JP2006001828A - Crystallized glass - Google Patents

Crystallized glass Download PDF

Info

Publication number
JP2006001828A
JP2006001828A JP2005128827A JP2005128827A JP2006001828A JP 2006001828 A JP2006001828 A JP 2006001828A JP 2005128827 A JP2005128827 A JP 2005128827A JP 2005128827 A JP2005128827 A JP 2005128827A JP 2006001828 A JP2006001828 A JP 2006001828A
Authority
JP
Japan
Prior art keywords
crystallized glass
spodumene
glass
total amount
solid solution
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.)
Pending
Application number
JP2005128827A
Other languages
Japanese (ja)
Inventor
Takahiro Matano
高宏 俣野
Satoshi Yoshihara
聡 吉原
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
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Nippon Electric Glass Co Ltd filed Critical Nippon Electric Glass Co Ltd
Priority to JP2005128827A priority Critical patent/JP2006001828A/en
Publication of JP2006001828A publication Critical patent/JP2006001828A/en
Pending legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C3/00—Glass compositions
    • C03C3/04—Glass compositions containing silica
    • C03C3/076—Glass compositions containing silica with 40% to 90% silica, by weight
    • C03C3/097—Glass compositions containing silica with 40% to 90% silica, by weight containing phosphorus, niobium or tantalum
    • 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
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C3/00—Glass compositions
    • C03C3/04—Glass compositions containing silica
    • C03C3/076—Glass compositions containing silica with 40% to 90% silica, by weight
    • C03C3/083—Glass compositions containing silica with 40% to 90% silica, by weight containing aluminium oxide or an iron compound
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C3/00—Glass compositions
    • C03C3/04—Glass compositions containing silica
    • C03C3/076—Glass compositions containing silica with 40% to 90% silica, by weight
    • C03C3/083—Glass compositions containing silica with 40% to 90% silica, by weight containing aluminium oxide or an iron compound
    • C03C3/085—Glass compositions containing silica with 40% to 90% silica, by weight containing aluminium oxide or an iron compound containing an oxide of a divalent metal

Landscapes

  • 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

<P>PROBLEM TO BE SOLVED: To provide crystallized glass which can be formed into a desired form and has higher heat resistance. <P>SOLUTION: The crystallized glass contains, as a main crystal, β-spodumene or β-spodumene solid solution. The crystallized glass contains, by mass, 21-34% Al<SB>2</SB>O<SB>3</SB>and is characterized in that the total amount of SiO<SB>2</SB>, Al<SB>2</SB>O<SB>3</SB>, Li<SB>2</SB>O, MgO and ZnO is 93.3-99.5%, the total amount of ZrO<SB>2</SB>, TiO<SB>2</SB>, and P<SB>2</SB>O<SB>5</SB>is 0.5-5%, and the total amount of Na<SB>2</SB>O, K<SB>2</SB>O, CaO, and BaO is 0-0.9%. Further, the crystallized glass contains, as a main crystal, β-spodumene or β-spodumene solid solution and has heat resistant temperature of ≥1,200°C. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

本発明は、β−スポジュメンまたはβ−スポジュメン固溶体を主結晶として析出した結晶化ガラスに関するものである。   The present invention relates to a crystallized glass in which β-spodumene or β-spodumene solid solution is precipitated as a main crystal.

ジルコニア等のセラミックスは、耐熱性が優れているため、種々の耐熱性を必要とする用途に使用されてきた。しかし、ジルコニア等のセラミックスは、粉末を焼結させて作製するため生産性が低いとともに、硬くて脆いため加工しにくいという問題がある。   Ceramics such as zirconia have excellent heat resistance and have been used for applications that require various heat resistances. However, ceramics such as zirconia have problems of low productivity because they are produced by sintering powder, and are difficult to process because they are hard and brittle.

結晶化ガラスは、溶融ガラスを冷却して所望の形状に成形した結晶性ガラスを熱処理することによって結晶を析出させて作製するため、生産性が高く、加工性に優れている。そのため、調理器用トッププレートや耐熱食器等の耐熱性を必要とする用途に使用されている。   The crystallized glass is produced by precipitating crystals by cooling the molten glass and heat-treating the crystalline glass formed into a desired shape, so that the productivity is high and the workability is excellent. For this reason, it is used for applications that require heat resistance, such as top plates for cookers and heat-resistant tableware.

これまで、耐熱性の高い結晶化ガラスとして、六方晶系バリウム長石を析出させた結晶化ガラス（特許文献１参照。）や頑火輝石を析出させた結晶化ガラス（特許文献２参照。）が開示されている。   Until now, as crystallized glass having high heat resistance, crystallized glass (see Patent Document 1) in which hexagonal barium feldspar is precipitated and crystallized glass in which pyroxene is precipitated (see Patent Document 2) are disclosed. Has been.

しかし、これらの結晶化ガラスは、耐熱性が高いものの熱膨張係数が大きいため熱衝撃によって破損しやすいという問題を有していた。   However, although these crystallized glasses have high heat resistance, they have a problem that they are easily damaged by thermal shock because they have a large coefficient of thermal expansion.

そこで、β−スポジュメンやβ−スポジュメン固溶体が主結晶として析出したＬｉ2Ｏ−Ａｌ2Ｏ3−ＳｉＯ2系の結晶化ガラスは、耐熱性が高く、また、結晶の熱膨張係数が小さく熱衝撃によって破損しにくいため、耐熱衝撃性が必要とされる用途にも適していた。（例えば、特許文献３、４参照。）。 Therefore, Li 2 O—Al 2 O 3 —SiO 2 -based crystallized glass in which β-spodumene or β-spodumene solid solution is precipitated as the main crystal has high heat resistance and a small thermal expansion coefficient of the crystal. It was also suitable for applications that require thermal shock resistance. (For example, refer to Patent Documents 3 and 4).

しかし、特許文献１〜３に記載の結晶化ガラスは、セラミックスほど耐熱性が高くないため、従来よりも高い耐熱性を有する結晶化ガラスが求められていた。   However, since the crystallized glass described in Patent Documents 1 to 3 is not as heat resistant as ceramics, a crystallized glass having higher heat resistance than before has been demanded.

また、特許文献４に記載の結晶化ガラスは、粉末にして焼成するため高い耐熱性を得ることができるが、塊状では、結晶化するための熱処理の際に破損するため、所望の形状の結晶化ガラスを得ることはできなかった。
特公昭４６−３８５１７号公報 特許第２６４８６７３号公報 特公昭４０−２０１８２号公報 特開平０１−２３４３４４号公報 The crystallized glass described in Patent Document 4 can obtain high heat resistance because it is powdered and fired. However, in the lump, the crystallized glass has a desired shape because it is broken during heat treatment for crystallization. A glass could not be obtained.
Japanese Examined Patent Publication No. 46-38517 Japanese Patent No. 2648673 Japanese Patent Publication No. 40-20182 JP-A-01-234344

本発明の目的は、所望の形状に成形でき、耐熱性のより高い結晶化ガラスを提供することである。   An object of the present invention is to provide a crystallized glass that can be molded into a desired shape and has higher heat resistance.

本発明者等は、種々の検討を行なった結果、主結晶であるβ−スポジュメンまたはβ−スポジュメン固溶体を構成する成分を可能な限り多くし、核形成剤を適量含有させることによって所望の形状に成形できるとともに結晶化ガラスの結晶化度が高くなり、その結果、結晶化ガラスの耐熱性が高くなることを見いだし、本発明として提案するものである。   As a result of various studies, the present inventors have increased the number of components constituting the main crystal β-spodumene or β-spodumene solid solution as much as possible, and added the nucleating agent in an appropriate amount to obtain a desired shape. It is found that the crystallized glass can be molded and the crystallinity of the crystallized glass is increased, and as a result, the heat resistance of the crystallized glass is increased, and is proposed as the present invention.

すなわち、本発明の結晶化ガラスは、β−スポジュメンまたはβ−スポジュメン固溶体を主結晶とする結晶化ガラスであって、質量％で、Ａｌ2Ｏ3 ２１〜３４％を含有し、ＳｉＯ2、Ａｌ2Ｏ3、Ｌｉ2Ｏ、ＭｇＯおよびＺｎＯの合量が９３．３〜９９．５％、ＺｒＯ2、ＴｉＯ2およびＰ2Ｏ5の合量が０．５〜５％、Ｎａ2Ｏ、Ｋ2Ｏ、ＣａＯおよびＢａＯの合量が０〜０．９％であることを特徴とする。 That is, the crystallized glass of the present invention is a crystallized glass having β-spodumene or β-spodumene solid solution as a main crystal, and contains 21 to 34% Al 2 O 3 by mass%, SiO 2 , Al The total amount of 2 O 3 , Li 2 O, MgO and ZnO is 93.3 to 99.5%, the total amount of ZrO 2 , TiO 2 and P 2 O 5 is 0.5 to 5%, Na 2 O, K The total amount of 2 O, CaO and BaO is 0 to 0.9%.

また、本発明の結晶化ガラスは、β−スポジュメンまたはβ−スポジュメン固溶体を主結晶とする結晶化ガラスであって、耐熱温度が１２００℃以上であることを特徴とする。   The crystallized glass of the present invention is a crystallized glass having β-spodumene or β-spodumene solid solution as a main crystal, and has a heat resistant temperature of 1200 ° C. or higher.

本発明の結晶化ガラスは、質量％で、Ａｌ2Ｏ3 ２１〜３４％を含有し、ＳｉＯ2、Ａｌ2Ｏ3、Ｌｉ2Ｏ、ＭｇＯおよびＺｎＯの合量が９３．３〜９９．５％、ＺｒＯ2、ＴｉＯ2およびＰ2Ｏ5の合量が０．５〜５％、Ｎａ2Ｏ、Ｋ2Ｏ、ＣａＯおよびＢａＯの合量が０〜０．９％であるため、所望の形状に成形することができ、耐熱温度を１２００℃以上とすることができる。 The crystallized glass of the present invention contains 21 to 34% Al 2 O 3 by mass%, and the total amount of SiO 2 , Al 2 O 3 , Li 2 O, MgO and ZnO is 93.3 to 99.5. %, ZrO 2 , TiO 2, and P 2 O 5 is 0.5 to 5%, and Na 2 O, K 2 O, CaO, and BaO are 0 to 0.9%. It can be formed into a shape, and the heat-resistant temperature can be 1200 ° C. or higher.

すなわち、析出するβ−スポジュメンまたはβ−スポジュメン固溶体の構成成分であるＳｉＯ2、Ａｌ2Ｏ3、Ｌｉ2Ｏ、ＭｇＯおよびＺｎＯの合量が９３．３〜９９．５％であり、核形成剤であるＺｒＯ2、ＴｉＯ2およびＰ2Ｏ5の合量が０．５〜５．０であるため、ガラス中に結晶が均一に析出して熱処理の際に破損せず、また、結晶化度が高くなり、高い耐熱性を得ることができる。 That is, the total amount of SiO 2 , Al 2 O 3 , Li 2 O, MgO and ZnO, which are constituent components of the precipitated β-spodumene or β-spodumene solid solution, is 93.3 to 99.5%, and the nucleating agent Since the total amount of ZrO 2 , TiO 2 and P 2 O 5 is 0.5 to 5.0, the crystals are uniformly precipitated in the glass and are not damaged during the heat treatment. Becomes high and high heat resistance can be obtained.

β−スポジュメンまたはβ−スポジュメン固溶体は、Ｌｉ2Ｏ：Ａｌ2Ｏ3：ＳｉＯ2が１：１：３〜４のモル比で形成され、Ｌｉ2Ｏの替わりにＭｇＯやＺｎＯが構成する場合がある。このように、β−スポジュメンまたはβ−スポジュメン固溶体の単位結晶あたりＡｌ2Ｏ3が常に１つ使用されるため、Ａｌ2Ｏ3の含有量が２１〜３４％であると結晶化度を高くすることが可能である。 The β-spodumene or β-spodumene solid solution is formed in a molar ratio of Li 2 O: Al 2 O 3 : SiO 2 of 1: 1: 3 to 4, and MgO or ZnO may be formed instead of Li 2 O. is there. Thus, since one Al 2 O 3 is always used per unit crystal of β-spodumene or β-spodumene solid solution, the crystallinity is increased when the content of Al 2 O 3 is 21 to 34%. It is possible.

また、Ｎａ2Ｏ、Ｋ2Ｏ、ＣａＯおよびＢａＯは、ガラスマトリックスの粘度を低下させる成分であり、それらの合量が０〜０．９％であるため、高温においてもガラスマトリックスの粘度が低下しにくく高い耐熱性が得られる。 Further, Na 2 O, K 2 O, CaO and BaO are components that lower the viscosity of the glass matrix, and since the total amount thereof is 0 to 0.9%, the viscosity of the glass matrix is lowered even at high temperatures. High heat resistance is obtained.

本発明の結晶化ガラスは、耐熱温度が１２００℃以上であるため従来使用できなかったセラミックス代替用途（例えばタービン、エンジン等）にも使用できるようになる。好ましい耐熱温度は１２３０℃以上であり、より好ましくは１２６０℃以上である。なお、耐熱温度は、径：８ｍｍφ、高さ：６ｍｍの円板形状に加工した試料の上に１ｍｍφの白金球を置き、１００ｇの荷重をかけ、平行板式粘度計（モトヤマ製）を用いて白金球が試料に貫入し始めるすなわち軟化変形する温度を軟化温度とした。   The crystallized glass of the present invention has a heat-resistant temperature of 1200 ° C. or higher, so that it can be used for ceramic substitute applications (eg, turbines, engines, etc.) that could not be used conventionally. The preferred heat resistant temperature is 1230 ° C. or higher, more preferably 1260 ° C. or higher. The heat-resistant temperature is platinum using a parallel plate viscometer (manufactured by Motoyama) by placing a platinum ball of 1 mmφ on a sample processed into a disk shape with a diameter of 8 mmφ and a height of 6 mm, applying a load of 100 g. The temperature at which the sphere begins to penetrate into the sample, that is, the temperature at which it softens and deforms was defined as the softening temperature.

また、本発明の結晶化ガラスは、曲げ強度が１８０ＭＰａ以上であることが好ましい。好ましい曲げ強度は、１９０ＭＰａ以上であり、より好ましくは２００ＭＰａ以上である。なお、曲げ強度は、ＪＩＳ Ｒ １６０１に準じて測定し、支点間距離３０ｍｍ、クロスヘッド速度０．５ｍｍ／ｍｉｎで３点曲げ試験を１０回行なった平均値とした。   In addition, the crystallized glass of the present invention preferably has a bending strength of 180 MPa or more. A preferable bending strength is 190 MPa or more, and more preferably 200 MPa or more. The bending strength was measured according to JIS R 1601, and was an average value obtained by performing a three-point bending test 10 times at a distance between supporting points of 30 mm and a crosshead speed of 0.5 mm / min.

本発明の結晶化ガラスは、主結晶がβ−スポジュメンまたはβ−スポジュメン固溶体であるが、ガーナイト、コーディエライト等の耐熱性の高い結晶を総結晶量の２５％までの範囲で含有することができる。   In the crystallized glass of the present invention, the main crystal is β-spodumene or β-spodumene solid solution, but it may contain crystals having high heat resistance such as garnite and cordierite in a range of up to 25% of the total crystal amount. it can.

本発明の結晶化ガラスは、結晶化度が９０質量％以上であると、耐熱温度が高くなりやすい。結晶化度の好ましい範囲は９１％以上、さらに好ましい範囲は９２％以上である。なお、結晶化度は、主結晶であるβ−スポジュメンまたはβ−スポジュメン固溶体だけでなく、上述した範囲で析出したガーナイト、コーディエライト等の結晶も対象とする。   If the crystallized glass of the present invention has a crystallinity of 90% by mass or more, the heat resistant temperature tends to be high. A preferable range of crystallinity is 91% or more, and a more preferable range is 92% or more. The crystallinity is not limited to β-spodumene or β-spodumene solid solution, which is the main crystal, but also crystals such as garnite and cordierite precipitated in the above range.

また、本発明の結晶化ガラスは、析出した結晶の平均結晶粒径が１．２〜１５μｍであると、曲げ強度が高くなりやすいため好ましい。平均結晶粒径が１．２μｍよりも小さいと、結晶化ガラスにクラックが発生しても、クラックの伝播を結晶粒によって阻害しにくいため、曲げ強度が向上しにくい。一方、１５μｍよりも大きいと、結晶化ガラスに加熱や冷却が繰り返される場合、結晶粒界に亀裂が生じやすく、曲げ強度が低くなりやすい。   In addition, the crystallized glass of the present invention is preferable if the average crystal grain size of the precipitated crystals is 1.2 to 15 μm because the bending strength tends to increase. If the average crystal grain size is smaller than 1.2 μm, even if cracks occur in the crystallized glass, the propagation of cracks is hardly hindered by the crystal grains, so that the bending strength is difficult to improve. On the other hand, if it is larger than 15 μm, when heating and cooling are repeated on the crystallized glass, cracks are likely to occur at the crystal grain boundaries, and the bending strength tends to be low.

本発明の結晶化ガラスは、３０〜９００℃における熱膨張係数が−１５〜＋３０×１０-7／℃であると、熱衝撃によって破損しにくいため好ましい。３０〜９００℃における熱膨張係数の好ましい範囲は、−１０〜＋２７×１０-7／℃、さらに好ましくは、−５〜＋２５×１０-7／℃である。 The crystallized glass of the present invention preferably has a thermal expansion coefficient at 30 to 900 ° C. of −15 to + 30 × 10 −7 / ° C. because it is difficult to be damaged by thermal shock. A preferable range of the thermal expansion coefficient at 30 to 900 ° C. is −10 to + 27 × 10 −7 / ° C., and more preferably −5 to + 25 × 10 −7 / ° C.

本発明の結晶化ガラスは、ビッカース硬度が６８０以上であるとキズがつきにくいため破損しにくくなるが、９００よりも大きいと研磨や掘削等の加工が困難となる。好ましくは７００〜８５０である。   If the Vickers hardness is 680 or more, the crystallized glass of the present invention is difficult to be damaged because it is hardly scratched, but if it is larger than 900, processing such as polishing and excavation becomes difficult. Preferably it is 700-850.

本発明の結晶化ガラスは、誘電損失が１．５〜３．５×１０-3であることが好ましい。誘電損失を１．５×１０-3よりも小さくすることは困難であり、３．５×１０-3よりも大きくすると電磁波によって発熱しやすくなる。なお、本発明の結晶化ガラスの誘電損失を小さくするには、ガラスマトリックス中のアルカリ金属酸化物およびアルカリ土類金属酸化物の含有量を少なくすれば良い。 The crystallized glass of the present invention preferably has a dielectric loss of 1.5 to 3.5 × 10 −3 . It is difficult to make the dielectric loss smaller than 1.5 × 10 −3 , and when it exceeds 3.5 × 10 −3 , heat is easily generated by electromagnetic waves. In order to reduce the dielectric loss of the crystallized glass of the present invention, the content of alkali metal oxide and alkaline earth metal oxide in the glass matrix may be reduced.

以下、本発明の結晶化ガラスの組成を限定した理由を説明する。   Hereinafter, the reason which limited the composition of the crystallized glass of this invention is demonstrated.

結晶構成成分であるＳｉＯ2、Ａｌ2Ｏ3、Ｌｉ2Ｏ、ＭｇＯおよびＺｎＯの合量が９３．３％よりも少ないと充分な結晶化度が得られないため、耐熱温度や曲げ強度を高くできない。一方、９９．５％よりも多いと、核形成剤を０．５％までしか含有させることができず、ガラスマトリックス中に均一に結晶が析出しにくく、また、結晶化度を高くすることができないため、耐熱温度を高くできない。結晶構成成分の合量の好ましい範囲は、９３．６〜９９．５％、より好ましい範囲は、９４．０〜９９．５％である。 SiO 2, Al 2 O 3 is a crystal component, Li 2 O, since the total amount of MgO and ZnO is not be obtained less a sufficient crystallinity than 93.3%, high heat-resistant temperature and flexural strength Can not. On the other hand, if it exceeds 99.5%, the nucleating agent can be contained only up to 0.5%, it is difficult for crystals to precipitate uniformly in the glass matrix, and the crystallinity can be increased. Because it is not possible, the heat-resistant temperature cannot be increased. A preferable range of the total amount of the crystal components is 93.6 to 99.5%, and a more preferable range is 94.0 to 99.5%.

ＳｉＯ2は、ガラスの網目を構成する主成分であるとともに、β−スポジュメンまたはβ−スポジュメン固溶体を構成する成分でもあり、４９〜７０％含有することが好ましい。ＳｉＯ2が４９％より少ないと、ガラス化しにくくなる。一方、７０％より多いと、ガラスの溶融温度が高くなる。ＳｉＯ2の好ましい範囲は、５０〜６９％、より好ましい範囲は、５２〜６８％である。 SiO 2 is a main component constituting the glass network and also a component constituting β-spodumene or β-spodumene solid solution, and it is preferably contained in 49 to 70%. When SiO 2 is less than 49%, vitrification becomes difficult. On the other hand, if it exceeds 70%, the melting temperature of the glass becomes high. A preferable range of SiO 2 is 50 to 69%, and a more preferable range is 52 to 68%.

Ａｌ2Ｏ3は、ＳｉＯ2と同様にガラスの網目を構成する成分であるとともに、β−スポジュメンまたはβ−スポジュメン固溶体を構成する成分でもある。Ａｌ2Ｏ3が２１％より少ないと、結晶化度を高くできないため高い耐熱性を得ることが困難となる。一方、３４％より多いと、ガラスが失透しやすくなるためガラスの成形が困難となる。Ａｌ2Ｏ3の好ましい範囲は、２２．５〜３３％、より好ましい範囲は、２３〜３２％である。 Al 2 O 3 is a component that constitutes a glass network in the same manner as SiO 2 and is also a component that constitutes β-spodumene or β-spodumene solid solution. If Al 2 O 3 is less than 21%, it is difficult to obtain high heat resistance because the degree of crystallinity cannot be increased. On the other hand, if it exceeds 34%, the glass tends to be devitrified, making it difficult to form the glass. A preferable range of Al 2 O 3 is 22.5 to 33%, and a more preferable range is 23 to 32%.

Ｌｉ2Ｏは、β−スポジュメンまたはβ−スポジュメン固溶体を構成する成分であり、３．８〜１０．０％含有することが好ましい。Ｌｉ2Ｏが３．８％より少ないと、結晶化度を高くすることが困難であるため、耐熱温度や曲げ強度を高くできない。一方、１０．０％より多くなると、ガラスが失透しやすくなる。特にＬｉ2Ｏが９％を超えると、全てのＬｉ2Ｏが結晶を構成するわけではなく、結晶を構成しないＬｉ2Ｏは、ガラスマトリックスを構成し、ガラスマトリックスの粘度を低下させるため、高い耐熱温度を得ることが困難となる。Ｌｉ2Ｏの好ましい範囲は、４．２〜９％、より好ましい範囲は、４．４〜７％である。 Li 2 O is a component constituting β-spodumene or β-spodumene solid solution, and is preferably contained in 3.8 to 10.0%. If the Li 2 O content is less than 3.8%, it is difficult to increase the crystallinity, so that the heat resistance temperature and bending strength cannot be increased. On the other hand, if it exceeds 10.0%, the glass tends to be devitrified. In particular when it exceeds 2 O is 9% Li, not all Li 2 O constitutes a crystal, Li 2 O which does not constitute a crystal constitutes the glass matrix, to reduce the viscosity of the glass matrix, high It becomes difficult to obtain a heat-resistant temperature. A preferable range of Li 2 O is 4.2 to 9%, and a more preferable range is 4.4 to 7%.

ＭｇＯは、Ｌｉ2Ｏと同様にβ−スポジュメンまたはβ−スポジュメン固溶体を構成する成分であり、結晶化度を高める働きを有し、８％まで含有することができる。ＭｇＯが８％より多くなると、ガラスが失透しやすいため成形が困難となるとともに、全てのＭｇＯが結晶を構成するわけではなく、結晶を構成しないＭｇＯは、ガラスマトリックスを構成する成分となり、ガラスマトリックスの粘度を低下させるため、高い耐熱温度を得ることが困難となる。ＭｇＯの好ましい範囲は０〜７％、より好ましい範囲は０〜６％である。 MgO is a component constituting β-spodumene or β-spodumene solid solution like Li 2 O, has a function of increasing the crystallinity, and can be contained up to 8%. If the MgO content exceeds 8%, the glass tends to be devitrified, making it difficult to mold, and not all MgO constitutes crystals, and MgO that does not constitute crystals becomes a component that constitutes a glass matrix. Since the viscosity of the matrix is lowered, it is difficult to obtain a high heat resistant temperature. A preferable range of MgO is 0 to 7%, and a more preferable range is 0 to 6%.

ＺｎＯは、Ｌｉ2ＯやＭｇＯと同様にβ−スポジュメンまたはβ−スポジュメン固溶体を構成する成分であり、結晶化度を高める働きを有し、９％まで含有することができる。ＺｎＯが９％より多くなると、ガラスが失透しやすいため成形が困難となるとともに、全てのＺｎＯが結晶を構成するわけではなく、結晶を構成しないＺｎＯは、ガラスマトリックスを構成する成分となり、ガラスマトリックスの粘度を低下させるため、高い耐熱温度を得ることが困難となる。ＺｎＯの好ましい範囲は０〜８％、より好ましい範囲は０〜７％である。 ZnO is a component that constitutes β-spodumene or β-spodumene solid solution like Li 2 O and MgO, has a function of increasing crystallinity, and can be contained up to 9%. If the ZnO content exceeds 9%, the glass tends to be devitrified, making it difficult to mold, and not all ZnO constitutes crystals, and ZnO that does not constitute crystals becomes a component that constitutes a glass matrix. Since the viscosity of the matrix is lowered, it is difficult to obtain a high heat resistant temperature. The preferable range of ZnO is 0 to 8%, and the more preferable range is 0 to 7%.

本発明の結晶化ガラスは、ＭｇＯとＺｎＯの合量が１〜１０％であると、結晶化度が高くなりやすく、耐熱温度が高くなりやすいため好ましい。すなわち、β−スポジュメンまたはβ−スポジュメン固溶体を主結晶として析出する結晶化ガラスでは、Ｌｉ2Ｏを７％以上としても、全てのＬｉ2Ｏが結晶を構成するわけではなく、結晶を構成しないＬｉ2Ｏはガラスマトリックスの成分となる。そこで、ＭｇＯおよび／またはＺｎＯを添加すると、結晶化度を高くすることが可能となる。ＭｇＯとＺｎＯの合量の好ましい範囲は１．２〜９．５％である。 The crystallized glass of the present invention is preferably 1 to 10% of the total amount of MgO and ZnO because the degree of crystallinity tends to increase and the heat resistant temperature tends to increase. That is, in the crystallized glass in which β-spodumene or β-spodumene solid solution is precipitated as a main crystal, even if Li 2 O is 7% or more, not all Li 2 O constitutes a crystal, and Li that does not constitute a crystal. 2 O is a component of the glass matrix. Therefore, when MgO and / or ZnO is added, the crystallinity can be increased. A preferable range of the total amount of MgO and ZnO is 1.2 to 9.5%.

核形成剤であるＴｉＯ2、ＺｒＯ2およびＰ2Ｏ5の合量が、０．５％よりも少ないとガラスマトリックス中に均一にまた充分な量の結晶が析出しないため、耐熱温度を高くできない。５％よりも多いとガラスが失透するため成形が困難となり、また、全ての核形成剤が結晶核にはならず、結晶核とならなかった核形成剤は、ガラスマトリックスを構成する成分となり、ガラスマトリックスの粘度を低下させるため、高い耐熱温度を得ることが困難となる。好ましい範囲は０．５〜４．５％、より好ましい範囲は０．５〜４．２％である。 If the total amount of the nucleating agents TiO 2 , ZrO 2 and P 2 O 5 is less than 0.5%, a sufficient amount of crystals will not precipitate in the glass matrix, so the heat resistance temperature cannot be increased. . If it exceeds 5%, the glass becomes devitrified, making it difficult to mold, and all nucleating agents do not become crystal nuclei, and the nucleating agents that have not become crystal nuclei become components constituting the glass matrix. Since the viscosity of the glass matrix is lowered, it is difficult to obtain a high heat resistant temperature. A preferable range is 0.5 to 4.5%, and a more preferable range is 0.5 to 4.2%.

ＺｒＯ2は、結晶核となる成分であり、０．５〜５％含有することが好ましい。ＺｒＯ2が０．５％より少ないと、核形成能力が不十分となり、結晶を均一に充分な量を析出させにくいため、耐熱温度が高くなりにくい。一方、４％より多くなると、失透が発生しやすくなるためガラスの成形が困難となりやすい。ＺｒＯ2の好ましい範囲は、０．７〜３．７％、より好ましい範囲は、１〜３．５％である。 ZrO 2 is a component that becomes a crystal nucleus, and is preferably contained in an amount of 0.5 to 5%. If ZrO 2 is less than 0.5%, the nucleation ability is insufficient, and it is difficult to precipitate a sufficient amount of crystals uniformly, so that the heat-resistant temperature is unlikely to increase. On the other hand, if it exceeds 4%, devitrification is likely to occur, so that it is difficult to form glass. A preferable range of ZrO 2 is 0.7 to 3.7%, and a more preferable range is 1 to 3.5%.

ＴｉＯ2は、ＺｒＯ2と同様に結晶核となる成分であり、２％まで含有することができる。ＴｉＯ2が２％より多いと、析出する結晶の平均粒径が小さくなる傾向があり、機械的強度が高くなりにくい。 TiO 2 is a component to be similarly crystal nuclei and ZrO 2, can contain up to 2%. When the content of TiO 2 is more than 2%, the average grain size of the precipitated crystals tends to be small, and the mechanical strength is hardly increased.

Ｐ2Ｏ5は、分相を促進させて結晶の析出を促す成分であり、３．０％まで含有することができる。３．０％より多いと、ガラスマトリックスの粘度を低下させるため、高い耐熱温度を得ることが困難となる。Ｐ2Ｏ5の好ましい範囲は、０〜２．８％、より好ましい範囲は、０〜２．５％である。 P 2 O 5 is a component that promotes phase separation and promotes crystal precipitation, and can be contained up to 3.0%. If the content is more than 3.0%, the viscosity of the glass matrix is lowered, so that it is difficult to obtain a high heat-resistant temperature. A preferable range of P 2 O 5 is 0 to 2.8%, and a more preferable range is 0 to 2.5%.

Ｎａ2Ｏ、Ｋ2Ｏ、ＣａＯおよびＢａＯの合量の好ましい範囲は、０〜０．７％、より好ましい範囲は、０〜０．５％であり、本質的にこれらの成分を含まないことが最も好ましい。 A preferable range of the total amount of Na 2 O, K 2 O, CaO and BaO is 0 to 0.7%, and a more preferable range is 0 to 0.5%, and these components are essentially not included. Is most preferred.

なお、本発明において、必要に応じて他の成分、例えば清澄剤としてＡｓ2Ｏ3、Ｓｂ2Ｏ3、ＳｎＯ2をそれぞれ２％まで添加しても良い。 In the present invention, other components, for example, As 2 O 3 , Sb 2 O 3 , and SnO 2 may be added up to 2%, respectively, as a clarifying agent as necessary.

以下に、本発明の結晶化ガラスの作製方法について説明する。   Below, the manufacturing method of the crystallized glass of this invention is demonstrated.

まず、所定の組成となるようにガラス原料を調合し、１５５０〜１７５０℃で４〜８時間溶融する。   First, a glass raw material is prepared so as to have a predetermined composition and melted at 1550 to 1750 ° C. for 4 to 8 hours.

次いで、溶融ガラスをロール成形、ブロー成形等の成形法によって所定の形状に成形し、常温まで冷却する。   Next, the molten glass is formed into a predetermined shape by a forming method such as roll forming or blow molding, and cooled to room temperature.

続いて、ガラス成形体を常温から２００〜３５０℃／ｈの速度で７００〜８５０℃まで昇温し、１〜４時間保持して結晶核を形成する。その後、７０〜１５０℃／ｈの速度で１０００〜１３５０℃まで昇温し、１〜４時間保持して結晶を析出させた後、２５０〜３５０℃／ｈの速度で室温まで冷却して、結晶化ガラスを作製する。   Subsequently, the glass molded body is heated from room temperature to 700 to 850 ° C. at a rate of 200 to 350 ° C./h and held for 1 to 4 hours to form crystal nuclei. Thereafter, the temperature was raised to 1000 to 1350 ° C. at a rate of 70 to 150 ° C./h, and the crystals were precipitated by holding for 1 to 4 hours, and then cooled to room temperature at a rate of 250 to 350 ° C./h, A vitrified glass is produced.

本発明の結晶化ガラスは、板状または塊状に成形した結晶性ガラスを熱処理することによって作製するため生産性が高くなる。   Since the crystallized glass of the present invention is produced by heat-treating the crystalline glass formed into a plate shape or a lump shape, the productivity becomes high.

以下、実施例に基づいて本発明の結晶化ガラスを詳細に説明する。   Hereinafter, based on an Example, the crystallized glass of this invention is demonstrated in detail.

表１、２は、実施例１〜８と、比較例１、２を示す。   Tables 1 and 2 show Examples 1 to 8 and Comparative Examples 1 and 2.

Figure 2006001828
Figure 2006001828

Figure 2006001828
Figure 2006001828

実施例１〜８および比較例１、２は、次のようにして作製した。   Examples 1 to 8 and Comparative Examples 1 and 2 were produced as follows.

まず、表中の組成となるように原料を調合した後、白金坩堝に入れ、１５８０℃で２０時間溶融した。次いで、カーボン板上に１０ｍｍの厚さのスペーサーを２本設置し、このスペーサーの間に溶融ガラスを流し出し、ローラーで表面をならすことによって、厚さ１０ｍｍのガラス板を成形し、室温まで冷却した。   First, after preparing the raw materials so as to have the composition in the table, they were put in a platinum crucible and melted at 1580 ° C. for 20 hours. Next, two 10 mm thick spacers are placed on the carbon plate, molten glass is poured between the spacers, and the surface is smoothed with a roller to form a 10 mm thick glass plate and cooled to room temperature. did.

次に、ガラス板を室温から３００℃／ｈの速度で昇温して７８０℃で３時間保持し、次いで、１００℃／ｈの速度で昇温して表中の結晶化処理温度で１時間保持した後、３００℃／ｈの速度で室温まで冷却して、結晶化ガラスを作製した。なお、Ｘ線回折法（リガク製 Ｘ線回折装置）を用いて測定した結果、主結晶はすべてβ−スポジュメン固溶体であった。   Next, the glass plate was heated from room temperature at a rate of 300 ° C./h and held at 780 ° C. for 3 hours, and then heated at a rate of 100 ° C./h for 1 hour at the crystallization treatment temperature in the table. After being held, it was cooled to room temperature at a rate of 300 ° C./h to produce crystallized glass. In addition, as a result of measuring using the X-ray-diffraction method (Rigaku X-ray-diffraction apparatus), all the main crystals were (beta) -spodumene solid solution.

結晶化度は、Ｘ線回折装置（リガク製）を用い、回折角２θが１０〜６０°の範囲において測定した結晶性ガラスの散乱強度面積と結晶化ガラスの結晶ピーク面積を多重ピーク分離法を用いて算出した値から求めた。   The degree of crystallinity is determined by a multiple peak separation method using the X-ray diffractometer (manufactured by Rigaku Corporation) to measure the scattering intensity area of crystalline glass and the crystal peak area of crystallized glass measured in the range of diffraction angle 2θ of 10-60 ° It calculated | required from the value calculated using.

平均結晶粒径は、試料の破断面を走査型電子顕微鏡（日本電子製 ＪＳＭ−５４００）で撮影し、その写真から無作為に選んだ１００個の結晶の粒径をノギスで測定した平均値とした。   The average crystal grain size is the average value obtained by photographing the fracture surface of the sample with a scanning electron microscope (JSM-5400 manufactured by JEOL Ltd.) and measuring the grain size of 100 crystals randomly selected from the photograph with a caliper. did.

耐熱温度は、径：８ｍｍφ×高さ：６ｍｍの円板形状に加工した試料の上に１ｍｍφの白金球を置き、１００ｇの荷重をかけ、平行板式粘度計（モトヤマ製）を用いて白金球が試料に貫入し始めるすなわち軟化変形する温度を軟化温度とした。   The heat-resistant temperature is set by placing a 1 mmφ platinum ball on a sample processed into a disk shape of diameter: 8 mmφ x height: 6 mm, applying a load of 100 g, and using a parallel plate viscometer (manufactured by Motoyama) The temperature at which penetration into the sample, that is, the softening and deformation occurs was defined as the softening temperature.

曲げ強度は、３×４×３６ｍｍの試験片を作製し、曲げ試験機（島津製作所製 ＥＺＴｅｓｔ−５００Ｎ）を用いてＪＩＳ Ｒ １６０１に準じ、支点間距離３０ｍｍ、クロスヘッド速度０．５ｍｍ／ｍｉｎで３点曲げ強度を１０回測定した平均値である。   The bending strength is a 3 × 4 × 36 mm test piece, and using a bending tester (EZTest-500N manufactured by Shimadzu Corporation) according to JIS R 1601, the distance between fulcrums is 30 mm, and the crosshead speed is 0.5 mm / min. It is the average value which measured 3 point | piece bending strength 10 times.

ビッカース硬度は、ビッカース硬度計（松沢精機製 ＭＸＴ５０）を用いて荷重２００ｇで試料にくぼみを形成し、測定した前記くぼみの面積からＪＩＳ Ｂ ７７３４に従って算出した。   The Vickers hardness was calculated according to JIS B 7734 from the measured area of the pit formed by forming a pit on the sample with a load of 200 g using a Vickers hardness tester (MXT50 manufactured by Matsuzawa Seiki Co., Ltd.).

耐熱衝撃性は、１００×１００×３ｍｍの形状に加工した試料を電気炉で加熱し、水中に投入してクラックまたは破損が発生した際の最も低い試料温度から水温を引いた値で評価した。   The thermal shock resistance was evaluated by a value obtained by subtracting the water temperature from the lowest sample temperature when a sample processed into a shape of 100 × 100 × 3 mm was heated in an electric furnace and introduced into water to cause cracks or breakage.

３０〜９００℃における熱膨張係数は、熱膨張計（マックサイエンス製 ＴＤ−５０００）を使用して測定した。   The thermal expansion coefficient at 30 to 900 ° C. was measured using a thermal dilatometer (TD-5000 manufactured by Mac Science).

誘電損失は、２５℃において１ＭＨｚでの誘電率（ε）と損失ｔａｎδを測定し、その積である誘電損失（ε・ｔａｎδ）を算出した。なお、測定にはインピーダンスアナライザ（横河ヒューレットパッカード製 ４１９２Ａ）を用いた。   The dielectric loss was obtained by measuring the dielectric constant (ε) and loss tan δ at 1 MHz at 25 ° C., and calculating the dielectric loss (ε · tan δ), which is the product of these. Note that an impedance analyzer (Yokogawa Hewlett Packard 4192A) was used for the measurement.

熱伝導率は、１０ｍｍφ×２ｍｍの形状に加工した試料をレーザーフラッシュ法（真空理工製 ＴＣ−７０００）により測定した。   The thermal conductivity was measured by a laser flash method (TC-7000 manufactured by Vacuum Riko Co., Ltd.) on a sample processed into a shape of 10 mmφ × 2 mm.

表１から明らかなように、実施例１〜８は、耐熱温度が１２３０〜１３３０℃、耐熱衝撃性が６００℃以上と高く、また、曲げ強度も２２０ＭＰａ以上と高かった。特に実施例１〜７は、耐熱温度が１３００〜１３３０℃、耐熱衝撃性が７００℃以上と、ともに高かった。   As apparent from Table 1, Examples 1 to 8 had a heat resistant temperature of 1230 to 1330 ° C., a thermal shock resistance as high as 600 ° C. or higher, and a bending strength as high as 220 MPa or higher. In particular, Examples 1 to 7 had high heat resistance temperatures of 1300 to 1330 ° C. and thermal shock resistance of 700 ° C. or higher.

一方、表２から明らかなように、比較例１および２は、結晶化度が８６％以下と低く、耐熱温度が１１５０℃、曲げ強度が１７０ＭＰａと、ともに低い値であった。   On the other hand, as is clear from Table 2, Comparative Examples 1 and 2 had a low crystallinity of 86% or less, a heat resistant temperature of 1150 ° C., and a bending strength of 170 MPa.

本発明の結晶化ガラスは、耐熱性が優れるとともに、耐熱衝撃性、機械的強度も優れるため、例えばタービンやエンジン等の用途に使用可能である。また、調理器用トッププレートや耐熱食器、もしくは焼成用セッター等の耐熱性を必要とする用途や低熱膨張、高強度であるため、光ファイバーを固定する光通信用途部材、例えば、カプラーケース等に使用可能である。   Since the crystallized glass of the present invention has excellent heat resistance, thermal shock resistance and mechanical strength, it can be used for applications such as turbines and engines. In addition, it can be used for optical communication applications such as coupler cases, etc. for fixing optical fibers because it has heat resistance such as top plates for cookers, heat-resistant dishes, baking setters, and low thermal expansion and high strength. It is.

Claims (9)

β−スポジュメンまたはβ−スポジュメン固溶体を主結晶とする結晶化ガラスであって、質量％で、Ａｌ2Ｏ3 ２１〜３４％を含有し、ＳｉＯ2、Ａｌ2Ｏ3、Ｌｉ2Ｏ、ＭｇＯおよびＺｎＯの合量が９３．３〜９９．５％、ＺｒＯ2、ＴｉＯ2およびＰ2Ｏ5の合量が０．５〜５％、Ｎａ2Ｏ、Ｋ2Ｏ、ＣａＯおよびＢａＯの合量が０〜０．９％であることを特徴とする結晶化ガラス。 A crystallized glass having β-spodumene or β-spodumene solid solution as a main crystal, and containing 21 to 34% by mass of Al 2 O 3 , SiO 2 , Al 2 O 3 , Li 2 O, MgO and the total amount of ZnO is 93.3~99.5%, ZrO 2, the total amount of TiO 2 and P 2 O 5 is 0.5~5%, Na 2 O, K 2 O, the total content of CaO and BaO is Crystallized glass characterized by being 0 to 0.9%. 質量％で、ＳｉＯ2 ４９〜７０％、Ｌｉ2Ｏ ３．８〜１０．０％を含有することを特徴とする請求項1に記載の結晶化ガラス。 2. The crystallized glass according to claim 1, wherein the crystallized glass contains 49 to 70% of SiO 2 and 3.8 to 10.0% of Li 2 O in mass%. 質量％で、ＭｇＯとＺｎＯの合量が１〜１０％であることを特徴とする請求項１または２に記載の結晶化ガラス。   The crystallized glass according to claim 1 or 2, wherein the total amount of MgO and ZnO is 1 to 10% by mass. 結晶化度が９０質量％以上であることを特徴とする請求項１〜３のいずれかに記載の結晶化ガラス。   Crystallization degree is 90 mass% or more, The crystallized glass in any one of Claims 1-3 characterized by the above-mentioned. 平均結晶粒径が１．２〜１５μｍであることを特徴とする請求項１〜４のいずれかに記載の結晶化ガラス。   The crystallized glass according to any one of claims 1 to 4, wherein the average crystal grain size is 1.2 to 15 µm. β−スポジュメンまたはβ−スポジュメン固溶体を主結晶とする結晶化ガラスであって、耐熱温度が１２００℃以上であることを特徴とする結晶化ガラス。   A crystallized glass having β-spodumene or β-spodumene solid solution as a main crystal, wherein the heat-resistant temperature is 1200 ° C. or higher. 曲げ強度が１８０ＭＰａ以上であることを特徴とする請求項６に記載の結晶化ガラス。   The crystallized glass according to claim 6, wherein the bending strength is 180 MPa or more. 結晶化度が９０質量％以上であることを特徴とする請求項６または７に記載の結晶化ガラス。   The crystallized glass according to claim 6 or 7, wherein the crystallinity is 90% by mass or more. 平均結晶粒径が１．２〜１５μｍであることを特徴とする請求項６〜８のいずれかに記載の結晶化ガラス。   The crystallized glass according to any one of claims 6 to 8, wherein the average crystal grain size is 1.2 to 15 µm.
JP2005128827A 2004-05-18 2005-04-27 Crystallized glass Pending JP2006001828A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP2005128827A JP2006001828A (en) 2004-05-18 2005-04-27 Crystallized glass

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2004147096 2004-05-18
JP2005128827A JP2006001828A (en) 2004-05-18 2005-04-27 Crystallized glass

Publications (1)

Publication Number Publication Date
JP2006001828A true JP2006001828A (en) 2006-01-05

Family

ID=35770533

Family Applications (1)

Application Number Title Priority Date Filing Date
JP2005128827A Pending JP2006001828A (en) 2004-05-18 2005-04-27 Crystallized glass

Country Status (1)

Country Link
JP (1) JP2006001828A (en)

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2006232661A (en) * 2005-01-31 2006-09-07 Ohara Inc Crystallized glass and its manufacturing method
WO2012020678A1 (en) * 2010-08-11 2012-02-16 日本電気硝子株式会社 Li2O-Al2O3-SiO2-BASED CRYSTALLIZED GLASS
JP2013063870A (en) * 2011-09-16 2013-04-11 Nippon Electric Glass Co Ltd Method for producing silicate glass
WO2020196171A1 (en) * 2019-03-22 2020-10-01 日本電気硝子株式会社 Li2o-al2o3-sio2-based crystallized glass
CN111732420A (en) * 2019-03-25 2020-10-02 京瓷株式会社 Heat-resistant member
WO2020203308A1 (en) * 2019-04-01 2020-10-08 日本電気硝子株式会社 Li2o-al2o3-sio2-based crystallized glass
WO2020217792A1 (en) * 2019-04-23 2020-10-29 日本電気硝子株式会社 Li2o-al2o3-sio2-based crystallized glass
CN116332516A (en) * 2023-02-24 2023-06-27 清远南玻节能新材料有限公司 Frosted glass ceramic, preparation method thereof and glass product

Cited By (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2006232661A (en) * 2005-01-31 2006-09-07 Ohara Inc Crystallized glass and its manufacturing method
WO2012020678A1 (en) * 2010-08-11 2012-02-16 日本電気硝子株式会社 Li2O-Al2O3-SiO2-BASED CRYSTALLIZED GLASS
JP2012056829A (en) * 2010-08-11 2012-03-22 Nippon Electric Glass Co Ltd Li2O-Al2O3-SiO2-BASED CRYSTALLIZED GLASS
US9126859B2 (en) 2010-08-11 2015-09-08 Nippon Electric Glass Co., Ltd. Li2O—Al2O3—SiO2—based crystallized glass
JP2013063870A (en) * 2011-09-16 2013-04-11 Nippon Electric Glass Co Ltd Method for producing silicate glass
JP2020189782A (en) * 2019-03-22 2020-11-26 日本電気硝子株式会社 Li2O-Al2O3-SiO2 BASED CRYSTALLIZED GLASS
WO2020196171A1 (en) * 2019-03-22 2020-10-01 日本電気硝子株式会社 Li2o-al2o3-sio2-based crystallized glass
CN111732420A (en) * 2019-03-25 2020-10-02 京瓷株式会社 Heat-resistant member
WO2020203308A1 (en) * 2019-04-01 2020-10-08 日本電気硝子株式会社 Li2o-al2o3-sio2-based crystallized glass
JP2020196664A (en) * 2019-04-01 2020-12-10 日本電気硝子株式会社 Li2O-Al2O3-SiO2-BASED CRYSTALLIZED GLASS
WO2020217792A1 (en) * 2019-04-23 2020-10-29 日本電気硝子株式会社 Li2o-al2o3-sio2-based crystallized glass
KR20210153593A (en) * 2019-04-23 2021-12-17 니폰 덴키 가라스 가부시키가이샤 Li2O-Al2O3-SiO2 based crystallized glass
KR102703956B1 (en) * 2019-04-23 2024-09-06 니폰 덴키 가라스 가부시키가이샤 Li2O-Al2O3-SiO2 system crystallized glass
CN116332516A (en) * 2023-02-24 2023-06-27 清远南玻节能新材料有限公司 Frosted glass ceramic, preparation method thereof and glass product

Similar Documents

Publication Publication Date Title
JP7498894B2 (en) Tempered glass and tempered glass
JP2006001828A (en) Crystallized glass
JP4451780B2 (en) Glass ceramic and method for producing the same
WO2020082328A1 (en) Microcrystalline glass product and microcrystalline glass for electronic equipment cover plate
JP5365975B2 (en) Crystallized glass article and method for producing the same
CN114126859B (en) Laminated member
TWI828718B (en) Methods of ceramming glass articles having improved warp
CN114956577A (en) High-strength transparent microcrystalline glass and preparation method thereof
JP2010116315A (en) Crystallized glass
JP2010503601A (en) Manufacturing method of glass ceramic material in thin plate shape, thin plate including them and method of using them
CN1944300B (en) Low expansion coefficient micro crystal glass and its heat processing method
WO2024109495A1 (en) 3d microcrystalline glass, preparation method therefor, and pre-crystallized microcrystalline glass
JP6675577B2 (en) Semiconductor wafer support substrate
US20230192540A1 (en) Chemically strengthened glass and crystallized glass, and manufacturing methods therefor
JP2010018512A (en) Crystallized glass
JP2624149B2 (en) Composition for low temperature firing glass ceramic substrate
JP2004168597A (en) Lead-free glass and composition for electronic circuit board
KR102153315B1 (en) Manufacturing method of bone china earthenware using the glaze composition for chemical strengthening of bone china earthenware
CN116969683A (en) Microcrystalline glass capable of being chemically strengthened and strengthening method and application thereof
JP4229045B2 (en) Electronic circuit board and lead-free glass for producing electronic circuit board
US10836680B2 (en) Yoshiokaite glass-ceramics obtained from glass frits
JP2004099429A (en) Crystallized glass
JP2013067525A (en) Crystallized glass article
JP2005281101A (en) Glass substrate for display device
CN115745411B (en) Composition for preparing low-expansion transparent glass ceramics, and preparation method and application thereof