JP2668075B2 - Transparent crystallized glass - Google Patents
Transparent crystallized glassInfo
- Publication number
- JP2668075B2 JP2668075B2 JP63008844A JP884488A JP2668075B2 JP 2668075 B2 JP2668075 B2 JP 2668075B2 JP 63008844 A JP63008844 A JP 63008844A JP 884488 A JP884488 A JP 884488A JP 2668075 B2 JP2668075 B2 JP 2668075B2
- Authority
- JP
- Japan
- Prior art keywords
- crystallized glass
- crystal
- glass
- transparent
- transparency
- 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
- 239000011521 glass Substances 0.000 title claims description 45
- 239000013078 crystal Substances 0.000 claims description 36
- 229910006404 SnO 2 Inorganic materials 0.000 claims description 11
- CNLWCVNCHLKFHK-UHFFFAOYSA-N aluminum;lithium;dioxido(oxo)silane Chemical compound [Li+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O CNLWCVNCHLKFHK-UHFFFAOYSA-N 0.000 claims description 8
- 239000006104 solid solution Substances 0.000 claims description 8
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 6
- 229910052644 β-spodumene Inorganic materials 0.000 claims description 6
- 229910018068 Li 2 O Inorganic materials 0.000 claims description 3
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 3
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 2
- 238000002425 crystallisation Methods 0.000 description 15
- 230000008025 crystallization Effects 0.000 description 15
- 238000010438 heat treatment Methods 0.000 description 13
- 238000010411 cooking Methods 0.000 description 7
- 230000000694 effects Effects 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- 229910000500 β-quartz Inorganic materials 0.000 description 6
- 239000003086 colorant Substances 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 4
- 238000002834 transmittance Methods 0.000 description 4
- 238000002844 melting Methods 0.000 description 3
- 230000008018 melting Effects 0.000 description 3
- 238000013001 point bending Methods 0.000 description 3
- 239000002245 particle Substances 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 229910052642 spodumene Inorganic materials 0.000 description 2
- 229910008556 Li2O—Al2O3—SiO2 Inorganic materials 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000006059 cover glass Substances 0.000 description 1
- 238000004031 devitrification Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000006025 fining agent Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 230000035939 shock Effects 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
- C03C10/00—Devitrified glass ceramics, i.e. glass ceramics having a crystalline phase dispersed in a glassy phase and constituting at least 50% by weight of the total composition
- C03C10/0036—Devitrified glass ceramics, i.e. glass ceramics having a crystalline phase dispersed in a glassy phase and constituting at least 50% by weight of the total composition containing SiO2, Al2O3 and a divalent metal oxide as main constituents
- C03C10/0045—Devitrified glass ceramics, i.e. glass ceramics having a crystalline phase dispersed in a glassy phase and constituting at least 50% by weight of the total composition containing SiO2, Al2O3 and a divalent metal oxide as main constituents containing SiO2, Al2O3 and MgO as main constituents
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Ceramic Engineering (AREA)
- Crystallography & Structural Chemistry (AREA)
- Dispersion Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Geochemistry & Mineralogy (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Glass Compositions (AREA)
Description
【発明の詳細な説明】 ［産業上の利用分野］ 本発明は、透明結晶化ガラスに関し、特に耐熱性に優
れ、硬度、機械的強度が高い堤膨張透明結晶化ガラスに
関する。Description: TECHNICAL FIELD The present invention relates to a transparent crystallized glass, and more particularly to a bank-expanded transparent crystallized glass having excellent heat resistance, high hardness and high mechanical strength.
［従来の技術］ 透明結晶化ガラスとしては、Li2O−Al2O3−SiO2系低
膨張透明結晶化ガラスが知られている。これらの結晶化
ガラスの中には、組成あるいは熱処理条件によって透明
なものが存在するが、その多くのものは、結晶化促進剤
としてTiO2を1.5〜５％程度含んだβ−石英固溶体結晶
を主結晶とする結晶化ガラスである。[Prior Art] As a transparent crystallized glass, a Li 2 O—Al 2 O 3 —SiO 2 -based low expansion transparent crystallized glass is known. Some of these crystallized glasses are transparent depending on the composition or heat treatment conditions, but most of them are β-quartz solid solution crystals containing about 1.5 to 5% of TiO 2 as a crystallization accelerator. It is a crystallized glass used as a main crystal.
この透明結晶化ガラスは、優れた透明性と小さな熱膨
張係数に基づく優れた耐熱衝撃性により、耐熱食器、調
理器具、反射望遠鏡、光学機器の反射鏡のミラーブラン
クスなどに用いられており、特に、Fe2O3、MnO2、V
2O5、NiOなどの着色剤を添加し、濃褐色、暗褐色などに
着色したものが、抵抗発熱体を熱源とした調理レンジの
トッププレートとして用いられている（例えば、特公昭
53−38090号、特公昭60−54896号公報）。This transparent crystallized glass is used for heat-resistant tableware, cooking utensils, reflecting telescopes, mirror blanks of reflecting mirrors of optical equipment, etc., due to its excellent transparency and excellent thermal shock resistance based on a small coefficient of thermal expansion. , Fe 2 O 3 , MnO 2 , V
Coloring agents such as 2 O 5 and NiO and colored in dark brown, dark brown, etc. are used as the top plate of a cooking range with a resistance heating element as a heat source (for example,
53-38090, Japanese Patent Publication No. 60-54896).
しかしながら、一般にβ−石英固溶体結晶を主たる析
出結晶として含む透明結晶化ガラスは、組成によって多
少の相違はあるものの、概ね800℃以上の温度で保持す
ると、β−石英固溶体結晶の粒成長あるいはβ−スポジ
ュメン固溶体結晶の析出によって白濁が増加する。この
白濁により、視認性のみならず赤外線透過性も低下して
加熱効率が低減するため、調理レンジのトッププレート
として用いる場合には、使用温度を800℃以下とせざる
を得ない。However, in general, a transparent crystallized glass containing a β-quartz solid solution crystal as a main precipitated crystal has some differences depending on the composition, but when maintained at a temperature of about 800 ° C. or higher, the grain growth of the β-quartz solid solution crystal or β-quartz solid solution crystal White turbidity increases due to the precipitation of Spodumene solid solution crystals. Due to this white turbidity, not only the visibility but also the infrared transparency is lowered and the heating efficiency is reduced. Therefore, when it is used as a top plate of a cooking range, the use temperature must be 800 ° C. or lower.
一方、β−スポジュメン固溶体結晶を主たる析出結晶
として含む結晶化ガラスは、より高い温度域まで使用可
能であるが、白色不透明であるかせいぜい白濁の濃い半
透明程度である。したがって、この結晶化ガラスを調理
レンジのトッププレートとして用いる場合には、高耐熱
性を引き替えに加熱部を透視できるという商品特性を犠
牲にすることになる。On the other hand, crystallized glass containing β-spodumene solid solution crystals as the main precipitated crystals can be used up to a higher temperature range, but it is white and opaque, and is at most semitranslucent with cloudiness. Therefore, when this crystallized glass is used as a top plate of a cooking range, the product characteristic of being able to see through the heating section at the expense of high heat resistance is sacrificed.
［発明が解決しようとする問題点］ 本発明は、かかる事情に鑑み、より高温まで透明性を
損なうことなく使用できる低膨張透明結晶化ガラスを提
供することを目的とする。[Problems to be Solved by the Invention] In view of such circumstances, an object of the present invention is to provide a low-expansion transparent crystallized glass that can be used at higher temperatures without impairing transparency.
［課題を解決するための手段］ 本発明は、重量％で Li2O 4.2〜 4.6 Na2O ０〜 3.0 K2O ０〜 3.0 Na2O＋K2O 0.3〜 3.0 MgO ０〜 2.0 ZnO ０〜 2.0 Al2O3 18.0〜24.0 SiO2 63.5〜72.0 SnO2 1.0〜 4.0 TiO2 ０〜 1 ZrO2 1.0〜 4.0 SnO2＋ZrO2 3.5〜 7.0 P2O5 ０〜 4.0 の組成を有し、β−スポジュメン固溶体結晶を主たる析
出結晶とする透明結晶化ガラスである。[Means for Solving the Problems] The present invention provides Li 2 O 4.2 to 4.6 Na 2 O 0 to 3.0 K 2 O 0 to 3.0 Na 2 O + K 2 O 0.3 to 3.0 MgO 0 to 2.0 ZnO 0 to 2.0 by weight. al 2 O 3 18.0~24.0 SiO 2 63.5~72.0 SnO 2 1.0~ 4.0 TiO 2 0~ 1 ZrO 2 1.0~ 4.0 has a composition of SnO 2 + ZrO 2 3.5~ 7.0 P 2 O 5 0~ 4.0, β- spodumene It is a transparent crystallized glass having a solid solution crystal as a main precipitated crystal.
この透明結晶化ガラスにFe2O3、MnO2、V2O5、NiOおよ
びCoOからなる群より選択した少なくとも１種の着色剤
を含ませることにより、調理レンジのトッププレートと
して好適な着色透明結晶化ガラスとすることができる。
着色剤は、0.01〜1.0wt％添加することが好ましい。0.0
1wt％より少ないと色が薄すぎ、1.0wt％よりも多いと色
が濃すぎるからである。By adding at least one colorant selected from the group consisting of Fe 2 O 3 , MnO 2 , V 2 O 5 , NiO and CoO to this transparent crystallized glass, a colored transparent glass suitable as a top plate for a cooking range is obtained. It can be crystallized glass.
It is preferable to add 0.01 to 1.0 wt% of the colorant. 0.0
If the amount is less than 1 wt%, the color is too light, and if it is more than 1.0 wt%, the color is too dark.
この結晶化ガラスは、上記成分を有する原料を溶融し
てガラス体を得た後に、このガラス体を900〜1000℃の
温度域で0.5〜10時間保持すること等により得ることが
できる。この熱処理により作成された結晶化ガラスは、
通常、粒径100nm以下の微細な結晶粒子をガラス層のマ
トリックス内に均一に分散させた構造となっている。This crystallized glass can be obtained, for example, by melting a raw material having the above components to obtain a glass body, and then holding the glass body in a temperature range of 900 to 1000 ° C. for 0.5 to 10 hours. Crystallized glass produced by this heat treatment,
Usually, it has a structure in which fine crystal particles having a particle size of 100 nm or less are uniformly dispersed in a matrix of a glass layer.
熱処理の加熱スケジュールは、１段階でも目的とする
結晶化物が得られるが、多段階熱処理（例えば２段階あ
るいは３段階）を行った方が、結晶粒径が小さくなり散
乱による透過率低下が低減してより透過率の高い結晶化
物が得られるので好ましい。The heating schedule of the heat treatment can obtain the desired crystallized product even in one step, but the multi-step heat treatment (for example, two steps or three steps) reduces the crystal grain size and reduces the decrease in transmittance due to scattering. It is preferable because a crystallized product having a higher transmittance can be obtained.
本発明における結晶化促進剤であるSnO2およびZrO2の
作用は明確ではない。しかしながら、本発明において限
定している程度の量のZrO2、SnO2をそれぞれ単独で加え
たのみでは、いずれも目的とする微細な結晶が均一に析
出した透明結晶化ガラスが得られなかった。The effects of the crystallization promoters SnO 2 and ZrO 2 in the present invention are not clear. However, only by adding the amounts of ZrO 2 and SnO 2 alone, which are limited in the present invention, the target transparent crystallized glass in which fine crystals were uniformly deposited could not be obtained.
すなわち、ZrO2のみを加えた場合には結晶化が非常に
起こりにくく、比較的高温でも長時間熱処理して初めて
結晶化が起こる状態であった。得られた結晶化ガラスも
粗大な結晶粒が不均一に析出した透明性の悪い、著しい
場合には、全く不透明な結晶化物であった。That is, when only ZrO 2 was added, crystallization was very unlikely to occur, and crystallization occurred only after a long-time heat treatment even at a relatively high temperature. The obtained crystallized glass was also a poorly transparent crystal in which coarse crystal grains were unevenly precipitated.
また、SnO2のみを加えた場合には、加熱処理の初期段
階でSnO2の微細な結晶が生じ、ガラスは白濁状態となっ
た。さらに加熱処理を継続するとこの結晶が発達して、
不透明となった。この不透明な結晶化ガラスは、さらに
高温で加熱しても不透明化が進行するだけで透明な結晶
化物は得られなかった。When only SnO 2 was added, fine crystals of SnO 2 were generated in the initial stage of the heat treatment, and the glass became cloudy. When the heat treatment is continued, this crystal develops,
It became opaque. Even if this opaque crystallized glass was further heated at a high temperature, only opacity progressed, and a transparent crystallized product could not be obtained.
本発明者らは、結晶化促進剤としてTiO2の代わりに結
晶化促進剤としてSnO2およびZrO2を採用することによ
り、これら問題点を解決したばかりではなく、さらにそ
の余の成分も上記所定範囲とすることにより、熱膨張率
が低く、より高温まで透明性を損なうことなく使用で
き、硬度、機械的強度がより高い低膨張透明結晶化ガラ
スを得ることに成功した。The present inventors not only solved these problems by adopting SnO 2 and ZrO 2 as the crystallization accelerator instead of TiO 2 as the crystallization accelerator, and further, the other components thereof were also the above-mentioned predetermined values. By setting the content within the range, a low expansion transparent crystallized glass having a low coefficient of thermal expansion, which can be used up to higher temperatures without impairing transparency, and having higher hardness and mechanical strength was successfully obtained.
本発明における組成限定理由は以下のとおりである。 The reasons for limiting the composition in the present invention are as follows.
SiO2:75wt％を越えると難溶となり結晶化コントロール
が困難となって目的とする結晶化物が得られず、60wt％
未満では結晶化ガラスの膨張係数が大きくなる。また、
透明性の確保のためには、63.5〜72.0wt％とする必要が
ある。If the content of SiO 2 exceeds 75 wt%, it becomes difficult to dissolve, making it difficult to control the crystallization.
If it is less than 10, the expansion coefficient of the crystallized glass becomes large. Also,
In order to ensure transparency, the content needs to be 63.5 to 72.0 wt%.
Al2O3:30wt％を越えると難溶となり膨張係数が大きくな
り、15wt％未満では結晶化物の透明性が悪くなる。ま
た、透明性の確保のためには、18.0〜24.0wt％とする必
要がある。If the content of Al 2 O 3 exceeds 30 wt%, it becomes insoluble and the expansion coefficient increases, and if it is less than 15 wt%, the transparency of the crystallized product deteriorates. Further, in order to ensure transparency, the content needs to be 18.0 to 24.0 wt%.
Li2O:6wt％を越えると熱処理時に急激な結晶化が起こり
目的とする結晶化ガラスは得られず、2.5wt％未満では
難溶となる。また、透明性の確保のためには3.0〜5.0wt
％とする必要がある。If the content of Li 2 O exceeds 6% by weight, rapid crystallization occurs during the heat treatment, and a target crystallized glass cannot be obtained. In addition, in order to ensure transparency, 3.0-5.0wt
%.
SnO2:4wt％を越えると結晶化促進の効果は変わらないも
のの未溶解が生じ、1wt％未満では難溶になるとともに
結晶化促進の効果が十分に得られず目的とする結晶化ガ
ラスが得られない。SnO 2: Effect of 4 wt% to exceed the crystallization promotion undissolved occur which do not change, crystallized glass obtained effect of crystallization promotion to sufficiently obtained without purpose together becomes poorly soluble in less than 1 wt% I can't.
ZrO2:4wt％を越えると未溶解が生じ、1wt％未満では難
溶になるとともに結晶化促進の効果が十分に得られず結
晶粒径が大きくなり透明性が悪くなる。If ZrO 2 : 4 wt% is exceeded, undissolved occurs, and if it is less than 1 wt%, it becomes insoluble and the effect of promoting crystallization is not sufficiently obtained, and the crystal grain size becomes large, resulting in poor transparency.
SnO2＋ZrO2:7wt％を越えると未溶解が生じ、3.5％未満
では十分な結晶化促進の効果が得られず目的とする結晶
化ガラスが得られない。If SnO 2 + ZrO 2 : more than 7% by weight, non-dissolution occurs, and if it is less than 3.5%, a sufficient effect of accelerating crystallization cannot be obtained and a target crystallized glass cannot be obtained.
必須成分ではないが、次の成分を添加することができ
る。Although not an essential component, the following components can be added.
TiO2:結晶を微細化させることにより透明性を改善して
光の透過率を上昇させることができる。ただし、1wt％
を越えて加えるとその紫外線吸収性のために紫外域の光
の透過率を減少させる。TiO 2 : By making the crystals finer, the transparency can be improved and the light transmittance can be increased. However, 1wt%
When added above, it reduces the transmittance of light in the ultraviolet region due to its UV absorption.
Na2OおよびK2O:溶融性を向上させるとともに結晶化度を
減少させ膨張係数を調整することができる。各々4wt％
を越えて加えると透明性を悪くする。透明性の良い結晶
化ガラスを得るためには、各々3.0wt％以下とする必要
がある。また、Na2O＋K2Oが3wt％よりも多い場合には、
白濁が増加して透明性が悪くなりやすく、0.3wt％より
少ないとガラスの溶融が困難になりやすい。Na 2 O and K 2 O: It is possible to improve the meltability and reduce the crystallinity to adjust the expansion coefficient. 4wt% each
If it is added over the range, the transparency will deteriorate. In order to obtain a crystallized glass having good transparency, it is necessary to set each of them to not more than 3.0 wt%. If Na 2 O + K 2 O is more than 3 wt%,
Transparency tends to be deteriorated due to an increase in white turbidity, and if it is less than 0.3 wt%, melting of the glass tends to be difficult.
MgO:溶融性を向上させるとともに少量の添加で膨張係数
を大きく増加させる。そのため、過度に加えると膨張係
数が増加したり、結晶化時にクラックが発生したりする
ので、2wt％以下とする必要がある。β−スポジュメン
固溶体結晶を主結晶とする本発明に係る結晶化ガラスに
おいては、添加しないことが好ましい。MgO: Improves the meltability and greatly increases the expansion coefficient with a small amount of addition. Therefore, if added excessively, the expansion coefficient increases or cracks occur during crystallization, so it is necessary to make it 2 wt% or less. In the crystallized glass according to the present invention having a β-spodumene solid solution crystal as a main crystal, it is preferable not to add it.
ZnO:溶融性を向上させるのに有効であるばかりでなく、
結晶化温度を低下させ、結晶粒径を微小化し、透明性を
も向上させる。しかし、過度に添加するとガラス除冷時
に失透を起こしやすく。熱コントロールが困難となりや
すいので、2wt％以下とすることが好ましい。特に、β
−スポジュメン固溶体結晶を主結晶とする本発明に係る
結晶化ガラスにおいては、2.0wt％以下とすることが好
ましい。ZnO: Not only effective in improving meltability,
It lowers the crystallization temperature, reduces the crystal grain size, and improves the transparency. However, if added excessively, devitrification tends to occur during glass cooling. Since heat control tends to be difficult, it is preferable to set it to 2 wt% or less. In particular, β
-In the crystallized glass according to the present invention having a spodumene solid solution crystal as a main crystal, the content is preferably 2.0% by weight or less.
P2O5:少量ではZrO2の溶融に有効であるが、4wt％を越え
ると未溶解物を生じる。P 2 O 5 : A small amount is effective for melting ZrO 2 , but if it exceeds 4 wt%, undissolved matter is generated.
また、上述のように、Fe2O3、MnO2などの着色剤を含
ませることにより、調理レンジのトッププレートとして
好適な着色透明結晶化ガラスとすることができる。Further, as described above, by including a coloring agent such as Fe 2 O 3 or MnO 2 , a colored transparent crystallized glass suitable as a top plate of a cooking range can be obtained.
さらに、任意の最終製品の性質を損なわない範囲で、
Cr2O3、CeO2、Na2O3などの着色剤およびAs2O3、Sb2O3な
どの清澄剤を添加することもできる。Furthermore, to the extent that it does not impair the properties of any final product,
Cr 2 O 3, CeO 2, colorants such as Na 2 O 3 and As 2 O 3, Sb 2 O 3 can be added to fining agents, such as.
［実施例］ 表１に示した組成となるように調合した原料を白金る
つぼを用いて1550℃で溶融し、型枠に流し込んで鋳込み
除冷してガラスを得た。このガラスを表１に示した１段
または２段の熱処理条件で結晶化した。得られた結晶化
物の、析出結晶、外観（透明性、色調）を表１に示す。
また、比較例として、従来のTiO2＋ZrO2を結晶化促進剤
として用いたものについての同様の結果も併せて示す。Example A raw material prepared to have the composition shown in Table 1 was melted at 1550 ° C. using a platinum crucible, poured into a mold and cast and cooled to obtain glass. This glass was crystallized under one-step or two-step heat treatment conditions shown in Table 1. Table 1 shows precipitated crystals and appearance (transparency, color tone) of the obtained crystallized product.
Further, as a comparative example, a similar result for the case where conventional TiO 2 + ZrO 2 is used as a crystallization accelerator is also shown.
表にも示したように、比較例の結晶化ガラスが透明で
あるのはβ−石英固溶体結晶を主たる析出結晶とするか
らであるのに対し、各実施例の結晶化ガラスは、より高
温で熱処理し、β−スポジュメン固溶体結晶を主たる析
出結晶とするにもかかわらず透明である。また、実施例
３および比較例１のヴィッカース硬度および３点曲げ強
度の値を測定した。その結果、実施例３の結晶化ガラス
は、ヴィッカース硬度1015kg/mm2、３点曲げ強度2050kg
/cm2であるのに対し、比較例１のヴィッカース硬度785k
g/mm2、３点曲げ強度1150kg/mm2であった。As shown in the table, the crystallized glass of the comparative example is transparent because the β-quartz solid solution crystal is the main precipitated crystal, whereas the crystallized glass of each example is higher in temperature. It is transparent despite being heat-treated to make β-spodumene solid solution crystals the main precipitated crystals. Further, the values of Vickers hardness and three-point bending strength of Example 3 and Comparative Example 1 were measured. As a result, the crystallized glass of Example 3 had a Vickers hardness of 1015 kg / mm 2 and a three-point bending strength of 2050 kg.
/ cm 2 , whereas the Vickers hardness of Comparative Example 1 is 785k
g / mm 2 , and the three-point bending strength was 1150 kg / mm 2 .
β−石英固溶体結晶が主たる析出結晶である結晶化ガ
ラスと比較し、本発明のβ−スポジュメン固溶体結晶が
主たる析出結晶である結晶化ガラスは、高い強度と機械
的強度を有することがわかる。Compared with the crystallized glass in which the β-quartz solid solution crystal is the main precipitated crystal, the crystallized glass in which the β-spodumene solid solution crystal of the present invention is the main precipitated crystal has higher strength and mechanical strength.
［発明の効果］ 本発明に係る透明結晶化ガラスは、優れた透明性と高
い硬度、機械的強度を有し、特に高温まで使用可能であ
って、種々の計器やカバーガラスや調理レンジのトップ
プレートとして好適に使用できる。[Effects of the Invention] The transparent crystallized glass according to the present invention has excellent transparency, high hardness, and mechanical strength, and can be used especially at high temperatures, and is suitable for various measuring instruments, cover glasses and cooking ranges. It can be suitably used as a plate.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 中垣 茂樹 大阪府大阪市東区道修町４丁目８番地 日本板硝子株式会社内 (56)参考文献 特開 昭59−116150（ＪＰ，Ａ) 特開 昭52−117311（ＪＰ，Ａ) 特公 昭44−24430（ＪＰ，Ｂ１) 特公 昭49−10134（ＪＰ，Ｂ１) ────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Shigeki Nakagaki 4-8 Doshomachi, Higashi-ku, Osaka City, Osaka Prefecture Nippon Sheet Glass Co., Ltd. (56) References JP-A-59-116150 (JP, A) JP-A-52 -1117311 (JP, A) JP-B-44-24430 (JP, B1) JP-B-49-10134 (JP, B1)
Claims (1)
出結晶とする低膨張透明結晶化ガラス。1. Li 2 O 4.2 to 4.6 Na 2 O 0 to 3.0 K 2 O 0 to 3.0 Na 2 O + K 2 O 0.3 to 3.0 MgO 0 to 2.0 ZnO 0 to 2.0 Al 2 O 3 18.0 to 24.0 SiO 2. 2 63.5~72.0 SnO 2 1.0~ 4.0 TiO 2 0~ 1 ZrO 2 1.0~ 4.0 has a composition of SnO 2 + ZrO 2 3.5~ 7.0 P 2 O 5 0~ 4.0, the β- spodumene solid solution crystal as a main precipitated crystal Low expansion transparent crystallized glass.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63008844A JP2668075B2 (en) | 1987-01-19 | 1988-01-19 | Transparent crystallized glass |
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP970187 | 1987-01-19 | ||
| JP62-9701 | 1987-01-19 | ||
| JP63008844A JP2668075B2 (en) | 1987-01-19 | 1988-01-19 | Transparent crystallized glass |
Related Child Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP25798196A Division JPH09169542A (en) | 1987-01-19 | 1996-09-30 | Transparent crystallized glass |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS6452631A JPS6452631A (en) | 1989-02-28 |
| JP2668075B2 true JP2668075B2 (en) | 1997-10-27 |
Family
ID=26343441
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP63008844A Expired - Fee Related JP2668075B2 (en) | 1987-01-19 | 1988-01-19 | Transparent crystallized glass |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2668075B2 (en) |
Families Citing this family (20)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0686310B2 (en) * | 1989-04-28 | 1994-11-02 | セントラル硝子株式会社 | Transparent non-expandable crystallized glass |
| FR2657079B1 (en) * | 1990-01-12 | 1993-04-09 | Corning France | VITROCERAMIC PRECURSOR GLASSES, PROCESS FOR CONVERTING THESE VERY LOW OR NULL DILATION VITROCERAMIC GLASSES AND VITROCERAMIC MATERIALS OBTAINED. |
| US5512520A (en) * | 1994-11-14 | 1996-04-30 | Corning Incorporated | Ivory color in opaque glass-ceramic |
| WO2000073225A1 (en) * | 1999-05-28 | 2000-12-07 | Nippon Electric Glass Co., Ltd. | Li2O-Al2O3-SiO2 TYPE TRANSPARENT CRYSTALIZED GLASS AND CRYSTALLINE GLASS |
| CN1146735C (en) * | 1999-07-07 | 2004-04-21 | 日本电气硝子株式会社 | Material for temp. compensation, and optical communication device |
| JP2003020254A (en) * | 2001-07-04 | 2003-01-24 | National Institute Of Advanced Industrial & Technology | Crystallized glass |
| JP2007085877A (en) * | 2005-09-22 | 2007-04-05 | Yamaha Corp | Probe unit |
| JP5656040B2 (en) * | 2006-05-29 | 2015-01-21 | 日本電気硝子株式会社 | Li2O-Al2O3-SiO2 based crystallized glass |
| JP4976058B2 (en) | 2006-06-06 | 2012-07-18 | 株式会社オハラ | Crystallized glass and method for producing crystallized glass |
| FR2909374B1 (en) * | 2006-11-30 | 2016-11-25 | Soc En Nom Collectif Dite : Eurokera | CLEAR, COLORLESS, COLORLESS BETA-QUARTZ GLAZE WITH LOW TIO2 CONTENT; ARTICLES THEREOF VITROCERAMIC; PRECURSOR GLASSES, METHODS OF PREPARATION |
| 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. |
| EP2364957A1 (en) * | 2010-02-26 | 2011-09-14 | Corning Incorporated | Glass ceramics with bulk scattering properties and methods of making them |
| FR3002532B1 (en) | 2013-02-28 | 2015-02-27 | Eurokera | LITHIUM ALUMINOSILICATE TYPE VITROCERAMIC COMPRISING A SOLID BETA-SPODUMENE SOLUTION |
| EP2961703B1 (en) * | 2013-02-28 | 2023-04-05 | Eurokera | Non-opaque arsenic-free beta-spodumene glass ceramic exhibiting brown-grey coloration |
| WO2016042679A1 (en) * | 2014-09-19 | 2016-03-24 | 貞雅 禹 | Manganese oxide-containing glass |
| KR102739654B1 (en) | 2017-07-26 | 2024-12-10 | 에이지씨 가부시키가이샤 | Crystallized glass and chemically strengthened glass |
| CN110958992A (en) * | 2017-07-26 | 2020-04-03 | Ａｇｃ株式会社 | Chemically strengthened glass and method for producing same |
| WO2019022033A1 (en) * | 2017-07-26 | 2019-01-31 | Ａｇｃ株式会社 | Glass for chemical strengthening, chemically strengthened glass, and electronic device case |
| CN108793728A (en) * | 2018-09-05 | 2018-11-13 | 中建材蚌埠玻璃工业设计研究院有限公司 | High-aluminum alkali-free borosilicate glass fining agent and defecation method |
| JP7244804B2 (en) * | 2019-03-22 | 2023-03-23 | 日本電気硝子株式会社 | Li2O-Al2O3-SiO2-based crystallized glass |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5038386B2 (en) * | 1972-05-30 | 1975-12-09 | ||
| US4018612A (en) * | 1976-03-25 | 1977-04-19 | Corning Glass Works | Transparent beta-quartz glass-ceramics |
| US4455160A (en) * | 1982-12-20 | 1984-06-19 | Corning Glass Works | Transparent glass-ceramics especially suitable for use as stove windows |
-
1988
- 1988-01-19 JP JP63008844A patent/JP2668075B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JPS6452631A (en) | 1989-02-28 |
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