CN106673424A - A crystal glass product free of lead and barium - Google Patents
A crystal glass product free of lead and barium Download PDFInfo
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- CN106673424A CN106673424A CN201610304907.6A CN201610304907A CN106673424A CN 106673424 A CN106673424 A CN 106673424A CN 201610304907 A CN201610304907 A CN 201610304907A CN 106673424 A CN106673424 A CN 106673424A
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- oxide
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- barium
- crystal glass
- potassium
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- 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
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- 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)
- Glass Compositions (AREA)
Abstract
A crystal glass product free of lead and barium is provided. The product comprises main components such as silica (SiO2), titanium dioxide (TiO2), alumina (Al2O3), sodium oxide (Na2O), potassium oxide (K2O), zinc oxide (ZnO), calcium oxide (CaO), magnesium oxide (MgO) and strontium oxide (SrO). Energy for melting glass is reduced by adding following hydroxides to replace the above mentioned main oxides: (1) sodium oxide (Na2O) obtained by adding sodium hydroxide (NaOH) in place of sodium carbonate (Na2CO3), (2) potassium oxide (K2O) obtained by adding potassium hydroxide (KOH) instead of potassium carbonate (K2CO3) and (3) calcium oxide obtained by adding calcium hydroxide (Ca(OH)2) instead of calcium carbonate (CaCO3).
Description
Technical field
The present invention relates to not leaded and barium crystal glass product.
Background technology
Generally according to the performance classification of glass, it is also applied to crystal glass to the type of glass, however,
Have determined that key property such as lead oxide (PbO), Barium monoxide (BaO), potassium oxide (K2O)
It is not less than by weight 10% with the amount of the combination of Zinc Oxide (ZnO), glass density is not less than 2.45
g/cm3And reflectance is not less than 1.52.
At present, crystal glass has become more popular and for various products, such as water tumbler, wineglass,
In the cutting of tableware or ornaments.Crystal glass generally has lead oxide (PbO) and Barium monoxide (BaO)
Used as composition, it helps glass to have excellent optical property, radiance, gloss, strikes with loud
Hit sound and there is high density, but the lead oxide (PbO) containing about 24-30% by weight.Need
It should be noted that lead has relatively high toxicity together with barium (it is also the composition in crystal glass).
Persisting exploitation and crystal glass is improved for many years, has concentrated on by the way that there is similar performance with other
Composition replaces reducing the amount of lead and barium.
According to US 5434111 and EP 0564802 A1 of nineteen ninety-five, the Schott AG of Germany are
Develop not leaded and barium crystal glass.Their main component is consisted of：By weight
Silicon dioxide (the SiO of 50-75%2), the titanium dioxide by weight less than 8%, each by weight
Zirconium oxide (ZrO less than 5%2) and aluminium oxide (Al2O3), by weight less than 10% oxidation
Boron (B2O3), by weight less than 5% lithium oxide (Li2O), the oxidation of 2-15% by weight
Sodium (Na2O), potassium oxide (K of 5-15% by weight2O), the calcium oxide of 2-12% by weight
(CaO) magnesium oxide (MgO), by weight less than 5%, the strontium oxide by weight less than 7%
(SrO) Zinc Oxide (ZnO), by weight less than 7%, the oxidation by weight less than 1.2%
Stannum (stanic oxide) (stannum oxide (tin oxide)) (SnO2), each by weight less than 5%
Niobium oxide (Nb2O5) and tantalum oxide (Ta2O5).In 2011, Schott AG were obtained in addition
The B2 patents of US 20110098172A1 and US 8629072.The main component of these patents is by weight
Silicon dioxide (the SiO of gauge 65-72%2), the aluminium oxide (Al of 11-17% by weight2O3), press
Sodium oxide (Na of the weight meter less than 8%2O), the potassium oxide, by weight by weight less than 2%
The calcium oxide (CaO) of 4-12%, the by weight magnesium oxide of 3-8% (MgO) and little by weight
In 10% Zinc Oxide (ZnO).Subsequently in 2014, the said firm have also obtained US 20140005027
A1 patents, with main component for example by weight the silicon dioxide of 65-75% (SiO2), by weight
Aluminium oxide (the Al of gauge 11-18%2O3), calcium oxide (CaO) each by weight less than 5-10%
With magnesium oxide (MgO).
Toyo Glass Co., Ltd.s originally developed their unleaded crystal glass, root in 1899
According to US 5897678, with main component, such as silicon dioxide (SiO of 50-60% by weight2)、
Titanium dioxide (the TiO of 3-10% by weight2), by weight less than 2% zirconium oxide (ZrO2)、
Boron oxide (B by weight less than 10%2O3), and each alkali by weight less than 10-20%
Metal-oxide (R2) and alkaline earth oxide (RO) and the Zinc Oxide of 5-15% by weight O.
In 2009, Toyo Sasaki Glass Co., Ltd.s obtained the A1 patents of US 20090286058, tool
There is the silicon dioxide (SiO of main component such as 62-65% by weight2), 2.2-3% by weight
Titanium dioxide (TiO2), the aluminium oxide (Al of 2-3.2% by weight2O3), 10-12% by weight
Sodium oxide (Na2O), potassium oxide (K of 8-10% by weight2O), 3-4.2% by weight
Calcium oxide (CaO), the by weight strontium oxide of 2-3.2% (SrO) and the by weight oxygen of 6-7.2%
Change zinc (ZnO).Subsequently in 2011, the said firm obtains the A1 patents of US 20110052907,
Silicon dioxide (SiO with main component such as 65-70% by weight2), 0.5-2% by weight
Titanium dioxide (TiO2), the aluminium oxide (Al of 1-3% by weight2O3), respective 8-10% by weight
Sodium oxide (Na2) and potassium oxide (K O2O), by weight the calcium oxide of 3-4.2% (CaO),
By weight the magnesium oxide of 2-3% (MgO), by weight the strontium oxide of 3.2-4.2% (SrO) and
The Zinc Oxide of 0.5-2% (ZnO) by weight.
F.X.Nachtmann Bleikristallwerker GmbH, Germany were developed not in 2002
The crystal glass of leaded and barium, according to the A1 of DE 10258923, with main component for example by weight
Silicon dioxide (the SiO of 55-68%2), the titanium dioxide (TiO of 8.5-14.0% by weight2), press
Sodium oxide (the Na of weight meter 5-12%2O), potassium oxide (K of 9-15% by weight2O), by weight
Strontium oxide (SrO), the by weight Zinc Oxide of 3-10% (ZnO) of the gauge less than 5%, Yi Jizhuan
The B1 of the sharp US 6391810 and A1 of DE 19936699, with main component such as 59-71% by weight
Silicon dioxide (SiO2), by weight less than 8% titanium dioxide (TiO2), it is little by weight
In 4% aluminium oxide (Al2O3), by weight less than 3% boron oxide (B2O3), by weight
Lithium oxide (Li less than 2%2O), sodium oxide (Na of 3-15.5% by weight2O), by weight
Potassium oxide (the K of meter 0.08-11%2O), by weight less than 0.1% strontium oxide (SrO), by weight
Zinc Oxide (ZnO) of the gauge less than 11% and the stannum oxide (stannum oxide) by weight less than 3%
(SnO2)。
Austrian D.Swarovski Co. develop not leaded and barium crystal glass, according to 2007
The A1 of United States Patent (USP) 20070032367 and the B2 of US 7202188 in year, with main component for example by weight
Silicon dioxide (the SiO of gauge 50-60%2), by weight less than 5% aluminium oxide (Al2O3), press
Boron oxide (B of the weight meter less than 4%2O3), the sodium oxide (Na of 12-15% by weight2O), press
Potassium oxide (K of the weight meter less than 3%2O), by weight the calcium oxide of 4-11% (CaO), by weight
Gauge is less than 2% magnesium oxide (MgO) and the by weight Zinc Oxide of 8-16% (ZnO).
Miroslav Rada et al., Czech Republic develop not leaded and barium crystal glass,
It is as follows with main component according to the A1 of United States Patent (USP) 20130252797 of 2010：By weight
Silicon dioxide (the SiO of 55-70%2), the titanium dioxide (TiO of respective 0.1-3.5% by weight2)、
Aluminium oxide (Al2O3) and boron oxide (B2O3), the ZrO less than 3.5% by weight2, by weight
Lithium oxide (the Li of meter 0.05-3.5%2O), sodium oxide (Na of 2-15% by weight2O), by weight
Potassium oxide (the K of gauge 3-5% and 15-19%2O), by weight the calcium oxide of 5-10% (CaO),
The Zinc Oxide (ZnO) of 1-4% by weight and 7-8%, the by weight phosphorus pentoxide of 0.05-1%
(P2O5) and 0.05-1% by weight Gadolinia. (Gd2O3)。
Crystal glass generally needs excellent optical property, but they should be containing the ferrum of low stain amount
Oxide (iron oxide), because the iron oxides of higher amount can cause glass to be changed into green and recognized
For unlimpid.Similarly, according to the raw material as composition for selecting, the crystal glass of not leaded and barium
Glass should contain the iron oxides less than 300ppm.Therefore, the production of crystal glass generally needs to add
Plus decolorising agent, the blue cobalt oxide (CoO) of the generation of such as about 0.1-6ppm or with 0.1-400ppm
Addition produces Dineodymium trioxide (Nd azury2O3) and produce ruddy Erbia (Er2O3),
To offset the pale bluish green occurred by the iron oxides pollution in the raw material as composition.
Clarifier or oxidant, such as arsenic trioxide (As should be used to be less than by weight 1%2O3)
Or antimony oxide (the Sb less than by weight 1.5%2O3).However, because there is relatively low poison
Property, the use of antimony oxide is preferred.Further, it is necessary to the amount for using is adjusted, because being excessively used
Arsenic oxide arsenoxide and antimony oxide cause glass to be changed into yellow.Therefore, it is possible to use a small amount of material with
Foam is excluded in melting process or stannum oxide (SnO can be used2) or sulphate cpd is as an alternative.
Most crystal glass factory still uses at present lead and barium as conventional composition.However, due to
Factory and the lasting research of other institutes from the crystal glass for developing not leaded and barium, substantially
Increased the trend of production improvement.In addition, also improved environment and safety criterion in this area.
As it is known in the art, all types of glass contain certain amount of pollution iron oxides, its
It is included in two forms in glass structure, i.e. ferrous oxide (FeO), with 2+The ferrum of ion and
Iron sesquioxide (Fe2O3), with 3+The ferrum of ion.The ferrum can be detected by spectrophotometer
The optical property of oxide compound.It was found that iron sesquioxide is located at the end of ultraviolet (UV) wavelength
Up to visible (VIS) wavelength.It was found that ferrous oxide is located at the end up to infrared (IR) of visible wavelength
Wavelength.Therefore, in order to the principle for passing through light absorbs reduces the energy for melten glass, need to reduce
The amount of heat absorption during the amount of ferrous oxide is to reduce infrared wavelength in glass.Then the melting heat energy of glass
Enough it is transmitted into bottom and is better dispersed in whole waterglass in melting process.Therefore, the principle
It is important for developing glass and reducing fusing energy by adjusting the factor for affecting ferrous oxide amount.
The content of the invention
The crystal glass of of the invention not leaded and barium includes main component, such as silicon dioxide
(SiO2), titanium dioxide (TiO2), aluminium oxide (Al2O3), sodium oxide (Na2O), potassium oxide
(K2O), Zinc Oxide (ZnO), calcium oxide (CaO), magnesium oxide (MgO) and strontium oxide (SrO)
Deng, the main oxides of the above are replaced by following addition hydroxide (OH-), reduce melting glass
The energy of glass：1. by replacement sodium carbonate (Na2CO3) add the oxygen that sodium hydroxide (NaOH) is obtained
Change sodium (Na2O) 2. by replacement potassium carbonate (K2CO3) addition potassium hydroxide (KOH) acquisition
Potassium oxide (K2) and 3. by replacement Calcium Carbonate (CaCO O3) addition calcium hydroxide (Ca (OH)2)
The calcium oxide of acquisition.
For produce drinking glass or tableware not leaded and barium crystal glass by primary raw materialss, example
Such as quartz sand, dolomite, limestone, titanium dioxide, strontium carbonate and secondary feedstock, for example, clarify
Agent and decolorising agent etc. are constituted, its optimal melting temperature before processing and forming is drinking glass or tableware
Degree is of about 1500 DEG C
Known glass industry needs higher fuel consumption so that above-mentioned raw material is melted as glass.Cause
This has been developed for the present invention to reduce melting the energy that not leaded and barium crystal glass is used, and because
This reduces fuel (such as natural gas or fuel oil) consumption, and it will be completed in future.
Description of the drawings
Fig. 1 is shown by using of the invention not leaded and the crystal glass of barium main component life
Produce the addition hydroxide (OH-) of the invention with melting of the temperature of melting original material in glass
Comparison chart (relatively low melting temperature uses relatively low energy) between the temperature of raw material, wherein
A is the basic main component of the crystal glass product of the not leaded and barium of the present invention；B is using by weight
Silicon dioxide (the SiO of the amount of gauge 58-72%2), the potassium oxide (K of the amount of 10-15% by weight2O)
The crystal glass of the not leaded and barium of the invention of the Zinc Oxide (ZnO) of the amount of 2-5% by weight
The basic main component of product.
Fig. 2 is shown from using of the invention not leaded and the crystal glass of barium main component
Glass production bubble amount with melting it is of the invention addition hydroxide (OH-) former material
Comparison chart (bubble is more few better) between the bubbles volume of material, wherein A is the not leaded of the present invention
With the basic main component of the crystal glass product of barium；B is using the amount of 58-72% by weight
Silicon dioxide (SiO2), the potassium oxide (K of the amount of 10-15% by weight2) and 2-5% by weight O
Amount Zinc Oxide (ZnO) not leaded and barium of the invention crystal glass product it is substantially main
Composition.
Fig. 3 is shown from using of the invention not leaded and the crystal glass of barium main component
Glass production glass in pollute iron oxide compounds such as ferrous oxide (FeO) and three oxygen
Change two ferrum (Fe2O3) amount with melting it is of the invention addition hydroxide (OH-) raw material
Comparison chart (the amount of the iron oxide compounds of reduction between the amount of the iron oxide compounds of pollution
Heat absorption can be reduced), wherein A is leading substantially for the crystal glass product of the not leaded and barium of the present invention
Want composition；B is the silicon dioxide (SiO using the amount of 58-72% by weight2), by weight
Potassium oxide (the K of the amount of 10-15%2O) and the by weight sheet of the Zinc Oxide (ZnO) of the amount of 2-5%
The basic main component of the crystal glass product of the not leaded and barium of invention.
Specific embodiment
The basic main component of the crystal glass of not leaded and barium includes following component：
The main component of the crystal glass of above not leaded and barium can be by following addition hydroxide
Thing (OH-) replaces the main oxides of the above reducing the energy for glass melting：
- by replacement sodium carbonate (Na2CO3) the addition sodium hydroxide of 0.1-100% (NaOH) by weight
Sodium oxide (the Na of the 5-16% by weight for obtaining2O)。
- by replacement potassium carbonate (K2CO3) the addition potassium hydroxide of 0.1-100% (KOH) by weight
Potassium oxide (the K of the 0.01-15% by weight for obtaining2O)。
- by replacement Calcium Carbonate (CaCO3) the addition calcium hydroxide of 0.1-100% (Ca (OH) by weight2)
The calcium oxide of 2-10% by weight (CaO) for obtaining.
Above-mentioned main component can use the appropriate silicon dioxide (SiO of 58-72% by weight2)、
Appropriate potassium oxide (the K of 10-15% by weight2O) and 2-5% by weight appropriate oxidation
Zinc (ZnO), can replace main oxides appropriate above to drop by following addition hydroxide
The energy of low glass melting：
- by replacement sodium carbonate (Na2CO3) the addition sodium hydroxide of 0.1-100% (NaOH) by weight
Sodium oxide (the Na of the 5-16% by weight for obtaining2O)。
- by replacement potassium carbonate (K2CO3) the addition potassium hydroxide of 0.1-100% (KOH) by weight
Potassium oxide (the K of the 10-15% by weight for obtaining2O)。
- by adding the calcium hydroxide of 0.1-100% (Ca (OH) by weight2) replace Calcium Carbonate (CaCO3)
The calcium oxide of 2-10% by weight (CaO) for obtaining.
Implement the preference pattern of the present invention
The crystal glass of not leaded and barium referred in the complete disclosure of the present invention it is basic mainly into
It is mitogenetic to produce the crystal glass having according to the qualification of EC indexs, i.e., by following every kind of or constitute：
Zinc Oxide (ZnO), Barium monoxide (BaO) more than or equal to by weight 10%, lead oxide (PbO)
And/or potassium oxide (K2O), equal to or less than 2.45g/cm3Glass density and not less than 1.52
Refractive index.Refer in the complete disclosure of the invention that the following is the favourable outcome for producing crystal glass
In the range of every kind of composition fixed value：
The crystal glass of composition above and value not leaded and barium of the production with following technical specification：
| Density | Refractive index | Fusing point |
| 2.556 | 1.5218 | 1480℃ |
On the other hand, if the scope of value that do not refer in the complete disclosure of the present invention of basic main component
Interior, the crystal glass of production will not have the qualification according to EC indexs and result in the need for more energy
For melten glass.The following is the example of the composition of scope using different values：
Composition above and value provide the crystal glass of the not leaded and barium with following technical specification：
| Density | Refractive index | Fusing point |
| 2.428 | 1.5072 | 1701℃ |
Claims (6)
1. the crystal glass product of not leaded and barium, wherein, the product includes following main component：
2. the crystal glass product of not leaded and barium according to claim 1, the product has
Following component：Silicon dioxide (the SiO of 58-72% by weight2), 10-15% by weight
Potassium oxide (K2O) and the by weight Zinc Oxide of 2-5% (ZnO).
3. the crystal glass product of not leaded and barium according to claim 1 and 2, comprising hydrogen-oxygen
Compound (OH), for reducing the energy for melten glass, wherein, by replacing carbonic acid
Sodium (Na2CO3) addition the sodium hydroxide of 0.1-100% (NaOH) by weight pressed
Sodium oxide (the Na of weight meter 5-16%2O)。
4. the crystal glass product of not leaded and barium according to claim 1, comprising hydroxide
(OH), for reducing the energy for melten glass, wherein, by replacing potassium carbonate
(K2CO3) the addition potassium hydroxide of 0.1-100% (KOH) acquisition by weight is by weight
Potassium oxide (the K of meter 0.01-15%2O)。
5. the crystal glass product of not leaded and barium according to claim 2, comprising hydroxide
(OH), for reducing the energy for melten glass, wherein, by replacing potassium carbonate
(K2CO3) the addition potassium hydroxide of 0.1-100% (KOH) acquisition by weight is by weight
Potassium oxide (the K of meter 10-15%2O)。
6. the crystal glass product of not leaded and barium according to claim 1 and 2, comprising hydrogen-oxygen
Compound (OH), for reducing the energy for melten glass, wherein, by replacing carbonic acid
Calcium (CaCO3) the addition calcium hydroxide of 0.1-100% (Ca (OH) by weight2) pressed
The calcium oxide (CaO) of weight meter 2-10%.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| TH1503001911U TH14204A3 (en) | 2015-11-10 | Lead-free and barium-free crystal glass products | |
| TH1503001911 | 2015-11-10 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN106673424A true CN106673424A (en) | 2017-05-17 |
Family
ID=58839832
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610304907.6A Pending CN106673424A (en) | 2015-11-10 | 2016-05-10 | A crystal glass product free of lead and barium |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106673424A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112592053A (en) * | 2020-12-28 | 2021-04-02 | 四川中科玻璃有限公司 | Novel environment-friendly glass suitable for glass bottle and can production and preparation process thereof |
-
2016
- 2016-05-10 CN CN201610304907.6A patent/CN106673424A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112592053A (en) * | 2020-12-28 | 2021-04-02 | 四川中科玻璃有限公司 | Novel environment-friendly glass suitable for glass bottle and can production and preparation process thereof |
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Application publication date: 20170517 |