JPH11100229A - Infrared ray transmitting glass ceramics - Google Patents

Infrared ray transmitting glass ceramics

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Publication number
JPH11100229A
JPH11100229A JP27959297A JP27959297A JPH11100229A JP H11100229 A JPH11100229 A JP H11100229A JP 27959297 A JP27959297 A JP 27959297A JP 27959297 A JP27959297 A JP 27959297A JP H11100229 A JPH11100229 A JP H11100229A
Authority
JP
Japan
Prior art keywords
glass
becomes
glass ceramics
transmitting glass
infrared ray
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.)
Granted
Application number
JP27959297A
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Japanese (ja)
Other versions
JP4120897B2 (en
Inventor
Narutoshi Shimatani
成俊 嶋谷
Akihiko Sakamoto
明彦 坂本
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Nippon Electric Glass Co Ltd
Original Assignee
Nippon Electric Glass Co Ltd
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Application filed by Nippon Electric Glass Co Ltd filed Critical Nippon Electric Glass Co Ltd
Priority to JP27959297A priority Critical patent/JP4120897B2/en
Publication of JPH11100229A publication Critical patent/JPH11100229A/en
Application granted granted Critical
Publication of JP4120897B2 publication Critical patent/JP4120897B2/en
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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
    • C03C4/00—Compositions for glass with special properties
    • C03C4/10—Compositions for glass with special properties for infrared transmitting glass
    • 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
    • C03C10/0018—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 monovalent metal oxide as main constituents
    • C03C10/0027—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 monovalent metal oxide as main constituents containing SiO2, Al2O3, Li2O as main constituents

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Geochemistry & Mineralogy (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Ceramic Engineering (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Dispersion Chemistry (AREA)
  • Glass Compositions (AREA)

Abstract

PROBLEM TO BE SOLVED: To provide an infrared ray transmitting glass ceramics free from the fear of environmental pollution and suitable as a top plate of cooking utensils. SOLUTION: The infrared ray transmitting glass ceramics has a composition by weight of 60-72% SiO2 , 14-28% Al2 O3 , 2.5-5.5% LiO2 , 0.1-3% MgO, 0.1,-3% ZnO, 0-3% Cab, 0-5% BaO, 0.1-1% Na2 O, 0-1% K2 O, 0.5-3.8% TiO2 , 0.5-5% ZrO2 , 0-3% P2 O5 , 0.03-0.5% V2 O5 , 0.1-2% SnO2 , 0-1% Cl and is structured by depositing β-quartz solid solution as a main crystal.

Description

【発明の詳細な説明】DETAILED DESCRIPTION OF THE INVENTION

【０００１】[0001]

【産業上の利用分野】本発明は赤外線透過ガラスセラミ
ックスに関し、特にスムーストップ型の調理器用トップ
プレートとして用いられる赤外線透過ガラスセラミック
スに関するものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an infrared transmitting glass ceramic, and more particularly to an infrared transmitting glass ceramic used as a top plate for a smooth stop cooker.

【０００２】[0002]

【従来の技術】調理器のトッププレートには、赤外線透
過率が高いこと、美観を損ねないように内部の発熱手段
が透視し難いこと、機械的強度や化学的耐久性が高いこ
と、耐熱衝撃性が高いこと等が要求され、従来より濃褐
色で赤外線透過率の高い低膨張のＬｉ2 Ｏ−Ａｌ2 Ｏ3
−ＳｉＯ2 系ガラスセラミックスが使用されている。こ
の種の材料として、例えば特公昭６０−５４８９６号に
Ｖ2 Ｏ5 を添加したＬｉ2 Ｏ−Ａｌ2 Ｏ3 −ＳｉＯ2 系
の赤外線透過ガラスセラミックスが開示されている。2. Description of the Related Art The top plate of a cooker has a high infrared transmittance, it is difficult to see through the internal heating means so as not to impair the aesthetic appearance, it has high mechanical strength and chemical durability, and it has a thermal shock resistance. And a low-expansion Li 2 O—Al 2 O 3 having a dark brown color and a higher infrared transmittance than before.
-SiO 2 based glass ceramics is used. As this type of material, for example, Li 2 O-Al 2 O 3 -SiO 2 based infrared transmitting glass ceramics which was added V 2 O 5 in Japanese Patent Publication No. 60-54896 is disclosed.

【０００３】ところでこの種のガラスセラミックスは、
１４００℃を超える高温溶融を必要とする。このためガ
ラス中に添加される清澄剤には、高温での溶融時に清澄
ガスを多量に発生することができるＡｓ2 Ｏ3 が使用さ
れている。[0003] By the way, this kind of glass ceramics is
Requires high temperature melting above 1400 ° C. For this reason, As 2 O 3, which can generate a large amount of fining gas at the time of melting at a high temperature, is used as a fining agent added to glass.

【０００４】[0004]

【発明が解決しようとする課題】バッチ溶融において、
原料中のＡｓ2 Ｏ3 は４００〜５００℃でＡｓ2 Ｏ5 に
酸化された後、１２００〜１８００℃で再びＡｓ2 Ｏ3
に還元され、酸素ガスを放出する。この酸素ガスがガラ
ス中の泡に拡散することにより、泡の拡大、浮上促進が
起こり、泡が除去される。Ａｓ2 Ｏ3 は、この作用によ
り、ガラスの清澄剤として広く使用されており、特に高
温溶融が必要なＬｉ2 Ｏ−Ａｌ2 Ｏ3 −ＳｉＯ2 系ガラ
スセラミックスの清澄剤として非常に有効である。とこ
ろがＡｓ2Ｏ3 は毒性が強く、ガラスの製造工程や廃ガ
ラスの処理時等で環境を汚染する可能性がある。SUMMARY OF THE INVENTION In batch melting,
After As 2 O 3 in the raw materials is oxidized to As 2 O 5 at 400 to 500 ° C., again As 2 O 3 at 1200 to 1800 ° C.
To release oxygen gas. The diffusion of the oxygen gas into the bubbles in the glass causes expansion and promotion of the floating of the bubbles, and the bubbles are removed. Due to this effect, As 2 O 3 is widely used as a fining agent for glass, and is particularly effective as a fining agent for Li 2 O—Al 2 O 3 —SiO 2 glass ceramics that require high-temperature melting. . However, As 2 O 3 is highly toxic, and may pollute the environment during the glass manufacturing process, waste glass treatment, and the like.

【０００５】本発明の目的は、環境を汚染するおそれが
なく、調理器のトッププレートとして好適な赤外線透過
ガラスセラミックスを提供することである。[0005] An object of the present invention is to provide an infrared-transmissive glass ceramic which has no risk of polluting the environment and is suitable as a top plate of a cooker.

【０００６】[0006]

【課題を解決するための手段】Ａｓ2 Ｏ3 以外の清澄剤
としては、ＳｎＯ2 、Ｓｂ2 Ｏ3 、ＣｅＯ2 、各種の塩
化物、及び各種の硫化物があるが、中でもＳｎＯ2 や塩
化物は１４００℃を超える温度域で清澄効果を発揮する
ため、高温溶融を要するガラスの清澄剤に適している。
しかしＳｎＯ2 を添加すると、その強い還元作用のた
め、バナジウムの発色が強められ、ガラスセラミックス
の色調が濃くなりすぎる。また調理器のトッププレート
として使用する場合、赤外域の透過率が減少し、加熱効
率が低下する。The fining agent other than As 2 O 3 includes SnO 2 , Sb 2 O 3 , CeO 2 , various chlorides, and various sulfides. Among them, SnO 2 and chloride Since the material exhibits a fining effect in a temperature range exceeding 1400 ° C., it is suitable as a fining agent for glass requiring high-temperature melting.
However, when SnO 2 is added, due to its strong reducing action, the coloration of vanadium is enhanced, and the color tone of the glass ceramic becomes too dark. Further, when used as a top plate of a cooker, the transmittance in the infrared region decreases, and the heating efficiency decreases.

【０００７】本発明者等は種々の実験を行った結果、バ
ナジウムの発色はＳｎＯ2 の他にもＴｉＯ2 の影響を受
けるため、ＳｎＯ2 により増強されたバナジウムの発色
はＴｉＯ2 の減量により補正し得ること、ＴｉＯ2 の減
量による結晶性の低下はＺｒＯ2 の添加で補正し得るこ
とを見いだし、本発明として提案するものである。[0007] The present inventors have results of various experiments, since the color development of vanadium affected by TiO 2 to other SnO 2, color development of vanadium was enhanced by SnO 2 is corrected by the reduction of TiO 2 The present inventors have found that a decrease in crystallinity due to a reduction in the amount of TiO 2 can be corrected by adding ZrO 2 , and the present invention proposes the present invention.

【０００８】即ち、本発明の赤外線透過ガラスセラミッ
クスは、重量百分率でＳｉＯ2 ６０〜７２％、Ａｌ2
Ｏ3 １４〜２８％、Ｌｉ2 Ｏ ２．５〜５．５％、Ｍ
ｇＯ０．１〜３％、ＺｎＯ ０．１〜３％、ＣａＯ ０
〜３％、ＢａＯ ０〜５％、Ｎａ2 Ｏ ０．１〜１％、
Ｋ2 Ｏ ０〜１％、ＴｉＯ2 ０．５〜３．８％、Ｚｒ
Ｏ2 ０．５〜５％、Ｐ2 Ｏ5 ０〜３％、Ｖ2 Ｏ5
０．０３〜０．５％、ＳｎＯ2 ０．１〜２％、Ｃｌ
０〜１％の組成を有し、主結晶としてβ−石英固溶体を
析出してなることを特徴とする。That is, the infrared transmitting glass ceramic of the present invention is composed of 60 to 72% of SiO 2 and Al 2
O 3 14~28%, Li 2 O 2.5~5.5%, M
gO 0.1-3%, ZnO 0.1-3%, CaO 0
３3%, BaO 0-5%, Na 2 O 0.1-1%,
K 2 O 0~1%, TiO 2 0.5~3.8%, Zr
O 2 0.5~5%, P 2 O 5 0~3%, V 2 O 5
0.03 to 0.5%, SnO 2 0.1 to 2 %, Cl
It has a composition of 0 to 1% and is characterized in that a β-quartz solid solution is precipitated as a main crystal.

【０００９】[0009]

【作用】本発明の赤外線透過ガラスセラミックスは、清
澄剤としてＳｎＯ2 を０．１〜２％（好ましくは０．３
〜１．８％）、Ｃｌを０〜１％（好ましくは０．０１〜
１％）含有する。ＳｎＯ2 は１４００℃以上の高温度域
で、Ｓｎイオンの価数変化による化学反応（ＳｎＯ2
［４価］→ＳｎＯ［２価］）によって清澄ガスである多
量の酸素ガスを放出する。一方、Ｃｌは塩化物としてガ
ラス原料に添加され、ガラス融液中Ｃｌイオンの形で存
在する。このＣｌイオンは、酸素ガスと同様、ガラスの
温度が高くなるとともに泡に拡散し、泡の拡大、浮上促
進を起こす。本発明においては、ＳｎＯ2 を単独で用い
てもよいが、より高い清澄性を得るためにＣｌを共存さ
せることが望ましい。The infrared transmitting glass ceramic of the present invention contains 0.1 to 2 % (preferably 0.3%) of SnO2 as a fining agent.
~ 1.8%), Cl is 0 ~ 1% (preferably 0.01 ~
1%). In a high temperature range of 1400 ° C. or higher, SnO 2 is subjected to a chemical reaction (SnO 2
A large amount of oxygen gas, which is a fining gas, is released by [tetravalent] → SnO [divalent]). On the other hand, Cl is added as a chloride to the glass raw material and exists in the form of Cl ions in the glass melt. Like the oxygen gas, the Cl ions diffuse into the bubbles as the temperature of the glass increases, and cause the bubbles to expand and to promote floating. In the present invention, SnO 2 may be used alone, but it is desirable to make Cl coexist in order to obtain higher clarity.

【００１０】本発明のガラスセラミックスは、β−石英
固溶体を主結晶とするＬｉ2 Ｏ−Ａｌ2 Ｏ3 −ＳｉＯ2
系ガラスセラミックスである。Ｌｉ2 Ｏ−Ａｌ2 Ｏ3 −
ＳｉＯ2 系ガラスセラミックスは、β−石英固溶体やβ
−スポジュメンを析出し、高い機械的強度や化学的耐久
性を示すものであるが、β−スポジュメンの析出量が多
くなるとガラスセラミックスが白濁して外観上問題があ
るだけでなく、熱膨張係数が高くなり、また赤外線透過
率が低下して好ましくない。このため本発明ではβ−石
英固溶体を主結晶とすることを特徴とする。[0010] The glass ceramic of the present invention is a Li 2 O-Al 2 O 3 -SiO 2 having a β-quartz solid solution as a main crystal.
It is a system glass ceramic. Li 2 O-Al 2 O 3-
SiO 2 -based glass ceramics include β-quartz solid solution and β
-Deposits spodumene and exhibits high mechanical strength and chemical durability, but when the amount of precipitated β-spodumene increases, not only does the glass ceramic become cloudy and there is no problem in appearance, And the infrared transmittance is undesirably reduced. Therefore, the present invention is characterized in that a β-quartz solid solution is used as a main crystal.

【００１１】以下、組成範囲を上記のように限定した理
由を述べる。Hereinafter, the reasons for limiting the composition range as described above will be described.

【００１２】ＳｉＯ2 が６０％より少ないと熱膨張係数
が大きくなりすぎる。一方、７２％より多いとガラス溶
融が困難になる。ＳｉＯ2 の好適な範囲は６１〜７０％
である。When the content of SiO 2 is less than 60%, the coefficient of thermal expansion becomes too large. On the other hand, if it is more than 72%, glass melting becomes difficult. The preferred range of SiO 2 is 61-70%
It is.

【００１３】Ａｌ2 Ｏ3 が１４％より少ないと化学的耐
久性が低下し、またガラスが失透し易くなる。一方、２
８％より多いとガラスの粘度が大きくなりすぎてガラス
溶融が困難になる。Ａｌ2 Ｏ3 の好適な範囲は１６〜２
５％である。When the content of Al 2 O 3 is less than 14%, the chemical durability is lowered and the glass is apt to be devitrified. Meanwhile, 2
If it is more than 8%, the viscosity of the glass becomes too large, and it becomes difficult to melt the glass. Suitable range of Al 2 O 3 is from 16 to 2
5%.

【００１４】Ｌｉ2 Ｏが２．５％より少ないと結晶物が
白濁し易くなり、また熱膨張係数が大きくなりすぎる。
一方、５．５％より多い場合も白濁し易くなり、またガ
ラスが失透し易くなる。Ｌｉ2 Ｏの好適な範囲は３〜５
％である。If the content of Li 2 O is less than 2.5%, the crystal tends to become cloudy, and the coefficient of thermal expansion becomes too large.
On the other hand, if it is more than 5.5%, the glass tends to be cloudy and the glass tends to be devitrified. Suitable range of Li 2 O is 3 to 5
%.

【００１５】ＭｇＯ及びＺｎＯがそれぞれ０．１％より
少ないと結晶性が低くなり、結晶化が困難になる。一
方、それぞれ３％より多いと結晶物が白濁し、また熱膨
張係数が大きくなりすぎる。ＭｇＯ及びＺｎＯの好適な
範囲は何れも０．２〜２．５％である。If the content of each of MgO and ZnO is less than 0.1%, the crystallinity becomes low and crystallization becomes difficult. On the other hand, if each is more than 3%, the crystal becomes cloudy and the thermal expansion coefficient becomes too large. The preferred ranges of MgO and ZnO are both 0.2 to 2.5%.

【００１６】ＣａＯが３％及びＢａＯが５％より多いと
結晶物が白濁し、また熱膨張係数が大きくなりすぎる。
ＣａＯ及びＢａＯの好適な範囲は、０〜２％及び０〜４
％である。If the content of CaO is more than 3% and the content of BaO is more than 5%, the crystal becomes cloudy and the thermal expansion coefficient becomes too large.
Suitable ranges for CaO and BaO are 0-2% and 0-4.
%.

【００１７】Ｎａ2 Ｏが０．１％より少ないと結晶性が
低くなり、１％より多いと結晶物が白濁し、また熱膨張
係数が大きくなりすぎる。Ｎａ2 Ｏの好適な範囲は０．
１〜０．８％である。If the content of Na 2 O is less than 0.1%, the crystallinity becomes low. If the content is more than 1%, the crystal becomes cloudy and the thermal expansion coefficient becomes too large. The preferred range of Na 2 O is 0.1.
1 to 0.8%.

【００１８】Ｋ2 Ｏが１％より多いと結晶物が白濁し、
また熱膨張係数が大きくなりすぎる。Ｋ2 Ｏの好適な範
囲は０〜０．８％である。If K 2 O is more than 1%, the crystal becomes cloudy,
Also, the coefficient of thermal expansion becomes too large. Suitable ranges of K 2 O is from 0 to 0.8%.

【００１９】ＴｉＯ2 が０．５％より少ないと結晶性が
低く小さくなり、３．８％を超えるとガラスが失透し易
くなり、またＶ2 Ｏ5 の発色が強くなりすぎて色調が濃
くなり、赤外線の透過率が低下する。ＴｉＯ2 の好適な
範囲は１〜３％である。If the content of TiO 2 is less than 0.5%, the crystallinity becomes low and small, and if it exceeds 3.8%, the glass tends to be devitrified, and the color development of V 2 O 5 becomes too strong, resulting in a deep color tone. And the transmittance of infrared rays decreases. A preferred range of the TiO 2 is 1-3%.

【００２０】ＺｒＯ2 が０．５％より少ないとＴｉＯ2
の減量による結晶性の低下を補うことができなくなり、
５％より多いとガラスが失透し易くなる。ＺｒＯ2 の好
適な範囲は０．５〜４．５％である。If ZrO 2 is less than 0.5%, TiO 2
Can not compensate for the decrease in crystallinity due to weight loss,
If it is more than 5%, the glass tends to be devitrified. Suitable range of ZrO 2 is 0.5 to 4.5%.

【００２１】Ｐ2 Ｏ5 が３％より多いと結晶物が白濁
し、また熱膨張係数が大きくなりすぎる。Ｐ2 Ｏ5 の好
適な範囲は０〜２．５％である。If the content of P 2 O 5 is more than 3%, the crystal becomes cloudy and the thermal expansion coefficient becomes too large. Suitable range of P 2 O 5 is 0 to 2.5%.

【００２２】Ｖ2 Ｏ5 が０．０３％より少ないと色調が
薄くなり、可視光での透過率が高くなりすぎる。一方、
０．５％より多いと色調が濃くなりすぎ、赤外線透過率
が低くなりすぎる。Ｖ2 Ｏ5 の好適な範囲は０．０３〜
０．４％である。When V 2 O 5 is less than 0.03%, the color tone becomes thin, and the transmittance of visible light becomes too high. on the other hand,
If it is more than 0.5%, the color tone becomes too dark and the infrared transmittance becomes too low. Suitable range of V 2 O 5 is 0.03
0.4%.

【００２３】ＳｎＯ2 が０．１％より少ないと清澄効果
がなく、２％より多いと色調が濃くなりすぎる。またガ
ラス溶融が困難になったり、失透し易くなる。ＳｎＯ2
の好適な範囲は０．３〜１．８％である。If SnO 2 is less than 0.1%, the fining effect is not obtained, and if it is more than 2%, the color tone becomes too deep. In addition, glass melting becomes difficult or devitrification tends to occur. SnO 2
Is in the range of 0.3 to 1.8%.

【００２４】Ｃｌが１％より多いと化学的耐久性が低下
する。Ｃｌの好適な範囲は０．０１〜１％である。When the Cl content is more than 1%, the chemical durability is reduced. The preferred range for Cl is 0.01-1%.

【００２５】上記組成を有するガラスセラミックスは、
板厚３ｍｍで、波長５００ｎｍにおいて５％以下の可視
光の透過率、波長１５００ｎｍにおいて７０％以上の赤
外線透過率を有する。また本発明のガラスセラミックス
は、３０〜７５０℃の範囲において−５〜３０×１０-7
／℃の平均線熱膨張係数を示す。The glass ceramic having the above composition is
It has a plate thickness of 3 mm and has a visible light transmittance of 5% or less at a wavelength of 500 nm and an infrared transmittance of 70% or more at a wavelength of 1500 nm. In addition, the glass ceramic of the present invention has a temperature in the range of 30 to 750 ° C. of −5 to 30 × 10 −7.
/ ° C indicates an average linear thermal expansion coefficient.

【００２６】本発明の赤外線透過ガラスセラミックス
は、以下のようにして製造することができる。The infrared transmitting glass ceramic of the present invention can be manufactured as follows.

【００２７】まず重量百分率でＳｉＯ2 ６０〜７２
％、Ａｌ2 Ｏ3 １４〜２８％、Ｌｉ2 Ｏ ２．５〜
５．５％、ＭｇＯ ０．１〜３％、ＺｎＯ ０．１〜３
％、ＣａＯ ０〜３％、ＢａＯ ０〜５％、Ｎａ2 Ｏ
０．１〜１％、Ｋ2 Ｏ ０〜１％、ＴｉＯ2 ０．５〜
３．８％、ＺｒＯ2 ０．５〜５％、Ｐ2 Ｏ5 ０〜３
％、Ｖ2 Ｏ5 ０．０３〜０．５％の組成となるように
ガラス原料を調合する。このとき清澄剤としてＳｎＯ2
を０．１〜２％及び塩化物をＣｌ換算で０〜５％添加す
る。First, SiO 2 60-72 by weight percentage.
%, Al 2 O 3 14~28% , Li 2 O 2.5~
5.5%, MgO 0.1-3%, ZnO 0.1-3
%, CaO 0-3%, BaO 0-5%, Na 2 O
0.1~1%, K 2 O 0~1% , TiO 2 0.5~
3.8%, ZrO 2 0.5~5%, P 2 O 5 0~3
%, V 2 O 5 0.03 to 0.5%. At this time, SnO 2 was used as a fining agent.
And 0.1 to 2% of chloride and 0 to 5% of chloride in terms of Cl.

【００２８】次に調合したガラス原料を１５５０〜１７
００℃で４〜２０時間溶融した後、成形する。Next, the prepared glass raw materials were mixed with 1550-17
After melting at 00 ° C. for 4 to 20 hours, it is molded.

【００２９】続いてガラス成形体を７００〜８００℃で
２〜４時間保持して核形成を行い、さらに８００〜９０
０℃で１〜３時間熱処理して結晶化させることにより、
上記組成を有する赤外線透過ガラスセラミックスを得る
ことができる。Subsequently, the glass molded body was held at 700 to 800 ° C. for 2 to 4 hours to form nuclei.
By crystallizing by heat treatment at 0 ° C. for 1 to 3 hours,
An infrared transmitting glass ceramic having the above composition can be obtained.

【００３０】なお得られたガラスセラミックスは、切
断、研磨等の後加工を施したり、表面に絵付け等を施し
て、トッププレート等の用途に供される。The obtained glass ceramics are subjected to post-processing such as cutting and polishing, or painted on the surface, and then used for applications such as top plates.

【００３１】[0031]

【実施例】以下、実施例に基づいて本発明の赤外線透過
ガラスセラミックスを説明する。EXAMPLES The infrared transmitting glass ceramics of the present invention will be described below based on examples.

【００３２】表１〜３は本発明の実施例（試料Ｎｏ．１
〜１０）及び参考例（試料Ｎｏ．１１及び１２）を示し
ている。Tables 1 to 3 show examples of the present invention (sample No. 1).
10 to 10) and Reference Examples (Sample Nos. 11 and 12).

【００３３】[0033]

【表１】 [Table 1]

【００３４】[0034]

【表２】 [Table 2]

【００３５】[0035]

【表３】 [Table 3]

【００３６】各試料は次のようにして調製した。Each sample was prepared as follows.

【００３７】まず表の組成を有するガラスとなるように
原料を調合し、均一に混合した後、白金坩堝を用いて電
気炉で１５５０〜１６５０℃で８〜２０時間溶融した。
次いで溶融したガラスをカーボン定盤上に流しだし、ス
テンレスローラーを用いて５ｍｍの厚さに成形し、さら
に徐冷炉を用いて室温まで冷却した。このガラス成形体
を電気炉に入れ、３００℃／ｈの速度で室温から７８０
℃まで昇温し、２時間保持して核形成を行った。続いて
８０℃／ｈの速度で８５０℃まで昇温し、１時間保持し
て結晶化を行った後、炉冷した。First, raw materials were prepared so as to obtain a glass having the composition shown in the table, uniformly mixed, and then melted at 1550-1650 ° C. for 8-20 hours in an electric furnace using a platinum crucible.
Next, the molten glass was poured on a carbon platen, formed into a thickness of 5 mm using a stainless steel roller, and further cooled to room temperature using a slow cooling furnace. This glass molded body was placed in an electric furnace, and was heated from room temperature to 780 at a rate of 300 ° C./h.
The temperature was raised to 0 ° C. and maintained for 2 hours to form nuclei. Subsequently, the temperature was raised to 850 ° C. at a rate of 80 ° C./h, and the temperature was maintained for 1 hour to perform crystallization, followed by furnace cooling.

【００３８】このようにして得られた実施例の各試料
は、濃褐色から黒色で白濁のない外観を呈し、光沢のあ
る平滑な表面を有していた。Ｘ線回折装置による測定の
結果、何れの試料も主結晶としてβ−石英固溶体を析出
していることが分かった。また２５×３０ｍｍの大きさ
の光学研磨を施した３ｍｍ厚の試料片を作成し、分光光
度計を用いて５００ｎｍ及び１５００ｎｍの波長におけ
る透過率を測定した。その結果、何れの試料も５００ｎ
ｍの波長において３．１％以下、１５００ｎｍの波長に
おいて７９．０％以上の透過率を示し、ＴｉＯ2 の含有
量が３．８％を超える試料Ｎｏ．１２よりも高い赤外線
透過率が得られた。さらに試料を５０ｍｍ×５ｍｍφの
無垢棒に加工し、３０〜７５０℃の温度域での平均線熱
膨張係数を測定したところ、−２〜１４×１０-7／℃で
あった。Each of the samples of the examples obtained in this way had a dark brown to black appearance without white turbidity, and had a glossy smooth surface. As a result of measurement using an X-ray diffractometer, it was found that β-quartz solid solution was precipitated as a main crystal in each sample. A 3 mm-thick sample piece that had been optically polished to a size of 25 × 30 mm was prepared, and the transmittance at wavelengths of 500 nm and 1500 nm was measured using a spectrophotometer. As a result, each sample was 500 n
m shows a transmittance of not more than 3.1% at a wavelength of 1500 nm and a transmittance of 79.0% or more at a wavelength of 1500 nm, and the content of TiO 2 exceeds 3.8%. An infrared transmittance higher than 12 was obtained. Further, the sample was processed into a solid bar of 50 mm × 5 mmφ, and the average linear thermal expansion coefficient in a temperature range of 30 to 750 ° C. was measured. As a result, it was −2 to 14 × 10 −7 / ° C.

【００３９】次に清澄性の評価を行った。評価は、１５
５０〜１６５０℃で４〜８時間溶融し、ロール成型して
試料を作製した後、試料中の単位重量当たりの泡数を計
数することによって行った。その結果、実施例であるＮ
ｏ．１〜１０の各試料は、清澄剤としてＡｓ2 Ｏ3 を用
いた参考例とほぼ同等の清澄性を示した。Next, the clarity was evaluated. Evaluation is 15
The sample was melted at 50 to 1650 ° C. for 4 to 8 hours, roll-formed to prepare a sample, and the number of bubbles per unit weight in the sample was counted. As a result, N
o. Each sample of 1 to 10 exhibited almost the same clarity as in Reference example using As 2 O 3 as a fining agent.

【００４０】[0040]

【発明の効果】以上説明したように、本発明の赤外線透
過ガラスセラミックスは、清澄剤としてＡｓ2 Ｏ3 を用
いる必要がないために、環境を汚染するおそれがない。
また赤外線透過率が高く、可視光の透過率が低い。しか
も機械的強度、化学的耐久性、耐熱衝撃性等の特性に優
れるため、特にスムーストップ型の調理器のトッププレ
ートとして好適である。As described above, the infrared transmitting glass ceramics of the present invention does not need to use As 2 O 3 as a fining agent, so that there is no possibility of polluting the environment.
In addition, it has high infrared transmittance and low visible light transmittance. In addition, since it has excellent properties such as mechanical strength, chemical durability, and thermal shock resistance, it is particularly suitable as a top plate for a smooth stop cooker.

Claims (2)

【特許請求の範囲】[Claims] 【請求項１】 重量百分率でＳｉＯ2 ６０〜７２％、
Ａｌ2 Ｏ3 １４〜２８％、Ｌｉ2 Ｏ ２．５〜５．５
％、ＭｇＯ ０．１〜３％、ＺｎＯ ０．１〜３％、Ｃ
ａＯ ０〜３％、ＢａＯ ０〜５％、Ｎａ2 Ｏ ０．１
〜１％、Ｋ2Ｏ ０〜１％、ＴｉＯ2 ０．５〜３．８
％、ＺｒＯ2 ０．５〜５％、Ｐ2 Ｏ5 ０〜３％、Ｖ
2 Ｏ5 ０．０３〜０．５％、ＳｎＯ2 ０．１〜２
％、Ｃｌ０〜１％の組成を有し、主結晶としてβ−石英
固溶体を析出してなることを特徴とする赤外線透過ガラ
スセラミックス。1. 60% to 72% by weight of SiO 2 ,
Al 2 O 3 14~28%, Li 2 O 2.5~5.5
%, MgO 0.1-3%, ZnO 0.1-3%, C
aO 0-3%, BaO 0-5%, Na 2 O 0.1
１1%, K 2 O 0 to 1%, TiO 2 0.5 to 3.8
%, ZrO 2 0.5~5%, P 2 O 5 0~3%, V
2 O 5 0.03 to 0.5%, SnO 2 0.1 to 2
%, Cl-0 to 1%, and β-quartz solid solution is precipitated as a main crystal. 【請求項２】 調理器のトッププレートとして用いられ
ることを特徴とする請求項１の赤外線透過ガラスセラミ
ックス。2. The infrared transmitting glass ceramic according to claim 1, which is used as a top plate of a cooker.
JP27959297A 1997-09-25 1997-09-25 Infrared transmitting glass ceramics Expired - Fee Related JP4120897B2 (en)

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