JPS62265166A - Manufacture of high temperature strength alumina silica baseceramic sintered body - Google Patents
Manufacture of high temperature strength alumina silica baseceramic sintered bodyInfo
- Publication number
- JPS62265166A JPS62265166A JP61105804A JP10580486A JPS62265166A JP S62265166 A JPS62265166 A JP S62265166A JP 61105804 A JP61105804 A JP 61105804A JP 10580486 A JP10580486 A JP 10580486A JP S62265166 A JPS62265166 A JP S62265166A
- Authority
- JP
- Japan
- Prior art keywords
- raw material
- sintered body
- material powder
- alumina
- silica
- 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.)
- Pending
Links
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 title claims description 43
- 239000000377 silicon dioxide Substances 0.000 title claims description 25
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 title claims description 20
- 238000004519 manufacturing process Methods 0.000 title claims description 5
- 239000000843 powder Substances 0.000 claims description 50
- 239000002994 raw material Substances 0.000 claims description 40
- 238000000034 method Methods 0.000 claims description 30
- 238000002156 mixing Methods 0.000 claims description 17
- 239000012535 impurity Substances 0.000 claims description 13
- 239000002002 slurry Substances 0.000 claims description 10
- 239000000919 ceramic Substances 0.000 claims description 7
- 239000007787 solid Substances 0.000 claims description 3
- 239000007858 starting material Substances 0.000 claims description 3
- 239000002245 particle Substances 0.000 claims description 2
- 239000008279 sol Substances 0.000 claims 1
- 239000011521 glass Substances 0.000 description 12
- 239000000203 mixture Substances 0.000 description 11
- KZHJGOXRZJKJNY-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Si]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O KZHJGOXRZJKJNY-UHFFFAOYSA-N 0.000 description 9
- 229910052863 mullite Inorganic materials 0.000 description 9
- 238000012360 testing method Methods 0.000 description 9
- 230000003301 hydrolyzing effect Effects 0.000 description 7
- -1 silicon alkoxide Chemical class 0.000 description 7
- 230000007423 decrease Effects 0.000 description 6
- 238000013001 point bending Methods 0.000 description 6
- 230000002194 synthesizing effect Effects 0.000 description 6
- 239000003513 alkali Substances 0.000 description 5
- 238000005452 bending Methods 0.000 description 4
- 239000013078 crystal Substances 0.000 description 4
- 238000004821 distillation Methods 0.000 description 4
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 4
- 229910052710 silicon Inorganic materials 0.000 description 4
- 239000010703 silicon Substances 0.000 description 4
- 238000005245 sintering Methods 0.000 description 4
- KKCBUQHMOMHUOY-UHFFFAOYSA-N Na2O Inorganic materials [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 description 3
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- 238000001354 calcination Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000010298 pulverizing process Methods 0.000 description 3
- 239000012264 purified product Substances 0.000 description 3
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- SMZOGRDCAXLAAR-UHFFFAOYSA-N aluminium isopropoxide Chemical compound [Al+3].CC(C)[O-].CC(C)[O-].CC(C)[O-] SMZOGRDCAXLAAR-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 229910052681 coesite Inorganic materials 0.000 description 2
- 229910052906 cristobalite Inorganic materials 0.000 description 2
- 238000006073 displacement reaction Methods 0.000 description 2
- 238000001879 gelation Methods 0.000 description 2
- 238000007493 shaping process Methods 0.000 description 2
- 235000012239 silicon dioxide Nutrition 0.000 description 2
- 229910052682 stishovite Inorganic materials 0.000 description 2
- 229910052905 tridymite Inorganic materials 0.000 description 2
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 1
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 1
- 229910000272 alkali metal oxide Inorganic materials 0.000 description 1
- 150000004703 alkoxides Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000000499 gel Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000011224 oxide ceramic Substances 0.000 description 1
- 229910052574 oxide ceramic Inorganic materials 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 238000005118 spray pyrolysis Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000009423 ventilation Methods 0.000 description 1
Landscapes
- Compositions Of Oxide Ceramics (AREA)
Abstract
(57)【要約】本公報は電子出願前の出願データであるた
め要約のデータは記録されません。(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.
Description
【発明の詳細な説明】
産業上の利用分
本発明は、アルミナ・シリカ系セラミックス焼結体、特
に１３００℃までの高温強度か常温強度よりも優れ、か
つその強度の絶対値か高い高強度アルミナ・シリカ系セ
ラミックス焼結体の製造方法に関する。DETAILED DESCRIPTION OF THE INVENTION For industrial use, the present invention is an alumina-silica ceramic sintered body, particularly a high-strength alumina which has a high temperature strength up to 1300°C or a strength superior to a room temperature strength, and has a high absolute value of the strength. -Relating to a method for producing a silica-based ceramic sintered body.
従来の技術
ムライトは、３Ａ立２０３・２ＳｉＯ，て表される組成
のアルミナ・シリカ系酸化物であり、熱膨張係数か酸化
物セラミックス中ては小さく、密度も小さい、そしてム
ライトは１代表的酸化物セラミックスであるアルミナに
比較して、高温ての耐クリープ特性が優れるなどの特徴
かある。そのため、耐熱性構造材料としての応用可億性
かあり１国内外での研究開発か盛んになりつつある。Conventional technology Mullite is an alumina-silica-based oxide with a composition expressed as 3A203.2SiO, and has a low thermal expansion coefficient among oxide ceramics and a low density. Compared to alumina, which is a solid ceramic, it has characteristics such as superior creep resistance at high temperatures. Therefore, there are billions of potential applications for it as a heat-resistant structural material, and research and development is becoming more active both domestically and internationally.
一般に、このムライト系焼結体は、原料粉末を仮焼し、
粉砕し、ＪＡ形し、焼結して得られる。そして、その原
料粉末を合成する方法としては、（１）粘土質（カオリ
ン質）原料にアルミナを添加する方法、
（２）アルミナゾルとシリカゾルを混合し、ゲル化して
、加熱する方法、
（３）ケイ醜ソーダとアルミニウム塩を混合し、加熱す
る方法、
か代表的である。しかし、（１）は、天然原料に含有す
る不純物の影響により焼結体中にガラス相か多量に生成
する、（２）はゲル化時に強固な仮置を作ることと、ア
ルミナゲルとシリカゲルのゲル化速度の相違から生しる
局部的な組成の不均質を生しることから、焼結性が低下
するとともに焼結体中にガラス相か生成しやすい、そし
て（３）はＮａ４を使用するため焼結体中にガラス相か
生じやすい、などの欠点かあった。Generally, this mullite-based sintered body is produced by calcining raw material powder.
Obtained by pulverizing, JA-shaping, and sintering. Methods for synthesizing the raw material powder include (1) adding alumina to clay (kaolin) raw material, (2) mixing alumina sol and silica sol, gelling, and heating; (3) A typical method is to mix and heat silica soda and aluminum salt. However, in (1), a large amount of glass phase is generated in the sintered body due to the influence of impurities contained in natural raw materials, and in (2), it is necessary to create a strong temporary position during gelation, and to combine alumina gel and silica gel. Because local compositional inhomogeneity arises from differences in gelation rates, sinterability decreases and a glass phase tends to form in the sintered body, and (3) uses Na4. Therefore, there were drawbacks such as the tendency to form a glass phase in the sintered body.
前記いずれの場合も、不純物、とりわけＮａ２Ｏ、Ｋ２
Ｏの存在により前記ガラス相の粘性か低下するため、焼
結体の強度、特に８００°Ｃ以上の高温強度を著しく低
下させる欠点かあった。In all of the above cases, impurities, especially Na2O, K2
The presence of O reduces the viscosity of the glass phase, which has the disadvantage of significantly reducing the strength of the sintered body, especially the high temperature strength at 800°C or higher.
最近ては、前記方法の他に、アルコキシドを利用してｂ
；（料粉末を合成する４つの方法、すなわち、
（４）シリコンアルコキシドとアルミニウム塩の共沈法
、
（５）シソコンアルコキシドとアルミニウムアルコキシ
ドとの混合溶液の加水分解法、
（５）シリコンアルコキシドとアルミニウム塩の噴霧熱
分解法、
（７）シリコンアルコキシドとアルミニウムアルコキシ
ドを加水分解して得られたスラリーを混合するスラリー
混合法、
などか提案されている。また、
（８）また、アルミナとシリカの粉末を混合する方法
も古くから知られている。Recently, in addition to the above method, b
(Four methods for synthesizing the raw powder, namely: (4) Co-precipitation method of silicon alkoxide and aluminum salt, (5) Hydrolysis method of a mixed solution of sisocon alkoxide and aluminum alkoxide, (5) Silicon alkoxide and A method of spray pyrolysis of aluminum salt, (7) a slurry mixing method of mixing a slurry obtained by hydrolyzing silicon alkoxide and aluminum alkoxide, and (8) a method of mixing alumina and silica have been proposed. Methods of mixing powders have also been known for a long time.
しかし、前記の方法において、いずれも不純物、特に極
〈微量のＮａ２ＯやＫ２Ｏの混入には配慮かはられれて
いなかった。However, in none of the above methods, consideration has been given to the incorporation of impurities, particularly extremely small amounts of Na2O and K2O.
上記の方法のうちわずかに（６）の方法（特開昭６０−
１６１３７１号公報）においてのみ、得られた焼結体の
強度か常温から１３００℃までほぼ４００ Ｍ Ｐ ａ
の曲げ強度を示しているか、いずれも温度の上昇ととも
に強度か低下する傾向を示してΣす、常温強度を越える
高温強度は得られていない。Of the above methods, only method (6)
161371), the strength of the obtained sintered body was approximately 400 MPa from room temperature to 1300°C.
However, the strength tends to decrease as the temperature increases, and high-temperature strength exceeding room temperature strength has not been obtained.
従来のムライト系焼結体の高温強度か低い原因としては
。The reason for the low high-temperature strength of conventional mullite-based sintered bodies is:
（イ）不純物、特にアルカリ金属酸化物かムライト結晶
の粒界に低融点低粘度のガラスを形成すること。(a) Impurities, especially alkali metal oxides or the formation of a low-viscosity glass at the grain boundaries of mullite crystals.
（［１）ムライトの合成過程において局部的な組成のズ
レか大きい場合、焼結途中で化学組成から推定されるよ
り多量のガラス相か焼結体中に形成されろこと。([1) If there is a large local compositional deviation during the mullite synthesis process, a larger amount of glass phase will be formed in the sintered body during sintering than estimated from the chemical composition.
の２点か挙げられ、特に原因（イ）は、８００°Ｃ以上
の晶−強、１■を箸しく低下させる主因となっている。There are two points mentioned above, and cause (a) in particular is the main cause of a significant decrease in the crystal strength at 800°C or higher and 1.
発１！（か解決しようとする問題点
未発１ｇ＋は、畠゛温強度よりも高温強度か高く、かつ
その強度の絶対値か高いアルミナ・シリカ系セラミック
ス焼結体を製造する方法を提供することにある。このよ
うな本発明の目的は、均質な原料粉末を用いてアルミナ
とシリカとの組成比を：Ａ整することと、原料中の不純
物の濃度をｐμｍオーダーという極めて少ない値以下に
低減せしめることによって達成される。Release 1! (The problem that we are trying to solve is to provide a method for producing an alumina-silica ceramic sintered body whose high temperature strength is higher than the field temperature strength, and whose absolute value is also high.) The purpose of the present invention is to use a homogeneous raw material powder to adjust the composition ratio of alumina and silica to:A, and to reduce the concentration of impurities in the raw material to an extremely small value of the order of ppm. achieved by.
問題点を解決するための手段及び作用
本発明の方法において、アルミナ・シリカ系原料粉末を
得るには、（ａ）アルミナゾルとシリカゾルを均一に混
合するゾル混合法、（ｂ）アルミナスラリーとシリカス
ラリーを均一に混合するスラリー混合法、または（Ｃ）
またはアルミナ微粉末とシリカ微粉末を均一に混合する
微粉末混合法などの方法か有効に使用てきる。また、原
料粉末のＡ文、０ユと５ｉＯｚとの含量に対するＡ交。Means and Effects for Solving Problems In the method of the present invention, in order to obtain alumina-silica raw material powder, (a) sol mixing method of uniformly mixing alumina sol and silica sol, (b) alumina slurry and silica slurry. Slurry mixing method to uniformly mix or (C)
Alternatively, a method such as a fine powder mixing method that uniformly mixes fine alumina powder and fine silica powder can be effectively used. In addition, the A statement of the raw material powder, the A exchange for the content of 0 U and 5 iOz.
０ ＊ （Ｄ ’、’、１合を６０〜７３ ％、 Ｈ’
Ｉ’（％ （モル％ テ４６．９〜６１．４％）、好ま
しくは６５〜７０屯量％の範囲に調整した原料粉末かイ
１効に用いられる。0 * (D', ', 1 go 60-73%, H'
The raw material powder adjusted to I'(% (mol% 46.9 to 61.4%), preferably in the range of 65 to 70 tonne %) is used for the first effect.
さらに、本発明の方法ては、後て述べる高温における不
純物の影響を調べた実施例（第４図応カー変位図）から
判るように、原料粉末中Ａ ｌ ｔＯ，３、Ｓ ｉ ０
２以外の不純物、すなわちＦｅ２Ｑ、、ＣａＯｌＭｚＯ
，Ｎａｔ ＯｌＫ２Ｏ゜Ｌｉ２Ｏ、ＴｉＯ２などを総量
で２５００ｐμｍより少なくする必要かあり、特にＮａ
ａ Ｏ及びＫ２Ｏの総量をｌｏｏＯｐμｍ以下、好まし
くは５００ｐμｍ以下になるように原料粉末か合成され
る。このようにアルカリ含有量を最少に抑制しするには
、精製した出発原料からアルミナ・シリカ系の均一な原
料粉末を合成すれば達成しうる。Furthermore, as can be seen from the example (FIG. 4) in which the influence of impurities at high temperatures was investigated (described later), the method of the present invention has the advantage that A l tO,3, S i 0 in the raw material powder
Impurities other than 2, i.e. Fe2Q, CaOlMzO
, NatOlK2O゜Li2O, TiO2, etc. need to be less than 2500 pμm in total, especially Na
The raw material powder is synthesized so that the total amount of a O and K2O is less than looOpμm, preferably less than 500pμm. In this way, minimizing the alkali content can be achieved by synthesizing a uniform alumina-silica raw material powder from purified starting materials.
この場合、原料粉末の合成方法は前記（１）〜（８）な
どの種々の方法かあり、それぞれの出発原料となる物質
を蒸留、再結品などの方法により精製して使用すればよ
い。In this case, there are various methods for synthesizing the raw material powder, such as those described in (1) to (8) above, and each starting material may be purified by methods such as distillation and reconsolidation before use.
次いで、このようにして合成された原料粉末は仮焼し、
粉砕し、成形した後、１５００〜１７００ ’Ｃ１好ま
しくは１６００〜１６５０の温度て、空気中での常圧焼
結、もしくは、空気中、真空又は不活性雰囲気中で加圧
焼結される。Next, the raw material powder synthesized in this way is calcined,
After crushing and shaping, it is sintered under normal pressure in air at a temperature of 1500-1700' C1, preferably 1600-1650°C, or pressure sintered in air, vacuum or an inert atmosphere.
前記のような不純物の規制は、特に高温強度を得るため
に不可欠である。またＡｌ２Ｏユと５ｉ０２との含量に
対するＡ ｌ ２０ ｘの４合を前記のように限定する
理由は、Ａｌ２Ｏ２の割合か６０％〜７３重量％まての
範囲において常温強度よりも高い１３００°Ｃての高温
強度か得られ、Ａ立。Control of impurities as described above is essential, especially in order to obtain high-temperature strength. Furthermore, the reason for limiting the amount of Al20 A high temperature strength of A is obtained.
０、の−１合か６５〜７０重量％の範囲において時に高
い高温強度か得られるからである。This is because high high temperature strength can sometimes be obtained in the range of 65 to 70% by weight.
前記Ａ ｌ ２Ｏ３の割合か６０重量％よりも少なくな
ると、ガラス相か増加してムライト粒子同士の接触点か
少なくなり、高温強度が低下するのて、好ましくない。If the proportion of Al 2 O 3 is less than 60% by weight, the glass phase increases, the number of contact points between mullite particles decreases, and high temperature strength decreases, which is not preferable.
従来の方法においては、アルミナ源とシリカ源との混合
物からアルミナ・シリカ系の原料粉末を合成する段階て
、１ｉｉ成の不均質か生しやすい。また、兆該原料粉末
中に不純物、特にＮａ、ＯやＫ２Ｏか過剰に存在すると
、シリカ過剰の組成てはムライト結品相の他に存在する
ＳｉＯ□ガラス相中にＮａ、０１Ｋ２０か溶は込み、Ｓ
ｔ Ｏ２ガラス相の粘性か温度上昇とともに低下する
。そのために、８００°Ｃ以上の高温度での焼結体の強
度が極端に低くなる傾向かあった。In conventional methods, the step of synthesizing an alumina-silica raw material powder from a mixture of an alumina source and a silica source tends to produce a heterogeneous 1ii composition. In addition, if impurities, especially Na, O, and K2O, are present in excess in the raw material powder, Na, O1K20, and 01K20 may be dissolved into the SiO□ glass phase that exists in addition to the mullite crystal phase, resulting in an excessive silica composition. , S
The viscosity of the tO2 glass phase decreases with increasing temperature. Therefore, the strength of the sintered body at high temperatures of 800° C. or higher tends to be extremely low.
本発明者らは、前記（ａ）、（ｂ）および（Ｃ）などの
固体状の方法でシリカ源とアルミナ源を混合してなる原
料粉末を合成し、かつＡ ｌ ２０、の割合を６０〜７
３重量％に調整した場合において、焼結体中のＳｉＯ２
ガラス相の量をその組成における最少限に抑制すること
、および不純物の雀、特にＮａｔ Ｏ及びＫ２Ｏの総量
をｐμｍオーターという極めて少ない量に低減すること
に−より、ＳｉＯ，ガラス相か高温度て低粘性化するこ
とを妨げうることを見いたした。それによれば、高温化
て高粘性のガラス相をムライト結晶の粒子境界部に存在
させることにより、外部からの応力を吸収させ、焼結体
か！４１成変形に近い挙動を示すようにすることかてき
る。その結果、これまての常識では考えかたい高温強度
、すなわちｌ３００°Ｃまての高温度て常温強度を越え
る強度か得られ、 Ａ ｌ ２０ ｙとＳｉＯ２の、１
合のより好ましい組成範囲を選べば、常温強度の約１．
５倍あるいはそれ以上という、いままてには得られなか
った曲げ強度を有する焼結体を得ることかてきる。The present inventors synthesized a raw material powder obtained by mixing a silica source and an alumina source using the solid methods described in (a), (b), and (C), and the ratio of Al 20 was 60. ~7
When adjusted to 3% by weight, SiO2 in the sintered body
By suppressing the amount of the glass phase to a minimum in its composition and by reducing the total amount of impurities, especially NatO and K2O, to extremely low amounts of pμm, SiO, the glass phase can be removed at high temperatures. We have found that this can prevent the viscosity from becoming low. According to this, by creating a high-temperature, highly viscous glass phase at the grain boundaries of mullite crystals, stress from the outside can be absorbed, resulting in a sintered body! It is possible to make it exhibit a behavior close to that of the 41-form deformation. As a result, we were able to obtain high-temperature strength that was unimaginable according to conventional wisdom, that is, strength that exceeds normal temperature strength at temperatures up to 300°C.
If a more preferable composition range is selected, the room temperature strength will be about 1.
It is possible to obtain a sintered body having a bending strength five times or more, which has not been previously available.
１Ｌ篇」１」２ ゾル混合法
精製したアルミナゾルとシリカゾルとを原料粉末中のＡ
文２０□の割合か６２〜７３重量％になるように調整し
たゾル混合物を、８０°Ｃて４８時間通風乾燥してアル
ミナ・シリカ系原料粉末を合成した。この原料粉末を１
２００°Ｃて１時間電気炉て仮焼した後、粉砕し、成形
し、１６５０°Ｃて４時間空気中て常圧焼結して、焼結
体を得た。1L Edition"1" 2 Sol Mixing Method A of the purified alumina sol and silica sol in the raw material powder.
A sol mixture adjusted to have a ratio of 62 to 73% by weight was dried at 80° C. for 48 hours to synthesize an alumina-silica raw material powder. 1 of this raw material powder
After calcining in an electric furnace at 200°C for 1 hour, it was crushed, molded, and sintered at 1650°C in air for 4 hours under normal pressure to obtain a sintered body.
次いてこの焼結体から３Ｘ４Ｘ４０ｍｍの試験片を作製
し、常温及び１３００°Ｃにおける３点曲げ強度を測定
した。その結果を第１１３に示す。Next, a test piece of 3 x 4 x 40 mm was prepared from this sintered body, and the three-point bending strength at room temperature and 1300°C was measured. The results are shown in No. 113.
なお、原料粉末中のＮａ２ＯおよびＫ２Ｏの総；１１．
は原子″表光分析（以下の実施例でも同し）によれば５
００ｐμｍであった。Note that the total amount of Na2O and K2O in the raw material powder; 11.
is 5 according to atomic surface optical analysis (the same applies to the following examples).
00 pμm.
第１図において、Ｑ印は゛、賞湿曲げ強度を、ムｌは１
３００°Ｃにおける曲げ強度を示し、点線はムライト（
３Ａ又、０３ ・２Ｓ ｉｏ□）の化学量論Ｍ１成（Ａ
文２０３７１．８屯着％、ＳｉＯ２２８．２重量％）の
位置を示すものである。In Fig. 1, the mark Q indicates the wet bending strength, and the mul is 1.
The bending strength at 300°C is shown, and the dotted line is mullite (
3A and 03 ・2S io□) stoichiometry M1 composition (A
20371.8% by weight, SiO2 228.2% by weight).
この図かられかるように、ｌ”−１ｔｏｘの割合か７３
重量％において常温強度と１３００’ｃ高温強度の傾向
線か交叉し、Ａ交、０．の割合が６４〜６８重量％の範
囲で常温強度の約１．５倍の強度か得られた。As you can see from this figure, the ratio of l”-1tox is 73
At weight%, the trend lines of normal temperature strength and 1300'c high temperature strength intersect, A intersection, 0. When the ratio was in the range of 64 to 68% by weight, strength approximately 1.5 times the room temperature strength was obtained.
実施例２ スラリー混合法
アルミニウムイソプロポキシド（Ａｎ
（ＱＣ２Ｈ７）ユニ蒸留による精製品を使用）を加水分
解して得たアルミナスラリーとオルソケイ酸エチル（Ｓ
ｉ Ｃ０Ｃｔ Ｈｓ ） ４ ：蒸留による精製品を
使用）を加水分解して得たシリカスラリーとを、原料粉
末中のＡ ｌ ２０ ｘの割合が６２〜７３重量％にな
るように混合した。このスラリーをろ通抜ｓｏ’ｃて２
４時間通風乾燥して原料粉末を合成した。この原料粉末
を１２００℃、１時間仮焼し、粉砕後、２０００ｋｇｆ
／ ａｍ″の圧力で成形してから、大気圧下で１６５
０″Ｃ４時間焼結して焼結体を得た。その焼結体から実
施例１と同寸法の試験片を作製し、常温及び１３００℃
における３点曲げ強度を測定した。その結果を第２図に
示す。Example 2 Slurry mixing method Alumina slurry obtained by hydrolyzing aluminum isopropoxide (purified product obtained by An (QC2H7) uni-distillation) and ethyl orthosilicate (S
silica slurry obtained by hydrolyzing i C0Ct Hs ) 4 (purified product by distillation) was mixed so that the proportion of Al 20 x in the raw material powder was 62 to 73% by weight. So'c through this slurry 2
The raw material powder was synthesized by ventilation drying for 4 hours. This raw material powder was calcined at 1200℃ for 1 hour, and after pulverization, 2000kgf
/ am'' pressure and then 165 mm under atmospheric pressure.
A sintered body was obtained by sintering for 4 hours at 0"C. A test piece with the same dimensions as in Example 1 was prepared from the sintered body and heated at room temperature and 1300°C.
The three-point bending strength was measured. The results are shown in FIG.
なお、Ｉａ科料粉末中Ｎａｇ Ｏ及びＫ２Ｏの総量は６
００ｐμｍであった。In addition, the total amount of Nag O and K2O in Ia powder is 6
00 pμm.
第２図において、Ｏ及びム印はそれぞれ常温強度及び１
３００℃における高温強度を示すものである。In Fig. 2, marks O and M indicate room temperature strength and 1, respectively.
This shows high temperature strength at 300°C.
実施例３ 微粉末混合法
アルミニウムイソプロポキシド（Ａｉ
（ＱＣ：ｌ Ｈ？ −１） ｘ ：蒸留による精製品を
使用）を加水分解して得たスラリーを２４時間８０℃て
通風乾燥して得たアルミナ微粉末と、オルソケイ酸エチ
ル（Ｓ ｉ （ＯＣｚ ）（ｓ ） ４ ：蒸留による
精製品を使用〕を加水分解して同様に得たシリカ微粉末
とを、原料粉末中のＡｎ、ｏｘの割合が６２〜７３重量
％になるように調整した。この原料粉末を１２００’ｃ
、１時間電気炉で仮焼した後、粉砕し、成形し、１６５
０°Ｃ１４時間空気中で常圧焼結して、焼結体を得た。Example 3 Fine powder mixing method A slurry obtained by hydrolyzing aluminum isopropoxide (Ai (QC:lH?-1) The fine alumina powder obtained in the same manner as above and the fine silica powder obtained in the same manner by hydrolyzing ethyl orthosilicate (S i (OCz ) (s ) 4 : a purified product by distillation) were added to The ratio was adjusted to 62 to 73% by weight.This raw material powder was heated to 1200'c
, after calcining in an electric furnace for 1 hour, crushing and molding, 165
A sintered body was obtained by normal pressure sintering in air at 0°C for 14 hours.
この原料粉末を１２００″Ｃで１時間仮焼し、粉砕後、
２０００ｋｇｆ ／ ｃｒｒｘ’の圧力で成形してから
、大気圧下て１６５０°Ｃで４時間焼結して焼結体を得
た。その焼結体から実施例１と同寸法の試験片を作製し
、常温及び１３００″Ｃにおける３点曲げ強度を測定し
た。その結果を結果を第３図に示す。This raw material powder was calcined at 1200″C for 1 hour, and after pulverization,
It was molded at a pressure of 2000 kgf/crrx' and then sintered at 1650°C for 4 hours under atmospheric pressure to obtain a sintered body. A test piece having the same dimensions as in Example 1 was prepared from the sintered body, and the three-point bending strength at room temperature and 1300''C was measured.The results are shown in FIG.
なお、原料粉末中のＮａ、Ｏ及びＫ２Ｏの総量は８００
ｐμｍてあった。In addition, the total amount of Na, O and K2O in the raw material powder is 800
It was pμm.
第３図において、○及びム印はそれぞれ常温強度および
１３００℃における高温強度を示すものである。試験結
果は第１図の場合とほぼ同じ傾向を示した。In FIG. 3, the circles and squares indicate the room temperature strength and the high temperature strength at 1300°C, respectively. The test results showed almost the same tendency as in the case of FIG.
以上の第１図、第２図及び第３図の試験結果に見られる
ように、原料粉末の合成方法において。As seen in the test results shown in FIGS. 1, 2, and 3 above, in the method for synthesizing raw material powder.
原料粉末か均質て、かつ原料粉末中の不純ｖｓ量を厳密
に制御することによって、合成方法か異なっても同傾向
の物理的特性をもった焼結体か得られることか判る。It can be seen that by making the raw material powder homogeneous and strictly controlling the amount of impurities in the raw material powder, it is possible to obtain a sintered body with the same physical properties even if the synthesis method is different.
又」Ｄ１４
実施例１て使用したＡ交２０．の割合を７０重量％に調
整した原料粉末を実施例１と同じ条件で処理し、焼結体
を得た。その際原料粉末中のアルカリ含有量を変化させ
て、１３００℃における応力−変位の関係を試験した。Also, D14 A cross 20 used in Example 1. A raw material powder in which the ratio of 20% was adjusted to 70% by weight was treated under the same conditions as in Example 1 to obtain a sintered body. At that time, the stress-displacement relationship at 1300°C was tested by changing the alkali content in the raw material powder.
試験結果は第４図のとおりである。第４図において、曲
線（イ）は原料粉末中のアルカリ量か５００ｐμｍの場
合であり、曲線（ロ）は２５００ｐμｍの場合である。The test results are shown in Figure 4. In FIG. 4, curve (a) is the case when the alkali content in the raw material powder is 500 pμm, and curve (b) is the case when the alkali amount is 2500 pμm.
この図にみられるように、本発明の方法によって製造さ
れた焼結体は、破壊にいたるまでに許容しつる耐力か優
れていることがわかる。As seen in this figure, it can be seen that the sintered body produced by the method of the present invention has an excellent tensile strength before breaking.
及１旦Ａ」
以上述べたごとく、本発明のアルミナ・シリカ系セラミ
ックス焼結体の製造方法では、不純物濃度を所定値以下
に低減せしめたため、従来の常識を破って、１３００″
Ｃにおける曲げ強度が常温における強度より高くするこ
とがてきる。そしてそのＡ交２０ユの割合の選び方によ
っては常温強度の約１．５倍にも達する高温強度が得ら
れ、かつその強度の絶対値も高い焼結体を得ることかて
きる。したかって、本発明の方法は工業的に極めて有用
な方法である。As stated above, in the method for producing an alumina-silica ceramic sintered body of the present invention, the impurity concentration is reduced to a predetermined value or less, and therefore, breaking the conventional wisdom,
The bending strength at C can be made higher than the strength at room temperature. Depending on the selection of the ratio of A-20 U, it is possible to obtain a sintered body that has high temperature strength that is about 1.5 times the room temperature strength and also has a high absolute value of the strength. Therefore, the method of the present invention is industrially extremely useful.
第１図は、アルミナゾルとシリカゾルとを種々のＡ ｌ
２０３の割合て混合して合成した原料粉末から製造し
た、焼結体の常温及び１３００°Ｃにおける３点曲げ強
度試験結果である。
第２図は、アルミナスラリーとシリカスラリーとを１種
々のＡｌＯ２の割合で混合して合成した原料粉末から得
られた焼結体の常温及び１３００°Ｃにおける３点曲げ
強度試験結果である。
第３図は、アルミニウムアルコキシドを加水分解して得
たアルミナ微粉末と、シリコンアルコキシドを加水分解
して得たシリカ微粉末とを１種々のＡ ｌ ＊ ０３の
割合で混合して得た合成粉末から得られた焼結体の、常
温及び１３００℃における３点曲げ強度試験結果である
。
第４図は、第１図に示された試料のＡｌｌ Ｏユの割合
が７０重量％の場合、１３００℃におけるアルカリ含有
量の影響を示す、応力−変位図である。
岬／薗
６０ ６２ Ｇメ ５（、４１Ｐ
Ｏ７コ ？資／ＪＬ１ユ０１童！（Ｚ）
皐２１」
Ａノ’ｘ、ｏａ Ｊ看％
第２，１」
Ａｌｘ０ａ ”を量、６７Figure 1 shows alumina sol and silica sol in various Al
These are the results of a 3-point bending strength test at room temperature and 1300° C. of a sintered body manufactured from raw material powders synthesized by mixing 203:203. FIG. 2 shows the results of three-point bending strength tests at room temperature and 1300° C. of sintered bodies obtained from raw material powders synthesized by mixing alumina slurry and silica slurry at various AlO2 ratios. Figure 3 shows synthetic powder obtained by mixing fine alumina powder obtained by hydrolyzing aluminum alkoxide and fine silica powder obtained by hydrolyzing silicon alkoxide at various ratios of Al*03. These are the results of a three-point bending strength test at room temperature and 1300° C. of the sintered body obtained from. FIG. 4 is a stress-displacement diagram showing the effect of alkali content at 1300° C. in the case where the proportion of All O in the sample shown in FIG. 1 is 70% by weight. Misaki/Sono 60 62 Gme 5 (, 41P
O7? Capital/JL1 Yu01 child! (Z) 琐21"Aノ'x, oa J seeing% 2nd, 1" Alx0a " amount, 67
Claims (1)
を合成し、この原料粉末を仮焼し、粉砕し、成形し、焼
結してアルミナ・シリカ系セラミックス焼結体を製造す
る方法において： ［ａ］ゾル、スラリー、もしくは粉末などの固体状のの
アルミナ源とシリカ源を混合して原料粉末を合成するこ
と、 ［ｂ］合成された原料粉末のＡｌ＿２Ｏ＿３とＳｉＯ＿
２との含量に対するＡｌ＿２Ｏ＿３の割合が６０〜７３
重量％の範囲に調整されていること、 並びに［ｃ］前記原料粉末のＡｌ＿２Ｏ＿３及びＳｉＯ
＿２以外の不純物がＮａ＿２Ｏ及びＫ＿２Ｏを含めて２
５００ｐμｍ未満に調整されていること、を特徴とする
、高温強度が優れたアルミナ・シリカ系セラミックス焼
結体の製造方法。[Claims] Alumina-silica based raw material powder is synthesized from purified starting materials, and this raw material powder is calcined, pulverized, molded, and sintered to produce an alumina-silica based ceramic sintered body. In the method of: [a] mixing a solid alumina source such as a sol, slurry, or powder and a silica source to synthesize a raw material powder, [b] combining Al_2O_3 and SiO_ of the synthesized raw material powder.
The ratio of Al_2O_3 to the content of 2 is 60 to 73
and [c] Al_2O_3 and SiO of the raw material powder.
Impurities other than _2 include Na_2O and K_2O
A method for producing an alumina-silica ceramic sintered body having excellent high-temperature strength, characterized in that the particle diameter is adjusted to less than 500 pμm.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61105804A JPS62265166A (en) | 1986-05-10 | 1986-05-10 | Manufacture of high temperature strength alumina silica baseceramic sintered body |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61105804A JPS62265166A (en) | 1986-05-10 | 1986-05-10 | Manufacture of high temperature strength alumina silica baseceramic sintered body |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS62265166A true JPS62265166A (en) | 1987-11-18 |
Family
ID=14417298
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP61105804A Pending JPS62265166A (en) | 1986-05-10 | 1986-05-10 | Manufacture of high temperature strength alumina silica baseceramic sintered body |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS62265166A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0408903A2 (en) * | 1989-06-19 | 1991-01-23 | Sumitomo Chemical Company, Limited | Magnetic recording medium |
| JP2007153644A (en) * | 2005-12-01 | 2007-06-21 | Ngk Insulators Ltd | Method for manufacturing refractory material and refractory material obtained thereby |
-
1986
- 1986-05-10 JP JP61105804A patent/JPS62265166A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0408903A2 (en) * | 1989-06-19 | 1991-01-23 | Sumitomo Chemical Company, Limited | Magnetic recording medium |
| JP2007153644A (en) * | 2005-12-01 | 2007-06-21 | Ngk Insulators Ltd | Method for manufacturing refractory material and refractory material obtained thereby |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JPH0545554B2 (en) | ||
| JPS62223009A (en) | Production of alpha-sialon powder | |
| JPS61275163A (en) | Manufacture of high temperature strength alumina silica baseceramic sintered body | |
| US5094677A (en) | Preparation of pollucite ceramics | |
| JPS62265166A (en) | Manufacture of high temperature strength alumina silica baseceramic sintered body | |
| JPH0339967B2 (en) | ||
| JPS60161371A (en) | Manufacture of high strength ceramic sintered body | |
| US4774068A (en) | Method for production of mullite of high purity | |
| JPS6360106A (en) | Spinel powder and its production | |
| JPS6272556A (en) | Manufacture of fine polycrystal mgal2o4 spinel | |
| JPS61281065A (en) | Manufacture of high temperature strength alumina silica baseceramic sintered body | |
| JPH03247557A (en) | Production of alumina-silica-based ceramic sintered body excellent in high-temperature strength | |
| JPH0497942A (en) | Production of mullite-zirconia composite ceramics | |
| JPS60141671A (en) | Manufacture of zirconia sintered body | |
| JPS61281013A (en) | Production of mullite powder of high purity | |
| JPH05124810A (en) | Starting material for mullite sintered compact, mullite sintered compact and its production | |
| JP4319866B2 (en) | Method for producing inorganic fibrous refractory insulation | |
| JPH03265600A (en) | Production of mullite whisker | |
| JPS5879869A (en) | Cordierite ceramics and manufacture | |
| KR0137092B1 (en) | Manufacturing method for dental ceramics | |
| JPS6272554A (en) | Manufacture of fine polycrystal al2o3 sintered body | |
| KR940010088B1 (en) | Process for producing low expansion glass | |
| JP3247688B2 (en) | Manufacturing method of high strength alumina-silica ceramics | |
| JP2652006B2 (en) | Ceramic molded product and its manufacturing method | |
| JPH0274563A (en) | Production of silicon nitride calcined compact |