JP3996017B2 - Glass member in contact with hydrofluoric acid of cleaning apparatus using hydrofluoric acid - Google Patents
Glass member in contact with hydrofluoric acid of cleaning apparatus using hydrofluoric acid Download PDFInfo
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- JP3996017B2 JP3996017B2 JP2002241266A JP2002241266A JP3996017B2 JP 3996017 B2 JP3996017 B2 JP 3996017B2 JP 2002241266 A JP2002241266 A JP 2002241266A JP 2002241266 A JP2002241266 A JP 2002241266A JP 3996017 B2 JP3996017 B2 JP 3996017B2
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- hydrofluoric acid
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Classifications
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- 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
- C03C3/12—Silica-free oxide glass compositions
- C03C3/16—Silica-free oxide glass compositions containing phosphorus
- C03C3/17—Silica-free oxide glass compositions containing phosphorus containing aluminium or beryllium
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- 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
- C03C27/00—Joining pieces of glass to pieces of other inorganic material; Joining glass to glass other than by fusing
-
- 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
- C03C4/00—Compositions for glass with special properties
- C03C4/20—Compositions for glass with special properties for chemical resistant glass
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- Organic Chemistry (AREA)
- Ceramic Engineering (AREA)
- Glass Compositions (AREA)
Description
【０００１】
【発明の属する技術分野】
本発明は、フッ酸（フッ化水素酸）に侵されにくいガラス部材で、特にフッ酸を用いる洗浄装置のフッ酸と接触する部分に用いるものに関する。
【０００２】
【従来の技術】
近年フッ素工業の進歩につれて耐フッ酸性のガラスが必要とされている。また、半導体やガラス基板の洗浄にはフッ酸が使用されるため、洗浄装置のフッ酸と接触する部材として耐フッ酸性のガラスの用途がある。また、実験用の容器、分光光度計のサファイアセルの接着剤としても、耐フッ酸性ガラスが必要とされる。
【０００３】
従来の耐フッ酸性のガラスとしては、Ｐ２Ｏ５が６２．８８mol％、Ａｌ２Ｏ３が２１．８８mol％、ＺｎＯが１５．２３mol％の組成からなるものが知られている。
【０００４】
【発明が解決しようとする課題】
従来の耐フッ酸性ガラスは、耐フッ酸性が不十分で、フッ酸と接触する部材として用いた場合、浸食されるのが早く、早期に交換しなければならなかった。本発明は、従来の耐フッ酸性ガラスよりも耐フッ酸性を格段に向上させることを課題としてなされたものである。
【０００５】
【課題を解決するための手段】
本発明は、Ｐ２Ｏ５を５５〜７０mol％、Ａｌ２Ｏ３を５〜１５mol％、ＺｎＯを２０〜３５mol％含有することを特徴とするフッ酸を用いる洗浄装置のフッ酸と接触するガラス部材である。すなわち、従来知られている耐フッ酸性ガラスに対して、Ａｌ２Ｏ３の割合を減らしてＺｎＯの割合を増やすことで、耐フッ酸性が著しく向上することを発見したのである。Ｐ２Ｏ５は５５mol％よりも少ないと耐フッ酸性が悪くなり、７０mol％よりも多いと耐水性が悪くなる。Ａｌ２Ｏ３は５mol％よりも少ないと耐水性が悪くなり、１５mol％よりも多いと耐フッ酸性が悪くなる。ＺｎＯは２０mol％よりも少ないと耐フッ酸性が悪くなり、３５mol％よりも多いと耐水性が悪くなる。
【０００６】
また本発明は、Ｐ２Ｏ５を５５〜７０mol％、Ａｌ２Ｏ３を５〜１５mol％、ＺｎＯを１５〜２５mol％、ＳｒＯ、Ｌｉ２Ｏ又はＮａ２Ｏを０．５〜１２mol％含有することを特徴とするフッ酸を用いる洗浄装置のフッ酸と接触するガラス部材である。これは、請求項１のガラス組成に対して、ＺｎＯをやや減らすかわりにＳｒＯ、Ｌｉ２Ｏ又はＮａ２Ｏを添加したものである。これによって、熱膨張係数を大きくし、屈服点を低くすることができる。ガラスを接着剤として用いる場合は被接着物の熱膨張率に近くするために熱膨張係数を調整する必要があり、また屈服点は６００℃以下とすることが望ましいが、ＳｒＯ、Ｌｉ２Ｏ又はＮａ２Ｏを適宜量添加することで、熱膨張係数を調整し、屈服点を低下することが可能となる。
【０００７】
【発明の実施の形態】
ガラス原料として関東化学株式会社製のリン酸（特級）、リン酸アルミニウム（鹿１級）及びリン酸亜鉛四水和物（鹿１級）を使用し、ガラス原料調合後、１００℃で２時間以上乾燥させた後、電気炉で１３５０〜１４５０℃の温度で１時間溶融し、徐冷して次の実施例１〜４及び比較例のガラスを作成した。実施例１から実施例４にかけては次第にＡｌ２Ｏ３の割合を減少させてＺｎＯの割合を増加させている。比較例は従来知られている耐フッ酸性ガラスである。
実施例１： Ｐ２Ｏ５＝６２．８８mol％、Ａｌ２Ｏ３＝１８．５０mol％、ＺｎＯ＝１８．６２mol％
実施例２： Ｐ２Ｏ５＝６２．８８mol％、Ａｌ２Ｏ３＝１５．００mol％、ＺｎＯ＝２２．１２mol％
実施例３： Ｐ２Ｏ５＝６２．８８mol％、Ａｌ２Ｏ３＝１０．００mol％、ＺｎＯ＝２７．１２mol％
実施例４： Ｐ２Ｏ５＝６２．８８mol％、Ａｌ２Ｏ３＝５．００mol％、ＺｎＯ＝３２．１２mol％
比較例１： Ｐ２Ｏ５＝６２．８８mol％、Ａｌ２Ｏ３＝２１．８８mol％、ＺｎＯ＝１５．２３mol％
【０００８】
各実施例及び比較例について耐フッ酸性試験、実施例３、４及び比較例１について耐水性試験を行った。
耐フッ酸性試験は次のように行った。粉砕して３００〜５００μｍに粒度調整した試料のガラス１ｇに４６％フッ酸溶液２５ｍｌを加え、常温で１時間３６〜４０ｒｐｍの往復運動を与え、その後濾過、水洗、乾燥したガラスの重量を測定し、ガラス重量減少率を求めた。
耐水性試験は次のように行った。粉砕して３００〜５００μｍに粒度調整した試料のガラス１ｇに蒸留水５０ｍｌを加え、煮沸状態で１時間３６〜４０ｒｐｍの往復運動を与え、その後濾過、水洗、乾燥したガラスの重量を測定し、ガラス重量減少率を求めた。
耐フッ酸性試験及び耐水性試験の結果を表１に示す。
【表１】
表１から明らかなように、実施例はいずれも比較例に比べて格段に耐フッ酸性に優れたものとなっているが、実施例３が最もよい結果を示し、比較例１に比べて７倍以上の耐フッ酸性の向上が見られる。また、実施例３が耐水性が高いことから、実施例１、２もほぼ同じ耐水性を有するものと推定できる。実施例４はやや耐水性が悪くなっている。
【００１０】
次に、最も結果のよかった実施例３の組成で、Ａｌ２Ｏ３の割合を固定とし、Ｐ２Ｏ５の割合を減少させると共にＺｎＯの割合を増加させるような実施例５及び比較例２を作成し、耐フッ酸性の試験を行った。実施例５、比較例２の組成は次の通りとした。
実施例５： Ｐ２Ｏ５＝５５．００mol％、Ａｌ２Ｏ３＝１０．０mol％、ＺｎＯ＝３５．００mol％
比較例２： Ｐ２Ｏ５＝５０．００mol％、Ａｌ２Ｏ３＝１０．０mol％、ＺｎＯ＝４０．００mol％
【００１１】
ここでの耐フッ酸性試験は常温で３時間３６〜４０ｒｐｍの往復運動を与えた以外（前記の試験では１時間）は、前記の耐フッ酸性試験と同じである。結果は以下の通りである。
実施例５： ガラス重量減少率＝１８％
比較例２： ガラス重量減少率＝８７％
Ｐ２Ｏ５の割合が５５mol％よりも少なくなると、耐フッ酸性は急激に悪化することがわかる。
【００１２】
次に、最も結果のよかった実施例３の組成で、Ｐ２Ｏ５及びＡｌ２Ｏ３の割合を固定とし、ＺｎＯの割合を減少させると共にＳｒＯ、Ｌｉ２Ｏ又はＮａ２Ｏを添加した実施例６〜１０を作成した。その組成は次の通りである。
実施例６： Ｐ２Ｏ５＝６２．８８mol％、Ａｌ２Ｏ３＝１０．００mol％、ＺｎＯ＝２２．１２mol％、ＳｒＯ＝５％
実施例７： Ｐ２Ｏ５＝６２．８８mol％、Ａｌ２Ｏ３＝１０．００mol％、ＺｎＯ＝１７．１２mol％、ＳｒＯ＝１０％
実施例８：Ｐ２Ｏ５＝６２．８８mol％、Ａｌ２Ｏ３＝１０．００mol％、ＺｎＯ＝１５．６２mol％、ＳｒＯ＝１１．５％
実施例９： Ｐ２Ｏ５＝６２．８８mol％、Ａｌ２Ｏ３＝１０．００mol％、ＺｎＯ＝１７．１２mol％、Ｌｉ２Ｏ＝１０％
実施例１０： Ｐ２Ｏ５＝６２．８８mol％、Ａｌ２Ｏ３＝１０．００mol％、ＺｎＯ＝１７．１２mol％、Ｎａ２Ｏ＝１０％
【００１３】
実施例３、６〜１０について耐フッ酸性試験（３時間）、熱膨張係数測定、屈服点測定を行った。その結果を表２に示す。
【表２】
表２に示されるように、ＳｒＯの添加量を増やしていくと、熱膨張係数は次第に大きくなり、屈服点は次第に低くなるが、耐フッ酸性は悪化する。また、添加量が０．５mol％未満では添加効果は小さい。したがって、添加量は０．５〜１２mol％程度が好ましい。Ｌｉ２Ｏ又はＮａ２Ｏのようなアルカリ成分を添加したときも、熱膨張係数は大きくなり、屈服点は低くなる。このように、ＳｒＯ、Ｌｉ２Ｏ又はＮａ２Ｏを適宜量添加することで、熱膨張係数及び屈服点を調整することができる。サファイアの接着剤として用いる場合には、サファイアの熱膨張係数が８３．３であるので、これに近い実施例８が適当である。
【００１５】
【発明の効果】
本発明の耐フッ酸性ガラスは、従来の耐フッ酸性ガラスに比べて格段の耐フッ酸性能を有するので、フッ酸を用いる洗浄装置のフッ酸と接触するガラス部材として用いた場合、浸食されにくく耐久性が格段に向上する。また、ＳｒＯやＬｉ２Ｏ、Ｎａ２Ｏのようなアルカリ成分を添加することで、熱膨張係数と屈服点を調整できるので、特に接着剤として用いる場合に所望の熱膨張係数や屈服点を有する耐フッ酸性ガラスを得ることができる。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a glass member that is not easily attacked by hydrofluoric acid (hydrofluoric acid) , and particularly to a glass member that is used for a portion that comes into contact with hydrofluoric acid in a cleaning apparatus using hydrofluoric acid .
[0002]
[Prior art]
In recent years, with the progress of the fluorine industry, hydrofluoric acid resistant glass is required. Further, since hydrofluoric acid is used for cleaning semiconductors and glass substrates, there is a use of hydrofluoric acid resistant glass as a member that comes into contact with hydrofluoric acid in a cleaning apparatus. Further, hydrofluoric acid resistant glass is also required as an adhesive for experimental containers and sapphire cells of spectrophotometers.
[0003]
As a conventional hydrofluoric acid resistant glass, a glass having a composition of 62.88 mol% P 2 O 5 , 21.88 mol% Al 2 O 3 and 15.23 mol% ZnO is known.
[0004]
[Problems to be solved by the invention]
Conventional hydrofluoric acid resistant glass has insufficient hydrofluoric acid resistance, and when used as a member in contact with hydrofluoric acid, it was eroded quickly and had to be replaced early. An object of the present invention is to significantly improve hydrofluoric acid resistance over conventional hydrofluoric acid resistant glass.
[0005]
[Means for Solving the Problems]
The present invention is a glass which contacts the P 2 O 5 55~70mol%, Al 2 O 3 of 5 to 15 mol%, and hydrofluoric acid cleaning apparatus using hydrofluoric acid, characterized in that the ZnO containing 20～35Mol% It is a member . That is, it has been found that the hydrofluoric acid resistance is remarkably improved by decreasing the Al 2 O 3 ratio and increasing the ZnO ratio with respect to the conventionally known hydrofluoric acid resistant glass. When P 2 O 5 is less than 55 mol%, the hydrofluoric acid resistance is deteriorated, and when it is more than 70 mol%, the water resistance is deteriorated. When Al 2 O 3 is less than 5 mol%, the water resistance is deteriorated, and when it is more than 15 mol%, the hydrofluoric acid resistance is deteriorated. When ZnO is less than 20 mol%, the hydrofluoric acid resistance is deteriorated, and when it is more than 35 mol%, the water resistance is deteriorated.
[0006]
The present invention, P 2 O 5 to 55~70mol%, Al 2 O 3 of 5 to 15 mol%, 15 to 25% of ZnO, SrO, containing 0.5～12Mol% of Li 2 O or Na 2 O It is a glass member which contacts the hydrofluoric acid of the washing | cleaning apparatus using the hydrofluoric acid characterized by the above-mentioned. This is obtained by adding SrO, Li 2 O or Na 2 O to the glass composition of claim 1 instead of slightly reducing ZnO. As a result, the thermal expansion coefficient can be increased and the yield point can be lowered. When glass is used as an adhesive, it is necessary to adjust the coefficient of thermal expansion in order to approximate the coefficient of thermal expansion of the adherend, and the yield point is preferably 600 ° C. or lower, but SrO, Li 2 O or By adding an appropriate amount of Na 2 O, the coefficient of thermal expansion can be adjusted and the yield point can be lowered.
[0007]
DETAILED DESCRIPTION OF THE INVENTION
Use phosphoric acid (special grade), aluminum phosphate (deer grade 1) and zinc phosphate tetrahydrate (deer grade 1) manufactured by Kanto Chemical Co., Ltd. as glass raw materials. After drying as described above, the glass was melted in an electric furnace at a temperature of 1350 to 1450 ° C. for 1 hour and slowly cooled to prepare the glasses of the following Examples 1 to 4 and Comparative Example. From Example 1 to Example 4, the proportion of Al 2 O 3 is gradually decreased to increase the proportion of ZnO. The comparative example is a conventionally known hydrofluoric acid resistant glass.
Example 1: P 2 O 5 = 62.88mol %, Al 2 O 3 = 18.50mol%, ZnO = 18.62mol%
Example 2: P 2 O 5 = 62.88mol %, Al 2 O 3 = 15.00mol%, ZnO = 22.12mol%
Example 3: P 2 O 5 = 62.88mol %, Al 2 O 3 = 10.00mol%, ZnO = 27.12mol%
Example 4: P 2 O 5 = 62.88mol %, Al 2 O 3 = 5.00mol%, ZnO = 32.12mol%
Comparative Example 1: P 2 O 5 = 62.88 mol%, Al 2 O 3 = 21.88 mol%, ZnO = 15.23 mol%
[0008]
A hydrofluoric acid resistance test was performed for each of the examples and comparative examples, and a water resistance test was performed for examples 3, 4 and comparative example 1.
The hydrofluoric acid resistance test was conducted as follows. To 1 g of a glass sample that has been pulverized and adjusted to a particle size of 300 to 500 μm, 25 ml of a 46% hydrofluoric acid solution is added, and a reciprocating motion of 36 to 40 rpm is given for 1 hour at room temperature. The glass weight reduction rate was determined.
The water resistance test was conducted as follows. Distilled water (50 ml) is added to 1 g of a glass sample that has been pulverized and adjusted to a particle size of 300 to 500 μm, and a reciprocating motion of 36 to 40 rpm is given for 1 hour in a boiled state. The weight loss rate was determined.
The results of the hydrofluoric acid resistance test and the water resistance test are shown in Table 1.
[Table 1]
As is clear from Table 1, all of the examples were much more excellent in hydrofluoric acid resistance than the comparative examples, but Example 3 showed the best results, and 7 Examples compared with Comparative Example 1. The hydrofluoric acid resistance is improved by a factor of 2 or more. Moreover, since Example 3 has high water resistance, it can be estimated that Examples 1 and 2 also have substantially the same water resistance. In Example 4, the water resistance is slightly deteriorated.
[0010]
Next, Example 5 and Comparative Example 2 in which the ratio of Al 2 O 3 is fixed, the ratio of P 2 O 5 is decreased, and the ratio of ZnO is increased with the composition of Example 3 which has the best results. Prepared and tested for resistance to hydrofluoric acid. The compositions of Example 5 and Comparative Example 2 were as follows.
Example 5: P 2 O 5 = 55.00 mol%, Al 2 O 3 = 10.0 mol%, ZnO = 35.00 mol%
Comparative Example 2: P 2 O 5 = 50.00 mol%, Al 2 O 3 = 10.0 mol%, ZnO = 40.00 mol%
[0011]
The hydrofluoric acid resistance test here is the same as the hydrofluoric acid resistance test except that a reciprocating motion of 36 to 40 rpm is given for 3 hours at room temperature (1 hour in the above test). The results are as follows.
Example 5: Glass weight reduction rate = 18%
Comparative Example 2: Glass weight reduction rate = 87%
It can be seen that when the proportion of P 2 O 5 is less than 55 mol%, the hydrofluoric acid resistance deteriorates rapidly.
[0012]
Next, in the composition of Example 3 that gave the best results, the ratio of P 2 O 5 and Al 2 O 3 was fixed, the ratio of ZnO was decreased, and SrO, Li 2 O, or Na 2 O was added. 6-10 were created. Its composition is as follows.
Example 6: P 2 O 5 = 62.88 mol%, Al 2 O 3 = 10.00 mol%, ZnO = 22.22 mol%, SrO = 5%
Example 7: P 2 O 5 = 62.88 mol%, Al 2 O 3 = 10.00 mol%, ZnO = 17.12 mol%, SrO = 10%
Example 8: P 2 O 5 = 62.88 mol%, Al 2 O 3 = 10.00 mol%, ZnO = 15.62 mol%, SrO = 11.5%
Example 9: P 2 O 5 = 62.88 mol%, Al 2 O 3 = 10.00 mol%, ZnO = 17.12 mol%, Li 2 O = 10%
Example 10: P 2 O 5 = 62.88 mol%, Al 2 O 3 = 10.00 mol%, ZnO = 17.12 mol%, Na 2 O = 10%
[0013]
Examples 3 and 6 to 10 were subjected to a hydrofluoric acid resistance test (3 hours), a thermal expansion coefficient measurement, and a yield point measurement. The results are shown in Table 2.
[Table 2]
As shown in Table 2, as the amount of SrO added is increased, the thermal expansion coefficient gradually increases and the yield point gradually decreases, but the hydrofluoric acid resistance deteriorates. Further, when the addition amount is less than 0.5 mol%, the addition effect is small. Therefore, the addition amount is preferably about 0.5 to 12 mol%. Also when an alkali component such as Li 2 O or Na 2 O is added, the coefficient of thermal expansion increases and the yield point decreases. Thus, the thermal expansion coefficient and yield point can be adjusted by adding an appropriate amount of SrO, Li 2 O or Na 2 O. When used as an adhesive for sapphire, the thermal expansion coefficient of sapphire is 83.3, so Example 8 close to this is appropriate.
[0015]
【The invention's effect】
Hydrofluoric acid resistance glass of the present invention has a remarkable resistance to hydrofluoric acid performance compared to conventional hydrofluoric acid resistance glass, if used as the glass member contacting the hydrofluoric acid cleaning apparatus using hydrofluoric acid, less likely to be eroded Durability is greatly improved. Moreover, since the thermal expansion coefficient and the yield point can be adjusted by adding an alkaline component such as SrO, Li 2 O, or Na 2 O, the desired thermal expansion coefficient or yield point is obtained particularly when used as an adhesive. A hydrofluoric acid resistant glass can be obtained.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2002241266A JP3996017B2 (en) | 2002-08-22 | 2002-08-22 | Glass member in contact with hydrofluoric acid of cleaning apparatus using hydrofluoric acid |
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| JP2002241266A JP3996017B2 (en) | 2002-08-22 | 2002-08-22 | Glass member in contact with hydrofluoric acid of cleaning apparatus using hydrofluoric acid |
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|---|---|
| JP2004075491A JP2004075491A (en) | 2004-03-11 |
| JP3996017B2 true JP3996017B2 (en) | 2007-10-24 |
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| JP6811657B2 (en) * | 2017-03-15 | 2021-01-13 | 石塚硝子株式会社 | Manufacturing method of zinc-containing oxide glass |
| US20220363595A1 (en) * | 2019-12-26 | 2022-11-17 | Hitachi Metals, Ltd. | Metallic laminate shaped flow path member and method of manufacturing the same |
| CN114634309B (en) * | 2022-03-09 | 2023-05-12 | 中国科学院上海光学精密机械研究所 | Hydrofluoric acid corrosion resistant glass and preparation method thereof |
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| JPS5438311A (en) * | 1977-08-31 | 1979-03-22 | Hoya Glass Works Ltd | Low temperature melting coating glass capable of highly absorbing laser |
| JPS62212244A (en) * | 1986-03-13 | 1987-09-18 | Asahi Glass Co Ltd | Phosphate glass having high water-resistance |
| JP2871163B2 (en) * | 1991-04-26 | 1999-03-17 | 日本板硝子株式会社 | Alkali-free glass |
| JPH0834635A (en) * | 1994-07-27 | 1996-02-06 | Hoya Corp | Fused glass for microchannel plate |
| JP2001180972A (en) * | 1999-12-27 | 2001-07-03 | Asahi Glass Co Ltd | Lead free glass with low melting point |
| JP4418086B2 (en) * | 2000-06-02 | 2010-02-17 | 東洋ガラス株式会社 | Water treatment agent consisting of glass that slowly elutes phosphate ions in water |
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