JPH0570174A - Crystallized glass and its production - Google Patents
Crystallized glass and its productionInfo
- Publication number
- JPH0570174A JPH0570174A JP3258349A JP25834991A JPH0570174A JP H0570174 A JPH0570174 A JP H0570174A JP 3258349 A JP3258349 A JP 3258349A JP 25834991 A JP25834991 A JP 25834991A JP H0570174 A JPH0570174 A JP H0570174A
- Authority
- JP
- Japan
- Prior art keywords
- glass
- temperature
- crystallized glass
- ions
- ion
- 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
Links
- 239000011521 glass Substances 0.000 title claims abstract description 61
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 12
- 239000013078 crystal Substances 0.000 claims abstract description 43
- 238000005452 bending Methods 0.000 claims abstract description 17
- 150000002500 ions Chemical class 0.000 claims abstract description 16
- 229910001416 lithium ion Inorganic materials 0.000 claims abstract description 9
- 229910008556 Li2O—Al2O3—SiO2 Inorganic materials 0.000 claims abstract description 7
- 229910000500 β-quartz Inorganic materials 0.000 claims abstract description 7
- 239000002344 surface layer Substances 0.000 claims abstract description 5
- 238000010438 heat treatment Methods 0.000 claims description 17
- 230000006911 nucleation Effects 0.000 claims description 12
- 238000010899 nucleation Methods 0.000 claims description 12
- 150000003839 salts Chemical class 0.000 claims description 10
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 abstract description 11
- 239000013307 optical fiber Substances 0.000 abstract description 5
- 230000003014 reinforcing effect Effects 0.000 abstract description 4
- 238000000151 deposition Methods 0.000 abstract 1
- 238000005342 ion exchange Methods 0.000 description 15
- 238000000034 method Methods 0.000 description 8
- 230000007797 corrosion Effects 0.000 description 5
- 238000005260 corrosion Methods 0.000 description 5
- 229910010413 TiO 2 Inorganic materials 0.000 description 3
- 230000006866 deterioration Effects 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 239000000919 ceramic Substances 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 239000010410 layer Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 229910001414 potassium ion Inorganic materials 0.000 description 2
- 239000010453 quartz Substances 0.000 description 2
- 238000005728 strengthening Methods 0.000 description 2
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 1
- 229910018068 Li 2 O Inorganic materials 0.000 description 1
- 229910011763 Li2 O Inorganic materials 0.000 description 1
- 229910004742 Na2 O Inorganic materials 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 229910052681 coesite Inorganic materials 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 239000005350 fused silica glass Substances 0.000 description 1
- 239000003673 groundwater Substances 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000002787 reinforcement Effects 0.000 description 1
- 239000012779 reinforcing material Substances 0.000 description 1
- 239000013535 sea water Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000006104 solid solution Substances 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
Landscapes
- Mechanical Coupling Of Light Guides (AREA)
- Surface Treatment Of Glass (AREA)
- Glass Compositions (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、結晶化ガラスとその製
造方法に関し、より具体的には、石英光ファイバーを融
着して接続する際に、接続部分を補強するための補強部
品として好適な結晶化ガラスとその製造方法に関するも
のである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a crystallized glass and a method for producing the same, and more specifically, it is suitable as a reinforcing component for reinforcing a connecting portion when a fused silica optical fiber is connected. The present invention relates to crystallized glass and a method for manufacturing the same.
【０００２】[0002]
【従来の技術】石英光ファイバーを永久接続する方法の
一つとして、それらの端部の露出部を融着する方法があ
り、その場合、接続部分の信頼性を高める目的でそれを
補強するための補強部品が用いられる。2. Description of the Related Art As one of the methods of permanently connecting quartz optical fibers, there is a method of fusing the exposed portions of their ends. In that case, in order to enhance the reliability of the connecting portions, they are reinforced. Reinforcement parts are used.
【０００３】この光ファイバーの補強部品材料には、外
力によって接続部分の信頼性が損なわれないように、Ｊ
ＩＳ Ｒ １６０１（１９８１）に規定される試験方法
において２５００ｋｇｆ／ｃｍ2 以上の高い曲げ強度を
有すること、光ファイバーに大きな熱応力が発生しない
ように、石英ガラスの熱膨張係数（５．９×１０-7／
℃）に近似した−３〜１０×１０-7／℃の熱膨張係数を
有すること、マンホール内や海底で使用された時、地下
水や海水又はその他の外部環境によって劣化しないよう
に優れた耐腐食性を有すること等の特性が要求され、従
来よりその材料としては、金属、セラミック、石英ガラ
ス及び結晶化ガラスが使用されているが、いずれも上記
特性を全て満足するものではない。In order to prevent the reliability of the connecting portion from being impaired by an external force, the reinforcing material of this optical fiber is
According to the test method specified in ISR 1601 (1981), it has a high bending strength of 2500 kgf / cm 2 or more, and a thermal expansion coefficient (5.9 × 10 − 7 /
℃) -3 ~ 10 × 10 -7 / ℃ has a coefficient of thermal expansion, when used in the manhole or the sea floor, excellent corrosion resistance so as not to be deteriorated by groundwater, seawater or other external environment It is required to have properties such as properties, and metals, ceramics, quartz glass, and crystallized glass have been conventionally used as the material, but none of them satisfy the above properties.
【０００４】[0004]
【発明が解決しようとする課題】すなわち金属は、曲げ
強度は高いが、熱膨張係数が高すぎ、且つ、腐食性があ
るという欠点を有し、セラミックは、曲げ強度が高く、
耐腐食性を有するが、熱膨張係数が高すぎるという欠点
を有する。また石英ガラスは、熱膨張係数、耐腐食性に
ついては、いずれも良好であるが、曲げ強度が低すぎ、
さらに結晶化ガラスは、耐腐食性を有し、熱膨張係数も
石英ガラスのそれに近似するものも存在するが、やはり
曲げ強度が低すぎるという欠点を有している。That is, metal has high flexural strength, but has the drawback of having too high a coefficient of thermal expansion and corrosiveness, and ceramic has high flexural strength.
It has corrosion resistance, but has the drawback of having a too high coefficient of thermal expansion. Quartz glass has good thermal expansion coefficient and corrosion resistance, but the bending strength is too low.
Further, although crystallized glass has corrosion resistance and a coefficient of thermal expansion similar to that of quartz glass, it still has the drawback of too low bending strength.
【０００５】ところで結晶化ガラスについては、それを
イオン交換することによって強化することが各種提案さ
れており、例えば特公昭４７−４９２９９号公報には、
結晶化ガラスの結晶相中のアルカリイオンを、より大き
なイオン半径のイオンと置換することによって強化する
方法が開示されている。しかしながらこの方法では、イ
オン交換に用いる溶融塩を高温にする必要があるため、
作業性が悪く、また設備の劣化が激しいという問題があ
る。さらに結晶化度が低い材料では、ガラス相にクラッ
クが入って、逆に強度が低下しやすいという問題もあ
る。By the way, with respect to crystallized glass, various proposals have been made to strengthen it by ion exchange, and for example, Japanese Patent Publication No. 47-49299 discloses a method.
A method of strengthening alkali ions in the crystalline phase of crystallized glass by replacing them with ions of larger ionic radius is disclosed. However, in this method, since it is necessary to raise the temperature of the molten salt used for ion exchange,
There is a problem that workability is poor and the deterioration of equipment is severe. Further, in the case of a material having a low crystallinity, there is a problem that the glass phase is cracked and the strength is apt to be decreased.
【０００６】本発明の目的は、石英ガラスの熱膨張係数
に近似した熱膨張係数を有しながら、２５００ｋｇｆ／
ｃｍ2 以上の高い曲げ強度を有しており、光ファイバー
の補強部品に要求される特性を全て満足する結晶化ガラ
ス及びその製造方法を提供することである。An object of the present invention is to have a coefficient of thermal expansion close to that of quartz glass, while maintaining a coefficient of 2500 kgf /
It is an object of the present invention to provide a crystallized glass having a high bending strength of not less than cm 2 and satisfying all the properties required for a reinforcing component of an optical fiber, and a manufacturing method thereof.
【０００７】[0007]
【課題を解決するための手段】本発明の結晶化ガラス
は、Ｌｉ2 Ｏ−Ａｌ2 Ｏ3 −ＳｉＯ2 系ガラス相中に、
β−石英固溶体結晶が２０〜７０体積％析出し、且つ、
表層のガラス相中のみのＬｉ+ イオンが、それよりもイ
オン半径の大きいイオンによって置換されてなり、３０
〜３８０℃における熱膨張係数が−３〜１０×１０-7／
℃、曲げ強度が２５００ｋｇｆ／ｃｍ2 以上であること
を特徴とする。The crystallized glass of the present invention comprises a Li 2 O--Al 2 O 3 --SiO 2 -based glass phase,
20 to 70% by volume of β-quartz solid solution crystals are deposited, and
Li + ions only in the surface glass phase are replaced by ions having a larger ionic radius,
Coefficient of thermal expansion at 380 ° C to -3 to 10 × 10 -7 /
It is characterized in that it has a bending strength of 2500 kgf / cm 2 or more at ℃.
【０００８】また本発明の結晶化ガラスの製造方法は、
Ｌｉ2 Ｏ−Ａｌ2 Ｏ3 −ＳｉＯ2 系ガラスを、その結晶
核生成速度が極大となる温度以外の温度域で一次熱処理
した後、さらに結晶成長速度の極大となる温度以外の温
度域で二次熱処理することによって、ガラス相中にβ−
石英固溶体結晶を２０〜７０体積％析出した結晶化ガラ
スを作製し、次いで該結晶化ガラスをＬｉ+ イオンより
もイオン半径の大きいイオンを含み、且つ、６００℃以
下の温度の溶融塩中に浸漬することによって、表層のガ
ラス相中のみのＬｉ+ イオンを、それよりもイオン半径
の大きいイオンと置換することを特徴とする。The method for producing crystallized glass of the present invention is
The Li 2 O—Al 2 O 3 —SiO 2 based glass is subjected to a primary heat treatment in a temperature range other than the temperature at which the crystal nucleation rate is maximized, and then is further treated in a temperature range other than the temperature at which the crystal growth rate is maximized. By the subsequent heat treatment, β-in the glass phase
A crystallized glass in which 20 to 70% by volume of a quartz solid solution crystal is precipitated is prepared, and then the crystallized glass is immersed in a molten salt containing ions having a larger ionic radius than Li + ions and having a temperature of 600 ° C. or less. By doing so, Li + ions only in the glass phase of the surface layer are replaced with ions having a larger ionic radius.
【０００９】さらに本発明の結晶化ガラスの他の製造方
法は、Ｌｉ2 Ｏ−Ａｌ2 Ｏ3 −ＳｉＯ2 系ガラスを、そ
の結晶核生成速度と結晶成長速度の各々の極大となる温
度の間の温度域で熱処理することによって、ガラス相中
にβ−石英固溶体結晶を２０〜７０体積％析出した結晶
化ガラスを作製し、次いで該結晶化ガラスをＬｉ+ イオ
ンよりもイオン半径の大きいイオンを含み、且つ、６０
０℃以下の温度の溶融塩中に浸漬することによって、表
層のガラス相中のみのＬｉ+ イオンを、それよりもイオ
ン半径の大きいイオンと置換することを特徴とする。Further, another method for producing a crystallized glass of the present invention is one in which a Li 2 O--Al 2 O 3 --SiO 2 glass is used between temperatures at which the crystal nucleation rate and the crystal growth rate reach their respective maxima. By heat treatment in the temperature range of 1 to prepare a crystallized glass in which β-quartz solid solution crystals are precipitated in the glass phase in an amount of 20 to 70% by volume, and then the crystallized glass is treated with ions having an ion radius larger than that of Li + ions. Including and 60
By immersing in a molten salt at a temperature of 0 ° C. or lower, Li + ions only in the glass phase of the surface layer are replaced with ions having a larger ionic radius.
【００１０】[0010]
【作用】本発明において、ガラス相中におけるβ−石英
固溶体結晶の析出割合、結晶化度を２０〜７０体積％に
した理由は、以下に述べるとおりである。In the present invention, the reason why the β-quartz solid solution crystal precipitation ratio and crystallinity in the glass phase are set to 20 to 70% by volume is as described below.
【００１１】すなわち結晶化度が７０体積％以上になる
と、イオン交換の対象であるガラス層が少なくなりす
ぎ、所望の曲げ強度を得ることができなくなると共に、
負の熱膨張係数を有する結晶相が優勢になりすぎるた
め、３０〜３８０℃における熱膨張係数が−３×１０-7
／℃以下となる。一方、結晶化度が２０体積％以下にな
ると、正の熱膨張係数を有するガラス相が優勢になりす
ぎるため、熱膨張係数が１０×１０-7／℃以上となる。That is, when the crystallinity is 70% by volume or more, the glass layer to be ion-exchanged becomes too small, and the desired bending strength cannot be obtained.
Since the crystal phase having a negative coefficient of thermal expansion becomes too predominant, the coefficient of thermal expansion at 30 to 380 ° C. is −3 × 10 −7.
/ ° C or less. On the other hand, when the crystallinity is 20% by volume or less, the glass phase having a positive coefficient of thermal expansion becomes too predominant, so that the coefficient of thermal expansion becomes 10 × 10 −7 / ° C. or more.
【００１２】また本発明においては、結晶核生成速度が
極大となる温度以外の温度域で一次熱処理した後、結晶
成長速度が極大となる温度以外の温度域で二次熱処理す
るため、あるいは結晶核生成速度と結晶成長速度の各々
の極大となる温度の間の温度で一度だけ熱処理するた
め、核の生成がゆっくりと行われ、任意の数の結晶核を
生成させた後、結晶の成長もゆっくりと行われ、任意の
大きさの結晶を析出させることができる。その結果、結
晶化度を２０〜７０体積％の所望の値に制御することが
可能となる。つまり結晶核生成速度又は結晶成長速度が
極大となる温度で熱処理すると、結晶化速度が速すぎ、
結晶化度を所望の値に制御できなくなるため好ましくな
い。In the present invention, the primary heat treatment is performed in a temperature range other than the temperature at which the crystal nucleation rate is maximized, and then the secondary heat treatment is performed in a temperature range other than the temperature at which the crystal growth rate is maximized. Since the heat treatment is performed only once at a temperature between the maximum of the production rate and the maximum of the crystal growth rate, the nucleation is performed slowly, and after the arbitrary number of crystal nuclei are produced, the crystal growth is also slow. Then, crystals of any size can be deposited. As a result, it becomes possible to control the crystallinity to a desired value of 20 to 70% by volume. That is, when heat treatment is performed at a temperature at which the crystal nucleation rate or the crystal growth rate is maximized, the crystallization rate is too fast,
It is not preferable because the crystallinity cannot be controlled to a desired value.
【００１３】尚、具体的な一次熱処理の条件としては、
結晶核生成速度が極大となる温度から２０℃以上離れた
温度で、０．２５〜４時間が適しており、また二次熱処
理の条件としては、結晶成長速度が極大となる温度から
２０℃以上離れた温度で０．２５〜４時間が適してい
る。さらに一度の熱処理で結晶化を行う場合は、結晶核
生成速度と結晶成長速度の各々の極大となる温度の中間
温度から２０℃以内の温度で、１〜１０時間が適してい
る。The specific conditions for the primary heat treatment are as follows:
Suitable for 0.25 to 4 hours at a temperature 20 ° C or more away from the temperature at which the crystal nucleation rate is maximum, and as the condition for the secondary heat treatment, 20 ° C or more from the temperature at which the crystal growth rate is maximum. 0.25 to 4 hours at remote temperatures are suitable. When crystallization is performed by a single heat treatment, it is suitable that the temperature is within 20 ° C. from the intermediate temperature between the maximum temperatures of the crystal nucleation rate and the crystal growth rate for 1 to 10 hours.
【００１４】さらに本発明において、イオン交換を６０
０℃以下の溶融塩を用いて行うのは、６００℃以上の高
温でイオン交換すると、装置の劣化が早く、作業性が悪
いと共に、ガラス相の表面にイオンが入りすぎてクラッ
クが生じ易くなるからである。またイオン交換を行うた
めの溶融塩としては、ＫＮＯ3 やＮａＮＯ3 が使用可能
であるが、短時間で高強度のものを得るためには、ＫＮ
Ｏ3 を使用するのが好ましく、これらの溶融塩の中に結
晶化ガラスを１〜２０時間浸漬することによって、結晶
化ガラスのガラス相の深さ数十ミクロンにまで強化層が
形成される。Further, in the present invention, ion exchange is performed at 60
When using a molten salt of 0 ° C or lower, when the ion exchange is performed at a high temperature of 600 ° C or higher, the apparatus is deteriorated quickly and the workability is poor, and the surface of the glass phase is excessively ionized and cracks easily occur. Because. KNO 3 or NaNO 3 can be used as a molten salt for ion exchange, but KN 3 or NaNO 3 can be used in order to obtain high strength in a short time.
O 3 is preferably used, and by immersing the crystallized glass in these molten salts for 1 to 20 hours, a strengthening layer is formed up to a depth of several tens of microns of the glass phase of the crystallized glass.
【００１５】溶融塩について、より具体的に述べると、
ＫＮＯ3 を使用する場合は、６００℃以下でイオン交換
を行うことができるが、作業性、設備の劣化を考慮する
と、５５０℃以下で行うことが好ましい。またＮａＮＯ
3 を使用する場合は、５００℃以下でイオン交換を行う
ことができるが、やはり作業性を考慮すると、４５０℃
以下で行うことが好ましい。More specifically, the molten salt will be described.
When KNO 3 is used, the ion exchange can be performed at 600 ° C. or lower, but it is preferably performed at 550 ° C. or lower in consideration of workability and deterioration of equipment. Also NaNO
When 3 is used, ion exchange can be performed at 500 ° C or lower, but considering workability, 450 ° C
It is preferable to do the following.
【００１６】尚、本発明において使用するＬｉ2 Ｏ−Ａ
ｌ2 Ｏ3 −ＳｉＯ2 系ガラスとしては、重量百分率で、
Ｌｉ2 Ｏ ３〜５％、Ａｌ2 Ｏ3 ２０〜３５％、Ｓｉ
Ｏ2５５〜７０％、ＴｉＯ2 １〜３％、ＺｒＯ2 １
〜４％、Ｐ2 Ｏ5 １〜５％、Ｎａ2 Ｏ ０〜４％、Ｋ
2 Ｏ ０〜４％、Ｎａ2 Ｏ＋Ｋ2 Ｏ ０．５〜４％の組
成を有するガラスが好適である。すなわちこのガラス
は、核形成材として、ＴｉＯ2 とＺｒＯ2 の両方を含有
するため、結晶核生成速度や結晶成長速度の調整を容易
に行うことが可能である。The Li 2 O--A used in the present invention
As the l 2 O 3 —SiO 2 glass, the weight percentage is:
Li 2 O 3-5%, Al 2 O 3 20-35%, Si
O 2 55 to 70%, TiO 2 1 to 3%, ZrO 2 1
~4%, P 2 O 5 1~5 %, Na 2 O 0~4%, K
2 O 0 to 4%, the glass having a composition of Na 2 O + K 2 O 0.5~4 % is preferred. That is, since this glass contains both TiO 2 and ZrO 2 as the nucleating material, it is possible to easily adjust the crystal nucleation rate and the crystal growth rate.
【００１７】[0017]
【実施例】以下、本発明を実施例に基づいて詳細に説明
する。EXAMPLES The present invention will be described in detail below based on examples.
【００１８】重量百分率で、ＳｉＯ2 ６６％、Ａｌ2 Ｏ
3 ２３％、Ｌｉ2 Ｏ ４％、ＴｉＯ 2 ２％、ＺｒＯ2 ３
％、Ｐ2 Ｏ5 １％、Ｎａ2 Ｏ ０．５％、Ｋ2 Ｏ ０．
５％の組成になるように原料を調合し、白金ルツボにお
いて１５８０℃で１６時間溶融した後、厚さ６ｍｍの板
状に成形し、次いで３×４×５０ｍｍの角柱に成形し
た。In weight percentage, SiO2 66%, Al2 O
3 23%, Li2 O 4%, TiO 2 2%, ZrO2 Three
%, P2 OFive 1%, Na2 O 0.5%, K2 O 0.
Mix the raw materials so that the composition is 5%, and put in a platinum crucible.
After melting at 1580 ° C for 16 hours, a plate with a thickness of 6 mm
And then into 3x4x50mm prisms
It was
【００１９】尚、このガラスの結晶核生成速度が極大と
なる温度は、７５０℃であり、結晶成長速度が極大とな
る温度は、８４０℃である。The temperature at which the crystal nucleus generation rate of this glass is maximized is 750 ° C., and the temperature at which the crystal growth rate is maximized is 840 ° C.
【００２０】次にこのガラス成形体を表１に示すよう
に、各種の条件で熱処理して結晶化させ、その結晶化度
と熱膨張係数を測定し、さらに各種の条件でイオン交換
して、その曲げ強度をＪＩＳ Ｒ １６０１（１９８
１）に従って測定した。Next, as shown in Table 1, this glass molded body was heat-treated under various conditions to be crystallized, its crystallinity and coefficient of thermal expansion were measured, and further ion exchanged under various conditions, The flexural strength was measured according to JIS R 1601 (198
It measured according to 1).
【００２１】[0021]
【表１】 [Table 1]
【００２２】実施例であるＮｏ．１〜６の各試料は、結
晶核生成速度が極大となる温度以外の温度域で一次熱処
理を行い、さらに結晶成長速度が極大となる温度以外の
温度域で二次熱処理を行い、またＮｏ．７の試料は、結
晶核生成速度と結晶成長速度の各々の極大となる温度の
間の温度域で一度だけ熱処理を行った後、各試料の結晶
化度と熱膨張係数を測定し、次いで４００〜５００℃で
３〜６時間イオン交換した後、曲げ強度を測定したもの
である。The example No. Each of the samples 1 to 6 was subjected to the primary heat treatment in a temperature range other than the temperature at which the crystal nucleation rate was maximized, and was further subjected to the secondary heat treatment in a temperature range other than the temperature at which the crystal growth rate was maximized. Sample No. 7 was heat-treated only once in a temperature range between the maximum temperatures of the crystal nucleation rate and the crystal growth rate, and the crystallinity and thermal expansion coefficient of each sample were measured. Bending strength was measured after ion exchange at ˜500 ° C. for 3 to 6 hours.
【００２３】一方、比較例であるＮｏ．８の試料は、結
晶核生成速度が極大となる温度、すなわち７５０℃で一
次熱処理を行い、さらに結晶成長速度が極大となる温
度、すなわち８４０℃で二次熱処理を行った後、結晶化
度と熱膨張係数を測定し、次いで５５０℃で６時間イオ
ン交換した後、曲げ強度を測定したものである。さらに
Ｎｏ．９の試料は、Ｎｏ．１の試料と同様の条件で熱処
理を行った後、結晶化度と熱膨張係数を測定し、次いで
Ｋ2 ＳＯ4 を４８重量％、ＫＣｌを５２重量％含有する
溶融塩を用いて、７２０℃で５時間イオン交換した後、
曲げ強度を測定したものである。On the other hand, No. Sample No. 8 was subjected to a first heat treatment at a temperature at which the crystal nucleus generation rate was a maximum, that is, 750 ° C., and a second heat treatment at a temperature at which the crystal growth rate was a maximum, that is, 840 ° C. The thermal expansion coefficient was measured, and then the ion exchange was performed at 550 ° C. for 6 hours, and then the bending strength was measured. Furthermore, No. The sample of No. 9 is No. After heat treatment under the same conditions as for the sample of No. 1, the crystallinity and the coefficient of thermal expansion were measured, and then a molten salt containing 48% by weight of K 2 SO 4 and 52% by weight of KCl was used to obtain 720 ° C. After ion exchange for 5 hours,
Bending strength is measured.
【００２４】表１から明らかなようにＮｏ．１〜７の各
試料は、結晶化度が３５〜６０％であり、−１．０〜
６．５×１０-7／℃の良好な熱膨張係数と３０００ｋｇ
ｆ／ｃｍ2 以上の高い曲げ強度を有していた。As is clear from Table 1, No. Each sample of 1 to 7 has a crystallinity of 35 to 60% and a crystallinity of -1.0 to
Good thermal expansion coefficient of 6.5 × 10 -7 / ° C and 3000 kg
It had a high bending strength of f / cm 2 or more.
【００２５】それに対し、Ｎｏ．８の試料は、、熱膨張
係数が−６．０×１０-7／℃と低すぎ、また曲げ強度も
１５００ｋｇｆ／ｃｍ2 と低かった。さらにＮｏ．９の
試料は、熱膨張係数は、６．５×１０-7／℃であった
が、曲げ強度が１１００ｋｇｆ／ｃｍ2 と低かった。On the other hand, No. Sample No. 8 had a thermal expansion coefficient of -6.0 × 10 -7 / ° C, which was too low, and a bending strength of 1500 kgf / cm 2 . Furthermore, No. The sample No. 9 had a thermal expansion coefficient of 6.5 × 10 −7 / ° C., but had a low bending strength of 1100 kgf / cm 2 .
【００２６】表２は、Ｎｏ．１の試料とＮｏ．９の試料
のイオン交換が、結晶化ガラス中のどの部位で行われた
のかを調べた結果を示すものである。Table 2 shows No. Sample No. 1 and No. 1 9 shows the results of investigating at which site in the crystallized glass the ion exchange of the sample 9 was performed.
【００２７】表２から明らかなようにＮｏ．１の試料
は、イオン交換前後で結晶単位格子の体積がほとんど変
化しておらず、従って結晶相中には、Ｋ+イオンが入り
込んでおらず、イオン交換反応がガラス相中のみで起こ
っていることが理解される。As is clear from Table 2, No. In the sample of No. 1, the volume of the crystal unit cell hardly changed before and after the ion exchange, therefore, K + ions did not enter the crystal phase, and the ion exchange reaction occurred only in the glass phase. Be understood.
【００２８】一方、Ｎｏ．９の試料は、結晶単位格子の
体積がイオン交換後に増大しており、従って結晶相中に
Ｋ+ イオンが入り込んだ事が明らかである。またＮｏ．
９の試料の曲げ強度が１１００Ｋｇｆ／ｃｍ と低いの
は、イオン交換温度が７２０℃と高いため、ガラス相中
にも大量のＫ+ が入り込み、ガラス相の構造を破壊し、
クラックが入ったためであると考えられる。On the other hand, No. In the sample of No. 9, the volume of the crystal unit cell was increased after the ion exchange, and therefore it is clear that K + ions were introduced into the crystal phase. In addition, No.
The bending strength of the sample 9 is as low as 1100 Kgf / cm, because the ion exchange temperature is as high as 720 ° C., so a large amount of K + enters the glass phase and destroys the structure of the glass phase.
It is thought that it was because of cracks.
【００２９】尚、上記の結晶化度は、Ｘ線回折法によっ
て測定し、熱膨張係数は、ディラトメーターによって測
定したものである。さらに曲げ強度は、ＪＩＳ Ｒ １
６０１（１９８１）に規定されている方法に従って測定
した。The crystallinity is measured by an X-ray diffraction method, and the thermal expansion coefficient is measured by a dilatometer. Furthermore, the bending strength is JIS R 1
It was measured according to the method defined in 601 (1981).
【００３０】[0030]
【発明の効果】以上のように本発明の結晶化ガラスは、
２５００ｋｇｆ／ｃｍ2 以上の高い曲げ強度を有し、熱
膨張係数が−３〜１０×１０-7／℃と、石英ガラスのそ
れに近似し、しかも耐腐食性に優れているため、光ファ
イバーの補強部品として好適であり、また本発明の製造
方法によると、それを作業性良く、且つ、設備の激しい
劣化を招くことなく製造することが可能である。As described above, the crystallized glass of the present invention is
It has a high flexural strength of 2500 kgf / cm 2 or more, a coefficient of thermal expansion of -3 to 10 x 10 -7 / ° C, which is similar to that of silica glass and is also excellent in corrosion resistance. According to the manufacturing method of the present invention, it is possible to manufacture it with good workability and without causing severe deterioration of equipment.
【表２】 [Table 2]
Claims (3)
ス相中に、β−石英固溶体結晶が２０〜７０体積％析出
し、且つ、表層のガラス相中のみのＬｉ+ イオンが、そ
れよりもイオン半径の大きいイオンによって置換されて
なり、３０〜３８０℃における熱膨張係数が−３〜１０
×１０-7／℃、曲げ強度が２５００ｋｇｆ／ｃｍ2 以上
であることを特徴とする結晶化ガラス。1. A β-quartz solid solution crystal is precipitated in a Li 2 O-Al 2 O 3 -SiO 2 -based glass phase in an amount of 20 to 70% by volume, and Li + ions only in the surface glass phase are It is replaced by ions having an ionic radius larger than that, and has a thermal expansion coefficient of -3 to 10 at 30 to 380 ° C.
A crystallized glass having a bending strength of 2500 kgf / cm 2 or more at × 10 -7 / ° C.
スを、その結晶核生成速度が極大となる温度以外の温度
域で一次熱処理した後、さらに結晶成長速度が極大とな
る温度以外の温度域で二次熱処理することによって、ガ
ラス相中にβ−石英固溶体結晶を２０〜７０体積％析出
した結晶化ガラスを作製し、次いで該結晶化ガラスをＬ
ｉ+ イオンよりもイオン半径の大きいイオンを含み、且
つ、６００℃以下の温度の溶融塩中に浸漬することによ
って、表層のガラス相中のみのＬｉ+ イオンを、それよ
りもイオン半径の大きいイオンと置換することを特徴と
する結晶化ガラスの製造方法。2. A Li 2 O—Al 2 O 3 —SiO 2 -based glass is subjected to a primary heat treatment in a temperature range other than the temperature at which the crystal nucleation rate is maximized, and then at a temperature other than the temperature at which the crystal growth rate is maximized. The second heat treatment in the temperature range of 1 to prepare a crystallized glass in which β-quartz solid solution crystals are precipitated in the glass phase in an amount of 20 to 70% by volume, and then the crystallized glass is mixed with L
An ion having a larger ionic radius than that of an i + ion and having a larger ionic radius than that of a Li + ion only in the glass phase of the surface layer is contained by being immersed in a molten salt at a temperature of 600 ° C. or less. And a method for producing a crystallized glass.
スを、その結晶核生成速度と結晶成長速度の各々の極大
となる温度の間の温度域で熱処理することによって、ガ
ラス相中にβ−石英固溶体結晶を２０〜７０体積％析出
した結晶化ガラスを作製し、次いで該結晶化ガラスをＬ
ｉ+ イオンよりもイオン半径の大きいイオンを含み、且
つ、６００℃以下の温度の溶融塩中に浸漬することによ
って、表層のガラス相中のみのＬｉ+ イオンを、それよ
りもイオン半径の大きいイオンと置換することを特徴と
する結晶化ガラスの製造方法。3. Li 2 O—Al 2 O 3 —SiO 2 -based glass is heat-treated in a temperature range between temperatures at which the crystal nucleation rate and the crystal growth rate reach their respective maximums, thereby forming a glass phase in the glass phase. To prepare a crystallized glass in which β-quartz solid solution crystals are precipitated in an amount of 20 to 70% by volume.
An ion having a larger ionic radius than that of an i + ion and having a larger ionic radius than that of a Li + ion only in the glass phase of the surface layer is contained by being immersed in a molten salt at a temperature of 600 ° C. or less. And a method for producing a crystallized glass.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3258349A JPH0737335B2 (en) | 1991-09-10 | 1991-09-10 | Crystallized glass and manufacturing method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3258349A JPH0737335B2 (en) | 1991-09-10 | 1991-09-10 | Crystallized glass and manufacturing method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0570174A true JPH0570174A (en) | 1993-03-23 |
| JPH0737335B2 JPH0737335B2 (en) | 1995-04-26 |
Family
ID=17319007
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP3258349A Expired - Lifetime JPH0737335B2 (en) | 1991-09-10 | 1991-09-10 | Crystallized glass and manufacturing method thereof |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0737335B2 (en) |
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| WO1999065837A1 (en) * | 1998-06-19 | 1999-12-23 | Nippon Electric Glass Co., Ltd. | Li2O-Al2O3-SiO2 TYPE TRANSPARENT CRYSTALLIZED GLASS |
| JP2007527354A (en) * | 2003-10-24 | 2007-09-27 | ピーピージー インダストリーズ オハイオ， インコーポレイテッド | Glass composition comprising lithia-alumina-silica and glass suitable for chemical tempering and articles made using chemically tempered glass |
| JP2008254984A (en) * | 2007-04-06 | 2008-10-23 | Ohara Inc | Inorganic composition article |
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Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS4999521A (en) * | 1972-12-23 | 1974-09-20 |
-
1991
- 1991-09-10 JP JP3258349A patent/JPH0737335B2/en not_active Expired - Lifetime
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS4999521A (en) * | 1972-12-23 | 1974-09-20 |
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