JPS5849635A - Crystalline glass having high strength and low expansion - Google Patents

Abstract

PURPOSE:To provide the titled glass having low thermal expansion and high mechanical strength, and useful as an industrial material, by heat-treating a glass material composed of specific amounts of SiO2, Al2O3, Li2O, TiO2, ZrO2, F, and As2O3. CONSTITUTION:The objective glass is prepared by heat-treatment of a glass material composed of 50-73(wt)% SiO2, 12-35% Al2O3, 2-10% Li2O, 0.1-6% TiO2, 0.1-6% ZrO2, 0.1-6% F, and 0.05-8% As2O3, wherein SiO2+Al2O3+ Li2O+TiO2+ZrO2+F+As2O3 is >=90%, SiO2+Al2O3+Li2O is >=81%, the con tent of Na2O, K2O, CaO, MgO and B2O3 is <=5%, and that of PbO, ZnO, BaO, SrO, and P2O5 is <=3%. The crystalline glass obtained by this process has a thermal expansion coefficient of <=20X10<-7>/ deg.C, between 50 deg.C and 500 deg.C, can be cut, machined or ground without loss of mechanical strength, and has excellent heat resistance and thermal-shock resistance.

Description

【発明の詳細な説明】 本発明は、殊に機械的強度が大きくかつ低熱膨関 腸性を有する結晶化ガラスに暖する。更に詳述すれば、
工業材料として特に有利に使用で門る高い機械的強度を
維持し得る元膨張性結晶化ガラスに関する。DETAILED DESCRIPTION OF THE INVENTION The present invention is particularly directed to crystallized glass having high mechanical strength, low thermal expansion, and enteric property. To be more detailed,
The present invention relates to expansible crystallized glass that can maintain high mechanical strength and can be particularly advantageously used as an industrial material.

従来、約１！ＯＸ　１０　”′ｂ（５０〜５００００）
以下の熱膨張係数を有する低膨張性結晶化ガラスは、Ｌ
ｉ２Ｏ−ム１□０３’−８ｉ０２系の結晶物例えばβ・
スボジュウメン或はβ・ニークリ１タイト若しくはそれ
らを主成分とする構成から成ることは良く知られている
。Conventionally, about 1! OX 10”’b (50-50000)
Low expansion crystallized glass having the following coefficient of thermal expansion is L
i2O-mu1□03'-8i02-based crystals, such as β.
It is well known that it is composed of subodumene or β-niquelinitite or a structure containing these as the main components.

係る結晶化ガラスの機械的強度殊に曲げ強度はほぼ２０
００〜３００　Ｑｋｇ／ｃｔＡ　程度の範囲内に限られ
ていた。The mechanical strength, especially the bending strength, of such crystallized glass is approximately 20
It was limited to a range of about 00 to 300 Qkg/ctA.

一方、別異の結晶構造の結晶化ガラスであって高い機械
的強度例えば曲げ強度で５０００〜６０００ｋｇ／ｃｄ
前後を有するものも種々開発されているが、いずれも熱
膨張係数が７０〜ｓ　ｏ　ｘ　ｉ　ｏ−７／／′ａ　（
５０〜５００°０）前後若しくはそれ以上であって、耐
熱性、−耐熱ｍｌ撃性については満足できるものではな
かった。したがって、このような結晶化ガラスは高温度
で薦負荷が要求される工業材料用としては不向きな素材
となっている。このような実態の中で、その後、高い曲
げ強度を有する低膨張性結晶化ガラスが開発され、例見
げ特公昭４５−３５５５　、特公昭４５−４ｓｑｏ　、
特公昭４６−５８３５．特公昭４６−４２９１８等の各
公報にて提案され泥が、これべの結晶化ガラスはいす。On the other hand, it is a crystallized glass with a different crystal structure and has a high mechanical strength, for example, a bending strength of 5000 to 6000 kg/cd.
Various types have been developed that have front and back sides, but all of them have thermal expansion coefficients of 70 to s o x i o -7//'a (
50 to 500[deg.]0) or more, and the heat resistance and heat-resistant ml impact resistance were not satisfactory. Therefore, such crystallized glass is an unsuitable material for industrial materials that require high temperatures and high loads. Under these circumstances, low-expansion crystallized glass with high bending strength was subsequently developed, and examples include Mige Tokko Sho 45-3555, Sho 45-4 SQO,
Tokuko Showa 46-5835. The crystallized glass was proposed in various publications such as Japanese Patent Publication No. 46-42918.

本内部結晶物ど表面結晶物とを鼻にする構造を有し、各
々の結晶物の熱膨張係数の相違から生ずる表面圧縮応力
によって高い機械的強度を得ているものすある。したが
って、これらの結晶化ガラスは切断、切削、研磨等の２
次加工により、圧縮応力が解放されると、前記強度を維
持することができなくなるという致命的な欠点を有して
いるので、前記２次加工を必要とする工業材料用素材と
して特に高機械的強度を必要とするものへの使用はほと
んど不可能であった。Some have a structure in which the inner crystalline material and the surface crystalline material form a nose, and high mechanical strength is obtained by the surface compressive stress resulting from the difference in the coefficient of thermal expansion of each crystalline material. Therefore, these crystallized glasses can be cut, cut, polished, etc.
It has the fatal disadvantage of not being able to maintain its strength once the compressive stress is released by the secondary processing, so it is particularly suitable for use as a material for industrial materials that require the secondary processing. It was almost impossible to use it for things that required strength.

本発明者らは　これらの実態を鑑み、切断・切削、研磨
等の２次加工を経ても、１柴材料として使用しうる高機
械的強度を維持しうる素材を提供すぺ〈鋭意研究を重ね
た結果、高機械的強度が表面圧縮応力によらず、結晶物
本来の強度を′維持し２次加工によって強度低下を来た
さない新規な高強度低膨張性結晶化ガラスを見い出した
。すなわち、本発明は、特許第８５４４６５号（特公昭
５ｌ−ｊ１９２６）明細書に記載されているＦとム５２
０３の相乗的効果に着目し、それらの併存と結晶核形成
剤との組合せが特定ガラス体において核形成の微細化な
すとの知見に基づく。In view of these circumstances, the inventors of the present invention have conducted extensive research to provide a material that can maintain high mechanical strength and can be used as a Shiba material even after undergoing secondary processing such as cutting, cutting, and polishing. As a result, we have discovered a new high-strength, low-expansion crystallized glass whose high mechanical strength is not dependent on surface compressive stress, maintains the original strength of the crystalline material, and does not suffer from a decrease in strength due to secondary processing. That is, the present invention is based on
Focusing on the synergistic effect of 03, it is based on the knowledge that the combination of their coexistence and a crystal nucleating agent results in finer nucleation in a specific glass body.

本発明の目的は、８０Ｘ１０　？／’ｏ（５０〜５００
°０）を越えない熱膨張係数を有する結晶化ガラスであ
って、切断、切削、研磨等の２次加工を経ても機械的強
度が低下せず依然として高い機械的強度を維持する高強
度低膨張性結晶化ガラスを提供することである。The object of the present invention is 80X10? /'o(50~500
High strength, low expansion crystallized glass with a coefficient of thermal expansion not exceeding °0), which maintains high mechanical strength without decreasing its mechanical strength even after secondary processing such as cutting, cutting, and polishing. An object of the present invention is to provide a transparent glass-ceramic.

前記目的を達成するに必要な本発明の要旨は重量％で８
４０２５０〜７３％、ム１，０３１２〜３５％＋　Ｌｉ
２０２〜ｌＯ％＋　ＴｉＯ２０−１〜６％、ＺｒＯ２０
，１〜６％、及びＦｏ、１〜６％。The gist of the present invention necessary to achieve the above object is 8% by weight.
40250~73%, Mu10312~35%+Li
202~1O% + TiO20-1~6%, ZrO20
, 1-6%, and Fo, 1-6%.

ム８□０３０．０５〜８％を必要成分とするガラス体を
熱処理することにより得られる結晶化ガラスに存する。It consists in crystallized glass obtained by heat-treating a glass body containing 0.05 to 8% of Mu8□03 as a necessary component.

本発明の結晶化ガラスにおいて、その強度増大に最も大
きく寄与するものは、上記成分にあってＦとム５２０３
の併存と結晶核形成剤（’ｒｉｏ、ｌ＋　ＺｒＯ２）と
の組合せであり、構造にあっては目２０・ム１□０３・
４８ｉ０２結晶の多量かつ緻密な存在である。In the crystallized glass of the present invention, the components that contribute most to the increase in strength are F and M5203 among the above components.
It is a combination of the coexistence of and a crystal nucleating agent ('rio, l + ZrO2), and the structure is 20, 1, 03,
48i02 crystals are abundant and dense.

更に詳述すれば、前記特許第８５４４６５号明細書には
、Ｌ　ｉ２０　８　ｉ　０２系又はＬＳ２０−　Ａｔ２
０３−８ｉ０２系のガ３− ブスにおいて、Ｆと五ａ２Ｏ３の組合せが核形成剤とし
てはたらき、Ｌｉ２０・２８ｉ０２結晶の析出起点とな
るべく極めて多量な結晶核となる旨が記載されているが
、本発明はこのＦとム８□０３の組合せがＬｉ２０−ム
１２０３−８　＋　０２系のガラスにおいて、Ｌｉ２０
−ム１２０３・４８１０、結晶の析出のために作用する
核形成剤（Ｔｉｅ２十ＺｒＯ２）による結晶核の生成に
関し、その核の微細化及び多量化に大きく寄与するとの
知見に基づきなされたものである。係るＬｉ２０−ム１
２０３−８　ｉ　０２系ガラス体が、一定の熱処理を受
けることによって、第１段階でＦとム８□０３との相乗
的効果を受けて微細かつ多量のＴｌ０２（／レチル）・
ＺｒＯ２（パップフィト）の共晶核が生成しかつ当該核
を起点としてＬ１□０・ムｌ、　０３・４８ｉ０２結晶
が開始されそして第２段階で前記結晶の成長が進む。し
かしながら、結晶核が極めて多量であるところから結晶
の成長が相互に干渉し、一定範囲内でその゛成長が進む
がほとんどは微細結晶のまま停止し、全体としてガラス
体は極めて微細かつ多量なＬｉ２Ｏ・ム１□０３・４８
ｉｏ□結晶より一番− 出したＬｉ２Ｏ・＾１２０３・４８　＊　０２結晶体は
、それ自体微細結晶を緻密に結合した安定な結晶結合構
造を維持するので、結晶相互の結合強度が大きく、外力
負荷が大きくなったにしても内部応力の発生が少なく結
晶間のズレ等結晶構造欠陥の発生がほとんどなく、結晶
体の機械的強度の維持及び増大につながっている。更に
Ｉ−＋２０・Ａ１２０３・４８１Ｏ□結晶それ自体は約
−２，４×１０−７１００（２ｏ　〜６ｏｏ°ｏ　）　
ノ熱ｇ脹係数を有するので、実際上マトリックスガラス
と前記結晶物を官有する結晶化ガラス体において、前記
結晶を４０％Ｌｕ上含有する結晶化ガラスでは約２５Ｘ
１０７／’ｏ　（５０〜５００°０）以内の熱膨張係数
を得ることができる１、なお、前記結晶の含有敏が多い
ほど、得られる結晶化ガラスの熱膨張係数は小さくなる
傾向にある。More specifically, in the specification of the above-mentioned patent No. 854465, L i20 8 i 02 series or LS20-At2
In the 03-8i02 series gas, it is stated that the combination of F and 5a2O3 acts as a nucleating agent and forms an extremely large number of crystal nuclei that serve as the starting point for the precipitation of Li20.28i02 crystals. is a Li20-mu1203-8 + 02 series glass in which the combination of F and Mu8□03 is Li20
- 1203/4810, was made based on the knowledge that a nucleating agent (Tie20ZrO2) that acts for crystal precipitation greatly contributes to the miniaturization and increase in the number of crystal nuclei. . The Li20-mu1
When the 203-8 i02 glass body is subjected to a certain heat treatment, a fine and large amount of Tl02 (/retyl) is formed in the first step due to the synergistic effect of F and Mu8
A eutectic nucleus of ZrO2 (Papphyto) is generated, and L1□0.mul, 03.48i02 crystal is started from this nucleus, and the growth of the crystal proceeds in the second stage. However, due to the extremely large number of crystal nuclei, the growth of crystals interferes with each other, and although the growth progresses within a certain range, most of the crystals stop as fine crystals, and the glass body as a whole is made up of extremely fine and large amounts of Li2O.・Mu1□03.48
The Li2O・^1203・48*02 crystal that is released from the io□ crystal itself maintains a stable crystal bond structure in which fine crystals are tightly bonded, so the bond strength between the crystals is high and it can withstand external force loads. Even if the crystal structure increases, internal stress is generated little and crystal structure defects such as misalignment between crystals hardly occur, leading to the maintenance and increase of the mechanical strength of the crystal body. Furthermore, the I−+20・A1203・481O□ crystal itself is approximately −2,4×10−7100 (2o ~ 6oo°o)
In practice, in a crystallized glass body containing a matrix glass and the crystalline material, a crystallized glass containing 40% Lu or more of the crystalline material has a thermal g-expansion coefficient of about 25X.
It is possible to obtain a coefficient of thermal expansion within 107/'o (50 to 500°0).The more the crystal content is, the smaller the coefficient of thermal expansion of the obtained crystallized glass tends to be.

一７／℃ 本発明において特に２５Ｘ１０　　　（５０〜５００°
Ｃ）以下の熱膨張係数を有する結晶化ガラス体を得んと
する。１、β・スボジュウメン結晶が約４０％以９０％
以上含有し、その中で■、＋２０十ム１□０３　＋　８
＋　０２が８１％占めていることが必要となる。-7/℃ In the present invention, especially 25X10 (50~500°
C) Try to obtain a crystallized glass body having the following thermal expansion coefficient. 1. Approximately 40% to 90% β-subodumene crystals
Contains more than ■, +200m1□03 +8
+02 must account for 81%.

なお、Ｆとム畠２０３　　との組合せによる作用効果は
、殊Ｇに、第１１一段階の熱処理で結晶核の多量形成及
び第２段階で結晶の微細化を相乗的に達成させることに
ある。すなわち、核形成補助剤として、Ｆのみの或はム
Ｓ２０．のみの添加でもその含有量を増大させることに
よって、前記該の多量形成化及び結晶の微細化はある程
度図れ得るが、前記目的を達成させるためには不十分で
ある。The effect of the combination of F and Muhata 203 is particularly that G synergistically achieves the formation of a large amount of crystal nuclei in the first step of heat treatment and the refinement of crystals in the second step. That is, as a nucleation aid, F alone or S20. Although it is possible to increase the formation of a large amount and to make the crystals finer to some extent by increasing the content even by adding just a single amount, it is not sufficient to achieve the above objectives.

Ｆとム畠、０３とを組合せて添加した結晶化ガラスの曲
げ強度が各々の一つを添加しない結晶化ガラスのそれに
比して約１．５〜２倍程大きくなることが実験データに
基づく第１表・及び＠２表から理解することができる。Based on experimental data, the bending strength of crystallized glass to which F and Muhata and 03 are added is approximately 1.5 to 2 times greater than that of crystallized glass without the addition of either one of them. This can be understood from Table 1 and @Table 2.

（第１表のム５２０３は外分比で示す。）７− 第　　　２　　　表 （第２表のＦは外分比で示す。） Ｂ− 第１表、第２表から、Ｆ、ム’２０３のそれぞれ一方を
含有しない結晶化ガラスの曲げ強度はそれぞれ１ａＯＯ
ｋｇ／ｉ、　２０５０に９／ｃｄであるのに対し、Ｆｌ
　ａｓ、ｏ。(Mu5203 in Table 1 is shown as an external ratio.) 7- Table 2 (F in Table 2 is shown as an external ratio.) B- From Tables 1 and 2, F, Mu'203 The bending strength of crystallized glass that does not contain either one of these is 1aOO, respectively.
kg/i, 9/cd in 2050, whereas Fl
as, o.

を組合せて含有させるとその機械的強度は飛躍的に増大
し、約５０００に９／ｄＫ達する高い曲げ強度を有する
結晶化ガラスが得られることがわかる。なお、第１表、
第２表のデータはいずれも表面を約１１ゝ程度研磨した
加工ズミの試料を測定したもので、試料数ｎ＝２０の平
均値である。ちなみに果研磨の試料の曲げ強度は第１表
階ｌが３８５０　ｋｇ／ｃＪ　。It can be seen that when these are contained in combination, the mechanical strength increases dramatically, and a crystallized glass having a high bending strength of about 50009/dK can be obtained. In addition, Table 1,
The data in Table 2 are all measured on samples with machining scratches on the surface polished by about 11 degrees, and are the average values of n=20 samples. By the way, the bending strength of the fruit-polished sample is 3850 kg/cJ in Table 1.

Ｎｏ３が４１１・ｋｇ／ｌ、ｄであった。No. 3 was 411 kg/l, d.

本発明において、８１０２．ム１□０３　＋　Ｌｉ２Ｏ
＊　Ｔ轟０２゜ＺｒＯ□、及びＦ、λ−２０３の必須成
分の含有量を上記の如く限宗したが、そめ限定理由は次
の如くである。In the present invention, 8102. Mu1□03 + Li2O
* The content of the essential components of Tdoro02°ZrO□, F, and λ-203 was limited as described above, and the reason for the limitation is as follows.

ｓｉｏ□が５６％未満であるとき、ｉＪ（られる結晶化
ガラスは耐化学性が悪く、又夾雑結晶物の析出が多くな
って、所望の機械的強度、低膨張性が得られ難くなる。When sio□ is less than 56%, the crystallized glass produced by iJ(iJ) has poor chemical resistance and precipitation of contaminant crystals increases, making it difficult to obtain the desired mechanical strength and low expansion property.

一方、７３％を越える場合、ガラス質な結晶物が得られ
難く、所望する特性が得られない。したがって、８ｉ０
２は５０〜７３％に限定される。On the other hand, if it exceeds 73%, it is difficult to obtain a glassy crystalline substance, and desired characteristics cannot be obtained. Therefore, 8i0
2 is limited to 50-73%.

ム１□０３が１２％未満であるとき、浴融時　ガラスの
液相温度が高くなり作業性に支障を来たし、又夾雑結晶
物の析出が多くなって、所望の緒特性が得られ難くなる
。一方、３５％　を越える場合はガラスが難溶性となり
又作業性も悪くなりそして所望の結晶物及び所望の強度
、低膨張性が得られない。したがって、ム１２０３は１
２〜３５％に限られる。When Mo1□03 is less than 12%, the liquidus temperature of the glass during bath melting becomes high, which hinders workability, and the precipitation of contaminant crystals increases, making it difficult to obtain the desired properties. . On the other hand, if it exceeds 35%, the glass becomes poorly soluble and the workability deteriorates, making it impossible to obtain the desired crystalline material, desired strength and low expansion properties. Therefore, mu 1203 is 1
Limited to 2-35%.

ＬｉｚＯが２〜１０％の範囲を逸脱すると、３０×１　
ｏ　−７／’（）　（δＯ〜５００°０）以下の線熱膨
張係数を示す結晶化ガラスが得られない。したがって、
Ｌｉ２Ｏは２〜ｌＯ％の範囲に限られる。If LizO deviates from the range of 2-10%, 30×1
A crystallized glass exhibiting a coefficient of linear thermal expansion of less than o −7/′() (δO˜500°0) cannot be obtained. therefore,
Li2O is limited to a range of 2-10%.

ＴｊＯ□は前記した如＜　ＺｒＯ２と共に核形成剤とし
て作用し、極めて微細な結晶核（Ｉｖチル結晶）が析出
する。殊にＴｉＯ□はＺｒＯ□よりも晶出速度が早く、
Ｌ　Ａ２０・ムｌ、０３・４８　＊　０２結晶の析出に
優先的に作用する。０．１％未満の場合、Ｆ及びム〜０
．の相乗効果を受けても核形成の絶体量が少なく、所望
する１−Ａ２０・Ａｔ２０３・４８１０．結晶の緻密性
を欠き、充分な機械的強度が得られない。７％を越える
とガラスの溶融性が豊くなると共に失透が発生し易すく
なり、諸性能に影響する夾雑結晶物の析出原因となる。As described above, TjO□ acts as a nucleating agent together with ZrO2, and extremely fine crystal nuclei (Iv chill crystals) are precipitated. In particular, TiO□ has a faster crystallization speed than ZrO□,
LA20.ml, 03.48 * Acts preferentially on the precipitation of 02 crystals. If less than 0.1%, F and Mu~0
．． Even with the synergistic effect of 1-A20, At203, 4810. The crystal lacks denseness and sufficient mechanical strength cannot be obtained. If it exceeds 7%, the melting properties of the glass will increase and devitrification will easily occur, causing the precipitation of contaminant crystals that will affect various performances.

したがって、Ｔ　Ｉ　Ａ２は０．１〜７％の範囲内に限
られる。Therefore, TIA2 is limited to a range of 0.1 to 7%.

Ｚ　ｒ　０２は　前記した如（ＴｉＯ２と共に核形成剤
としテ作用するが、殊に７トリツクスガラヌの存在量を
減少させる効果を有する。すなわち、結晶化ガラスにお
ける結晶緻密性を更に向トさせ強度を向上させるには、
夾雑結晶物であったとしても　マトリックスガラスの存
在よりも結晶物の存在のほうが有利である。ＺｒＯ□は
Ｔｉｎ２の併存下で　核形成条件の相趨から特にマトリ
ックスガラスの結晶化に作用する。更にＺｒＯ２は結晶
化ガラスの耐化学性を向上させるはたらきがある。０．
１％未満のときは前記効果が発揮されず、殊に機械的強
度のもう一歩の向上に不十分である。一方、６％を越え
ると、スカムが生じてその溶融性を悪くすると共に失透
の大きな原因となり、夾雑結晶物が多量に析１１− 出し　殊に所望の低膨張性が得られない。したがって、
７ｒＯ□は０．１〜６％の範囲に限られる。As mentioned above, Zr02 acts as a nucleating agent together with TiO2, but has the effect of reducing the amount of 7-trix galanus in particular. In other words, it further improves the crystal density in crystallized glass and improves its strength. To let
Even if it is a contaminant crystal, the presence of the crystal is more advantageous than the presence of matrix glass. In the coexistence of Tin2, ZrO□ particularly acts on the crystallization of the matrix glass due to the trend of nucleation conditions. Furthermore, ZrO2 has the function of improving the chemical resistance of crystallized glass. 0.
If it is less than 1%, the above effect is not exhibited, and it is particularly insufficient to further improve mechanical strength. On the other hand, if it exceeds 6%, scum is formed, which impairs the meltability and becomes a major cause of devitrification, and a large amount of contaminant crystals precipitates out, making it particularly difficult to obtain the desired low expansion property. therefore,
7rO□ is limited to a range of 0.1 to 6%.

Ｆは、Ａ・２０３の存在下でその相乗作用で、ＴｉＯ２
の核形成を補助し、その結Ｊ＆核の多量析出に必要であ
る。そして、ＺｒＯ２の溶融性を補助する作用を有し　
又ＺｒＯ□の核形成を早める作用を示す。したがって、
ｋ゛が０．１％未満のときは１．ｉｓ□０３との組合せ
相乗効果を得ても、前記効果を充分に得ることができな
い。又、その過少はｆＲ融待時スカム発生傾向増大し、
溶融条件の厳しい調整を余鍜なくされる。一方、６％を
越えるとガラス溶融時、炉材の損傷を著しくし　かつ溶
融面からのＦの揮散が著しくなるためガラスが不均質に
なって最終製品にとける均質な結晶の析出を妨ける。し
たがって、Ｆは０．１〜６％の範囲内でなければならな
い。In the presence of A.203, F has a synergistic effect on TiO2
It assists in nucleation and is necessary for its formation and precipitation of a large amount of nuclei. It also has the effect of assisting the melting properties of ZrO2.
It also shows the effect of accelerating the nucleation of ZrO□. therefore,
1 when k゛ is less than 0.1%. Even if a synergistic effect is obtained in combination with is□03, the above effect cannot be sufficiently obtained. In addition, its deficiency increases the tendency for scum to occur during fR merchandising.
Strict adjustment of melting conditions is required. On the other hand, if it exceeds 6%, damage to the furnace material will be significant during glass melting, and the volatilization of F from the melting surface will become significant, making the glass non-uniform and preventing the precipitation of homogeneous crystals in the final product. Therefore, F must be within the range of 0.1-6%.

他方、Ａ３２０３はＦとの共存において核形成剤Ｔｉｅ
２゜Ｚｒ、０２の核形成を補助し、その結晶核及び所望
結晶の多量形成に欠かせない。丈に、結晶化のための熱
処理時のＦ揮散によって内部結晶物と表面結晶物とが相
違して析出するのを防ぐ効果がある２゜Ｉｇ− ム８２０３が　０．０５％　未満のとき、充分な量のＦ
が存在していても充分な量のＴｉＯ２・Ｚ　ｒ　０２共
晶結晶核の形成を補助しψｆｔ　＜　、切断、切削、研
磨等の２次加工による弛度低下を防止し得る緻密な微結
体全得ることができない。一方、８％を越えると結晶物
が脆弱化し、所望の強度が得られなくなる。したがって
、ム５２０３は０．０５Ｃ−８％の範囲に限られる。On the other hand, A3203 has a nucleating agent Tie in coexistence with F.
2°Zr assists in the nucleation of 02 and is indispensable for the formation of large amounts of crystal nuclei and desired crystals. When the content of 2゜Ig-me 8203 is less than 0.05%, it is effective in preventing different precipitation of internal crystals and surface crystals due to F volatilization during heat treatment for crystallization. amount of F
Dense microcrystals that can assist in the formation of a sufficient amount of TiO2 Z r 02 eutectic crystal nuclei even in the presence of I can't get it all. On the other hand, if it exceeds 8%, the crystalline material becomes brittle and the desired strength cannot be obtained. Therefore, Mu 5203 is limited to a range of 0.05C-8%.

々お、前記８ｉ０２　＋　Ａｌ２Ｏ３＋Ｌｉ２Ｏ＋Ｔｉ
Ｏ２＋　ＺｒＯ２＋Ｆ＋ム１□０３の合計が９０％未満
のとき若しくは８ｉ０□＋ム１ｉｉＯ３＋Ｌｉ２Ｏの合
計が８１％未満のとき、マトリックスガラス、夾雑結晶
物の占める１合が大きくなって所望とするβ・スボジュ
ウメン結晶が少なくなるので、十分な低膨張性が得られ
難くなる。8i02 + Al2O3 + Li2O + Ti
When the sum of O2+ ZrO2 + F + Mu1□03 is less than 90%, or when the sum of 8i0□+Mu1iiO3+Li2O is less than 81%, the proportion of matrix glass and impurities increases to form the desired β-subodumene crystal. Since this decreases, it becomes difficult to obtain sufficient low expansion properties.

したがって、殊に２０Ｘ１０　”００　（５０〜５００
°０）以下の熱膨張係数を有する結晶化ガラスを得んと
するときは、８ｉ０２　＋　Ａｌ２Ｏ３＋　Ｌｉ２Ｏ＋
　ＴｉＯ２＋ＺｒＯ２＋Ｆ’＋Ａａ７０３の合計を９３
％以上、その中で８ｓ０２　＋Ａｌ２Ｏ３＋　Ｌｉ２Ｏ
が８６％以上占めていることが必要である。Therefore, in particular 20X10"00 (50-500
When trying to obtain crystallized glass having a coefficient of thermal expansion of less than °0), 8i02 + Al2O3 + Li2O+
The total of TiO2 + ZrO2 + F' + Aa703 is 93
% or more, among which 8s02 +Al2O3+ Li2O
must account for 86% or more.

なお、その他Ｎａ２０１　Ｋ２０＋　ＰｂＯ，ＺｎＯ，
Ｈａｌｔ　８ｒｌ）＋０＆ＯＩ　Ｍｌ（）＋　Ｂ２０３
　＋　ＰｇｏＳ等の１種又は２種以上を本発明の特性に
大なる影響を与えない程度、たとえば、Ｎａ２Ｏ，に２
Ｑ＋　ＯａＯＩＭＩＯ＋　Ｂ２Ｏ３については５％以下
、ＰｂＯ，ＺｎＯ＋　Ｅａｏ、８ｒＯ＋　Ｂ２Ｏ５につ
いては３％以下添加しても差支えない。これらの成分は
ガラスの溶融性９作業性の向上等のために使用されるも
のであるが、一定量以上の含有はマトリックスガラスの
含有量の増加、夾雑結晶物の多量生成等によって、強度
の低下、熱膨張係数の増大を招くので好ましくない。In addition, other Na201 K20+ PbO, ZnO,
Halt 8rl)+0&OI Ml()+B203
+ One or more types of PgoS etc. are added to an extent that does not significantly affect the characteristics of the present invention, for example, Na2O, 2
Q+ OaOIMIO+ B2O3 may be added in an amount of 5% or less, and PbO, ZnO+ Eao, 8rO+ B2O5 may be added in an amount of 3% or less. These components are used to improve the meltability and workability of the glass, but if they are contained in excess of a certain amount, the strength may be deteriorated due to an increase in the content of matrix glass, the formation of a large amount of contaminant crystals, etc. This is not preferable because it causes a decrease in the coefficient of thermal expansion and an increase in the coefficient of thermal expansion.

次に本発明に基づ〈実施例を記載する。Next, examples based on the present invention will be described.

第　　　３　　　表　　−−−−一 ガラス組成が第３表のｍ　１−５に示す値となるように
原料調合したバッチをガラス炉に投入し約１６− １５００〜１６００°０で３〜６時間溶融した後、直径
約６ｒｎｙａ・長さ約１００Ｔ＆”の丸棒を成形した。Table 3 ----- A batch of raw materials prepared so that the glass composition would be the value shown in m 1-5 in Table 3 was put into a glass furnace and melted at about 16-1500 to 1600°0 for 3 to 6 hours. After that, a round bar with a diameter of about 6rnya and a length of about 100T&'' was formed.

このガラス棒を電気炉中で５°０／分の加熱速度で約７
５０８０まで昇温し、その温度で１・５時間保持し、そ
の後約１１００’Ｏまで約３°０層の速度で昇温しその
温度で約２時間保持することによってガラス体を結晶体
に変質させた。そしてその後炉外へ取出し、放冷した。This glass rod was heated in an electric furnace at a heating rate of about 7°C.
The glass body is transformed into a crystalline substance by increasing the temperature to 5080°C, holding it at that temperature for 1.5 hours, then increasing the temperature to about 1100'O at a rate of about 3°0 and holding it at that temperature for about 2 hours. I let it happen. Then, it was taken out of the furnace and left to cool.

得られた結晶化ガラス棒の表面を約１１″切削し、各々
について曲げ強度、熱膨張係数を測定した。なお、第３
表の測定値は試料数ｎ−２０本による平均値を示す。The surface of the obtained crystallized glass rod was cut by approximately 11 inches, and the bending strength and coefficient of thermal expansion of each rod were measured.
The measured values in the table show the average value based on the number of samples (n-20).

以上、詳述した如く、本発明は従来の結晶化ガラスにな
い、切断、切削、研磨等の２次加工をしず ても、機械的強度の低下をはとんと来ださか−かつ　す
ぐれた耐熱性、耐熱衝撃性を保有する結晶化ガラスを提
供し得たものであり、前記緒特性が年、々高度な水準で
要求される工業材料用素材として正に適合するものであ
る。As described in detail above, the present invention can reduce mechanical strength without undergoing secondary processing such as cutting, cutting, polishing, etc., which conventional crystallized glass does not have, and has excellent heat resistance. The present invention has provided a crystallized glass having high properties and thermal shock resistance, and is suitable as a material for industrial materials, which are required to have the above-mentioned properties at increasingly higher levels.

その他、結晶の微細性、緻密性によって　結晶化ガラス
の表面硬度は、２次加工の有無にかかわ１６− らす、ビツカーヌ硬度（３００を荷重）で約７２０に９
／７１Ｌｍ２以上、を保有するので、前記機械部品、電
子部品等の工業材料用のみならず、建築材料、装飾用素
材１日用品材料等その他　その用途は極めて広範である
。In addition, depending on the fineness and density of the crystals, the surface hardness of crystallized glass is approximately 720 to 9 on the Bitcane hardness (loaded at 300), regardless of the presence or absence of secondary processing.
/71Lm2 or more, its uses are extremely wide, not only for industrial materials such as the mechanical parts and electronic parts, but also for building materials, decorative materials, daily necessities materials, and others.

特許出願人　石塚硝子株式会社Patent applicant: Ishizuka Glass Co., Ltd.

Claims (1)

【特許請求の範囲】 ｌ）重量％で８！０２５０〜７３％、ム１２０３１２〜
３５％。 Ｌｉ、０２〜１０％、　　〒ｔｏ、　　０．１〜６　％
　＋　　ＺｒＯ２ｏ、　１〜６％　。 ７０９１〜６％、ム畠２ｏ、　０．０５〜８％を必須成
分とするガラス体を熱処理して得られた高強度低膨張性
結晶化ガラス。 ９　）　８　ｉ　０２＋ム１２０３　＋　Ｌｉ２Ｏ＋　
ＴｉＯ２＋　ＺｒＯ２＋　Ｆ　＋　Ａｇ２Ｏ３の合計が
９０％　以上であって、その中で５ｉｏ２＋ム１２０．
　＋　Ｌｌ、Ｏが８１％以上占めている特許請求の範囲
第１項記載の高強度低膨張性結晶化ガラス。[Claims] l) 8!0250 to 73% by weight, 120312 to 73% by weight
35%. Li, 02~10%, 〒to, 0.1~6%
+ ZrO2o, 1-6%. A high-strength, low-expansion crystallized glass obtained by heat-treating a glass body containing as essential components 7091-6%, Muhata 2o, 0.05-8%. 9) 8 i02+mu1203+Li2O+
The total of TiO2+ ZrO2+ F + Ag2O3 is 90% or more, of which 5io2+ M120.
+ The high-strength, low-expansion crystallized glass according to claim 1, in which Ll, O accounts for 81% or more.