WO1992019559A1 - Lead-free crystal glass - Google Patents
Lead-free crystal glass Download PDFInfo
- Publication number
- WO1992019559A1 WO1992019559A1 PCT/CS1992/000012 CS9200012W WO9219559A1 WO 1992019559 A1 WO1992019559 A1 WO 1992019559A1 CS 9200012 W CS9200012 W CS 9200012W WO 9219559 A1 WO9219559 A1 WO 9219559A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- oxide
- weight
- glass
- dioxide
- lead
- Prior art date
Links
- 239000005355 lead glass Substances 0.000 title description 25
- 239000011521 glass Substances 0.000 claims abstract description 45
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 26
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 25
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 23
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims abstract description 22
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Inorganic materials O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 claims abstract description 20
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 claims abstract description 14
- FUJCRWPEOMXPAD-UHFFFAOYSA-N Li2O Inorganic materials [Li+].[Li+].[O-2] FUJCRWPEOMXPAD-UHFFFAOYSA-N 0.000 claims abstract description 12
- KKCBUQHMOMHUOY-UHFFFAOYSA-N Na2O Inorganic materials [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 claims abstract description 12
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000013078 crystal Substances 0.000 claims abstract description 9
- 229910052681 coesite Inorganic materials 0.000 claims abstract description 8
- 229910052906 cristobalite Inorganic materials 0.000 claims abstract description 8
- 229910052682 stishovite Inorganic materials 0.000 claims abstract description 8
- 239000004408 titanium dioxide Substances 0.000 claims abstract description 8
- 229910052905 tridymite Inorganic materials 0.000 claims abstract description 8
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims abstract description 7
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000011591 potassium Substances 0.000 claims abstract description 7
- 229910052700 potassium Inorganic materials 0.000 claims abstract description 7
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 7
- 235000012239 silicon dioxide Nutrition 0.000 claims abstract description 7
- 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 abstract description 6
- 239000011734 sodium Substances 0.000 claims abstract description 6
- 229910052708 sodium Inorganic materials 0.000 claims abstract description 6
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims abstract description 5
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims abstract description 5
- 239000011575 calcium Substances 0.000 claims abstract description 5
- 229910052791 calcium Inorganic materials 0.000 claims abstract description 5
- 239000011777 magnesium Substances 0.000 claims abstract description 5
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 5
- JKWMSGQKBLHBQQ-UHFFFAOYSA-N diboron trioxide Chemical compound O=BOB=O JKWMSGQKBLHBQQ-UHFFFAOYSA-N 0.000 claims abstract description 4
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims abstract description 3
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 claims abstract 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 24
- QVQLCTNNEUAWMS-UHFFFAOYSA-N barium oxide Chemical compound [Ba]=O QVQLCTNNEUAWMS-UHFFFAOYSA-N 0.000 claims description 19
- 239000011787 zinc oxide Substances 0.000 claims description 12
- 239000000203 mixture Substances 0.000 claims description 6
- 229910001947 lithium oxide Inorganic materials 0.000 claims description 4
- 229910052788 barium Inorganic materials 0.000 abstract description 10
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 abstract description 10
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 abstract description 5
- 229910052725 zinc Inorganic materials 0.000 abstract description 5
- 239000011701 zinc Substances 0.000 abstract description 5
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 abstract description 4
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 abstract description 4
- 229910052796 boron Inorganic materials 0.000 abstract description 4
- 229910052744 lithium Inorganic materials 0.000 abstract description 4
- 239000003607 modifier Substances 0.000 abstract description 2
- GHPGOEFPKIHBNM-UHFFFAOYSA-N antimony(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Sb+3].[Sb+3] GHPGOEFPKIHBNM-UHFFFAOYSA-N 0.000 abstract 4
- 229910052593 corundum Inorganic materials 0.000 abstract 1
- XUCJHNOBJLKZNU-UHFFFAOYSA-M dilithium;hydroxide Chemical compound [Li+].[Li+].[OH-] XUCJHNOBJLKZNU-UHFFFAOYSA-M 0.000 abstract 1
- 229910001845 yogo sapphire Inorganic materials 0.000 abstract 1
- 229910000464 lead oxide Inorganic materials 0.000 description 12
- 239000006060 molten glass Substances 0.000 description 10
- 239000000292 calcium oxide Substances 0.000 description 8
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 8
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 7
- YEXPOXQUZXUXJW-UHFFFAOYSA-N oxolead Chemical compound [Pb]=O YEXPOXQUZXUXJW-UHFFFAOYSA-N 0.000 description 7
- 239000000395 magnesium oxide Substances 0.000 description 6
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 6
- 238000002844 melting Methods 0.000 description 6
- 230000008018 melting Effects 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 4
- CHWRSCGUEQEHOH-UHFFFAOYSA-N potassium oxide Chemical compound [O-2].[K+].[K+] CHWRSCGUEQEHOH-UHFFFAOYSA-N 0.000 description 4
- 229910001950 potassium oxide Inorganic materials 0.000 description 4
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 3
- 229910052742 iron Inorganic materials 0.000 description 3
- 229910001948 sodium oxide Inorganic materials 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 238000000137 annealing Methods 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- 238000000227 grinding Methods 0.000 description 2
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 229940072033 potash Drugs 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 235000015320 potassium carbonate Nutrition 0.000 description 2
- 238000007670 refining Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000000654 additive Substances 0.000 description 1
- 229910052785 arsenic Inorganic materials 0.000 description 1
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 description 1
- 235000013361 beverage Nutrition 0.000 description 1
- 229910052810 boron oxide Inorganic materials 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000001627 detrimental effect Effects 0.000 description 1
- 229910003460 diamond Inorganic materials 0.000 description 1
- 239000010432 diamond Substances 0.000 description 1
- 238000007496 glass forming Methods 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 230000035939 shock Effects 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
- C03C3/00—Glass compositions
- C03C3/04—Glass compositions containing silica
- C03C3/076—Glass compositions containing silica with 40% to 90% silica, by weight
- C03C3/083—Glass compositions containing silica with 40% to 90% silica, by weight containing aluminium oxide or an iron compound
- C03C3/085—Glass compositions containing silica with 40% to 90% silica, by weight containing aluminium oxide or an iron compound containing an oxide of a divalent metal
- C03C3/087—Glass compositions containing silica with 40% to 90% silica, by weight containing aluminium oxide or an iron compound containing an oxide of a divalent metal containing calcium oxide, e.g. common sheet or container glass
-
- 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
- C03C3/00—Glass compositions
- C03C3/04—Glass compositions containing silica
- C03C3/076—Glass compositions containing silica with 40% to 90% silica, by weight
- C03C3/089—Glass compositions containing silica with 40% to 90% silica, by weight containing boron
-
- 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
- C03C3/00—Glass compositions
- C03C3/04—Glass compositions containing silica
- C03C3/076—Glass compositions containing silica with 40% to 90% silica, by weight
- C03C3/089—Glass compositions containing silica with 40% to 90% silica, by weight containing boron
- C03C3/091—Glass compositions containing silica with 40% to 90% silica, by weight containing boron containing aluminium
- C03C3/093—Glass compositions containing silica with 40% to 90% silica, by weight containing boron containing aluminium containing zinc or zirconium
-
- 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
- C03C4/00—Compositions for glass with special properties
- C03C4/0028—Compositions for glass with special properties for crystal glass, e.g. lead-free crystal glass
Definitions
- This invention relates to crystal lead-free glass which is intended especially for the man-made and machine-made utility glassware, with the refractive index within the range from 1,53 to 1,58.
- the glass contains silicon dioxide Si0 2 , aluminium oxide A1 2 0 3 , zirconium dioxide Zr0 2 , calcium CaO and/or magnesium MgO oxide, potassium K 2 0 and/or sodium Na 2 0 oxide.
- the crystal soda potash glass which is a czech speciality from the historical point of view.
- Remaining crystal glass types correspond to EC - directions.
- the first two crystal glass types mentioned above are being used for products from so called cheap crystal glass which are accented above all by a low price and refractive index ranges about the value of 1,51.
- Barium BaO and lead oxides being used by some manufacturers and in smaller amounts only, as is stated e.g. by A. Smrcek in the journal Sklaf a kera ik 38, /1988/, p. 286-294.
- the group of specialty crystal glass types represents more noble products in which the refractive index is observed to range about the value 1,52 and which is obtained by dosing of barium BaO and zinc ZnO oxides, alternatively also of lead oxide, as is specified e.g. in BRD-patent from 1987 No.
- such a glass according to the said patent contains in % by weight as follows: silicon dioxide Si0 2 65 to 75, aluminium oxide A1 2 0 3 0,1 to 2, calcium oxide CaO 2 to 12, magnesium oxide MgO 0 to 8, sodium oxide Na 2 0 7 to 15, potassium oxide K 2 0 0 to 10, lithium oxide Li 2 0 0 to 3, barium oxide BaO 1 to 6, zinc oxide ZnO 0,2 to 3, lead oxide 0 to 10 and titanium dioxide Ti0 2 0,2 to 5.
- This invention covers by its chemical composition, with the exception of titanium dioxide Ti0 2 , most of crystal glass types being produced excepting of lead and high-lead crystal glass types with the content of lead oxide 2 24 % by weight.
- the disadvantages mentioned above are removed or substantially reduced by using the crystal lead-free glass with the content of zirconium dioxide Zr0 2 which is characterized by the content from 50 to 65 % by weight of silicon dioxide Si0 2 , from 0,1 to 10 % by weight of aluminium oxide A1 2 0 3 , from 0,5 to 17 % by weight of zirconium dioxide Zr0 2 , from 10 to 22 % by weight of potassium K 2 0 and/or sodium Na 2 0 oxide, from 2 to 10 % by weight of calcium CaO and/or magnesium MgO oxide, the total amount of iron Fe expressed as iron trioxide Fe 2 0 3 (ferric oxide) being ranged from 0,01 to 0,025 % by weight.
- zirconium dioxide Zr0 2 which is characterized by the content from 50 to 65 % by weight of silicon dioxide Si0 2 , from 0,1 to 10 % by weight of aluminium oxide A1 2 0 3 , from 0,5 to 17 % by weight of zirconium dioxide Zr0 2 ,
- the functional and technological properties are with advantage modified by using at least one oxide from the group containing barium BaO, zinc ZnO, boron B 2 0 3 and lithium Li 2 0 oxides amounted from 0,1 to 10 % by weight of barium BaO, zinc ZnO, boron B 2 0 3 and lithium Li 2 0 oxides .
- This glass type can with advantage contain traces to 1 % by weight of antimony trioxide Sb 2 0 3 , titanium dioxide Ti0 2 and stannic dioxide Sn0 2 either separately or in combination as further modifiers.
- the advantage of said glass type is the decorative cutting and engraving ability comparable with the lead crystal glass, while having no content of lead oxide which is unhealthy and environmentally harmful. During melting of said glass type there does not occur the volatilization of environmentally harmful lead oxides and arsenic that are used in the manufacture of lead crystal glass.
- the lead-free glass type is preferred which is intended especially for the utility glass, i.e. also for beverage packing glass and domestic glass, it features the advantage of undesirable and unhealthy lead oxide being not penetrated into the leach.
- the melting and refining of said molten glass types is easier when compared with lead crystal molten glass types as the lead-free glass types feature lower melting temperatures.
- the melting temperature and the temperature point of liquidus are improved by addition of modifying additives, namely of barium BaO, zinc ZnO, boron B 2 0 3 and lithium Li 2 0 oxides.
- modifying additives namely of barium BaO, zinc ZnO, boron B 2 0 3 and lithium Li 2 0 oxides.
- said oxides positively affect the refractive index of glass.
- the antimony trioxide Sb 2 0 3 is used for the refining ability to be improved.
- Both titanium dioxide Ti0 2 and stannic oxide SnO including antimony trioxide Sb 2 0 3 also increase the value of the refractive index.
- the grindability is expressed by a loss of sample weight in ⁇ m.min ""1 onto a diamond grinding wheel with the dimensions of grain 120 ⁇ m under loading of 1,71 g.mm -2
- glass types according to this invention is either comparable with lead glass types or e.g. in accordance with the examples No. 1 and No. 6 or lowered by 30 °C for the molten glass type according to the example No. 7, by 75 "C for the molten glass according to the example No. 5, by 92 °C for the molten glass according to the example No. 4, by 70 °C for the molten glass according to the example No. 3 and by 95 °C for the molten glass according to the example No. 2.
- the refractive index is approximately 1,545, for the glass types according to this invention it ranges within 1,542 and 1,572.
- the optical properties of final products are comparable or better ones when comparing with products made of lead crystal glass which will especially reflect on decorative cut and engraved products.
- the mean coefficient of linear thermal expansivity ⁇ within range from 20 to 300 °C is in all cases lower than for so far used crystal glass types in general which is favourable for the resistance of glass against the thermal shock.
- the grindability for the lead crystal glass is according to the chosen method 0,266 ⁇ m.min "1 and for embodiments according to the composition No. 1 to No. 5 it is higher which will favourable affect the velocity of processing of these glass types by means of decorative cutting and engraving.
- the lead-free crystal glass according to this invention with the content of zirconium dioxide Zr0 2 is intended for man-made and machine-made utility glassware with a higher refractive index, it is suitable particularly for glass decorated by cutting and engraving and by further decorative techniques for products of the luxurious character.
- This glass type is hygienic unharmful concerning the content of detrimental substances in the leach and by its brilliance can compete with the products made of lead crystal glass.
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Geochemistry & Mineralogy (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Crystallography & Structural Chemistry (AREA)
- Glass Compositions (AREA)
Abstract
Crystal lead-free glass suitable for man-made and machine-made utility glass especially of luxurious character with a higher refractive index, containing in % by weight from 50 to 65 of silicon dioxide SiO2, from 0.1 to 10 of aluminium oxide Al2O3, from 0.5 to 17 of zirconium dioxide ZrO2, from 10 to 22 of potassium K2O and/or sodium Na2O oxide, from 2 to 10 of calcium CaO and/or magnesium MgO oxide, the content of ferric oxide Fe2O3 being within the range from 0.01 to 0.025 % by weight. The properties of said glass are modified at least by one oxide from the group comprising barium BaO, zinc ZnO, boron B2O3 and lithium Li2O oxides. The further modifiers are either individually or in combination antimony trioxide Sb2O3, titanium dioxide TiO2 and stannic dioxide SnO2 within the range from a trace to 1 % by weight of antimony trioxide Sb2O3, titanium dioxide TiO2 and stannic dioxide SnO2.
Description
Lead-free crystal glass
Technical field This invention relates to crystal lead-free glass which is intended especially for the man-made and machine-made utility glassware, with the refractive index within the range from 1,53 to 1,58. The glass contains silicon dioxide Si02, aluminium oxide A1203, zirconium dioxide Zr02, calcium CaO and/or magnesium MgO oxide, potassium K20 and/or sodium Na20 oxide.
Background art
The classification of crystal utility glass types according to CSN 70 001 is as follows: crystal soda potash glass containing in total potassium K20 and sodium Na20 oxides 1 10 % by weight, the value of refractive index being not required crystal glass containing potassium K20, barium BaO and lead oxides in total 2 10 % by weight, with the refractive index of about 1,51 special crystal glass containing potassium oxide K20, zirconium dioxide Zr02, barium BaO and lead oxides in total 1 10 % by weight, with the refractive index from 1 ,51 to 1 ,525 lead crystal glass with the content of lead oxide > 24 % by weight with the refractive index of 1 1,545 high lead crystal glass with the content of lead oxide 2 30 % by weight with the refractive index >> 1,545.
Also, the crystal soda potash glass which is a czech speciality from the historical point of view. Remaining crystal glass types correspond to EC - directions. The first two crystal glass types mentioned above are being used for products from so called cheap crystal glass which are accented above all by a low price and refractive index ranges about the value of 1,51.
Barium BaO and lead oxides being used by some manufacturers and in smaller amounts only, as is stated e.g. by A. Smrcek in the journal Sklaf a kera ik 38, /1988/, p. 286-294. The group of specialty crystal glass types represents more noble products in which the refractive index is observed to range about the value 1,52 and which is obtained by dosing of barium BaO and zinc ZnO oxides, alternatively also of lead oxide, as is specified e.g. in BRD-patent from 1987 No. 2839645, such a glass according to the said patent contains in % by weight as follows: silicon dioxide Si02 65 to 75, aluminium oxide A1203 0,1 to 2, calcium oxide CaO 2 to 12, magnesium oxide MgO 0 to 8, sodium oxide Na20 7 to 15, potassium oxide K20 0 to 10, lithium oxide Li20 0 to 3, barium oxide BaO 1 to 6, zinc oxide ZnO 0,2 to 3, lead oxide 0 to 10 and titanium dioxide Ti02 0,2 to 5. This invention covers by its chemical composition, with the exception of titanium dioxide Ti02, most of crystal glass types being produced excepting of lead and high-lead crystal glass types with the content of lead oxide 2 24 % by weight.
For the products of luxurious character which are decorated predominatingly by grinding the lead and high- lead crystal glass types are being used where the refractive index of 2 1,545 is required. At the present time the unharmful hygienic properties are being preferred particularly concerning the content of lead and barium in the leach. With regard to a fact that in the production of those special crystal glass types the refractive index of the desired value is being elevated largely by an increased amount of barium BaO and lead oxides, the said hygiene properties that are required induce insolvable problems in the production of such glass types.
Disclosure of the invention
According to this invention the disadvantages
mentioned above are removed or substantially reduced by using the crystal lead-free glass with the content of zirconium dioxide Zr02 which is characterized by the content from 50 to 65 % by weight of silicon dioxide Si02, from 0,1 to 10 % by weight of aluminium oxide A1203, from 0,5 to 17 % by weight of zirconium dioxide Zr02, from 10 to 22 % by weight of potassium K20 and/or sodium Na20 oxide, from 2 to 10 % by weight of calcium CaO and/or magnesium MgO oxide, the total amount of iron Fe expressed as iron trioxide Fe203 (ferric oxide) being ranged from 0,01 to 0,025 % by weight.
The functional and technological properties are with advantage modified by using at least one oxide from the group containing barium BaO, zinc ZnO, boron B203 and lithium Li20 oxides amounted from 0,1 to 10 % by weight of barium BaO, zinc ZnO, boron B203 and lithium Li20 oxides .
This glass type can with advantage contain traces to 1 % by weight of antimony trioxide Sb203, titanium dioxide Ti02 and stannic dioxide Sn02 either separately or in combination as further modifiers.
The advantage of said glass type is the decorative cutting and engraving ability comparable with the lead crystal glass, while having no content of lead oxide which is unhealthy and environmentally harmful. During melting of said glass type there does not occur the volatilization of environmentally harmful lead oxides and arsenic that are used in the manufacture of lead crystal glass. Thus, as the lead-free glass type is preferred which is intended especially for the utility glass, i.e. also for beverage packing glass and domestic glass, it features the advantage of undesirable and unhealthy lead oxide being not penetrated into the leach. The melting and refining of said molten glass types is easier when compared with lead crystal molten glass types as the lead-free glass types feature lower melting temperatures.
Especially, the melting temperature and the
temperature point of liquidus are improved by addition of modifying additives, namely of barium BaO, zinc ZnO, boron B203 and lithium Li20 oxides. Moreover, said oxides positively affect the refractive index of glass. The antimony trioxide Sb203 is used for the refining ability to be improved. Both titanium dioxide Ti02 and stannic oxide SnO including antimony trioxide Sb203 also increase the value of the refractive index.
Examples of carrying out invention
The invention will be further described, by way of the following examples of carrying out. E x a m p l e N o. 1 2 3 4 Glass component content in % by weight
Silicium dioxide Si02 60,68 58,31 61,75 60,77
Aluminium oxide A1203 5,00 0,38 5,00 5,00 Zirconium dioxide Zr02 8,3 14,9 3,5 3,5
Calcium oxide CaO 6,00 5,58 5,40 5,40
Magnesium oxide MgO 0,00 0,40 0,00 0,00
Sodium oxide Na20 12,00 19,87 7,00 8,00
Potassium oxide K20 8,00 0,25 6,00 6,00 Barium oxide B203 0,00 0,00 9,00 0,00
Zinc oxide ZnO 0,00 0,00 0,00 9,00
Lithium oxide Li20 0,00 0,00 0,00 2,00
Antimony trioxide Sb203 0,00 0,29 0,33 0,32 Iron content expressed by amount of iron trioxide 0,015 0,02 0,02 0,01
2,628
«20-300"c- 1 Q6 [°C_1] 9 * 16
grindability [μm.min-1] 0,312 0,343 0,329 0,372
E x a m p l e N o. 5 6 7 Glass components content in % by weight
Silicium dioxide Si02 Aluminium oxide A1203 Zirconium dioxide Zr02 Calcium oxide CaO Sodium oxide Na20 Potassium oxide K20 Lithium oxide Li20 Barium oxide BaO Zinc oxide ZnO Boron oxide B203 Antimony trioxide Sb203 Titanium dioxide Ti02 Stannic dioxide Sn02
Iron content expressed by amount of iron trioxide 0,02 0,01 0,02
The melting temperature that corresponds to the molten glass viscosity of log η = 2 is approximately 1500 °C for the lead glass types. For glass types according to this invention is either comparable with lead glass types or e.g. in accordance with the examples No. 1 and No. 6 or lowered by 30 °C for the molten glass type according to the example No. 7, by 75 "C for the molten glass according to the example No. 5, by 92 °C for the molten glass according to the example No. 4, by 70 °C for the molten glass according to the example No. 3 and by 95 °C for the molten glass according to the example No. 2.
All temperatures of point of liquidus except of the composition No. 2 that is characterized by a high content of zirconium dioxide, are lower than the forming temperatures corresponding to the temperature at a viscosity of molten glass log η = 4 so that with these molten glass types the tendency to undesirable crystallization is restrained.
For the lead crystal the refractive index is approximately 1,545, for the glass types according to this invention it ranges within 1,542 and 1,572. Thus, the optical properties of final products are comparable or better ones when comparing with products made of lead crystal glass which will especially reflect on decorative cut and engraved products.
The mean coefficient of linear thermal expansivity α within range from 20 to 300 °C is in all cases lower than for so far used crystal glass types in general which is favourable for the resistance of glass against the thermal shock.
The grindability for the lead crystal glass is according to the chosen method 0,266 μm.min"1 and for embodiments according to the composition No. 1 to No. 5 it is higher which will favourable affect the velocity of processing of these glass types by means of decorative cutting and engraving.
Industrial applicability
The lead-free crystal glass according to this invention with the content of zirconium dioxide Zr02 is intended for man-made and machine-made utility glassware with a higher refractive index, it is suitable particularly for glass decorated by cutting and engraving and by further decorative techniques for products of the luxurious character. This glass type is hygienic unharmful concerning the content of detrimental substances in the leach and by its brilliance can compete with the products made of lead crystal glass.
The question there is both the production of glass objects used in households and restaurants, e.g. small cups, tumblers, carafes, bowls and vessels of various shapes and sizes used for decorative purposes, such as vases, dishes etc.
Claims
1. Crystal lead-free glass suitable especially for man-made and machine-made utility glass with the refractive index within the range from 1,53 to 1,58, containing silicon dioxide Si02, aluminium oxide A1203, zirconium dioxide Zr02, calcium CaO and/or magnesium MgO oxide, potassium K20 and or sodium Na20 oxide, characterized by its composition, with the content of 50 to 65 % by weight of silicon dioxide Si02, 0.1 to 10 % by weight of aluminium oxide A1203, 0,5 to 17 % by weight of zirconium dioxide Zr02, 10 to 22 % by weight of potassium K20 and/or sodium Na20 oxide, 2 to 10 % by weight of calcium CaO and/or magnesium MgO oxide, the content of ferric oxide Fe203 being within the range from 0,01 to 0,025 % by weight.
2. Crystal lead-free glass according to claim 1, characterized by its composition, with the range from 0,1 to 10 % by weight of barium oxide BaO, zinc oxide ZnO, boron trioxide B203 and lithium oxide Li20.
3. Crystal lead-free glass according to claims 1 and 2, characterized by its composition, with the content, individually or in a combination, of the traces to 1% by weight of antimony trioxide Sb203, titanium dioxide Ti02 and stannic dioxide Sn02.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CS911344A CZ278892B6 (en) | 1991-05-08 | 1991-05-08 | Lead-free crystal glass |
| CS1344-91 | 1991-05-08 | ||
| EP91121730A EP0547263B1 (en) | 1991-05-08 | 1991-12-18 | Lead-free zinc silicate crystal glass and its use |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| WO1992019559A1 true WO1992019559A1 (en) | 1992-11-12 |
Family
ID=40292547
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| PCT/CS1992/000012 WO1992019559A1 (en) | 1991-05-08 | 1992-05-06 | Lead-free crystal glass |
Country Status (9)
| Country | Link |
|---|---|
| EP (1) | EP0547263B1 (en) |
| AT (1) | ATE127435T1 (en) |
| CZ (1) | CZ278892B6 (en) |
| DE (1) | DE59106436D1 (en) |
| DK (1) | DK0547263T3 (en) |
| ES (1) | ES2078419T3 (en) |
| GR (1) | GR3017684T3 (en) |
| SK (1) | SK277737B6 (en) |
| WO (1) | WO1992019559A1 (en) |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0564802A2 (en) * | 1992-04-10 | 1993-10-13 | Schott Glaswerke | Lead- and barium-free crystal glass with high light transmission |
| EP0594422A1 (en) * | 1992-10-20 | 1994-04-27 | Toyo Glass Company Limited | Glass composition |
| EP0616984A1 (en) * | 1993-03-25 | 1994-09-28 | Schott Glaswerke | Lead-free crystal glass with a high light transmission |
| WO1995013993A1 (en) * | 1993-11-03 | 1995-05-26 | Vysoká S^¿Kola Chemicko - Technologická | Lead-free crystal glass with the refractive index higher than 1,52 |
| FR2756821A1 (en) * | 1996-12-06 | 1998-06-12 | Schott Glaswerke | LEAD FREE CROWNS |
| US6391810B1 (en) * | 1999-08-04 | 2002-05-21 | F. X. Nachtmann Bleikristallwerke Gmbh | Lead- and barium-free crystal glass |
| WO2004063108A1 (en) * | 2003-01-14 | 2004-07-29 | Companhia Brasileira De Metalurgia E Mineração | Glass compositions for the production of lead-free crystals |
| FR2921357A1 (en) * | 2007-09-21 | 2009-03-27 | Saint Gobain | SILICO-SODO-CALCIUM GLASS COMPOSITION |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| SK285523B6 (en) * | 2004-10-19 | 2007-03-01 | Rona, A. S. | Crystal glass free from lead, barium, niobium and their compounds and a method of its preparation |
| CN1982244B (en) * | 2005-12-16 | 2010-10-27 | 王瑛 | Health-care fluorescent-lamp tube glass against osteoporosis |
| CZ2011176A3 (en) * | 2011-03-30 | 2012-04-11 | Vysoká škola chemicko-technologická v Praze | Lead- and barium-free crystal glass containing lanthanum and niobium oxides |
| GB201108052D0 (en) | 2011-05-13 | 2011-06-29 | Nazeing Glass Works Ltd | Non-toxic crystal glass |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| SU330119A1 (en) * | 1970-07-03 | 1972-04-07 | Tare glass | |
| US4065317A (en) * | 1971-10-28 | 1977-12-27 | Nippon Electric Glass Company, Ltd. | Novel glass compositions |
| EP0405579A1 (en) * | 1989-06-30 | 1991-01-02 | Kirin Beer Kabushiki Kaisha | Glass bottles and glass compositions therefor |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4012131A (en) * | 1975-08-20 | 1977-03-15 | American Optical Corporation | High strength ophthalmic lens |
| GB2115403B (en) * | 1982-02-20 | 1985-11-27 | Zeiss Stiftung | Optical and opthalmic glass |
| FR2558152B1 (en) * | 1984-01-13 | 1992-03-27 | Corning Glass Works | LOW DENSITY OPHTHALMIC LENSES, ABSORBING ULTRAVIOLET RADIATION AND HAVING HIGH TRANSMISSION INTO THE VISIBLE AND CORRECTIVE LENSES MADE OF SUCH LENSES |
-
1991
- 1991-05-08 SK SK1344-91A patent/SK277737B6/en unknown
- 1991-05-08 CZ CS911344A patent/CZ278892B6/en unknown
- 1991-12-18 ES ES91121730T patent/ES2078419T3/en not_active Expired - Lifetime
- 1991-12-18 DK DK91121730.5T patent/DK0547263T3/en active
- 1991-12-18 EP EP91121730A patent/EP0547263B1/en not_active Expired - Lifetime
- 1991-12-18 DE DE59106436T patent/DE59106436D1/en not_active Expired - Fee Related
- 1991-12-18 AT AT91121730T patent/ATE127435T1/en not_active IP Right Cessation
-
1992
- 1992-05-06 WO PCT/CS1992/000012 patent/WO1992019559A1/en active Application Filing
-
1995
- 1995-10-10 GR GR950402789T patent/GR3017684T3/en unknown
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| SU330119A1 (en) * | 1970-07-03 | 1972-04-07 | Tare glass | |
| US4065317A (en) * | 1971-10-28 | 1977-12-27 | Nippon Electric Glass Company, Ltd. | Novel glass compositions |
| EP0405579A1 (en) * | 1989-06-30 | 1991-01-02 | Kirin Beer Kabushiki Kaisha | Glass bottles and glass compositions therefor |
Non-Patent Citations (4)
| Title |
|---|
| CHEMICAL ABSTRACTS, vol. 106, no. 18, 4 May 1987, Columbus, Ohio, US; abstract no. 142815A, page 287 ; * |
| CHEMICAL ABSTRACTS, vol. 109, no. 16, 9 October 1988, Columbus, Ohio, US; abstract no. 133790Y, page 292 ; * |
| CHEMICAL ABSTRACTS, vol. 85, no. 8, 23 August 1976, Columbus, Ohio, US; abstract no. 50963S, page 282 ; * |
| WORLD PATENTS INDEX Week 7242, Derwent Publications Ltd., London, GB; AN 72-67211T & SU,A,330 119 (VLADIMIR POLYTECHNIC) 24 February 1972 * |
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0564802A2 (en) * | 1992-04-10 | 1993-10-13 | Schott Glaswerke | Lead- and barium-free crystal glass with high light transmission |
| EP0564802A3 (en) * | 1992-04-10 | 1994-12-21 | Schott Glaswerke | Lead- and barium-free crystal glass with high light transmission |
| US5434111A (en) * | 1992-04-10 | 1995-07-18 | Schott Glaswerke | Lead- and barium-free crystal glass having high optical transmission |
| EP0594422A1 (en) * | 1992-10-20 | 1994-04-27 | Toyo Glass Company Limited | Glass composition |
| EP0616984A1 (en) * | 1993-03-25 | 1994-09-28 | Schott Glaswerke | Lead-free crystal glass with a high light transmission |
| WO1995013993A1 (en) * | 1993-11-03 | 1995-05-26 | Vysoká S^¿Kola Chemicko - Technologická | Lead-free crystal glass with the refractive index higher than 1,52 |
| FR2756821A1 (en) * | 1996-12-06 | 1998-06-12 | Schott Glaswerke | LEAD FREE CROWNS |
| US6391810B1 (en) * | 1999-08-04 | 2002-05-21 | F. X. Nachtmann Bleikristallwerke Gmbh | Lead- and barium-free crystal glass |
| WO2004063108A1 (en) * | 2003-01-14 | 2004-07-29 | Companhia Brasileira De Metalurgia E Mineração | Glass compositions for the production of lead-free crystals |
| FR2921357A1 (en) * | 2007-09-21 | 2009-03-27 | Saint Gobain | SILICO-SODO-CALCIUM GLASS COMPOSITION |
| WO2009047463A1 (en) * | 2007-09-21 | 2009-04-16 | Saint-Gobain Glass France | Silico-sodo-calcic glass sheet |
| US8937028B2 (en) | 2007-09-21 | 2015-01-20 | Saint-Gobain Glass France | Silico—sodo—calcic glass sheet |
Also Published As
| Publication number | Publication date |
|---|---|
| CZ278892B6 (en) | 1994-08-17 |
| EP0547263B1 (en) | 1995-09-06 |
| ES2078419T3 (en) | 1995-12-16 |
| ATE127435T1 (en) | 1995-09-15 |
| DK0547263T3 (en) | 1996-01-22 |
| DE59106436D1 (en) | 1995-10-12 |
| SK134491A3 (en) | 1994-03-09 |
| SK277737B6 (en) | 1994-10-12 |
| CZ134491A3 (en) | 1994-06-15 |
| EP0547263A1 (en) | 1993-06-23 |
| GR3017684T3 (en) | 1996-01-31 |
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