JPH0210777B2 - - Google Patents
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- Publication number
- JPH0210777B2 JPH0210777B2 JP60023979A JP2397985A JPH0210777B2 JP H0210777 B2 JPH0210777 B2 JP H0210777B2 JP 60023979 A JP60023979 A JP 60023979A JP 2397985 A JP2397985 A JP 2397985A JP H0210777 B2 JPH0210777 B2 JP H0210777B2
- Authority
- JP
- Japan
- Prior art keywords
- weight
- glass
- concentrate
- melting
- rare earth
- 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 - Lifetime
Links
- 239000011521 glass Substances 0.000 claims description 32
- 239000012141 concentrate Substances 0.000 claims description 17
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 13
- 238000002844 melting Methods 0.000 claims description 13
- 230000008018 melting Effects 0.000 claims description 13
- 239000000203 mixture Substances 0.000 claims description 12
- 239000005354 aluminosilicate glass Substances 0.000 claims description 10
- 238000010438 heat treatment Methods 0.000 claims description 9
- 239000002994 raw material Substances 0.000 claims description 9
- 229910052761 rare earth metal Inorganic materials 0.000 claims description 8
- 150000002910 rare earth metals Chemical class 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 4
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 3
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 12
- 239000000126 substance Substances 0.000 description 8
- 238000000034 method Methods 0.000 description 6
- 229910052697 platinum Inorganic materials 0.000 description 6
- 229910052782 aluminium Inorganic materials 0.000 description 5
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 5
- 229910004298 SiO 2 Inorganic materials 0.000 description 4
- 239000003513 alkali Substances 0.000 description 4
- 230000007797 corrosion Effects 0.000 description 4
- 238000005260 corrosion Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 229910052727 yttrium Inorganic materials 0.000 description 4
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 description 4
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
- 229910000323 aluminium silicate Inorganic materials 0.000 description 3
- 238000000354 decomposition reaction Methods 0.000 description 3
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical group O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 229910000272 alkali metal oxide Inorganic materials 0.000 description 2
- 229910000287 alkaline earth metal oxide Inorganic materials 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 229910052593 corundum Inorganic materials 0.000 description 2
- 239000005357 flat glass Substances 0.000 description 2
- 239000003365 glass fiber Substances 0.000 description 2
- 239000000155 melt Substances 0.000 description 2
- UXBZSSBXGPYSIL-UHFFFAOYSA-N phosphoric acid;yttrium(3+) Chemical compound [Y+3].OP(O)(O)=O UXBZSSBXGPYSIL-UHFFFAOYSA-N 0.000 description 2
- -1 rare earth hydroxide Chemical class 0.000 description 2
- 229910001404 rare earth metal oxide Inorganic materials 0.000 description 2
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 2
- 229910010271 silicon carbide Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 229910001845 yogo sapphire Inorganic materials 0.000 description 2
- 229910000164 yttrium(III) phosphate Inorganic materials 0.000 description 2
- 229910021193 La 2 O 3 Inorganic materials 0.000 description 1
- KKCBUQHMOMHUOY-UHFFFAOYSA-N Na2O Inorganic materials [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 description 1
- 229910017493 Nd 2 O 3 Inorganic materials 0.000 description 1
- 241000975357 Salangichthys microdon Species 0.000 description 1
- 239000003258 bubble free glass Substances 0.000 description 1
- 239000004568 cement Substances 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 231100000989 no adverse effect Toxicity 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000012264 purified product Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000005361 soda-lime glass Substances 0.000 description 1
- 235000011121 sodium hydroxide Nutrition 0.000 description 1
- 239000001488 sodium phosphate Substances 0.000 description 1
- 229910000162 sodium phosphate Inorganic materials 0.000 description 1
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C3/00—Glass compositions
- C03C3/04—Glass compositions containing silica
- C03C3/076—Glass compositions containing silica with 40% to 90% silica, by weight
- C03C3/095—Glass compositions containing silica with 40% to 90% silica, by weight containing rare earths
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Geochemistry & Mineralogy (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Glass Compositions (AREA)
Description
産業上の利用分野
本発明は1550℃以下の温度で溶融して製造し得
られる希土類含有アルミノけい酸塩ガラスの製造
法に関する。
従来技術
シリカとアルミナからなるアルミノけい酸塩ガ
ラスは、耐熱性が高く、機械的強度も良好であ
り、また耐食性、耐風化性の優れたガラスであ
る。しかし、この系のガラスを得るためには非常
に高温を必要とする。
一般の炭化けい素発熱体を使用する電気炉で
は、1550℃程度の温度までが限度であるために、
この系のガラスは一般の電気炉による溶融法では
製造することができなかつた。
一般にアルカリ酸化物、アルカリ土類酸化物を
含有させると、溶融温度が低下し、1550℃程度の
温度で、一般の炭化けい素を発熱体として使用し
た電気炉を使用してガラスを製造することが可能
となる。しかし、アルカリ酸化物、アルカリ土類
酸化物を含有させると、耐熱性、機械的性質、耐
化学性、耐食性及び耐風化性の諸性質を低下させ
る問題点がある。
本発明者らはさきに、Y2O3を含有させると、
1550℃程度の一般の電気炉を使用してガラスを製
造し得られると共に、得られるガラスは機械的に
優れたものであることを明らかにした。〔米国窯
業協会誌61巻247〜249頁（1978年）〕しかし、分
離Y2O3は高価であるため、それだけコスト高と
なる問題点があつた。
この問題点を解決するため、本発明者らはさき
にY2O3を製造する中間精製物であるイツトリウ
ムコンセントレートを利用すべく研究したとこ
ろ、Y2O3の原鉱石、例えばゼノタイムより精製
して得られるイツトリウムコンセントレートは、
数10％のY2O3と、残りはDy2O3，Nd2O3，CeO2，
Ho2O3，Yb2O3，Sm2O3，La2O3，Gd2O3，
Er2O3等の希土類酸化物よりなつているが、これ
をY2O3、に代え添加使用してアルミノけい酸塩
ガラスを製造したところ、(1)Y2O3のほかの他の
含有不純物はアルミノけい酸塩ガラスの特性、特
に耐アルカリ性などに悪影響がない。(2)これを使
用すると分離Y2O3を使用した場合よりもガラス
の溶融点を約50℃低下し得られ、しかもその価格
も1/5であるため、安価となることが分つた。（特
願昭57−180498号）
本発明者らは更にコストダウンについて研究を
重ねた結果、九州に広く分散する火山灰のシラス
は、その主成分がアルミノけい酸塩のガラス質の
ものであり、シラスの二次堆積物である二次シラ
スは、その化学組成がほぼ一定であることに着目
し、これを利用すべく検討を加えた。二次シラス
の化学組成を示すと次の通りである。
SiO2 82.59モル％ 75.87重量％
Al2O3 9.16 〃 14.28 〃
Fe2O3 0.92 〃 2.14 〃
CaO 1.54 〃 1.32 〃
MgO 0.49 〃 0.30 〃
Na2O 3.35 〃 3.18 〃
K2O 1.95 〃 2.80 〃
このように、SiO2とAl2O3の成分合計は約92モ
ル％で、大部分がアルミノけい酸塩であるので、
Y2O3コンセントレート、二次シラス及びAl2O3を
原料としてガラスを製造することを試みたとこ
ろ、これらの成分のほかに上記二次シラスに含ま
れる前記表にあるFe2O3、CaO、MgO、Na2O、
K2Oが全量で約５モル以下含有するガラスが得ら
れること、及びこれを原料とすると、SiO2，
Al2O3を原料とした場合に比べて、ガラス溶融時
間が約1/3に短縮し得られることが分つた。これ
らの知見に基いて本発明を完成した。
本発明の要旨は二次シラス30〜53重量％、
Al2O39〜30重量％、Y2O3コンセントレート23〜
54重量％を原料とし、これらの混合物を加熱溶融
してガラス化することを特徴とする希土類含有ア
ルミノけい酸塩ガラスの製造法にある。
本発明において言うY2O3コンセントレートと
は、Y2O3の原鉱石、例えばゼノタイムを硫酸分
解法またはアルカリ分解法によつて得られる中間
精製物である。アルカリ分解法で示すと、ゼノタ
イムを徐々に400℃の溶融した苛性ソーダに加え
る。反応は発熱反応で反応終了後冷却して反応物
を水で抽出してリン酸ソーダ、過剰のアルカリは
除去される。得られた希土類水酸化物を少量の塩
酸に溶解し、この溶液にしゆう酸を加えて希土し
ゆう酸塩とし、これを900℃で焼焼成するイツト
リウムコンセントレートが得られる。その分析例
を示すと次の通りである。
INDUSTRIAL APPLICATION FIELD The present invention relates to a method for producing a rare earth-containing aluminosilicate glass which can be produced by melting at a temperature of 1550° C. or lower. Prior Art Aluminosilicate glass made of silica and alumina has high heat resistance, good mechanical strength, and excellent corrosion resistance and weathering resistance. However, obtaining this type of glass requires extremely high temperatures. Electric furnaces that use general silicon carbide heating elements have a temperature limit of about 1550℃, so
This type of glass could not be manufactured by a general melting method using an electric furnace. Generally, when alkali oxides and alkaline earth oxides are included, the melting temperature decreases, and glass can be manufactured at a temperature of about 1550°C using an electric furnace that uses general silicon carbide as a heating element. becomes possible. However, when alkali oxides and alkaline earth oxides are contained, there is a problem that various properties such as heat resistance, mechanical properties, chemical resistance, corrosion resistance, and weathering resistance are deteriorated. The present inventors first found that when Y 2 O 3 is included,
It was revealed that glass can be produced using a general electric furnace at a temperature of about 1550℃, and that the resulting glass has excellent mechanical properties. [Journal of the American Ceramics Association, Vol. 61, pp. 247-249 (1978)] However, since separated Y 2 O 3 is expensive, there was a problem in that the cost increased accordingly. In order to solve this problem , the present inventors previously conducted research to utilize yttrium concentrate, which is an intermediate refined product for producing Y 2 O 3 . Yttrium concentrate obtained by purification is
Several 10% of Y 2 O 3 and the rest are Dy 2 O 3 , Nd 2 O 3 , CeO 2 ,
Ho 2 O 3 , Yb 2 O 3 , Sm 2 O 3 , La 2 O 3 , Gd 2 O 3 ,
It consists of rare earth oxides such as Er 2 O 3 , but when this was added in place of Y 2 O 3 to produce aluminosilicate glass, ( 1 ) The contained impurities have no adverse effect on the properties of the aluminosilicate glass, particularly on the alkali resistance. (2) It was found that using this method lowers the melting point of the glass by about 50°C compared to using isolated Y 2 O 3 , and it is also 1/5th the price, making it cheaper. (Patent Application No. 57-180498) As a result of further research into cost reduction, the present inventors found that the volcanic ash shirasu widely dispersed in Kyushu is a glassy substance whose main component is aluminosilicate. We focused on the fact that the chemical composition of secondary shirasu, which is a secondary deposit of whitebait, is almost constant, and investigated how to utilize this fact. The chemical composition of secondary shirasu is as follows. SiO 2 82.59 mol% 75.87 wt% Al 2 O 3 9.16 〃 14.28 〃 Fe 2 O 3 0.92 〃 2.14 〃 CaO 1.54 〃 1.32 〃 MgO 0.49 〃 0.30 〃 Na 2 O 3.35 〃 3.18 〃 K 2 O 1.95 〃 2.80 〃 Like this The total content of SiO 2 and Al 2 O 3 is about 92 mol%, and most of it is aluminosilicate, so
When we tried to produce glass using Y 2 O 3 concentrate, secondary Shirasu and Al 2 O 3 as raw materials, we found that in addition to these components, Fe 2 O 3 contained in the above secondary Shirasu, which is listed in the table above, CaO, MgO, Na2O ,
A glass containing about 5 moles or less of K 2 O in total can be obtained, and if this is used as a raw material, SiO 2 ,
It was found that the glass melting time could be reduced to about 1/3 compared to when Al 2 O 3 was used as the raw material. The present invention was completed based on these findings. The gist of the present invention is 30 to 53% by weight of secondary shirasu,
Al2O3 9 ~ 30% by weight , Y2O3 concentrate 23~
A method for producing rare earth-containing aluminosilicate glass is characterized by using 54% by weight as a raw material and heating and melting a mixture thereof to vitrify it. The Y 2 O 3 concentrate referred to in the present invention is an intermediate purified product obtained from Y 2 O 3 raw ore, such as xenotime, by a sulfuric acid decomposition method or an alkali decomposition method. In the alkaline decomposition method, xenotime is gradually added to molten caustic soda at 400°C. The reaction is exothermic and after the reaction is completed, it is cooled and the reactants are extracted with water to remove sodium phosphate and excess alkali. The obtained rare earth hydroxide is dissolved in a small amount of hydrochloric acid, oxalic acid is added to this solution to form a rare earth oxalate salt, and this is fired at 900°C to obtain a yttrium concentrate. An example of the analysis is as follows.
【表】
すなわち、鉱石中の成分元素のままで分離操作
を行わないで含有しているものである。
本発明のガラス原料において、二次シラスが30
重量％より少ないと溶融温度が高くなり、1550℃
ではガラス化できない。また、53重量％を超える
と希土類含有アルミノけい酸塩ガラスの特性が発
揮できなくなる。
Al2O3が９重量％より少ないとガラス化しな
く、30重量％を超えると溶融温度が高くなり、
1550℃ではガラスが得られない。
Y2O3コンセントレートが23重量％より少ない
と希土類酸化物含有ガラスとしての特性が発揮で
きず、また1550℃ではガラスが得られなく、54重
量％を超えると結晶化してしまいガラスが得られ
ない。
従つて、二次シラスは30〜53重量％、Al2O3は
９〜30重量％、Y2O3コンセントレートは23〜54
重量％の範囲の量であることが必要である。
前記の原料のほかに、必要に応じTiO2，13重
量％、およびまたはZrO29重量％を超えない量添
加してもよい。TiO2の添加は耐化学性、耐食性、
耐風化性を高める作用をするが、13重量％を超え
ると結晶化してしまいガラスが得られない。
ZrO2の添加は耐化学性、耐食性、耐風化性、機
械的性質、耐熱性を高める作用をするが９重量％
を超えると結晶化してしまいガラスが得られな
い。
以上のような原料は1550℃以下の温度で溶解し
ガラス化し、希土類含有アルミノけい酸塩ガラス
が得られる。
実施例 １
二次シラス51.93重量％、Al2O312.60重量％、
Y2O3コンセントレート35.47重量％の割合で混合
したものを白金るつぼに入れ、電気炉中で1500℃
で２時間加熱溶融した後にアルミニウム板上に流
し出し放冷した。明るい薄褐色の泡のない透明な
ガラスが得られた。
このガラスの熱膨張率は53.1×10-71／℃であ
り、一般の窓ガラスよりもはるかに低熱膨張率で
ある。そのために窓ガラスとして使用する際の耐
熱衝撃性は一般のソーダ石灰系のガラス（熱膨張
率は約90×10-71／℃）より高い。このガラスが
溶融した状態で炉外に白金るつぼを取り出し、手
引きによりガラス繊維化を行つたところ、数μm
〜数mmの各種太さで1m以上の長さのガラス繊維
を容易に得ることができた。密度は3.258g／cm3、
ビイカース硬度は860Kg／mmで、硬いガラスであ
る。
その化学組成は、原料割合から計算すると、
SiO239.40重量％、（以下％は重量）、Al2O320.02
％、Fe2O31.16％、CaO0.69％、MgO0.16％、
Na2O1.65％、K2O1.45％、イツトリウムコンセ
ントレート35.47％である。
実施例 ２
二次シラス36.08重量％、Al2O326.03重量％、
イツトリアコンセントレート37.89重量％の割合
で混合したものを白金るつぼに入れ、電気炉中で
1450℃で1.5時間、続いて電気炉の温度を1500℃
にあげ20分間加熱溶融した後、アルミニウム板上
に流し出し放冷した。明るい薄褐色の透明なガラ
スが得られた。このガラスの熱膨張率は53.0×
10-71／℃、密度は3.456g／cm3であつた。
実施例 ３
二次シラス40.28重量％、Al2O317.53重量％、
イツトリアコンセントレート42.19重量％の割合
で混合したものを白金るつぼに入れ、電気炉中で
1500℃で1.5時間加熱溶融した後、アルミニウム
板上に流し出し放冷した。明るい薄褐色の泡のな
い透明なガラスが得られた。このガラスの熱膨張
率は59.2×10-71／℃、密度は3.521g／cm3であつ
た。また、このガラスも実施例１と同様に容易に
繊維化することができた。
実施例 ４
二次シラス30.19重量％、Al2O318.26重量％、
イツトリアコンセントレート40.00重量％、
TiO211.55重量％の割合で混合したものを白金る
つぼに入れ、これを電気炉中で1550℃で1.5時間
加熱溶融した。この溶融物をアルミニウム板上に
流し出し放冷した。
赤味を帯びた茶褐色の泡のない透明なガラスが
得られた。このガラスの熱膨張率は56.0×
10-71／℃、密度は3.612g／cm3であつた。
実施例 ５
二次シラス35.12重量％、Al2O317.06重量％、
イツトリアコンセントレート39.11重量％、
ZrO28.71重量％の割合で混合したものを白金るつ
ぼに入れ、これを電気炉中で1550℃で1.5時間加
熱溶融した。この溶融物をアルミニウム板上に流
し出し放冷した。明るい薄褐色の泡のない透明な
ガラスが得られた。このガラスの熱膨張率は53.0
×10-71／℃、密度は3.621g／cm3であつた。
発明の効果
本発明の方法によると、二次シラス及びイツト
リアコンセントレートを使用するため、Y2O3を
含有するアルミノけい酸塩が安価に得られ、且つ
溶融温度も低いので一般の電気炉で溶融し得ら
れ、また加熱時間も短かくてすみ、得られるガラ
スはアルミノけい酸塩ガラスの特性をそのまま保
有する優れた効果を有する。また得られるガラス
は高弾性率を有し、耐アルカリ性が高いのでセメ
ントと複合して使用するこができる。そして、
Fe2O3とCeO2を含有するため紫外線吸収特性を
有し、紫外線吸収着色透明ガラスとしてサンルー
ムの窓、自動車用ルーフ窓、その他各種の理化学
用の紫外線吸収容器、窓材としても有効に使用し
得られる。[Table] In other words, it is the elemental element contained in the ore without any separation operation. In the glass raw material of the present invention, the secondary shirasu is 30
If it is less than % by weight, the melting temperature will be high, 1550℃
It cannot be vitrified. Moreover, if it exceeds 53% by weight, the characteristics of the rare earth-containing aluminosilicate glass cannot be exhibited. If Al 2 O 3 is less than 9% by weight, it will not vitrify, and if it exceeds 30% by weight, the melting temperature will be high.
Glass cannot be obtained at 1550℃. If the Y 2 O 3 concentrate is less than 23% by weight, the properties of the glass containing rare earth oxides cannot be exhibited, and at 1550°C, glass cannot be obtained, and if it exceeds 54% by weight, it will crystallize and no glass will be obtained. do not have. Therefore, secondary Shirasu is 30-53% by weight, Al2O3 is 9-30% by weight, Y2O3 concentrate is 23-54% by weight .
It is necessary that the amount be in the range of % by weight. In addition to the above-mentioned raw materials, if necessary, TiO 2 may be added in an amount not exceeding 13% by weight and/or ZrO 2 in an amount not exceeding 9% by weight. Addition of TiO2 improves chemical resistance, corrosion resistance,
It has the effect of increasing weathering resistance, but if it exceeds 13% by weight, it will crystallize and glass will not be obtained.
The addition of ZrO 2 has the effect of increasing chemical resistance, corrosion resistance, weathering resistance, mechanical properties, and heat resistance, but it is 9% by weight.
If it exceeds this amount, crystallization will occur and glass will not be obtained. The raw materials described above are melted and vitrified at a temperature of 1550°C or lower to obtain rare earth-containing aluminosilicate glass. Example 1 Secondary shirasu 51.93% by weight, Al 2 O 3 12.60% by weight,
A mixture of Y2O3 concentrate at a ratio of 35.47% by weight was placed in a platinum crucible and heated to 1500℃ in an electric furnace .
After heating and melting the mixture for 2 hours, it was poured onto an aluminum plate and allowed to cool. A light brown, bubble-free, transparent glass was obtained. The coefficient of thermal expansion of this glass is 53.1×10 -7 1/°C, which is much lower than that of ordinary window glass. Therefore, when used as window glass, its thermal shock resistance is higher than that of ordinary soda-lime glass (its thermal expansion coefficient is approximately 90×10 -7 1/°C). When this glass was molten, the platinum crucible was taken out of the furnace, and when it was made into glass fiber by hand, it turned out to be several μm thick.
It was possible to easily obtain glass fibers of various thicknesses up to several mm and lengths of over 1 m. Density is 3.258g/cm 3 ,
It is a hard glass with a beaker hardness of 860Kg/mm. Its chemical composition is calculated from the proportion of raw materials.
SiO 2 39.40% by weight, (% is weight below), Al 2 O 3 20.02
%, Fe 2 O 3 1.16%, CaO 0.69%, MgO 0.16%,
Na 2 O 1.65%, K 2 O 1.45%, yttrium concentrate 35.47%. Example 2 Secondary shirasu 36.08% by weight, Al 2 O 3 26.03% by weight,
A mixture of Ittria concentrate at a ratio of 37.89% by weight was placed in a platinum crucible and placed in an electric furnace.
1450℃ for 1.5 hours, followed by electric furnace temperature 1500℃
After heating and melting the mixture for 20 minutes, it was poured out onto an aluminum plate and left to cool. A light brown transparent glass was obtained. The coefficient of thermal expansion of this glass is 53.0×
10 -7 1/°C, and the density was 3.456 g/cm 3 . Example 3 Secondary shirasu 40.28% by weight, Al 2 O 3 17.53% by weight,
A mixture of Ittria concentrate at a ratio of 42.19% by weight was placed in a platinum crucible and placed in an electric furnace.
After heating and melting at 1500°C for 1.5 hours, it was poured onto an aluminum plate and allowed to cool. A light brown, bubble-free, transparent glass was obtained. This glass had a coefficient of thermal expansion of 59.2×10 −7 1/° C. and a density of 3.521 g/cm 3 . Further, this glass could also be easily made into fibers as in Example 1. Example 4 Secondary shirasu 30.19% by weight, Al 2 O 3 18.26% by weight,
Ittria Concentrate 40.00% by weight,
A mixture of 11.55% by weight of TiO 2 was placed in a platinum crucible, and this was heated and melted at 1550° C. for 1.5 hours in an electric furnace. This melt was poured onto an aluminum plate and allowed to cool. A clear, bubble-free glass with a reddish brown color was obtained. The coefficient of thermal expansion of this glass is 56.0×
10 -7 1/°C, and the density was 3.612 g/cm 3 . Example 5 Secondary shirasu 35.12% by weight, Al 2 O 3 17.06% by weight,
Ittria Concentrate 39.11% by weight,
A mixture of 8.71% by weight of ZrO 2 was placed in a platinum crucible and melted by heating at 1550° C. for 1.5 hours in an electric furnace. This melt was poured onto an aluminum plate and allowed to cool. A light brown, bubble-free, transparent glass was obtained. The coefficient of thermal expansion of this glass is 53.0
×10 -7 1/°C, and the density was 3.621 g/cm 3 . Effects of the Invention According to the method of the present invention, since secondary shirasu and ittria concentrate are used, aluminosilicate containing Y 2 O 3 can be obtained at low cost, and the melting temperature is low, so it can be used in a general electric furnace. Furthermore, the heating time is short, and the resulting glass has the excellent effect of retaining the properties of aluminosilicate glass. Furthermore, the resulting glass has a high modulus of elasticity and high alkali resistance, so it can be used in combination with cement. and,
Because it contains Fe 2 O 3 and CeO 2 , it has ultraviolet absorbing properties, and as ultraviolet absorbing colored transparent glass, it is effective as sunroom windows, automobile roof windows, and various other types of physical and chemical ultraviolet absorbing containers and window materials. can be used and obtained.
Claims (1)
％、Y2O3コンセントレート23〜54重量％を原料
とし、これらの混合物を加熱溶融してガラス化す
ることを特徴とする希土類含有アルミノけい酸塩
ガラスの製造法。 ２ 二次シラス30〜53重量％、Al2O39〜30重量
％、Y2O3コンセントレート23〜54重量％のほか、
更にTiO213重量％または及びZrO29重量％を超え
ない量添加し、これを加熱溶融してガラス化する
ことを特徴とする希土類含有アルミノけい酸塩ガ
ラスの製造法。[Claims] 1. 30 to 53% by weight of secondary shirasu, 9 to 30% by weight of Al 2 O 3 and 23 to 54% by weight of Y 2 O 3 concentrate are used as raw materials, and a mixture of these is heated and melted to produce glass. A method for producing a rare earth-containing aluminosilicate glass characterized by the following: 2 Secondary Shirasu 30-53% by weight, Al 2 O 3 9-30% by weight, Y 2 O 3 concentrate 23-54% by weight, as well as
A method for producing rare earth-containing aluminosilicate glass, which further comprises adding TiO 2 in an amount not exceeding 13% by weight or ZrO 2 in an amount not exceeding 9% by weight, and heating and melting this to vitrify it.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP60023979A JPS623041A (en) | 1985-02-09 | 1985-02-09 | Production of aluminosilicate glass containing rare earth metal |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP60023979A JPS623041A (en) | 1985-02-09 | 1985-02-09 | Production of aluminosilicate glass containing rare earth metal |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS623041A JPS623041A (en) | 1987-01-09 |
| JPH0210777B2 true JPH0210777B2 (en) | 1990-03-09 |
Family
ID=12125674
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP60023979A Granted JPS623041A (en) | 1985-02-09 | 1985-02-09 | Production of aluminosilicate glass containing rare earth metal |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS623041A (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4515255B2 (en) * | 2001-08-02 | 2010-07-28 | スリーエム イノベイティブ プロパティズ カンパニー | Al2O3-Y2O3-ZrO2 material |
| JP5148807B2 (en) * | 2001-08-02 | 2013-02-20 | スリーエム イノベイティブ プロパティズ カンパニー | Al2O3-rare earth oxide-ZrO2 / HfO2 material and method for producing and using the same |
| US7179526B2 (en) * | 2002-08-02 | 2007-02-20 | 3M Innovative Properties Company | Plasma spraying |
-
1985
- 1985-02-09 JP JP60023979A patent/JPS623041A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS623041A (en) | 1987-01-09 |
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