JPS6331423B2 - - Google Patents
Info
- Publication number
- JPS6331423B2 JPS6331423B2 JP7795683A JP7795683A JPS6331423B2 JP S6331423 B2 JPS6331423 B2 JP S6331423B2 JP 7795683 A JP7795683 A JP 7795683A JP 7795683 A JP7795683 A JP 7795683A JP S6331423 B2 JPS6331423 B2 JP S6331423B2
- Authority
- JP
- Japan
- Prior art keywords
- glass
- tio
- crystallized glass
- zro
- crystallized
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
- 239000011521 glass Substances 0.000 claims description 29
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 10
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 9
- 239000000203 mixture Substances 0.000 claims description 8
- 229910021489 α-quartz Inorganic materials 0.000 claims description 5
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 4
- 229910018068 Li 2 O Inorganic materials 0.000 claims description 3
- 229910021493 α-cristobalite Inorganic materials 0.000 claims description 3
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 2
- 239000013078 crystal Substances 0.000 description 9
- 238000002425 crystallisation Methods 0.000 description 4
- 230000008025 crystallization Effects 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 238000005191 phase separation Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 238000004031 devitrification Methods 0.000 description 3
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 229910052593 corundum Inorganic materials 0.000 description 2
- 229910052906 cristobalite Inorganic materials 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 229910001845 yogo sapphire Inorganic materials 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 229910001676 gahnite Inorganic materials 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 239000006060 molten glass Substances 0.000 description 1
- 239000002667 nucleating agent Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 229910052844 willemite Inorganic materials 0.000 description 1
Description
本発明は、熱膨脹係数の大きい結晶化ガラスに
関する。
本発明の結晶化ガラスは、重量％でSiO250〜
65％、Al2O310〜22％、ZnO15〜30％、MgO0〜
３％、BaO0〜３％、ZrO22〜４％、TiO21〜５
％、Na2O0〜５％、Li2O0〜５％、B2O30〜５％、
As2O30〜５％の組成を有するガラスを熱処理し
て得られ主たる結晶相がα−石英、α−クリスト
バライトであり、30〜500℃の熱膨脹係数が高膨
脹の130〜180×10-7／℃であることを特徴とする
ものである。
以下、本発明において結晶化するガラス組成の
範囲を上記のように限定した理由について述べ
る。
SiO2が50％以下の場合は、所望の緻密な結晶
が充分量得られ難くまた結晶化ガラスの化学的耐
久性が悪くなり、65％以上の場合は、ガラスの粘
度が高くなり溶解性、成形性が悪くなる。Al2O3
が10％以下の場合には、ガラスが分相を起こし易
くなり、また結晶化ガラスの化学的耐久性が悪く
なり、22％以上の場合は高膨脹のα−石英、α−
クリストバライトの析出量が少くなり所望の高膨
脹の結晶化ガラスが得られない。ZnOを15％以下
にすると溶融しにくくなり、30％以上のときは、
分相または失透を生じ易くなると共に結晶化ガラ
スの化学的耐久性が悪くなる。BaOの３％以下
の含有は、ガラスの分相の発生を抑制し液相温度
を下げて溶融時の失透の発生を防止する効果があ
る。MgOが３％以上のときは、結晶化熱処理に
おいて結晶が粗大に成長し、また結晶化度を低く
する。ZrO2及びTiO2は、高膨脹のα−石英、α
−クリストバライトを主結晶相として析出させる
ための核形成剤として作用する成分であるが、
ZrO22％以下のとき、またTiO21％以下のときは
その作用が発揮されず、一方ZrO2が４％以上の
ときは液相温度が上昇し、溶融時にガラスが失透
し易くなり、TiO2が５以上のときは、ガラスに
分相や失透が生じ易く、また所望する高膨脹の結
晶が少量しか析出しない。このZrO2とTiO2の更
に好ましい関係はZrO2＋TiO2≧４且つZrO2／
TiO2＞0.7である。さらに本発明では上記説明の
成分以外にガラスの溶解性、清澄性、成形性等の
改善のためにNa2O、Li2O、B2O3、As2O3を各々
５％まで添加することができる。
下表は、本発明の実施例で、同表にはガラス組
成、そのガラスを熱処理する最高の結晶化温度、
得られた結晶化ガラスの30〜500℃における熱膨
脹係数、及び主結晶相を示す。
The present invention relates to crystallized glass having a large coefficient of thermal expansion. The crystallized glass of the present invention contains SiO 2 50 to 50% by weight.
65%, Al2O3 10~22%, ZnO15~ 30 %, MgO0~
3%, BaO0~3%, ZrO2 2 ~4%, TiO2 1~5
%, Na 2 O 0-5%, Li 2 O 0-5%, B 2 O 3 0-5%,
It is obtained by heat treating a glass having a composition of 0 to 5% As 2 O 3 , and the main crystal phases are α-quartz and α-cristobalite, and the coefficient of thermal expansion at 30 to 500°C is a high expansion of 130 to 180 × 10 - 7 /℃. The reason why the range of the glass composition to be crystallized in the present invention is limited as described above will be described below. If SiO 2 is less than 50%, it will be difficult to obtain a sufficient amount of the desired dense crystals, and the chemical durability of the crystallized glass will deteriorate; if it is more than 65%, the viscosity of the glass will increase, resulting in poor solubility and Formability deteriorates. Al2O3 _
If it is less than 10%, the glass tends to undergo phase separation, and the chemical durability of the crystallized glass deteriorates.If it is more than 22%, highly expanded α-quartz, α-
The amount of cristobalite precipitated decreases, making it impossible to obtain the desired high expansion crystallized glass. When ZnO is less than 15%, it becomes difficult to melt, and when it is more than 30%,
Phase separation or devitrification tends to occur, and the chemical durability of the crystallized glass deteriorates. The BaO content of 3% or less has the effect of suppressing the occurrence of phase separation of the glass, lowering the liquidus temperature, and preventing the occurrence of devitrification during melting. When MgO is 3% or more, crystals grow coarsely during crystallization heat treatment, and the degree of crystallinity decreases. ZrO 2 and TiO 2 are highly expanded α-quartz, α
- It is a component that acts as a nucleating agent to precipitate cristobalite as the main crystal phase,
When ZrO 2 is less than 2% and TiO 2 is less than 1%, this effect is not exhibited, while when ZrO 2 is more than 4%, the liquidus temperature increases and the glass becomes more likely to devitrify during melting. , TiO 2 is 5 or more, phase separation and devitrification are likely to occur in the glass, and only a small amount of desired high expansion crystals are precipitated. A more preferable relationship between ZrO 2 and TiO 2 is ZrO 2 +TiO 2 ≧4 and ZrO 2 /
TiO 2 >0.7. Furthermore, in the present invention, in addition to the above-mentioned components, up to 5% each of Na 2 O, Li 2 O, B 2 O 3 and As 2 O 3 is added to improve the solubility, clarity, moldability, etc. of the glass. be able to. The table below shows examples of the present invention, and the table includes the glass composition, the highest crystallization temperature at which the glass is heat-treated,
The thermal expansion coefficient at 30 to 500°C and the main crystal phase of the obtained crystallized glass are shown.
【表】【table】
【表】
上記実施例の結晶化ガラスは、次のようにして
製造される。
第１表の組成になる様に、ガラス原料を調合
し、白金ルツボを使用して1550〜1600℃で７〜16
時間溶融した後、溶融ガラスをカーボン鋳型に流
し込んで、成形し、これを700〜750℃に保持した
電気炉内に入れて徐冷、その後放冷してガラスを
得た。次に結晶化のための熱処理は２段処理法で
行つた。即ち、ガラスを電気炉中で室温から750
℃までは300℃／時間の昇温速度で加熱し、その
温度で１時間保持した後、同表に記載の最高の結
晶化温度まで40〜80℃／時間の昇温速度で加熱
し、その温度に１〜５時間保持した後、室温に放
冷して外観が白色不透明で同表に記載の熱膨脹係
数及び主結晶相を有する結晶化ガラスを得た。
尚、α−石英、α−クリストバライトの主結晶相
以外にガーナイト（ZnO・Al2O3）、ウイレマイ
ト（2ZnO・SiO2）等の結晶が少量析出する。
以上説明した本発明の結晶化ガラスは、大きな
熱膨脹係数を有し、結晶組織が緻密で優れた機械
的強度を有すると共に化学的耐久性に優れている
ので、電気機器の製造分野において表面に高膨脹
の金属薄膜が形成される基板材料として特に有用
な用途が期待される。[Table] The crystallized glass of the above example is manufactured as follows. Mix the glass raw materials so that they have the composition shown in Table 1, and use a platinum crucible at 1550-1600℃ for 7 to 16 hours.
After being melted for a period of time, the molten glass was poured into a carbon mold and molded, placed in an electric furnace maintained at 700 to 750°C, slowly cooled, and then left to cool to obtain glass. Next, heat treatment for crystallization was performed using a two-stage treatment method. That is, glass is heated from room temperature to 750°C in an electric furnace.
℃ at a heating rate of 300℃/hour, hold at that temperature for 1 hour, and then heat at a heating rate of 40 to 80℃/hour to the highest crystallization temperature listed in the table. After maintaining the temperature for 1 to 5 hours, the mixture was allowed to cool to room temperature to obtain a crystallized glass having a white, opaque appearance and having a coefficient of thermal expansion and a main crystalline phase as shown in the same table.
In addition to the main crystal phases of α-quartz and α-cristobalite, small amounts of crystals such as gahnite (ZnO.Al 2 O 3 ) and willemite (2ZnO.SiO 2 ) are precipitated. The crystallized glass of the present invention described above has a large coefficient of thermal expansion, a dense crystal structure, excellent mechanical strength, and excellent chemical durability. Particularly useful applications are expected as substrate materials on which expanded metal thin films are formed.
Claims (1)
ZnO15〜30％、MgO0〜３％、BaO0〜３％、
ZrO22〜４％、TiO21〜５％、Na2O0〜５％、
Li2O0〜５％、B2O30〜５％、As2O30〜５％の組
成を有するガラスを熱処理して得た結晶化ガラス
であつて、該結晶化ガラスは主たる結晶相がα−
石英、α−クリストバライトであり、30〜500℃
の熱膨張係数が130〜180×10-7／℃である結晶化
ガラス。 ２ ガラス組成は、更にZrO2＋TiO2≧４、
ZrO2／TiO2＞0.7である特許請求の範囲第１項に
記載の結晶化ガラス。[Claims] 1% by weight: SiO 2 50-65%, Al 2 O 3 10-22%,
ZnO15-30%, MgO0-3%, BaO0-3%,
ZrO 2 2-4%, TiO 2 1-5%, Na 2 O 0-5%,
A crystallized glass obtained by heat treating a glass having a composition of 0 to 5% Li 2 O , 0 to 5% B 2 O 3 and 0 to 5% As 2 O 3 , the crystallized glass has a main crystalline phase. is α−
Quartz, α-cristobalite, 30-500℃
A crystallized glass having a coefficient of thermal expansion of 130 to 180×10 -7 /°C. 2 The glass composition further includes ZrO 2 +TiO 2 ≧4,
The crystallized glass according to claim 1, wherein ZrO 2 /TiO 2 >0.7.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP7795683A JPS59203736A (en) | 1983-05-02 | 1983-05-02 | Crystallized glass |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP7795683A JPS59203736A (en) | 1983-05-02 | 1983-05-02 | Crystallized glass |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS59203736A JPS59203736A (en) | 1984-11-17 |
| JPS6331423B2 true JPS6331423B2 (en) | 1988-06-23 |
Family
ID=13648443
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP7795683A Granted JPS59203736A (en) | 1983-05-02 | 1983-05-02 | Crystallized glass |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS59203736A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH06174060A (en) * | 1992-12-14 | 1994-06-21 | Tsuda Kogyo Kk | Lever main body of transmission lever for automatic transmission |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2517710B2 (en) * | 1986-06-13 | 1996-07-24 | 株式会社 オハラ | Method for manufacturing glass ceramic products |
| US4714687A (en) * | 1986-10-27 | 1987-12-22 | Corning Glass Works | Glass-ceramics suitable for dielectric substrates |
| JPH0629152B2 (en) * | 1987-02-26 | 1994-04-20 | 株式会社オハラ | Method for producing crystallized glass for substrate |
| WO2005028388A1 (en) * | 2003-09-19 | 2005-03-31 | Ngk Insulators, Ltd. | Zinc oxide-alumina-silica based crystallized glass and reflecting mirror substrate using the same |
-
1983
- 1983-05-02 JP JP7795683A patent/JPS59203736A/en active Granted
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH06174060A (en) * | 1992-12-14 | 1994-06-21 | Tsuda Kogyo Kk | Lever main body of transmission lever for automatic transmission |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS59203736A (en) | 1984-11-17 |
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