CA2302247A1 - Raw material composition for soda-lime glass - Google Patents
Raw material composition for soda-lime glass Download PDFInfo
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- CA2302247A1 CA2302247A1 CA002302247A CA2302247A CA2302247A1 CA 2302247 A1 CA2302247 A1 CA 2302247A1 CA 002302247 A CA002302247 A CA 002302247A CA 2302247 A CA2302247 A CA 2302247A CA 2302247 A1 CA2302247 A1 CA 2302247A1
- Authority
- CA
- Canada
- Prior art keywords
- raw material
- glass
- soda
- glass raw
- nis
- 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.)
- Abandoned
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- 239000002994 raw material Substances 0.000 title claims abstract description 110
- 239000000203 mixture Substances 0.000 title claims abstract description 23
- 239000005361 soda-lime glass Substances 0.000 title claims abstract description 21
- 239000011521 glass Substances 0.000 claims abstract description 132
- 229910052751 metal Inorganic materials 0.000 claims abstract description 26
- 239000002184 metal Substances 0.000 claims abstract description 26
- 239000000654 additive Substances 0.000 claims abstract description 23
- 230000000996 additive effect Effects 0.000 claims abstract description 17
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims abstract description 10
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 15
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 13
- 239000010446 mirabilite Substances 0.000 claims description 13
- 229910002651 NO3 Inorganic materials 0.000 claims description 12
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 12
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Chemical compound [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 claims description 12
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims description 11
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 claims description 11
- 239000011669 selenium Substances 0.000 claims description 10
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 9
- 239000011572 manganese Substances 0.000 claims description 8
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 claims description 8
- 239000011734 sodium Substances 0.000 claims description 8
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 claims description 7
- 229910052684 Cerium Inorganic materials 0.000 claims description 5
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 claims description 5
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 claims description 5
- 239000006103 coloring component Substances 0.000 claims description 5
- 239000007769 metal material Substances 0.000 claims description 5
- 229910052711 selenium Inorganic materials 0.000 claims description 5
- 235000010344 sodium nitrate Nutrition 0.000 claims description 5
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 4
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 4
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 4
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 4
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 4
- 229910017052 cobalt Inorganic materials 0.000 claims description 4
- 239000010941 cobalt Substances 0.000 claims description 4
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 4
- 229910052744 lithium Inorganic materials 0.000 claims description 4
- 229910052748 manganese Inorganic materials 0.000 claims description 4
- 229910052700 potassium Inorganic materials 0.000 claims description 4
- 239000011591 potassium Substances 0.000 claims description 4
- 229910052708 sodium Inorganic materials 0.000 claims description 4
- 239000004317 sodium nitrate Substances 0.000 claims description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 abstract description 34
- 238000002844 melting Methods 0.000 abstract description 14
- 230000015572 biosynthetic process Effects 0.000 abstract description 13
- 230000008018 melting Effects 0.000 abstract description 13
- WWNBZGLDODTKEM-UHFFFAOYSA-N sulfanylidenenickel Chemical compound [Ni]=S WWNBZGLDODTKEM-UHFFFAOYSA-N 0.000 abstract description 11
- 239000000463 material Substances 0.000 abstract description 8
- 229910052717 sulfur Inorganic materials 0.000 abstract description 7
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 abstract description 5
- 238000006243 chemical reaction Methods 0.000 abstract description 5
- 229910052759 nickel Inorganic materials 0.000 abstract description 5
- 239000011593 sulfur Substances 0.000 abstract description 5
- 229910044991 metal oxide Inorganic materials 0.000 abstract description 4
- 150000004706 metal oxides Chemical class 0.000 abstract description 4
- 229910001220 stainless steel Inorganic materials 0.000 abstract description 4
- 239000010935 stainless steel Substances 0.000 abstract description 4
- 229910001960 metal nitrate Inorganic materials 0.000 abstract description 3
- 239000002923 metal particle Substances 0.000 abstract description 2
- 229910004809 Na2 SO4 Inorganic materials 0.000 abstract 1
- 229910001510 metal chloride Inorganic materials 0.000 abstract 1
- 239000000126 substance Substances 0.000 abstract 1
- 239000002245 particle Substances 0.000 description 20
- 239000000843 powder Substances 0.000 description 18
- 239000012535 impurity Substances 0.000 description 10
- 239000005341 toughened glass Substances 0.000 description 8
- 238000004519 manufacturing process Methods 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 4
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 description 4
- 230000002950 deficient Effects 0.000 description 4
- YEXPOXQUZXUXJW-UHFFFAOYSA-N oxolead Chemical compound [Pb]=O YEXPOXQUZXUXJW-UHFFFAOYSA-N 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 238000002791 soaking Methods 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 3
- 229910013553 LiNO Inorganic materials 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 2
- 229910000359 iron(II) sulfate Inorganic materials 0.000 description 2
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(III) nitrate Inorganic materials [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 description 2
- 239000010410 layer Substances 0.000 description 2
- 239000006060 molten glass Substances 0.000 description 2
- 230000002269 spontaneous effect Effects 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229910015400 FeC13 Inorganic materials 0.000 description 1
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 1
- 235000019738 Limestone Nutrition 0.000 description 1
- 229910006853 SnOz Inorganic materials 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 229910000428 cobalt oxide Inorganic materials 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000006063 cullet Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 239000010459 dolomite Substances 0.000 description 1
- 229910000514 dolomite Inorganic materials 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 230000005496 eutectics Effects 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- DEOPWJHDYPLPRX-UHFFFAOYSA-M iron chloride hydrate Chemical compound O.[Cl-].[Fe] DEOPWJHDYPLPRX-UHFFFAOYSA-M 0.000 description 1
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 1
- XBDUTCVQJHJTQZ-UHFFFAOYSA-L iron(2+) sulfate monohydrate Chemical compound O.[Fe+2].[O-]S([O-])(=O)=O XBDUTCVQJHJTQZ-UHFFFAOYSA-L 0.000 description 1
- NEOOEFDJRSCWOU-UHFFFAOYSA-N iron(2+);dinitrate;hydrate Chemical compound O.[Fe+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O NEOOEFDJRSCWOU-UHFFFAOYSA-N 0.000 description 1
- 229910000464 lead oxide Inorganic materials 0.000 description 1
- HTUMBQDCCIXGCV-UHFFFAOYSA-N lead oxide Chemical compound [O-2].[Pb+2] HTUMBQDCCIXGCV-UHFFFAOYSA-N 0.000 description 1
- 239000006028 limestone Substances 0.000 description 1
- 239000013528 metallic particle Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 235000010333 potassium nitrate Nutrition 0.000 description 1
- 239000004323 potassium nitrate Substances 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 235000017550 sodium carbonate Nutrition 0.000 description 1
- 239000012798 spherical particle Substances 0.000 description 1
- 150000004763 sulfides Chemical class 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- 238000007669 thermal treatment Methods 0.000 description 1
- 229910001887 tin oxide Inorganic materials 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 238000004017 vitrification Methods 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
- C03C1/00—Ingredients generally applicable to manufacture of glasses, glazes, or vitreous enamels
-
- 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
- C03C1/00—Ingredients generally applicable to manufacture of glasses, glazes, or vitreous enamels
- C03C1/004—Refining agents
Abstract
A raw material composition for a soda-lime glass which can effectively inhibit the formation of nickel sulfide (NiS) during melting of the material. A
foreign substance of nickel sulfide (NiS) which is present in a soda-lime glass is formed by the reaction, during vitrifying reaction at an elevated temperature, of Ni components contained in a metal particle containing nickel and in stainless steel used in a glass-melting furnace with sulfur (S) components contained in Na2 SO4 used as a material for glass. The inventive raw material composition for a soda-lime glass comprises a small amount of an additive comprising a metal oxide, a metal chloride, a metal sulfate or a metal nitrate. The composition can be used for reducing or completely vanishing the formation of NiS by the reaction of Ni and S during melting.
foreign substance of nickel sulfide (NiS) which is present in a soda-lime glass is formed by the reaction, during vitrifying reaction at an elevated temperature, of Ni components contained in a metal particle containing nickel and in stainless steel used in a glass-melting furnace with sulfur (S) components contained in Na2 SO4 used as a material for glass. The inventive raw material composition for a soda-lime glass comprises a small amount of an additive comprising a metal oxide, a metal chloride, a metal sulfate or a metal nitrate. The composition can be used for reducing or completely vanishing the formation of NiS by the reaction of Ni and S during melting.
Description
Description Raw Material Composition for Soda-Lime Glass Technical Field The present invention relates to a raw material composition for soda-lime glass, and more particularly to a raw material composition for soda-lime glass capable of effectively suppressing formation of nickel sulfide (NiS) in a glass base in the course of melting of the glass raw material, to thereby produce a glass product of high quality.
Background Art In a conventional method for producing soda-lime glass, in a step for melting glass raw material at a temperature as high as near 1,500°C in a melting furnace, a nic~Cel (Ni) component contained in stainless steel used for the interior of the melting furnace and Ni-containing metal particles (e.g., stainless steel particles) present in glass raw material as an impurity may be mixed into molten glass, and the Ni component may react with a sulfur (S) component in mirabilite (Na2S04) serving as a glass raw material. As a result, nickel sulfide (NiS) may be present as a fine impurity in a melt-molded glass substrate. The incidence of an NiS impurity in a defective glass product is very low;
i.e., the number of impurities is about one in some 10 tons (t) of glass products. In addition, the impurity has a ' CA 02302247 2000-03-03 spherical particle and the particle size is as small as 0.3 mm or less, and thus detection of the impurity in a production line is very difficult.
In order to process a substrate formed of such soda-lime glass into glass for a building or a toughened glass plate for an automobile, the substrate is heated to the softening point (near 600°C) and quenched, to thereby produce compressive stress in the surface layers of the glass plate.
When nickel sulfide (NiS) is contained as an impurity in toughened glass which is heated and cooled to ambient temperature in a toughening step, a-phase NiS, which is stable at about 350°C or higher, is present in an unstable state. Since a-Phase NiS is unstable at ambient temperature, with passage of time it is transformed into ~-phase NiS, which is stable at ambient temperature. The volume of NiS
increases concomitant with phase transformation. A toughened glass plate contains a tensile stress layer having a thickness which is about 2/3 the overall thickness of the plate, and thus cracks grow rapidly due to an increase in NiS
volume in the tensile stress layer, to thereby cause spontaneous breakage of the glass plate.
In order to prevent such spontaneous breakage of toughened glass, a method for removing a defective product containing an NiS impurity is known (which method is called soaking treatment). In the method, toughened glass which is heated and cooled to ambient temperature in a toughening step is placed in a firing furnace (a soaking furnace) and re-heated and maintained therein for a predetermined period of time, and any unstable a-phase NiS contained in the toughened glass is transformed into ~-phase NiS, which is stable at about 300°C or less, to thereby increase the volume of NiS and compulsorily break the defective glass.
However, in such steps mainly comprising thermal treatment, a long period time and a great amount of thermal energy are used in order to raise temperature, and thus production cost may increase. In addition, such steps raise a serious problem against reduction in production time and enhancement of productivity.
Disclosure of the Invention In order to solve the aforementioned problems involved in conventional techniques, an object of the present invention is to provide a raw material composition for soda-lime glass capable of effectively suppressing formation of nickel sulfide (NiS) in the course of melting of the glass raw material.
Another object of the present invention is to provide a raw material composition of soda-lime glass capable of effectively suppressing formation of NiS in the course of melting of the glass raw material when the material contains, as a coloring component, ferric oxide (Fe203), selenium (Se), cerium (Ce), or other metallic materials in a very small amount.
A nickel sulfide (NiS) impurity in soda-lime glass is formed in a high-temperature vitrification step in which metallic particles containing Ni and an Ni component contained in stainless steel used for a melting furnace, which are mixed into glass raw material, react with a sulfur (S) component in Na2S04 serving as a glass raw material.
When an additive including an oxide, chloride, sulfate, or a nitrate of a metal is added in a very small amount and in advance to glass raw material, formation of NiS by reaction between Ni and S in the course of melting may be suppressed or completely eliminated, for the reasons described below.
When a metal oxide is added in a very small amount to glass raw material, NiS reacts with other metals to form a eutectic compound, and the decomposition temperature decreases. When a chloride, sulfate, or a nitrate of a metal is added in a very small amount to glass raw material, oxidation is promoted, and thus formation of sulfides of Ni becomes difficult. As a result, formation of NiS may be suppressed.
In one embodiment of the present invention, the raw material composition is characterized by comprising a mirabilite(Na2SOa)-containing glass raw material to which an additive containing an oxide, a chloride, a sulfate, or a nitrate of a metal is incorporated.
In another embodiment of the present invention, the raw material composition is characterized by comprising a glass raw material including mirabilite (Na2S04) and, as a coloring component, at least one species selected from the group consisting of ferric oxide (Fe20,), selenium (Se), cerium (Ce), and other metallic materials, wherein the glass raw material further include an additive containing an oxide, a chloride, a sulfate, or a nitrate of a metal.
The aforementioned metal is at least one species selected from the group consisting of tin (Sn), iron (Fe), cobalt (Co), manganese (Mn), lead (Pb), lithium (Li), potassium (K), and sodium (Na). The percentage by weight of the aforementioned additives may he 0.15 or less on the basis of the total weight of the aforementioned glass raw material.
The incidence of an NiS impurity in a defective glass product is about one in some 10 tons (t) of glass products in a float-type melting furnace in practice, and the amount of Ni component contained in glass products is very low; i.e., ppm (0.001 wt.$) or less. Therefore, only a ultra-very small amount of a metal oxide or the like is required to be added to glass raw material for the present invention to exhibit sufficient effects on reduction or complete elimination of formation of nickel sulfide (NiS).
Best Mode for Carrying Out the Invention (Example 1) There was performed a test simulating the case in which nickel (Ni) metal reacts with a sulfur (S) component to thereby form nickel sulfide (NiS) in the course of melting of glass raw material in a float-type melting furnace in practice.
Background Art In a conventional method for producing soda-lime glass, in a step for melting glass raw material at a temperature as high as near 1,500°C in a melting furnace, a nic~Cel (Ni) component contained in stainless steel used for the interior of the melting furnace and Ni-containing metal particles (e.g., stainless steel particles) present in glass raw material as an impurity may be mixed into molten glass, and the Ni component may react with a sulfur (S) component in mirabilite (Na2S04) serving as a glass raw material. As a result, nickel sulfide (NiS) may be present as a fine impurity in a melt-molded glass substrate. The incidence of an NiS impurity in a defective glass product is very low;
i.e., the number of impurities is about one in some 10 tons (t) of glass products. In addition, the impurity has a ' CA 02302247 2000-03-03 spherical particle and the particle size is as small as 0.3 mm or less, and thus detection of the impurity in a production line is very difficult.
In order to process a substrate formed of such soda-lime glass into glass for a building or a toughened glass plate for an automobile, the substrate is heated to the softening point (near 600°C) and quenched, to thereby produce compressive stress in the surface layers of the glass plate.
When nickel sulfide (NiS) is contained as an impurity in toughened glass which is heated and cooled to ambient temperature in a toughening step, a-phase NiS, which is stable at about 350°C or higher, is present in an unstable state. Since a-Phase NiS is unstable at ambient temperature, with passage of time it is transformed into ~-phase NiS, which is stable at ambient temperature. The volume of NiS
increases concomitant with phase transformation. A toughened glass plate contains a tensile stress layer having a thickness which is about 2/3 the overall thickness of the plate, and thus cracks grow rapidly due to an increase in NiS
volume in the tensile stress layer, to thereby cause spontaneous breakage of the glass plate.
In order to prevent such spontaneous breakage of toughened glass, a method for removing a defective product containing an NiS impurity is known (which method is called soaking treatment). In the method, toughened glass which is heated and cooled to ambient temperature in a toughening step is placed in a firing furnace (a soaking furnace) and re-heated and maintained therein for a predetermined period of time, and any unstable a-phase NiS contained in the toughened glass is transformed into ~-phase NiS, which is stable at about 300°C or less, to thereby increase the volume of NiS and compulsorily break the defective glass.
However, in such steps mainly comprising thermal treatment, a long period time and a great amount of thermal energy are used in order to raise temperature, and thus production cost may increase. In addition, such steps raise a serious problem against reduction in production time and enhancement of productivity.
Disclosure of the Invention In order to solve the aforementioned problems involved in conventional techniques, an object of the present invention is to provide a raw material composition for soda-lime glass capable of effectively suppressing formation of nickel sulfide (NiS) in the course of melting of the glass raw material.
Another object of the present invention is to provide a raw material composition of soda-lime glass capable of effectively suppressing formation of NiS in the course of melting of the glass raw material when the material contains, as a coloring component, ferric oxide (Fe203), selenium (Se), cerium (Ce), or other metallic materials in a very small amount.
A nickel sulfide (NiS) impurity in soda-lime glass is formed in a high-temperature vitrification step in which metallic particles containing Ni and an Ni component contained in stainless steel used for a melting furnace, which are mixed into glass raw material, react with a sulfur (S) component in Na2S04 serving as a glass raw material.
When an additive including an oxide, chloride, sulfate, or a nitrate of a metal is added in a very small amount and in advance to glass raw material, formation of NiS by reaction between Ni and S in the course of melting may be suppressed or completely eliminated, for the reasons described below.
When a metal oxide is added in a very small amount to glass raw material, NiS reacts with other metals to form a eutectic compound, and the decomposition temperature decreases. When a chloride, sulfate, or a nitrate of a metal is added in a very small amount to glass raw material, oxidation is promoted, and thus formation of sulfides of Ni becomes difficult. As a result, formation of NiS may be suppressed.
In one embodiment of the present invention, the raw material composition is characterized by comprising a mirabilite(Na2SOa)-containing glass raw material to which an additive containing an oxide, a chloride, a sulfate, or a nitrate of a metal is incorporated.
In another embodiment of the present invention, the raw material composition is characterized by comprising a glass raw material including mirabilite (Na2S04) and, as a coloring component, at least one species selected from the group consisting of ferric oxide (Fe20,), selenium (Se), cerium (Ce), and other metallic materials, wherein the glass raw material further include an additive containing an oxide, a chloride, a sulfate, or a nitrate of a metal.
The aforementioned metal is at least one species selected from the group consisting of tin (Sn), iron (Fe), cobalt (Co), manganese (Mn), lead (Pb), lithium (Li), potassium (K), and sodium (Na). The percentage by weight of the aforementioned additives may he 0.15 or less on the basis of the total weight of the aforementioned glass raw material.
The incidence of an NiS impurity in a defective glass product is about one in some 10 tons (t) of glass products in a float-type melting furnace in practice, and the amount of Ni component contained in glass products is very low; i.e., ppm (0.001 wt.$) or less. Therefore, only a ultra-very small amount of a metal oxide or the like is required to be added to glass raw material for the present invention to exhibit sufficient effects on reduction or complete elimination of formation of nickel sulfide (NiS).
Best Mode for Carrying Out the Invention (Example 1) There was performed a test simulating the case in which nickel (Ni) metal reacts with a sulfur (S) component to thereby form nickel sulfide (NiS) in the course of melting of glass raw material in a float-type melting furnace in practice.
The respective raw materials shown in Table 1 were mixed, to thereby prepare a glass raw material (200 g).
Subsequently, powder of metallic Ni (particle size: 149 hum) was added to the glass raw material in an amount by weight of 0.07 on the basis of the total weight of the material, to thereby prepare Ni-powder-containing glass raw material 1.
TabJ a 1 Raw material Amo u n t used ( g ) Silica sand _ __ _ ~ 92.0 Soda ash 26.5 Dolomite 23.6 Limestone 5.8 Mirabilite 2.0 Carbon 0.1 Cullet 50.0 Total 200.0 Ni-powder-containing glass raw material 1 was placed in an alumina crucible (volume: 250 cc),~and the crucible was pre-heated at 600°C for 30 minutes and placed in an electric furnace maintained at 1,370°C. The temperature was raised to 1,400°C over 10 minutes. The crucible was maintained in the furnace at the temperature for 2.2 hours and removed from the furnace. The thus-heated glass material was cast, to thereby prepare sample glass 1.
Table 2 shows the amount of added Ni powder (wt.$), the maximum particle size of NiS particles (N,m), and the number of NiS particles per glass weight (number/g) in sample glass 1. The number of NiS particles was determined by observation under a stereoscopic microscope.
Subsequently, powder of metallic Ni (particle size: 149 hum) was added to the glass raw material in an amount by weight of 0.07 on the basis of the total weight of the material, to thereby prepare Ni-powder-containing glass raw material 1.
TabJ a 1 Raw material Amo u n t used ( g ) Silica sand _ __ _ ~ 92.0 Soda ash 26.5 Dolomite 23.6 Limestone 5.8 Mirabilite 2.0 Carbon 0.1 Cullet 50.0 Total 200.0 Ni-powder-containing glass raw material 1 was placed in an alumina crucible (volume: 250 cc),~and the crucible was pre-heated at 600°C for 30 minutes and placed in an electric furnace maintained at 1,370°C. The temperature was raised to 1,400°C over 10 minutes. The crucible was maintained in the furnace at the temperature for 2.2 hours and removed from the furnace. The thus-heated glass material was cast, to thereby prepare sample glass 1.
Table 2 shows the amount of added Ni powder (wt.$), the maximum particle size of NiS particles (N,m), and the number of NiS particles per glass weight (number/g) in sample glass 1. The number of NiS particles was determined by observation under a stereoscopic microscope.
Table 2 Amount of Maximum particle Number addition size (~.im) (number/g) (wt.~) Sample 1 0.0700 120 1.13 There were prepared five sets of glass raw material having the same composition as glass raw material 1 used for preparing sample glass 1 in which NiS was formed.
Tin oxide (Sn02), an oxide of tin (Sn), was added to one of the above five sets of glass raw material, to thereby prepare glass raw material containing Ni metal powder and SnOz; i.e., glass raw material 2.
In the same manner, iron oxide (Fe203), an oxide of iron (Fe), was added to one of the above five sets of glass raw material, to thereby prepare glass raw material containing Ni metal powder and Fe203; i.e., glass raw material 3.
In the same manner, cobalt oxide~(Co0), an oxide of cobalt (Co), was added to one of the above five sets of glass raw material, to thereby prepare glass raw material containing Ni metal powder and CoO; i.e., glass raw material 4.
In the same manner, manganese oxide (Mn0), an oxide of manganese (Mn), was added to one of the above five sets of glass raw material, to thereby prepare glass raw material containing Ni metal powder and MnO; i.e., glass raw material 5.
In the same manner, lead oxide (Pb0), an oxide of lead (Pb), was added to one of the above five sets of glass raw material, to thereby prepare glass raw material containing Ni metal powder and PbO; i.e., glass raw material 6.
Each of these glass raw materials 2 to 6 was placed in an alumina crucible, and the crucible was placed in an electric furnace, heated, and maintained in the furnace.
Thereafter, the crucible was removed from the furnace. The thus-heated glass materials were cast, to thereby obtain sample classes 2 to 6. Table 3 shows the amount of added additives (wt.~), the maximum particle size of NiS particles (~.im), and the number of NiS particles per glass weight (number/g) in the respective sample glasses.
Table 3 Additive Amount of Maximum Number addition particle size (number/g) (wt.~) (~) Sample 2 Sn02 0.1500 200 0.52 Sample 3 Fe203 0.1500 ~ 120 0.50 Sample 4 Co0 0.1500 - 0.00 Sam le 5 Mn0 0.1500 200 _ 0.47 Sample 6 Pb0 0.1500 200 0.67 As is apparent from Table 3, when a metal oxide is added in a very small amount to the glass raw material, formation of NiS in a glass product is effectively suppressed.
(Example 2) There were prepared three sets of glass raw material having the same composition as glass raw material 1 used for preparing sample glass 1 in which NiS was formed.
Subsequently, sodium nitrate (NaNO,), a nitrate of sodium (Na), was added to one of the above three sets of glass raw material, in an amount of 50% on the basis of the total amount of NaN03 and mirabilite (NazS04) in the glass raw material, to thereby prepare glass raw material containing Ni metal powder and NaNO,; i.e., glass raw material 7.
In the same manner, potassium nitrate (KN03), a nitrate of potassium (K), was added to one of the above three sets of glass raw material, in an amount of 50% on the basis of the total amount of KN03 and mirabilite (NaZSOQ) in the glass raw material, to thereby prepare glass raw material containing Ni metal powder and KN03; i.e., glass raw material 8.
In the same manner, lithium nitrate (LiNO,), a nitrate of lithium (Li), was added to one of the above three sets of glass raw material, in an amount of 50% on the basis of the total amount of LiNO, and mirabilite (NaZS04) in the glass raw material, to thereby prepare glass raw material containing Ni metal powder and LiN03; i.e., glass raw material 9.
Each of these glass raw materials 7 to 9 was placed in an alumina crucible, and the crucible was placed in an electric furnace, heated, and maintained in the furnace.
Thereafter, the crucible was removed from the furnace. The thus-heated glass materials were cast, to thereby obtain sample glasses 7 to 9. Table 4 shows the addition condition of metal nitrates, the maximum particle size of NiS particles (E.im), and the number of NiS particles per glass weight (number/g) in the respective sample glasses.
Tin oxide (Sn02), an oxide of tin (Sn), was added to one of the above five sets of glass raw material, to thereby prepare glass raw material containing Ni metal powder and SnOz; i.e., glass raw material 2.
In the same manner, iron oxide (Fe203), an oxide of iron (Fe), was added to one of the above five sets of glass raw material, to thereby prepare glass raw material containing Ni metal powder and Fe203; i.e., glass raw material 3.
In the same manner, cobalt oxide~(Co0), an oxide of cobalt (Co), was added to one of the above five sets of glass raw material, to thereby prepare glass raw material containing Ni metal powder and CoO; i.e., glass raw material 4.
In the same manner, manganese oxide (Mn0), an oxide of manganese (Mn), was added to one of the above five sets of glass raw material, to thereby prepare glass raw material containing Ni metal powder and MnO; i.e., glass raw material 5.
In the same manner, lead oxide (Pb0), an oxide of lead (Pb), was added to one of the above five sets of glass raw material, to thereby prepare glass raw material containing Ni metal powder and PbO; i.e., glass raw material 6.
Each of these glass raw materials 2 to 6 was placed in an alumina crucible, and the crucible was placed in an electric furnace, heated, and maintained in the furnace.
Thereafter, the crucible was removed from the furnace. The thus-heated glass materials were cast, to thereby obtain sample classes 2 to 6. Table 3 shows the amount of added additives (wt.~), the maximum particle size of NiS particles (~.im), and the number of NiS particles per glass weight (number/g) in the respective sample glasses.
Table 3 Additive Amount of Maximum Number addition particle size (number/g) (wt.~) (~) Sample 2 Sn02 0.1500 200 0.52 Sample 3 Fe203 0.1500 ~ 120 0.50 Sample 4 Co0 0.1500 - 0.00 Sam le 5 Mn0 0.1500 200 _ 0.47 Sample 6 Pb0 0.1500 200 0.67 As is apparent from Table 3, when a metal oxide is added in a very small amount to the glass raw material, formation of NiS in a glass product is effectively suppressed.
(Example 2) There were prepared three sets of glass raw material having the same composition as glass raw material 1 used for preparing sample glass 1 in which NiS was formed.
Subsequently, sodium nitrate (NaNO,), a nitrate of sodium (Na), was added to one of the above three sets of glass raw material, in an amount of 50% on the basis of the total amount of NaN03 and mirabilite (NazS04) in the glass raw material, to thereby prepare glass raw material containing Ni metal powder and NaNO,; i.e., glass raw material 7.
In the same manner, potassium nitrate (KN03), a nitrate of potassium (K), was added to one of the above three sets of glass raw material, in an amount of 50% on the basis of the total amount of KN03 and mirabilite (NaZSOQ) in the glass raw material, to thereby prepare glass raw material containing Ni metal powder and KN03; i.e., glass raw material 8.
In the same manner, lithium nitrate (LiNO,), a nitrate of lithium (Li), was added to one of the above three sets of glass raw material, in an amount of 50% on the basis of the total amount of LiNO, and mirabilite (NaZS04) in the glass raw material, to thereby prepare glass raw material containing Ni metal powder and LiN03; i.e., glass raw material 9.
Each of these glass raw materials 7 to 9 was placed in an alumina crucible, and the crucible was placed in an electric furnace, heated, and maintained in the furnace.
Thereafter, the crucible was removed from the furnace. The thus-heated glass materials were cast, to thereby obtain sample glasses 7 to 9. Table 4 shows the addition condition of metal nitrates, the maximum particle size of NiS particles (E.im), and the number of NiS particles per glass weight (number/g) in the respective sample glasses.
Table 4 Addition condition Maximum particle Number size (~u,m) (number/g) Sample NaNO,:NaZSOa = 1:1 300 0.25 Sample KN03:Na2S0,, - 1:1 400 0.39 Sample LiN03:Na2S04 = 1:1 300 0.20 As is apparent from Table 4, when a metal nitrate is added in a very small amount to the glass raw material, formation of NiS in a glass product is effectively suppressed.
(Example 3) There were prepared seven sets of glass raw material having the same composition as glass raw material 1 used for producing sample glass 1 in which NiS was formed.
Iron (Fe) powder was added to one of the above seven sets of glass raw material, to thereby prepare glass raw material containing Ni metal powder and Fe; i.e., glass raw material 10.
In the same manner, iron oxide (Fe203), an oxide of Fe, was added to one of the above seven sets of glass raw material, to thereby prepare glass raw material containing Ni metal powder and Fe20,; i.e., glass raw material 11.
In the same manner, iron chloride hydrate (FeCl,~6H20), a chloride of Fe, was added to one of the above seven sets of glass raw material, to thereby prepare glass raw material containing Ni metal powder and FeC13~6H20; i.e., glass raw material 12.
In the same manner, iron sulfate hydrate (FeS0a~7H20), a sulfate of Fe, was added to one of the above seven sets of glass raw material, to thereby prepare glass raw material containing Ni metal powder and FeS04~7H2o; i.e., glass raw material 13.
In the same manner, iron nitrate hydrate (Fe(N03)3~9H20), a nitrate of Fe, was added in different amounts (wt.%) to three of the above seven sets of glass raw material, to thereby prepare glass raw materials containing Ni metal powder and Fc(NO,),~9HZ0; i.e., glass raw materials 14 to l6.
Each of these glass raw materials 10 to 16 was placed in an alumina crucible, and the crucible was placed in an electric furnace, heated, and maintained in the furnace.
Thereafter, the crucible was removed from the furnace. The thus-heated glass materials were cast, to thereby obtain sample glasses 10 to 16.
Table 5 shows the additives, the amount of added additives (wt.~), the maximum particle size of NiS particles (~.~m), and the number of NiS particles per glass weight (number/g) in the respective sample glasses.
Table 5 Additive Amount of Maximum Number addition particle (number/g) (wt.~) size (E,im) Sample 10 Fe 0.1500 300 1.70 Sam le 11 Fe 03 0.1500 120 0.50 Sample 12 FeCl3 ~ 6H20 0 . 1500 300 0. 80 Sample 13 FeS04 ~ 7HZ0 0. 1500 120 0. 73 Sample 14 Fe(N0,)3~9H200.1500 50 0.01 Sample 15 Fe(N03)3~9H200.1000 500 0.66 Sample 16 Fe(N0,),~9Hz00.0750 137 1.03 As is apparent from Table 5, when an oxide, chloride, sulfate, or nitrate of Fe is added in a very small amount to the glass raw material, formation of NiS in a glass product is effectively suppressed.
In glass products actually produced in practice, the Ni content of glass is much lower than the value shown in Table 2; i.e., the content is 10 ppm (0.001 wt.~) or less as described above, and therefore, the amount of the additive added to glass raw material is small. As is apparent from the results of the examples, even when the amount of additive is 0.01 wt.~ or less on the basis of the weight of glass raw material, sufficient effects may be obtained.
The above-described examples are applicable to glass raw material having a composition including a coloring component; for example, ferric oxide (Fe20,), selenium (Se), cerium (Ce), or other metallic materials in a very small amount.
Industrial Applicability In the present invention, glass raw material comprises an additive containing an oxide, a chloride, a sulfate, or a nitrate of a metal in a very small amount, and thus formation of nickel sulfide (NiS) by reaction between nickel (Ni) and a sulfur (S) component in molten glass can be suppressed. In addition, the amount of NiS in a glass product can be greatly reduced.
Even when the aforementioned additives are added in very small amounts to a glass plate, physical properties of glass, including color, viscosity, and expansion coefficient, do not change, and the glass plate can maintain its original quality, which is very advantageous in practice.
As described above, in the present invention, a glass product containing substantially no NiS can be produced. In practice, even when additives are added in amounts of 0.01 wt.~ or less to glass raw material, nickel sulfide (NiS) can be ~;ufficiently reduced or eliminated. In addition, the production process for toughened glass does not require a soaking process, and thus production cost for the glass can be reduced.
Furthermore, soda-lime glass can be produced through a method similar to a conventionally-employed one, and thus conventional production equipment can be used as is, and therefore it is not necessary to modify the equipment or to build additional equipment. Therefore, quality of toughened glass can be enhanced and equipment operating cost can be reduced.
(Example 3) There were prepared seven sets of glass raw material having the same composition as glass raw material 1 used for producing sample glass 1 in which NiS was formed.
Iron (Fe) powder was added to one of the above seven sets of glass raw material, to thereby prepare glass raw material containing Ni metal powder and Fe; i.e., glass raw material 10.
In the same manner, iron oxide (Fe203), an oxide of Fe, was added to one of the above seven sets of glass raw material, to thereby prepare glass raw material containing Ni metal powder and Fe20,; i.e., glass raw material 11.
In the same manner, iron chloride hydrate (FeCl,~6H20), a chloride of Fe, was added to one of the above seven sets of glass raw material, to thereby prepare glass raw material containing Ni metal powder and FeC13~6H20; i.e., glass raw material 12.
In the same manner, iron sulfate hydrate (FeS0a~7H20), a sulfate of Fe, was added to one of the above seven sets of glass raw material, to thereby prepare glass raw material containing Ni metal powder and FeS04~7H2o; i.e., glass raw material 13.
In the same manner, iron nitrate hydrate (Fe(N03)3~9H20), a nitrate of Fe, was added in different amounts (wt.%) to three of the above seven sets of glass raw material, to thereby prepare glass raw materials containing Ni metal powder and Fc(NO,),~9HZ0; i.e., glass raw materials 14 to l6.
Each of these glass raw materials 10 to 16 was placed in an alumina crucible, and the crucible was placed in an electric furnace, heated, and maintained in the furnace.
Thereafter, the crucible was removed from the furnace. The thus-heated glass materials were cast, to thereby obtain sample glasses 10 to 16.
Table 5 shows the additives, the amount of added additives (wt.~), the maximum particle size of NiS particles (~.~m), and the number of NiS particles per glass weight (number/g) in the respective sample glasses.
Table 5 Additive Amount of Maximum Number addition particle (number/g) (wt.~) size (E,im) Sample 10 Fe 0.1500 300 1.70 Sam le 11 Fe 03 0.1500 120 0.50 Sample 12 FeCl3 ~ 6H20 0 . 1500 300 0. 80 Sample 13 FeS04 ~ 7HZ0 0. 1500 120 0. 73 Sample 14 Fe(N0,)3~9H200.1500 50 0.01 Sample 15 Fe(N03)3~9H200.1000 500 0.66 Sample 16 Fe(N0,),~9Hz00.0750 137 1.03 As is apparent from Table 5, when an oxide, chloride, sulfate, or nitrate of Fe is added in a very small amount to the glass raw material, formation of NiS in a glass product is effectively suppressed.
In glass products actually produced in practice, the Ni content of glass is much lower than the value shown in Table 2; i.e., the content is 10 ppm (0.001 wt.~) or less as described above, and therefore, the amount of the additive added to glass raw material is small. As is apparent from the results of the examples, even when the amount of additive is 0.01 wt.~ or less on the basis of the weight of glass raw material, sufficient effects may be obtained.
The above-described examples are applicable to glass raw material having a composition including a coloring component; for example, ferric oxide (Fe20,), selenium (Se), cerium (Ce), or other metallic materials in a very small amount.
Industrial Applicability In the present invention, glass raw material comprises an additive containing an oxide, a chloride, a sulfate, or a nitrate of a metal in a very small amount, and thus formation of nickel sulfide (NiS) by reaction between nickel (Ni) and a sulfur (S) component in molten glass can be suppressed. In addition, the amount of NiS in a glass product can be greatly reduced.
Even when the aforementioned additives are added in very small amounts to a glass plate, physical properties of glass, including color, viscosity, and expansion coefficient, do not change, and the glass plate can maintain its original quality, which is very advantageous in practice.
As described above, in the present invention, a glass product containing substantially no NiS can be produced. In practice, even when additives are added in amounts of 0.01 wt.~ or less to glass raw material, nickel sulfide (NiS) can be ~;ufficiently reduced or eliminated. In addition, the production process for toughened glass does not require a soaking process, and thus production cost for the glass can be reduced.
Furthermore, soda-lime glass can be produced through a method similar to a conventionally-employed one, and thus conventional production equipment can be used as is, and therefore it is not necessary to modify the equipment or to build additional equipment. Therefore, quality of toughened glass can be enhanced and equipment operating cost can be reduced.
Claims (8)
1. A raw material composition for soda-lime glass, comprising a mirabilite(Na2SO4)-containing glass raw material to which an additive containing an oxide, a chloride, a sulfate, or a nitrate of a metal is incorporated.
2. A raw material composition for soda-lime glass according to claim 1, wherein the metal is at least one species selected from the group consisting of tin (Sn), iron (Fe), cobalt (Co), manganese (Mn), lead (Pb), lithium (Li), potassium (K), and sodium (Na).
3. A raw material composition for soda-lime glass according to claim 2, wherein the percentage by weight of the additive is 0.15% or less on the basis of the total weight of the glass raw material.
4. A raw material composition for soda-lime glass, comprising a mirabilite(Na2SO4)-containing glass raw material to which an additive selected from the group consisting of sodium nitrate (NaNO3), potassium nitrate (KNO3), and lithium nitrate (LiNO3) is incorporated, wherein about 50% of the amount of mirabilite (Na2SO4) contained in the glass raw material is replaced by the additive.
5. A raw material composition for soda-lime glass, comprising a glass raw material including mirabilite (Na2SO4) and, as a coloring component, at least one species selected from the group consisting of ferric oxide (Fe2O3), selenium (Se), cerium (Ce), and other metallic materials, wherein the glass raw material further include an additive containing an oxide, a chloride, a sulfate, or a nitrate of a metal.
6. A raw material composition for soda-lime glass according to claim 5, wherein the metal is at least one species selected from the group consisting of tin (Sn), iron (Fe), cobalt (Co), manganese (Mn), lead (Pb), lithium (Li), potassium (K), and sodium (Na).
7. A raw material composition for soda-lime glass according to claim 6, wherein the percentage by weight of the additive is 0.15 or less on the basis of the total weight of the glass raw material.
8. A raw material composition for soda-lime glass, comprising a glass raw material including mirabilite (Na2SO4) and, as a coloring component, at least one species selected from the group consisting of ferric oxide (Fe2O3), selenium (Se), cerium (Ce), and other metallic materials, wherein the glass raw material further include an additive selected from the group consisting of sodium nitrate (NaNO3), potassium nitrate (KNO3), and lithium nitrate (LiNO3) is incorporated, wherein about 50% of the amount of mirabilite (Na2SO4) contained in the glass raw material is replaced by the additive.
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
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JP19122198A JP3670489B2 (en) | 1998-07-07 | 1998-07-07 | Method for producing soda-lime glass |
JP10-191221 | 1998-07-07 | ||
PCT/JP1999/003630 WO2000001631A1 (en) | 1998-07-07 | 1999-07-06 | Raw material composition for soda-lime glass |
Publications (1)
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CA2302247A1 true CA2302247A1 (en) | 2000-01-13 |
Family
ID=16270919
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Application Number | Title | Priority Date | Filing Date |
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CA002302247A Abandoned CA2302247A1 (en) | 1998-07-07 | 1999-07-06 | Raw material composition for soda-lime glass |
Country Status (7)
Country | Link |
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US (1) | US6780801B1 (en) |
EP (1) | EP1029826A4 (en) |
JP (1) | JP3670489B2 (en) |
KR (1) | KR100591489B1 (en) |
CN (1) | CN1171816C (en) |
CA (1) | CA2302247A1 (en) |
WO (1) | WO2000001631A1 (en) |
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KR100847618B1 (en) | 2001-09-05 | 2008-07-21 | 니혼 이타가라스 가부시키가이샤 | High transmission glass plates and method for manufacturing the same |
JP2009107850A (en) * | 2006-02-14 | 2009-05-21 | Nippon Sheet Glass Co Ltd | Method for producing glass article |
FR3068347B1 (en) * | 2017-06-30 | 2020-08-28 | Arc France | GLASS MANUFACTURING PREPARATION AND GLASS FURNITURE |
CA3088780A1 (en) * | 2018-03-07 | 2019-09-12 | Guardian Glass, Llc. | Method and system for reducing glass failures from nickel sulfide based inclusions |
CN110282873B (en) * | 2019-07-05 | 2021-08-10 | 齐鲁工业大学 | Large bottle and can glass with long material property and preparation method thereof |
Family Cites Families (18)
Publication number | Priority date | Publication date | Assignee | Title |
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US3296004A (en) * | 1963-08-12 | 1967-01-03 | Pittsburgh Plate Glass Co | Neutral brown heat absorbing glass composition |
US3375095A (en) * | 1964-10-09 | 1968-03-26 | Brockway Glass Co Inc | Treatment of melting glass with so2 |
US3589885A (en) * | 1969-04-07 | 1971-06-29 | Owens Illinois Inc | Glass melting with a refining agent |
US3652303A (en) * | 1970-01-26 | 1972-03-28 | Ppg Industries Inc | Heat absorbing blue soda-lime-silica glass |
JPS4929284B1 (en) * | 1970-12-18 | 1974-08-02 | ||
JPS49118711A (en) * | 1973-03-17 | 1974-11-13 | ||
JPS517006A (en) | 1974-07-08 | 1976-01-21 | Central Glass Co Ltd | GARASUGENRYOSOSEIBUTSU |
US4062689A (en) * | 1975-04-11 | 1977-12-13 | Asahi Glass Company Ltd. | Glass composition which is resistant to alkali |
US4270945A (en) * | 1979-12-03 | 1981-06-02 | Ppg Industries, Inc. | Method of melting flat glass using nitrates to suppress sulfurous emissions |
US4792536A (en) * | 1987-06-29 | 1988-12-20 | Ppg Industries, Inc. | Transparent infrared absorbing glass and method of making |
US5112778A (en) * | 1990-01-30 | 1992-05-12 | Libbey-Owens-Ford Co. | Batch composition for making infrared and ultraviolet radiation absorbing green glass |
MX9403013A (en) * | 1993-04-27 | 1995-01-31 | Libbey Owens Ford Co | GLASS COMPOSITION. |
US5401287A (en) | 1993-08-19 | 1995-03-28 | Ppg Industries, Inc. | Reduction of nickel sulfide stones in a glass melting operation |
US5436206A (en) * | 1994-06-10 | 1995-07-25 | Corning Incorporated | Champagne colored glasses |
JP3040708B2 (en) | 1995-10-19 | 2000-05-15 | 日本板硝子株式会社 | Method for producing soda-lime glass |
US5725628A (en) * | 1996-08-05 | 1998-03-10 | Ford Motor Company | Reduction of nickel sulfide stones in glass |
JPH10265239A (en) * | 1997-03-26 | 1998-10-06 | Nippon Sheet Glass Co Ltd | Ultraviolet ray and infrared ray absorption glass |
JP4086211B2 (en) * | 1998-04-17 | 2008-05-14 | Hoya株式会社 | Glass composition and method for producing the same |
-
1998
- 1998-07-07 JP JP19122198A patent/JP3670489B2/en not_active Expired - Fee Related
-
1999
- 1999-07-06 CA CA002302247A patent/CA2302247A1/en not_active Abandoned
- 1999-07-06 KR KR1020007002368A patent/KR100591489B1/en not_active IP Right Cessation
- 1999-07-06 CN CNB998010782A patent/CN1171816C/en not_active Expired - Fee Related
- 1999-07-06 EP EP99926942A patent/EP1029826A4/en not_active Withdrawn
- 1999-07-06 WO PCT/JP1999/003630 patent/WO2000001631A1/en active IP Right Grant
- 1999-07-06 US US09/486,973 patent/US6780801B1/en not_active Expired - Fee Related
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EP1029826A4 (en) | 2003-06-18 |
JP2000026134A (en) | 2000-01-25 |
CN1171816C (en) | 2004-10-20 |
JP3670489B2 (en) | 2005-07-13 |
WO2000001631A1 (en) | 2000-01-13 |
US6780801B1 (en) | 2004-08-24 |
KR20010023714A (en) | 2001-03-26 |
KR100591489B1 (en) | 2006-06-20 |
CN1273570A (en) | 2000-11-15 |
EP1029826A1 (en) | 2000-08-23 |
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