JPH04149040A - Crystallized glass - Google Patents
Crystallized glassInfo
- Publication number
- JPH04149040A JPH04149040A JP26942190A JP26942190A JPH04149040A JP H04149040 A JPH04149040 A JP H04149040A JP 26942190 A JP26942190 A JP 26942190A JP 26942190 A JP26942190 A JP 26942190A JP H04149040 A JPH04149040 A JP H04149040A
- Authority
- JP
- Japan
- Prior art keywords
- phase
- raw material
- glass
- anorthite
- melted
- 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 description 19
- 238000002844 melting Methods 0.000 claims abstract description 8
- 230000008018 melting Effects 0.000 claims abstract description 8
- 238000002425 crystallisation Methods 0.000 claims abstract description 6
- 230000008025 crystallization Effects 0.000 claims abstract description 6
- 239000002131 composite material Substances 0.000 claims abstract description 5
- 239000000126 substance Substances 0.000 claims abstract description 4
- 239000000203 mixture Substances 0.000 claims description 4
- 238000001556 precipitation Methods 0.000 claims description 2
- 239000000463 material Substances 0.000 abstract description 13
- 239000002994 raw material Substances 0.000 abstract description 10
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 abstract description 8
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 abstract description 6
- 229910052593 corundum Inorganic materials 0.000 abstract description 6
- 229910001845 yogo sapphire Inorganic materials 0.000 abstract description 6
- 229910052681 coesite Inorganic materials 0.000 abstract description 4
- 229910052906 cristobalite Inorganic materials 0.000 abstract description 4
- 239000000377 silicon dioxide Substances 0.000 abstract description 4
- 235000012239 silicon dioxide Nutrition 0.000 abstract description 4
- 229910052682 stishovite Inorganic materials 0.000 abstract description 4
- 229910052905 tridymite Inorganic materials 0.000 abstract description 4
- 238000001816 cooling Methods 0.000 abstract description 3
- KKCBUQHMOMHUOY-UHFFFAOYSA-N Na2O Inorganic materials [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 abstract description 2
- 229910052661 anorthite Inorganic materials 0.000 abstract 2
- GWWPLLOVYSCJIO-UHFFFAOYSA-N dialuminum;calcium;disilicate Chemical compound [Al+3].[Al+3].[Ca+2].[O-][Si]([O-])([O-])[O-].[O-][Si]([O-])([O-])[O-] GWWPLLOVYSCJIO-UHFFFAOYSA-N 0.000 abstract 2
- 229910052882 wollastonite Inorganic materials 0.000 abstract 2
- 239000010456 wollastonite Substances 0.000 abstract 2
- 239000002928 artificial marble Substances 0.000 description 11
- 239000013078 crystal Substances 0.000 description 8
- 239000004579 marble Substances 0.000 description 4
- 239000002244 precipitate Substances 0.000 description 4
- 239000011148 porous material Substances 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000003063 flame retardant Substances 0.000 description 2
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- 239000011362 coarse particle Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 239000002667 nucleating agent Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000013001 point bending Methods 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 230000003313 weakening effect Effects 0.000 description 1
Landscapes
- Glass Compositions (AREA)
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明は結晶化ガラスに関し、特に人工建材として適用
するのに好都合な結晶化ガラスに関する。DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to crystallized glass, and particularly to crystallized glass that is conveniently applied as an artificial building material.
従来、大理石は外観の美しさのため建築構造用材料とし
て多く用いられている。しかしながら、このような大理
石は元来、産出地域や産出量が限られ非常に高価なもの
となっている。このため、Ｃａｎ−Ａｌ２Ｏ３３ｉＯ２
系の限定された組成でβ−ウオルステナイ） （Ｓ＋
Ｌ・Ｃａｎ）の結晶を析出するガラスが人工大理石とし
て商品化されている。Traditionally, marble has been widely used as a material for architectural structures due to its beautiful appearance. However, such marble is originally produced in limited areas and in limited quantities, making it very expensive. Therefore, Can-Al2O33iO2
β-Wolstenite) (S+
Glass that precipitates crystals of L.Can) has been commercialized as artificial marble.
しかし、β−ウオルステナイト系の人工大理石は高温強
度が低い欠点をもっている。本来、大理石の特徴はその
優れた美観と共に、防火や防炎性能に優れていることが
あげられている。However, β-wolstenite-based artificial marble has the drawback of low high-temperature strength. Originally, marble is characterized by its excellent aesthetic appearance, as well as its excellent fire and flame retardant properties.
β−ウオルステナイト系の人工大理石は高温強度が低い
ため８００℃前後の熱を受゛けると軟化変形する危険性
があり、火災時の取付部の弱化により脱落する可能性が
ある。Since β-wolstenite artificial marble has low high-temperature strength, there is a risk of softening and deforming when exposed to heat of around 800°C, and there is a possibility that it will fall off due to weakening of the attachment part in the event of a fire.
本発明は従来の上述の欠点を解消し、天然大理石と同等
の美観を有し、かつ、高温強度の優れた結晶化ガラスを
提供しようとするものである。The present invention aims to eliminate the above-mentioned conventional drawbacks and provide a crystallized glass that has an aesthetic appearance equivalent to that of natural marble and has excellent high-temperature strength.
本発明はＳｉＯ２： ５０智ｔ％以上、Ａｌ２Ｏ３：
１０〜２０ｗｔ％、Ｃａ［ｌ ： ５〜１５ｗｔ％、残
部が２ｎ［Ｉ 。The present invention uses SiO2: 50% or more, Al2O3:
10-20 wt%, Ca[l: 5-15 wt%, balance 2n[I].
ＢａＯ、Ｎａ２Ｏ及びＫ２Ｏからなる群のうちの少なく
とも１種よりなる組成分を溶融してなるガラス質物質を
、結晶化条件で熱処理してＴノルサイト（Ｃａｎ・Ａ１
□０３・２ＳｉＯ□）単相又は同相とβ−ウオルステナ
イ） （ＣａＯ・５ｉｎ２）相の複合相を析出させてな
る結晶化ガラスである。A glassy substance made by melting a composition consisting of at least one of the group consisting of BaO, Na2O, and K2O is heat-treated under crystallization conditions to produce T norsite (Can・A1
It is a crystallized glass formed by precipitating a composite phase of □03.2SiO□) single phase or the same phase and β-Wolstenite) (CaO.5in2) phase.
本発明の結晶化ガラスは、先ず上記成分を配合した原料
を溶融して均一化した後、急冷してフレーク状あるいは
粒状の非晶質材とすることより始まる。この非晶質材は
、昇温時９００℃前後で前記結晶を析出すると共に、徐
々に、溶融が始まり、粘度が低くなでくる特性をもって
いる。また、完全溶融した後の降温時は、Ｔｉｎ２やＺ
ｒＯ２等のような核生成剤を添加していないため、結晶
が析出しにくい特性をもっている。The crystallized glass of the present invention begins by first melting and homogenizing raw materials containing the above-mentioned components, and then rapidly cooling them to form a flaky or granular amorphous material. This amorphous material precipitates the crystals at a temperature of about 900° C. and gradually begins to melt, resulting in a low viscosity. In addition, when the temperature is lowered after complete melting, Tin2 and Z
Since no nucleating agent such as rO2 is added, it has the property of making it difficult for crystals to precipitate.
従って、本発明では、前記非晶質材を棚板上の所定の枠
内に充填した後、温度を上げる。この時、９００℃前後
で、結晶が析出するため、透明から不透明に変わる。こ
の後、更に温度を上げることにより軟化が進み、粒子間
の隙間が埋っていく。この温度が約１１５０℃である。Therefore, in the present invention, after filling the amorphous material into a predetermined frame on the shelf board, the temperature is raised. At this time, crystals precipitate at around 900°C, so the color changes from transparent to opaque. Thereafter, by further increasing the temperature, softening progresses and the gaps between particles are filled. This temperature is about 1150°C.
この後、冷却して結晶層を有する人工大理石を得るが、
冷却時、急冷すると結晶の成長が遅くなり良好な美観を
呈するものが得られない。また熱歪による割れも生じや
すくなるた杓、９００℃前後までは５０℃／ｈｒ程度で
徐冷する。この後は人工大理石に割れを生じない程度に
冷却（約り００℃／ｈｒ以下）して人工大理石を得る。After this, it is cooled to obtain artificial marble with a crystal layer,
When cooling, if it is rapidly cooled, the growth of crystals will be slow and it will not be possible to obtain a product with a good aesthetic appearance. In addition, cracks are likely to occur due to thermal strain, so it is slowly cooled at a rate of about 50°C/hr up to around 900°C. Thereafter, the artificial marble is cooled to an extent that no cracks occur in the artificial marble (approximately 00° C./hr or less) to obtain an artificial marble.
本発明における原料は、ＳｉＯ２．Ａ１２０３ 、 ［
：ａＯ等のガラス原料を適当な割合で調合し、これを高
温のガラス窯等で一旦溶融しフリット化することにより
均一化し、これを急冷して非晶質化したものである。こ
のガラス原料の主成分（５０ｗｔ％以上）はＳｉｎ、で
あるが、これにＡｌ２Ｏ３１０〜２０ｗｔ％、ＣａＯ３
〜１５ｗｔ％を化合させて、本発明の特徴であるアノル
サイト（Ｃａｎ・Ａ１２［１３・２ＳｉＯ，）単相又は
同相とβ−ウオルステナイト（Ｓ１０□・Ｃａｂ）相と
の複合相を析出させたものである。The raw material in the present invention is SiO2. A1203, [
: Glass raw materials such as aO are prepared in appropriate proportions, and this is once melted in a high-temperature glass oven or the like to form a frit to make it homogeneous, and then it is rapidly cooled to become amorphous. The main component (50 wt% or more) of this glass raw material is Sin, but it also contains 10 to 20 wt% of Al2O3 and CaO3.
~15wt% is combined to precipitate a composite phase of anorsite (Can・A12[13・2SiO,) single phase or the same phase and β-wolstenite (S10□・Cab) phase, which is a feature of the present invention. It is.
この組成式から明らかなように、アノルソサイトを構成
するためのＣａｎ 、Ａ１２［］３ 、ＳｉＯ２のモル
比はｌ：１：２である。従って、アノルソサイトを析出
させるためには、このモル比で配合すればよいのである
が、実際には気孔のない美観の優れた人工大理石を作る
ためには、結晶化率を４０％以下程度の少ない範囲に抑
える必要がある。この場合、添加したＡｌ２Ｏ３やＣａ
Ｏは非晶質部（ガラス）に固溶され易い傾向がある。As is clear from this compositional formula, the molar ratio of Can, A12[]3, and SiO2 to constitute the anorthosite is 1:1:2. Therefore, in order to precipitate anorthosite, it is sufficient to mix it at this molar ratio, but in reality, in order to make artificial marble with no pores and an excellent appearance, the crystallization rate must be as low as 40% or less. It is necessary to keep it within a range. In this case, added Al2O3 and Ca
O tends to be easily dissolved in the amorphous portion (glass).
そこで本発明はＣａＯやＡｌ２Ｏ３の一部がガラスへ固
溶してしまうことを考慮し、Ａｌ２Ｏ３とＣａＯの範囲
を特定するものである。すなわち、ＡＩ、０３について
は１０ｗｔ％以下ではガラスに大部分が固溶し、アノル
ソサイト相が析出せず、２０ｗｔ％以上では結晶化率が
４０％以上はと高くなりすぎて気孔の発生を防止できな
い。また、ＣａＤについても５ｗｔ％以下ではγノルソ
サイトの形成に必要なＣａ口分が供給できず、１５ｗｔ
％以上では結晶化率が前述の如く高くなりすぎること及
びアノルソサイトが生成せずβ−ウオルステナイト相の
みが析出してしまうためである。Therefore, the present invention specifies the range of Al2O3 and CaO in consideration of the fact that some of CaO and Al2O3 will be dissolved in the glass. That is, for AI, 03, if it is less than 10 wt%, most of it will be dissolved in the glass and the anorthosite phase will not precipitate, and if it is more than 20 wt%, the crystallization rate will be too high as 40% or more, and the generation of pores cannot be prevented. . In addition, with regard to CaD, if it is less than 5wt%, the amount of Ca necessary for the formation of γ-northosites cannot be supplied, and if the CaD content is less than 5wt%,
% or more, the crystallization rate becomes too high as mentioned above, and anorthosite is not generated and only the β-wolstenite phase is precipitated.
また、本発明では、２ｎｌｌ 、 ＢａＯ，Ｎａ２Ｄ及
びＫ２Ｏのうち１種以上を配合するものであるが、これ
らの成分はいずれもガラスの融点を低げ、作業をしやす
くすること及び気孔のないガラスを得るためには不可欠
の材料で、特に、ガラス相を安定させるための成分であ
るが、本発明の特定する結晶相の析出には特別な意味を
もたないため、その量的範囲は特定されるものではない
。In addition, in the present invention, one or more of 2nll, BaO, Na2D, and K2O is blended, and all of these ingredients lower the melting point of the glass, making it easier to work with, and making the glass free of pores. It is an indispensable material for obtaining the crystalline phase, and in particular, it is a component for stabilizing the glass phase, but since it has no special meaning for the precipitation of the crystalline phase specified in the present invention, its quantitative range is not specified. It is not something that will be done.
〔実施例〕 以下、本発明の一実施例について説明する。〔Example〕 An embodiment of the present invention will be described below.
第１表はこの例で使用する原料ガラスの組成及び後述す
る熱処理によって得られた材料をＸ線回折法によって結
晶相を同定した結果を示すものである。それぞれの組成
で配合した原料をガラス窯にて約１６５０℃で溶融後、
室温の鉄板上に流し、熱衝撃を与えることである程度の
粗粒に破砕された非晶質の原料を得た。この原料を５〜
２ ｍｍの範囲で分級したものを試験材とした。Table 1 shows the composition of the raw material glass used in this example and the results of identifying the crystal phase of the material obtained by the heat treatment described below by X-ray diffraction. After melting the raw materials blended with each composition at about 1650℃ in a glass kiln,
By pouring it onto an iron plate at room temperature and subjecting it to thermal shock, an amorphous raw material crushed into a certain amount of coarse particles was obtained. This raw material is 5~
The material classified within the range of 2 mm was used as the test material.
この試験材を所定の枠内に充填した後、電気炉で１１．
５０℃で軟化溶融後、９００℃までを５０℃／Ｈｒ、室
温までを１００℃／Ｈｒで徐冷して結晶相を得た。結果
から明らかなように、この実施例によればアノルソサイ
トを主体とする結晶を得ることができた。After filling this test material into a predetermined frame, 11.
After softening and melting at 50°C, it was slowly cooled at 50°C/Hr up to 900°C and at 100°C/Hr up to room temperature to obtain a crystalline phase. As is clear from the results, according to this example, crystals mainly composed of anorthosite could be obtained.
第２表は第１表で得られた人工大理石の曲げ試験結果を
示すものである。試験片は巾４ ｍｍ Ｘ厚３ ｍｍ
Ｘ ４ Ｑ ｍ＋ｎに加工し、スパン３０ｍｍの３点曲
げ試験で評価した。この方法はＪＩＳ Ｒ１６旧に準拠
したものである。Table 2 shows the bending test results of the artificial marble obtained in Table 1. The test piece is 4 mm wide x 3 mm thick.
It was processed into X 4 Q m+n and evaluated by a three-point bending test with a span of 30 mm. This method is based on JIS R16 old.
結果から明らかなように、比較材である従来のβ−ウオ
ラステナイトを主体とする比較材Ｎα１は室温での強度
は高いものの８００℃では自重で軟化してしまう。これ
に対し、Ｔノルソサイトを主体とする本発明品であるＮ
α２〜Ｎａ ４は高温でも高い強度を保っている。As is clear from the results, although the comparative material Nα1, which is a conventional comparative material mainly composed of β-wolastenite, has high strength at room temperature, it softens under its own weight at 800°C. In contrast, N
α2~Na4 maintains high strength even at high temperatures.
第
表
〔発明の効果〕
本発駄によれば、従来の人工大理石の欠点であった高温
強度を改善することが可能で、防火や防災性能に優れ、
かつ美観の優れた人工大理石を供給できる。Table [Effects of the invention] According to the present invention, it is possible to improve the high temperature strength, which was a drawback of conventional artificial marble, and it has excellent fire and disaster prevention performance.
We can also supply artificial marble with excellent aesthetic appearance.
Claims (1)
２０ｗｔ％、ＣａＯ：５〜１５ｗｔ％、残部がＺｎＯ、
ＢａＯ、Ｎａ＿２Ｏ及びＫ＿２Ｏからなる群のうちの少
なくとも１種よりなる組成分を溶融してなるガラス質物
質を、結晶化条件で熱処理してアノルサイト単相又は同
相とβ−ウオルステナイト相の複合相を析出させてなる
ことを特徴とする結晶化ガラス。SiO_2: 50wt% or more, Al_2O_3: 10~
20 wt%, CaO: 5 to 15 wt%, the balance is ZnO,
A glassy substance obtained by melting a composition consisting of at least one of the group consisting of BaO, Na_2O and K_2O is heat-treated under crystallization conditions to form a single anorsite phase or a composite phase of the same phase and β-wolstenite phase. Crystallized glass characterized by being formed by precipitation.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2269421A JP2781650B2 (en) | 1990-10-09 | 1990-10-09 | Crystallized glass |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2269421A JP2781650B2 (en) | 1990-10-09 | 1990-10-09 | Crystallized glass |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH04149040A true JPH04149040A (en) | 1992-05-22 |
| JP2781650B2 JP2781650B2 (en) | 1998-07-30 |
Family
ID=17472190
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2269421A Expired - Lifetime JP2781650B2 (en) | 1990-10-09 | 1990-10-09 | Crystallized glass |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2781650B2 (en) |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS4865210A (en) * | 1971-12-10 | 1973-09-08 | ||
| JPS50116515A (en) * | 1974-02-26 | 1975-09-11 | ||
| JPS6287435A (en) * | 1985-10-14 | 1987-04-21 | Sasaki Glass Kk | Crystallized glass articles like naturally occurring rock |
-
1990
- 1990-10-09 JP JP2269421A patent/JP2781650B2/en not_active Expired - Lifetime
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS4865210A (en) * | 1971-12-10 | 1973-09-08 | ||
| JPS50116515A (en) * | 1974-02-26 | 1975-09-11 | ||
| JPS6287435A (en) * | 1985-10-14 | 1987-04-21 | Sasaki Glass Kk | Crystallized glass articles like naturally occurring rock |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2781650B2 (en) | 1998-07-30 |
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