JP3063760B2 - Li2O-Al2O3-SiO2-based transparent crystallized glass and crystalline glass - Google Patents
Li2O-Al2O3-SiO2-based transparent crystallized glass and crystalline glassInfo
- Publication number
- JP3063760B2 JP3063760B2 JP11149426A JP14942699A JP3063760B2 JP 3063760 B2 JP3063760 B2 JP 3063760B2 JP 11149426 A JP11149426 A JP 11149426A JP 14942699 A JP14942699 A JP 14942699A JP 3063760 B2 JP3063760 B2 JP 3063760B2
- Authority
- JP
- Japan
- Prior art keywords
- glass
- sio
- crystallized glass
- transparent crystallized
- sample
- 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 - Fee Related
Links
Landscapes
- Glass Compositions (AREA)
Description
【０００１】[0001]
【発明の属する技術分野】本発明は石油、石炭、ガス、
木材等の燃焼装置、すなわち暖房器具や加熱炉、徐冷炉
等の前面窓或いは覗き窓に用いる透明結晶化ガラスに関
するものである。The present invention relates to oil, coal, gas,
The present invention relates to a transparent crystallized glass used for a combustion device for wood or the like, that is, a front window or a viewing window of a heating appliance, a heating furnace, an annealing furnace, or the like.
【０００２】[0002]
【従来の技術】暖房器具等における前面窓の機能は、内
部の炎から発する熱線を外部へ透過させて暖房効果をあ
げると共に炎が目に見えるようにすることによって視覚
的な暖かさを増すことである。また、覗き窓の機能は外
部から炎の燃焼状態を観察するのを可能にすることであ
り、これらの窓は炎の発する高温や着火時の熱衝撃に耐
えねばならない。従って、燃焼装置の窓に使用する窓ガ
ラス材料は透明であると同時に低熱膨張、高強度で耐熱
性、耐熱衝撃性に優れていることが必要である。2. Description of the Related Art The function of a front window in a heater or the like is to increase the heating effect by transmitting heat rays emitted from an internal flame to the outside and increase the visual warmth by making the flame visible. It is. Also, the function of the viewing window is to enable the external observation of the burning state of the flame, and these windows must withstand the high temperature of the flame and the thermal shock at the time of ignition. Therefore, it is necessary that the window glass material used for the window of the combustion device be transparent, have low thermal expansion, high strength, and have excellent heat resistance and thermal shock resistance.
【０００３】現在、暖房器具等の窓に使われている材料
としてはホウケイ酸ガラス、石英ガラスおよびＬｉ2 Ｏ
−Ａｌ2 Ｏ3 −ＳｉＯ2 系透明結晶化ガラスがあるが、
ホウケイ酸ガラスは耐熱性、耐熱衝撃性が十分とは言え
ず、石英ガラスは熱的性質は優れているが高価である。
これに対してＬｉ2 Ｏ−Ａｌ2 Ｏ3 −ＳｉＯ2 系透明結
晶化ガラスは熱膨張係数が小さく強度が高いため、耐熱
性および耐熱衝撃性に優れており、また比較的安価に製
造することが可能であるため広く用いられている。At present, borosilicate glass, quartz glass and Li 2 O are used as materials for windows of heaters and the like.
-Al 2 O 3 -SiO 2 transparent crystallized glass,
Borosilicate glass cannot be said to have sufficient heat resistance and thermal shock resistance, and quartz glass has excellent thermal properties but is expensive.
On the other hand, since the Li 2 O—Al 2 O 3 —SiO 2 transparent crystallized glass has a small coefficient of thermal expansion and a high strength, it has excellent heat resistance and thermal shock resistance, and must be manufactured at a relatively low cost. Is widely used because it is possible.
【０００４】[0004]
【発明が解決しようとする課題】しかしながら、Ｌｉ2
Ｏ−Ａｌ2 Ｏ3 −ＳｉＯ2 系透明結晶化ガラスは、燃焼
雰囲気に置かれると窓の内表面、すなわち燃焼側の表面
に化学的腐食を受けて微細なクラックが発生し、透明性
や強度が著しく低下するという問題がある。SUMMARY OF THE INVENTION However, Li 2
O-Al 2 O 3 -SiO 2 based transparent crystallized glass, the inner surface of the window when placed in a combustion atmosphere, i.e. fine cracks undergoes chemical corrosion on the surface of the combustion side occurs and transparency and strength Is significantly reduced.
【０００５】上記の問題が生じる原因は以下の通りであ
る。石油、石炭、ガス、木材等の燃焼装置の燃焼雰囲気
には、燃料中の硫黄分から生じたＳＯｘが存在し、燃焼
によって生じたＨ2 Ｏと反応してＨ2 ＳＯ4 を生成す
る。このＨ2 ＳＯ4 から生じる水素イオンがＬｉ2 Ｏ−
Ａｌ2 Ｏ3 −ＳｉＯ2 系透明結晶化ガラスの結晶中のリ
チウムイオンとイオン交換反応を起こし、結晶の体積を
収縮させ、クラックを発生させる。The causes of the above problems are as follows. Oil, coal, gas, in the combustion atmosphere of the combustion apparatus, such as wood, there are SOx resulting from sulfur in the fuel, reacts with H 2 O produced by combustion to produce a H 2 SO 4. The hydrogen ions generated from this H 2 SO 4 are converted into Li 2 O—
It causes an ion exchange reaction with lithium ions in the crystal of the Al 2 O 3 —SiO 2 transparent crystallized glass, thereby reducing the volume of the crystal and generating cracks.
【０００６】上記の問題を防止するために、Ｌｉ2 Ｏ−
Ａｌ2 Ｏ3 −ＳｉＯ2 系透明結晶化ガラスの表面にＳｉ
Ｏ2 等の被膜を設ける方法が実施されているが、製造コ
ストが高くなるため好ましくない。また、Ｌｉ2 Ｏ−Ａ
ｌ2 Ｏ3 −ＳｉＯ2 系透明結晶化ガラス中のリチウムイ
オンの含有量を低くして、水素イオンとのイオン交換反
応が起こりにくくすることも可能であるが、透明性が悪
化したり熱膨張係数が大きくなるという問題が生じる。In order to prevent the above problem, Li 2 O—
Al 2 O 3 -SiO 2 -based transparent crystallized glass
Although a method of providing a coating such as O 2 has been practiced, it is not preferable because the manufacturing cost increases. In addition, Li 2 O-A
Although the content of lithium ions in the l 2 O 3 —SiO 2 -based transparent crystallized glass can be reduced so that an ion exchange reaction with hydrogen ions does not easily occur, transparency deteriorates or thermal expansion occurs. There is a problem that the coefficient becomes large.
【０００７】本発明の目的は、石油、石炭、ガス、木材
等の燃料によって発生するＨ2 ＳＯ 4 を含む雰囲気に長
時間曝されても、微細なクラックを生じないＬｉ2 Ｏ−
Ａｌ 2 Ｏ3 −ＳｉＯ2 系透明結晶化ガラスと、このよう
な結晶化ガラスを得るための結晶性ガラスを提供するこ
とである。An object of the present invention is to provide oil, coal, gas, and wood.
Generated by fuels such asTwo SO Four Including long atmosphere
Li that does not generate fine cracks even if exposed to timeTwo O-
Al Two OThree -SiOTwo System transparent crystallized glass and
To provide crystalline glass for obtaining a highly crystallized glass.
And
【０００８】[0008]
【課題を解決するための手段】本発明者等は、種々の実
験を行った結果、Ｌｉ2 Ｏ−Ａｌ2 Ｏ3 −ＳｉＯ2 系透
明結晶化ガラス中のβ−ＯＨが、水素イオンとのイオン
交換反応による微細クラックの発生を抑制するのに重要
な役割を果たすことを見いだし、本発明として提案する
ものである。As a result of various experiments, the present inventors have found that β-OH in Li 2 O—Al 2 O 3 —SiO 2 -based transparent crystallized glass is The present invention has been found to play an important role in suppressing the generation of fine cracks due to the ion exchange reaction, and is proposed as the present invention.
【０００９】即ち、本発明のＬｉ2 Ｏ−Ａｌ2 Ｏ3 −Ｓ
ｉＯ2 系透明結晶化ガラスは、主結晶としてβ−石英固
溶体を析出し、３０〜３８０℃の範囲の平均線熱膨張係
数が−１０〜１０×１０-7／℃であり、かつ、β−ＯＨ
を０．３５／ｍｍ以上含むことを特徴とする。That is, the Li 2 O—Al 2 O 3 —S of the present invention is used.
The iO 2 -based transparent crystallized glass precipitates a β-quartz solid solution as a main crystal, has an average linear thermal expansion coefficient in a range of 30 to 380 ° C. of −10 to 10 × 10 −7 / ° C., and has a β-quartz solid solution. OH
Of 0.35 / mm or more.
【００１０】また本発明のＬｉ2 Ｏ−Ａｌ2 Ｏ3 −Ｓｉ
Ｏ2 系結晶性ガラスは、主結晶としてβ−石英固溶体を
析出し、３０〜３８０℃の範囲の平均線熱膨張係数が−
１０〜１０×１０-7／℃であり、かつ、β−ＯＨを０．
３５／ｍｍ以上含む結晶化ガラスとなる性質を有するこ
とを特徴とする。The Li 2 O—Al 2 O 3 —Si of the present invention
The O 2 -based crystalline glass precipitates a β-quartz solid solution as a main crystal and has an average linear thermal expansion coefficient in the range of 30 to 380 ° C.
10 to 10 × 10 −7 / ° C., and β-OH at 0.1.
It is characterized by having the property of being crystallized glass containing 35 / mm or more.
【００１１】ここで、β−ＯＨの量は、当該結晶化ガラ
スの赤外線吸収スペクトルにおいて次式によって求めら
れるものである。Here, the amount of β-OH is determined by the following equation in the infrared absorption spectrum of the crystallized glass.
【００１２】 β−ＯＨ量＝｛ｌｏｇ（Ｔ3850／Ｔ3500）｝／ｔ ここで、 Ｔ3850：３８５０ｃｍ-1付近の透過率 Ｔ3500：３５００ｃｍ-1付近の吸収帯の最低透過率 ｔ ：スペクトル測定時の結晶化ガラスの板厚（ｍ
ｍ）[0012] beta-OH amount = {log (T 3850 / T 3500)} / t where, T 3850: 3850cm -1 vicinity of the transmittance T 3500: 3500 cm minimum transmittance of absorption band near -1 t: Spectrum The thickness of the crystallized glass at the time of measurement (m
m)
【００１３】[0013]
【発明の実施の形態】本発明において、Ｌｉ2 Ｏ−Ａｌ
2 Ｏ3 −ＳｉＯ2 系透明結晶化ガラスは、ガラス中にβ
−ＯＨを０．３５／ｍｍ以上、好ましくは０．４０〜
２．０／ｍｍの範囲で含有する。β−ＯＨは、ガラスが
結晶化する際にガラス表面の結晶構成成分の濃度を低下
させ、それ以外の元素の濃度を増加させることに寄与す
る。この結果、結晶化ガラス表面における、結晶中のリ
チウムイオンと水素イオンとの交換反応が抑制され、微
細クラックの発生を防止することができる。ガラス中に
β−ＯＨが０．３５／ｍｍ以上含まれていると、例え燃
焼雰囲気中にＨ2 ＳＯ4 が含まれていても、微細クラッ
クの発生を大幅に抑制することができるが、β−ＯＨの
含有量が０．３５／ｍｍよりも少ないと微細クラックの
抑制効果が不十分となる。なおガラス中のβ−ＯＨ量
は、ガラス溶融の際の燃焼ガス中の水分量を増加させた
り、溶融ガラス中で水蒸気バブリングを行ったり、含水
ＯＨ量の高い原料を選択する等により、増加させること
ができる。DETAILED DESCRIPTION OF THE INVENTION In the present invention, Li 2 O—Al
2 O 3 —SiO 2 transparent crystallized glass contains β in the glass.
-OH is not less than 0.35 / mm, preferably 0.40 to
It is contained in the range of 2.0 / mm. β-OH contributes to lowering the concentration of crystal components on the glass surface and increasing the concentration of other elements when the glass is crystallized. As a result, the exchange reaction between lithium ions and hydrogen ions in the crystal on the surface of the crystallized glass is suppressed, and the occurrence of fine cracks can be prevented. If β-OH is contained in the glass in an amount of 0.35 / mm or more, even if H 2 SO 4 is contained in the combustion atmosphere, the generation of fine cracks can be greatly suppressed. When the content of -OH is less than 0.35 / mm, the effect of suppressing fine cracks becomes insufficient. The amount of β-OH in the glass is increased by increasing the amount of water in the combustion gas at the time of melting the glass, performing steam bubbling in the molten glass, selecting a material having a high water content of OH, and the like. be able to.
【００１４】本発明では、ガラス中にβ−石英固溶体を
主結晶として析出させることで、平均熱膨張係数を−１
０〜１０×１０-7／℃の範囲に調整することを特徴とす
るが、平均熱膨張係数がこの範囲を外れると燃焼装置窓
として十分な耐熱性、耐熱衝撃性を確保することができ
ない。In the present invention, the β-quartz solid solution is precipitated as a main crystal in glass, so that the average thermal expansion coefficient is −1.
It is characterized in that it is adjusted to a range of 0 to 10 × 10 −7 / ° C. However, if the average coefficient of thermal expansion is out of this range, sufficient heat resistance and thermal shock resistance cannot be ensured as a combustion device window.
【００１５】また本発明のＬｉ2 Ｏ−Ａｌ2 Ｏ3 −Ｓｉ
Ｏ2 系透明結晶化ガラス及びその原ガラスである結晶性
ガラスは、Ｌｉ2 Ｏ、ＳｉＯ2 およびＡｌ2 Ｏ3 の各成
分を、重量比で０．０５８≧｛Ｌｉ2 Ｏ／（ＳｉＯ2 ＋
Ａｌ2 Ｏ3 ）｝≧０．０３１の関係を満たすように含有
させることが好ましい。上式の値が０．０５８よりも大
きくなると結晶の析出量が多くなり、β−ＯＨによる、
表面の結晶成分の濃度低下が起こりにくくなるため、リ
チウムイオンと水素イオンの交換反応を防止できなくな
る。また上式の値が０．０３１よりも小さくなると熱膨
張係数が大きくなりやすいと共に、透明な外観が得られ
にくくなる。The Li 2 O—Al 2 O 3 —Si of the present invention
The O 2 -based transparent crystallized glass and the crystalline glass that is the raw glass thereof are obtained by mixing each component of Li 2 O, SiO 2 and Al 2 O 3 in a weight ratio of 0.058 ≧ ｛Li 2 O / (SiO 2 +
Al 2 O 3 )｝ is preferably contained so as to satisfy the relationship of ≧≧ 0.031. When the value of the above equation is larger than 0.058, the amount of precipitated crystals increases,
Since the concentration of the crystal component on the surface hardly decreases, the exchange reaction between lithium ions and hydrogen ions cannot be prevented. When the value of the above equation is smaller than 0.031, the coefficient of thermal expansion tends to increase, and a transparent appearance is hardly obtained.
【００１６】さらに本発明の結晶化ガラスや結晶性ガラ
スは、Ｌｉ2 Ｏ、ＳｉＯ2 およびＡｌ2 Ｏ3 以外にも、
種々の成分を含有しうる。例えば溶融を助けるととも
に、熱膨張係数をコントロールする成分としてＮａ2
Ｏ、Ｋ2 Ｏ、ＭｇＯ、ＺｎＯ、ＢａＯ等を、核形成剤と
してＴｉＯ2 、ＺｒＯ2 等を、核形成を促進する成分と
してＰ2 Ｏ5 等を、清澄剤としてＡｓ2 Ｏ3 、Ｓｂ2 Ｏ
3 、ＳｎＯ2 、Ｃｌ、ＳＯ 3 等を含みうる。なおこれら
成分中、特にＺｎＯの含有量を１重量％以下、ＢａＯの
含有量を１．５重量％以下にすることが好ましい。Ｚｎ
ＯはＬｉ2 Ｏの一部を補う目的で３％程度まで添加可能
であるが、主結晶であるβ−石英固溶体に固溶する成分
であるため、１％を越えて含有させると結晶の析出量が
多くなってイオン交換反応が起こりやすくなり、β−Ｏ
Ｈによる微細クラック抑制効果が機能しにくくなる。ま
たＢａＯはガラスの溶融を助ける成分として５％程度ま
で添加可能であるが、１．５％をこえて添加するとガラ
スに茶褐色の着色が起こりやすく、燃焼装置の窓用とし
て好ましい外観が得にくくなる。Further, the crystallized glass or crystalline glass of the present invention
Is LiTwo O, SiOTwo And AlTwo OThree Besides,
It may contain various components. For example, to help melting
Na as a component for controlling the coefficient of thermal expansionTwo
O, KTwo O, MgO, ZnO, BaO, etc., as nucleating agents
TiOTwo , ZrOTwo Etc. with components that promote nucleation
Then PTwo OFive And the like as a fining agentTwo OThree , SbTwo O
Three , SnOTwo , Cl, SO Three Etc. may be included. Note that these
In the components, particularly, the content of ZnO is 1% by weight or less,
Preferably, the content is 1.5% by weight or less. Zn
O is LiTwo Can be added up to about 3% to supplement part of O
But a component that forms a solid solution with the β-quartz solid solution that is the main crystal
Therefore, if the content exceeds 1%, the amount of precipitated crystals
The ion exchange reaction becomes more likely to occur, and β-O
H makes the effect of suppressing fine cracks difficult to function. Ma
BaO is about 5% as a component that helps the melting of glass.
Can be added, but if added over 1.5%,
Brown color is likely to occur on the
And it is difficult to obtain a favorable appearance.
【００１７】なお本発明において、Ｌｉ2 Ｏ−Ａｌ2 Ｏ
3 −ＳｉＯ2 系透明結晶化ガラス及びその原ガラスであ
る結晶性ガラスの好適な組成範囲は、重量百分率でＳｉ
Ｏ2５５〜７５％（好ましくは６０〜７５％）、Ａｌ2
Ｏ3 １５〜３０％（好ましくは１７〜２７％）、Ｌｉ
2 Ｏ ２〜５％（好ましくは２〜４．８％）、Ｎａ2 Ｏ
０〜３％（好ましくは０〜１％）、Ｋ2 Ｏ ０〜３％
（好ましくは０〜１％）、ＭｇＯ ０〜５％（好ましく
は０〜５％）、ＺｎＯ ０〜３％（好ましくは０〜１
％）、ＢａＯ ０〜５％（好ましくは０〜１．５％）、
ＴｉＯ2 ０〜５％（好ましくは１〜５％）、ＺｒＯ2
０〜４％（好ましくは０．５〜４％）、Ｐ2 Ｏ5 ０
〜５％（好ましくは０〜４％）、Ａｓ2 Ｏ3 ０〜２．
５％（好ましくは０〜２％）、Ｓｂ2 Ｏ3 ０〜２．５
％（好ましくは０〜２％）、ＳｎＯ2 ０〜２．５％
（好ましくは０〜２％）である。In the present invention, Li 2 O—Al 2 O
3 preferred composition range of the crystalline glass is -SiO 2 based transparent crystallized glass and its raw glass is, Si in weight percent
O 2 55-75% (preferably 60-75%), Al 2
O 3 15 to 30% (preferably 17 to 27%), Li
2 O 2 to 5% (preferably 2 to 4.8%), Na 2 O
0-3% (preferably 0~1%), K 2 O 0~3 %
(Preferably 0-1%), MgO 0-5% (preferably 0-5%), ZnO 0-3% (preferably 0-1%)
%), BaO 0-5% (preferably 0-1.5%),
TiO 2 0-5% (preferably 1-5%), ZrO 2
0-4% (preferably 0.5~4%), P 2 O 5 0
5% (preferably 0~4%), As 2 O 3 0~2.
5% (preferably 0~2%), Sb 2 O 3 0~2.5
% (Preferably 0 to 2%), SnO 2 0 to 2.5%
(Preferably 0 to 2%).
【００１８】[0018]
【実施例】以下、実施例にもとづいて本発明を説明す
る。DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below with reference to embodiments.
【００１９】表１は、本発明の実施例（試料Ｎｏ．１〜
６）及び比較例（試料Ｎｏ．７）を示している。Table 1 shows examples of the present invention (samples No. 1 to No. 1).
6) and a comparative example (Sample No. 7).
【００２０】[0020]
【表１】 [Table 1]
【００２１】各試料は次のようにして調製した。先ず、
表に示す組成およびβ−ＯＨ含有量を有するように、Ｌ
ｉ2 Ｏ−Ａｌ2 Ｏ3 −ＳｉＯ2 系結晶性ガラスを溶融、
成型した。次いで、電気炉中で７８０℃で１時間、次い
で８５０℃で１時間保持することで結晶化させて試料を
得た。ガラス中のβ−ＯＨ量の増減は、溶融の熱源とな
る石油、ガス等の燃焼の際に、燃料に供給する酸素の濃
度を調整し、燃焼ガス中の水分の量を増減させることで
行った。ガラスの溶融は耐火物中で行ったが、白金中で
行ってもかまわない。Each sample was prepared as follows. First,
In order to have the composition and β-OH content shown in the table,
i 2 O-Al 2 O 3 -SiO 2 system melting crystallizable glass,
Molded. Then, the sample was kept at 780 ° C. for 1 hour and then at 850 ° C. for 1 hour in an electric furnace to be crystallized to obtain a sample. The amount of β-OH in the glass can be increased or decreased by adjusting the concentration of oxygen supplied to the fuel and increasing or decreasing the amount of moisture in the combustion gas when burning oil, gas, or the like, which is a heat source for melting. Was. The melting of the glass was performed in a refractory material, but may be performed in platinum.
【００２２】β−ＯＨの含有量は、厚さ約３ｍｍに研磨
加工した試料を用いて赤外分光光度計によって求めた。
析出結晶の同定はＸ線回折により、熱膨張係数はディラ
トメータによってそれぞれ行った。なお表中の「β−
Ｑ．」は、β−石英固溶体を示している。The β-OH content was determined by an infrared spectrophotometer using a sample polished to a thickness of about 3 mm.
The identification of the precipitated crystal was performed by X-ray diffraction, and the coefficient of thermal expansion was measured by a dilatometer. Note that “β-
Q. "Indicates a β-quartz solid solution.
【００２３】表に示すように、何れの試料も主結晶はβ
−石英固溶体であり、平均線熱膨張係数は−１０〜１０
×１０-7／℃の範囲であった。また試料Ｎｏ．１〜６の
β−ＯＨ量は０．４２〜０．７８／ｍｍであり、試料Ｎ
ｏ．７のβ−ＯＨ量は０．２７／ｍｍであった。なお試
料の外観は何れも透明であったが、試料Ｎｏ．１は僅か
に乳白しており、試料Ｎｏ．５はやや茶褐色がかってい
た。As shown in the table, the main crystal of each sample was β
-A quartz solid solution having an average linear thermal expansion coefficient of -10 to 10
× 10 -7 / ° C. Sample No. The β-OH amounts of Nos. 1 to 6 were 0.42 to 0.78 / mm, and the sample N
o. The β-OH content of No. 7 was 0.27 / mm. Although the appearance of each sample was transparent, the sample No. Sample No. 1 was slightly milky, and sample No. 5 was slightly brownish.
【００２４】次に各試料について、耐微細クラック性を
評価した。耐微細クラック性は加速試験と燃焼装置への
実装試験の二種類の方法によって行った。Next, the fine crack resistance of each sample was evaluated. The micro crack resistance was measured by two methods, an acceleration test and a mounting test on a combustion device.
【００２５】加速試験は次のようにして行った。まず容
積１リットルのビーカーに濃度６ｖｏｌ％の硫酸水溶液
２０ミリリットルを入れた。続いてビーカー内に網を設
置し、その上に試料を載せて硫酸の蒸気に曝されるよう
にした後、ガラス板で軽く蓋をした。続いて３２０℃で
３０分間加熱した後、試料を取り出し、顕微鏡で表面を
観察した。表中、クラックが認められなかったものには
「無」、認められたものには「有」の表示を行った。The acceleration test was performed as follows. First, 20 ml of a 6 vol% sulfuric acid aqueous solution was placed in a 1 liter beaker. Subsequently, a net was placed in a beaker, and the sample was placed thereon to be exposed to the vapor of sulfuric acid, and then lightly covered with a glass plate. Subsequently, after heating at 320 ° C. for 30 minutes, the sample was taken out and the surface was observed with a microscope. In the table, "no" was given to those in which no cracks were found, and "yes" was given to those in which cracks were found.
【００２６】実装試験は、硫黄を含んだ軽油を燃料とす
るストーブの前面に試料結晶化ガラスを取り付け、通常
の条件で燃焼を続けながら、目視で微小クラックが観測
されるようになるまでの経過日数によって評価を行っ
た。In the mounting test, a sample crystallized glass was attached to the front of a stove using light oil containing sulfur as fuel, and progress was made until small cracks were visually observed while continuing burning under normal conditions. The evaluation was based on the number of days.
【００２７】その結果、本発明の実施例であるＮｏ．１
〜６の各試料は、加速試験でクラックが発生したものは
なく、また実装試験でも３５日以上に亘って微小クラッ
クの発生が認められず、耐微細クラック性が良好であっ
た。特にＺｎＯの含有量が１％以下であるＮｏ．１、
３、４、及び６の試料は、実装試験で５０日経過後も微
小クラックの発生が認められず、非常に優れた耐微細ク
ラック性を有していた。As a result, in the embodiment of the present invention, No. 1
In each of the samples No. to No. 6, no crack was generated in the accelerated test, and no micro crack was observed for 35 days or more in the mounting test, and the micro crack resistance was good. In particular, No. 1 having a ZnO content of 1% or less. 1,
Samples 3, 4, and 6 did not show any microcracks even after 50 days in the mounting test, and had very excellent microcrack resistance.
【００２８】一方、比較例であるＮｏ．７の試料は、試
料Ｎｏ．３と同じ酸化物組成を有する結晶化ガラスであ
るが、β−ＯＨの含有量が少ないため、加速試験、実装
試験の双方において、実施例の各試料よりもはるかに劣
っており、耐微細クラック性が悪いことがわかった。On the other hand, in Comparative Example No. Sample No. 7 is Sample No. 3 is a crystallized glass having the same oxide composition as that of Example 3. However, since the content of β-OH is small, both of the accelerated test and the mounting test are much inferior to each of the samples of the examples, It turned out to be bad.
【００２９】これらの事実は、本発明による結晶化ガラ
スが優れた耐微細クラック性を有することを示してい
る。These facts show that the crystallized glass according to the present invention has excellent resistance to fine cracks.
【００３０】[0030]
【発明の効果】上述のように、本発明のＬｉ2 Ｏ−Ａｌ
2 Ｏ3 −ＳｉＯ2 系透明結晶化ガラスは、石油、石炭、
ガス、木材等の燃料によって発生するＨ2 ＳＯ4 を含む
雰囲気に長時間曝されても微細なクラックを生じない。
それゆえ、暖房器具や加熱炉、徐冷炉等の燃焼装置の前
面窓や覗き窓の窓ガラス材料として極めて有効である。As described above, according to the present invention, the Li 2 O—Al
2 O 3 —SiO 2 transparent crystallized glass is used for petroleum, coal,
Even when exposed to an atmosphere containing H 2 SO 4 generated by a fuel such as gas or wood for a long time, fine cracks do not occur.
Therefore, it is extremely effective as a window glass material for a front window or a viewing window of a combustion apparatus such as a heating appliance, a heating furnace, and a lehr.
【００３１】また本発明のＬｉ2 Ｏ−Ａｌ2 Ｏ3 −Ｓｉ
Ｏ2 系結晶性ガラスを用いれば、暖房器具や加熱炉、徐
冷炉等の燃焼装置の前面窓や覗き窓の材料として好適な
透明結晶化ガラスを作製することができる。The Li 2 O—Al 2 O 3 —Si of the present invention
When the O 2 -based crystalline glass is used, a transparent crystallized glass suitable as a material for a front window or a viewing window of a combustion apparatus such as a heating appliance, a heating furnace, a slow cooling furnace, or the like can be produced.
───────────────────────────────────────────────────── フロントページの続き (58)調査した分野(Int.Cl.7，ＤＢ名) C03C 1/00 - 14/00 ＪＩＣＳＴファイル（ＪＯＩＳ) ＷＰＩ／Ｌ（ＱＵＥＳＴＥＬ)────────────────────────────────────────────────── ─── Continued on the front page (58) Fields surveyed (Int. Cl. 7 , DB name) C03C 1/00-14/00 JICST file (JOIS) WPI / L (QUESTEL)
Claims (5)
３０〜３８０℃の範囲の平均線熱膨張係数が−１０〜１
０×１０-7／℃であり、かつ、β−ＯＨを０．３５／ｍ
ｍ以上含むことを特徴とするＬｉ2 Ｏ−Ａｌ2 Ｏ3 −Ｓ
ｉＯ2 系透明結晶化ガラス。1. A β-quartz solid solution is precipitated as a main crystal,
The average linear thermal expansion coefficient in the range of 30 to 380 ° C is -10 to 1
0 × 10 −7 / ° C. and β-OH of 0.35 / m
m 2 or more, characterized by containing Li 2 O—Al 2 O 3 —S
iO 2 -based transparent crystallized glass.
成分の含有量が、重量比で０．０５８≧｛Ｌｉ2 Ｏ／
（ＳｉＯ2 ＋Ａｌ2 Ｏ3 ）｝≧０．０３１の関係を満た
すことを特徴とする請求項１のＬｉ2 Ｏ−Ａｌ2 Ｏ3 −
ＳｉＯ2 系透明結晶化ガラス。 2. The content of each component of Li 2 O, SiO 2 and Al 2 O 3 is 0.058 ≧ {Li 2 O /
(SiO 2 + Al 2 O 3 )} according to claim 1, characterized by satisfying the relation of ≧ 0.031 Li 2 O-Al 2 O 3 -
SiO 2 transparent crystallized glass.
特徴とする請求項１又は２のＬｉ2 Ｏ−Ａｌ2 Ｏ3 −Ｓ
ｉＯ2 系透明結晶化ガラス。3. The Li 2 O—Al 2 O 3 —S according to claim 1, which is used for a window of a combustion device.
iO 2 -based transparent crystallized glass.
３０〜３８０℃の範囲の平均線熱膨張係数が−１０〜１
０×１０-7／℃であり、かつ、β−ＯＨを０．３５／ｍ
ｍ以上含む結晶化ガラスとなる性質を有することを特徴
とするＬｉ2Ｏ−Ａｌ2 Ｏ3 −ＳｉＯ2 系結晶性ガラ
ス。4. A β-quartz solid solution is precipitated as a main crystal,
The average linear thermal expansion coefficient in the range of 30 to 380 ° C is -10 to 1
0 × 10 −7 / ° C. and β-OH of 0.35 / m
Li 2 O—Al 2 O 3 —SiO 2 -based crystalline glass, which has the property of becoming a crystallized glass containing m or more.
成分の含有量が、重量比で０．０５８≧｛Ｌｉ2 Ｏ／
（ＳｉＯ2 ＋Ａｌ2 Ｏ3 ）｝≧０．０３１の関係を満た
すことを特徴とする請求項４のＬｉ2 Ｏ−Ａｌ2 Ｏ3 −
ＳｉＯ2 系結晶性ガラス。5. The content of each component of Li 2 O, SiO 2 and Al 2 O 3 is 0.058 ≧ {Li 2 O /
(SiO 2 + Al 2 O 3 )} according to claim 4, characterized in that to satisfy the relation of ≧ 0.031 Li 2 O-Al 2 O 3 -
SiO 2 crystalline glass.
Priority Applications (7)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP11149426A JP3063760B2 (en) | 1998-05-29 | 1999-05-28 | Li2O-Al2O3-SiO2-based transparent crystallized glass and crystalline glass |
| US09/744,120 US6593258B1 (en) | 1999-05-28 | 1999-06-21 | Li2O-Al2O3-SiO2 transparent crystallized glass and crystallizable |
| DE69927511T DE69927511T3 (en) | 1999-05-28 | 1999-06-21 | Transparent crystallized LI2O-Al2O3-SiO2 glass |
| DK99973870T DK1114803T3 (en) | 1999-05-28 | 1999-06-21 | Transparent, crystallized and crystalline glass of type L12-A12O3-SIO2 |
| EP99973870A EP1114803B2 (en) | 1999-05-28 | 1999-06-21 | Li2o-al2o3-sio2 type transparent crystalized glass and crystalline glass |
| PCT/JP1999/003293 WO2000073225A1 (en) | 1999-05-28 | 1999-06-21 | Li2O-Al2O3-SiO2 TYPE TRANSPARENT CRYSTALIZED GLASS AND CRYSTALLINE GLASS |
| CA002338354A CA2338354C (en) | 1999-05-28 | 1999-06-21 | Li2o-al2o3-sio2 type transparent crystallized glass and crytallizable glass |
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP10-166373 | 1998-05-29 | ||
| JP16637398 | 1998-05-29 | ||
| JP11149426A JP3063760B2 (en) | 1998-05-29 | 1999-05-28 | Li2O-Al2O3-SiO2-based transparent crystallized glass and crystalline glass |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2000044282A JP2000044282A (en) | 2000-02-15 |
| JP3063760B2 true JP3063760B2 (en) | 2000-07-12 |
Family
ID=26479320
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP11149426A Expired - Fee Related JP3063760B2 (en) | 1998-05-29 | 1999-05-28 | Li2O-Al2O3-SiO2-based transparent crystallized glass and crystalline glass |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3063760B2 (en) |
Families Citing this family (22)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100631501B1 (en) * | 2000-02-18 | 2006-10-09 | 엘지전자 주식회사 | Clear dielectric of semiconductor display device and fabricating method thereof |
| JP2001342036A (en) * | 2000-03-31 | 2001-12-11 | Ngk Insulators Ltd | Glass material, crystallized glass product and method of manufacturing crystallized glass material |
| JP2002098817A (en) * | 2000-09-21 | 2002-04-05 | Nippon Electric Glass Co Ltd | Reflecting mirror |
| JP2004075441A (en) * | 2002-08-14 | 2004-03-11 | Huzhou Daikyo Hari Seihin Yugenkoshi | Lithium oxide-alumina-silica-based crystalline glass and crystallized glass, and method of manufacturing the crystalline glass and the crystallized glass |
| JP4677742B2 (en) * | 2004-08-05 | 2011-04-27 | 日本電気硝子株式会社 | Li2O-Al2O3-SiO2 crystalline glass for combustion apparatus window and Li2O-Al2O3-SiO2 crystallized glass for combustion apparatus window obtained by heat treatment thereof |
| JP4677743B2 (en) * | 2004-08-05 | 2011-04-27 | 日本電気硝子株式会社 | Li2O-Al2O3-SiO2 transparent crystallized glass for combustion device window |
| JP2007003140A (en) * | 2005-06-27 | 2007-01-11 | Nippon Electric Glass Co Ltd | Window material for combustion device |
| JP4976058B2 (en) * | 2006-06-06 | 2012-07-18 | 株式会社オハラ | Crystallized glass and method for producing crystallized glass |
| JP4936216B2 (en) * | 2006-09-27 | 2012-05-23 | 日本電気硝子株式会社 | Dust-proof member for heat treatment furnace and heat treatment furnace |
| FR2909373B1 (en) | 2006-11-30 | 2009-02-27 | Snc Eurokera Soc En Nom Collec | TRANSPARENT AND COLORLESS BETA-QUARTZ GLAZE, FREE OF TIO2; ARTICLES THEREOF VITROCERAMIC; PRECURSOR GLASSES, METHODS OF PREPARATION. |
| JP5458532B2 (en) | 2008-09-08 | 2014-04-02 | 日本電気硝子株式会社 | LAS float glass |
| EP2650264B1 (en) | 2010-05-31 | 2018-06-27 | Nippon Electric Glass Co., Ltd. | Production method for a li2o-al2o3-sio2 based crystallised glass |
| DE102010027461B4 (en) * | 2010-07-17 | 2019-08-22 | Schott Ag | Lithium-containing, transparent glass ceramic with low thermal expansion, a largely amorphous, lithium-depleted, predominantly glassy surface zone and high transmission, their preparation and use |
| JP2012041260A (en) * | 2010-07-22 | 2012-03-01 | Nippon Electric Glass Co Ltd | Li2o-al2o3-sio2 based crystallized glass and production method for the same |
| JP2016108180A (en) * | 2014-12-05 | 2016-06-20 | 京セラメディカル株式会社 | Glass ceramic |
| KR102638938B1 (en) * | 2017-07-26 | 2024-02-22 | 에이지씨 가부시키가이샤 | Crystallized glass and chemically strengthened glass |
| WO2019022033A1 (en) | 2017-07-26 | 2019-01-31 | Ａｇｃ株式会社 | Glass for chemical strengthening, chemically strengthened glass, and electronic device case |
| CN110958992A (en) | 2017-07-26 | 2020-04-03 | Ａｇｃ株式会社 | Chemically strengthened glass and method for producing same |
| CN118420230A (en) * | 2019-04-01 | 2024-08-02 | 日本电气硝子株式会社 | Li2O－Al2O3－SiO2Crystallizing glass |
| CN110590165B (en) * | 2019-10-21 | 2022-07-29 | 成都光明光电有限责任公司 | Low-expansion glass ceramics and manufacturing method thereof |
| CN110981188B (en) * | 2019-12-05 | 2022-05-24 | 四川虹科创新科技有限公司 | Inorganic chemically strengthened glass and preparation method and application thereof |
| CN111943513A (en) * | 2020-08-21 | 2020-11-17 | 广东科迪微晶玻璃实业有限公司 | Lithium-aluminum-silicon ceramic white microcrystalline glass and manufacturing method thereof |
-
1999
- 1999-05-28 JP JP11149426A patent/JP3063760B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JP2000044282A (en) | 2000-02-15 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP3063760B2 (en) | Li2O-Al2O3-SiO2-based transparent crystallized glass and crystalline glass | |
| JP2602188B2 (en) | Transparent crystallized glass based on Li lower 2 O-A1 lower 2 O lower 3-SiO lower 2 for combustion device windows | |
| US6593258B1 (en) | Li2O-Al2O3-SiO2 transparent crystallized glass and crystallizable | |
| JP4000500B2 (en) | Li2O-Al2O3-SiO2 based crystallized glass and crystalline glass | |
| JP5385507B2 (en) | Optically detectable, floatable, arsenic and antimony free, glasable lithium-aluminosilicate glass | |
| US4455160A (en) | Transparent glass-ceramics especially suitable for use as stove windows | |
| JP6230775B2 (en) | Method for tempering ceramics of float crystallized glass | |
| JP2013520387A (en) | Lithium aluminosilicate glass having high elastic modulus and method for producing the same | |
| JPH07172862A (en) | Transparent or semi-transparent inorganic material with highconductivity in wave length of 2,700-3,300 nm | |
| JPH11100231A (en) | Infrared transmissive glass ceramics | |
| CA2300967C (en) | Li2o-al2o3-sio2 type transparent crystallized glass | |
| JP5701500B2 (en) | Transparent glass ceramic with low density | |
| JPH1025129A (en) | Glass for substrate | |
| JPH1025130A (en) | Glass for substrate | |
| JP2006240951A (en) | Li2O-Al2O3-SiO2-BASED CRYSTALLINE GLASS AND Li2O-Al2O3-SiO2-BASED TRANSPARENT CRYSTALLIZED GLASS FORMED BY HEAT-TREATING THE SAME | |
| JP4677743B2 (en) | Li2O-Al2O3-SiO2 transparent crystallized glass for combustion device window | |
| JPH1025128A (en) | Glass for substrate | |
| JP4677742B2 (en) | Li2O-Al2O3-SiO2 crystalline glass for combustion apparatus window and Li2O-Al2O3-SiO2 crystallized glass for combustion apparatus window obtained by heat treatment thereof | |
| JPH07309636A (en) | Transparent glass ceramic articles and their production | |
| JP2003300752A (en) | Fire-proof glass article | |
| JP2012041260A (en) | Li2o-al2o3-sio2 based crystallized glass and production method for the same | |
| WO2012086390A1 (en) | Method for producing crystallized glass | |
| JP2012001388A (en) | Crystallized glass and method for producing the same | |
| JP2012012290A (en) | Li2o-al2o3-sio2 based crystallized glass and production method for the same | |
| JPS59223249A (en) | Crystallized glass having large coefficient of thermal expansion |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20090512 Year of fee payment: 9 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20100512 Year of fee payment: 10 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20100512 Year of fee payment: 10 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20110512 Year of fee payment: 11 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20120512 Year of fee payment: 12 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20130512 Year of fee payment: 13 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20140512 Year of fee payment: 14 |
|
| LAPS | Cancellation because of no payment of annual fees |