CN1880251A - Li*o-al*o*-sio*-mgo-k*o-f series microcrystalline glass, micritization glass and its production method - Google Patents

Li*o-al*o*-sio*-mgo-k*o-f series microcrystalline glass, micritization glass and its production method Download PDF

Info

Publication number
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
Authority
CN
China
Prior art keywords
glass
sio
mgo
lithionite
raw material
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
CNA2006100741131A
Other languages
Chinese (zh)
Other versions
CN100564296C (en
Inventor
许国铨
曾建梁
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
HUZHOU DAXIANG GLASS PRODUCT CO Ltd
Original Assignee
HUZHOU DAXIANG GLASS PRODUCT CO Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by HUZHOU DAXIANG GLASS PRODUCT CO Ltd filed Critical HUZHOU DAXIANG GLASS PRODUCT CO Ltd
Publication of CN1880251A publication Critical patent/CN1880251A/en
Application granted granted Critical
Publication of CN100564296C publication Critical patent/CN100564296C/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

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

Li 2O-Al 2O 3-SiO 2-MgO-K 2O-F is crystallite glass, microcrystalline glass and manufacture method thereof
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)

1. Li 2O-Al 2O 3-SiO 2-MgO-K 2O-F is a crystallite glass, it is characterized in that the weight percent of each composition that described crystallite glass is formed consists of:
SiO 250.0 Al～65.0%, 2O 310.0～25.0%, MgO 6.0～15.0%, Li 2O 2.5～4.0%, Na 2O 0.5～4.0%, K 2O 2.1～7.5%, F 1.2～4.8%, TiO 20.1 ZrO～4.0%, 20.1 P～4.0%, 2O 50.5～3.0%, BaO 0～3.0%, As 2O 30.4 Rb～1.5%, 2O 0.3～1.6%, Cs 2O 0.03～0.4%, MnO 20.06 Fe～0.7%, 2O 30.03～0.3% and Sb 2O 30～1.5%.
2. by the described Li of claim 1 2O-Al 2O 3-SiO 2-MgO-K 2O-F is a crystallite glass, it is characterized in that the weight percent of each composition that described crystallite glass is formed consists of:
SiO 255～60.0%, Al 2O 315.0～20.0%, MgO 8.0～14.0%, Li 2O 3.0～4.0%, Na 2O1.5～3.0%, K 2O 3.0～6.0%, F 1.2～2.5%, TiO 21.0 ZrO～3.0%, 21.5 P～3.0%, 2O 51.0～2.0%, BaO 0～3.0%, As 2O 30.5 Rb～1.0%, 2O 0.3～1.6%, Cs 2O 0.03～0.4%, MnO 20.06 Fe～0.7%, 2O 30.03～0.3% and Sb 2O 30～1.5%.
3. prepare Li as claimed in claim 1 or 2 2O-Al 2O 3-SiO 2-MgO-K 2O-F is the method for crystallite glass, it is characterized in that adopting lithionite or contains the lithium waste as the glass main raw material, and processing step is:
(a) be SiO with weight percentage 250.0 Al～60.0%, 2O 320.0～30.0%, MgO 0～0.5%, Li 2O 3.5～5.0%, Na 2O 1.0～3.0%, K 2O 7.0～9.0%, F 4.0～6.0%, Rb 2O 1.0～2.0%, Cs 2O 0.1～0.5%, MnO 20.2 Fe～0.8%, 2O 30.1～0.3% lithionite or contain the lithium waste and evenly stir as the main raw material of crystallite glass, its usage quantity are the frit weight percent form 30～80%;
(b) at the lithionite of the even stirring of step (a) preparation or contain and add other material compositions in the lithium waste raw material, each component content that makes the frit prescription mixes shown in claim 1 or 2 once more, stirs;
(c) prepared mixing of fusion step (b) and the frit that stirs, melt temperature is 1450～1600 ℃, the fusion time is 5～20 hours.
4. by the described Li of claim 3 2O-Al 2O 3-SiO 2-MgO-K 2O-F is the manufacture method of crystallite glass, the usage quantity that it is characterized in that lithionite or contain the lithium waste be that the component of glass raw material weight percent forms 30～50%.
5. by the described Li of claim 4 2O-Al 2O 3-SiO 2-MgO-K 2O-F is the manufacture method of crystallite glass, the usage quantity that it is characterized in that lithionite or contain the lithium waste be that the component of glass raw material weight percent forms 30～40%.
6. by the described Li of claim 3 2O-Al 2O 3-SiO 2-MgO-K 2O-F is the manufacture method of crystallite glass, it is characterized in that the described melt temperature of step (c) is 1500～1600 ℃, and the fusion time is 5～15 hours.
7. Li 2O-Al 2O 3-SiO 2-MgO-K 2O-F is a microcrystalline glass, it is characterized in that the weight percent of each composition that described microcrystalline glass is formed consists of:
SiO 250.0 Al～65.0%, 2O 310.0～25.0%, MgO 6.0～15.0%, Li 2O 2.5～4.0%, Na 2O 0.5～4.0%, K 2O 2.1～7.5%, F 1.2～4.8%, TiO 20.1 ZrO～4.0%, 20.1 P～4.0%, 2O 50.5～3.0%, BaO 0～3.0%, As 2O 30.4 Rb～1.5%, 2O 0.3～1.6%, Cs 2O 0.03～0.4%, MnO 20.06 Fe～0.7%, 2O 30.03～0.3% and Sb 2O 30～1.5%.
8. by the described Li of claim 7 2O-Al 2O 3-SiO 2-MgO-K 2O-F is a microcrystalline glass, it is characterized in that the weight percent of each composition that described microcrystalline glass is formed consists of:
SiO 255～60.0%, Al 2O 315.0～20.0%, MgO 8.0～14.0%, Li 2O 3.0～4.0%, Na 2O1.5～3.0%, K 2O 3.0～6.0%, F 1.2～2.5%, TiO 21.0 ZrO～3.0%, 21.5 P～3.0%, 2O 51.0～2.0%, BaO 0～3.0%, As 2O 30.5 Rb～1.0%, 2O 0.3～1.6%, Cs 2O 0.03～0.4%, MnO 20.06 Fe～0.7%, 2O 30.03～0.3% and Sb 2O 30～1.5%.
9. preparation is as claim 7 or 8 described Li 2O-Al 2O 3-SiO 2-MgO-K 2O-F is the method for microcrystalline glass, it is characterized in that adopting lithionite or contains the lithium waste as the glass main raw material, and processing step is:
(a) be SiO with weight percentage 250.0 Al～60.0%, 2O 320.0～30.0%, MgO 0～0.5%, Li 2O 3.5～5.0%, Na 2O 1.0～3.0%, K 2O 7.0～9.0%, F 4.0～6.0%, Rb 2O 1.0～2.0%, Cs 2O 0.1～0.5%, MnO 20.2 Fe～0.8%, 2O 30.1～0.3% lithionite or contain the lithium waste and evenly stir as the main raw material of microcrystalline glass, its usage quantity are the frit weight percent form 30～80%;
(b) at the lithionite of the even stirring of step (a) preparation or contain and add other material compositions in the lithium waste raw material, each component content that makes the frit prescription mixes shown in claim 7 or 8 once more, stirs;
(c) prepared mixing of fusion step (b) and the frit that stirs, melt temperature is 1450～1600 ℃, the fusion time is 5～20 hours.
(d) behind step (c) melt-shaping, heat-treat, heat-up rate is 1～1O ℃/minute, and temperature is 700～1000 ℃, holds temperature 1～4 hour.
10. by the described Li of claim 7 2O-Al 2O 3-SiO 2-MgO-K 2O-F is the manufacture method of microcrystalline glass, the usage quantity that it is characterized in that lithionite or contain the lithium waste be that the component of glass raw material weight percent forms 30～50%.
11. by the described Li of claim 10 2O-Al 2O 3-SiO 2-MgO-K 2O-F is the manufacture method of microcrystalline glass, the usage quantity that it is characterized in that lithionite or contain the lithium waste be that the component of glass raw material weight percent forms 30～40%.
12. by the described Li of claim 9 2O-A1 2O 3-SiO 2-MgO-K 2O-F is the manufacture method of microcrystalline glass, it is characterized in that the described melt temperature of step (c) is 1500～1550 ℃, and the fusion time is 5～15 hours.
13. by the described Li of claim 9 2O-Al 2O 3-SiO 2-MgO-K 2O-F is the manufacture method of microcrystalline glass, it is characterized in that the thermal treatment heat-up rate is 2～5 ℃/minute, and temperature is 800～900 ℃, holds warm l～2 hour.
14. by the described Li of claim 9 2O-Al 2O 3-SiO 2-MgO-K 2O-F is the manufacture method of microcrystalline glass, it is characterized in that prepared devitrified glass separate out at least K (Li, Al) 3(Al, Si) 4O 10(OH, F) 2, KLiMg 2Si 4O 10F 2, ZrO 2, Li 2Al 2Si 3O 10, LiAlSi 3O 8, Li xAl xSi 3-xO 6, β-LiAlSi 2O 6, Mg 2Al 4Si 5O 18, KMg 3(Si 3AlO 10) (OH) 2And KMgAlSi 4O 10(OH) 2Any one or two or more crystallization.
CNB2006100741131A 2005-11-01 2006-03-28 Li 2O-Al 2O 3-SiO 2-MgO-K 2O-F is crystallite glass, microcrystalline glass and manufacture method thereof Active CN100564296C (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
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
JP2005317900 2005-11-01

Publications (2)

Publication Number Publication Date
CN1880251A true CN1880251A (en) 2006-12-20
CN100564296C CN100564296C (en) 2009-12-02

Family

ID=37518643

Family Applications (1)

Application Number Title Priority Date Filing Date
CNB2006100741131A Active CN100564296C (en) 2005-11-01 2006-03-28 Li 2O-Al 2O 3-SiO 2-MgO-K 2O-F is crystallite glass, microcrystalline glass and manufacture method thereof

Country Status (2)

Country Link
JP (1) JP4430001B2 (en)
CN (1) CN100564296C (en)

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102050581A (en) * 2009-11-06 2011-05-11 湖州大享玻璃制品有限公司 MgO-Al2O3-SiO2-based crystallizable glass and crystallized glass, and manufacturing method thereof
CN105936588A (en) * 2015-02-28 2016-09-14 肖特玻璃科技(苏州)有限公司 Glass ceramics capable of being mechanically processed and chemically tempered
CN108117264A (en) * 2018-01-09 2018-06-05 湖州大享玻璃制品有限公司 Li2O-Al2O3-SiO2Based crystallized glass and its manufacturing method
CN108821598A (en) * 2015-12-03 2018-11-16 成都光明光电有限责任公司 Devitrified glass and preparation method thereof
CN108911517A (en) * 2018-07-30 2018-11-30 中国地质大学（武汉） A kind of silicate glass ceramic and preparation method thereof comprising rubidium oxide
CN112939472A (en) * 2019-12-11 2021-06-11 四川旭虹光电科技有限公司 Microcrystalline glass and preparation method and application thereof
CN113264686A (en) * 2020-02-17 2021-08-17 佛山市顺德区美的电热电器制造有限公司 Glass ceramics, panel and electric appliance
TWI751779B (en) * 2020-06-22 2022-01-01 大陸商湖州大享玻璃制品有限公司 Lio-alo-sio-based crystallized glass and lio-alo-sio-based crystalline glass
CN117088610A (en) * 2022-05-12 2023-11-21 清远南玻节能新材料有限公司 Fluorine-containing glass and preparation method and application thereof

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2010150086A (en) * 2008-12-25 2010-07-08 Tohoku Univ Method of producing crystallized glass
DE102009011850B3 (en) * 2009-03-05 2010-11-25 Schott Ag Process for the environmentally friendly melting and refining of a glass melt for a starting glass of a lithium-aluminum-silicate (LAS) glass ceramic and their use
WO2015029902A1 (en) * 2013-08-30 2015-03-05 Hoya株式会社 Glass substrate for information recording media
US10626046B2 (en) 2016-10-12 2020-04-21 Corning Incorporated Glass ceramics

Cited By (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8431498B2 (en) 2009-11-06 2013-04-30 Huzhou Ta Hsiang Glass Products Co., Ltd. MgO—Al2O3—SiO2-based crystallizable glass and crystallized glass, and manufacturing method thereof
CN102050581A (en) * 2009-11-06 2011-05-11 湖州大享玻璃制品有限公司 MgO-Al2O3-SiO2-based crystallizable glass and crystallized glass, and manufacturing method thereof
US10766807B2 (en) 2015-02-28 2020-09-08 Schott Glass Technologies (Suzhou) Co. Ltd. Machinable and chemically toughenable fluorine glass-ceramic
CN105936588A (en) * 2015-02-28 2016-09-14 肖特玻璃科技(苏州)有限公司 Glass ceramics capable of being mechanically processed and chemically tempered
CN108821598B (en) * 2015-12-03 2021-09-28 成都光明光电有限责任公司 Microcrystalline glass and preparation method thereof
CN108821598A (en) * 2015-12-03 2018-11-16 成都光明光电有限责任公司 Devitrified glass and preparation method thereof
CN108117264A (en) * 2018-01-09 2018-06-05 湖州大享玻璃制品有限公司 Li2O-Al2O3-SiO2Based crystallized glass and its manufacturing method
CN108911517A (en) * 2018-07-30 2018-11-30 中国地质大学（武汉） A kind of silicate glass ceramic and preparation method thereof comprising rubidium oxide
CN112939472A (en) * 2019-12-11 2021-06-11 四川旭虹光电科技有限公司 Microcrystalline glass and preparation method and application thereof
CN113264686A (en) * 2020-02-17 2021-08-17 佛山市顺德区美的电热电器制造有限公司 Glass ceramics, panel and electric appliance
TWI751779B (en) * 2020-06-22 2022-01-01 大陸商湖州大享玻璃制品有限公司 Lio-alo-sio-based crystallized glass and lio-alo-sio-based crystalline glass
CN113896417A (en) * 2020-06-22 2022-01-07 湖州大享玻璃制品有限公司 Li2O-Al2O3-SiO2Crystallized glass and crystallized glass
CN117088610A (en) * 2022-05-12 2023-11-21 清远南玻节能新材料有限公司 Fluorine-containing glass and preparation method and application thereof

Also Published As

Publication number Publication date
JP4430001B2 (en) 2010-03-10
CN100564296C (en) 2009-12-02
JP2007126299A (en) 2007-05-24

Similar Documents

Publication Publication Date Title
CN1880251A (en) Li*o-al*o*-sio*-mgo-k*o-f series microcrystalline glass, micritization glass and its production method
JP5848258B2 (en) Beta quartz glass ceramic and related precursor glass
CN1278973C (en) Transparent glass ceramics that can be darkened by adding vanadium oxide
KR102001265B1 (en) Beta-quartz glass ceramics with controlled transmission and methods of making same
JP2023534887A (en) Transparent β-quartz glass-ceramic with specific transmittance
JP5300474B2 (en) Preparation of β-quartz and / or β-spodumene glass ceramics, preparation of articles made from such glass ceramics, glass ceramics, glass ceramics thereof and precursor glasses
JP5088901B2 (en) β-spodumene glass ceramic material and its manufacturing process
CN108373267B (en) Glass ceramic plate
CN113015709A (en) Transparent beta-quartz glass ceramic with low lithium content
CN1699230A (en) Li2O-Al2O3-SiO2 microcrystalline glass and microcrystalline glass and making process thereof
CN110753677A (en) β -Quartz glass ceramics with high Zinc content
JP5207966B2 (en) β-quartz and / or β-spodumene glass-ceramics, precursor glasses, articles made from the glass-ceramics, preparation of the glass-ceramics and articles
KR101764953B1 (en) Lithium aluminosilicate glasses; glass-ceramics of β-quartz and/or β-spodumene; articles in said glasses and glass-ceramics; methods for obtaining the same
EP2086896A1 (en) Transparent, colorless titania-free beta-quartz glass-ceramic material
EP2086895A1 (en) Transparent, colorless low-titania beta-quartz glass-ceramic material
CN107667076B (en) Transparent, substantially colorless tin-clear LAS glass-ceramics with improved microstructure and thermal expansion properties
CN1898170A (en) Glass and glass-ceramic material, article and method of preparing the same
CN100349816C (en) Vitrifiable inorganic glass, preparation of glass-ceramic product and its described product
JP2023001207A (en) Method of manufacturing lithium aluminosilicate glass product for glass-ceramic product
CN108117264A (en) Li2O-Al2O3-SiO2Based crystallized glass and its manufacturing method
JPH08253346A (en) Opaque glass ceramic with ivory color and method for controlling its color
CN104909562B (en) A kind of environmentally friendly ruby glass of high refraction and preparation method
CN1552650A (en) Lacte glass
JP5041324B2 (en) Natural marble-like crystallized glass and method for producing the same
CN1688515A (en) Low-temperature, fluoride free fiber glass compositions and products made using same

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
C14 Grant of patent or utility model
GR01 Patent grant