A kind of Aluminiu, boron silicate glass without alkali and its application
Technical field
The present invention relates to a kind of Aluminiu, boron silicate glass without alkali and its applications, belong to glass technology field.
Technical background
Currently, TFT can be divided into amorphous silicon (a-Si) TFT, polysilicon (p-Si) TFT and monocrystalline silicon (SCS) TFT.It is non-at present
Often mature TFT-LCD display device, mainly uses amorphous silicon (a-Si) TFT technology, processing temperature in process of production
Degree can be accomplished below at 600 DEG C.And for Activematric OLED (AMOLED), since OLED is electric current driving electronic
Device needs higher driving current, and current amorphous silicon (a-Si) technology is primarily adapted for use in the TFT- of voltage driving
LCD, driving current is lower, is not able to satisfy requirement of the AMOLED to driving current, and LTPS polysilicon (p-Si) TFT have compared with
High driving current and electron mobility can satisfy requirement of the AMOLED to driving current.LTPS polysilicon (p-Si) simultaneously
The response time of display can be improved in TFT, improves the brightness of display, and can directly construct display on the glass substrate
Device driving circuit can manufacture more frivolous display device.LTPS polysilicon (p-Si) TFT need in the fabrication process compared with
It is repeatedly handled under high-temperature, this just puts forward higher requirements base plate glass performance, and strain point should be high as far as possible, preferably
Higher than 650 DEG C.Meanwhile the coefficient of expansion of glass substrate needs the expansion coefficient similar with silicon, as far as possible reduction stress and destruction,
Therefore the preferred thermal linear expansion coefficient of base plate glass is 3.3~3.8 × 10-6/ DEG C between.For the ease of production, production is reduced
Cost, the glass as display base plate should have lower fusion temperature and liquidus temperature.Now with portable
The quick of electronic equipment (such as laptop, smart phone, PDA) is popularized, and proposes requirements at the higher level to the lightweight of accessory.By
More stringent requirements are proposed for this composition to glass substrate, to guarantee to adapt to the needs of modern liquid crystal displays.Glass substrate must
It must have the property that tool chemical resistance;Thermal expansion coefficient must be close with the silicon of thin film transistor (TFT);Strain point of glass is improved, with
Reduce thermal shrinking quantity;With lesser density, in order to carry and hold.
The method of regulation thermal expansion coefficient, which mainly has, at present introduces low-expansion coefficient filler, introduces rare earth ion, introduces weight
Metallic element.Introduce low-expansion coefficient even negative thermal expansion coefficient filler can by glass ingredient to thermal expansion coefficient of glass
It is adjusted, inside glass different heat expansion coefficient area may be caused to be unevenly distributed accordingly, especially producing ultra-thin glass
Glass substrate reduces the thermal stability of glass.Rare-earth oxide is introduced, i.e., effect is gathered by rare earth ion, makes glass
Network structure densification, reduces the thermal expansion coefficient of glass, but rare earth amount is larger, also can pole when introduction volume is smaller
The earth causes density to increase, and furthermore rare-earth oxide is expensive, is not suitable for large-scale industrial production use.Heavy metal
Ion is similar to rare earth ion effect, and common heavy metal ion, mostly poisonous and harmful substance are managed by Countries,
A large amount of uses will increase environmental pressure.
CN101489944A discloses a kind of suitable for the molding alkali-free glass substrate of float glass process, 50~350 DEG C of lines expansion systems
Number is 3~4 × 10-6/ DEG C, the containing ratio molar percentage of each ingredient is SiO2: 57.0~65.0%, Al2O3: 10.0~
12.0%, B2O3: 6.0~9.0%, MgO:5.0~10.0%, CaO:5.0~10.0%, SrO:2.5~5.5%, and meet
MgO+CaO+SrO:16.0~19.0%, MgO/ (MgO+CaO+SrO) >=0.40, B2O3/(SiO2+Al2O3+B2O3)≤0.12。
In the patent use a certain amount of clarifying agent not only increase technical process difficulty and cost, while often introduce it is harmful at
Point, SnO is contained in glass2, the transmitance of glass can be reduced accordingly, this is for belonging to adverse effect for TFT glass substrate
Factor.
CN104211300A discloses a kind of formula of the glass substrate of high specific modulus, the Mole percent score of each constituent
It is not SiO2: 66%~74%, Al2O3: 11%~16%, B2O3: 2%~9.5%, MgO:1%~6.5%, CaO:3%~
7%, SrO:0.5%~4%, Y2O3: 0.01~1.5%, SnO:0.01%~0.15%, thermal expansion coefficient be 2.8~3.6 ×
10-6/℃.But the patent application uses rare earth oxide Y2O3, and viscosity be 200 pool (i.e. η=1.3 log) when, ability
Guarantee less than 1650 DEG C.
Summary of the invention
The technical problem to be solved by the present invention is to provide a kind of alkali-free aluminium in view of the deficiency of the prior art
Borosilicate glass does not use rare-earth oxide and poisonous and harmful substance, (viscosity is melted guaranteeing that glass melting temperature is lower
When down to log η=1, fusion temperature is less than 1630 DEG C) while, strain point is greater than 650 DEG C, and thermal expansion coefficient is 2.75~
4.83×10-6/ DEG C within the scope of it is adjustable.The present invention is intended to provide a kind of biggish glass matrix material of thermal expansion coefficient modification scope
Material is suitble to the processing of glass substrate float glass process for providing basis for the composition of glass substrate material.
The present invention be solve the problems, such as it is set forth above used by technical solution are as follows:
A kind of Aluminiu, boron silicate glass without alkali, basic components are formed by following molar percentage: SiO2: 61.00~
65.00%, Al2O3: 11.00~12.00%, B2O3: 6.00~8.00%, R1O:(16.00-x) %, R2O:x% (x=0~
16);Wherein R1O、R2O is selected from one kind in the alkaline earth oxides such as MgO, SrO, CaO, and R1O、R2O is identical or not phase
Together.
According to the above scheme, the thermal expansion coefficient of the Aluminiu, boron silicate glass without alkali is 2.75~4.83 × 10-6/ DEG C within the scope of
It is adjustable, adjustment constant (16mol%) by alkaline earth oxide integral molar quantity in fixed Aluminiu, boron silicate glass without alkali system
R1O、R2The ratio of O has regulated and controled the thermal expansion coefficient of glass.
Further, the present invention provides a kind of preferably Aluminiu, boron silicate glass without alkali, and basic components press following mole hundred
Divide than composition: SiO2: 61.00~65.00%, Al2O3: 11.00~12.00%, B2O3: 6.00~8.00%, MgO:(16.00-
X) (x=0~16) %, CaO:x%, and thermal expansion coefficient range is 2.75~4.27 × 10-6/℃.Especially 0.25 < MgO/
(MgO+CaO) < 0.5 when, thermal expansion coefficient is 3.43~3.77 × 10-6/℃。
Further, the present invention provides second of preferably Aluminiu, boron silicate glass without alkali, and basic components press following mole
Percentage composition: SiO2: 61.00~65.00%, Al2O3: 11.00~12.00%, B2O3: 6.00~8.00%, SrO:y%,
CaO:(16-y) (y=0~16) %, and thermal expansion coefficient range is 4.00~4.83 × 10-6/℃.Especially CaO/ (CaO+
When SrO)=0.5, thermal expansion coefficient is 4.00 × 10-6/℃。
Further, the present invention provides the third preferably Aluminiu, boron silicate glass without alkali, and basic components press following mole
Percentage composition: SiO2: 61.00~65.00%, Al2O3: 11.00~12.00%, B2O3: 6.00~8.00%, MgO:
(16.00-z) %, SrO:z% (z=0~16), and thermal expansion coefficient range is 2.75~4.83 × 10-6/℃.Especially MgO/
(MgO+SrO)=0.5, thermal expansion coefficient is 3.67 × 10-6/℃。
Aluminiu, boron silicate glass without alkali of the present invention, it is preferred to use float glass process, the specific steps are as follows: press
According to dosage needed for each raw material in calculation glass batch of the present invention, platinum is added in all raw materials after mixing
It in rhodium alloy crucible, is then transferred in 1600~1640 DEG C of high temperature furnace, by 1600~1640 DEG C of heat preservation 2.5-3.5h;
After heat preservation, platinum-rhodium alloy crucible is taken out, the glass metal wherein melted is poured into warmed-up cast iron die and is formed, formed
After be immediately placed into annealing furnace, annealing temperature is set as 700~750 DEG C, and annealing time is 2~3h, and furnace cooling later is to get arriving
Aluminiu, boron silicate glass without alkali.
Aluminiu, boron silicate glass without alkali of the present invention can reach in 20 DEG C~300 DEG C of the controllable range of thermal expansion coefficient
2.75~4.83 × 10-6/ DEG C, density is respectively less than 2.73g/cm3, strain point at 640 DEG C or more, be melted viscosity down to log η=
When 1, fusion temperature uses glass base less than 1630 DEG C, preferably as display (such as Thin Film Transistor-LCD TFT-LCD)
Plate is applied.
In the present invention, silica SiO2Content have a significant impact for the thermal expansion coefficient of glass, single-phase SiO2Stone
English thermal expansion coefficient of glass is 5~7 × 10-7/ DEG C, SiO2Content is bigger, and thermal expansion coefficient of glass is lower.SiO2When content is higher
High temperature viscosity of glass increases, and is not easy clarifying and homogenizing.Boron oxide B2O3Different coordination structures for the thermal expansion coefficient of glass have weight
It influences, when boron atom co-ordination state is by BO3To BO4The thermal expansion coefficient of glass reduces when transformation.Magnesia (MgO), calcium oxide
(CaO), strontium oxide strontia (SrO) is alkaline earth oxide, it is possible to provide glass melting forms cation required for liquid phase, alkaline earth gold
When the concentration of category oxide is too low, the viscosity of glass is larger;When the concentration of alkaline earth oxide is too high, it can make to generate glass
Thermal expansion coefficient is excessively high.MgO makes glass be easy to the characteristics of melting with high temperature viscosity is reduced in the case where not reducing strain point.
Relative to other alkaline earth oxides, the presence of MgO can bring the lower coefficient of expansion and density.CaO is same as MgO,
High temperature viscometrics are reduced in the case where not reducing strain point, are the ingredients for significantly improving meltbility.
Compared with prior art, the beneficial effects of the present invention are:
Firstly, the present invention passes through in fixed SiO2、Al2O3、B2O3In the case that total moles content is constant, by adjusting alkaline earth
Metal oxide ratio acquisition substantially adjusts thermal expansion coefficient, while having both good thermal property, is convenient for float process.This
Outside, the embodiment of the present invention shows that single glass containing MgO, CaO, SrO is not in crystallization.
Secondly, the present invention while guaranteeing lower fusion temperature, is not assisted using any clarifying agent, clarifying agent adds
Add and not only increase technical process difficulty and cost, while being often introduced into harmful ingredient and (containing SnO in such as glass2, can be corresponding
Reduction glass transmitance) this is for belonging to adverse effect factor for TFT glass substrate, the present invention is to glass ingredient and system
Standby technique is rationally designed, and prepares the alkali-free alumina silicate glass without visible bubble in bubble in the case where not outer plus clarifying agent
Glass, the especially temperature of η=2 log are less than or equal to 1440 DEG C.
Specific embodiment
For a better understanding of the present invention, below with reference to the embodiment content that the present invention is furture elucidated, but the present invention is not
It is limited only to the following examples.
In following embodiments, the thermal dilatometer pair for the model DIL402PC that German Nai Chi Netzsch company produces is used
The thermal expansion coefficient that the glass bar having a size of 5 × 5 × 25mm is cut into after annealing is measured, and heating rate is 5 DEG C/min.This
In invention, linear expansion coefficient refers to 20~300 DEG C of average linear expansion coefficient.
In following embodiments, the production technology of Aluminiu, boron silicate glass without alkali, the specific steps are as follows: according to designed group
Divide and calculates each raw material in batch: SiO2、Al2O3、B2O3、MgCO3、CaCO3、SrCO3Required dosage, with assay balance into
Row weigh, then all raw materials be placed in mixing in mixing bottle be uniformly mixed, later be added platinum-rhodium alloy crucible in, in high temperature furnace
Platinum-rhodium alloy crucible is added in high temperature furnace at 1600~1640 DEG C, takes out crucible after 1600~1640 DEG C of heat preservation 3h, it will
The glass metal of melting is poured into cast iron die preheated in advance and is formed, and is immediately placed into annealing furnace after molding, and annealing temperature is set
It is 700~750 DEG C, annealing time is 2~3h, and furnace cooling later is taken out.
Embodiment 1-5
(each component is with molar percent for the chemical composition for the Aluminiu, boron silicate glass without alkali that embodiment 1-5 is provided respectively
Amount), performance indicator, see Table 1 for details, alkaline earth oxide use MgO, CaO.
The glass of 1. difference MgO-CaO ratio of table forms
Embodiment 6-10
(each component is with molar percent for the chemical composition for the Aluminiu, boron silicate glass without alkali that embodiment 6-10 is provided respectively
Amount), performance indicator, see Table 2 for details, alkaline earth oxide use CaO, SrO.
The glass of 2. difference CaO-SrO ratio of table forms
It forms (mol%) |
Embodiment 6 |
Embodiment 7 |
Embodiment 8 |
Embodiment 9 |
Embodiment 10 |
SiO2 |
65 |
65 |
65 |
65 |
65 |
Al2O3 |
11 |
11 |
11 |
11 |
11 |
B2O3 |
8 |
8 |
8 |
8 |
8 |
CaO |
16 |
12 |
8 |
4 |
0 |
SrO |
0 |
4 |
8 |
12 |
16 |
The coefficient of expansion (× 10-6/℃) |
4.27 |
4.23 |
4.00 |
4.45 |
4.83 |
Density (g/cm3) |
2.46 |
2.50 |
2.59 |
2.68 |
2.73 |
Strain point (DEG C) |
660 |
648 |
659 |
645 |
648 |
η=1 fusion temperature (DEG C) log |
1616 |
1600 |
1598 |
1612 |
1588 |
η=1.5 fusion temperature (DEG C) log |
1520 |
1498 |
1496 |
1512 |
1490 |
η=2 fusion temperature (DEG C) log |
1433 |
1406 |
1405 |
1424 |
1405 |
η=2.5 fusion temperature (DEG C) log |
1347 |
1336 |
1336 |
1338 |
1318 |
η=3 fusion temperature (DEG C) log |
1275 |
1262 |
1262 |
1268 |
1252 |
η=4 fusion temperature (DEG C) log |
1142 |
1147 |
1145 |
1140 |
1125 |
Embodiment 11-15
(each component is with molar percentage for the chemical composition for the Aluminiu, boron silicate glass without alkali that embodiment 11-15 is provided respectively
Metering), performance indicator, see Table 3 for details, alkaline earth oxide use MgO, SrO.
The glass of 3. difference MgO-SrO ratio of table forms
As shown in Table 1, as MgO+CaO=16mol%, the thermal expansion coefficient that MgO/CaO ratio has regulated and controled glass is adjusted,
(when MgO+CaO < 0.5, embodiment 3 and 4 can make thermal expansion coefficient in optimum range to especially 0.25 < MgO/, and density is respectively less than
2.46g/cm3, for strain point at 650 DEG C or more, the corresponding temperature of log η=1 is respectively less than 1630 DEG C.
As shown in Table 2, as CaO+SrO=16mol%, the thermal expansion coefficient that CaO/SrO ratio has regulated and controled glass is adjusted,
When especially CaO/ (CaO+SrO)=0.5, embodiment 8 can make thermal expansion coefficient close to optimum range, and density is less than 2.60g/
cm3, strain point is at 650 DEG C or more, and the corresponding temperature of log η=1 is less than 1600 DEG C.
As shown in Table 3, as MgO+SrO=16mol%, the thermal expansion coefficient that MgO/SrO ratio has regulated and controled glass is adjusted,
When especially MgO/ (MgO+SrO)=0.5, embodiment 13 can make thermal expansion coefficient in optimum range, and density is less than 2.55g/
cm3, strain point is at 650 DEG C or more, and the corresponding temperature of log η=1 is less than 1630 DEG C.
To sum up, the Aluminiu, boron silicate glass without alkali linear expansion coefficient provided by the invention suitable for float process technique regulates and controls
Method, linear expansion coefficient modification scope is up to 2.75~4.83 × 10-6/ DEG C, density is 2.40~2.73g/cm3, strain point is
645~687 DEG C, meet the performance requirement of TFT-LCD glass substrate.
The above is only a preferred embodiment of the present invention, it is noted that come for those of ordinary skill in the art
It says, without departing from the concept of the premise of the invention, several modifications and variations can also be made, these belong to of the invention
Protection scope.