JPH0444612B2 - - Google Patents
Info
- Publication number
- JPH0444612B2 JPH0444612B2 JP59220796A JP22079684A JPH0444612B2 JP H0444612 B2 JPH0444612 B2 JP H0444612B2 JP 59220796 A JP59220796 A JP 59220796A JP 22079684 A JP22079684 A JP 22079684A JP H0444612 B2 JPH0444612 B2 JP H0444612B2
- Authority
- JP
- Japan
- Prior art keywords
- glass
- zno
- zro
- mgo
- less
- 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 - Lifetime
Links
- 239000011521 glass Substances 0.000 claims description 41
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 10
- 239000000203 mixture Substances 0.000 claims description 7
- 238000003426 chemical strengthening reaction Methods 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
- 238000002844 melting Methods 0.000 description 12
- 230000008018 melting Effects 0.000 description 12
- 230000000694 effects Effects 0.000 description 6
- 238000009792 diffusion process Methods 0.000 description 5
- 229910001413 alkali metal ion Inorganic materials 0.000 description 4
- 238000005342 ion exchange Methods 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- KKCBUQHMOMHUOY-UHFFFAOYSA-N Na2O Inorganic materials [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-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
- 238000004031 devitrification Methods 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229910001845 yogo sapphire Inorganic materials 0.000 description 2
- 229910017493 Nd 2 O 3 Inorganic materials 0.000 description 1
- 206010040925 Skin striae Diseases 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 239000005345 chemically strengthened glass Substances 0.000 description 1
- 229910052681 coesite Inorganic materials 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 239000006060 molten glass Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- 238000005728 strengthening Methods 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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
- C03C3/089—Glass compositions containing silica with 40% to 90% silica, by weight containing boron
- C03C3/091—Glass compositions containing silica with 40% to 90% silica, by weight containing boron containing aluminium
- C03C3/093—Glass compositions containing silica with 40% to 90% silica, by weight containing boron containing aluminium containing zinc or zirconium
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Geochemistry & Mineralogy (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Surface Treatment Of Glass (AREA)
- Glass Compositions (AREA)
Description
〔産業上の利用分野〕
本発明はイオン交換による化学強化用ガラス組
成物に関する。
〔従来の技術〕
ガラスを歪点以下の温度のアルカリ金属イオン
を含む溶融塩中に浸漬し、ガラス中のアルカリ金
属イオンを溶融塩中のより原子半径の大きいアル
カリ金属イオンと交換させてガラス表面に圧縮応
力を生ぜしめる謂る化学強化法は古くから知られ
ている。さらに用いられるアルカリ金属イオンと
して、ガラス中のNa+を溶融塩中のK+に交換す
ることはS.S.Kistler（J.Amer.Ceram.Soc.Vol.45）
に発表されている。そしてガラス中でのK+の拡
散速度を早めるためにガラスにAl2O3又はZrO2を
含有せしめることはCorning社の特許（例えば特
公昭41−20629、特公昭47−47970、特公昭48−
11327等）に記載されている。しかしAl2O3又は
ZrO2を多く含むガラスは溶融温度や成形温度が
高いという欠点を有する。
ガラスの溶融性を向上させかつK+の拡散速度
を大きくした化学強化用ガラスとして特公昭46−
42108号が提案されている。そのガラス組成は
SiO2 69〜74％，Na2Ｏ ５〜13％，K2Ｏ ６
〜12％，Na2Ｏ＋K2Ｏ 13〜19％，Al2O3 ４％
以下，ZrO2 ４％以下，Al2O3＋ZrO2 ２〜７
％，MgO 10％以下，ZnO ５％以下，MgO＋
ZnO ２〜12％，B2O3 ４％以下，SiO2＋Na2Ｏ
＋K2Ｏ＋Al2O3＋ZrO2＋MgO＋ZnO＋B2O3 96
％以上からなる。しかしながらこの組成のガラス
でも依然溶融温度が高く、ガラスの粘性が102ポ
イズで定義される溶融点は1500℃以上である。
〔発明が解決しようとする問題点〕
本発明はイオン交換時におけるK+の拡散速度
が大きくかつ溶融点が1500℃以下の溶融性及び成
形性に優れた化学強化用ガラス組成を提供するこ
とを課題とする。
〔問題点を解決するための手段〕
前記課題を解決するため、本発明のガラス組成
は重量％で表示した基本成分が次記範囲にある。
SiO2 60〜72
B2O3 ５〜10
Al2O3 ３〜６
（但しAl2O3＋ZrO2３〜６）
MgO ５〜10
ZnO ０〜６
Li2Ｏ ０〜２
Na2Ｏ ８〜14
K2Ｏ ３〜６
〔作用〕
SiO2：ガラス骨格を形成する主要成分であり、
60％未満ではガラスが化学的に不安定で
耐水性や耐酸性などに乏しくなり、72％
を越えると溶融温度が高くなる。
B2O3：ガラス骨格を形成するとともにガラス
の溶融温度、成形温度を低下せしめる
が、５％未満では溶融温度低下の効果が
乏しくなり、10％を越えると溶融、成形
時にB2O3が揮発しやすく、組成変動に
よつて脈理や失透などの欠点が生じ易く
なる。
Al2O3：ガラスを化学的に安定にするととも
に、Na+〓K+のイオン交換を促進する。
３％未満ではイオン交換促進の効果が小
さく、６％を越えるとガラスの溶融温度
が高くなり、かつガラスが失透しやすく
なる。なおZrO2もAl2O3と同じ作用を果
すのでAl2O3＋ZrO2の範囲も３〜６％と
する。
MgO：K+のガラス中での拡散速度を減じるこ
となくガラスの高温での粘性を低下させ
ガラスを溶しやすくする。５％未満では
その効果に乏しく、10％を越えるとガラ
スが失透しやすくなる。
ZnO：MgOと同様ガラスの溶融性を向上させ
るが、本願ではB2O3とMgOの添加によ
つて溶融性が改良されているので必須で
はない。しかし還元性雰囲気において溶
融ガラス中に溶解しているSO3が還元さ
れてアンバー着色を起す様な条件下では
ガラス中にZnOが存在すると還元された
Ｓを無色のZnSとして固定しアンバー着
色を防ぐので、２％以上含有するのが好
ましい。
例えばフロートバスを用いてガラスを板
状に成形する場合、Ｓ分を含んだガラス
はアンバー着色を起しやすいが、ガラス
中にZnOを２％以上含ませておけば防ぐ
ことができる。しかしZnOはガラスの温
粘曲線を急勾配にして成形性を悪くする
欠点もあるので６％を越えてはならな
い。
Li2Ｏ：ガラスの溶融性を向上させるので0.3％
程度含有するのが好ましいが、原料が高
価であるので必須ではない。また２％を
越えても溶融性向上の効果はないので２
％を上限とする。
Na2Ｏ：K+とイオン交換してガラス表層部に
所要の圧縮応力を生ぜしめるのに８％は
必要である。しかし14％を越えるとガラ
スの化学的耐久性を低下させる。
K2Ｏ：Na2Ｏと共存することによりK+の拡散
を促進させるので少なくとも３％は必要
である。しかし６％を越えるとガラス中
のアルカリ金属分が多くなりすぎ、ガラ
スの化学的耐久性を低下させる。
以上の成分の他に本発明の主旨を害わない範囲
で清澄剤（例えばAS2O3，Sb2O3，SO3，Cl，Ｆ
等），着色剤（例えばNiO，CoO，Se，MnO2，
Nd2O3，Pr6O11等）や不純物を含有しても構わな
い。
〔実施例〕
第１表の組成となるようガラス原料を調合し、
白金ルツボ中で溶融し、型枠に鋳込み徐冷して試
料を得た。試料ガラスをKNO3溶融塩に20時間浸
漬して化学強化処理した後表面圧縮応力値を測
[Industrial Application Field] The present invention relates to a glass composition for chemical strengthening by ion exchange. [Prior art] Glass is immersed in a molten salt containing alkali metal ions at a temperature below the strain point, and the alkali metal ions in the glass are exchanged with alkali metal ions with a larger atomic radius in the molten salt to form a surface of the glass. The so-called chemical strengthening method that generates compressive stress in steel has been known for a long time. Furthermore, as an alkali metal ion used, replacing Na + in the glass with K + in the molten salt is SSKistler (J.Amer.Ceram.Soc.Vol.45)
It has been announced. In order to accelerate the diffusion rate of K + in the glass, the inclusion of Al 2 O 3 or ZrO 2 in the glass is covered by Corning's patents (for example, Japanese Patent Publication No. 41-20629, Japanese Patent Publication No. 47-47970, Japanese Patent Publication No. 48-1988).
11327 etc.). But Al 2 O 3 or
Glasses containing a large amount of ZrO 2 have the disadvantage of high melting and forming temperatures. 1974 Special Publication as a chemically strengthened glass that improves the meltability of glass and increases the diffusion rate of K +
No. 42108 is proposed. Its glass composition is
SiO2 69-74%, Na2O 5-13%, K2O6
~12%, Na2O + K2O 13~19%, Al2O3 4 %
Below, ZrO 2 4% or less, Al 2 O 3 + ZrO 2 2 to 7
%, MgO 10% or less, ZnO 5% or less, MgO+
ZnO 2-12%, B 2 O 3 4% or less, SiO 2 + Na 2 O
+ K2O + Al2O3 + ZrO2 + MgO +ZnO+ B2O3 96
Consists of % or more. However, even glass with this composition still has a high melting temperature, and the melting point defined by the glass viscosity of 10 2 poise is 1500°C or higher. [Problems to be Solved by the Invention] The present invention aims to provide a glass composition for chemical strengthening that has a high diffusion rate of K + during ion exchange, has a melting point of 1500°C or less, and has excellent meltability and formability. Take it as a challenge. [Means for Solving the Problems] In order to solve the above problems, the glass composition of the present invention has basic components expressed in weight percent within the following ranges. SiO 2 60-72 B 2 O 3 5-10 Al 2 O 3 3-6 (However, Al 2 O 3 + ZrO 2 3-6) MgO 5-10 ZnO 0-6 Li 2 O 0-2 Na 2 O 8- 14 K 2 O 3-6 [Function] SiO 2 : Main component forming the glass skeleton,
If it is less than 60%, the glass will be chemically unstable and will have poor water resistance and acid resistance;
If the temperature exceeds , the melting temperature will increase. B 2 O 3 : Forms a glass skeleton and lowers the melting temperature and forming temperature of the glass, but if it is less than 5%, the effect of lowering the melting temperature will be poor, and if it exceeds 10%, B 2 O 3 will be reduced during melting and forming. It easily volatizes and causes defects such as striae and devitrification due to compositional fluctuations. Al 2 O 3 : Makes glass chemically stable and promotes ion exchange of Na + 〓K + .
If it is less than 3%, the effect of promoting ion exchange will be small, and if it exceeds 6%, the melting temperature of the glass will be high and the glass will be prone to devitrification. Note that since ZrO 2 also has the same effect as Al 2 O 3 , the range of Al 2 O 3 +ZrO 2 is also set to 3 to 6%. MgO: Lowers the viscosity of the glass at high temperatures without reducing the diffusion rate of K + in the glass, making it easier to melt the glass. If it is less than 5%, the effect is poor, and if it exceeds 10%, the glass tends to devitrify. ZnO: Like MgO, ZnO improves the melting properties of glass, but is not essential in this application because the melting properties are improved by the addition of B 2 O 3 and MgO. However, under conditions where SO 3 dissolved in molten glass is reduced in a reducing atmosphere and causes amber coloration, the presence of ZnO in the glass fixes the reduced S as colorless ZnS and prevents amber coloration. Therefore, it is preferable to contain 2% or more. For example, when forming glass into a plate shape using a float bath, glass containing S tends to develop amber coloration, but this can be prevented by containing 2% or more of ZnO in the glass. However, ZnO has the disadvantage of making the temperature-viscosity curve of the glass steep and impairing formability, so its content should not exceed 6%. Li 2 O: 0.3% as it improves the meltability of glass
Although it is preferable to contain a certain amount, it is not essential because the raw materials are expensive. In addition, even if it exceeds 2%, there is no effect of improving meltability.
The upper limit is %. Na 2 O: 8% is required to exchange ions with K + and generate the required compressive stress in the glass surface layer. However, if it exceeds 14%, the chemical durability of the glass decreases. K 2 O: Coexistence with Na 2 O promotes the diffusion of K + , so at least 3% is required. However, if it exceeds 6%, the alkali metal content in the glass becomes too large, reducing the chemical durability of the glass. In addition to the above components, clarifiers (for example, AS 2 O 3 , Sb 2 O 3 , SO 3 , Cl, F
etc.), colorants (e.g. NiO, CoO, Se, MnO 2 ,
Nd 2 O 3 , Pr 6 O 11 , etc.) or impurities may be contained. [Example] Glass raw materials were mixed to have the composition shown in Table 1,
It was melted in a platinum crucible, cast into a mold, and slowly cooled to obtain a sample. After chemically strengthening the sample glass by immersing it in KNO 3 molten salt for 20 hours, the surface compressive stress value was measured.
本発明のガラスは従来のガラスに較べて化学強
化処理によつて高い強度を発現するとともに、溶
融点・作業点が低いので溶融・成形が容易であ
る。
The glass of the present invention exhibits higher strength than conventional glasses through chemical strengthening treatment, and has a lower melting point and working point, making it easier to melt and mold.
Claims (1)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP22079684A JPS61101433A (en) | 1984-10-20 | 1984-10-20 | Glass composition for chemical reinforcing |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP22079684A JPS61101433A (en) | 1984-10-20 | 1984-10-20 | Glass composition for chemical reinforcing |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS61101433A JPS61101433A (en) | 1986-05-20 |
| JPH0444612B2 true JPH0444612B2 (en) | 1992-07-22 |
Family
ID=16756698
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP22079684A Granted JPS61101433A (en) | 1984-10-20 | 1984-10-20 | Glass composition for chemical reinforcing |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS61101433A (en) |
Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2547994B2 (en) * | 1987-01-16 | 1996-10-30 | ティーディーケイ株式会社 | Magnetic recording media |
| FR2761978B1 (en) * | 1997-04-11 | 1999-05-07 | Saint Gobain Vitrage | GLASS COMPOSITION AND CHEMICALLY TEMPERED GLASS SUBSTRATE |
| DE10064808B4 (en) * | 2000-12-22 | 2005-09-01 | Schott Ag | Zinc oxide-containing borosilicate glass and its uses |
| TWI424972B (en) * | 2007-03-02 | 2014-02-01 | Nippon Electric Glass Co | Reinforced plate glass |
| JP5621239B2 (en) * | 2009-10-20 | 2014-11-12 | 旭硝子株式会社 | GLASS PLATE FOR DISPLAY DEVICE, PLATE GLASS FOR DISPLAY DEVICE, AND METHOD FOR PRODUCING THE SAME |
| CN102775061B (en) * | 2012-07-03 | 2015-10-28 | 华南理工大学 | A kind of Lead-free fusible environmental protection glass and preparation method thereof |
| JP6131154B2 (en) * | 2013-09-11 | 2017-05-17 | Hoya株式会社 | Glass for magnetic recording medium substrate and magnetic recording medium substrate |
| EP3118174A1 (en) * | 2015-07-17 | 2017-01-18 | AGC Glass Europe | Center console for vehicle |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS4939897A (en) * | 1972-08-26 | 1974-04-13 |
-
1984
- 1984-10-20 JP JP22079684A patent/JPS61101433A/en active Granted
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS4939897A (en) * | 1972-08-26 | 1974-04-13 |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS61101433A (en) | 1986-05-20 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| LAPS | Cancellation because of no payment of annual fees |