JPH0656471A - Black natural marble-like crystallized glass - Google Patents
Black natural marble-like crystallized glassInfo
- Publication number
- JPH0656471A JPH0656471A JP22795992A JP22795992A JPH0656471A JP H0656471 A JPH0656471 A JP H0656471A JP 22795992 A JP22795992 A JP 22795992A JP 22795992 A JP22795992 A JP 22795992A JP H0656471 A JPH0656471 A JP H0656471A
- Authority
- JP
- Japan
- Prior art keywords
- glass
- crystallized glass
- black
- natural marble
- color
- Prior art date
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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
- C03C10/00—Devitrified glass ceramics, i.e. glass ceramics having a crystalline phase dispersed in a glassy phase and constituting at least 50% by weight of the total composition
- C03C10/0036—Devitrified glass ceramics, i.e. glass ceramics having a crystalline phase dispersed in a glassy phase and constituting at least 50% by weight of the total composition containing SiO2, Al2O3 and a divalent metal oxide as main constituents
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Ceramic Engineering (AREA)
- Crystallography & Structural Chemistry (AREA)
- Dispersion Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Geochemistry & Mineralogy (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Glass Compositions (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は黒色天然大理石様結晶化
ガラスに関するものである。FIELD OF THE INVENTION The present invention relates to black natural marble-like crystallized glass.
【０００２】[0002]
【従来の技術】従来、主結晶としてβ−ウオラストナイ
ト（ＣａＯ・ＳｉＯ2 ）を析出する結晶化ガラスは、化
学耐久性や機械的強度等の特性に優れ、しかも天然大理
石様の美しい外観を呈するために、外装材や内装材等の
建築材料として広く使用されている。この代表的例とし
て特公昭５３−３９８８４号の天然大理石様結晶化ガラ
スがある。2. Description of the Related Art Conventionally, crystallized glass in which β-wollastonite (CaO · SiO 2 ) is deposited as a main crystal is excellent in characteristics such as chemical durability and mechanical strength, and has a beautiful appearance like natural marble. In order to exhibit, it is widely used as a building material such as exterior materials and interior materials. A typical example of this is natural marble-like crystallized glass of Japanese Examined Patent Publication No. 53-39884.
【０００３】上記した天然大理石様結晶化ガラスは、ガ
ラス原料中に着色酸化物を添加しておくことによって種
々の色調に着色することが可能であり、例えば同特公に
はＦｅ2 Ｏ3 を用いて黒色に着色した結晶化ガラスが開
示されている。[0003] natural marble-like crystallized glass described above, it is possible to color the various color tones by leaving the addition of coloring oxides in a glass material, for example, the same Japanese public is Fe 2 O 3 A black colored crystallized glass is disclosed.
【０００４】しかしながらＦｅ2 Ｏ3 を用いて結晶化ガ
ラスを黒色に着色する場合、ガラス中でＦｅイオンの価
数変化が起こり易いため、溶融条件や結晶化条件の僅か
な変動によって色調が変化し易く、安定して均一な黒色
の結晶化ガラスを得ることが難しい。それゆえ炉内の温
度分布や昇降温速度等が均一でないトンネル窯等の大型
焼成炉を利用することができず、生産性が悪いという欠
点がある。However, when the crystallized glass is colored black with Fe 2 O 3 , the valence of Fe ions is apt to change in the glass, and therefore the color tone changes due to slight changes in the melting conditions and the crystallization conditions. It is difficult to obtain a stable and uniform black crystallized glass. Therefore, it is not possible to use a large-scale firing furnace such as a tunnel kiln in which the temperature distribution in the furnace and the temperature rising / falling rate are not uniform, and there is a drawback that productivity is poor.
【０００５】また曲面板を作る場合、一度結晶化させて
製造した平面板を再加熱して曲げ加工するが、その再加
熱処理によってさらにＦｅイオンの価数変化が起こり、
色調の変化が増長されてしまう。このため建築物の壁面
等に、曲面板と平面板とを一緒に使用すると色調の違い
が目立つという問題を有している。Further, when a curved plate is made, a flat plate which is once crystallized and manufactured is reheated and bent, and the reheating treatment causes a change in the valence of Fe ions.
The change in color tone is increased. Therefore, there is a problem that when the curved plate and the flat plate are used together on the wall surface of a building, the difference in color tone is noticeable.
【０００６】このような事情に鑑み開発されたのが、特
開昭６３−２０１０３７号に開示の黒色天然大理石様結
晶化ガラスである。The black natural marble-like crystallized glass disclosed in JP-A-63-201037 has been developed in view of such circumstances.
【０００７】[0007]
【発明が解決しようとする課題】上記特開昭６３−２０
１０３７号の黒色天然大理石様結晶化ガラスは、Ｆｅ2
Ｏ3 とともにＴｉＯ2 とＭｎＯ2 を含有させることによ
って、Ｆｅイオンの価数変化を抑制し、色調を安定させ
ようとするものである。DISCLOSURE OF THE INVENTION Problems to be Solved by the Invention
1037 black natural marble-like crystallized glass is Fe 2
By containing TiO 2 and MnO 2 together with O 3 , the valence change of Fe ions is suppressed and the color tone is stabilized.
【０００８】しかしながら、この結晶化ガラスにおいて
もＦｅイオンの価数変化を完全に抑制することができ
ず、色調の安定性が十分でない。それゆえ大量生産する
場合、やはり所望の色調を得難く、生産性が悪いという
問題を有している。However, even in this crystallized glass, the change in the valence of Fe ions cannot be completely suppressed, and the stability of the color tone is not sufficient. Therefore, in the case of mass production, it is difficult to obtain a desired color tone and the productivity is poor.
【０００９】本発明の目的は、溶融条件や結晶化条件が
多少変動しても、安定して均一な黒色が得られ、また曲
げ加工のための再加熱を行っても色調が変化しない黒色
天然大理石様結晶化ガラスを提供することである。The object of the present invention is to obtain a stable and uniform black color even if the melting conditions and the crystallization conditions are changed to some extent, and the color tone does not change even when reheated for bending. It is to provide a marble-like crystallized glass.
【００１０】[0010]
【課題を解決するための手段】本発明者等は種々の実験
を行った結果、ＳｉＯ2 −Ａｌ2 Ｏ3 −ＣａＯ系の結晶
化ガラスにおいて、着色酸化物としてＦｅ2 Ｏ3 の代わ
りにＮｉＯとＣｏＯを共存させることにより、色調の安
定性が非常に良好な黒色の結晶化ガラスが得られること
を見いだし、本発明として提案するものである。Means for Solving the Problems As a result of various experiments conducted by the present inventors, in SiO 2 —Al 2 O 3 —CaO-based crystallized glass, NiO was used instead of Fe 2 O 3 as a coloring oxide. It was found that the coexistence of CoO and CoO makes it possible to obtain a black crystallized glass excellent in stability of color tone, and is proposed as the present invention.
【００１１】即ち、本発明の黒色天然大理石様結晶化ガ
ラスは、重量百分率でＳｉＯ2 ４５〜７５％、Ａｌ2 Ｏ
3 １〜１５％、ＣａＯ ６〜２０％、Ｎａ2 Ｏ＋Ｋ2 Ｏ
１〜１５％、ＢａＯ ０〜１８％、ＺｎＯ ０〜１８
％、ＢａＯ＋ＺｎＯ ４〜２５％、ＮｉＯ ０．０５〜
５％、ＣｏＯ ０．０１〜５％の組成を有し、主結晶と
してβ−ウオラストナイトを析出してなることを特徴と
する。That is, the black natural marble-like crystallized glass of the present invention has a weight percentage of SiO 2 45 to 75% and Al 2 O.
3 1~15%, CaO 6~20%, Na 2 O + K 2 O
1-15%, BaO 0-18%, ZnO 0-18
%, BaO + ZnO 4-25%, NiO 0.05-
It has a composition of 5% and CoO 0.01 to 5%, and is characterized in that β-wollastonite is precipitated as a main crystal.
【００１２】[0012]
【作用】本発明の黒色天然大理石様結晶化ガラスは、着
色酸化物としてＮｉＯとＣｏＯが共存することによって
黒色を呈するものであるが、これらの成分はＳｉＯ2 −
Ａｌ2 Ｏ3 −ＣａＯ系ガラス（結晶化ガラス）中では溶
融条件や結晶化条件が多少変動しても、或は再加熱した
場合でも価数変化が殆ど起こらないために色調の安定性
に優れている。[Action] black natural marble-like crystallized glass of the present invention are those exhibiting a black color by NiO and CoO coexist as coloring oxides, the components SiO 2 -
Excellent stability of the color tone in Al 2 O 3 -CaO glass (crystallized glass), even if the melting conditions and crystallization conditions fluctuate to some extent, or even when reheated, valence changes hardly occur. ing.
【００１３】また主結晶として化学耐久性や機械的強度
が高いβ−ウオラストナイトを析出するため、これらの
特性に優れている。Since β-wollastonite, which has high chemical durability and high mechanical strength, is deposited as the main crystal, these properties are excellent.
【００１４】以下に本発明の組成範囲を上記のように限
定した理由を述べる。The reasons for limiting the composition range of the present invention as described above will be described below.
【００１５】ＳｉＯ2 はβ−ウオラストナイトの構成成
分であり、その含有量は４５〜７５％である。ＳｉＯ2
が４５％より少ないと失透が著しくなるとともに流動性
が悪くなり、７５％より多いと結晶化熱処理時にガラス
の粘度が高くなって流動性が悪くなる。SiO 2 is a constituent component of β-wollastonite, and its content is 45 to 75%. SiO 2
If it is less than 45%, devitrification becomes remarkable and the fluidity deteriorates, and if it exceeds 75%, the viscosity of the glass increases during the heat treatment for crystallization and the fluidity deteriorates.
【００１６】Ａｌ2 Ｏ3 はガラスを安定させる成分であ
り、その含有量は１〜１５％である。Ａｌ2 Ｏ3 が１％
より少ないと結晶化速度が速くなり過ぎて流動性が悪く
なり、１５％より多いと溶解性が低下するとともにβ−
ウオラストナイトが析出しなくなる。Al 2 O 3 is a component that stabilizes glass, and its content is 1 to 15%. Al 2 O 3 is 1%
If it is less, the crystallization rate becomes too fast and the fluidity deteriorates, and if it is more than 15%, the solubility decreases and β-
Wollastonite does not precipitate.
【００１７】ＣａＯはβ−ウオラストナイトの構成成分
であり、その含有量は６〜２０％である。ＣａＯが６％
より少ないとβ−ウオラストナイトが析出し難くなっ
て、機械的強度や化学耐久性が低下し、建材として実用
に耐えなくなる。また２０％より多いと結晶化度が高く
なり過ぎて黒色が得難くなるとともに、流動性が悪くな
る。CaO is a constituent component of β-wollastonite, and its content is 6 to 20%. 6% CaO
If the amount is less, β-wollastonite is less likely to precipitate, the mechanical strength and the chemical durability are lowered, and it becomes unusable for practical use as a building material. On the other hand, if it exceeds 20%, the crystallinity becomes too high and it becomes difficult to obtain a black color, and the fluidity becomes poor.
【００１８】Ｎａ2 ＯとＫ2 Ｏはフラックス剤であり、
その含有量は合量で１〜１５％である。これらの成分が
合量で１％より少ないと流動性が悪くなり、１５％より
多いと異種結晶が析出して平面板に反りが生じる。Na 2 O and K 2 O are flux agents,
The total content is 1 to 15%. If the total amount of these components is less than 1%, the fluidity becomes poor, and if the total amount is more than 15%, dissimilar crystals precipitate and the flat plate warps.
【００１９】ＢａＯとＺｎＯは流動性を向上させる成分
であり、その含有量はそれぞれ０〜１８％、合量で４〜
２５％である。これらの成分が合量で４％より少ないと
流動性が悪くなり、また各成分がそれぞれ１８％より多
い場合や合量で２５％を越える場合はβ−ウオラストナ
イトが析出し難くなる。BaO and ZnO are components that improve fluidity, and their contents are 0 to 18%, respectively, and the total amount is 4 to 4.
25%. If the total amount of these components is less than 4%, the fluidity becomes poor, and if each component exceeds 18% or exceeds 25% in total, β-wollastonite is difficult to precipitate.
【００２０】ＮｉＯとＣｏＯは共存することによって結
晶化ガラスを黒色に着色する成分であり、その含有量は
ＮｉＯ ０．０５〜５％、ＣｏＯ ０．０１〜５％であ
る。ＮｉＯが０．０５％より、またＣｏＯが０．０１％
より少ないと十分な黒色が得られない。一方ＮｉＯが５
％より多いと失透が著しくなり、またＣｏＯが５％より
多いと黒色以外の色調（青色）になってしまう。NiO and CoO are components for coloring the crystallized glass black by coexisting, and their contents are 0.05 to 5% NiO and 0.01 to 5% CoO. NiO is more than 0.05%, CoO is 0.01%
If it is less, sufficient black color cannot be obtained. On the other hand, NiO is 5
If it is more than 5%, the devitrification becomes remarkable, and if CoO is more than 5%, the color tone (blue) becomes other than black.
【００２１】また本発明の天然大理石様結晶化ガラス
は、上記成分の他にもＢ2 Ｏ3 、ＴｉＯ2 、ＳｒＯ、Ｌ
ｉ2 Ｏ等のようなガラスの溶解性や流動性を向上させる
成分や、黒色の色調を微妙に調節するＭｎＯ2、Ｃｒ2
Ｏ3 、ＣｕＯ等の着色酸化物を合計１０．０％まで、ま
たＡｓ2 Ｏ3 、Ｓｂ2 Ｏ3 等の清澄剤を１．０％まで添
加可能である。なお色調の安定性を著しく低下させるＦ
ｅ2 Ｏ3 の添加は好ましくない。The natural marble-like crystallized glass of the present invention comprises B 2 O 3 , TiO 2 , SrO and L in addition to the above components.
Components such as i 2 O that improve the solubility and fluidity of glass, and MnO 2 and Cr 2 that finely adjust the color tone of black
Colored oxides such as O 3 and CuO can be added up to 10.0%, and fining agents such as As 2 O 3 and Sb 2 O 3 can be added up to 1.0%. In addition, F, which significantly reduces the stability of color tone,
The addition of e 2 O 3 is not preferred.
【００２２】次に、本発明の黒色天然大理石様結晶化ガ
ラスの好適な製造方法を説明する。Next, a preferred method for producing the black natural marble-like crystallized glass of the present invention will be described.
【００２３】まず、先記した組成になるように調合した
ガラス原料を溶融し、ガラス化した後、水砕等の方法に
より、ガラス小体を作製する。次いで耐火性の型枠内に
該ガラス小体を集積し、熱処理すると、各ガラス小体が
融着一体化するとともに、各ガラス小体の表面から内部
へ向かって針状のβ−ウオラストナイト結晶が析出し、
結晶化が完了する。このようにして得られた結晶化ガラ
スの表面を研磨すると、ガラス小体の形状に起因した黒
色の天然大理石模様を呈する結晶化ガラスを得ることが
できる。First, glass raw materials prepared so as to have the composition described above are melted and vitrified, and then glass bodies are produced by a method such as water granulation. Then, the glass small bodies are collected in a fireproof mold and subjected to heat treatment, whereby each glass small body is fused and integrated, and needle-like β-wollastonite from the surface of each glass small body toward the inside. Crystals precipitate,
Crystallization is complete. By polishing the surface of the crystallized glass thus obtained, it is possible to obtain crystallized glass exhibiting a black natural marble pattern due to the shape of the glass bodies.
【００２４】[0024]
【実施例】以下、本発明の天然大理石様結晶化ガラスを
実施例に基づいて説明する。表１は本発明の実施例（試
料Ｎｏ．１〜６）及び比較例（試料Ｎｏ．７、８）を示
している。EXAMPLES The natural marble-like crystallized glass of the present invention will be described below based on examples. Table 1 shows Examples (Sample Nos. 1 to 6) of the present invention and Comparative Examples (Samples Nos. 7 and 8).
【００２５】[0025]
【表１】 [Table 1]
【００２６】表１の各試料は次のようにして調製した。
表に示す組成になるように調合したバッチ原料を白金坩
堝に入れて電気炉中で１４００〜１６００℃で５〜２０
時間溶融した。この溶融ガラスを水中に投入して水砕し
た後、乾燥、分級し、粒径１〜５ｍｍのガラス小体を得
た。次いでこのガラス小体を、内壁に離型剤としてアル
ミナ粉を塗布した耐火性の型枠内に集積し、これを焼成
炉の中にいれて、６０℃／時の速度で昇温し、この温度
で２時間保持することによって、各ガラス小体を融着一
体化させるとともに結晶化させ、試料を得た。得られた
試料は全て黒色を呈しており、また各試料の析出結晶を
Ｘ線回折により定性したところ、すべての試料において
主結晶としてβ−ウオラストナイトが析出していた。Each sample in Table 1 was prepared as follows.
The batch raw materials prepared so as to have the composition shown in the table were put in a platinum crucible and heated at 1400 to 1600 ° C for 5 to 20 in an electric furnace.
Melted for hours. The molten glass was put into water, water-granulated, dried and classified to obtain a glass body having a particle size of 1 to 5 mm. Then, the glass particles are accumulated in a fireproof mold whose inner wall is coated with alumina powder as a mold release agent, which is put in a firing furnace and heated at a rate of 60 ° C./hour. By holding at a temperature for 2 hours, each glass small body was fused and integrated and crystallized to obtain a sample. All the obtained samples were black, and when the precipitated crystals of each sample were qualitatively determined by X-ray diffraction, β-wollastonite was precipitated as a main crystal in all the samples.
【００２７】次に得られた各試料について、耐酸性、耐
アルカリ性、及び曲げ強度を測定した結果を表１に示
す。なお比較のために、天然大理石についてこれらの特
性を測定したところ、耐酸性が３４．０ｍｇ／ｃｍ2 、
耐アルカリ性が３．０ｍｇ／ｃｍ2 、曲げ強度が１７０
ｋｇｆ／ｃｍ2 であった。Table 1 shows the results of measuring the acid resistance, alkali resistance, and bending strength of each of the obtained samples. For comparison, when these characteristics were measured for natural marble, the acid resistance was 34.0 mg / cm 2 ,
Alkali resistance is 3.0 mg / cm 2 , bending strength is 170
It was kgf / cm 2 .
【００２８】表１から明らかなように、各試料は、耐酸
性が０．２〜０．９ｍｇ／ｃｍ2 、耐アルカリ性が０．
１〜１．５ｍｇ／ｃｍ2 、曲げ強度が３２０〜４２０ｋ
ｇｆ／ｃｍ2 であり、全ての特性において天然大理石よ
り優れていた。As is clear from Table 1, each sample has an acid resistance of 0.2 to 0.9 mg / cm 2 and an alkali resistance of 0.
1 to 1.5 mg / cm 2 , bending strength 320 to 420 k
It was gf / cm 2 , which was superior to natural marble in all properties.
【００２９】また各試料の表面を研磨したところ、何れ
も少量の研磨で美しい黒色の天然大理石模様が現れた。When the surface of each sample was polished, a beautiful black natural marble pattern appeared with a small amount of polishing.
【００３０】なお、曲げ強度は５０×２５０×１７ｍｍ
の試料を用いて４点荷重法により測定した。耐酸性、耐
アルカリ性はそれぞれ９０℃、１％のＨ2 ＳＯ4 、Ｎａ
ＯＨの水溶液中に、２５×２５×５ｍｍの試料（鏡面研
磨品）を２４時間浸漬した後の重量減により評価した。The bending strength is 50 × 250 × 17 mm.
It measured by the 4-point load method using the sample of. Acid resistance and alkali resistance are 90 ° C, 1% H 2 SO 4 and Na respectively
The sample (mirror-polished product) of 25 × 25 × 5 mm was immersed in an aqueous solution of OH for 24 hours, and then evaluated by weight reduction.
【００３１】次に、表１に示した各ガラスを用いて、色
調安定性の評価を行った。表２は、本発明の実施例（試
料Ｎｏ．１〜６）及び比較例（試料Ｎｏ．７、８）の評
価結果を示している。Next, the color stability was evaluated using each of the glasses shown in Table 1. Table 2 has shown the evaluation result of the Example (sample No. 1-6) of this invention and a comparative example (sample No. 7, 8).
【００３２】[0032]
【表２】 [Table 2]
【００３３】色調安定性の評価は次のようにして行っ
た。まず、先記と同様にして表１に示す組成を有するガ
ラス小体を作製した。次いでこのガラス小体を型枠内に
集積した後、焼成炉中に入れ、１２０℃／時（条件
）、６０℃／時（条件）、３０℃／時（条件）の
昇温速度でそれぞれ昇温し、１０７０℃で２時間保持す
ることによって試料を作製した。次に得られた試料につ
いて色差計を用いて明度（Ｌ値）を測定し、各試料毎に
昇温速度の違いからくる明度の差、即ち色差（ΔＬ）を
算出した。The evaluation of color stability was performed as follows. First, glass bodies having the composition shown in Table 1 were prepared in the same manner as described above. Then, the glass bodies are collected in a mold, placed in a baking furnace, and heated at 120 ° C./hour (condition), 60 ° C./hour (condition), and 30 ° C./hour (condition). Samples were prepared by warming and holding at 1070 ° C. for 2 hours. Next, the lightness (L value) of the obtained sample was measured using a color difference meter, and the difference in lightness due to the difference in temperature rising rate, that is, the color difference (ΔL) was calculated for each sample.
【００３４】また条件で作製した試料について、曲面
板を作製する場合の加熱温度である８００℃で１時間再
加熱し、再加熱の前後における明度の変化（ΔＬ）を測
定した。The sample produced under the conditions was reheated at 800 ° C., which is the heating temperature for producing a curved plate, for 1 hour, and the change in brightness (ΔL) before and after reheating was measured.
【００３５】表２から明らかなように、本発明の実施例
である試料Ｎｏ．１〜６は昇温速度の違いによる色差が
０．６〜１．１であり、また再加熱前後の色差も０．３
以下であった。これに対して試料Ｎｏ．７及び８は昇温
速度の違いによる色差が１２．５及び１０．９と非常に
大きく、また再加熱前後の色差も３．８及び３．０と大
きかった。一般に建築材料は色差が２以上あると、目視
で色の違いを判別できるため、試料Ｎｏ．７及び８は大
量生産したり、曲面板として使用するには不適当な材料
であることがわかる。As is clear from Table 2, the sample No. which is an example of the present invention. 1 to 6 have a color difference of 0.6 to 1.1 due to the difference in temperature rising rate, and the color difference before and after reheating is 0.3.
It was below. On the other hand, the sample No. 7 and 8, the color difference due to the difference in temperature rising rate was very large at 12.5 and 10.9, and the color difference before and after reheating was also large at 3.8 and 3.0. Generally, if the building material has a color difference of 2 or more, the color difference can be visually identified. It can be seen that 7 and 8 are unsuitable materials for mass production and use as curved plates.
【００３６】[0036]
【発明の効果】以上説明したように、本発明の黒色天然
大理石様結晶化ガラスは、化学耐久性や機械的強度が高
く、また美しい黒色の天然大理石模様を呈する。しかも
焼成条件が多少変動しても、また曲げ加工のために再加
熱しても安定して均一な黒色を呈するため、生産性が良
く、建築材料として好適である。As described above, the black natural marble-like crystallized glass of the present invention has high chemical durability and mechanical strength, and exhibits a beautiful black natural marble pattern. In addition, even if the firing conditions are changed to some extent, and even if it is reheated for bending, a stable and uniform black color is obtained, and thus the productivity is good and it is suitable as a building material.
Claims (1)
ｌ2 Ｏ3 １〜１５％、ＣａＯ ６〜２０％、Ｎａ2 Ｏ＋
Ｋ2 Ｏ １〜１５％、ＢａＯ ０〜１８％、ＺｎＯ ０
〜１８％、ＢａＯ＋ＺｎＯ ４〜２５％、ＮｉＯ ０．
０５〜５％、ＣｏＯ ０．０１〜５％の組成を有し、主
結晶としてβ−ウオラストナイトを析出してなることを
特徴とする黒色天然大理石様結晶化ガラス。1. SiO 2 45-75% by weight percentage, A
l 2 O 3 1 to 15%, CaO 6 to 20%, Na 2 O +
K 2 O 1-15%, BaO 0-18%, ZnO 0
-18%, BaO + ZnO 4-25%, NiO 0.
A black natural marble-like crystallized glass having a composition of 05 to 5% and CoO of 0.01 to 5%, wherein β-wollastonite is deposited as a main crystal.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP22795992A JP3173529B2 (en) | 1992-08-03 | 1992-08-03 | Black natural marble-like crystallized glass |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP22795992A JP3173529B2 (en) | 1992-08-03 | 1992-08-03 | Black natural marble-like crystallized glass |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0656471A true JPH0656471A (en) | 1994-03-01 |
| JP3173529B2 JP3173529B2 (en) | 2001-06-04 |
Family
ID=16868943
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP22795992A Expired - Fee Related JP3173529B2 (en) | 1992-08-03 | 1992-08-03 | Black natural marble-like crystallized glass |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3173529B2 (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5612263A (en) * | 1995-01-13 | 1997-03-18 | U.S. Philips Corporation | Glass composition for a lamp envelope of a black light blue lamp |
| WO2006135049A1 (en) * | 2005-06-16 | 2006-12-21 | Nippon Electric Glass Co., Ltd | Natural marble like crystallized glass and process for production thereof |
| WO2009028561A1 (en) * | 2007-08-28 | 2009-03-05 | Nippon Electric Glass Co., Ltd. | Natural marble-like crystallized glass, natural marble-like crystallized glass articles, and process for the production of the same |
-
1992
- 1992-08-03 JP JP22795992A patent/JP3173529B2/en not_active Expired - Fee Related
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5612263A (en) * | 1995-01-13 | 1997-03-18 | U.S. Philips Corporation | Glass composition for a lamp envelope of a black light blue lamp |
| WO2006135049A1 (en) * | 2005-06-16 | 2006-12-21 | Nippon Electric Glass Co., Ltd | Natural marble like crystallized glass and process for production thereof |
| WO2009028561A1 (en) * | 2007-08-28 | 2009-03-05 | Nippon Electric Glass Co., Ltd. | Natural marble-like crystallized glass, natural marble-like crystallized glass articles, and process for the production of the same |
| JP2009073726A (en) * | 2007-08-28 | 2009-04-09 | Nippon Electric Glass Co Ltd | Natural marble-like crystallized glass, natural marble-like crystallized glass articles, and its manufacturing method |
Also Published As
| Publication number | Publication date |
|---|---|
| JP3173529B2 (en) | 2001-06-04 |
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