CN1880251A - Li2O-Al2O3-SiO2-MgO-K2O-F series microcrystalline glass, microcrystalline glass and manufacturing method thereof - Google Patents
Li2O-Al2O3-SiO2-MgO-K2O-F series microcrystalline glass, microcrystalline glass and manufacturing method thereof Download PDFInfo
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- CN1880251A CN1880251A CNA2006100741131A CN200610074113A CN1880251A CN 1880251 A CN1880251 A CN 1880251A CN A2006100741131 A CNA2006100741131 A CN A2006100741131A CN 200610074113 A CN200610074113 A CN 200610074113A CN 1880251 A CN1880251 A CN 1880251A
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- 239000011521 glass Substances 0.000 title claims abstract description 142
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 25
- 238000000034 method Methods 0.000 claims abstract description 33
- 238000002425 crystallisation Methods 0.000 claims abstract description 27
- 230000008025 crystallization Effects 0.000 claims abstract description 27
- 239000002994 raw material Substances 0.000 claims description 48
- 229910052744 lithium Inorganic materials 0.000 claims description 46
- 239000000203 mixture Substances 0.000 claims description 37
- 239000002699 waste material Substances 0.000 claims description 31
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 28
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 24
- 229910052708 sodium Inorganic materials 0.000 claims description 20
- 229910008556 Li2O—Al2O3—SiO2 Inorganic materials 0.000 claims description 19
- 229910052792 caesium Inorganic materials 0.000 claims description 19
- 229910052701 rubidium Inorganic materials 0.000 claims description 19
- 229910052629 lepidolite Inorganic materials 0.000 claims description 17
- 238000002844 melting Methods 0.000 claims description 17
- 230000008018 melting Effects 0.000 claims description 17
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 14
- 238000010438 heat treatment Methods 0.000 claims description 13
- 229910010100 LiAlSi Inorganic materials 0.000 claims description 12
- 229910052787 antimony Inorganic materials 0.000 claims description 11
- 229910052785 arsenic Inorganic materials 0.000 claims description 11
- 238000003756 stirring Methods 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 3
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims 6
- 229910018068 Li 2 O Inorganic materials 0.000 claims 6
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 abstract description 6
- 238000002360 preparation method Methods 0.000 abstract description 4
- KKCBUQHMOMHUOY-UHFFFAOYSA-N Na2O Inorganic materials [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 abstract description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 abstract 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 abstract 2
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 abstract 2
- KOPBYBDAPCDYFK-UHFFFAOYSA-N Cs2O Inorganic materials [O-2].[Cs+].[Cs+] KOPBYBDAPCDYFK-UHFFFAOYSA-N 0.000 abstract 1
- FUJCRWPEOMXPAD-UHFFFAOYSA-N Li2O Inorganic materials [Li+].[Li+].[O-2] FUJCRWPEOMXPAD-UHFFFAOYSA-N 0.000 abstract 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 abstract 1
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Inorganic materials O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 abstract 1
- 229910052681 coesite Inorganic materials 0.000 abstract 1
- 229910052593 corundum Inorganic materials 0.000 abstract 1
- 229910052906 cristobalite Inorganic materials 0.000 abstract 1
- 239000013078 crystal Substances 0.000 abstract 1
- AKUNKIJLSDQFLS-UHFFFAOYSA-M dicesium;hydroxide Chemical compound [OH-].[Cs+].[Cs+] AKUNKIJLSDQFLS-UHFFFAOYSA-M 0.000 abstract 1
- XUCJHNOBJLKZNU-UHFFFAOYSA-M dilithium;hydroxide Chemical compound [Li+].[Li+].[OH-] XUCJHNOBJLKZNU-UHFFFAOYSA-M 0.000 abstract 1
- 229910001953 rubidium(I) oxide Inorganic materials 0.000 abstract 1
- 239000000377 silicon dioxide Substances 0.000 abstract 1
- 235000012239 silicon dioxide Nutrition 0.000 abstract 1
- 229910052682 stishovite Inorganic materials 0.000 abstract 1
- YEAUATLBSVJFOY-UHFFFAOYSA-N tetraantimony hexaoxide Chemical compound O1[Sb](O2)O[Sb]3O[Sb]1O[Sb]2O3 YEAUATLBSVJFOY-UHFFFAOYSA-N 0.000 abstract 1
- 229910052905 tridymite Inorganic materials 0.000 abstract 1
- 229910001845 yogo sapphire Inorganic materials 0.000 abstract 1
- 238000010792 warming Methods 0.000 description 22
- 239000000395 magnesium oxide Substances 0.000 description 19
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 19
- 239000000126 substance Substances 0.000 description 17
- 230000004927 fusion Effects 0.000 description 15
- 229910052700 potassium Inorganic materials 0.000 description 14
- 229910001760 lithium mineral Inorganic materials 0.000 description 12
- 239000005357 flat glass Substances 0.000 description 10
- 238000004031 devitrification Methods 0.000 description 8
- 239000003795 chemical substances by application Substances 0.000 description 6
- 229910052878 cordierite Inorganic materials 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 239000011777 magnesium Substances 0.000 description 6
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 6
- 229910000502 Li-aluminosilicate Inorganic materials 0.000 description 5
- 229910052656 albite Inorganic materials 0.000 description 5
- HEHRHMRHPUNLIR-UHFFFAOYSA-N aluminum;hydroxy-[hydroxy(oxo)silyl]oxy-oxosilane;lithium Chemical compound [Li].[Al].O[Si](=O)O[Si](O)=O.O[Si](=O)O[Si](O)=O HEHRHMRHPUNLIR-UHFFFAOYSA-N 0.000 description 5
- 229910052670 petalite Inorganic materials 0.000 description 5
- 239000000463 material Substances 0.000 description 4
- 229910052628 phlogopite Inorganic materials 0.000 description 4
- 238000007493 shaping process Methods 0.000 description 4
- 239000000292 calcium oxide Substances 0.000 description 3
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 3
- 239000006071 cream Substances 0.000 description 3
- 238000007669 thermal treatment Methods 0.000 description 3
- 230000008901 benefit Effects 0.000 description 2
- 238000004364 calculation method Methods 0.000 description 2
- 238000010276 construction Methods 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 229910000500 β-quartz Inorganic materials 0.000 description 2
- 239000004768 A.C.E Substances 0.000 description 1
- 229910052822 amblygonite Inorganic materials 0.000 description 1
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 239000004579 marble Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C3/00—Glass compositions
- C03C3/04—Glass compositions containing silica
- C03C3/076—Glass compositions containing silica with 40% to 90% silica, by weight
- C03C3/11—Glass compositions containing silica with 40% to 90% silica, by weight containing halogen or nitrogen
- C03C3/112—Glass compositions containing silica with 40% to 90% silica, by weight containing halogen or nitrogen containing fluorine
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Geochemistry & Mineralogy (AREA)
- Organic Chemistry (AREA)
- Crystallography & Structural Chemistry (AREA)
- Dispersion Chemistry (AREA)
- Ceramic Engineering (AREA)
- Glass Compositions (AREA)
- Glass Melting And Manufacturing (AREA)
- Re-Forming, After-Treatment, Cutting And Transporting Of Glass Products (AREA)
Abstract
The present invention provides microcrystalline glass, crystallization glass and the method of preparation, characterized in that the components include 50.0 to 65.0 wt% SiO2, 10.0- 25.0 wt% Al2O3, 6.0-15.0wt% MgO, 2.5-4.0 wt% Li2O, 0.5-4.0wt% Na2O, 2.1- 7.5wt% K2O, 1.2-4.8wt% F, 0.1-4.0wt% TiO2, 0.1-4.0wt% ZrO2, 0.5-3.0 wt% P2O5, 0-3.0wt% BaO2, 0.4-1.5wt% As2O, 0.3-1.6wt% Rb2O, 0.03-0.4wt% Cs2O, 0.06-0.7wt% MnO2, 3 0.03-0.3wt% Fe2O, 0-1.5wt% Sb2O3. The characteristics of method are mass-producing, low-temperature of crystal and low cost of manufacture.
Description
Technical field
The present invention relates to a kind of Li
2O-Al
2O
3-SiO
2-MgO-K
2O-F is crystallite glass and Li
2O-Al
2O
3-SiO
2-MgO-K
2O-F is a microcrystalline glass, and the manufacture method of this crystallite glass and microcrystalline glass.
Background technology
In recent years, Li
2O-Al
2O
3-SiO
2Be that microcrystalline glass is widely used in colored filter, image sensor burns till with materials such as face-port glass before refractory slab, electromagnetism conditioner panel, light part, microwave oven refractory slab, fire prevention window glass, petroleum stove and the timber stove with high-tech goods such as substrate substrate, electronic component.
About above-mentioned Li
2O-Al
2O
3-SiO
2Be microcrystalline glass, for example, in each communique of patent documentation 1～patent documentation 7 grades, open and shown with β-quartz solid solution (Li
2OAl
2O
3N SiO
2N 〉=2) or β-triphane sosoloid (Li
2OAl
2O
3N SiO
2N 〉=4) Li that separates out for primary crystallization
2O-Al
2O
3-SiO
2It is microcrystalline glass.
Because above-mentioned Li
2O-Al
2O
3-SiO
2Be that microcrystalline glass has low thermal expansivity and high physical strength, so thermal property is good.
In addition, above-mentioned Li
2O-Al
2O
3-SiO
2Be to obtain crystallite glass after the fusion of microcrystalline glass raw material process, the shaping.Because this crystallite glass is in the crystallization engineering, can change it by the change heat-treat condition and separate out the crystalline kind, so can produce the microcrystalline glass (β-when triphane sosoloid is separated out) of transparent microcrystalline glass (when β-quartz solid solution is separated out) and White-opalescent by the same frit of forming, have the advantage that separately to use according to purposes.
But, made above-mentioned Li in the past
2O-Al
2O
3-SiO
2When being crystallite glass, usually need surpass 1600 ℃, sometimes in addition need continue a few hours～20 under near 1700 ℃ high temperature hour could be with the frit fusion.So exist the problem that to prepare the melting furnace that under this high temperature, can use for a long time and necessary fuel.
Also have, when making White-opalescent microcrystalline glass (β-triphane sosoloid is separated out), frit obtains crystallite glass through fusion, shaping, forms the back in this crystallite glass core and carries out crystallization thermal treatment in order to make crystalline growth.But up to the present the temperature of this crystalline growth must be set in 1000 ℃～1300 ℃ high temperature.
For the foregoing reasons, Li
2O-Al
2O
3-SiO
2Be crystallite glass and Li
2O-Al
2O
3-SiO
2Be microcrystalline glass manufacturing cost height, seldom the microcrystalline glass with this system is used for material of construction.
In addition, in CN1091399A and CN1101015A application, disclosed with the microcrystalline glass and the manufacture method thereof that lithium minerals is a main raw material that contain of composition near lithionite.
In the specification sheets of CN1091399A, use composition near the mine waste of lithionite as main raw material, mine waste usage quantity for prescription form 80～100%.For this reason, except reducing the melting temperature (Tm), simultaneously, also can reduce crystallized temperature.Therefore, can reduce manufacturing cost.Simultaneously, make full use of the mine waste and except turning waste into wealth, also can reach the environmental protection purpose.
But disclosing the mine waste that is grouped near lithionite with one-tenth in CN1091399A is main raw material, accounts for 80%～100% of prescription composition.Because the waste ratio that accounts in mine is too high in the prescription, the suitable difficulty of the adjustment of each component content sometimes, even can't be adjusted in the prescription.Therefore, each component content can become along with each component content in the waste in the goods.So the one-tenth of goods is grouped into and becomes unstable, this becomes the rerum natura and the instability quality reason of goods.
Also have, disclose to contain lithium minerals, account for 50%～81% of prescription composition, can reduce melting temperature (Tm) and crystallized temperature simultaneously, therefore, can reduce manufacturing cost as main raw material at CN1101015A.But, in the CN1101015A application, the content of claim 1 is: a kind of devitrified glass, during its raw material admixtion is formed, contain raw materials such as lithium minerals, titanium oxide, it is characterized in that the raw material admixtion contains that lithium minerals accounts for 50～81% weight parts, titanium oxide accounts for 0.5～4% weight part in forming, in raw material admixtion chemical constitution, Li
2The content of O is 0.5～8.1% weight part.
According to the document record, containing lithium minerals has 4 kinds, and it is quite big that it forms difference as shown in table 2.The content of the request item 1 of patent request scope is among the CN1101015A: contain during the raw material admixtion is formed that lithium minerals accounts for 50～81% weight parts, titanium oxide accounts for 0.5～4% weight part, Li
2The content of O is 0.5～8.1% weight part.Such expression mode can't be formed by its prescription of clear and definite standard.Moreover lithium minerals accounts for 50～81% weight parts and table 2 data is calculated and can be obtained according to containing: the Li that comes self-contained lithium minerals in the prescription
2The content of O is 2.245～6.869% weight parts of prescription.Obviously, come the Li of self-contained lithium minerals in the prescription
2Minimum 2.245% weight part of the content of O for prescription.0.5% weight part of this numerical value disclosed patent request scope in the CN1101015A exists contradiction each other.
[table 2]
The chemical constitution (wt%) that contains lithium minerals
| Composition | Lithionite | Triphane | amblygonite | Petalite |
| SiO 2 | 52.89 | 62.91 | 5.16 | 76.16 |
| Al 2O 3 | 26.77 | 28.42 | 22.96 | 17.21 |
| Li 2O | 4.65 | 6.78 | 8.48 | 4.49 |
| Na 2O | 0.13 | 0.46 | 1.63 | 0.16 |
| K 2O | 10.33 | 0.69 | 0.30 | 0.39 |
| MgO | 0.31 | 0.13 | 0.24 | |
| CaO | 0.92 | 0.11 | 0.15 | 0.21 |
| F | 3.68 | 2.67 | 0.11 | |
| MnO 2 | 0.59 | |||
| Fe 2O 3And/or FeO | 0.19 | 0.53 | 0.019 | 0.18 |
| P 2O 5 | 54.42 | |||
| Scorching hot decrement | 0.66 | 0.28 | 4.08 | 0.80 |
In addition, the cited embodiment of CN1101015A consists of:
Composition of raw materials (wt%):
Lithium aluminosilicate ore deposit 78% albite, 10.25% Quilonum Retard 7.7%
Titanium oxide 1.65% calcium oxide 1% magnesium oxide 1.4%
Chemical constitution (wt%)
SiO
2 68.02％ Al
2O
3 17.68％ Li
2O 4.10％ CaO 1.47％
MgO 2.89％ Fe
2O
3 0.17％ Na
2O 0.53％ K
2O 0.11％
TiO
21.74% burns loses 3.29%
If with the SiO in the chemical constitution (wt%) that contains lithium minerals shown in the table 2
2Content is as judgment standard, and can judge immediate with the foregoing description is petalite, therefore, if hypothesis the foregoing description employed lithium aluminosilicate ore deposit is a petalite, then in the prescription from the SiO of petalite
2Content is 59.40wt%.In addition, according to the document record, albite consists of SiO
268.7wt%, Al
2O
319.5wt%, Na2O 11.8wt%.Therefore, in the Example formulations from the SiO of albite
2Be 7.04wt%.So, from the SiO of petalite and albite
2Be 59.40wt%+7.04wt%=66.44wt%.Can get Al with this method reckoning
2O
3Be 15.42wt%, Li
2O 6.62wt%.Obviously, the SiO in the composition of raw materials chemical constitution among this result and the embodiment
2, Al
2O
3, Li
2O content does not meet.
Suppose that the employed lithium aluminosilicate of the foregoing description ore deposit is a lithionite, then from the SiO of lithionite
2, Al
2O
3, Li
2O content is respectively 41.25wt%, 20.88wt%, 3.63wt%, from the SiO of albite
2Content is 7.04wt%, Al
2O
3Content is 2.0wt%, from the Li of Quilonum Retard
2O is 3.07wt%, according to this SiO in the calculation result composition of raw materials chemical constitution
2, Al
2O
3, Li
2O content is respectively 48.29wt%, 22.88wt%, 6.7wt%.Obviously, the SiO in the composition of raw materials chemical constitution among this result and the embodiment
2, Al
2O
3, Li
2O content does not meet.
Suppose that the lithium aluminosilicate ore deposit that the foregoing description uses is triphane, then use identical method of calculation, can obtain the SiO in the composition of raw materials chemical constitution
2, Al
2O
3, Li
2O content is respectively 56.16wt%, 24.17wt%, 8.36wt%.Obviously, the SiO in the composition of raw materials chemical constitution among this result and the embodiment
2, Al
2O
3, Li
2O content does not meet yet.
In sum, can it is evident that, if there is not the one-tenth in standard lithium aluminosilicate ore deposit to be grouped into, the SiO in the uncontrollable composition of raw materials chemical constitution
2, Al
2O
3, Li
2O ... become the content of branch Deng each.Therefore, can judge, in the disclosed content of CN1101015A, if the one-tenth that does not have standard to contain lithium minerals is grouped into, in manufacturing processed with the SiO in the uncontrollable composition of raw materials chemical constitution
2, Al
2O
3, Li
2Each becomes the content of branch O etc.Also therefore make the one-tenth of goods be grouped into and to stablize.Because become to be grouped into and can't to be difficult to provide stabile physics, chemical property by stable goods, so, be difficult to keep stable product property.
Summary of the invention
The present invention is in order to solve above-mentioned each problem in the past, to have proposed six purposes of the present invention, that is
First purpose of the present invention is: providing can mass-produced Li
2O-Al
2O
3-SiO
2-MgO-K
2O-F is a crystallite glass.
Second purpose of the present invention is: provide the crystalline growth temperature lower Li
2O-Al
2O
3-SiO
2-MgO-K
2O-F is a microcrystalline glass, and this microcrystalline glass has superior thermal and physical strength.
The 3rd purpose of the present invention is: a kind of low cost of manufacture is provided, is applicable to the Li as material of construction
2O-Al
2O
3-SiO
2-MgO-K
2O-F is a microcrystalline glass.
The 4th purpose of the present invention is: provide that a kind of one-tenth is grouped into, the rerum natura of goods and chemical property, product property etc. all stablize it, with lithionite or contain the Li that the lithium waste is a main raw material
2O-Al
2O
3-SiO
2-MgO-K
2O-F is crystallite glass and this microcrystalline glass.
The 5th purpose of the present invention is: Li is provided
2O-Al
2O
3-SiO
2-MgO-K
2O-F is crystallite glass and microcrystalline glass.It is characterized by from this crystallite glass minimum can separate out K (Li, Al)
3(Al, Si)
4O
10(OH, F)
2(Lepidolite), KLiMg
2Si
4O
10F
2(Tainiolite), Li
2Al
2Si
3O
10, LiAlSi
3O
8, Li
xAl
xSi
3-xO
6(Virgilite), β-LiAlSi
2O
6(β-triphane sosoloid Li
2O.Al
2O
3.nSiO
2N 〉=4), Mg
2Al
4Si
5O
18(μ-cordierite), KMg
3(Si
3AlO
10) (OH)
2(Phlogopite), KMgAlSi
4O
10(OH)
2(Leucophyllite) and ZrO
2In the microcrystalline glass that forms of any one or two or more crystallization.
The 6th purpose of the present invention is: above-mentioned Li is provided
2O-Al
2O
3-SiO
2-MgO-K
2O-F is the manufacture method of crystallite glass and this microcrystalline glass.
For reaching above purpose, the main technical schemes that the present invention takes is:
Li provided by the invention
2O-Al
2O
3-SiO
2-MgO-K
2O-F is that crystallite glass is formed
(1) has each component content SiO
250.0～65.0wt%, Al
2O
310.0～25.0wt%, MgO 6.0～15.0wt%, Li
2O 2.5～4.0wt%, Na
2O 0.5～4.0wt%, K
2O 2.1～7.5wt%, F 1.2～4.8wt%, TiO
20.1～4.0wt%, ZrO
20.1～4.0wt%, P
2O
50.5～3.0wt%, BaO 0～3.0wt%, As
2O
30.4～1.5wt%, Rb
2O 0.3～1.6wt%, Cs
2O 0.03～0.4wt%, MnO
20.06～0.7wt%, Fe
2O
30.03～0.3wt%, Sb
2O
30～1.5wt% is the Li of its feature
2O-Al
2O
3-SiO
2-MgO-K
2O-F is a crystallite glass.
(2) Li of above-mentioned (1) record
2O-Al
2O
3-SiO
2-MgO-K
2O-F is a crystallite glass, it is characterized by, and adopting each component content is SiO
250.0～60.0wt%, Al
2O
320.0～30.0wt%, MgO 0～0.5wt%, Li
2O 3.5～5.0wt%, Na
2O 1.0～3.0wt%, K
2O 7.0～9.0wt%, F 4.0～6.0wt%, Rb
2O 1.0～2.0wt%, Cs
2O 0.1～0.5wt%, MnO
20.2～0.8wt%, Fe
2O
30.1 the lithionite of～0.3wt% or contain the lithium waste, and account for 30～80wt% that prescription is formed as main raw material.
Li of the present invention
2O-Al
2O
3-SiO
2-MgO-K
2O-F is a microcrystalline glass
(3) has each component content SiO
250.0～65.0wt%, Al
2O
310.0～25.0wt%, MgO 6.0～15.0wt%, Li
2O 2.5～4.0wt%, Na
2O0.5～4.0wt%, K
2O 2.1～7.5wt%, F 1.2～4.8wt%, TiO
20.1～4.0wt%, ZrO
20.1～4.0wt%, P
2O
50.5～3.0wt%, BaO 0～3.0wt%, As
2O
30.4～1.5wt%, Rb
2O 0.3～1.6wt%, Cs
2O 0.03～0.4wt%, MnO
20.06～0.7wt%, Fe
2O
30.03～0.3wt%, Sb
2O
30～1.5wt% is the Li of its feature
2O-Al
2O
3-SiO
2-MgO-K
2O-F is a microcrystalline glass.
(4) Li of above-mentioned (3) record
2O-Al
2O
3-SiO
2-MgO-K
2O-F is a microcrystalline glass, it is characterized by, and adopting each component content is SiO
250.0～60.0wt%, Al
2O
320.0～30.0wt%, MgO 0～0.5wt%, Li
2O 3.5～5.0wt%, Na
2O 1.0～3.0wt%, K
2O 7.0～9.0wt%, F 4.0～6.0wt%, Rb
2O 1.0～2.0wt%, Cs
2O 0.1～0.5wt%, MnO
20.2～0.8wt%, Fe
2O
30.1 the lithionite of～0.3wt% or contain the lithium waste, and account for 30～80wt% that prescription is formed as main raw material.
(5) Li of (1) and (2) record
2O-Al
2O
3-SiO
2-MgO-K
2O-F is a crystallite glass, it is characterized by, the minimum glass of crystallite from then on separate out K (Li, Al)
3(Al, Si)
4O
10(OH, F)
2(Lepidolite), KLiMg
2Si
4O
10F
2(Tainiolite), Li
2Al
2Si
3O
10, LiAlSi
3O
8, LixAlxSi
3-xO
6(Virgilite), β-LiAlSi
2O
6(β-triphane sosoloid Li
2O.Al
2O
3NSiO
2N 〉=4), Mg
2Al
4Si
5O
18(μ-cordierite), KMg
3(Si
3AlO
10) (OH)
2(Phlogopite), KMgAlSi
4O
10(OH)
2(Leucophyllite) and ZrO
2In any one or two kinds of crystallizations and become Li
2O-Al
2O
3-SiO
2-MgO-K
2O-F is a microcrystalline glass.
Li of the present invention
2O-Al
2O
3-SiO
2-MgO-K
2O-F is the manufacture method of crystallite glass, it is characterized in that concrete processing step is:
1. prescription is consisted of SiO
250.0～65.0wt%, Al
2O
310.0～25.0wt%, MgO 6.0～15.0wt%, Li
2O 2.5～4.0wt%, Na
2O 0.5～4.0wt%, K
2O 2.1～7.5wt%, F 1.2～4.8wt%, TiO
20.1～4.0wt%, ZrO
20.1～4.0wt%, P
2O
50.5～3.0wt%, BaO 0～3.0wt%, As
2O
30.4～1.5wt%, Rb
2O 0.3～1.6wt%, Cs
2O 0.03～0.4wt%, MnO
20.06～0.7wt%, Fe
2O
30.03～0.3wt%, Sb
2O
3The A processing procedure of the frit uniform mixing of 0～1.5wt%.
2. the B processing procedure that dissolved of the frit that the A processing procedure is obtained.
3. the glass that the B processing procedure is obtained is shaped and is obtained Li
2O-Al
2O
3-SiO
2-MgO-K
2O-F is the C processing procedure of crystallite glass.
The Li of above-mentioned record
2O-Al
2O
3-SiO
2-MgO-K
2O-F is in the manufacture method of crystallite glass, and the composition preparation of step (1) is characterised in that:
(a) be SiO with each component content
250.0～60.0wt%, Al
2O
320.0～30.0wt%, MgO 0～0.5wt%, Li
2O 3.5～5.0wt%, Na
2O 1.0～3.0wt%, K
2O 7.0～9.0wt%, F 4.0～6.0wt%, Rb
2O 1.0～2.0wt%, Cs
2O 0.1～0.5wt%, MnO
20.2～0.8wt%, Fe
2O
30.1 the lithionite of～0.3wt% or contain lithium waste raw material and evenly stir.
(b) evenly stir the lithionite of finishing or contain the raw material composition that adds other in the lithium waste raw material in (a) process, make each component content of frit prescription become SiO
250.0～65.0wt%, Al
2O
310.0～25.0wt%, MgO 6.0～15.0wt%, Li
2O 2.5～4.0wt%, Na
2O 0.5～4.0wt%, K
2O 2.1～7.5wt%, F 1.2～4.8wt%, TiO
20.1～4.0wt%, ZrO
20.1～4.0wt%, P
2O
50.5～3.0wt%, BaO 0～3.0wt%, As
2O
30.4～1.5wt%, Rb
2O 0.3～1.6wt%, Cs
2O 0.03～0.4wt%, MnO
20.06～0.7wt%, Fe
2O
30.03～0.3wt%, Sb
2O
30～1.5wt%.The frit that mixes is evenly stirred.
Li of the present invention
2O-Al
2O
3-SiO
2-MgO-K
2O-F is the manufacture method of microcrystalline glass, it is characterized in that concrete preparation steps is:
1. prescription is consisted of SiO
250.0～65.0wt%, Al
2O
310.0～25.0wt%, MgO 6.0～15.0wt%, Li
2O 2.5～4.0wt%, Na
2O 0.5～4.0wt%, K
2O 2.1～7.5wt%, F 1.2～4.8wt%, TiO
20.1～4.0wt%, ZrO
20.1～4.0wt%, P
2O
50.5～3.0wt%, BaO0～3.0wt%, As
2O
30.4～1.5wt%, Rb
2O 0.3～1.6wt%, Cs
2O 0.03～0.4wt%, MnO
20.06～0.7wt%, Fe
2O
30.03～0.3wt%, Sb
2O
3The A processing procedure of the frit uniform mixing of 0～1.5wt%.
2. the B processing procedure that dissolved of the frit that the A processing procedure is obtained.
3. the glass that the B processing procedure is obtained is shaped and is obtained Li
2O-Al
2O
3-SiO
2-MgO-K
2O-F is the C processing procedure of crystallite glass.
4. the Li that the C processing procedure is obtained
2O-Al
2O
3-SiO
2-MgO-K
2The crystallization thermal treatment and obtain Li in addition of O-F crystallite glass
2O-Al
2O
3-SiO
2-MgO-K
2O-F is the D processing procedure of microcrystalline glass.
Li recited above
2O-Al
2O
3-SiO
2-MgO-K
2O-F is in the manufacture method of microcrystalline glass, and the composition preparation of step (1) is characterised in that:
(a) be SiO with each component content earlier
250.0～60.0wt%, Al
2O
320.0～30.0wt%, MgO 0～0.5wt%, Li
2O 3.5～5.0wt%, Na
2O 1.0～3.0wt%, K
2O 7.0～9.0wt%, F 4.0～6.0wt%, Rb
2O 1.0～2.0wt%, Cs
2O 0.1～0.5wt%, MnO
20.2～0.8wt%, Fe
2O
30.1 the lithionite of～0.3wt% or contain lithium waste raw material and evenly stir.
(b) evenly stir the lithionite of finishing or contain the raw material composition that adds other in the lithium waste raw material in (a) process, make each component content of frit prescription become SiO
250.0～65.0wt%, Al
2O
310.0～25.0wt%, MgO 6.0～15.0wt%, Li
2O 2.5～4.0wt%, Na
2O 0.5～4.0wt%, K
2O 2.1～7.5wt%, F 1.2～4.8wt%, TiO
20.1～4.0wt%, ZrO
20.1～4.0wt%, P
2O
50.5～3.0wt%, BaO 0～3.0wt%, As
2O
30.4～1.5wt%, Rb
2O 0.3～1.6wt%, Cs
2O 0.03～0.4wt%, MnO
20.06～0.7wt%, Fe
2O
30.03～0.3wt%, Sb
2O
30～1.5wt%.Deployed frit is evenly stirred.
Can provide a kind of Li according to content of the present invention
2O-Al
2O
3-SiO
2-MgO-K
2O-F is crystallite glass and microcrystalline glass, and the manufacture method of this crystallite glass and microcrystalline glass.Via the present invention, the component content in the composition of raw materials chemical constitution is controlled easily, the one-tenth of goods is grouped into can stabilization, and its result can make crystallite glass and microcrystalline glass have stabile physics, chemical property.
Describe the present invention below in detail
About crystallite glass of the present invention and microcrystalline glass, limit each component content and the reasons are as follows:
SiO
2Content be 50.0～65.0wt%, better content is 55.0～60.0wt%.SiO
2Content if be lower than 50.0wt% then the easy devitrification of glass, difficulty is shaped.On the other hand, SiO
2Content if be higher than 65.0wt%, then the glass melting temperature uprises, and is unfavorable for operation.
Al
2O
3Content be 10.0～25.0wt%, better content is 15.0～20.0wt%.Al
2O
3Content if be lower than 10.0wt%, crystallization difficulty then, on the other hand, Al
2O
3Content if be higher than 25.0wt%, the then easy devitrification of glass, and meltbility descends.
The content of MgO is 6.0～15.0wt%, and better content is 8.0～14.0wt%.The content of MgO is if be lower than 6.0wt%, and then dissolving of glass becomes difficulty, and is not easy crystallization.On the other hand, the content of MgO is if be higher than 15.0wt%, and then easy devitrification of glass and shaping are difficult.
Li
2The content of O is 2.5～4.0wt%, and better content is 3.0～4.0wt%.Li
2The content of O then contains Li if be lower than 2.5wt%
2The O crystalline is separated out and is become difficulty.On the other hand, Li
2The content of O is if be higher than 4.0wt%, and then glass becomes easy devitrification, and difficulty is shaped.
Na
2The content of O is 0.5～4.0wt%, and better content is 1.5～3.0wt%.Na
2The content of O is if be lower than 0.5wt%, and then dissolving of glass becomes difficulty.Na
2The content of O is if be higher than 4.0wt%, then the chemical durability variation of microcrystalline glass.
K
2The content of O is 2.1～7.5wt%, and better content is 3.0～6.0wt%.The content of K2O is if be lower than 2.1wt%, and then dissolving of glass becomes difficulty, and contains K
2Separating out of O crystallization becomes difficulty.K
2The content of O is if be higher than 7.5wt%, and then glass becomes easy devitrification, shaping difficulty, and the chemical durability variation of microcrystalline glass.
Forming the F that agent is added as nucleus, is that fusing assistant also is the crystallization constituent, simultaneously, has and reduces the effect that crystallization is separated out temperature and promoted crystalline growth.Its content is 1.2～4.8wt%, and better content is 1.2～2.5wt%.The content of F then contains separating out of F crystallization and becomes difficulty if is lower than 1.2wt%.The content of F is if be higher than 4.8wt%, and then glass becomes easy devitrification, difficulty is shaped.
Form the TiO that agent is added as nucleus
2Content is 0.1～4.0wt%, and better content is 1.0～3.0wt%.TiO
2Content if be lower than 0.1wt%, then form the poor effect of agent, TiO as nucleus
2Content if be higher than 4.0wt%, then glass becomes easy devitrification, and microcrystalline glass that impurity takes place easily is painted.
Form the ZrO that agent is added as nucleus
2Content is 0.1～4.0wt%, and better content is 1.5～3.0wt%.ZrO
2Content if be lower than 0.1wt%, then form the poor effect of agent, ZrO as nucleus
2Content if be higher than 4.0wt%, then glass melting becomes difficulty, simultaneously, glass becomes easy devitrification.
P
2O
5Form agent ZrO for nucleus
2Separating property of the infusibility effect that improves significantly.P
2O
5Content be 0.5～3.0wt%, better content is 1.0～2.0wt%, P
2O
5Content if be lower than 0.5wt%, then improve DeGrain.P
2O
5Content if be higher than 3.0wt%, then phase-splitting and be difficult to obtain uniform glass easily.
BaO has the composition of the glass melting of improvement, and is still, strong for the aggressiveness of refractory body.The addition of BaO is in the 3.0wt%.
As the finings interpolation
2O
3Content is 0.4～1.5wt%, and better content is 0.5～1.0wt%.As
2O
3Content if be lower than 0.4wt%, then as the poor effect of finings.As
2O
3Content if be higher than 1.5wt%, then environmental pollution is more serious.
Sb
2O
3With As
2O
3Be all finings, content is 0～1.5wt%.With As
2O
3The same, environment there is detrimentally affect, simultaneously, clarifying effect does not have As
2O
3Good, and cause that easily impurity is painted.Sb
2O
3Content be in the 1.5wt%.
Below, further specify the manufacture method of crystallite glass of the present invention and microcrystalline glass.
At first, be SiO with weight percent
250.0～65.0wt%, Al
2O
310.0～25.0wt%, MgO 6.0～15.0wt%, Li
2O 2.5～4.0wt%, Na
2O 0.5～4.0wt%, K
2O 2.1～7.5wt%, F 1.2～4.8wt%, TiO
20.1～4.0wt%, ZrO
20.1～4.0wt%, P
2O
50.5～3.0wt%, BaO 0～3.0wt%, As
2O
30.4～1.5wt%, Rb
2O 0.3～1.6wt%, Cs
2O 0.03～0.4wt%, MnO
20.06～0.7wt%, Fe
2O
30.03～0.3wt%, Sb
2O
3The frit of 0～1.5wt% composition is mixed, is evenly stirred.With lithionite or contain the lithium waste and use as main raw material.
As lithionite or contain the lithium waste, the content of each composition is with SiO
250.0～60.0wt%, Al
2O
320.0～30.0wt%, MgO 0～0.5wt%, Li
2O 3.5～5.0wt%, Na
2O 1.0～3.0wt%, K
2O 7.0～9.0wt%, F 4.0～6.0wt%, Rb
2O 1.0～2.0wt%, Cs
2O 0.1～0.5wt%, MnO
20.2～0.8wt%, Fe
2O
30.1 the composition of～0.3wt% is preferable.This lithionite or the usage quantity that contains the lithium waste be that the material composition weight percent forms 30～80%, preferable content is 30～50wt%, better content is 30～40wt%.Lithionite or contain the addition of lithium waste if be lower than 30wt% then economic benefit is not good, addition becomes difficulty if be higher than the adjustment that 80wt% then forms.
Secondly, with the in addition fusion of the frit that mixes, melt temperature is 1450～1600 ℃, and preferable melt temperature is 1500～1600 ℃, and the fusion time is 5～20 hours, and the preferable fusion time is 5～15 hours.
[0043]
Secondly, melten glass is configured as crystallite glass,, makes its crystallization and become the microcrystalline glass that has high mechanical strength and present beautiful natural marble apperance again with the in addition thermal treatment of crystallite glass.Heat treated heat-up rate is 1～10 ℃/minute, and preferable heat-up rate is 2～5 ℃/minute.Held temperature 1～4 hour at 700～1000 ℃, be preferably 800～900 ℃ and held temperature 1～4 hour, preferable to hold temperature be 1～2 hour the time.
Embodiment
By the description of embodiment, further illustrating substantive distinguishing features of the present invention and obvious improvement, but the present invention only is confined to embodiment.
In each embodiment, use contain the lithium waste composed as follows shown in:
SiO
2 52.46wt％、Al
2O
3 22.89wt％、Li
2O 4.36wt％、F 5.01wt％、Na
2O 1.54wt％、K
2O 8.25wt％、Fe
2O
3 0.195wt％、MnO
2 0.333wt％、Rb
2O 1.21wt％、Cs
2O 0.21wt％。With respect to the raw material composition, represent with weight percent, handle the % of prescription shown in the designation as following each and adjust the addition that contains the lithium waste.
The weight percentage that test portion shown in the table 1 numbering 1-9 contains the lithium waste with respect to use is 30%, 35%, 40%, 45%, 50%, 55%, 60%, 70% and 80% 9 kind.Full and accurate as follows:
Embodiment 1
The composition that frit is mixed into test portion shown in the table 1 numbering 1 is placed in the crucible, at 1550 ℃ with the frit fusion and make the tabular test piece of 250mm * 250mm * 18mm.After the cooling, sheet glass is put into heat treatment furnace, speed with 90 ℃/hr after 200 ℃ are held warm 10min is warming up to 800 ℃, speed with 60 ℃/hr after 800 ℃ are held warm 20min is warming up to 900 ℃, speed with 60 ℃/hr after 900 ℃ are held warm 20min is warming up to 1000 ℃, and stove is cold afterwards to hold warm 1hr at 1000 ℃.As a result, separate out K (Li, Al)
3(Al, Si)
4O
10(OH, F)
2(Lepidolite), KLiMg
2Si
4O
10F
2(Tainiolite), ZrO
2Deng crystallization and become microcrystalline glass.The beautiful appearance of microcrystalline glass plate, color are white.
Embodiment 2
The composition that frit is mixed into test portion shown in the table 1 numbering 2 is placed in the crucible, at 1550 ℃ with the frit fusion and make the tabular test piece of 250mm * 250mm * 18mm.After the cooling, sheet glass is put into heat treatment furnace, speed with 90 ℃/hr after 200 ℃ are held warm 10min is warming up to 800 ℃, speed with 60 ℃/hr after 800 ℃ are held warm 20min is warming up to 900 ℃, speed with 60 ℃/hr after 900 ℃ are held warm 20min is warming up to 1000 ℃, and stove is cold afterwards to hold warm 1hr at 1000 ℃.As a result, separate out K (Li, Al)
3(Al, Si)
4O
10(OH, F)
2(Lepidolite), KLiMg
2Si
4O
10F
2(Tainiolite) etc. crystallization and become microcrystalline glass.The beautiful appearance of microcrystalline glass plate, color are beige.
Embodiment 3
The composition that frit is mixed into test portion shown in the table 1 numbering 3 is placed in the crucible, at 1580 ℃ with the frit fusion and make the tabular test piece of 250mm * 250mm * 18mm.Afterwards, sheet glass is put into heat treatment furnace, speed with 120 ℃/hr after 500 ℃ are held warm 10min is warming up to 620 ℃, speed with 90 ℃/hr after 620 ℃ are held warm 30min is warming up to 740 ℃, speed with 90 ℃/hr after 740 ℃ are held warm 40min is warming up to 850 ℃, and stove is cold afterwards to hold warm 40min at 850 ℃.As a result, separate out KLiMg
2Si
4O
10F
2(Tainiolite), ZrO
2, Li
2Al
2Si
3O
10Deng crystallization and become microcrystalline glass.The beautiful appearance of microcrystalline glass plate, color are white.
Embodiment 4
The composition that frit is mixed into test portion shown in the table 1 numbering 4 is placed in the crucible, at 1580 ℃ with the frit fusion and make the tabular test piece of 250mm * 250mm * 18mm.Afterwards, sheet glass is put into heat treatment furnace, the speed with 120 ℃/hr after 560 ℃ are held warm 30min is warming up to 650 ℃, and the speed with 90 ℃/hr after 650 ℃ are held warm 40min is warming up to 760 ℃, and stove is cold afterwards to hold warm 40min at 760 ℃.As a result, separate out K (Li, Al)
3(Al, Si)
4O
10(OH, F)
2(Lepidolite), KLiMg
2Si
4O
10F
2(Tainiolite), ZrO
2, LiAlSi
3O
8Deng crystallization and become microcrystalline glass.The beautiful appearance of microcrystalline glass plate, color are grey.
Embodiment 5
The composition that frit is mixed into test portion shown in the table 1 numbering 5 is placed in the crucible, at 1560 ℃ with the frit fusion and make the tabular test piece of 250mm * 250mm * 18mm.Afterwards, sheet glass is put into heat treatment furnace, the speed with 90 ℃/hr after 620 ℃ are held warm 30min is warming up to 650 ℃, and the speed with 90 ℃/hr after 650 ℃ are held warm 40min is warming up to 830 ℃, and stove is cold afterwards to hold warm 40min at 830 ℃.As a result, separate out K (Li, Al)
3(Al, Si)
4O
10(OH, F)
2(Lepidolite), ZrO
2, LiAlSi
3O
8Deng crystallization and become microcrystalline glass.The beautiful appearance of microcrystalline glass plate, color are white.
Embodiment 6
The composition that frit is mixed into test portion shown in the table 1 numbering 6 is placed in the crucible, at 1560 ℃ with the frit fusion and make the tabular test piece of 250mm * 250mm * 18mm.Afterwards, sheet glass is put into heat treatment furnace, speed with 180 ℃/hr after 550 ℃ are held warm 20min is warming up to 620 ℃, speed with 120 ℃/hr after 620 ℃ are held warm 20min is warming up to 660 ℃, speed with 90 ℃/hr after 660 ℃ are held warm 30min is warming up to 880 ℃, and stove is cold afterwards to hold warm 40min at 880 ℃.As a result, separate out KLiMg
2Si
4O
10F
2(Tainiolite), ZrO
2, LiAlSi
3O
8Deng crystallization and become microcrystalline glass.The beautiful appearance of microcrystalline glass plate, color are white.
Embodiment 7
The composition that frit is mixed into test portion shown in the table 1 numbering 7 is placed in the crucible, at 1600 ℃ with the frit fusion and make the tabular test piece of 250mm * 250mm * 18mm.Afterwards, sheet glass is put into heat treatment furnace, the speed with 90 ℃/hr after 560 ℃ are held warm 30min is warming up to 650 ℃, and the speed with 100 ℃/hr after 650 ℃ are held warm 1hr is warming up to 850 ℃, and stove is cold afterwards to hold warm 1hr at 850 ℃.As a result, separate out Li
xAl
xSi
3-xO
6(Virgilite), β-LiAlSi
2O
6(β-triphane sosoloid), Mg
2Al
4Si
5O
18(the crystallization that μ-cordierite) waits and become microcrystalline glass.The beautiful appearance of microcrystalline glass plate, color are dark brown.
Embodiment 8
The composition that frit is mixed into test portion shown in the table 1 numbering 8 is placed in the crucible, at 1600 ℃ with the frit fusion and make the tabular test piece of 250mm * 250mm * 18mm.Afterwards, sheet glass is put into heat treatment furnace, the speed with 90 ℃/hr after 560 ℃ are held warm 30min is warming up to 650 ℃, and the speed with 100 ℃/hr after 650 ℃ are held warm 1hr is warming up to 850 ℃, and stove is cold afterwards to hold warm 1hr at 850 ℃.As a result, separate out Li
xAl
xSi
3-xO
6(Virgilite), Mg
2Al
4Si
5O
18(μ-cordierite), KMg
3(Si
3AlO
10) (OH)
2(Phlogopite) etc. crystallization and become microcrystalline glass.The beautiful appearance of microcrystalline glass plate, color are beige.
Embodiment 9
The composition that frit is mixed into test portion shown in the table 1 numbering 9 is placed in the crucible, at 1600 ℃ with the frit fusion and make the tabular test piece of 250mm * 250mm * 18mm.Afterwards, sheet glass is put into heat treatment furnace, the speed with 90 ℃/hr after 560 ℃ are held warm 30min is warming up to 650 ℃, and the speed with 100 ℃/hr after 650 ℃ are held warm 1hr is warming up to 850 ℃, and stove is cold afterwards to hold warm 1hr at 850 ℃.As a result, separate out Li
xAl
xSi
3-xO
6(Virgilite), Mg
2Al
4Si
5O
18(μ-cordierite), KMgAlSi
4O
10(OH)
2(Leucophyllite) etc. crystallization and become microcrystalline glass.The beautiful appearance of microcrystalline glass plate, color are beige.
Be convenient contrast, the spy lists in table 1 with the described content of above embodiment 1-9, and following crystallization represented respectively in each crystallization phases A～J code name shown in the table:
A：K(Li，Al)
3(Al，Si)
4O
10(OH，F)
2(Lepidolite)
B：KLiMg
2Si
4O
10F
2(Tainiolite)
C：ZrO
2
D：Li
2Al
2Si
3O
10
E：LiAlSi
3O
8
F：Li
xAl
xSi
3-xO
6(Virgilite)
G: β-LiAlSi
2O
6(β-triphane sosoloid)
H：Mg
2Al
4Si
5O
18(μ-cordierite)
I：KMg
3(Si
3AlO
10)(OH)
2(Phlogopite)
J：KMgAlSi
4O
10(OH)
2(Leucophyllite)
Table 1
| Test portion | 1 | 2 | 3 | 4 | 5 | 6 | 7 | 8 | 9 |
| SiO 2 | 50.0 | 50.0 | 50.0 | 50.0 | 52.0 | 58.5 | 56.0 | 53.4 | 50.0 |
| Al 2O 3 | 14.0 | 14.0 | 14.0 | 17.0 | 18.1 | 12.6 | 18.0 | 16.9 | 18.5 |
| MgO | 9.0 | 9.0 | 14.5 | 9.0 | 9.0 | 9.0 | 6.0 | 8.5 | 8.3 |
| Li 2O | 4.0 | 4.0 | 4.0 | 2.5 | 3.5 | 3.5 | 3.5 | 3.5 | 3.5 |
| Na 2O | 4.0 | 4.0 | 4.0 | 4.0 | 2.0 | 2.0 | 1.5 | 1.5 | 1.5 |
| K 2O | 7.0 | 7.0 | 4.0 | 7.0 | 5.0 | 5.0 | 5.0 | 5.8 | 7.0 |
| F | 4.0 | 4.0 | 4.0 | 4.0 | 4.8 | 3.8 | 3.0 | 3.5 | 4.2 |
| TiO 2 | 0.1 | 3.5 | 0.1 | 0.1 | 0.1 | 0.1 | 1.9 | 1.9 | 1.8 |
| ZrO 2 | 3.5 | 0.1 | 3.5 | 3.5 | 3.5 | 3.5 | 2.4 | 2.3 | 2.2 |
| P 2O 5 | 0.7 | 0.7 | 0.7 | 0.7 | 0.5 | 0.5 | 1.0 | 0.9 | 0.9 |
| BaO | 2.5 | 2.5 | |||||||
| As 2O 3 | 0.4 | 0.52 | 0.4 | 0.52 | 0.4 | 0.4 | 0.52 | 0.43 | 0.53 |
| Sb 2O 3 | 0.22 | 0.03 | 0.11 | 0.18 | |||||
| Rb 2O | 0.36 | 0.42 | 0.48 | 0.54 | 0.61 | 0.67 | 0.73 | 0.85 | 0.97 |
| Cs 2O | 0.06 | 0.07 | 0.08 | 0.09 | 0.11 | 0.12 | 0.13 | 0.15 | 0.17 |
| MnO 2 | 0.10 | 0.12 | 0.13 | 0.15 | 0.17 | 0.18 | 0.20 | 0.23 | 0.27 |
| Fe 2O 3 | 0.06 | 0.07 | 0.08 | 0.09 | 0.10 | 0.11 | 0.12 | 0.14 | 0.16 |
| Crystallization phases ※ | A.B.C | A.B | B.C.D | A.B.C.E | A.C.E | B.C.E | F.G.H | F.H.I | F.H.J |
| Crystalline growth temperature/time | 1000 ℃ 60min | 1000 ℃ 60min | 850℃ 40min | 760℃ 40min | 830℃ 40min | 880℃ 40min | 900℃ 60min | 850℃ 60min | 850℃ 60min |
| Outward appearance | Well | Well | Well | Well | Well | Well | Well | Well | Well |
| Tone | White | Cream colour | White | Grey | White | White | Dark brown | Cream colour | Cream colour |
Claims (14)
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2005317900 | 2005-11-01 | ||
| JP2005317900A JP4430001B2 (en) | 2005-11-01 | 2005-11-01 | Li2O-Al2O3-SiO2-MgO-K2O-F-based crystalline glass and crystallized glass, and method for producing the crystalline glass and crystallized glass |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1880251A true CN1880251A (en) | 2006-12-20 |
| CN100564296C CN100564296C (en) | 2009-12-02 |
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| CNB2006100741131A Expired - Fee Related CN100564296C (en) | 2005-11-01 | 2006-03-28 | Li2O-Al2O3-SiO2-MgO-K2O-F series microcrystalline glass, microcrystalline glass, and manufacturing method thereof |
Country Status (2)
| Country | Link |
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| JP (1) | JP4430001B2 (en) |
| CN (1) | CN100564296C (en) |
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2005
- 2005-11-01 JP JP2005317900A patent/JP4430001B2/en not_active Expired - Fee Related
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Also Published As
| Publication number | Publication date |
|---|---|
| JP2007126299A (en) | 2007-05-24 |
| CN100564296C (en) | 2009-12-02 |
| JP4430001B2 (en) | 2010-03-10 |
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