒部、微粒部から成り、粗粒部とは約２ｍｍ
〜１ｍｍ、細粒部とは約１ｍｍ以下、微粒部とは約０．
３ｍｍ以下の粒度分布をもつものとする。表１に示すよ
うに、粗い粒度と微粒部はイットリア安定化ジルコニア
で、また、その間の細粒部域のイットリア安定化ジルコ
ニアの一部または全部を、粒度分布が１０μｍ〜３００
μｍの未安定化ジルコニアで置き換えて試料とした。The particle size composition of the raw material is composed of a coarse particle portion, a fine particle portion and a fine particle portion, like the ordinary refractory material, and the coarse particle portion is about 2 mm.
.About.1 mm, the fine grain portion is about 1 mm or less, and the fine grain portion is about 0.
It has a particle size distribution of 3 mm or less. As shown in Table 1, the coarse grain size and the fine grain portion are yttria-stabilized zirconia, and a part or all of the yttria-stabilized zirconia in the fine grain portion region therebetween has a grain size distribution of 10 μm to 300 μm.
The sample was replaced with μm unstabilized zirconia.
【００１７】[0017]
【表１】 [Table 1]
【００１８】このようにして得た原料組成物に対し、市
販のカルボキシメチルセルロース粉末と水を重量比率で
１対２０に混合したものを３重量％の割合でバインダー
として加え、混練した後、一軸プレスにて成形圧約３０
０ｋｇ／ｃｍ2 で成形した。A mixture of commercially available carboxymethylcellulose powder and water in a weight ratio of 1 to 20 was added as a binder at a ratio of 3% by weight to the raw material composition thus obtained, and the mixture was kneaded and then uniaxially pressed. Molding pressure at about 30
It was molded at 0 kg / cm 2 .
【００１９】この成形体を１８５０℃で５時間焼成し、
ジルコニア質耐火物を得た。耐火物の寸法を測定し、再
び１８５０℃、５時間熱処理した。さらに同様の操作を
し、同じ条件で熱処理した。The compact was fired at 1850 ° C. for 5 hours,
A zirconia refractory was obtained. The size of the refractory was measured, and heat treatment was performed again at 1850 ° C. for 5 hours. Further, the same operation was performed and heat treatment was performed under the same conditions.
【００２０】熱処理による体積の安定性を評価する方法
として、熱処理前後の寸法の変化（線変化率）を測定し
た。すなわち熱処理の前後における線変化率の絶対値が
０に近いほど寸法の変化が少なく、より体積の安定性が
得られていると評価した。試験の結果を表２に示す。As a method for evaluating the stability of the volume by heat treatment, the dimensional change (line change rate) before and after the heat treatment was measured. That is, it was evaluated that the closer the absolute value of the linear change rate before and after the heat treatment was to 0, the smaller the dimensional change and the more stable the volume was obtained. The test results are shown in Table 2.
【００２１】表２から、線変化率の絶対値が０に近い配
合量は約１０重量％付近からこの発明における上限、す
なわち２０重量％までであり、それを越えると熱処理を
繰り返す毎に線変化率は増加、すなわち膨張していくこ
とがわかる。From Table 2, the compounding amount in which the absolute value of the linear change rate is close to 0 is from about 10% by weight to the upper limit of the present invention, that is, up to 20% by weight. Above that amount, the linear change occurs every time the heat treatment is repeated. It can be seen that the rate increases, that is, expands.
【００２２】[0022]
【表２】 [Table 2]
【００２３】[0023]
【実施例２】表３に示すように、実施例１と同様に、
粗、細、微粒部の３部からなる通常の耐火物の配合にお
いて、微粉粒度域の安定化ジルコニアの一部または全体
を、粒度分布が０．５μｍ〜８０μｍの未安定化ジルコ
ニアで置き換えて配合し、実施例１と同様にジルコニア
質耐火物を製造し、試験した。試験の結果を表４に示
す。Example 2 As shown in Table 3, as in Example 1,
In the normal refractory compound consisting of 3 parts of coarse, fine, and fine particle parts, part or whole of the stabilized zirconia in the fine powder particle size range is replaced with unstabilized zirconia having a particle size distribution of 0.5 μm to 80 μm. Then, a zirconia-based refractory material was manufactured and tested in the same manner as in Example 1. The test results are shown in Table 4.
【００２４】表４から、線変化率の絶対値が０に近い配
合量は７重量％付近であることがわかる。また、実施例
１に対し未安定化ジルコニアの粒度分布が小さいこの実
施例の場合、本発明の目的を達成するための未安定ジル
コニアの配合量は下限値７％に近づくことがわかる。ま
た、それより少ない配合量では熱処理を繰り返す毎に線
変化率は減少すなわち収縮し、多い配合量では熱処理を
繰り返す毎に線変化率は増加すなわち膨張していくこと
がわかる。From Table 4, it can be seen that the compounding amount in which the absolute value of the linear change rate is close to 0 is around 7% by weight. In addition, in the case of this example in which the particle size distribution of the unstabilized zirconia is smaller than that in Example 1, it can be seen that the compounding amount of the unstable zirconia for achieving the object of the present invention approaches the lower limit value of 7%. It is also understood that the linear change rate decreases or shrinks each time the heat treatment is repeated with a smaller compounding amount, and the linear change rate increases or expands each time the heat treatment is repeated with a larger compounding amount.
【００２５】[0025]
【表３】 [Table 3]
【００２６】[0026]
【表４】 [Table 4]
【００２７】[0027]
【実施例３】表５に示す原料配合で、実施例１と同様の
方法で得たジルコニア質耐火物について、成形寸法を測
定した後、１７００℃、５時間の熱処理を２回繰り返
し、実施例１同様に試験した。試験の結果を表６に示
す。[Example 3] With the raw material formulations shown in Table 5, the zirconia-based refractory obtained in the same manner as in Example 1 was subjected to heat treatment at 1700 ° C for 5 hours, and then the heat treatment was repeated twice at 1700 ° C. 1 was tested in the same manner. The test results are shown in Table 6.
【００２８】表６から熱処理によりどの配合量において
も線変化は膨張を示すことがわかる。例え、線変化率が
小さくても、その方向性が正を示す場合には、熱交換器
用耐火物などの複数個の成形体を組み合わせて使用する
条件では、互いに突っ張りの応力がはたらくことになる
ため、使用可能な材質として適切であるとはいえない。It can be seen from Table 6 that the linear change shows expansion at any blending amount by the heat treatment. For example, even if the linear change rate is small, if the direction is positive, under the condition that a plurality of molded products such as refractory for heat exchangers are used in combination, the tension stresses will be applied to each other. Therefore, it cannot be said that it is suitable as a usable material.
【００２９】[0029]
【表５】 [Table 5]
【００３０】[0030]
【表６】 [Table 6]
【００３１】[0031]
【実施例４】実施例１の結果から、線変化率が負であり
且つ絶対値が最も小さい試番１−４について、１８５０
℃、５時間を５回繰り返す熱処理の前後の線変化率と曲
げ強度の測定した。また、比較として１５００℃、５時
間、５回繰り返し熱処理について同様に測定した。その
結果を表７に示す。この結果から、強度的には１８００
℃と１５００℃の熱処理とでは大差ないことがわかる
が、寸法の安定性は１８００℃以上の熱処理を受ける際
に有効であることがわかる。[Embodiment 4] From the result of Embodiment 1, 1850 is obtained for the trial number 1-4 in which the linear change rate is negative and the absolute value is the smallest.
The linear change rate and the bending strength before and after the heat treatment of repeating 5 hours at 5 ° C. were measured. As a comparison, the same heat treatment was repeated for 5 hours at 1500 ° C. for 5 hours. The results are shown in Table 7. From this result, the strength is 1800
It can be seen that there is no great difference between the heat treatment at ℃ and 1500 ° C, but it can be seen that the dimensional stability is effective when the heat treatment at 1800 ° C or higher is performed.
【００３２】[0032]
【表７】 [Table 7]
【００３３】[0033]
【発明の効果】本発明のジルコニア質耐火物は、１８０
０℃以上の高温における安定化ジルコニアの焼結による
収縮と冷却時における未安定化ジルコニアの膨張とを組
み合わせることにより、室温から１８００℃以上の高温
までの間の加熱冷却に対して、寸法すなわち体積の安定
性が得られるものであり、１８００℃以上で使用され、
且つ複数個の耐火物を組み合わせて構造体を成すような
高温熱交換器の蓄熱体や高温工業炉などの構造材料耐火
物として適している。The zirconia refractory material of the present invention is 180
By combining shrinkage due to sintering of stabilized zirconia at a high temperature of 0 ° C. or higher and expansion of unstabilized zirconia at the time of cooling, the size or volume for heating and cooling from room temperature to a high temperature of 1800 ° C. or higher can be obtained. Stability is obtained, and it is used at 1800 ℃ or higher,
Moreover, it is suitable as a refractory for a structural material such as a heat storage body of a high temperature heat exchanger or a high temperature industrial furnace in which a plurality of refractories are combined to form a structure.
【図１】 図１は、実施例１及び実施例２における、未
安定化ジルコニアの配合量と線変化率（合計）との関係
を示した図である。FIG. 1 is a diagram showing the relationship between the blending amount of unstabilized zirconia and the linear change rate (total) in Example 1 and Example 2.
白丸は実施例１の結果を、黒丸は実施例２の結果を示
す。White circles show the results of Example 1, and black circles show the results of Example 2.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 山村 利和 兵庫県高砂市荒井町新浜２丁目３番１号 株式会社神戸製鋼所高砂製作所内 (72)発明者 那谷 修平 兵庫県高砂市荒井町新浜２丁目３番１号 株式会社神戸製鋼所高砂製作所内 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Toshikazu Yamamura 2-3-1, Niihama, Arai-cho, Takasago, Hyogo Prefecture Takasago Works, Kobe Steel Co., Ltd. (72) Shuhei Naya 2-3, Niihama, Arai-cho, Takasago, Hyogo Prefecture No. 1 Inside Takasago Works, Kobe Steel, Ltd.
Claims (2)
安定化されたジルコニアと未安定化ジルコニアとの組成
物であって、未安定化ジルコニアの組成比が７重量％〜
２０重量％の割合であり、かつ１８００℃以上の温度で
の焼成体であることを特徴とするジルコニア質耐火物。1. A composition of zirconia stabilized or partially stabilized by yttria and unstabilized zirconia, wherein the composition ratio of unstabilized zirconia is 7% by weight to.
A zirconia-based refractory, which is a sintered body at a ratio of 20% by weight and at a temperature of 1800 ° C. or higher.
安定化されたジルコニアと未安定化ジルコニアとの組成
物であって、未安定化ジルコニアの組成比が７重量％〜
２０重量％の割合であると共に、１８００℃以上の温度
での焼成体で、かつ２０％〜２７％の見掛け気孔率を有
するものであることを特徴とするジルコニア質耐火物。2. A composition of zirconia stabilized or partially stabilized by yttria and unstabilized zirconia, wherein the composition ratio of unstabilized zirconia is 7% by weight to.
A zirconia-based refractory material, which has a proportion of 20% by weight, a fired body at a temperature of 1800 ° C. or higher, and an apparent porosity of 20% to 27%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5239486A JP2783969B2 (en) | 1993-09-27 | 1993-09-27 | Zirconia refractories |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5239486A JP2783969B2 (en) | 1993-09-27 | 1993-09-27 | Zirconia refractories |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0797259A true JPH0797259A (en) | 1995-04-11 |
| JP2783969B2 JP2783969B2 (en) | 1998-08-06 |
Family
ID=17045499
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP5239486A Expired - Fee Related JP2783969B2 (en) | 1993-09-27 | 1993-09-27 | Zirconia refractories |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2783969B2 (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8278231B2 (en) * | 2008-11-24 | 2012-10-02 | Exxonmobil Chemical Patents Inc. | Heat stable formed ceramic, apparatus and method of using the same |
| US10407349B2 (en) | 2015-04-24 | 2019-09-10 | Corning Incorporated | Bonded zirconia refractories and methods for making the same |
| CN118684491A (en) * | 2024-08-01 | 2024-09-24 | 中钢集团洛阳耐火材料研究院有限公司 | A method for preparing low expansion and high thermal shock zirconium oxide products |
-
1993
- 1993-09-27 JP JP5239486A patent/JP2783969B2/en not_active Expired - Fee Related
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8278231B2 (en) * | 2008-11-24 | 2012-10-02 | Exxonmobil Chemical Patents Inc. | Heat stable formed ceramic, apparatus and method of using the same |
| US10407349B2 (en) | 2015-04-24 | 2019-09-10 | Corning Incorporated | Bonded zirconia refractories and methods for making the same |
| CN118684491A (en) * | 2024-08-01 | 2024-09-24 | 中钢集团洛阳耐火材料研究院有限公司 | A method for preparing low expansion and high thermal shock zirconium oxide products |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2783969B2 (en) | 1998-08-06 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JPH0333673B2 (en) | ||
| JPS6324951B2 (en) | ||
| CN106045505A (en) | Preparation method of magnesium oxide doped yttria-stabilized zirconia (5Y-PSZ) ceramic | |
| JP2783969B2 (en) | Zirconia refractories | |
| JP3103480B2 (en) | Method for producing zirconia refractory for thermal insulation | |
| JPH0236547B2 (en) | ||
| JPS6186466A (en) | Spinel ceramics | |
| JPH0437646A (en) | Production of zirconia ceramics film and its calcination method as well as zirconia conductive ceramics produced by this method and solid electrolyte fuel battery utilizing this ceramics | |
| JPH0258232B2 (en) | ||
| JP2004315293A (en) | Zirconia member for heat treatment and method for manufacturing the same | |
| JPH0656537A (en) | Lightweight zirconia-based firing jig material | |
| JP2541726B2 (en) | Ceramic composite conductive heat resistant material composition | |
| JPH06219831A (en) | High toughness zirconia-based sintered compact | |
| JP2641149B2 (en) | Manufacturing method of thermal shock resistant ceramics | |
| KR100246145B1 (en) | Method of manufacturing a zirconia ceramics | |
| JPH0558748A (en) | Alumina-zirconia-based calcining tool material | |
| JP3155054B2 (en) | Zirconia refractory setter | |
| JP2725732B2 (en) | Zirconia porous body and method for producing the same | |
| JPH0517210A (en) | Production of alumina-based composite sintered body and the sintered body | |
| JPH02164767A (en) | Production of zirconia refractory | |
| JP2959402B2 (en) | High strength porcelain | |
| JP2854527B2 (en) | Method for producing porous body | |
| JPH01208366A (en) | Production of zirconia-reinforced mullite ceramics | |
| JP3165205B2 (en) | High strength low thermal conductive ceramics and method of manufacturing the same | |
| JPH01219062A (en) | Production of silicon nitride sintered body |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| LAPS | Cancellation because of no payment of annual fees |