CN106477877B - Extra-high refraction high density environment-friendly type cameo glass of one kind and preparation method thereof - Google Patents
Extra-high refraction high density environment-friendly type cameo glass of one kind and preparation method thereof Download PDFInfo
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- CN106477877B CN106477877B CN201610901666.3A CN201610901666A CN106477877B CN 106477877 B CN106477877 B CN 106477877B CN 201610901666 A CN201610901666 A CN 201610901666A CN 106477877 B CN106477877 B CN 106477877B
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- glass
- cameo
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- high density
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Classifications
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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
- C03C3/062—Glass compositions containing silica with less than 40% silica by weight
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
- C03B25/00—Annealing glass products
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
- C03B5/00—Melting in furnaces; Furnaces so far as specially adapted for glass manufacture
- C03B5/16—Special features of the melting process; Auxiliary means specially adapted for glass-melting furnaces
-
- 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
Abstract
The present invention relates to a kind of extra-high refraction high density environmental protection cameo glasses, belong to cameo glass field of material technology, including each component as follows by weight percentage: SiO21-3%, TiO240-55%, La2O340-50%, ZrO28-16%, Y2O30-10%, alkali metal oxide 0-5% control glass melting temperature and melting time appropriate, and cameo glass is prepared using secondary, which has excellent optical property, and refractive index is up to 2.0-2.3, visible light permeability reaches 75-82%, and density reaches 4.5-4.7g/cm3.The cameo glass has preferable thermal stability, excellent chemical stability and mechanical performance, and is suitable for block pressing forming process, and without harmful substances such as lead and arsenic, there is no harmful substances to dissolve out problem, safety and environmental protection for product.
Description
Technical field
The invention belongs to cameo glass field of material technology, it is related to a kind of cameo glass and preparation method thereof, especially one
Extra-high refraction high density environment-friendly type cameo glass of kind and preparation method thereof.
Background technique
Why rare natural gemstone is is not only in that rare characteristic, is more to present after its processed polishing bright-coloured
Color and unique quality, shown that its is magnificent and noble.However natural gemstone is rare after all, at high price, common people are difficult
To bear.The continuous development of industrial materials and production technology and processing technology therewith has had a large amount of imitative diamond materials to go out
Existing, some even are enough to mix the spurious with the genuine, while can also allow ordinary people that can buy the dress to match in excellence or beauty with true jewel with lower price
Ornaments.
It is more that cameo glass type is imitated currently on the market, such as lead crystal glass, milkiness and half emulsion opal glass, but leaded crystalline substance
Matter glass will appear dissolution problem due to there is higher lead tolerance in use, affect human health, in addition, lead
Crystal glass in melting process be volatized into atmosphere after caused various diseases in human body suction body.Milkiness and half milkiness
Glass and cameo glass difference are big, opaque, and the effect of cameo glass is not achieved.It is inadequate that cameo glass quality is imitated currently on the market
Height, it is irregular, though have preferable sample, such as optical glass, be mostly using high lead or rare earth as main component, environmental problem and
Cost price is very big.
Patent CN101381202A discloses a kind of stibium-containing ruby glass formula and preparation method, though environment-friendly type,
Its with 2.0 or more refractive index and dispersion compared with jewel compared with poor quality away from larger.
Patent CN1569706A introduces a kind of optical glass of high refraction, and refractive index is also very high, contains higher TiO2With
BaO, but the BaO of high-content is equally harmful to human body, and refractive index is difficult to reach value of the invention.
Summary of the invention
It is an object of the invention to against the above technical problems, provide a kind of extra-high refraction high density environment-friendly type jewel glass
Glass, the cameo glass Environmental Safety, excellent in optical properties, and there is preferable thermal stability, excellent chemical temperatures and machine
Tool performance, is suitable for block pressing forming process.
Technological means adopted by the present invention is:
A kind of extra-high refraction high density environment-friendly type cameo glass, including each component as follows by weight percentage: SiO2
1-3%, TiO240-55%, La2O340-50%, ZrO28-16%, Y2O30-10%, alkali metal oxide 0-5%.
The TiO2Weight and SiO2、TiO2、La2O3、ZrO2And Y2O3The ratio between total weight be greater than 0.4.
The TiO2Weight and SiO2、TiO2、La2O3、ZrO2And Y2O3The ratio between total weight >=0.5.
The alkali metal oxide is Li2O、Na2O、K2One of O, two or three, the weight of alkali metal oxide
Amount percentage is 0-3%.
Preferably, the SiO2Weight percent is 2-3%.
Preferably, the ZrO2Weight percent be 14-16%.
Preferably, the La2O3Weight percent be 47-50%.
The preparation method of the cameo glass, steps are as follows:
(1) precise analyzes pure grade each component and mixes 4-6h using wet ball grinding technique；
(2) mixed material is kept the temperature into 2-3.5h in 100-150 DEG C of high temperature oven with vaporized alcohol is clean then dry-mixed
1-2h；
(3) material after will be dry-mixed is placed in platinum crucible, then platinum crucible is put into and is connected with N2And H2Protective gas
8-12h is melted in high temperature furnace, control glass melting temperature is 1400-1500 DEG C, later, the glass metal after being melted is poured into 5-15 DEG C
Water quenching is carried out in distilled water to form glass particle, dries ball milling 1-2h again；
(4) glass for drying milled is placed in corundum crucible, the atmosphere that corundum crucible is placed in 1350-1450 DEG C is protected
Secondary melted 4-7h in furnace retaining, and stir evenly, molding die is poured into after furnace temperature is down to 1250-1350 DEG C of heat preservation 0.5-1.5h
Molding, moves in annealing furnace, and control annealing temperature is 600-700 DEG C, and it is cold to close furnace after to be annealed by annealing time 12-24h
But to room temperature up to cameo glass.
Preferably, annealing temperature described in step (4) is 600 DEG C.
Preferably, annealing time described in step (4) is 12h.
The invention has the advantages that by feed change and raw material proportioning, control glass melting temperature appropriate and it is melted when
Between, and cameo glass is prepared using secondary, it ensure that the melting quality of glass, before guaranteeing cameo glass high transmittance
It puts, greatly improves its refractive index, density, refractive index reaches 2.0-2.3, it is seen that photopermeability reaches 75-82%, density 4.5-
4.7g/cm3, and chemical stability is good, is readily formed, processes, meanwhile, lead oxide and oxygen are free of in the component of the cameo glass
Change the harmful substances such as arsenic and fluorine, barium, there is no harmful substances to dissolve out problem for product, safety and environmental protection in production process and when using.
Specific embodiment
Below with reference to the specific example method and step that the present invention will be described in detail:
The present invention relates to a kind of extra-high refraction high density environment-friendly type cameo glass, including by weight percentage each as follows
Component: SiO21-3%, TiO240-55%, La2O340-50%, ZrO28-16%, Y2O30-10%, alkali metal oxide
0-5%.
Wherein, TiO2And La2O3And ZrO2To guarantee the refractive index and density of cameo glass, by oxide mass percentage
Than meter: TiO240-50%, La2O340-50%, ZrO28-16%, and the sum of content of three is 90-96%, preferably 92-
96%, 0-10%Y2O3For controlling the tendency towards devitrification of glass, the alkali metal oxide of 0-5% is conducive to the forming of glass structure,
Reduce the devitrification of glass.
TiO2Weight and SiO2、TiO2、La2O3、ZrO2And Y2O3The ratio between total weight be greater than 0.4.
TiO2Weight and SiO2、TiO2、La2O3、ZrO2And Y2O3The ratio between total weight be preferably greater than 0.4, more preferably
≥0.5。
Alkali metal oxide is Li2O、Na2O、K2One of O, two or three, the weight percent of alkali metal oxide
Than being preferably 0-3%.
In said components, SiO2It is important network former, is not advised with the structural component formation of oxygen-octahedron
Contiguous network then becomes the skeleton of glass.It can not only form glass, and can improve the mechanical strength of glass, chemistry
Stability, thermal stability etc., but it is more infusibilized substance again, therefore SiO2Content has its optimum value.Phase of the present invention
There are more special place, SiO to general glass2It is not main glass network former in the glass kind, second is that improving glass
The oxide of glass structure, content are suitable, preferably 2-3% in the range of 1-3%.
TiO2Have the function of increasing glass refraction, while the dispersion of glass can also be increased, replaces in the present invention
Main oxides for PbO and essential.TiO2Content less than 40% when, the refractive index of glass does not reach requirement；If super
Cross 50%, can make glass coloration and devitrification of glass be inclined to become larger it is uncontrollable, since strong absorb to ultraviolet light makes glass yellow
Tendency enhancing, while TiO2The Fe in glass can be made to colour enhancing again, this is to the crystal glass for focusing on transparency and pure color
It is unfavorable.The present invention effectively solves the problems, such as glass coloration, and TiO using high purity titanium2Appropriate level in 40-55% range
It is interior, preferred scope 45-50%, more preferably 48-50%.
La2O3It is to have the rare earth oxide well helped to raising glass refraction and density, other opposite rare earth oxides
Its reasonable price, is easy to get, most important to effect of the invention without fluorescence, the La of low content2O3Height is not achieved
Refraction and highdensity effect, high-content it is unfavorable to the increased devitrification resistance of glass, lot of experiment validation is to have within the scope of 40-50%
Benefit, it is preferably preferable in 47-50%.
Y2O3With the tendency towards devitrification of control glass, while the refractive index and fluorescent effect of cameo glass can be improved.
ZrO2Improving glass refraction and density has the oxide well helped, the ZrO of low content2Be not achieved high refraction and
Highdensity effect, high-content it is unfavorable to the increased devitrification resistance of glass, within the scope of 8-16% be it is beneficial, preferably in 12-16%
It is interior preferable, more preferably in 14-16%.
Cameo glass of the present invention composition is suitable for pouring, and the preparation processes such as suppresses, rolls.
In particular it relates to extra-high refraction high density environmental protection cameo glass preparation method, include the following steps:
(1) precise analyzes pure grade each component and mixes 4-6h using wet ball grinding technique；
(2) mixed material is kept the temperature to 2-3.5h in 150 DEG C of high temperature ovens so that vaporized alcohol is clean, then dry-mixed 1-
2h；
(3) material after will be dry-mixed is placed in platinum crucible, then platinum crucible is put into and is connected with N2And H2Protective gas
8-12h is melted in high temperature furnace, control glass melting temperature is 1400-1500 DEG C, later, the glass metal after being melted is poured into 5-15 DEG C
Water quenching is carried out in distilled water to form glass particle, dries ball milling 1-2h again；
(4) glass for drying milled is placed in corundum crucible, the atmosphere that corundum crucible is placed in 1350-1450 DEG C is protected
Secondary melted 4-7h in furnace retaining, and stir evenly, molding die is poured into after furnace temperature is down to 1250-1350 DEG C of heat preservation 0.5-1.5h
Molding, moves in annealing furnace, and control annealing temperature is 600-700 DEG C, and it is cold to close furnace after to be annealed by annealing time 12-24h
But to room temperature up to cameo glass.
Annealing temperature described in step (4) is preferably 600 DEG C.
Annealing time described in step (4) is preferably 12h.
Glass composition of the present invention guarantees to make refractive index reach 2.2-2.5, market while glass high transmitance
Upper sold cameo glass is not up to the value, and its density is up to 4.5-4.7g/cm3, lead oxide and arsenic oxide arsenoxide are free of in composition
Harmful substance is not present and dissolves out problem with harmful substances, production process environmental protection, products such as fluorine, barium.The cameo glass refractive index exists
Between up to 2.0-2.3, it is seen that light transmission rate is between 75-82%, and pure color, glass melting temperature is moderate, and chemical stability is good
It is good, and have and be easy to the characteristics such as polishing processing.
The preparation of cameo glass of the present invention use it is secondary be melted to guarantee the melting quality of glass, and proper temperature is needed to melt
Change the long period, to control influence of the impurity to glass quality.
Each embodiment is prepared referring to table 1 according to the proportion relation feeding of each embodiment in table 1 with following methods:
(1) precise analyzes pure grade each component and mixes 4-6h using wet ball grinding technique；
(2) mixed material is kept the temperature to 3.5h in 150 DEG C of high temperature ovens so that vaporized alcohol is clean, then dry-mixed 1-2h
To guarantee the uniformity of material；
(3) material after will be dry-mixed is placed in platinum crucible, then platinum crucible is put into and is connected with N2And H2Protective gas
12h is melted in high temperature furnace, control glass melting temperature is 1500 DEG C, later, the glass metal after being melted is poured into 10 DEG C or so of distillation
Water quenching is carried out in water to form glass particle, dries ball milling 1.5h again；
(4) glass for drying milled is placed in corundum crucible, corundum crucible is placed in 1450 DEG C of atmosphere protection stove
In secondary melted 6h, and stir evenly, furnace temperature be down to after 1350 DEG C of heat preservation 0.5h and pours into molding die molding, moves to annealing furnace
In, control annealing temperature is 600 DEG C, and annealing time 12h closes furnace after to be annealed and is cooled to room temperature up to cameo glass.
Embodiment 2-7 preparation method is substantially same as Example 1, the difference is that only that temperature is melted in step (2) for the first time
The change of degree, step (3) secondary glass melting temperature, step (4) annealing temperature and annealing time, concrete technology condition are shown in Table 1.
The preparation method of embodiment 8 is substantially the same manner as Example 1, the difference is that the temperature of step (2) high temperature baking oven
Degree is 120 DEG C, soaking time 2.5h, and melting time is 10h in step (3), secondary melting time is 5h in step (4).
Table 1
Claims (9)
1. a kind of extra-high refraction high density environment-friendly type cameo glass, it is characterised in that: by each group as follows by weight percentage
It is grouped as: SiO21-3%, TiO240-50%, La2O340-50%, ZrO28-16%, Y2O30-10%, alkali metal oxidation
Object 0-5%；The cameo glass is prepared by the following method, and steps are as follows:
(1) precise analyzes pure grade each component and mixes 4-6h using wet ball grinding technique；
(2) by mixed material in 100-150 DEG C of high temperature oven heat preservation 2-3.5h with vaporized alcohol is clean, then dry-mixed 1-
2h；
(3) material after will be dry-mixed is placed in platinum crucible, then platinum crucible is put into and is connected with N2And H2Protective gas high temperature
8-12h is melted in furnace, control glass melting temperature is 1400-1500 DEG C, later, the glass metal after being melted is poured into 5-15 DEG C of distillation
Water quenching is carried out in water to form glass particle, dries ball milling 1-2h again；
(4) glass for drying milled is placed in corundum crucible, corundum crucible is placed in 1350-1450 DEG C of atmosphere protection stove
In secondary melted 4-7h, and stir evenly, furnace temperature is down to after 1250-1350 DEG C of heat preservation 0.5-1.5h pour into molding die at
Type moves in annealing furnace, and control annealing temperature is 600-700 DEG C, and it is cooling to close furnace after to be annealed by annealing time 12-24h
To room temperature up to cameo glass.
2. the extra-high refraction high density environment-friendly type cameo glass of one kind according to claim 1, it is characterised in that: the TiO2
Weight and SiO2、TiO2、La2O3、ZrO2And Y2O3The ratio between total weight be greater than 0.4.
3. the extra-high refraction high density environment-friendly type cameo glass of one kind according to claim 2, it is characterised in that: the TiO2
Weight and SiO2、TiO2、La2O3、ZrO2And Y2O3The ratio between total weight >=0.5.
4. the extra-high refraction high density environment-friendly type cameo glass of one kind according to claim 1, it is characterised in that: the alkali
Metal oxide is Li2O、Na2O、K2One of O, two or three, the weight percent of alkali metal oxide are 0-3%.
5. the extra-high refraction high density environment-friendly type cameo glass of one kind according to claim 1, it is characterised in that: described
SiO2Weight percent is 2-3%.
6. the extra-high refraction high density environment-friendly type cameo glass of one kind according to claim 1, it is characterised in that: described
ZrO2Weight percent be 14-16%.
7. the extra-high refraction high density environment-friendly type cameo glass of one kind according to claim 1, it is characterised in that: the La2O3
Weight percent be 47-50%.
8. the extra-high refraction high density environment-friendly type cameo glass of one kind according to claim 1, it is characterised in that: step (4)
Described in annealing temperature be 600 DEG C.
9. the extra-high refraction high density environment-friendly type cameo glass of one kind according to claim 1, it is characterised in that: step (4)
Described in annealing time be 12h.
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| CN109761579B (en) * | 2019-03-26 | 2022-01-04 | 成都奇彩珠宝有限公司 | High-refraction high-density colour artificial gem |
| CN109734303B (en) * | 2019-03-26 | 2022-03-18 | 成都奇彩珠宝有限公司 | High-refraction colorless transparent artificial synthetic gem |
| JP2020172427A (en) * | 2019-04-05 | 2020-10-22 | 日本電気硝子株式会社 | Decorative glass article |
| US20220169558A1 (en) * | 2019-04-05 | 2022-06-02 | Nippon Electric Glass Co., Ltd. | Decorative glass article |
| CN110128006B (en) * | 2019-06-21 | 2022-05-10 | 鲁米星特种玻璃科技股份有限公司 | Environment-friendly high-refractive-index ultraviolet-transmitting glass and preparation method thereof |
| CN110143758B (en) * | 2019-06-24 | 2022-05-17 | 鲁米星特种玻璃科技股份有限公司 | Artificial sapphire jade glass and preparation method thereof |
| CN111204974A (en) * | 2020-02-28 | 2020-05-29 | 丽水博耀特种玻璃有限公司 | Preparation process of toughened glass |
| CN114835380B (en) * | 2022-04-07 | 2023-08-25 | 齐鲁工业大学 | Melting production process for inhibiting volatilization of borosilicate glass components |
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| CN1244851A (en) * | 1997-01-29 | 2000-02-16 | 康宁股份有限公司 | Glasses with very high refractive index |
| US7297647B2 (en) * | 2004-02-26 | 2007-11-20 | Schott Ag | Lead- and arsenic-free optical lanthanum flint glasses |
| CN102320715A (en) * | 2011-08-30 | 2012-01-18 | 河北省沙河玻璃技术研究院 | Presintering treatment process of glass batch and device thereof |
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| JP4446982B2 (en) * | 2005-09-21 | 2010-04-07 | Ｈｏｙａ株式会社 | Optical glass, glass gob for press molding, glass molded body, optical element and production method thereof |
| CN104445925A (en) * | 2014-12-01 | 2015-03-25 | 河北省沙河玻璃技术研究院 | Ultra-high-refractivity environment-friendly cameo glass and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1244851A (en) * | 1997-01-29 | 2000-02-16 | 康宁股份有限公司 | Glasses with very high refractive index |
| US7297647B2 (en) * | 2004-02-26 | 2007-11-20 | Schott Ag | Lead- and arsenic-free optical lanthanum flint glasses |
| CN102320715A (en) * | 2011-08-30 | 2012-01-18 | 河北省沙河玻璃技术研究院 | Presintering treatment process of glass batch and device thereof |
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