CN108117264A - Li2O-Al2O3-SiO2Based crystallized glass and its manufacturing method - Google Patents
Li2O-Al2O3-SiO2Based crystallized glass and its manufacturing method Download PDFInfo
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- CN108117264A CN108117264A CN201810019314.4A CN201810019314A CN108117264A CN 108117264 A CN108117264 A CN 108117264A CN 201810019314 A CN201810019314 A CN 201810019314A CN 108117264 A CN108117264 A CN 108117264A
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- 239000011521 glass Substances 0.000 title claims abstract description 110
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 16
- 239000002994 raw material Substances 0.000 claims abstract description 45
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 28
- 229910052593 corundum Inorganic materials 0.000 claims abstract description 28
- 229910001845 yogo sapphire Inorganic materials 0.000 claims abstract description 28
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 26
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 26
- GOLCXWYRSKYTSP-UHFFFAOYSA-N arsenic trioxide Inorganic materials O1[As]2O[As]1O2 GOLCXWYRSKYTSP-UHFFFAOYSA-N 0.000 claims abstract description 20
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 19
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims abstract description 18
- 229910052681 coesite Inorganic materials 0.000 claims abstract description 17
- 229910052906 cristobalite Inorganic materials 0.000 claims abstract description 17
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 17
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 17
- 229910052682 stishovite Inorganic materials 0.000 claims abstract description 17
- 229910052905 tridymite Inorganic materials 0.000 claims abstract description 17
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 claims abstract description 16
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Inorganic materials O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000004615 ingredient Substances 0.000 claims abstract description 6
- 239000002699 waste material Substances 0.000 claims abstract description 5
- 239000000203 mixture Substances 0.000 claims description 25
- 229910008556 Li2O—Al2O3—SiO2 Inorganic materials 0.000 claims description 19
- 238000010438 heat treatment Methods 0.000 claims description 14
- FUJCRWPEOMXPAD-UHFFFAOYSA-N Li2O Inorganic materials [Li+].[Li+].[O-2] FUJCRWPEOMXPAD-UHFFFAOYSA-N 0.000 claims description 11
- XUCJHNOBJLKZNU-UHFFFAOYSA-M dilithium;hydroxide Chemical compound [Li+].[Li+].[OH-] XUCJHNOBJLKZNU-UHFFFAOYSA-M 0.000 claims description 11
- 238000002425 crystallisation Methods 0.000 claims description 7
- 230000008025 crystallization Effects 0.000 claims description 7
- 238000000034 method Methods 0.000 claims description 7
- 238000003756 stirring Methods 0.000 claims description 7
- 239000002241 glass-ceramic Substances 0.000 abstract description 21
- 239000000463 material Substances 0.000 abstract description 3
- 239000003208 petroleum Substances 0.000 abstract description 2
- 230000002265 prevention Effects 0.000 abstract description 2
- 239000002023 wood Substances 0.000 abstract description 2
- 238000001816 cooling Methods 0.000 description 16
- 239000013078 crystal Substances 0.000 description 13
- 239000006104 solid solution Substances 0.000 description 12
- CNLWCVNCHLKFHK-UHFFFAOYSA-N aluminum;lithium;dioxido(oxo)silane Chemical compound [Li+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O CNLWCVNCHLKFHK-UHFFFAOYSA-N 0.000 description 9
- 239000000155 melt Substances 0.000 description 8
- 238000012360 testing method Methods 0.000 description 8
- 238000010792 warming Methods 0.000 description 8
- 229910052644 β-spodumene Inorganic materials 0.000 description 8
- 239000000126 substance Substances 0.000 description 7
- 238000002844 melting Methods 0.000 description 6
- 230000008018 melting Effects 0.000 description 6
- 229910000500 β-quartz Inorganic materials 0.000 description 6
- 239000003086 colorant Substances 0.000 description 5
- 238000004031 devitrification Methods 0.000 description 5
- 238000001556 precipitation Methods 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000004575 stone Substances 0.000 description 4
- 239000000654 additive Substances 0.000 description 3
- 230000000996 additive effect Effects 0.000 description 3
- 235000019993 champagne Nutrition 0.000 description 3
- 239000006025 fining agent Substances 0.000 description 3
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 3
- 229910052808 lithium carbonate Inorganic materials 0.000 description 3
- 230000006641 stabilisation Effects 0.000 description 3
- 238000011105 stabilization Methods 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 2
- 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 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 229910001760 lithium mineral Inorganic materials 0.000 description 2
- 229910052670 petalite Inorganic materials 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000005352 clarification Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000009931 harmful effect Effects 0.000 description 1
- 239000003317 industrial substance Substances 0.000 description 1
- 239000006060 molten glass Substances 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000012797 qualification Methods 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 229910052642 spodumene Inorganic materials 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 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
- C03C10/00—Devitrified glass ceramics, i.e. glass ceramics having a crystalline phase dispersed in a glassy phase and constituting at least 50% by weight of the total composition
- C03C10/0018—Devitrified glass ceramics, i.e. glass ceramics having a crystalline phase dispersed in a glassy phase and constituting at least 50% by weight of the total composition containing SiO2, Al2O3 and monovalent metal oxide as main constituents
- C03C10/0027—Devitrified glass ceramics, i.e. glass ceramics having a crystalline phase dispersed in a glassy phase and constituting at least 50% by weight of the total composition containing SiO2, Al2O3 and monovalent metal oxide as main constituents containing SiO2, Al2O3, Li2O as main constituents
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
- C03B32/00—Thermal after-treatment of glass products not provided for in groups C03B19/00, C03B25/00 - C03B31/00 or C03B37/00, e.g. crystallisation, eliminating gas inclusions or other impurities; Hot-pressing vitrified, non-porous, shaped glass products
- C03B32/02—Thermal crystallisation, e.g. for crystallising glass bodies into glass-ceramic articles
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C1/00—Ingredients generally applicable to manufacture of glasses, glazes, or vitreous enamels
- C03C1/002—Use of waste materials, e.g. slags
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C10/00—Devitrified glass ceramics, i.e. glass ceramics having a crystalline phase dispersed in a glassy phase and constituting at least 50% by weight of the total composition
- C03C10/0009—Devitrified glass ceramics, i.e. glass ceramics having a crystalline phase dispersed in a glassy phase and constituting at least 50% by weight of the total composition containing silica as main constituent
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Crystallography & Structural Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Geochemistry & Mineralogy (AREA)
- Ceramic Engineering (AREA)
- Dispersion Chemistry (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Glass Compositions (AREA)
Abstract
The invention discloses a kind of Li2O‑Al2O3‑nSiO2Based crystallized glass and its manufacturing method have each quality very ingredient：SiO260.0~70.0wt%、Al2O318.0~24.0wt%、Li2O2.0~5.0wt%、TiO20.5~4.0wt%、ZrO20.5~4.0wt%、P2O50.3~2.0wt%、Na2O0~2.0wt%、K2O0~2.0wt%、MgO0.1~1.6wt%、ZnO0.5~2.0wt%、BaO0.1~1.6wt%、As2O30~1.0wt%、Sb2O30~1.0wt%、F0~1.0wt%、Fe2O30~1.0wt%、B2O30~1.0wt%、CaO0~1.0wt%、C0~1.0wt%.The glass of the present invention uses primary raw material of the discarded object containing lithium as glass, this sintered glass ceramics, can with mass production, can turn waste into wealth, manufacture it is at low cost, suitable for materials such as face-port glass before electromagnetism conditioner panel, micro-wave oven refractory slab, fire prevention glass pane, petroleum stove and wood stove.
Description
Technical field
The present invention relates to a kind of Li2O-Al2O3-SiO2Based crystallized glass and its manufacturing method belong to glass manufacture neck
Domain.
Background technology
In recent years, Li2O-Al2O3-SiO2Based crystallized glass is widely used in colored filter, image sensor is used
The high-tech product substrate such as substrate, electronic component are burnt till with refractory slab, electromagnetism conditioner panel, light part, micro-wave oven canopy
The materials such as face-port glass before plate, fire prevention glass pane, petroleum stove and wood stove.
On above-mentioned Li2O-Al2O3-SiO2Based crystallized glass, for example, each in 1~patent document of patent document, 7 grade
In a publication, the Li shown using β-quartz solid solution or β-spodumene solid solution as primary crystallization precipitation is opened2O-Al2O3-SiO2System
Sintered glass ceramics.Due to above-mentioned Li2O-Al2O3-SiO2Based crystallized glass has low coefficient of thermal expansion and high machinery by force
Degree, so thermal characteristics is good.
In addition, above-mentioned Li2O-Al2O3-SiO2Based crystallized glass raw material obtains crystallinity glass after melting, shaping.
Since the crystallinity glass is in engineering is crystallized, it can be changed by change heat treatment condition, the species of crystallization, institute is precipitated
Transparent sintered glass ceramics while being precipitated (β-quartz solid solution) and opaque can be produced by the same glass raw material formed
Sintered glass ceramics while being precipitated (β-spodumene solid solution), there is the sharp point that can be used separately according to purposes.
But above-mentioned Li was manufactured in the past2O-Al2O3-SiO2During based crystallized glass, it is often necessary to a large amount of spodumenes of use,
Petalite etc. contains lithium minerals or lithium carbonate industrial chemicals, in recent years, since Development of Electric Vehicles is rapid, lithium battery demand
Amount is quick to be increased, and lithium battery manufacturer is caused to rush to purchase lithium carbonate, is appreciated with the mad of lithium carbonate is write, spodumene, petalite etc.
It also appreciates at double containing lithium minerals, in order to reduce cost, becomes future trend using discarded object containing lithium as glass primary raw material, such as
What uses discarded object containing lithium that must be solved the problems, such as future as glass primary raw material.
[patent document 1] examined patent publication 39-21049
[patent document 2] examined patent publication 40-20182
[patent document 3] Unexamined Patent 1-308845
[patent document 4] Unexamined Patent 6-329439
[patent document 5] Unexamined Patent 9-188538
[patent document 6] special open 2001-48582
[patent document 7] special open 2001-48583
The present invention is intended to provide a kind of Li2O-Al2O3-SiO2Based crystallized glass, this sintered glass ceramics are with β-quartz
Solid solution (Li2O-Al2O3-nSiO2N≤2) or β-spodumene solid solution (Li2O-Al2O3-nSiO2N≤4) it is precipitated for primary crystallization
Li2O-Al2O3-SiO2Based crystallized glass.By being formulated the optimization with technique, sintered glass ceramics of the invention has excellent
Thermal characteristics, mechanical strength, the physics of stabilization and chemical characteristic.This sintered glass ceramics is to contain lithium discarded object as primary raw material.This
Invention also provides above-mentioned Li2O-Al2O3-SiO2The manufacturing method of based crystallized glass.
The content of the invention
Technical problems based on background technology, the present invention provide a kind of Li2O-Al2O3-SiO2Based crystallized glass,
This sintered glass ceramics is with β-quartz solid solution (Li2O-Al2O3-nSiO2N≤2) or β-spodumene solid solution (Li2O-
Al2O3-nSiO2N≤4) be primary crystallization precipitation Li2O-Al2O3-SiO2Based crystallized glass.This sintered glass ceramics has excellent
Good thermal characteristics, mechanical strength, the physics of stabilization and chemical characteristic.This sintered glass ceramics is to contain lithium discarded object as primary raw material.
The present invention also provides above-mentioned Li2O-Al2O3-SiO2The manufacturing method of based crystallized glass.
Technical scheme is as follows：
Li of the present invention2O-Al2O3-nSiO2Based crystallized glass has each quality very ingredient：SiO260.0~
70.0wt%, Al2O318.0~24.0wt%, Li2O2.0~5.0wt%, TiO20.5~4.0wt%, ZrO20.5~
4.0wt%, P2O50.3~2.0wt%, Na2O0~2.0wt%, K2O0~2.0wt%, MgO0.1~1.6wt%, ZnO0.5~
2.0wt%, BaO0.1~1.6wt%, As2O30~1.0wt%, Sb2O30~1.0wt%, F0~1.0wt%, Fe2O30~
1.0wt%, B2O30~1.0wt%, CaO0~1.0wt%, C0~1.0wt%.
Above-mentioned Li2O-Al2O3-SiO2Based crystallized glass, it is characterized in that this sintered glass ceramics is made using discarded object containing lithium
For the primary raw material of glass, each component content of the discarded object containing lithium is SiO255.0~75.0wt%, Al2O315.0~
25.0wt%, Li2O0.5~5.0wt%, TiO20~4.0wt%, ZrO20~4.0wt%, P2O50~2.0wt%, Na2O0~
2.0wt%, K2O0~2.0wt%, MgO0~2.0wt%, ZnO0~2.5wt%, BaO0~2.0wt%, As2O30~
1.0wt%, Sb2O30~1.0wt%, F0~1.0wt%, Fe2O30~1.0wt%, B2O30~1.0wt%, CaO0~
1.0wt%, C0~1.0wt%, the usage amount of discarded object containing lithium are 30~80wt% of glass formula raw material.
Above-mentioned Li2O-Al2O3-SiO2Based crystallized glass is with β-quartz solid solution (Li2O·Al2O3·nSiO2n≧2)
Or β-spodumene solid solution (Li2O·Al2O3·nSiO2N≤4) be primary crystallization precipitation Li2O·Al2O3·SiO2Tying is brilliant
Change glass.This sintered glass ceramics has superior thermal, mechanical strength, the physics of stabilization and chemical characteristic.
The Li of the present invention2O-Al2O3-SiO2The manufacturing method of based crystallized glass comprises the steps of：
(1) it is SiO by formula composition260.0~70.0wt%, Al2O318.0~24.0wt%, Li2O2.0~
5.0wt%, TiO20.5~4.0wt%, ZrO20.5~4.0wt%, P2O50.3~2.0wt%, Na2O0~2.0wt%, K2O0
~2.0wt%, MgO0.1~1.6wt%, ZnO0.5~2.0wt%, BaO0.1~1.6wt%, As2O30~1.0wt%,
Sb2O30~1.0wt%, F0~1.0wt%, Fe2O30~1.0wt%, B2O30~1.0wt%, CaO0~1.0wt%, C0~
The glass raw material of 1.0wt% uniformly mixes；
(2) glass raw material that step (1) obtains is dissolved；
(3) glass that step (2) obtains is shaped and obtains Li2O-Al2O3-SiO2It is crystallinity glass.
(4) Li for obtaining step (3)2O-Al2O3-SiO2Be crystallinity glass crystallized heat treatment obtain
Li2O-Al2O3-SiO2Based crystallized glass.
Wherein described step (1) is divided into following A-1.A-2 steps：
A-1. step：It is SiO by each component content255.0~75.0wt%, Al2O315.0~25.0wt%, Li2O0.5
~5.0wt%, TiO20~4.0wt%, ZrO20~4.0wt%, P2O50~2.0wt%, Na2O0~2.0wt%, K2O0~
2.0wt%, MgO0~2.0wt%, ZnO0~2.5wt%, BaO0~2.0wt%, As2O30~1.0wt%, Sb2O30~
1.0wt%, F0~1.0wt%, Fe2O30~1.0wt%, B2O30~1.0wt%, CaO0~1.0wt%, C0~1.0wt%
The uniform stirring of waste materials containing lithium.
A-2. step：Other raw material compositions are added in the waste materials containing lithium completed in A-1. steps uniform stirring,
Make each component content of glass raw material formula become SiO260.0~70.0wt%, Al2O318.0~24.0wt%, Li2O2.0~
5.0wt%, TiO20.5~4.0wt%, ZrO20.5~4.0wt%, P2O50.3~2.0wt%, Na2O0~2.0wt%, K2O0
~2.0wt%, MgO0.1~1.6wt%, ZnO0.5~2.0wt%, BaO0.1~1.6wt%, As2O30~1.0wt%,
Sb2O30~1.0wt%, F0~1.0wt%, Fe2O30~1.0wt%, B2O30~1.0wt%, CaO0~1.0wt%, C0~
1.0wt%.By deployed glass raw material uniform stirring.
SiO2Content for 60.0~70.0wt%, more preferably content is 62.0~68.0wt%.SiO2If content be less than
The 60.0wt% then easy devitrification of glass, forming difficulty.On the other hand, SiO2If content higher than 70.0wt%, glass melting
Temperature becomes higher, and is unfavorable for operating.
Al2O3Content for 18.0~24.0wt%, more preferably content is 20.0~23.0wt%.Al2O3If content be less than
18.0wt% then crystallizes difficulty, on the other hand, Al2O3If content higher than 24.0wt%, the easy devitrification of glass, and melting
Property decline.
Li2The content of O is 2.0~5.0wt%, and more preferably content is 3.0~4.0wt%.Li2If the content of O is less than
2.0wt%, then containing Li2The precipitation of O crystallizations becomes difficult.On the other hand, Li2If the content of O is higher than 5.0wt%, glass becomes
Easy devitrification, forming difficulty.
TiO as nucleators addition2Content is 0.5~4.0wt%, and more preferably content is 1.0~3.0wt%.TiO2
If content less than 0.5wt%, as the ineffective of nucleators, TiO2If content higher than 4.0wt%, glass
Become easy devitrification, and sintered glass ceramics easily occurs impurity and stains.
ZrO as nucleators addition2Content is 0.5~4.0wt%, and more preferably content is 1.0~3.0wt%.ZrO2
If content less than 0.5wt%, as the ineffective of nucleators, ZrO2If content higher than 4.0wt%, glass
Melting become difficult, meanwhile, glass becomes easy devitrification.
P2O5For nucleators ZrO2Difficult meltability improve significantly effect.P2O5Content for 0.3~
2.0wt%, P2O5If content less than 0.3wt%, improvement unobvious, P2O5If content higher than 2.0wt%, hold
Uniform glass is easily difficult to obtain due to split-phase.
Na2The content of O is 0.0~2.0wt%, and more preferably content is 0.2~1.0wt%.Na2If the content of O is less than
0.2wt%, then dissolving for glass become difficult.Na2If the content of O is higher than 2.0wt%, the chemical durability of sintered glass ceramics
It is deteriorated.
K2The content of O is 0.0~2.0wt%, and more preferably content is 0.2~1.0wt%.If the content of K2O is less than
0.2wt%, then dissolving for glass become difficult.If the content of K2O is higher than 2.0wt%, the chemical durability of sintered glass ceramics
It is deteriorated.
MgO be with improving dissolubility, meanwhile, can prevent the composition of bubble generation.But if the content of MgO is less than
0.1wt% then without effect, easily generates bubble.On the other hand, if the content of MgO is higher than 1.6wt%, because of coefficient of thermal expansion
The thermal characteristics that becomes larger declines.In addition, during clear crystals glass manufacture, since the presence of TiO2 can make glass slightly stain, MgO's
Content can make to stain if exceeding above range to be deepened and damages the transparency.
ZnO is also to have to improve dissolubility, meanwhile, it can prevent the composition of bubble generation.But if the content of ZnO is low
In 0.5wt% then without effect, the content of ZnO is higher than if 2.0wt%, since dielectric absorption becomes larger, for meeting during micro-wave oven
Generation hot spot causes failure.In addition, during clear crystals glass manufacture, can make to stain as MgO deepens and damages the transparency.
BaO is also to have to improve dissolubility, meanwhile, it can prevent the composition of bubble generation.But if the content of BaO is low
In 0.1wt% then without effect, for the content of BaO higher than if 1.6wt%, coefficient of thermal expansion becomes too big, meanwhile, dielectric absorption
It also becomes larger.
As fining agent addition2O3Content is 0.1~1.0wt%, As2O3If content less than 0.1wt%, make
For the ineffective of fining agent, As2O3If content higher than 1.0wt%, environmental pollution is more serious.
Sb2O3With As2O3It is all fining agent, content is 0.1~1.0wt%, with As2O3One Sample has harmful effect to environment,
Meanwhile clarification Xiao Guo No have As2O3It is good, moreover, during manufacture clear crystals glass impurity is easily caused to stain, Sb2O3Contain
If amount is higher than 1.0wt%, environmental pollution is more serious.
F、Fe2O3、B2O3, the ingredients such as CaO, C not necessarily ingredient, still, these ingredients carry out self-contained lithium discarded object, therefore,
It needs to be any limitation as, each component content is F0~1.0wt%, Fe2O30~1.0wt%, B2O30~1.0wt%, CaO0~
1.0wt%, C0~1.0wt%, beyond this scope, then product characteristic is unstable.
V2O5.CoO ... wait as colorant, colorant total content is 0.1~1.0wt%, if the total content of colorant is less than
0.1wt%, then as the ineffective of colorant, if the total content of colorant is higher than 1.0wt%, cost is too high.
The invention has the beneficial effects that：
The present invention provides a kind of Li2O-Al2O3-SiO2Based crystallized glass, using discarded object containing lithium as the main of glass
Raw material, the usage amount of discarded object containing lithium are 30~80wt% of glass formula raw material and the manufacturing method of the sintered glass ceramics；This
Raw material and technique is optimized in invention, the component content in composition of raw materials chemical composition is easy to control, product into grouping
Into that can stabilize, as a result, can make sintered glass ceramics that there is the physics of good stable, chemical property.
Specific embodiment
Embodiment 1：
Hereinafter, the crystallinity glass of the present invention and the manufacturing method of sintered glass ceramics are illustrated.
First, it is SiO by weight percent260.0~70.0wt%, Al2O318.0~24.0wt%, Li2O2.0~
5.0wt%, TiO20.5~4.0wt%, ZrO20.5~4.0wt%, P2O50.3~2.0wt%, Na2O0~2.0wt%, K2O0
~2.0wt%, MgO0.1~1.6wt%, ZnO0.5~2.0wt%, BaO0.1~1.6wt%, As2O30~1.0wt%,
Sb2O30~1.0wt%, F0~1.0wt%, Fe2O30~1.0wt%, B2O30~1.0wt%, CaO0~1.0wt%, C0~
The glass raw material of 1.0wt% compositions is concocted, uniform stirring.Lithium discarded object will be contained to use as primary raw material.
As discarded object containing lithium, the content of each composition is with SiO255.0~75.0wt%, Al2O315.0~25.0wt%,
Li2O0.5~5.0wt%, TiO20~4.0wt%, ZrO20~4.0wt%, P2O50~2.0wt%, Na2O0~2.0wt%,
K2O0~2.0wt%, MgO0~2.0wt%, ZnO0~2.5wt%, BaO0~2.0wt%, As2O30~1.0wt%, Sb2O30
~1.0wt%, F0~1.0wt%, Fe2O30~1.0wt%, B2O30~1.0wt%, CaO0~1.0wt%, C0~1.0wt%
Composition it is preferable.The usage amount of this discarded object containing lithium is the 30~80% of material composition weight percent composition, and preferable content is
30~50wt%, more preferably content are 30~40wt%.The additive amount of the discarded object containing lithium economic benefit if 30wt% is less than is bad,
Additive amount forms adjustment if 80wt% is higher than and becomes difficult.
Secondly, glass raw material concoct is melted, melting temperature be 1600~1680 DEG C, melting the time be 5~
20 it is small when.
Secondly, molten glass into crystallinity glass, then crystallinity glass is heat-treated, make its crystallize and
As the sintered glass ceramics with high mechanical properties, low-expansion coefficient.The heating rate of heat treatment is 1~30 DEG C/minute, preferably
Heating rate is 5~20 DEG C/minute, 700~1200 DEG C hold temperature 0.5~4 it is small when, preferably 800~950 DEG C to hold temperature 0.5~4 small
When, preferably hold the warm time for 2~3 it is small when.
Hereinafter, the present invention is illustrated according to embodiment.
In embodiments, formed using its discarded object containing lithium as follows：SiO263.5wt%, Al2O321.7wt%,
Li2O3.7wt%, TiO22.6wt%, ZrO21.3wt%, P2O51.0wt%, Na2O0.7wt%, K2O0.3wt%,
MgO0.4wt%, ZnO1.6wt%, BaO1.5wt%, As2O30.3wt%, Fe2O30.1wt%, B2O30.5wt%,
CaO0.2wt%, C0.4wt%.
It is formed compared with raw material, in terms of weight percentage, composition % adjustment is containing lithium shown in such as following each processing number
The additive amount of discarded object.
Handle number 1-30wt%
Handle number 2-40wt%
Handle number 3-50wt%
Handle number 4-60wt%
Handle number 5-70wt%
Handle number 6-80wt%
Embodiment 1：
The composition that glass raw material is mixed into sample number 1 shown in table 1 is placed in crucible, at 1650 DEG C by glass raw material
It melts and is made the plate test piece of 100mm × 100mm × 5mm, after cooling, glass plate is put into heat-treatment furnace, is held at 200 DEG C
950 DEG C are warming up to the speed of 1 DEG C/min after warm 10min, furnace cooling after warm 20min are held at 950 DEG C, as a result, β-stone is precipitated
English solid solution (Li2O·Al2O3·nSiO2N≤2) and as champagne clear crystals glass.
Embodiment 2：
The composition that glass raw material is mixed into sample number 2 shown in table 1 is placed in crucible, at 1650 DEG C by glass raw material
It melts and is made the plate test piece of 100mm × 100mm × 5mm, after cooling, glass plate is put into heat-treatment furnace, is held at 200 DEG C
Be warming up to 1060 DEG C with the speed of 1 DEG C/min after warm 10min, furnace cooling after warm 20min held at 1060 DEG C, as a result, be precipitated β-
Spodumene solid solution (Li2O·Al2O3·nSiO2N≤4) and as white crystals glass.
Embodiment 3：
The composition that glass raw material is mixed into sample number 3 shown in table 1 is placed in crucible, at 1650 DEG C by glass raw material
It melts and is made the plate test piece of 100mm × 100mm × 5mm, after cooling, glass plate is put into heat-treatment furnace, is held at 200 DEG C
950 DEG C are warming up to the speed of 1 DEG C/min after warm 10min, furnace cooling after warm 20min are held at 950 DEG C, as a result, β-stone is precipitated
English solid solution (Li2O·Al2O3·nSiO2N≤2) and as black transparent sintered glass ceramics.
Embodiment 4：
The composition that glass raw material is mixed into sample number 4 shown in table 1 is placed in crucible, at 1650 DEG C by glass raw material
It melts and is made the plate test piece of 100mm × 100mm × 5mm, after cooling, glass plate is put into heat-treatment furnace, is held at 200 DEG C
950 DEG C are warming up to the speed of 1 DEG C/min after warm 10min, furnace cooling after warm 20min are held at 950 DEG C, as a result, β-stone is precipitated
English solid solution (Li2O·Al2O3·nSiO2N≤2) and as black transparent sintered glass ceramics.
Embodiment 5：
The composition that glass raw material is mixed into sample number 5 shown in table 1 is placed in crucible, at 1650 DEG C by glass raw material
It melts and is made the plate test piece of 100mm × 100mm × 5mm, after cooling, glass plate is put into heat-treatment furnace, is held at 200 DEG C
950 DEG C are warming up to the speed of 1 DEG C/min after warm 10min, furnace cooling after warm 20min are held at 950 DEG C, as a result, β-stone is precipitated
English solid solution (Li2O·Al2O3·nSiO2N≤2) and as champagne clear crystals glass.
Embodiment 6：
The composition that glass raw material is mixed into sample number 6 shown in table 1 is placed in crucible, at 1650 DEG C by glass raw material
It melts and is made the plate test piece of 100mm × 100mm × 5mm, after cooling, glass plate is put into heat-treatment furnace, is held at 200 DEG C
Be warming up to 1060 DEG C with the speed of 1 DEG C/min after warm 10min, furnace cooling after warm 20min held at 1060 DEG C, as a result, be precipitated β-
Spodumene solid solution (Li2O·Al2O3·nSiO2N≤4) and as white crystals glass.
Comparative example 1
The composition that glass raw material is mixed into sample number comparative example shown in table 11 is placed in crucible, at 1650 DEG C by glass
Glass raw material melts and is made the plate test piece of 100mm × 100mm × 5mm, and after cooling, glass plate is put into heat-treatment furnace,
It holds for 200 DEG C and is warming up to 950 DEG C with the speed of 1 DEG C/min after warm 10min, furnace cooling after warm 20min is held at 950 DEG C, as a result, analysis
Go out β-quartz solid solution (Li2O·Al2O3·nSiO2N≤2) and as champagne clear crystals glass, still, due to crystal
Amount of precipitation is very little, and crystal can not be uniformly distributed,
So clear area is uneven, uneven color.
Comparative example 2
The composition that glass raw material is mixed into sample number comparative example shown in table 12 is placed in crucible, at 1650 DEG C by glass
Glass raw material melts and is made the plate test piece of 100mm × 100mm × 5mm, and after cooling, glass plate is put into heat-treatment furnace,
It holds for 200 DEG C and is warming up to 1060 DEG C with the speed of 1 DEG C/min after warm 10min, furnace cooling after warm 20min is held at 1060 DEG C, as a result,
β-spodumene solid solution (Li is precipitated2O·Al2O3·nSiO2N≤4) and as white crystals glass, still, since crystal is analysed
Going out too soon, crystal can not be uniformly distributed,
So uneven color.
The results are shown in table below：
* 5 Ge points of plate face are impacted using 0.5j jump bits, is clicked on per Ge under 3.
Plate is put into 750 DEG C of stove Inner and heated by * to be made plate face be evenly heated Hou Lost in 30 minutes to enter in normal-temperature water, do not break
It damages as qualification.
The foregoing is only a preferred embodiment of the present invention, but protection scope of the present invention be not limited thereto,
Any one skilled in the art in the technical scope disclosed by the present invention, technique according to the invention scheme and its
Inventive concept is subject to equivalent substitution or change, should be covered by the protection scope of the present invention.
Claims (6)
1. a kind of Li2O-Al2O3-nSiO2Based crystallized glass, it is characterised in that it is with each quality very ingredient：
SiO260.0~70.0wt%、Al2O318.0~24.0wt%、Li2O2.0~5.0wt%、TiO20.5~4.0wt%、ZrO20.5~
4.0wt%、P2O50.3~2.0wt%、Na2O0~2.0wt%、K2O0~2.0wt%、MgO0.1~1.6wt%、ZnO0.5~2.0wt%、
BaO0.1~1.6wt%、As2O30~1.0wt%、Sb2O30~1.0wt%、F0~1.0wt%、Fe2O30~1.0wt%、B2O30~1.0wt%、
CaO0~1.0wt%、C0~1.0wt%。
2. Li described in claim 12O-Al2O3-nSiO2The production method of based crystallized glass, it is characterised in that：The crystallization
Change glass and use primary raw material of the discarded object containing lithium as glass.
3. method as claimed in claim 2, it is characterised in that：
Each component content of the discarded object containing lithium is：SiO255.0~75.0wt%、Al2O315.0~25.0wt%、Li2O0.5~
5.0wt%、TiO20~4.0wt%、ZrO20~4.0wt%、P2O50~2.0wt%、Na2O0~2.0wt%、K2O0~2.0wt%、MgO0~
2.0wt%、ZnO0~2.5wt%、BaO0~2.0wt%、As2O30~1.0wt%、Sb2O30~1.0wt%、F0~1.0wt%、Fe2O30~
1.0wt%、B2O30~1.0wt%、CaO0~1.0wt%、C0~1.0wt%。
4. method as claimed in claim 2 or claim 3, it is characterised in that：
The usage amount of discarded object containing lithium is 30 ~ 80wt% of glass formula raw material.
5. such as claim 2-4 any one of them methods, it is characterised in that step is as follows：
（1）It is SiO by formula composition260.0~70.0wt%、Al2O318.0~24.0wt%、Li2O2.0~5.0wt%、TiO20.5~
4.0wt%、ZrO20.5~4.0wt%、P2O50.3~2.0wt%、Na2O0~2.0wt%、K2O0~2.0wt%、MgO0.1~1.6wt%、
ZnO0.5~2.0wt%、BaO0.1~1.6wt%、As2O30~1.0wt%、Sb2O30~1.0wt%、F0~1.0wt%、Fe2O30~
1.0wt%、B2O30 ~ 1.0wt%, CaO0 ~ 1.0wt%, the glass raw material of C0 ~ 1.0wt% uniformly mix；
（2）By step（1）Obtained glass raw material is dissolved；
（3）By step（2）Obtained glass, which is shaped, obtains Li2O-Al2O3-SiO2It is crystallinity glass；
（4）By step（3）Obtained Li2O-Al2O3-SiO2Be crystallinity glass crystallized heat treatment obtain Li2O-
Al2O3-SiO2Based crystallized glass.
6. such as claim 2-5 any one of them methods, it is characterised in that wherein described step（1）It is divided into following A-1.A-2
Step：
A-1. step：It is SiO by each component content255.0~75.0wt%、Al2O315.0~25.0wt%、Li2O
0.5~5.0wt%、TiO20~4.0wt%、ZrO20~4.0wt%、P2O50~2.0wt%、Na2O0~2.0wt%、
K2O0~2.0wt%、MgO0~2.0wt%、ZnO0~2.5wt%、BaO0~2.0wt%、As2O3
0~1.0wt%、Sb2O30~1.0wt%、F0~1.0wt%、Fe2O30~1.0wt%、B2O30~1.0wt%、
The uniform stirring of waste materials containing lithium of CaO0 ~ 1.0wt%, C0 ~ 1.0wt%；
A-2. step：Other raw material compositions are added in the waste materials containing lithium completed in A-1. steps uniform stirring, make glass
Each component content of glass composition of raw materials becomes SiO260.0~70.0wt%、Al2O318.0~24.0wt%、Li2O2.0~5.0wt%、
TiO20.5~4.0wt%、ZrO20.5~4.0wt%、P2O50.3~2.0wt%、Na2O0~2.0wt%、K2O0~2.0wt%、MgO0.1~
1.6wt%、ZnO0.5~2.0wt%、BaO0.1~1.6wt%、As2O30~1.0wt%、Sb2O30~1.0wt%、F0~1.0wt%、Fe2O30
~1.0wt%、B2O30 ~ 1.0wt%, CaO0 ~ 1.0wt%, C0 ~ 1.0wt%, by deployed glass raw material uniform stirring.
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| CN111302631A (en) * | 2018-12-12 | 2020-06-19 | 佛山市顺德区美的电热电器制造有限公司 | Microcrystalline glass and preparation method and application thereof |
| CN111302632A (en) * | 2018-12-12 | 2020-06-19 | 佛山市顺德区美的电热电器制造有限公司 | Glass ceramics with low high-temperature viscosity, preparation method thereof, glass product and cooking utensil |
| CN111484245A (en) * | 2020-04-30 | 2020-08-04 | 四川旭虹光电科技有限公司 | High-strength low-dielectric-constant low-dielectric-loss glass and preparation and application thereof |
| CN114380506A (en) * | 2020-10-19 | 2022-04-22 | 湖州大享玻璃制品有限公司 | Li2O-Al2O3-SiO2Crystallized glass and Li2O-Al2O3-SiO2Crystalline glass |
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| CN111484245A (en) * | 2020-04-30 | 2020-08-04 | 四川旭虹光电科技有限公司 | High-strength low-dielectric-constant low-dielectric-loss glass and preparation and application thereof |
| CN114380506A (en) * | 2020-10-19 | 2022-04-22 | 湖州大享玻璃制品有限公司 | Li2O-Al2O3-SiO2Crystallized glass and Li2O-Al2O3-SiO2Crystalline glass |
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Application publication date: 20180605 |