WO2006135049A1 - Marbre naturel comme du verre cristallisé et processus de fabrication idoine - Google Patents

Marbre naturel comme du verre cristallisé et processus de fabrication idoine Download PDF

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Publication number
WO2006135049A1
WO2006135049A1 PCT/JP2006/312135 JP2006312135W WO2006135049A1 WO 2006135049 A1 WO2006135049 A1 WO 2006135049A1 JP 2006312135 W JP2006312135 W JP 2006312135W WO 2006135049 A1 WO2006135049 A1 WO 2006135049A1
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Prior art keywords
crystallized glass
natural marble
glass
crystals
precipitated
Prior art date
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PCT/JP2006/312135
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English (en)
Japanese (ja)
Inventor
Yoshio Hashibe
Masahiro Sawada
Original Assignee
Nippon Electric Glass Co., Ltd
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Application filed by Nippon Electric Glass Co., Ltd filed Critical Nippon Electric Glass Co., Ltd
Priority to CN2006800216546A priority Critical patent/CN101198558B/zh
Publication of WO2006135049A1 publication Critical patent/WO2006135049A1/fr

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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
    • C03C8/00—Enamels; Glazes; Fusion seal compositions being frit compositions having non-frit additions
    • C03C8/02—Frit compositions, i.e. in a powdered or comminuted form
    • C03C8/04—Frit compositions, i.e. in a powdered or comminuted form containing zinc
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
    • C03B19/00—Other methods of shaping glass
    • C03B19/09—Other methods of shaping glass by fusing powdered glass in a shaping mould
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
    • C03B32/00—Thermal after-treatment of glass products not provided for in groups C03B19/00, C03B25/00 - C03B31/00 or C03B37/00, e.g. crystallisation, eliminating gas inclusions or other impurities; Hot-pressing vitrified, non-porous, shaped glass products
    • C03B32/02—Thermal crystallisation, e.g. for crystallising glass bodies into glass-ceramic articles
    • 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
    • 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
    • C03C10/0045—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 containing SiO2, Al2O3 and MgO as main constituents
    • 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
    • C03C10/0054—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 PbO, SnO2, B2O3
    • E—FIXED CONSTRUCTIONS
    • E04—BUILDING
    • E04F—FINISHING WORK ON BUILDINGS, e.g. STAIRS, FLOORS
    • E04F13/00—Coverings or linings, e.g. for walls or ceilings
    • E04F13/07—Coverings or linings, e.g. for walls or ceilings composed of covering or lining elements; Sub-structures therefor; Fastening means therefor
    • E04F13/08—Coverings or linings, e.g. for walls or ceilings composed of covering or lining elements; Sub-structures therefor; Fastening means therefor composed of a plurality of similar covering or lining elements
    • E04F13/14—Coverings or linings, e.g. for walls or ceilings composed of covering or lining elements; Sub-structures therefor; Fastening means therefor composed of a plurality of similar covering or lining elements stone or stone-like materials, e.g. ceramics concrete; of glass or with an outer layer of stone or stone-like materials or glass
    • E04F13/144—Coverings or linings, e.g. for walls or ceilings composed of covering or lining elements; Sub-structures therefor; Fastening means therefor composed of a plurality of similar covering or lining elements stone or stone-like materials, e.g. ceramics concrete; of glass or with an outer layer of stone or stone-like materials or glass with an outer layer of marble or other natural stone
    • 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
    • C03C2209/00—Compositions specially applicable for the manufacture of vitreous glazes
    • C03C2209/02—Compositions specially applicable for the manufacture of vitreous glazes to produce non-uniformly coloured glazes
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P40/00—Technologies relating to the processing of minerals
    • Y02P40/50—Glass production, e.g. reusing waste heat during processing or shaping
    • Y02P40/57—Improving the yield, e-g- reduction of reject rates

Definitions

  • the present invention relates to crystallized glass, and more particularly to natural calcite-like crystallized glass used for interior and exterior materials of buildings and a method for producing the same.
  • Crystallized glass with a natural marble pattern is excellent in chemical durability and mechanical strength, and initially has a beautiful appearance as a substitute for natural stone and with many options that do not exist in nature. Therefore, the interior materials of many buildings that pursue design are now used as exterior materials.
  • Patent Documents 1 and 2 are natural large stones formed by precipitating wollastonite crystals (CaO'SiO) as main crystals by heat-treating the crystalline glass composition. A similar crystallized glass is disclosed.
  • Patent Document 1 in terms of mass percentage, Si 0 50 to 75%, Al 2 O 1 to: 15%, CaO
  • a natural marble-like crystallized glass obtained by precipitating / 3_wollastonite crystal as a main crystal is disclosed.
  • This natural marble-like crystallized glass has excellent color stability for the purpose of improving productivity.
  • Patent Document 2 in terms of mass percentage, Si ⁇ 45 to 77%, Al O 1 to 25%, CaO
  • a natural marble-like crystallized glass formed by depositing lastonite is disclosed. This natural marble-like crystallized glass has a whiteness equal to or higher than that of conventional products containing no AsO or SbO.
  • Patent Document 3 includes SiO 45 to 75%, A10 1 to 25%, CaO 1 in mass percentage.
  • a natural marble-like crystallized glass can be manufactured with a high yield without requiring a crystal nucleating agent such as cocoon and F, the raw material cost and the manufacturing cost can be significantly reduced. Is possible.
  • the desired natural marble pattern can be obtained by adjusting the particle size of the glass body. Furthermore, since it can be bent by re-heat treatment, it can also be used for curved portions of wall surfaces.
  • Patent Document 1 JP-A-6-247744
  • Patent Document 2 Japanese Patent Laid-Open No. 9-295831
  • Patent Document 3 JP-A-3-205323
  • the present invention pays attention to the above circumstances, and natural marble-like crystallized glass having a whiteness higher than that of a conventional natural marble-like crystallized glass and exhibiting a color tone different from that of a conventional product, and the crystallized glass. It is providing the manufacturing method which enabled manufacture.
  • the present inventors have found that a crystallized glass article with a whiter impression than the prototype of the conventional product has a color coordinate a * and b * in the L * a * b * color system chromaticity of the crystallized glass surface. It has been found that the L * value is in a range different from that of the conventional crystallized glass article and is higher than the whiteness of the conventional crystallized glass article.
  • the natural marble-like crystallized glass of the present invention is measured with a standard light D in a 10-degree field of view.
  • L * a * b * Color coordinates in the color system chromaticity a * and b * are ⁇ 1.0 or less and whiteness L * force S93.5 or more Is.
  • Natural marble-like crystallized glass having such L * a * b * color system chromaticity is preferable because it has a suitable color tone as an achromatic white product. If the color coordinates a * and b * deviate from ⁇ 1.0 or the whiteness L * is less than 93.5, coloring occurs and the color tone of the conventional product is almost unchanged. It is more preferable that the color coordinates a * and b * are ⁇ 0.7 or less because the difference in hue from the conventional product can be clearly felt not only in color tone but also visually.
  • the natural marble-like crystallized glass of the present invention has an X of 0 in the XYZ color system chromaticity diagram.
  • Natural marble-like crystallized glass having such a color system chromaticity is a coordinate point having no hue and the lowest saturation, and is suitable as a new achromatic white product.
  • X is 0.3 125 to 0.3130 and y-force SO. 3300 to 0.3320
  • the difference in hue clearly feels visually. Is more preferable.
  • the XYZ color system chromaticity is defined in JIS Z8701.
  • the inventors of the present invention have found that when the Fe 2 O content in the glass is controlled to 200 ppm or less by selecting the silica raw material, the alumina raw material, the calcium raw material, and the lithium raw material, the crystallization glass
  • L * a * b * color coordinate in the color system chromaticity a * and b * is in a range different from that of conventional crystallized glass articles, and is higher than the whiteness of conventional crystallized glass articles L * It was found to be a natural marble-like crystallized glass having a value.
  • the natural marble-like crystallized glass of the present invention has a content of FeO as an impurity of 2
  • a glass raw material used in preparing a glass containing the above-mentioned components is selected, and the content of FeO as an impurity is set to 200 ppm or less, whereby the glass
  • a high-quality natural marble-like crystallized glass can be produced with a higher transmittance than in the past and further enhanced whiteness of the crystallized glass after heat treatment.
  • the Fe O content is 15
  • the amount of precipitated crystals in the natural calcite-like crystallized glass of the present invention is preferably 30 to 40% by mass in terms of whiteness L * and fluidity.
  • the crystallized glass is expressed in terms of mass percentage of SiO 45 to 75%, A1 0 1 to 25%, CaO 2 to 25%, ZnO 0 to 18%. , Ba 0 0
  • the content of SiO is 45 to 75%, preferably 50 to 70%. If the SiO force is higher than 75%, the melting temperature of the glass increases and the viscosity increases, resulting in poor fluidity during heat treatment.
  • the content of A10 is:! ⁇ 25%, preferably 3 ⁇ : 15%. If the Al O force exceeds 3 ⁇ 45%, the glass solubility deteriorates and different crystals (ananosite) precipitate, resulting in poor fluidity during heat treatment. If less than 1%, devitrification increases and chemical durability increases. descend.
  • the content of Ca 0 is 2 to 25%, preferably 8 to 18%. If CaO is more than 25%, devitrification becomes strong and molding becomes difficult, and the amount of / 3_wollastonite crystal precipitated becomes too large, making it difficult to obtain the desired surface smoothness. On the other hand, if it is less than 2% —the amount of precipitated wollastonite crystals becomes too small and the mechanical strength decreases, making it unusable as a building material.
  • CaO is a component of diopside, its content is 2-20%
  • CaO is less than 2%, diopside crystals will not precipitate, and if it is more than 20%, fluidity will deteriorate and ⁇ -wollastonite crystals will precipitate.
  • ⁇ O is a component added to promote the fluidity of the glass during crystallization, and its content is 0 to 18%, preferably 2 to 15%. If ⁇ is more than 18%, / 3 —wollastonite crystals will be difficult to precipitate.
  • BaO is a component having the same effect as ⁇ , and its content is 0 to 20%, preferably 1 to
  • MgO and SrO are components that promote the solubility and fluidity of the glass, but when it exceeds 1.5%, different crystals are precipitated. It is not preferable in terms of characteristics.
  • MgO is a constituent component of diopside
  • the content thereof is 1.5 to 17%, preferably 1.5 to 12%. If MgO is less than 1.5%, diopside crystals are difficult to precipitate, and if it is more than 17%, the fluidity is poor.
  • the content of Na 2 O is:! ⁇ 15%, preferably 3 ⁇ : 10%. If NaO is more than 15%, scientific durability deteriorates and the expansion coefficient becomes high, which is not preferable as a building material. If it is less than 1%, the viscosity of the glass increases and the solubility and fluidity deteriorate.
  • the content of K 2 O is 0 to 7%, preferably 0 to 5%. If K 2 O is more than 7%, chemical durability decreases.
  • Li 2 O has the effect of increasing the crystallization speed and the effect of promoting fluidity, and its content is 0
  • Li 2 O is more than 5%, the chemical durability is lowered and the viscosity is lowered too much, so that foaming tends to occur.
  • the content of B 0 is 0 to: 1.5%, preferably 0 to 1%. If B 2 O exceeds 1.5%, heterogeneous crystals will precipitate and the desired properties will not be obtained.
  • CeO is not preferred from the viewpoint of environmental conservation, asO or SbO as a clarifier is not preferred, the whiteness of the crystallized product is drastically reduced when its content is 0.1% or less. In this case, it is a component that suppresses the decrease in whiteness.
  • C to suppress the decrease in whiteness The content of eO is 0.01-0.5%, preferably 0.05-0.3%. The effect is to suppress the coloration of Fe 2+ by Fe 2 O contained as an impurity in a glass melting environment under a reducing atmosphere. Appears in the book. When CeO is more than 0.5%, the brown coloration by Ce 4+ becomes strong, and when it is less than 0.01%, the above-mentioned effects are hardly obtained.
  • the SO content is 0.01 to 0.5%, preferably 0.02 to 0.4%.
  • SO is more than 0.5%, different crystals are precipitated, while when it is less than 0.01%, the clarifying agents AsO and Sb
  • the crystallized glass is expressed in terms of mass percentage of SiO 45 to 75%, A1 0 1 to 25%. CaO 2 to 20%, Mg 0 1.5 to : 17%, ZnO
  • It has a composition of 1%, As 0 to 1%, and is characterized by depositing diopside crystals as main crystals.
  • the method for producing a natural marble-like crystallized glass according to the present invention comprises filling a fireproof container with a plurality of crystalline glass bodies having a content of Fe 2 O as an impurity of 200 ppm or less, By heat-treating the glass body at a temperature higher than the softening point, 20 to 50% by mass of crystals are precipitated, and the whiteness L * a * b * colorimetric chromaticity of the crystallized glass surface L * is over 93.5 And a natural marble-like crystallized glass having color coordinates a * and b * of ⁇ 1.0 or less.
  • the content of FeO is 200 ppm or less as a raw material batch in which a glass raw material is prepared according to the composition range shown above and melted.
  • feldspar with the highest content of Fe 2 O Si 60-70%, A10 12-12
  • the content of O can be measured and confirmed by fluorescent X-ray analysis or chemical analysis.
  • a plurality of crystalline glass bodies are expressed in terms of mass percentage: Si 45-75%, AlO 1-25%, CaO 2 ⁇ twenty five%
  • It has a composition of O 0 to 0.5%, Sb O 0 to 1%, As O 0 to 1%, and is characterized by precipitating ⁇ -wollastonite crystals as main crystals by heat treatment.
  • a glass raw material is prepared so as to have the above composition, melted, and granulated by a process such as pulverization to produce a crystalline glass body, and a softening point.
  • a process such as pulverization to produce a crystalline glass body, and a softening point.
  • 20-50 mass% of ⁇ -wollastonite crystal is precipitated as the main crystal, and whiteness L * a * b * colorimetric chromaticity on the crystallized glass surface L * force S93
  • a natural marble-like crystallized glass having a color coordinate of a * and b * of ⁇ 1.0 or less is 5 or more.
  • a plurality of crystalline glass bodies are expressed by mass percentage in terms of Si0 45 to 75%, AlO 1 to 25%, CaO. 2-20
  • a diopside crystal is further precipitated as a main crystal.
  • a glass raw material is prepared so as to have the above composition, melted, and granulated by a process such as pulverization to produce a crystalline glass body, and a softening point.
  • Heat treatment at a higher temperature causes 20-50 mass% of the diopside crystal to precipitate as the main crystal, and the whiteness of the L * a * b * color system chromaticity L * force S93.5 on the crystallized glass surface
  • a natural marble-like crystallized glass with the color coordinates a * and b * of ⁇ 1.0 or less is produced.
  • the natural marble-like crystallized glass manufacturing method of the present invention has an average visible light transmittance (380 nm to 780 nm) of 89% or more when the thickness is 10 mm, and an XYZ color system chromaticity diagram.
  • crystalline glass bodies with X force 0.3100 to 0.3115 and y force SO. 3160 to 0.3190 (C photogen 2 degrees) the surface of crystallized glass is expressed. is there.
  • the glass raw material used in the natural marble-like crystallized glass of the present invention obtained in the present invention has a high glass transmittance when the content of impure FeO is low, and crystallization after heat treatment is performed.
  • the whiteness of the glass increases. However, since the glass cost is high, it is necessary to balance the quality of crystallized glass with the glass cost.
  • a crystalline glass body having X in the XYZ color system chromaticity diagram of crystalline glass having a X of 0.3100 to 0.3115 and a y force of SO 3160 to 0.3190 can be obtained. By using it, it is preferable to express the desired natural marble-like crystallized glass surface.
  • the natural marble-like crystallized glass according to the present invention has a color coordinate a * and b * in the L * a * b * color system chromaticity of the crystallized glass surface of ⁇ 1.0 or less and a whiteness of L * is 93.5 or more, preferably X in the XYZ color system chromaticity diagram is 0.3120-0.3130 and y is 0.3290-0.3320. It becomes a natural marble-like crystallized glass that has a certain appearance.
  • the natural marble-like crystallized glass of the present invention has a Fe 2 O content of 200 ppm or less.
  • the amount of precipitated crystals is 20-50% by mass, so that the mechanical strength and chemical durability are not impaired, and the whiteness is very high.
  • These interior materials are suitable as exterior materials.
  • the natural marble-like crystallized glass of the present invention is represented by SiO 45-7 in mass percentage.
  • the natural marble-like crystallized glass of the present invention is expressed in terms of mass percentage.
  • % Composition preferably Fe O content of 200 ppm or less, and formed by depositing a dipside crystal as the main crystal.
  • the chemical durability is excellent as long as a natural marble-like pattern with an appearance is obtained.
  • a plurality of crystalline glass bodies having a content of Fe 2 O as an impurity of 200 ppm or less are filled in a refractory container, and the crystallinity is obtained.
  • the plurality of crystalline glass bodies have an FeO content of 200 ppm or less, and expressed in mass percentage, SiO 45-7
  • J3 _ wollastonite crystal is precipitated as the main crystal by heat treatment of the crystalline glass body with a composition of ⁇ 1%.
  • the plurality of crystalline glass bodies have an FeO content of 200 ppm or less, and are expressed in terms of mass percentage.
  • a diopside crystal is precipitated as a main crystal having a composition of ⁇ 1% and a crystal precipitation amount of 20-50% by mass by heat-treating the crystalline glass body.
  • Natural marble-like crystallized glass with excellent chemical durability as well as natural marble-like patterns with needle-like crystals with a high-grade appearance can be obtained.
  • Table 1 shows examples of the present invention:! To 6 and shows a glass composition that does not use feldspar as a glass raw material so that the content of Fe 2 O as an impurity is 200 ppm or less.
  • Example 1 in the table shows that SiO raw material is converted into normal A silica sand, CaO raw material into normal calcium carbonate, and LiO raw material into When normal spojumen is used, Fe O content in glass batch is 200p
  • SiO raw material is normal A silica sand
  • CaO raw material is normal calcium carbonate
  • the content of FeO in the bush will be 150ppm.
  • the SiO raw material contains Fe 2 O
  • Example 5 is the same as Example 2. However, it is a case where Sb 2 O, which is a clarifier and a harmful substance, is not used. It was. Ma
  • Example 6 uses the same raw materials as in Example 2 and MgO raw material, and Fe O in the glass batch.
  • the content of 2 3 is 150 ppm, and the composition has a composition for precipitating diopside crystals.
  • Each sample was prepared as follows. First, mix silica sand, aluminum oxide or aluminum hydroxide, calcium carbonate, zinc white, barium carbonate, soda ash, potassium carbonate, spodumene or lithium carbonate, sodium nitrate, antimony oxide so that the composition shown in Table 1 is obtained. Melted at C temperature for 12 hours. Next, the molten glass was formed into a predetermined shape, and after annealing, it was used as a measurement sample for visible light transmittance and x and y values. Further, the molten glass was crushed with water, dried and classified to obtain a crystalline glass body having a particle size of 1 to 5 mm.
  • this glass body is accumulated in a fire-resistant mold with the inner wall coated with alumina powder, placed in an electric furnace, heated at a rate of 2 ° C / min, and at 1050-1100. By maintaining for 1 hour, each glass body was fused and crystallized, and then the appearance was evaluated by color tone (L *, a *, b *). The results are shown in Table 1.
  • Table 2 shows comparative examples:! These have a glass composition using feldspar usually used as a glass raw material.
  • the feldspar used contains about 1200 ppm of Fe 2 O.
  • SiO raw material is normal A silica sand
  • CaO raw material is normal calcium carbonate
  • Comparative Example 2 SiO raw material is low in FeO content B silica sand, CaO raw material is low iron calcium carbonate in low FeO content, LiO raw material is low in FeO content in lithium carbonate In this case, the FeO content in the glass batch is 450 ppm. Since Comparative Example 1 4 uses feldspar as the glass raw material, The content of FeO is 450ppm or more. Moreover, Comparative Example 3 was the same as Comparative Example 1 and did not use SbO, which is a strength clarifying agent and harmful, and the results were also the same. Furthermore, Comparative Example 4 uses the same raw material and MgO raw material as Comparative Example 1 to
  • X represents 0.3105 to 0.3113
  • y represents 0.3172 to 0.3185
  • a * and b * showed a value of ⁇ 1.0 or less.
  • the main crystals of Examples 1 to 5 were / 3_wollastonite crystals, and the main crystals of Example 6 were diopside crystals.
  • the transmittance of the crystalline glass before the heat treatment of each sample of the comparative example is less than 89.0%, and that of the comparative example 1 is reduced to 88.5% or less.
  • the straight of x and y have an X force S0.3115 to 0.3118 and a y force SO.3200 to 0.3208, respectively, and the color of the glass is green.
  • the whiteness L * after heat treatment was less than 93.5
  • a * and b * showed a hue with a value exceeding ⁇ 1.0
  • the force SO. 3140 to 0.3145 and the y force SO. 3335 to 0.3340 The force SO. 3140 to 0.3145 and the y force SO. 3335 to 0.3340.
  • comparative column 1 was a natural marble-like crystallized glass showing a darker appearance than the greenish examples.
  • Comparative Example 2 although the whiteness was improved, the degree of improvement in whiteness was insufficient, as the difference from the conventional product was not clear.
  • Comparative Example 4 the whiteness L * was further decreased as compared with Comparative Examples 1 and 3. This indicates that diopside crystals are susceptible to Fe 2 O.
  • crystallized glasses were natural marble-like crystallized glasses in which one wollastonite crystal and diopside crystal were precipitated as the main crystals as in the examples.
  • the average transmittance was measured as follows. First, molten glass was formed to obtain a glass plate having a thickness of 1 :! to 12 mm, and was gradually cooled at around 650 ° C. Next, the glass plate was mirror-polished so as to have a thickness of 10 mm ⁇ 0.1 mm, and then obtained by a spectrophotometer. At the same time XYZ table In the color system chromaticity diagram, x and straight were obtained.
  • the whiteness L * and a * b * of the crystallized glass after the heat treatment were obtained with a colorimeter.
  • the main crystal was determined by an X-ray diffractometer.

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Abstract

L’invention concerne un marbre naturel comme du verre cristallisé dont la blancheur est améliorée et possédant un ton de couleur inégalé, de même qu’un processus de production idoine. Le marbre naturel comme du verre cristallisé est caractérisé en ce que la surface du verre cristallisé présente, dans le modèle de couleur L*a*b*, des valeurs a* et b* inférieures ou égales à ±1,0 et un degré de blancheur L* supérieur ou égal à 93,5. Le processus consiste à garnir de plusieurs petits morceaux de verre cristallisables un récipient réfractaire, à traiter thermiquement les morceaux à une température supérieure au point de ramollissement pour constituer de 20 à 50 % en masse de cristaux, et ainsi à obtenir un marbre naturel comme du verre cristallisé présentant, dans le modèle de couleur L*a*b*, des valeurs a* et b* inférieures ou égales à ±1,0 et un degré de blancheur L* supérieur ou égal à 93,5.
PCT/JP2006/312135 2005-06-16 2006-06-16 Marbre naturel comme du verre cristallisé et processus de fabrication idoine WO2006135049A1 (fr)

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JP2005-175889 2005-06-16
JP2005175889 2005-06-16
JP2005236619 2005-08-17
JP2005-236619 2005-08-17

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JP2008223411A (ja) * 2007-03-15 2008-09-25 Nippon Electric Glass Co Ltd ガラスブロック
EP3945078A1 (fr) * 2020-07-30 2022-02-02 Sibelco Nederland N.V. Matériau vitrocéramique, procédé de formation d'un matériau vitrocéramique et utilisation d'un matériau vitrocéramique

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CN103663964B (zh) * 2013-12-06 2017-01-04 辽宁红山玉科技有限公司 一种高硅玉石状微晶玻璃
CN113003939A (zh) * 2019-12-19 2021-06-22 湖州大享玻璃制品有限公司 SiO2-CaO系结晶化玻璃及其制造方法
CN115784616A (zh) * 2022-11-15 2023-03-14 常熟佳合显示科技有限公司 一种mas微晶玻璃及其制备方法

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EP3945078A1 (fr) * 2020-07-30 2022-02-02 Sibelco Nederland N.V. Matériau vitrocéramique, procédé de formation d'un matériau vitrocéramique et utilisation d'un matériau vitrocéramique
WO2022023205A1 (fr) * 2020-07-30 2022-02-03 Sibelco Nederland N.V. Matériau vitrocéramique, procédé de formation d'un matériau vitrocéramique et utilisations d'un matériau vitrocéramique

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