CN109369025A - A kind of crystal glass material, its feedstock composition and manufacturing method - Google Patents
A kind of crystal glass material, its feedstock composition and manufacturing method Download PDFInfo
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- CN109369025A CN109369025A CN201811647462.7A CN201811647462A CN109369025A CN 109369025 A CN109369025 A CN 109369025A CN 201811647462 A CN201811647462 A CN 201811647462A CN 109369025 A CN109369025 A CN 109369025A
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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
- C03C10/00—Devitrified glass ceramics, i.e. glass ceramics having a crystalline phase dispersed in a glassy phase and constituting at least 50% by weight of the total composition
- C03C10/0009—Devitrified glass ceramics, i.e. glass ceramics having a crystalline phase dispersed in a glassy phase and constituting at least 50% by weight of the total composition containing silica as main constituent
-
- 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
- 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
- C03C3/095—Glass compositions containing silica with 40% to 90% silica, by weight containing rare earths
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Life Sciences & Earth Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Geochemistry & Mineralogy (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Ceramic Engineering (AREA)
- Crystallography & Structural Chemistry (AREA)
- Dispersion Chemistry (AREA)
- Glass Compositions (AREA)
Abstract
The invention discloses a kind of crystal glass material, its feedstock composition and manufacturing methods.SiO of its crystal glass material including 65-75 parts by weight in terms of the weight of oxide2, 1-2 parts by weight Al2O3, 4-8 parts by weight CaO, 10-12 parts by weight Na2O, the K of 2-4 parts by weight2O, the BaO of ZnO, 4-8 parts by weight of 0.8-1.5 parts by weight.Sodium nitrate, fluoride, arsenic oxide arsenoxide are free of in crystal glass material of the invention, introduce high price cerium as clarifying agent, oxygen is persistently released in glass fusion process, plays good clarification.Crystal glass material of the invention has the advantages that harmless environmental protection.
Description
Technical field
The present invention relates to glass composition, especially a kind of crystal glass material, its feedstock composition and its manufacturing method.
Background technique
Crystal glass refers to very high transparency and biggish refractive index, bright and clean sparkling and crystal-clear, such as mineral crystal, also known as crystal
Glass.Crystal glass has broad sense and narrow sense two types, and the crystal glass of broad sense includes: lead crystal glass, barium crystal glass, zinc
Crystal glass, titanium crystal glass and zirconium crystal glass and mixed type crystal glass, narrow sense only refer to lead crystal glass.
One of key factor is exactly the bubble contained in glass in terms of glass quality, and glass is by by silica sand, soda ash, stone
After the raw materials such as lime stone mix, being melted at high temperature, the glass after high temperature melting is a kind of highly viscous liquid,
In include a large amount of bubble, when not using any clarifying agent, carbon dioxide, the content of nitrogen are most in bubble, and they
Cannot melt again with melten glass liquid, if it is single rise to metal level by bubble after rupture release, that will need to consume big
The time of amount is unacceptable to industrialized production.The bubble that glass melting generates usually is eliminated by two ways,
The skin breakage of glass metal is risen to one is bubble and is discharged, and another kind is that bubble is dissolved in melten glass liquid.It is melting
The gas that can be melted in glass metal mainly has sulfur dioxide, oxygen, hydrogen etc., and the gas that cannot be melted mainly has nitrogen, two
Carbonoxide and some other inert gas.In the past, in order to reduce the bubble in glass, using arsenic and nitrate cooperate as
A kind of clarifying agent is introduced into glass batch, but arsenic can partially volatilize cause environmental pollution at high temperature, and arsenic is made
For a kind of extremely toxic substance, it is difficult to be managed, therefore, the continuous improvement with people to environmental requirement, more and more countries
It has begun and recognizes the harm of arsenic in glass, the developed countries such as Europe and Japan strictly forbid using in glass
Arsenic.In recent years, in glass production frequently with sodium nitrate, fluoride and arsenic oxide arsenoxide as clarifying agent.Since sodium nitrate is in glass
Toxic gas nitrogen dioxide (the NO of brownish red sharp aroma is decomposed to give off in glass fusion process2).Nitrogen dioxide (NO2) by human body
Respiratory tract can be damaged after sucking.Nitrogen dioxide (NO2) to be discharged into brought environmental effect in atmosphere varied, comprising: to wet
The influence with composition variation, the reduction of atmospheric visibility, the acidification of surface water, eutrophy are competed between ground and terrestrial plant species
Change and (lead to anoxic due to being rich in the nutrients algal bloom such as nitrogen, phosphorus in water) and increase be harmful in water body fish and
The content of toxins of other aquatiles.And fluoride category high poison substance, human body is entered by respiratory tract, mucous membrane can be caused to pierce
The symptoms such as sharp, poisoning, and the normal physiological function of each tissue and organ can be influenced, danger can also be generated to growth, the development of plant
Evil.And arsenic oxide arsenoxide belongs to inorganic toxic articles.Human body sucking, main influence nervous system and capillary permeability after eating, it is right
Skin and the irritating effect of mucous membrane.Therefore, above-mentioned clarifying agent has toxic action to environment and human body.
Summary of the invention
In order to overcome the shortcomings in the prior art, the purpose of the present invention is to provide a kind of crystal glass materials of harmless environmental protection
Material, its feedstock composition and its manufacturing method.
In one aspect of the invention, a kind of crystal glass material is provided, the crystal glass material is with oxide
Poidometer include 65-75 parts by weight SiO2, 1-2 parts by weight Al2O3, 4-8 parts by weight CaO, 10-12 parts by weight
Na2O, the K of 2-4 parts by weight2O, the BaO of ZnO, 4-8 parts by weight of 0.8-1.5 parts by weight.
The present invention other in terms of, the crystal glass material is in terms of the weight of oxide including 70.5 parts by weight
SiO2, 1.4 parts by weight Al2O3, the CaO of 6 parts by weight, 11.3 parts by weight Na2O, the K of 3 parts by weight2O, the ZnO of 1 parts by weight, 6
The BaO of parts by weight.
The present invention other in terms of, the crystal glass material further includes 1.5-3.5 weight in terms of the weight of oxide
The V of MgO, 0.03-0.05 parts by weight of part2O5With the MnO of 0.1-0.15 parts by weight2。
The present invention other in terms of, the crystal glass material further includes 2.4 parts by weight in terms of the weight of oxide
The V of MgO, 0.042 parts by weight2O5With the MnO of 0.12 parts by weight2。
The present invention other in terms of, the crystal glass material also includes the other impurities of not more than 0.8 parts by weight.
In other aspects of the present invention, the feedstock composition of the above crystal glass material, the crystalloid glass are additionally provided
The feedstock composition of glass material according to quartz sand, 1.5-3.1 parts by weight that poidometer includes 65-75 parts by weight aluminium hydroxide,
The calcite of 7.1-14.3 parts by weight, the soda ash of 17.1-20.5 parts by weight, the potassium carbonate of 2.9-5.9 parts by weight, 0.8-1.5 weight
Measure the oxidation of the barium carbonate of ZnO, 5.1-10.3 parts by weight, the cerium oxide of 0.8-1.6 parts by weight and 0.03-0.07 parts by weight of part
Erbium.
In currently preferred aspect, the feedstock composition of the crystal glass material includes 70.5 weights according to poidometer
Measure the quartz sand of part, the aluminium hydroxide of 2.1 parts by weight, the calcite of 10.7 parts by weight, the soda ash of 19.3 parts by weight, 4.4 weight
The potassium carbonate, the ZnO of 1.0 parts by weight, the barium carbonate of 7.7 parts by weight, the cerium oxide of 1.2 parts by weight and the oxygen of 0.05 parts by weight of part
Change erbium.
The present invention other in terms of, the feedstock composition of the crystal glass material further includes 1.5- according to poidometer
3.5 the V of MgO, 0.03-0.05 parts by weight of parts by weight2O5With the MnO of 0.1-0.15 parts by weight2。
The present invention other in terms of, the feedstock composition of the crystal glass material further includes 2.4 weights according to poidometer
Measure the MgO of part, the V of 0.042 parts by weight2O5With the MnO of 0.12 parts by weight2。
In other aspects of the present invention, additionally provide more than crystal glass material preparation method comprising by crystalloid
The feedstock composition of glass material Hybrid Heating in crucible and is kept stirring to obtain glass melt to molten condition.
Enter high price cerium in crystal glass material of the invention as clarifying agent, is persistently released in glass fusion process
Oxygen plays the important foundation guarantee that can cancel sodium nitrate in good clarification, and formula.Crystal glass of the invention
Material has the advantages that harmless environmental protection.
Specific embodiment
Embodiment 1
In the present embodiment, the feedstock composition of the crystal glass material used includes 70.5 kilograms of quartz according to poidometer
Sand, 2.1 kilograms of aluminium hydroxide, 10.7 kilograms of calcite, 19.3 kilograms of soda ash, 4.4 kilograms of potassium carbonate, 1.0 kilograms
ZnO, 7.7 kilograms of barium carbonate, 1.2 kilograms of cerium oxide and 0.05 kilogram of erbium oxide.According to this proportional arrangement raw material group
Object is closed, and is melted 4 hours at 1460 degrees Celsius, and progressively cool to 1280 degrees Celsius of sizings, after then glass is annealed,
Polishing becomes the thin slice of 3.2mm thickness.
Embodiment 2
In the present embodiment, the feedstock composition of the crystal glass material used according to the quartz sand that poidometer includes 65 kilograms,
1.5 kilograms of aluminium hydroxide, 14.3 kilograms of calcite, 17.1 kilograms of soda ash, 5.9 kilograms of potassium carbonate, 0.8 kilogram
ZnO, 10.3 kilograms of barium carbonate, 0.8 kilogram of cerium oxide and 0.07 kilogram of erbium oxide.According to this proportional arrangement material combination
Object, and be melted 4 hours at 1460 degrees Celsius, and progressively cool to 1280 degrees Celsius of sizings, after then glass is annealed, beat
It wears into as the thin slice of 3.2mm thickness.
Embodiment 3
In the present embodiment, the feedstock composition of the crystal glass material used according to the quartz sand that poidometer includes 75 kilograms,
3.1 kilograms of aluminium hydroxide, 7.1 kilograms of calcite, 20.5 kilograms of soda ash, 2.9 kilograms of potassium carbonate, 1.5 kilograms
ZnO, 5.1 kilograms of barium carbonate, 1.6 kilograms of cerium oxide and 0.03 kilogram of erbium oxide.According to this proportional arrangement material combination
Object, and be melted 4 hours at 1460 degrees Celsius, and progressively cool to 1280 degrees Celsius of sizings, after then glass is annealed, beat
It wears into as the thin slice of 3.2mm thickness.
Embodiment 4
The difference with embodiment 1 is in the present embodiment, and the feedstock composition of the crystal glass material is with oxide
Poidometer further includes 2.4 kilograms of MgO, 0.042 kilogram of V2O5With 0.12 kilogram of MnO2。
Embodiment 5
The difference with embodiment 1 is in the present embodiment, and the feedstock composition of the crystal glass material is with oxide
Poidometer further includes 3.5 kilograms of MgO, 0.05 kilogram of V2O5With 0.15 kilogram of MnO2。
Embodiment 6
The difference with embodiment 1 is in the present embodiment, and the feedstock composition of the crystal glass material is with oxide
Poidometer further includes 1.5 kilograms of MgO, 0.03 kilogram of V2O5With 0.1 kilogram of MnO2。
Embodiment 7
The difference with embodiment 1 is in the present embodiment, and the feedstock composition of the crystal glass material is with oxide
Poidometer further includes 2.4 kilograms of MgO and 0.12 kilogram of MnO2。
Embodiment 8
The difference with embodiment 1 is in the present embodiment, and the feedstock composition of the crystal glass material is with oxide
Poidometer further includes 3.5 kilograms of MgO and 0.05 kilogram of V2O5。
Comparative example 1
It is in this comparative example with the difference of embodiment 1, does not use erbium oxide and cerium oxide.
One, the comparative test of bubble
The glass flake that acquirement embodiment 1-8 and comparative example 1 obtain catches irradiation from glass edge using major light, measures 100*
The bubble of all sizes within the scope of 100mm.The glass that each embodiment provides 100 specifications is tested.Specifically
Ground carries out test experiments according to method disclosed in GB/T-7962.8-2010, obtains the average bubble of each glass sample
Quantity, and be documented in table 1.0.3mm bubble below is not recorded.
Table 1: the Air Bubble Size quantity record sheet of glass flake obtained in embodiment 1-8
It can be appreciated that the formula of embodiment 1-8 all realizes preferable glass blister degree effect from table 1.Wherein implement
Example 4-6 realizes the sharp fall of air bubble content.It is worth noting that, being added without small when manganese oxide in embodiment 7
Bubble largely occurs.
Two, inclusion content analysis experiment
In addition to this, also the content of the field trash in glass is analyzed, equally takes sample and the test of embodiment 10
Condition carries out, and describes the field trash that all length is greater than 0.3mm, and observed number and be recorded in table 2.
Table 2: the amount of inclusions record sheet of glass flake obtained in embodiment 1-8
Experimental group | 0.3mm or more the amount of inclusions/every square metre |
Embodiment 1 | 4.7 |
Embodiment 2 | 5.6 |
Embodiment 3 | 6.1 |
Embodiment 4 | 2.2 |
Embodiment 5 | 1.7 |
Embodiment 6 | 1.3 |
Embodiment 7 | 0.6 |
Embodiment 8 | 6.4 |
Comparative example 1 | 11.0 |
It can see from the test data of table 2, the amount of inclusions of embodiment 4-6 is declined., it is surprising that embodiment
7 have very superior inclusion content, and then the amount of inclusions significantly increases embodiment 8.
Claims (10)
1. a kind of crystal glass material, which is characterized in that the crystal glass material is in terms of the weight of oxide including 65-75
The SiO of parts by weight2, 1-2 parts by weight Al2O3, 4-8 parts by weight CaO, 10-12 parts by weight Na2O, the K of 2-4 parts by weight2O、
The BaO of ZnO, 4-8 parts by weight of 0.8-1.5 parts by weight.
2. a kind of crystal glass material according to claim 1, which is characterized in that the crystal glass material is to aoxidize
The poidometer of object includes the SiO of 70.5 parts by weight2, 1.4 parts by weight Al2O3, the CaO of 6 parts by weight, 11.3 parts by weight Na2O、
The K of 3 parts by weight2O, the ZnO of 1 parts by weight, 6 parts by weight BaO.
3. a kind of crystal glass material according to claim 1, which is characterized in that the crystal glass material also includes
The not more than other impurities of 0.8 parts by weight.
4. a kind of crystal glass material according to claim 1, which is characterized in that the crystal glass material is to aoxidize
The poidometer of object further includes the V of MgO, 0.03-0.05 parts by weight of 1.5-3.5 parts by weight2O5With 0.1-0.15 parts by weight
MnO2。
5. a kind of crystal glass material according to claim 4, which is characterized in that the crystal glass material is to aoxidize
The poidometer of object further includes the V of the MgO of 2.4 parts by weight, 0.042 parts by weight2O5With the MnO of 0.12 parts by weight2。
6. being used to prepare the feedstock composition of crystal glass material according to any one of claims 1-5, feature exists
In quartz sand, the 1.5-3.1 that the feedstock composition of the crystal glass material includes 65-75 parts by weight according to poidometer are heavy
Measure the aluminium hydroxide of part, the calcite of 7.1-14.3 parts by weight, the soda ash of 17.1-20.5 parts by weight, 2.9-5.9 parts by weight carbon
Sour potassium, the barium carbonate of ZnO, 5.1-10.3 parts by weight of 0.8-1.5 parts by weight, 0.8-1.6 parts by weight cerium oxide and 0.03-
The erbium oxide of 0.07 parts by weight.
7. the feedstock composition according to claim 6 for being used to prepare crystal glass material, which is characterized in that the crystalline substance
The feedstock composition of matter glass material according to quartz sand, 2.1 parts by weight that poidometer includes 70.5 parts by weight aluminium hydroxide,
The calcite of 10.7 parts by weight, the soda ash of 19.3 parts by weight, the potassium carbonate of 4.4 parts by weight, the ZnO of 1.0 parts by weight, 7.7 weight
The barium carbonate, the cerium oxide of 1.2 parts by weight and the erbium oxide of 0.05 parts by weight of part.
8. the feedstock composition according to claim 6 for being used to prepare crystal glass material, which is characterized in that the crystalline substance
The feedstock composition of matter glass material further includes MgO, 0.03-0.05 weight of 1.5-3.5 parts by weight in terms of the weight of oxide
The V of part2O5With the MnO of 0.1-0.15 parts by weight2。
9. the feedstock composition according to claim 8 for being used to prepare crystal glass material, which is characterized in that the crystalline substance
The feedstock composition of matter glass material further includes the V of the MgO of 2.4 parts by weight, 0.042 parts by weight in terms of the weight of oxide2O5With
The MnO of 0.12 parts by weight2。
10. the preparation method of crystal glass material according to any one of claims 1-5, which is characterized in that it includes
By the feedstock composition of crystal glass material described in any one of claim 6-9 in crucible Hybrid Heating to molten
State, and be kept stirring to obtain glass melt.
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Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB1353935A (en) * | 1971-07-06 | 1974-05-22 | Glasforskningsinstitutet | Glass for the manufacture of art and household glassware |
CN1105343A (en) * | 1993-11-03 | 1995-07-19 | 化学技术大学 | Lead-free crystal glass with the refractive index higher than 1.52 |
CN1891650A (en) * | 2006-05-16 | 2007-01-10 | 福耀集团双辽有限公司 | Antiradiation crystal yellow glass composition |
CN102659314A (en) * | 2012-04-27 | 2012-09-12 | 中南大学 | Barium oxide based crystal lead-free glass and preparation method thereof |
CN103189325A (en) * | 2011-09-01 | 2013-07-03 | 普莱西奥萨公司 | Crystal glass having refractive index higher than 1,53 without a content of compounds of lead, barium and arsenic |
JP2016056025A (en) * | 2013-01-29 | 2016-04-21 | オーエムジー株式会社 | Optical glass filter |
-
2018
- 2018-12-30 CN CN201811647462.7A patent/CN109369025A/en active Pending
Patent Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB1353935A (en) * | 1971-07-06 | 1974-05-22 | Glasforskningsinstitutet | Glass for the manufacture of art and household glassware |
CN1105343A (en) * | 1993-11-03 | 1995-07-19 | 化学技术大学 | Lead-free crystal glass with the refractive index higher than 1.52 |
CN1891650A (en) * | 2006-05-16 | 2007-01-10 | 福耀集团双辽有限公司 | Antiradiation crystal yellow glass composition |
CN103189325A (en) * | 2011-09-01 | 2013-07-03 | 普莱西奥萨公司 | Crystal glass having refractive index higher than 1,53 without a content of compounds of lead, barium and arsenic |
CN102659314A (en) * | 2012-04-27 | 2012-09-12 | 中南大学 | Barium oxide based crystal lead-free glass and preparation method thereof |
JP2016056025A (en) * | 2013-01-29 | 2016-04-21 | オーエムジー株式会社 | Optical glass filter |
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