JP3173529B2 - Black natural marble-like crystallized glass - Google Patents
Black natural marble-like crystallized glassInfo
- Publication number
- JP3173529B2 JP3173529B2 JP22795992A JP22795992A JP3173529B2 JP 3173529 B2 JP3173529 B2 JP 3173529B2 JP 22795992 A JP22795992 A JP 22795992A JP 22795992 A JP22795992 A JP 22795992A JP 3173529 B2 JP3173529 B2 JP 3173529B2
- Authority
- JP
- Japan
- Prior art keywords
- crystallized glass
- black
- glass
- natural marble
- color
- 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 - Fee Related
Links
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)
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。The present invention relates to a 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 that precipitates β-wollastonite (CaO.SiO 2 ) as a main crystal has excellent properties such as chemical durability and mechanical strength, and has a beautiful appearance similar to natural marble. It is widely used as a building material such as an exterior material or an interior material to exhibit. A typical example thereof is a natural marble-like crystallized glass disclosed in JP-B-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 crystallized glass colored with black 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 using Fe 2 O 3 , the valence of Fe ions easily changes in the glass, so that the color tone changes due to slight fluctuations in the melting conditions and crystallization conditions. It is difficult to obtain a stable and uniform black crystallized glass. Therefore, it is not possible to use a large-scale sintering furnace such as a tunnel kiln in which the temperature distribution and the rate of temperature rise and fall in the furnace are not uniform, and there is a disadvantage 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。When a curved plate is produced, a flat plate produced by crystallization once is reheated and bent, and the valence of Fe ions further changes due to the reheating treatment.
The change in color tone is increased. For this reason, when a curved board and a plane board are used together on a wall surface of a building, there is a problem that a difference in color tone is conspicuous.
【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。In view of such circumstances, a black natural marble-like crystallized glass disclosed in JP-A-63-201037 has been developed.
【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。SUMMARY OF THE INVENTION The above-mentioned JP-A-63-20
No. 1037 black natural marble-like crystallized glass is made of Fe 2
By including TiO 2 and MnO 2 together with O 3 , a change in the valence 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, when mass-produced, it is still difficult to obtain a desired color tone, and there is a problem that 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。[0009] It is an object of the present invention to provide a stable and uniform black color even if the melting conditions and crystallization conditions are slightly changed, and a black natural color which does not change its color tone 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。As a result of various experiments, the present inventors have found that, in a crystallized glass of the SiO 2 —Al 2 O 3 —CaO system, NiO is used instead of Fe 2 O 3 as a colored oxide. It has been found that coexistence of CoO and CoO makes it possible to obtain a black crystallized glass having very good color tone stability, and proposes 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 contains 45 to 75% by weight of SiO 2 and Al 2 O by weight percentage.
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 of 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 color tone in Al 2 O 3 —CaO-based glass (crystallized glass), even if the melting conditions and crystallization conditions fluctuate somewhat, or even when reheated, valence change hardly occurs. 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。[0013] Further, since β-wollastonite having high chemical durability and high mechanical strength is precipitated as a main crystal, these characteristics 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%, the devitrification becomes remarkable and the fluidity deteriorates. If it is more than 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 for stabilizing glass, and its content is 1 to 15%. Al 2 O 3 is 1%
If the amount is less than the above, the crystallization speed becomes too fast and the fluidity becomes poor. If the amount is more than 15%, the solubility decreases and the β-
No wollastonite is deposited.
【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 component of β-wollastonite, and its content is 6 to 20%. 6% CaO
If the amount is less than the above, β-wollastonite hardly precipitates, mechanical strength and chemical durability decrease, and the material cannot be put to practical use as a building material. On the other hand, if it is more than 20%, the crystallinity becomes too high, so that it is difficult to obtain black color, and the fluidity is 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 fluxing agents,
Its content is 1 to 15% in total. If the total amount of these components is less than 1%, the fluidity will be poor. If the total amount is more than 15%, heterogeneous crystals will precipitate and the flat plate will be warped.
【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 for improving the fluidity, and their contents are respectively 0 to 18%, and the total amount is 4 to 4%.
25%. If the total amount of these components is less than 4%, the fluidity becomes poor. If the total amount of each component exceeds 18% or the total amount exceeds 25%, β-wollastonite hardly precipitates.
【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 that color the crystallized glass in black by coexistence, and the content is 0.05 to 5% of NiO and 0.01 to 5% of CoO. NiO is less than 0.05% and CoO is 0.01%
If less, sufficient black color cannot be obtained. On the other hand, NiO is 5
%, Devitrification becomes remarkable, and when CoO is more than 5%, a color tone (blue) other than black is obtained.
【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。Further, the natural marble-like crystallized glass of the present invention comprises B 2 O 3 , TiO 2 , SrO, L
Components such as i 2 O for improving the solubility and fluidity of glass, and MnO 2 and Cr 2 for finely adjusting the color tone of black.
Colored oxides such as O 3 and CuO can be added up to 10.0% in total, and fining agents such as As 2 O 3 and Sb 2 O 3 can be added up to 1.0%. F which significantly lowers 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, a glass raw material prepared so as to have the above-described composition is melted and vitrified, and then a glass body is prepared by a method such as water granulation. Next, when the glass particles are accumulated in a refractory mold and heat-treated, the glass particles are fused and integrated, and a needle-like β-wollastonite is formed from the surface to the inside of each glass particle. Crystals precipitate,
The crystallization is completed. When the surface of the crystallized glass thus obtained is polished, crystallized glass exhibiting a black natural marble pattern due to the shape of the glass body can be obtained.
【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 Hereinafter, the natural marble-like crystallized glass of the present invention will be described based on examples. Table 1 shows Examples (Samples Nos. 1 to 6) and Comparative Examples (Samples Nos. 7 and 8) of the present invention.
【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 materials prepared so as to have the compositions shown in the table were put in a platinum crucible and placed in an electric furnace at 1400 to 1600 ° C. for 5 to 20 minutes.
Melted for hours. This molten glass was put into water, water-granulated, dried and classified to obtain glass particles having a particle size of 1 to 5 mm. Next, the glass particles are accumulated in a refractory mold having an inner wall coated with alumina powder as a mold release agent, placed in a firing furnace, and heated at a rate of 60 ° C./hour. By holding at a temperature for 2 hours, each glass body was fused and integrated and crystallized to obtain a sample. All of the obtained samples were black, and the precipitated crystals of each sample were qualitatively determined by X-ray diffraction. As a result, 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。Next, the results of measuring the acid resistance, alkali resistance, and bending strength of each of the obtained samples are shown in Table 1. For comparison, when these properties were measured for natural marble, the acid resistance was 34.0 mg / cm 2 ,
Alkali resistance is 3.0 mg / cm 2 , flexural strength is 170
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 0.9 mg / cm 2 .
1-1.5mg / cm 2 , flexural strength 320-420k
gf / cm 2 , 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
Was measured by a four-point load method using the sample No. 1. Acid resistance and alkali resistance are 90 ° C., 1% H 2 SO 4 and Na, respectively.
A 25 × 25 × 5 mm sample (mirror-polished product) was immersed in an aqueous solution of OH for 24 hours, and the weight loss was evaluated.
【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 tone stability was evaluated using each of the glasses shown in Table 1. Table 2 shows the evaluation results of Examples (Samples Nos. 1 to 6) and Comparative Examples (Samples Nos. 7 and 8) of the present invention.
【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 tone stability was performed as follows. First, a glass body having the composition shown in Table 1 was prepared in the same manner as described above. Next, the glass bodies are accumulated in a mold, placed in a firing furnace, and heated at a heating rate of 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 samples was measured using a color difference meter, and the difference in lightness resulting from the difference in the rate of temperature rise, 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 prepared under the conditions was heated again at 800 ° C., which is the heating temperature for manufacturing a curved plate, for 1 hour, and the change in lightness (ΔL) before and after the 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 can be seen from Table 2, the sample No. 1 to 6 have a color difference of 0.6 to 1.1 due to a difference in heating rate, and also have a color difference of 0.3 before and after reheating.
It was below. On the other hand, the sample No. 7 and 8 had a very large color difference of 12.5 and 10.9 due to the difference in heating rate, and also had a large color difference of 3.8 and 3.0 before and after reheating. In general, if a building material has a color difference of 2 or more, the difference in color can be visually determined. It turns out that 7 and 8 are unsuitable materials for mass production or for 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 fluctuate somewhat, and even if re-heated for bending, the material exhibits a stable and uniform black color, and thus has high productivity and 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. 45% to 75% by weight of SiO 2 ,
l 2 O 3 1~15%, CaO 6~20%, Na 2 O +
K 2 O 1 to 15%, BaO 0 to 18%, ZnO 0
１８18%, BaO + ZnO 4-25%, NiO 0.
A black natural marble-like crystallized glass having a composition of 0.5 to 5% and 0.01 to 5% of CoO, wherein β-wollastonite is precipitated 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 JPH0656471A (en) | 1994-03-01 |
| JP3173529B2 true 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) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH09511733A (en) * | 1995-01-13 | 1997-11-25 | フィリップス エレクトロニクス ネムローゼ フェンノートシャップ | Glass composition used for lamp envelope of black light blue lamp |
| CN101198558B (en) * | 2005-06-16 | 2013-05-08 | 日本电气硝子株式会社 | Natural marble like crystallized glass and process for production thereof |
| 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 |
-
1992
- 1992-08-03 JP JP22795992A patent/JP3173529B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0656471A (en) | 1994-03-01 |
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