JPH1160330A - Production of fused silica-based refractory - Google Patents
Production of fused silica-based refractoryInfo
- Publication number
- JPH1160330A JPH1160330A JP22408997A JP22408997A JPH1160330A JP H1160330 A JPH1160330 A JP H1160330A JP 22408997 A JP22408997 A JP 22408997A JP 22408997 A JP22408997 A JP 22408997A JP H1160330 A JPH1160330 A JP H1160330A
- Authority
- JP
- Japan
- Prior art keywords
- fused
- fused silica
- refractory
- weight
- apparent porosity
- 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 abstract description 52
- 239000005350 fused silica glass Substances 0.000 title claims abstract description 47
- 238000004519 manufacturing process Methods 0.000 title claims description 15
- 239000002245 particle Substances 0.000 claims abstract description 49
- 239000000843 powder Substances 0.000 claims abstract description 23
- 238000000465 moulding Methods 0.000 claims abstract description 17
- 239000000203 mixture Substances 0.000 claims abstract description 11
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229910052796 boron Inorganic materials 0.000 claims abstract description 10
- 229910000149 boron phosphate Inorganic materials 0.000 claims abstract description 6
- 239000011819 refractory material Substances 0.000 claims abstract description 5
- 239000011521 glass Substances 0.000 claims description 29
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims description 19
- 238000000034 method Methods 0.000 claims description 17
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 16
- 238000010304 firing Methods 0.000 claims description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 14
- 239000004327 boric acid Substances 0.000 claims description 12
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 9
- 150000001875 compounds Chemical class 0.000 claims description 9
- 239000002184 metal Substances 0.000 claims description 9
- 229910052751 metal Inorganic materials 0.000 claims description 9
- 229910052698 phosphorus Inorganic materials 0.000 claims description 9
- 239000011574 phosphorus Substances 0.000 claims description 9
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 8
- YZYDPPZYDIRSJT-UHFFFAOYSA-K boron phosphate Chemical compound [B+3].[O-]P([O-])([O-])=O YZYDPPZYDIRSJT-UHFFFAOYSA-K 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 4
- 230000002265 prevention Effects 0.000 abstract description 3
- 229910003887 H3 BO3 Inorganic materials 0.000 abstract 1
- 229910003944 H3 PO4 Inorganic materials 0.000 abstract 1
- 239000008187 granular material Substances 0.000 abstract 1
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 abstract 1
- 230000005484 gravity Effects 0.000 description 23
- 238000005452 bending Methods 0.000 description 22
- 230000000052 comparative effect Effects 0.000 description 16
- 238000010438 heat treatment Methods 0.000 description 15
- 238000001816 cooling Methods 0.000 description 12
- 238000000280 densification Methods 0.000 description 10
- 239000000126 substance Substances 0.000 description 9
- 239000005388 borosilicate glass Substances 0.000 description 8
- 230000000694 effects Effects 0.000 description 7
- 239000005360 phosphosilicate glass Substances 0.000 description 7
- 230000000704 physical effect Effects 0.000 description 7
- 230000035939 shock Effects 0.000 description 7
- 238000001035 drying Methods 0.000 description 6
- 238000005245 sintering Methods 0.000 description 6
- 230000007797 corrosion Effects 0.000 description 5
- 238000005260 corrosion Methods 0.000 description 5
- JKWMSGQKBLHBQQ-UHFFFAOYSA-N diboron trioxide Chemical compound O=BOB=O JKWMSGQKBLHBQQ-UHFFFAOYSA-N 0.000 description 5
- 150000002739 metals Chemical class 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 4
- 229910052810 boron oxide Inorganic materials 0.000 description 4
- 238000007796 conventional method Methods 0.000 description 4
- 239000010440 gypsum Substances 0.000 description 4
- 229910052602 gypsum Inorganic materials 0.000 description 4
- 230000008595 infiltration Effects 0.000 description 4
- 238000001764 infiltration Methods 0.000 description 4
- 239000008119 colloidal silica Substances 0.000 description 3
- 239000011230 binding agent Substances 0.000 description 2
- 238000001354 calcination Methods 0.000 description 2
- 238000005266 casting Methods 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 229920002037 poly(vinyl butyral) polymer Polymers 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- YWEUIGNSBFLMFL-UHFFFAOYSA-N diphosphonate Chemical compound O=P(=O)OP(=O)=O YWEUIGNSBFLMFL-UHFFFAOYSA-N 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910001392 phosphorus oxide Inorganic materials 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- VSAISIQCTGDGPU-UHFFFAOYSA-N tetraphosphorus hexaoxide Chemical compound O1P(O2)OP3OP1OP2O3 VSAISIQCTGDGPU-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Compositions Of Oxide Ceramics (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】この発明は、溶融シリカ質耐
火物の製造方法に関し、さらに言えば、表面粒子の剥離
現象が生じない溶融シリカ質耐火物が得られる溶融シリ
カ質耐火物の製造方法に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing a fused siliceous refractory, and more particularly, to a method for producing a fused siliceous refractory capable of producing a fused siliceous refractory which does not cause surface particles to peel off. .
【０００２】[0002]
【従来の技術】溶融シリカ（ＳｉＯ2）は一般に、熱膨
張率が低く耐熱衝撃性に優れているだけでなく、耐化学
薬品性、溶融金属（例えば、溶鋼など）に対する耐食性
においても優れている。このような性質を持つ溶融シリ
カを主原料として製造される溶融シリカ質耐火物は、溶
融シリカと同等の優れた耐熱衝撃性や耐化学薬品性を持
っているが、化学薬品や溶融金属に対する耐食性や耐浸
潤性が不十分であり、使用中に亀裂、剥離などの損傷を
受ける場合が多い。これは、従来の一般的な溶融シリカ
質耐火物が高い見掛気孔率（通常、１０％程度）を持つ
ことに起因する。 2. Description of the Related Art In general, fused silica (SiO 2 ) has not only a low coefficient of thermal expansion but excellent thermal shock resistance, but also excellent chemical resistance and corrosion resistance to molten metal (for example, molten steel). . Fused siliceous refractories made from fused silica as a main raw material have excellent thermal shock resistance and chemical resistance equivalent to fused silica, but corrosion resistance to chemicals and molten metals. And inadequate infiltration resistance, often causing damage such as cracks and peeling during use. This is because the conventional general fused siliceous refractory has a high apparent porosity (usually about 10%).
【０００３】そこで、従来より、溶融シリカ質耐火物の
見掛気孔率を低くして、換言すれば、溶融シリカ質耐火
物を緻密化して、化学薬品や溶融金属に対する耐食性や
耐浸潤性を改善する方法が種々提案されている。[0003] Therefore, conventionally, the apparent porosity of the fused siliceous refractory has been reduced, in other words, the fused siliceous refractory has been densified to improve the corrosion resistance and infiltration resistance to chemicals and molten metals. Various methods have been proposed.
【０００４】例えば、特公平１−５４３０１号公報に
は、「粒径１０μｍ以下の粒子を１０ｗｔ％以上含む溶
融シリカ粉を主骨材とした配合物を鋳込み成形し、得ら
れた成形体を水蒸気雰囲気下で焼成することを特徴とし
た溶融シリカ質焼結体の製造方法」が開示されている。
焼成温度は、好ましくは１０５０〜１２５０℃の範囲に
設定される。この従来方法によれば、見掛気孔率を一般
的な１０％程度より低くすることができ、見掛気孔率が
１％以下の緻密な溶融シリカ質焼結体（耐火物）を得る
ことも可能である、とされている。[0004] For example, Japanese Patent Publication No. 1-54301 discloses that a composition containing a fused silica powder containing 10 wt% or more of particles having a particle size of 10 μm or less as a main aggregate is cast and molded, and the obtained molded product is steamed. A method for producing a fused siliceous sintered body characterized by firing in an atmosphere ".
The firing temperature is preferably set in the range of 1050 to 1250 ° C. According to this conventional method, the apparent porosity can be made lower than a general value of about 10%, and a dense fused siliceous sintered body (refractory) having an apparent porosity of 1% or less can be obtained. It is possible.
【０００５】また、特公昭４７−２３１６７号公報に
は、「溶融石英（溶融シリカ）を主原料とし、これにコ
ロイダルシリカおよび（又は）超微粉体シリカ５〜１５
％と燐酸、硼酸もしくはそれらの塩類を１〜１０％添加
混練して成形し、１０００〜１２００℃で焼成すること
を特徴とする溶融石英を主体とする耐火物の製造法」が
開示されている。この従来方法によれば、コロイダルシ
リカは焼成時に燐酸、硼酸などと反応してガラス相を形
成し、それによって溶融石英本来の性質を損なわずかつ
気孔率も小さく極めて良く焼結した耐火物を得ることが
可能である、とされている。ただし、この場合の見掛気
孔率はせいぜい１０％程度である。Further, Japanese Patent Publication No. 47-23167 discloses that “fused quartz (fused silica) is used as a main raw material and colloidal silica and / or
% Of phosphoric acid, boric acid or a salt thereof is added, kneaded, molded and fired at 1000 to 1200 ° C., and a process for producing a refractory mainly containing fused quartz is disclosed. . According to this conventional method, colloidal silica reacts with phosphoric acid, boric acid, and the like at the time of calcination to form a glass phase, thereby impairing the intrinsic properties of fused quartz and obtaining a very well-fired refractory with a small porosity and a small porosity. It is possible. However, the apparent porosity in this case is at most about 10%.
【０００６】[0006]
【発明が解決しようとする課題】しかし、特公平１−５
４３０１号公報に開示された従来方法では、製造された
溶融シリカ質焼結体（耐火物）の見掛気孔率は低くなる
が、表面の粒子が剥離しやすい性質を持つ。その結果、
化学薬品の熱処理容器や溶融金属の容器として使用する
と、その化学薬品や溶融金属を汚染する恐れがあるとい
う問題がある。Problems to be solved by the Invention
According to the conventional method disclosed in Japanese Patent No. 4301, although the apparent porosity of the manufactured fused siliceous sintered body (refractory) is reduced, particles on the surface are easily peeled off. as a result,
When used as a heat treatment container for chemicals or a container for molten metal, there is a problem that the chemicals or molten metal may be contaminated.
【０００７】また、特公昭４７−２３１６７号公報に開
示された従来方法では、製造された溶融シリカ質耐火物
の見掛気孔率はせいぜい１０％程度であり、緻密化（す
なわち見掛気孔率の低下）が不十分である。このため、
化学薬品や溶融金属に対する耐浸潤性や耐食性が満足で
きるレベルに達していないという問題がある。In the conventional method disclosed in Japanese Patent Publication No. 47-23167, the apparent porosity of the manufactured fused siliceous refractory is at most about 10%, and it is densified (that is, the apparent porosity is reduced). Drop) is insufficient. For this reason,
There is a problem that infiltration resistance and corrosion resistance to chemicals and molten metals have not reached a satisfactory level.
【０００８】そこで、この発明の目的は、溶融シリカ質
耐火物の持つ低熱膨張性、すなわち良好な耐熱衝撃性を
維持しながら、１〜２％程度の見かけ気孔率と耐火物表
面の粒子の剥離防止とを実現できる溶融シリカ質耐火物
の製造方法を提供することにある。Accordingly, an object of the present invention is to provide an apparent porosity of about 1 to 2% and separation of particles on the surface of a refractory while maintaining the low thermal expansion property of the fused silica refractory, that is, good thermal shock resistance. An object of the present invention is to provide a method for producing a fused siliceous refractory capable of realizing prevention.
【０００９】[0009]
（１） この発明の溶融シリカ質耐火物の製造方法は、
粒度調整された溶融シリカ粉末１００重量％に、硼素お
よび燐よりなる群から選ばれる少なくとも一種の元素を
含有する化合物をＢ2Ｏ3、またはＰ2Ｏ5に換算した合計
量で０．５重量％〜１０重量％の範囲となるように添加
し、さらに適当な成形助剤を混合して成形用混合物を生
成する第１工程と、前記成形用混合物を所望形状に成形
して成形体を得る第２工程と、前記成形体を５０容量％
以上の水蒸気を含む雰囲気下で焼成する第３工程とを備
えてなることを特徴とする。(1) The method for producing a fused siliceous refractory of the present invention comprises:
A compound containing at least one element selected from the group consisting of boron and phosphorus is added to B 2 O 3 or P 2 O 5 in a total amount of 0.5% by weight with respect to 100% by weight of the fused silica powder whose particle size has been adjusted. % To be in the range of 10% by weight to 10% by weight, further mixing an appropriate molding aid to form a molding mixture, and molding the molding mixture into a desired shape to obtain a molded article. The second step, and 50% by volume of the molded body
And a third step of firing in an atmosphere containing water vapor as described above.
【００１０】（２） 一般に、硼素（Ｂ）または燐
（Ｐ）を含有する化合物がシリカ（ＳｉＯ2）と反応す
ると、硼珪酸ガラスまたは燐珪酸ガラスをそれぞれ形成
する。このため、硼素または燐あるいはその双方を含有
する化合物を溶融シリカ粉末に添加して焼成すると、得
られた溶融シリカ質耐火物の粒界に硼珪酸ガラスまたは
燐珪酸ガラスの相あるいはそれら双方の相が形成され
る。この発明の溶融シリカ質耐火物の製造方法では、こ
のガラス相の作用を利用して、溶融シリカ質耐火物の表
面の粒子の剥離を防止する。(2) Generally, when a compound containing boron (B) or phosphorus (P) reacts with silica (SiO 2 ), borosilicate glass or phosphosilicate glass is formed, respectively. For this reason, when a compound containing boron and / or phosphorus is added to the fused silica powder and calcined, the phase of the borosilicate glass and / or the phase of the phosphosilicate glass is formed at the grain boundaries of the obtained fused siliceous refractory. Is formed. In the method for producing a fused siliceous refractory of the present invention, the action of the glass phase is used to prevent the particles on the surface of the fused siliceous refractory from being separated.
【００１１】前述の通り、特公昭４７−２３１６７号公
報には、「コロイダルシリカが焼成時に燐酸、硼酸など
と反応してガラス相を形成し、それによって気孔率を低
減できる」旨が開示されている。しかし、当該公報で
は、得られる見掛気孔率はせいぜい１０％程度であり、
近年の一般的な溶融シリカ質耐火物のそれと同じであ
る。よって、１〜２％程度の見かけ気孔率を実現するこ
の発明の溶融シリカ質耐火物の製造方法とは、明らかに
達成すべき目標値が異なるものである。As described above, Japanese Patent Publication No. 47-23167 discloses that "colloidal silica reacts with phosphoric acid, boric acid, etc. at the time of calcination to form a glass phase, thereby reducing porosity." I have. However, in the publication, the apparent porosity obtained is at most about 10%,
It is the same as that of recent general fused siliceous refractories. Therefore, the target value to be achieved is clearly different from the method for producing a fused siliceous refractory of the present invention which achieves an apparent porosity of about 1 to 2%.
【００１２】（３） 本発明者らの調査・研究によれ
ば、このガラス相が過剰に存在すると、溶融シリカ本来
の低熱膨張性が低下あるいは喪失し、逆に、このガラス
相が過少であると、所望のガラス相が形成されないこと
が判明した。そこで、この発明の溶融シリカ質耐火物の
製造方法では、硼素または燐あるいはその双方を含有す
る化合物の添加量を、Ｂ2Ｏ3、またはＰ2Ｏ5に換算した
合計量で０．５重量％〜１０重量％の範囲に調整してい
る。こうすることにより、ガラス相の過剰により溶融シ
リカ本来の低熱膨張性が低下あるいは喪失するのを防止
しながら、溶融シリカ質耐火物の表面の粒子の剥離を防
止するものである。(3) According to the investigations and researches of the present inventors, when this glass phase is present in excess, the low thermal expansion property of fused silica is reduced or lost, and conversely, this glass phase is too small. It was found that the desired glass phase was not formed. Therefore, in the method for producing a fused siliceous refractory of the present invention, the added amount of the compound containing boron or phosphorus or both of them is 0.5 wt% in terms of the total amount in terms of B 2 O 3 or P 2 O 5. % To 10% by weight. By doing so, it is possible to prevent the particles of the surface of the fused silica refractory from peeling while preventing the intrinsic low thermal expansion property of the fused silica from being reduced or lost due to the excess of the glass phase.
【００１３】（４） 前記第３工程において、前記成形
体を所定量の水蒸気を含む雰囲気下で焼成するのは、前
記焼結体を十分緻密にするためである。雰囲気中に含ま
れる水蒸気は、前記溶融シリカ質の成形体を焼成する際
にその成形体中の溶融シリカ粒子が拡散するのを促進す
る作用を持つ。このため、前記成形体は焼結しやすくな
り、その結果、得られる焼結体は緻密となる。水蒸気の
含有量を５０容量％以上とするのは、水蒸気の含有量が
５０容量％未満では焼結体組織の緻密化作用（見掛気孔
率の低下作用）が不十分であり、また、焼結体の表面粒
子の剥離防止作用も不足するからである。(4) In the third step, the compact is fired in an atmosphere containing a predetermined amount of steam in order to make the sintered compact sufficiently dense. Water vapor contained in the atmosphere has an effect of promoting the diffusion of the fused silica particles in the molded body of the fused silica when the molded body is fused. For this reason, the molded body is easily sintered, and as a result, the obtained sintered body is dense. The reason why the content of water vapor is set to 50% by volume or more is that if the content of water vapor is less than 50% by volume, the effect of densifying the structure of the sintered body (the effect of decreasing the apparent porosity) is insufficient, and This is because the effect of preventing the surface particles of the binder from peeling is also insufficient.
【００１４】（５） 前記第１工程において使用する前
記溶融シリカ粉末としては、必要とする溶融シリカ質耐
火物の物性に応じて、任意に粒度調整された溶融シリカ
の粉末を使用できる。例えば、粒径１００μｍ以下の粒
子を５０重量％以上含むものを使用できる。前記溶融シ
リカ粉末の形態も任意である。すなわち、破砕片状であ
ってもよいし、球状であってもよいし、その他の形状で
あってもよい。(5) As the fused silica powder used in the first step, a fused silica powder whose particle size has been arbitrarily adjusted according to the required physical properties of the fused siliceous refractory can be used. For example, those containing 50% by weight or more of particles having a particle size of 100 μm or less can be used. The form of the fused silica powder is also arbitrary. That is, the shape may be a crushed piece, a sphere, or another shape.
【００１５】硼素および燐よりなる群から選ばれる少な
くとも一種の元素を含有する前記化合物としては、硼素
または燐あるいはその双方を含有する化合物であれば任
意のものを使用可能である。例えば、硼酸（Ｈ3Ｂ
Ｏ3）、燐酸（Ｈ3ＰＯ4）または燐酸硼素（ＢＰＯ4）を
使用できる。As the compound containing at least one element selected from the group consisting of boron and phosphorus, any compound can be used as long as it contains boron and / or phosphorus. For example, boric acid (H 3 B
O 3 ), phosphoric acid (H 3 PO 4 ) or boron phosphate (BPO 4 ) can be used.
【００１６】前記成形助剤としては、必要な物性に応じ
て任意の液体やバインダーを使用できるが、入手の容易
性やコストなどを考慮すると、水が好ましい。しかし、
例えばポリビニルブチラール（ＰＶＢ）溶液のようなア
ルコール溶液なども使用可能である。As the molding aid, any liquid or binder can be used depending on the required physical properties, but water is preferred in view of availability and cost. But,
For example, an alcohol solution such as a polyvinyl butyral (PVB) solution can be used.
【００１７】（６） 前記第２工程における前記成形用
混合物の成形方法は、鋳込み法であるのが好ましい。そ
れは、鋳込み法では、粒子がより緻密に充填されるの
で、高密度な成形体を得やすいからである。しかし、他
の成形法（例えば、プレス成形法）も使用可能である。(6) The molding method of the molding mixture in the second step is preferably a casting method. This is because, in the casting method, the particles are more densely packed, so that a high-density molded body is easily obtained. However, other molding methods (eg, press molding) can be used.
【００１８】前記成形工程の後、必要に応じて、前記成
形体を乾燥させる乾燥工程を設けてもよい。乾燥しない
で焼成すると、昇温時に水分が急激に蒸発して焼結体に
亀裂などを生じ易いからである。その乾燥工程には任意
の乾燥法を使用できる。前記焼成工程において前記成形
体を徐々に加熱する場合は、乾燥工程は不要である。After the molding step, a drying step for drying the molded body may be provided, if necessary. If sintering is performed without drying, the moisture will rapidly evaporate when the temperature rises, and cracks and the like are likely to occur in the sintered body. Any drying method can be used in the drying step. When the compact is gradually heated in the firing step, the drying step is unnecessary.
【００１９】（７） 前記第３工程における前記成形体
の焼成温度は、１０５０〜１２５０℃の範囲に設定され
るのが好ましい。１０５０℃未満では焼結効果が十分で
ないからであり、１２５０℃を超えると、クリストバラ
イトが生成されて前記焼結体の強度が低下するからであ
る。(7) The firing temperature of the compact in the third step is preferably set in the range of 1050 to 1250 ° C. If the temperature is lower than 1050 ° C., the sintering effect is not sufficient. If the temperature exceeds 1250 ° C., cristobalite is generated and the strength of the sintered body is reduced.
【００２０】前記焼第３工程における前記成形体の焼成
時間は、０．５〜２０時間であるのが好ましい。焼結時
間が０．５時間未満であると、十分な焼結強度が得られ
ず、反面、２０時間を超えても、焼結効果にほとんど寄
与しないからである。The firing time of the compact in the third firing step is preferably 0.5 to 20 hours. If the sintering time is less than 0.5 hour, sufficient sintering strength cannot be obtained, and if it exceeds 20 hours, it hardly contributes to the sintering effect.
【００２１】[0021]
【発明の実施の形態】以下、この発明の実施の形態を具
体的実施例に基づいて説明する。DESCRIPTION OF THE PREFERRED EMBODIMENTS Embodiments of the present invention will be described below based on specific examples.
【００２２】（実施例１）粒度４８ｍｅｓｈＦ（Ｆは
「ｆｉｎｅ」を意味する）（粒径２９７μｍ以下）の溶
融シリカ粉末１００重量％に、粒度１４５ｍｅｓｈＦ
（粒径１０５μｍ以下）の硼酸（Ｈ3ＢＯ3）粉末を１重
量％（これは酸化硼素（Ｂ2Ｏ3）に換算すると、０．５
６重量％に相当する）添加・混合した。その後、この混
合物に成形助剤として水を１６重量％添加・混練してス
リップを得た。次に、このスリップを公知の石膏型に流
し込んで鋳込み成形した。さらに、得られた成形体を１
００容量％の濃度の水蒸気を含む空気中で、１１５０℃
の温度で１０時間焼成し、３０ｍｍ×３０ｍｍ×１００
ｍｍの四角柱形の溶融シリカ質耐火物を得た。(Example 1) 100% by weight of fused silica powder having a particle size of 48 meshF (F means "fine") (particle size of 297 μm or less) was added to a particle size of 145 meshF.
1% by weight of boric acid (H 3 BO 3 ) powder having a particle diameter of 105 μm or less (this is 0.5% in terms of boron oxide (B 2 O 3 )).
(Corresponding to 6% by weight). Thereafter, 16% by weight of water was added and kneaded as a molding aid to this mixture to obtain a slip. Next, the slip was poured into a known gypsum mold and cast. Further, the obtained molded body is
1150 ° C. in air containing water vapor at a concentration of 00% by volume
Baking for 10 hours at a temperature of 30 mm x 30 mm x 100
mm of fused silica-based refractory having a square column shape was obtained.
【００２３】この溶融シリカ質耐火物の見掛気孔率、か
さ比重、常温曲げ強さ、熱間線膨張率をＪＩＳ−Ｒ１６
０１の規定に従って測定したところ、見掛気孔率は０．
９％、かさ比重は２．１８、常温曲げ強さは１２．５Ｍ
Ｐａ、１０００℃における熱間線膨張率は０．０４であ
った。The apparent porosity, bulk specific gravity, room temperature flexural strength and hot linear expansion coefficient of this fused siliceous refractory were measured according to JIS-R16.
01, the apparent porosity was 0.1.
9%, bulk specific gravity 2.18, room temperature bending strength 12.5M
The coefficient of linear thermal expansion at Pa and 1000 ° C. was 0.04.
【００２４】また、ガラス相の有無を顕微鏡による組織
観察により調べたところ、硼珪酸ガラスの相の存在が確
認された。When the presence or absence of a glass phase was examined by microscopic observation of the structure, the presence of a borosilicate glass phase was confirmed.
【００２５】さらに、加熱・冷却による耐火物の表面粒
子の剥離の有無を次のようにして調べた。すなわち、得
られた３０ｍｍ×３０ｍｍ×１００ｍｍの四角柱形の溶
融シリカ質耐火物を１０００℃で１５分間加熱した後、
室温まで冷却して１５分間放置した。以後、この加熱・
冷却工程を５回繰り返し、この耐火物の表面から粒子が
剥離するか否かを調べた。その結果、実施例１では、表
面粒子の剥離は見られなかった。これは、この耐火物が
化学薬品や溶融金属用の熱処理容器として使用可能であ
ることを意味する。Further, the presence or absence of peeling of surface particles of the refractory due to heating and cooling was examined as follows. That is, after heating the obtained 30 mm × 30 mm × 100 mm quadrangular prism-shaped fused silica refractory at 1000 ° C. for 15 minutes,
Cooled to room temperature and left for 15 minutes. Hereafter, this heating
The cooling step was repeated five times, and it was examined whether or not the particles were separated from the surface of the refractory. As a result, in Example 1, peeling of the surface particles was not observed. This means that the refractory can be used as a heat treatment vessel for chemicals and molten metals.
【００２６】見掛気孔率とかさ比重の上記値により、こ
の溶融シリカ質耐火物の緻密化が十分なされていること
が分かる。これは、化学薬品や溶融金属に対する耐浸潤
性および耐食性が良好であることを意味する。常温曲げ
強さの上記値により、この溶融シリカ質耐火物の常温に
おける機械的強度が十分高いことが分かる。熱間線膨張
率の上記値により、この溶融シリカ質耐火物では、溶融
シリカ本来の良好な耐熱衝撃性が維持されていることが
分かる。The above values of the apparent porosity and the bulk specific gravity indicate that the densification of the fused siliceous refractory is sufficient. This means that the infiltration resistance and corrosion resistance to chemicals and molten metals are good. The above values of the room temperature bending strength indicate that the mechanical strength of the fused silica refractory at room temperature is sufficiently high. From the above value of the coefficient of linear thermal expansion, it is understood that the fused silica-based refractory maintains the excellent thermal shock resistance inherent in fused silica.
【００２７】（実施例２）実施例１と同じ溶融シリカ粉
末１００重量％に、実施例１と同じ硼酸（Ｈ3ＢＯ3）粉
末を実施例１より多い８重量％（これは酸化硼素（Ｂ2
Ｏ3）に換算すると、４．５０重量％に相当する）添加
・混合した。その後、この混合物に水を１７重量％添加
・混練してスリップを得た。次に、このスリップを実施
例１と同じ石膏型に流し込んで鋳込み成形した。さら
に、得られた成形体を実施例１と同じ条件で焼成し、実
施例１と同じ形状の溶融シリカ質耐火物を得た。(Example 2) 8% by weight of boric acid (H 3 BO 3 ) powder, which is the same as in Example 1, was added to 100% by weight of the same fused silica powder as in Example 1 (this was boron oxide (B Two
O 3 ) (equivalent to 4.50% by weight). Thereafter, 17% by weight of water was added to the mixture and kneaded to obtain a slip. Next, the slip was cast into the same gypsum mold as in Example 1 and cast. Further, the obtained molded body was fired under the same conditions as in Example 1 to obtain a fused silica refractory having the same shape as that of Example 1.
【００２８】この溶融シリカ質耐火物の見掛気孔率、か
さ比重、常温曲げ強さ、熱間線膨張率を実施例１と同様
にして測定したところ、見掛気孔率は０．６％、かさ比
重は２．１９、常温曲げ強さは１１．２ＭＰａ、１００
０℃における熱間線膨張率は０．０４であった。The apparent porosity, bulk specific gravity, room temperature bending strength and hot linear expansion coefficient of this fused siliceous refractory were measured in the same manner as in Example 1. The apparent porosity was 0.6%. Bulk specific gravity is 2.19, room temperature bending strength is 11.2 MPa, 100
The coefficient of linear thermal expansion at 0 ° C. was 0.04.
【００２９】また、ガラス相の有無を実施例１と同様に
して調べたところ、実施例１と同じ硼珪酸ガラス相の存
在が確認された。さらに、加熱・冷却による表面粒子の
剥離の有無を実施例１と同様にして調べたところ、表面
粒子の剥離は見られなかった。When the presence or absence of a glass phase was examined in the same manner as in Example 1, the presence of the same borosilicate glass phase as in Example 1 was confirmed. Further, when the presence or absence of peeling of the surface particles due to heating and cooling was examined in the same manner as in Example 1, no peeling of the surface particles was observed.
【００３０】これらの結果より、実施例２の方法で得ら
れた溶融シリカ質耐火物は、実施例１と同等の緻密化と
ガラス相の形成がなされており、その結果、実施例１と
同等の物性を有することが分かる。From these results, the fused siliceous refractory obtained by the method of Example 2 had the same densification and glass phase formation as in Example 1, and as a result, had the same properties as in Example 1. It can be seen that they have the following physical properties.
【００３１】なお、実施例２において見掛気孔率が実施
例１よりも低いのは、硼酸の添加量が増えたことに起因
すると推測される。この結果より、硼酸の添加量が増加
すると、それに応じて見掛気孔率が低下すると推測され
る。The reason why the apparent porosity in Example 2 is lower than that in Example 1 is presumed to be due to an increase in the amount of boric acid added. From this result, it is presumed that as the amount of boric acid increases, the apparent porosity decreases accordingly.
【００３２】（実施例３）実施例１と同じ溶融シリカ粉
末１００重量％に、実施例１と同じ硼酸（Ｈ3ＢＯ3）粉
末を実施例２よりもさらに多い１６重量％（これは酸化
硼素（Ｂ2Ｏ3）に換算すると、９．０１重量％に相当す
る）添加・混合した。その後、この混合物に水を１８重
量％添加・混練してスリップを得た。次に、このスリッ
プを実施例１と同じ石膏型に流し込んで鋳込み成形し
た。さらに、得られた成形体を実施例１と同じ条件で焼
成し、実施例１と同じ形状の溶融シリカ質耐火物を得
た。(Example 3) The same boric acid (H 3 BO 3 ) powder as in Example 1 was added to 100% by weight of the same fused silica powder as in Example 1 and 16% by weight (which was boron oxide) more than in Example 2. (Equivalent to 9.01% by weight in terms of (B 2 O 3 )). Thereafter, 18% by weight of water was added to the mixture and kneaded to obtain a slip. Next, the slip was cast into the same gypsum mold as in Example 1 and cast. Further, the obtained molded body was fired under the same conditions as in Example 1 to obtain a fused silica refractory having the same shape as that of Example 1.
【００３３】この溶融シリカ質耐火物の見掛気孔率、か
さ比重、常温曲げ強さ、熱間線膨張率を実施例１と同様
にして測定したところ、見掛気孔率は０．５％、かさ比
重は２．１９、常温曲げ強さは１１．０ＭＰａ、１００
０℃における熱間線膨張率は０．０６であった。The apparent porosity, bulk specific gravity, room temperature bending strength and hot linear expansion coefficient of this fused siliceous refractory were measured in the same manner as in Example 1. The apparent porosity was 0.5%. Bulk specific gravity is 2.19, room temperature bending strength is 11.0 MPa, 100
The coefficient of linear thermal expansion at 0 ° C. was 0.06.
【００３４】また、ガラス相の有無を実施例１と同様に
して調べたところ、実施例１と同じ硼珪酸ガラス相の存
在が確認された。さらに、加熱・冷却による表面粒子の
剥離の有無を実施例１と同様にして調べたところ、表面
粒子の剥離は見られなかった。When the presence or absence of a glass phase was examined in the same manner as in Example 1, the presence of the same borosilicate glass phase as in Example 1 was confirmed. Further, when the presence or absence of peeling of the surface particles due to heating and cooling was examined in the same manner as in Example 1, no peeling of the surface particles was observed.
【００３５】これらの結果より、実施例３の方法で得ら
れた溶融シリカ質耐火物は、実施例１と同等の緻密化と
ガラス相の形成がなされており、その結果、実施例１と
同等の物性を有することが分かる。From these results, the fused siliceous refractory obtained by the method of Example 3 had the same densification and glass phase formation as in Example 1, and as a result, had the same properties as in Example 1. It can be seen that they have the following physical properties.
【００３６】なお、実施例３において見掛気孔率が実施
例２よりも高いのは、硼酸の添加量がさらに増えたこと
に起因すると推測される。The reason why the apparent porosity is higher in Example 3 than in Example 2 is presumed to be due to the further increase in the amount of boric acid added.
【００３７】（実施例４）硼酸（Ｈ3ＢＯ3）粉末に代え
て、燐酸（Ｈ3ＰＯ4）を５重量％（これは酸化燐（Ｐ2
Ｏ5）に換算すると、３．６２重量％に相当する）添加
・混合した以外は、実施例２と同じ条件で溶融シリカ質
耐火物を得た。Example 4 Instead of boric acid (H 3 BO 3 ) powder, phosphoric acid (H 3 PO 4 ) was replaced by 5% by weight (this was phosphorus oxide (P 2
A fused silica refractory was obtained under the same conditions as in Example 2 except that it was added and mixed in terms of O 5 ) (equivalent to 3.62% by weight).
【００３８】この溶融シリカ質耐火物の見掛気孔率、か
さ比重、常温曲げ強さ、熱間線膨張率を実施例１と同様
にして測定したところ、見掛気孔率は０．７％、かさ比
重は２．１８、常温曲げ強さは１０．６ＭＰａ、１００
０℃における熱間線膨張率は０．０４であった。The apparent porosity, bulk specific gravity, room temperature bending strength and hot linear expansion coefficient of this fused siliceous refractory were measured in the same manner as in Example 1. The apparent porosity was 0.7%. Bulk specific gravity is 2.18, room temperature bending strength is 10.6 MPa, 100
The coefficient of linear thermal expansion at 0 ° C. was 0.04.
【００３９】また、ガラス相の有無を実施例１と同様に
して調べたところ、燐珪酸ガラス相の存在が確認され
た。さらに、加熱・冷却による表面粒子の剥離の有無を
実施例１と同様にして調べたところ、表面粒子の剥離は
見られなかった。When the presence or absence of a glass phase was examined in the same manner as in Example 1, the presence of a phosphosilicate glass phase was confirmed. Further, when the presence or absence of peeling of the surface particles due to heating and cooling was examined in the same manner as in Example 1, no peeling of the surface particles was observed.
【００４０】これらの結果より、実施例４の方法で得ら
れた溶融シリカ質耐火物は、実施例２と同等の緻密化と
ガラス相の形成がなされており、その結果、実施例１と
同等の物性を有することが分かる。From these results, the fused siliceous refractory obtained by the method of Example 4 had the same densification and the formation of a glass phase as in Example 2, and as a result, had the same properties as in Example 1. It can be seen that they have the following physical properties.
【００４１】（実施例５）硼酸（Ｈ3ＢＯ3）粉末に代え
て、燐酸硼素（ＢＰＯ4）を３重量％（これは酸化燐
（Ｐ2Ｏ5）に換算すると、３．００重量％に相当する）
添加・混合した以外は、実施例２と同じ条件で溶融シリ
カ質耐火物を得た。Example 5 Instead of boric acid (H 3 BO 3 ) powder, boron phosphate (BPO 4 ) was replaced by 3% by weight (this is 3.00% by weight in terms of phosphorus oxide (P 2 O 5 )). Is equivalent to
A fused siliceous refractory was obtained under the same conditions as in Example 2 except for adding and mixing.
【００４２】この溶融シリカ質耐火物の見掛気孔率、か
さ比重、常温曲げ強さ、熱間線膨張率を実施例１と同様
にして測定したところ、見掛気孔率は０．４％、かさ比
重は２．２０、常温曲げ強さは１２．７ＭＰａ、１００
０℃における熱間線膨張率は０．０４であった。When the apparent porosity, bulk specific gravity, room temperature bending strength and hot linear expansion coefficient of this fused siliceous refractory were measured in the same manner as in Example 1, the apparent porosity was 0.4%. Bulk specific gravity is 2.20, room temperature bending strength is 12.7 MPa, 100
The coefficient of linear thermal expansion at 0 ° C. was 0.04.
【００４３】また、ガラス相の有無を実施例１と同様に
して調べたところ、硼珪酸ガラス相と燐珪酸ガラス相の
存在が確認された。さらに、加熱・冷却による表面粒子
の剥離の有無を実施例１と同様にして調べたところ、表
面粒子の剥離は見られなかった。When the presence or absence of a glass phase was examined in the same manner as in Example 1, the presence of a borosilicate glass phase and a phosphosilicate glass phase was confirmed. Further, when the presence or absence of peeling of the surface particles due to heating and cooling was examined in the same manner as in Example 1, no peeling of the surface particles was observed.
【００４４】これらの結果より、実施例５の方法で得ら
れた溶融シリカ質耐火物は、実施例２と同等の緻密化と
ガラス相の形成がなされており、その結果、実施例１と
同等の物性を有することが分かる。From these results, the fused siliceous refractory obtained by the method of Example 5 was densified and formed a glass phase equivalent to that of Example 2, and as a result, equivalent to that of Example 1. It can be seen that they have the following physical properties.
【００４５】（実施例６）焼成時の水蒸気濃度を５５容
積％（残部は空気）に下げた以外は、実施例４と同じ条
件で溶融シリカ質耐火物を得た。Example 6 A fused silica refractory was obtained under the same conditions as in Example 4 except that the steam concentration during firing was reduced to 55% by volume (the remainder was air).
【００４６】この溶融シリカ質耐火物の見掛気孔率、か
さ比重、常温曲げ強さ、熱間線膨張率を実施例１と同様
にして測定したところ、見掛気孔率は２．８％、かさ比
重は２．１１、常温曲げ強さは９．５ＭＰａ、１０００
℃における熱間線膨張率は０．０４であった。The apparent porosity, bulk specific gravity, room-temperature bending strength and hot linear expansion coefficient of this fused siliceous refractory were measured in the same manner as in Example 1. The apparent porosity was 2.8%. Bulk specific gravity is 2.11, room temperature bending strength is 9.5 MPa, 1000
The coefficient of linear thermal expansion at 0 ° C. was 0.04.
【００４７】また、ガラス相の有無を実施例１と同様に
して調べたところ、燐珪酸ガラス相の存在が確認され
た。さらに、加熱・冷却による表面粒子の剥離の有無を
実施例１と同様にして調べたところ、表面粒子の剥離は
見られなかった。When the presence or absence of a glass phase was examined in the same manner as in Example 1, the presence of a phosphosilicate glass phase was confirmed. Further, when the presence or absence of peeling of the surface particles due to heating and cooling was examined in the same manner as in Example 1, no peeling of the surface particles was observed.
【００４８】これらの結果より、実施例６の方法で得ら
れた溶融シリカ質耐火物は、実施例１と同等の緻密化と
ガラス相の形成がなされており、その結果、実施例１と
同等の物性を有することが分かる。From these results, the fused siliceous refractory obtained by the method of Example 6 had the same densification and glass phase formation as in Example 1, and as a result, had the same properties as in Example 1. It can be seen that they have the following physical properties.
【００４９】なお、実施例６において見掛気孔率が実施
例４の４倍になっているのは、焼成時の水蒸気濃度を５
５容積％に下げたことに起因する。この現象から、焼成
時の水蒸気濃度が、焼結体の緻密化すなわち見掛気孔率
の低下に大きな影響を及ぼしていることが分かる。It should be noted that the apparent porosity in Example 6 was four times that of Example 4 because the steam concentration during firing was 5 times.
This is due to the reduction to 5% by volume. From this phenomenon, it can be seen that the water vapor concentration at the time of sintering has a great effect on the densification of the sintered body, that is, the decrease in the apparent porosity.
【００５０】上記実施例１〜６をまとめて示すと、次の
表１のようになる。Tables 1 to 6 show the above Examples 1 to 6 collectively.
【００５１】[0051]
【表１】 [Table 1]
【００５２】（比較例１）実施例１と同じ溶融シリカ粉
末１００重量％に、実施例１と同じ硼酸（Ｈ3ＢＯ3）粉
末を実施例１より少ない０．５重量％（これは酸化硼素
（Ｂ2Ｏ3）に換算すると、０．２８重量％に相当する）
添加・混合した以外は、実施例１と同様にして、実施例
１と同じ形状の溶融シリカ質耐火物を得た。Comparative Example 1 The same boric acid (H 3 BO 3 ) powder as in Example 1 was used in an amount of 0.5% by weight (less than that in Example 1) in 100% by weight of the same fused silica powder as in Example 1 (this was boron oxide). in terms of (B 2 O 3), equivalent to 0.28 wt%)
A fused silica refractory having the same shape as in Example 1 was obtained in the same manner as in Example 1, except for adding and mixing.
【００５３】この溶融シリカ質耐火物の見掛気孔率、か
さ比重、常温曲げ強さ、熱間線膨張率を実施例１と同様
にして測定したところ、見掛気孔率は１．１％、かさ比
重は２．１７、常温曲げ強さは１１．０ＭＰａ、１００
０℃における熱間線膨張率は０．０４であった。The apparent porosity, bulk specific gravity, room temperature bending strength and hot linear expansion coefficient of this fused siliceous refractory were measured in the same manner as in Example 1. The apparent porosity was 1.1%. The bulk specific gravity is 2.17, the room temperature bending strength is 11.0 MPa, 100
The coefficient of linear thermal expansion at 0 ° C. was 0.04.
【００５４】また、ガラス相の有無を実施例１と同様に
して調べたところ、硼珪酸ガラス相の存在が確認できな
かった。さらに、加熱・冷却による表面粒子の剥離の有
無を実施例１と同様にして調べたところ、表面粒子の剥
離が見られた。When the presence or absence of a glass phase was examined in the same manner as in Example 1, the presence of the borosilicate glass phase could not be confirmed. Furthermore, the presence or absence of peeling of surface particles due to heating and cooling was examined in the same manner as in Example 1. As a result, peeling of surface particles was observed.
【００５５】これらの結果より、比較例１の方法で得ら
れた溶融シリカ質耐火物は、実施例１と同等に緻密化は
なされているが、ガラス相が存在しないことにより、表
面粒子の剥離が防止できていないことが分かる。これ
は、硼酸粉末の添加量が不足していることに起因すると
推測される。From these results, the fused siliceous refractory obtained by the method of Comparative Example 1 was densified in the same manner as in Example 1, but the absence of the glass phase caused the separation of the surface particles. It can be seen that was not prevented. This is presumed to be due to an insufficient amount of boric acid powder added.
【００５６】（比較例２）実施例１と同じ溶融シリカ粉
末１００重量％に、実施例１と同じ硼酸（Ｈ3ＢＯ3）粉
末を実施例１よりはるかに多い３０重量％（これは酸化
硼素（Ｂ2Ｏ3）に換算すると、１６．８９重量％に相当
する）添加・混合した以外は、実施例１と同様にして、
実施例１と同じ形状の溶融シリカ質耐火物を得た。Comparative Example 2 The same boric acid (H 3 BO 3 ) powder as in Example 1 was added to 100% by weight of the same fused silica powder as in Example 1 and 30% by weight (which was boron oxide) (Equivalent to 16.89% by weight in terms of (B 2 O 3 )).
A fused silica refractory having the same shape as in Example 1 was obtained.
【００５７】この溶融シリカ質耐火物の見掛気孔率、か
さ比重、常温曲げ強さ、熱間線膨張率を実施例１と同様
にして測定したところ、見掛気孔率は１．２％、かさ比
重は２．１７、常温曲げ強さは１０．９ＭＰａ、１００
０℃における熱間線膨張率は０．３８であった。The apparent porosity, bulk specific gravity, room temperature bending strength and hot linear expansion coefficient of this fused silica refractory were measured in the same manner as in Example 1. The apparent porosity was 1.2%. The bulk specific gravity is 2.17, the room temperature bending strength is 10.9 MPa, 100
The coefficient of linear thermal expansion at 0 ° C. was 0.38.
【００５８】また、ガラス相の有無を実施例１と同様に
して調べたところ、硼珪酸ガラス相の存在が確認され
た。さらに、加熱・冷却による表面粒子の剥離の有無を
実施例１と同様にして調べたところ、表面粒子の剥離は
見られなかった。When the presence or absence of a glass phase was examined in the same manner as in Example 1, the presence of a borosilicate glass phase was confirmed. Further, when the presence or absence of peeling of the surface particles due to heating and cooling was examined in the same manner as in Example 1, no peeling of the surface particles was observed.
【００５９】これらの結果より、比較例２の方法で得ら
れた溶融シリカ質耐火物は、実施例１と同等に緻密化は
なされているが、熱間線膨張率が飛び抜けて高いことに
より、耐熱衝撃性が大幅に低下していることが分かる。
これは、硼酸粉末の添加量が過大であることに起因する
と推測される。From these results, the fused siliceous refractory obtained by the method of Comparative Example 2 was densified similarly to Example 1, but the refractory coefficient of hot linear expansion was extremely high. It can be seen that the thermal shock resistance is significantly reduced.
This is presumed to be due to the excessive amount of boric acid powder added.
【００６０】（比較例３）焼成時の水蒸気濃度を４０容
積％に下げた以外は、実施例４と同じ条件で溶融シリカ
質耐火物を得た。Comparative Example 3 A fused silica refractory was obtained under the same conditions as in Example 4 except that the steam concentration during firing was reduced to 40% by volume.
【００６１】この溶融シリカ質耐火物の見掛気孔率、か
さ比重、常温曲げ強さ、熱間線膨張率を実施例１と同様
にして測定したところ、見掛気孔率は６．０％、かさ比
重は２．０５、常温曲げ強さは９．０ＭＰａ、１０００
℃における熱間線膨張率は０．０４であった。The apparent porosity, bulk specific gravity, room temperature bending strength and hot linear expansion coefficient of this fused silica refractory were measured in the same manner as in Example 1. The apparent porosity was 6.0%. Bulk specific gravity is 2.05, room temperature bending strength is 9.0 MPa, 1000
The coefficient of linear thermal expansion at 0 ° C. was 0.04.
【００６２】また、ガラス相の有無を実施例１と同様に
して調べたところ、燐珪酸ガラス相の存在が確認され
た。さらに、加熱・冷却による表面粒子の剥離の有無を
実施例１と同様にして調べたところ、表面粒子の剥離が
見られた。When the presence or absence of a glass phase was examined in the same manner as in Example 1, the presence of a phosphosilicate glass phase was confirmed. Furthermore, the presence or absence of peeling of surface particles due to heating and cooling was examined in the same manner as in Example 1. As a result, peeling of surface particles was observed.
【００６３】これらの結果より、比較例３の方法で得ら
れた溶融シリカ質耐火物は、ガラス相は存在するが、実
施例１に比べて緻密化の程度が著しく劣っており、その
結果、表面粒子の剥離を防止できていないことが分か
る。From these results, the fused siliceous refractory obtained by the method of Comparative Example 3 has a glass phase, but the degree of densification is remarkably inferior to that of Example 1. As a result, It can be seen that peeling of the surface particles could not be prevented.
【００６４】なお、比較例３において見掛気孔率が実施
例１の６．７倍程度に高くなっているのは、焼成時の水
蒸気濃度を４０容積％に下げたため、組織の緻密化が不
足したことに起因すると推測される。The reason why the apparent porosity in Comparative Example 3 is about 6.7 times higher than that in Example 1 is that the density of water vapor at the time of firing was reduced to 40% by volume, resulting in insufficient densification of the structure. It is presumed to be due to the above.
【００６５】（比較例４）焼成時の水蒸気濃度を０とし
た以外は、実施例４（および比較例３）と同じ条件で溶
融シリカ質耐火物を得た。Comparative Example 4 A fused silica refractory was obtained under the same conditions as in Example 4 (and Comparative Example 3) except that the steam concentration during firing was set to 0.
【００６６】この溶融シリカ質耐火物の見掛気孔率、か
さ比重、常温曲げ強さ、熱間線膨張率を実施例１と同様
にして測定したところ、見掛気孔率は９．２％、かさ比
重は１．９６、常温曲げ強さは８．５ＭＰａ、１０００
℃における熱間線膨張率は０．０４であった。The apparent porosity, bulk specific gravity, room temperature bending strength and hot linear expansion coefficient of this fused siliceous refractory were measured in the same manner as in Example 1. The apparent porosity was 9.2%. Bulk specific gravity is 1.96, room temperature bending strength is 8.5 MPa, 1000
The coefficient of linear thermal expansion at 0 ° C. was 0.04.
【００６７】また、ガラス相の有無を実施例１と同様に
して調べたところ、燐珪酸ガラス相の存在が確認され
た。さらに、加熱・冷却による表面粒子の剥離の有無を
実施例１と同様にして調べたところ、表面粒子の剥離が
見られた。When the presence or absence of a glass phase was examined in the same manner as in Example 1, the presence of a phosphosilicate glass phase was confirmed. Furthermore, the presence or absence of peeling of surface particles due to heating and cooling was examined in the same manner as in Example 1. As a result, peeling of surface particles was observed.
【００６８】これらの結果より、比較例４の方法で得ら
れた溶融シリカ質耐火物は、ガラス相は存在するが、実
施例１に比べて緻密化の程度が著しく劣っており、その
結果、表面粒子の剥離を防止できていないことが分か
る。From these results, the fused siliceous refractory obtained by the method of Comparative Example 4 has a glass phase, but has a significantly lower degree of densification than that of Example 1. As a result, It can be seen that peeling of the surface particles could not be prevented.
【００６９】なお、比較例４において見掛気孔率が実施
例１の１０倍程度に高くなっているのは、焼成時の水蒸
気をゼロとしたため、組織の緻密化がほとんどできなか
ったことに起因すると推測される。The reason that the apparent porosity in Comparative Example 4 is about 10 times higher than that of Example 1 is that the structure was hardly densified because the steam at the time of firing was set to zero. It is guessed.
【００７０】（比較例５）硼酸、燐酸、燐酸硼素のいず
れも添加せずに、実施例１と同じ溶融シリカ粉末１００
重量％のみに水を１６重量％添加・混練し、スリップを
得た。次に、このスリップを実施例１と同じ石膏型に流
し込んで鋳込み成形した。さらに、得られた成形体を比
較例４と同じ条件で焼成し、実施例１と同じ形状の溶融
シリカ質耐火物を得た。Comparative Example 5 The same fused silica powder 100 as in Example 1 was used without adding any of boric acid, phosphoric acid and boron phosphate.
Only 16% by weight of water was added and kneaded to obtain a slip. Next, the slip was cast into the same gypsum mold as in Example 1 and cast. Further, the obtained molded body was fired under the same conditions as in Comparative Example 4 to obtain a fused silica refractory having the same shape as in Example 1.
【００７１】この溶融シリカ質耐火物の見掛気孔率、か
さ比重、常温曲げ強さ、熱間線膨張率を実施例１と同様
にして測定したところ、見掛気孔率は１０．３％、かさ
比重は１．９６、常温曲げ強さは８．２ＭＰａ、１００
０℃における熱間線膨張率は０．０４であった。The apparent porosity, bulk specific gravity, room temperature bending strength and hot linear expansion coefficient of this fused siliceous refractory were measured in the same manner as in Example 1. The apparent porosity was 10.3%. Bulk specific gravity is 1.96, room temperature bending strength is 8.2 MPa, 100
The coefficient of linear thermal expansion at 0 ° C. was 0.04.
【００７２】また、ガラス相の有無を実施例１と同様に
して調べたところ、ガラス相の存在が確認されなかっ
た。さらに、加熱・冷却による表面粒子の剥離の有無を
実施例１と同様にして調べたところ、表面粒子の剥離が
見られた。When the presence or absence of a glass phase was examined in the same manner as in Example 1, no existence of a glass phase was confirmed. Furthermore, the presence or absence of peeling of surface particles due to heating and cooling was examined in the same manner as in Example 1. As a result, peeling of surface particles was observed.
【００７３】これらの結果より、比較例５の方法で得ら
れた溶融シリカ質耐火物は、ガラス相が存在せず、実施
例１に比べて緻密化の程度が著しく劣っており、その結
果、表面粒子の剥離を防止できていないことが分かる。From these results, the fused siliceous refractory obtained by the method of Comparative Example 5 did not have a glass phase and had a significantly lower degree of densification than that of Example 1. It can be seen that peeling of the surface particles could not be prevented.
【００７４】なお、比較例５において見掛気孔率が実施
例１の１１．４倍程度に高くなっているのは、硼酸、燐
酸、燐酸硼素のいずれも添加しなかったことと、焼成時
の水蒸気をゼロとしたことに起因すると推測される。The reason why the apparent porosity in Comparative Example 5 was about 11.4 times higher than that of Example 1 was that neither boric acid, phosphoric acid, nor boron phosphate was added, It is presumed to be due to zero water vapor.
【００７５】上記比較例１〜５をまとめて示すと表２の
ようになる。Table 2 shows the above Comparative Examples 1 to 5 collectively.
【００７６】[0076]
【表２】 [Table 2]
【００７７】[0077]
【発明の効果】以上説明した通り、この発明の溶融シリ
カ質耐火物の製造方法によれば、溶融シリカ質耐火物の
持つ低熱膨張性、すなわち良好な耐熱衝撃性を維持しな
がら、１〜２％程度の見かけ気孔率と耐火物表面の粒子
の剥離防止とを実現できる。As described above, according to the method for producing a fused siliceous refractory of the present invention, a low thermal expansion property of a fused siliceous refractory, that is, a good thermal shock resistance is maintained while maintaining a good thermal shock resistance. % Porosity and prevention of peeling of particles on the surface of the refractory.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 森 弘之 長崎県東彼杵郡川棚町百津郷296番地 川 棚東芝セラミックス株式会社内 ──────────────────────────────────────────────────の Continuing from the front page (72) Inventor Hiroyuki Mori 296, Motsugo, Kawatana-cho, Higashisonogi-gun, Nagasaki Pref.
Claims (5)
量％に、硼素および燐よりなる群から選ばれる少なくと
も一種の元素を含有する化合物をＢ2Ｏ3、またはＰ2Ｏ5
に換算した合計量で０．５重量％〜１０重量％の範囲と
なるように添加し、さらに適当な成形助剤を混合して成
形用混合物を生成する第１工程と、 前記成形用混合物を所望形状に成形して成形体を得る第
２工程と、 前記成形体を５０容量％以上の水蒸気を含む雰囲気下で
焼成する第３工程とを備えてなることを特徴とする溶融
シリカ質耐火物の製造方法。1. A compound containing at least one element selected from the group consisting of boron and phosphorus in 100% by weight of fused silica powder whose particle size has been adjusted, is mixed with B 2 O 3 or P 2 O 5.
A first step of adding a mixture in an amount of 0.5% by weight to 10% by weight in terms of a total amount converted to and further mixing an appropriate molding aid to form a mixture for molding; A fused silica refractory, comprising: a second step of forming a molded article into a desired shape to obtain a molded article; and a third step of firing the molded article in an atmosphere containing 50% by volume or more of water vapor. Manufacturing method.
なくとも一種の元素を含有する前記化合物が、前記第３
工程において前記溶融シリカと反応してその溶融シリカ
の粒子の粒界にガラス相を形成する性質を持つ請求項１
に記載の溶融シリカ質耐火物の製造方法。2. The compound containing at least one element selected from the group consisting of boron and phosphorus,
2. A process for forming a glass phase at a grain boundary of particles of the fused silica by reacting with the fused silica in the step.
3. The method for producing a fused siliceous refractory according to item 1.
なくとも一種の元素を含有する前記化合物が、硼酸、燐
酸および燐酸硼素よりなる群から選ばれる少なくとも一
種である請求項１または２に記載の溶融シリカ質耐火物
の製造方法。3. The molten metal according to claim 1, wherein the compound containing at least one element selected from the group consisting of boron and phosphorus is at least one kind selected from the group consisting of boric acid, phosphoric acid and boron phosphate. A method for producing siliceous refractories.
温度が、１０５０〜１２５０℃の範囲に設定されている
請求項１〜３のいずれかに記載の溶融シリカ質耐火物の
製造方法。4. The method for producing a fused siliceous refractory according to claim 1, wherein a firing temperature of the molded body in the third step is set in a range of 1050 to 1250 ° C.
時間が、０．５〜２０時間の範囲に設定されている請求
項１〜４のいずれかに記載の溶融シリカ質耐火物の製造
方法。5. The method for producing a fused siliceous refractory according to claim 1, wherein a firing time of the molded body in the third step is set in a range of 0.5 to 20 hours. .
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP22408997A JPH1160330A (en) | 1997-08-20 | 1997-08-20 | Production of fused silica-based refractory |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP22408997A JPH1160330A (en) | 1997-08-20 | 1997-08-20 | Production of fused silica-based refractory |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH1160330A true JPH1160330A (en) | 1999-03-02 |
Family
ID=16808386
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP22408997A Pending JPH1160330A (en) | 1997-08-20 | 1997-08-20 | Production of fused silica-based refractory |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH1160330A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1840101A2 (en) | 2006-03-31 | 2007-10-03 | Nichias Corporation | Fused siliceous refractory and production method thereof |
| JP2008156181A (en) * | 2006-12-26 | 2008-07-10 | Nippon Sheet Glass Co Ltd | Method for producing silica ceramic |
| US20140147664A1 (en) * | 2012-11-29 | 2014-05-29 | Corning Incorporated | Fused Silica Based Cellular Structures |
| CN115340394A (en) * | 2022-08-10 | 2022-11-15 | 武汉科技大学 | Boron phosphate reinforced quartz material and preparation method thereof |
-
1997
- 1997-08-20 JP JP22408997A patent/JPH1160330A/en active Pending
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1840101A2 (en) | 2006-03-31 | 2007-10-03 | Nichias Corporation | Fused siliceous refractory and production method thereof |
| JP2008156181A (en) * | 2006-12-26 | 2008-07-10 | Nippon Sheet Glass Co Ltd | Method for producing silica ceramic |
| US20140147664A1 (en) * | 2012-11-29 | 2014-05-29 | Corning Incorporated | Fused Silica Based Cellular Structures |
| US10370304B2 (en) * | 2012-11-29 | 2019-08-06 | Corning Incorporated | Fused silica based cellular structures |
| CN115340394A (en) * | 2022-08-10 | 2022-11-15 | 武汉科技大学 | Boron phosphate reinforced quartz material and preparation method thereof |
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