JPS6042182B2 - Tin oxide refractories for glass melting furnaces - Google Patents
Tin oxide refractories for glass melting furnacesInfo
- Publication number
- JPS6042182B2 JPS6042182B2 JP53040124A JP4012478A JPS6042182B2 JP S6042182 B2 JPS6042182 B2 JP S6042182B2 JP 53040124 A JP53040124 A JP 53040124A JP 4012478 A JP4012478 A JP 4012478A JP S6042182 B2 JPS6042182 B2 JP S6042182B2
- Authority
- JP
- Japan
- Prior art keywords
- tin oxide
- glass melting
- weight
- refractories
- melting furnaces
- 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.)
- Expired
Links
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 title claims description 15
- 229910001887 tin oxide Inorganic materials 0.000 title claims description 13
- 238000002844 melting Methods 0.000 title claims description 8
- 230000008018 melting Effects 0.000 title claims description 8
- 239000011521 glass Substances 0.000 title claims description 6
- 239000011819 refractory material Substances 0.000 title description 9
- 239000006060 molten glass Substances 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 4
- 238000005260 corrosion Methods 0.000 description 4
- 230000007797 corrosion Effects 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 238000011038 discontinuous diafiltration by volume reduction Methods 0.000 description 3
- 239000005355 lead glass Substances 0.000 description 3
- 229910052851 sillimanite Inorganic materials 0.000 description 3
- 229910052845 zircon Inorganic materials 0.000 description 3
- GFQYVLUOOAAOGM-UHFFFAOYSA-N zirconium(iv) silicate Chemical compound [Zr+4].[O-][Si]([O-])([O-])[O-] GFQYVLUOOAAOGM-UHFFFAOYSA-N 0.000 description 3
- 239000004372 Polyvinyl alcohol Substances 0.000 description 2
- 239000005388 borosilicate glass Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000010304 firing Methods 0.000 description 2
- 238000007654 immersion Methods 0.000 description 2
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- 229920002451 polyvinyl alcohol Polymers 0.000 description 2
- 238000005245 sintering Methods 0.000 description 2
- BPPVUXSMLBXYGG-UHFFFAOYSA-N 4-[3-(4,5-dihydro-1,2-oxazol-3-yl)-2-methyl-4-methylsulfonylbenzoyl]-2-methyl-1h-pyrazol-3-one Chemical compound CC1=C(C(=O)C=2C(N(C)NC=2)=O)C=CC(S(C)(=O)=O)=C1C1=NOCC1 BPPVUXSMLBXYGG-UHFFFAOYSA-N 0.000 description 1
- 101100096653 Arabidopsis thaliana SRO1 gene Proteins 0.000 description 1
- 241001091551 Clio Species 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 229920000609 methyl cellulose Polymers 0.000 description 1
- 239000001923 methylcellulose Substances 0.000 description 1
- HFLAMWCKUFHSAZ-UHFFFAOYSA-N niobium dioxide Inorganic materials O=[Nb]=O HFLAMWCKUFHSAZ-UHFFFAOYSA-N 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
Landscapes
- Glass Melting And Manufacturing (AREA)
- Compositions Of Oxide Ceramics (AREA)
Description
【発明の詳細な説明】
本発明はガラス溶解炉に用いられる酸化錫耐火物に関す
るものである。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a tin oxide refractory used in a glass melting furnace.
従来、ガラス溶解炉の内張材にはジルコン質耐火物、シ
リマナイト質耐火物等が用いられている。Conventionally, zircon refractories, sillimanite refractories, and the like have been used as lining materials for glass melting furnaces.
しかしながら、これら耐火物は溶解ガラス（たとえば溶
解鉛ガラス等）に容易に溶損されて体積減少が起こり、
短期間で炉の内張機能が消滅する問題がある。一方、ガ
ラス溶解用電極として酸化錫焼結体が用いられているが
、この焼結体は電気導電性を維持する必要上高純度（９
９．９％以上）なため、焼結が困難で大型形状の製造が
難しいばかりか、価格面でも非常に高価となる欠点があ
る。However, these refractories are easily damaged by molten glass (such as molten lead glass), resulting in volume reduction.
There is a problem that the furnace lining function disappears in a short period of time. On the other hand, a tin oxide sintered body is used as an electrode for glass melting, but this sintered body has a high purity (9%) because it is necessary to maintain electrical conductivity.
9.9% or more), it is difficult to sinter and manufacture large-sized shapes, and it is also very expensive.
このようなことから、本発明者は上記欠点を解消するた
めに鋭意研究を重ねた結果、Ｓｎ０。For this reason, the inventors of the present invention have conducted extensive research to solve the above drawbacks, and as a result, have developed Sn0.
と、。゜、ＡＳ２Ｏ３、ＰｂＯ）Ｆｅ２０ａ）レア・ア
ース等とから構成され、かつ各成分量を所定範囲に規制
することによつて、Ｓｎ０。粒界の焼結性を高め緻密性
が向上でき、溶解ガラスに対して優れた耐蝕性を有し、
かつ大型で安価な酸化錫耐火物が得られることを見い出
した。すなわち、本発明は５ｎ００８５〜９９重量％と
、ａ゜、Ａｓ。and,.゜, AS2O3, PbO) Fe20a) Rare earths, etc., and by regulating the amount of each component within a predetermined range, Sn0. It can improve the sinterability of grain boundaries, improve density, and has excellent corrosion resistance against molten glass.
It has also been discovered that a large and inexpensive tin oxide refractory can be obtained. That is, the present invention contains 5n0085 to 99% by weight, a°, and As.
０３、ＰｂＯ各々１重量％以下、Ｆｅ。03, PbO each 1% by weight or less, Fe.
０３４重量％以下及びレア・アース８重量％以下とから
なるものである。034% by weight or less and rare earths by 8% by weight or less.
本発明においてＣＵＯ）ＡＳ２Ｏ３、ｐｂｏＮＦｅ２ｏ
３及びレア・アースの量を限定した理由はそれらの量が
上記各値より越えると、ＳｎＯ。In the present invention, CUO) AS2O3, pboNFe2o
The reason for limiting the amounts of 3 and rare earths is that if their amounts exceed the above values, SnO.
粒界への焼結剤量が多くなり過ぎ、該粒界の強度、耐蝕
性が低下し、ひいては得られた酸化錫耐火物が溶解ガラ
スにより短期間で溶損、体積減少を起こすからである。
本発明における焼結耐火物としては上記構成成分の他、
合計で２％以下のＭｎＮＮｉ）ＣＯＮＮｂ）Ｚｎ）Ｂｉ
ＮＣｄ） Ｙ）ＴａＮＴｉ等の酸化物の存在も許１容す
ることができる。This is because the amount of sintering agent at the grain boundaries becomes too large, the strength and corrosion resistance of the grain boundaries decrease, and as a result, the obtained tin oxide refractory will be eroded by molten glass and its volume will decrease in a short period of time. .
In addition to the above-mentioned components, the sintered refractory in the present invention includes:
Total of 2% or less MnNNi)CONNb)Zn)Bi
The presence of oxides such as NCd) Y) TaNTi can also be tolerated.
本発明におけるレア・アースとしては、例えばＮの、Ｙ
。Examples of rare earths in the present invention include N, Y,
.
Ｏ。、ｃｅｏ２、Ｌ。０３、Ｄｙ２Ｏ。O. , CEO2, L. 03, Dy2O.
、Ｓｍ。Ｏ。等を挙げることができ、このうち特にＮｂ
Ｏ．．Ｙ２Ｏ３が好ましい。なお、本発明の酸化錫耐火
物を製造するには、たとえは上記構成成分を有するＳＩ
Ｏ２鉱石を焼結したものでもよく、又高純度のＳｎＯ２
粉に焼結剤としてのＣＵＯ，．，ＡＳ２Ｏ３、ＰｂＯ，
．Ｆｅ２Ｏ３、レァ．アースを上述した範囲で添加して
酸化錫原料粉として、この原料物に適宜なバインダー（
たとえばポリビニルアルコール、カルボニルメチルセル
ロース等）を添加し、金型成形、ララバープレス等の通
常の成形法により成形した後、、この成形体を１４００
〜１６００℃程度の温度で焼成せしめ方法が採用し得る
。, Sm. O. Among these, Nb
O. ．． Y2O3 is preferred. In addition, in order to manufacture the tin oxide refractory of the present invention, for example, SI having the above-mentioned components
Sintered O2 ore may be used, or high purity SnO2
CUO as a sintering agent in the powder. , AS2O3, PbO,
．． Fe2O3, rare. Earth is added in the range mentioned above to obtain tin oxide raw material powder, and an appropriate binder (
For example, polyvinyl alcohol, carbonyl methylcellulose, etc.) are added and molded by a normal molding method such as mold molding or rubber press, and then the molded product is
A method of firing at a temperature of about 1600° C. can be employed.
次に本発明の実施例を説明する。Next, embodiments of the present invention will be described.
実施例１及ひ比較例１、２
ｓｎ０２粉にＣＬｌＯ．．ＡＳ２Ｏ３、ＰｌＯ各々０．
５重量％、Ｆｅ２Ｏ３３．５重量％及びレア・アース（
ＮｂＯ２、Ｙ２Ｏ３）５．鍾量％を添加して粒度分布が
１〜３Ｔｎ４０％、４４μ〜１Ｔｆ０ｎ２０％及び４４
ｐ以下４０％の原料粉を調合した。Example 1 and Comparative Examples 1 and 2 CLIO. ．． AS2O3, PlO each 0.
5% by weight, 3.5% by weight of Fe2O3 and rare earths (
NbO2, Y2O3)5. The particle size distribution is 1-3Tn40%, 44μ-1Tf0n20% and 44
A raw material powder with a p content of 40% or less was prepared.
次いで、この原料粉１０鍾量部にポリビニルアルコール
溶液５重量部を添加混練し、金型成形機により５００ｋ
９１ａ１の圧力下で成形して５０７Ｔ１！Ｎｗ×１００
ＴｎＩｎ０×２−０の成形体とした後、この成形体を１
４００℃の温度下にて３時間焼成せしめて酸化錫耐火物
を得た。得られた酸化錫耐火物の諸物性を調べたところ
、寸法収縮率０％、見掛気孔率２１．０％、カサ比×以
上詳述した如く、本発明によればＳｒＯ２粒界※重５．
３であつた。Next, 5 parts by weight of polyvinyl alcohol solution was added to 10 parts by weight of this raw material powder and kneaded, and the mixture was molded into 500 kg by a mold forming machine.
Molded under 91a1 pressure to form 507T1! Nw×100
After forming a molded body of TnIn0×2-0, this molded body was
A tin oxide refractory was obtained by firing at a temperature of 400° C. for 3 hours. When various physical properties of the obtained tin oxide refractory were investigated, it was found that the dimensional shrinkage rate was 0%, the apparent porosity was 21.0%, the bulk ratio was ．．
It was 3.
また、本実施例１の酸化錫耐火物を切断して寸法２０×
２０×２−の試験片を作成し、かつ同寸法のジルコン質
耐火物の試験片（比較例１）、シリマナイト質耐火物の
試験片（比較例２）を用意し、これら試験片を１４００
℃の溶解硼珪酸ガラス及び同温度の溶解鉛ガラスに夫々
１０Ｃ＠間浸漬し、浸漬後の各試験片の溶損率（体積減
少率％）を調べた。In addition, the tin oxide refractory of Example 1 was cut and the size was 20×.
A 20 x 2- test piece was prepared, and a test piece of zircon refractory (Comparative Example 1) and a test piece of sillimanite refractory (Comparative Example 2) of the same size were prepared.
The specimens were immersed in molten borosilicate glass at 10° C. and molten lead glass at the same temperature for 10 C, respectively, and the melting loss rate (volume reduction rate %) of each test piece after immersion was examined.
その結果、下記第１表の如くなつた。上第１表より明ら
かな如く、本発明の酸化錫耐火物は従来のジルコン質耐
火物、シリマナイト質耐火物に比して溶解ガラスに対す
る耐蝕性が著しく優れていることがわかる。The results were as shown in Table 1 below. As is clear from Table 1 above, the tin oxide refractories of the present invention are significantly superior in corrosion resistance to molten glass compared to conventional zircon refractories and sillimanite refractories.
実施例２、３及び比較例３〜７
前記実施例１と同様な方法により、下記第２表に示す各
原料組成の酸化錫耐火物を得た。Examples 2 and 3 and Comparative Examples 3 to 7 Tin oxide refractories having respective raw material compositions shown in Table 2 below were obtained in the same manner as in Example 1.
得られた各耐火物の試験片を１４００℃の溶融硼珪酸ガ
ラス及び同温度の溶解鉛ガラスに夫々１００時間浸漬し
、浸漬後の各試験片の溶損率（体積減少率）を調べた。
その結果を同第２表に併設した。の焼結性が高く緻密性
を向上てき、もつて各種の溶解ガラスに対して優れた耐
蝕性を有し、しかも大型かつ安価でガラス溶解炉の内張
材として長期間安定的に使用できる酸化錫耐火物を提供
できるものである。Each obtained refractory test piece was immersed in molten borosilicate glass at 1400°C and molten lead glass at the same temperature for 100 hours, and the melting loss rate (volume reduction rate) of each test piece after immersion was examined.
The results are also included in Table 2. It has high sinterability and improved density, and has excellent corrosion resistance for various types of molten glass.It is also large and inexpensive, and can be used stably for a long period of time as a lining material for glass melting furnaces. It can provide tin refractories.
Claims (1)
Ｏ＿３、ＰｂＯ各々１重量％以下、Ｆｅ＿２Ｏ＿３４重
量％以下及びレア・アース８重量％以下とからなるガラ
ス溶解炉用酸化錫耐火物。1 SnO_285-99% by weight, CuO, As_2
A tin oxide refractory for a glass melting furnace, comprising 1% by weight or less each of O_3 and PbO, 34% by weight or less of Fe_2O_34, and 8% by weight or less of rare earths.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP53040124A JPS6042182B2 (en) | 1978-04-05 | 1978-04-05 | Tin oxide refractories for glass melting furnaces |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP53040124A JPS6042182B2 (en) | 1978-04-05 | 1978-04-05 | Tin oxide refractories for glass melting furnaces |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS54132611A JPS54132611A (en) | 1979-10-15 |
| JPS6042182B2 true JPS6042182B2 (en) | 1985-09-20 |
Family
ID=12572065
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP53040124A Expired JPS6042182B2 (en) | 1978-04-05 | 1978-04-05 | Tin oxide refractories for glass melting furnaces |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS6042182B2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US9586847B2 (en) | 2011-12-28 | 2017-03-07 | Asahi Glass Company, Limited | Tin oxide refractory and method for its production |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2015044693A (en) * | 2011-12-28 | 2015-03-12 | 旭硝子株式会社 | Tin oxide refractories |
| WO2014208620A1 (en) | 2013-06-26 | 2014-12-31 | 旭硝子株式会社 | Powder composition for tin oxide monolithic refractory, production method for tin oxide monolithic refractory, glass melting furnace, and waste-product melting furnace |
-
1978
- 1978-04-05 JP JP53040124A patent/JPS6042182B2/en not_active Expired
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US9586847B2 (en) | 2011-12-28 | 2017-03-07 | Asahi Glass Company, Limited | Tin oxide refractory and method for its production |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS54132611A (en) | 1979-10-15 |
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