CN105330161B - TiO2Saturating infrared aluminate glass ceramics of doping and preparation method thereof - Google Patents
TiO2Saturating infrared aluminate glass ceramics of doping and preparation method thereof Download PDFInfo
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Abstract
The present invention is on a kind of TiO2Saturating infrared aluminate glass ceramics of doping and preparation method thereof, the TiO2The component of infrared aluminate glass ceramics and the weight of each component are thoroughly for doping：Al2O3：35% 50%, CaO：30% 40%, R：10% 20%, M：7% 15%, TiO2：3% 6%；Wherein, R is the one or more in BaO, SrO, MgO；M is Na2O and/or K2O.Preparation method is to prepare infrared aluminate substrate glass using the method for vacuum melt, then glass is carried out specifically to be thermally treated resulting in TiO2Infrared aluminate glass is ceramic thoroughly for doping.The TiO of the present invention2Infrared aluminate glass ceramics have excellent spectral transmission performance in visible region and nearly middle-infrared band thoroughly for doping；With good mechanical performance, it is demonstrated experimentally that after glass heat treatment, glass hard (HRC65Yi Shang) is significantly improved；It is suitable for carrying out the making of the abnormal complex shape infrared windows such as ball cover；Without noble metals such as rare earth, germanium, galliums, cost of material is low；The toxic components such as fluorine-containing, chlorine, sulphur, lead it are not related in preparation process, environmental safety is good.
Description
Technical field
The present invention relates to a kind of infrared optical material, more particularly to a kind of TiO2Infrared aluminate glass is ceramic thoroughly for doping
And preparation method thereof.
Background technology
Glasses for infrared use are the special glass materials with infrared transmission performance, not only with excellent infrared breathability
Can, while having, optical homogeneity is good, manufacturing cost is cheap, be easily processed into large scale or complicated shape product, all the time
All it is one of emphasis of infra-red material research application.Realize that practical infrared glass material includes aluminate, germanium gallic acid at present
Salt, heavy metal fluoride and chalcogenide glass etc..Aluminate glass is with Al2O3With the infrared glass that CaO is main component
Glass, with excellent multispectral through performance, infrared (0.4~6 μm) has good transmitance from visible, makes simultaneously
It is with low cost, it is infrared transmission window, the ideal material of head-shield in manufacture closely.
Glass material generally existing fragility is big, hardness is low, bad mechanical property the shortcomings of, be used as directly contact external environment
Optical window material, using being very limited.Research shows both at home and abroad, and controlled micro crystallization processing is carried out to glass material can be made glass
Glass ceramic material (also known as devitrified glass), can significantly improve the mechanical performance and thermodynamic property of material, so as to improve material
To the adaptability of the environment such as high temperature, high pressure, erosion.
At present, sulphur halogen system glass ceramics, heavy metal fluorine (oxygen) compound glass ceramics and germanium gallate are had reported both at home and abroad
Infrared glass ceramics such as glass ceramics and preparation method thereof, using raw materials such as expensive germanium, galliums more than above-mentioned material, also simultaneously
It is related to the toxic components such as heavy metal and F, Cl, in addition, is limited by technology of preparing, cost of manufacture is higher, hardness is low, change
Learn stability poor, window material should not be used as.
The content of the invention
It is a primary object of the present invention to there is provided a kind of TiO2The saturating infrared aluminate glass ceramics of doping and its preparation side
Method, technical problem to be solved is it is had good through performance at 0.4~5 μm, while having higher softening temperature
And case hardness, to meet the demand for making the infrared transmission window of large scale, thus more suitable for practicality.
The object of the invention to solve the technical problems is realized using following technical scheme.According to present invention proposition
TiO2The percentage by weight of the doping ceramic each component of infrared aluminate glass thoroughly is：Al2O3：35%-50%, CaO：30%-
40%, R：10%-20%, M：7%-15%, TiO2：3%-6%；Wherein, R is the one or more in BaO, SrO, MgO；M
For Na2O and/or K2O。
The object of the invention to solve the technical problems can be also applied to the following technical measures to achieve further.
It is preferred that, foregoing TiO2Infrared aluminate glass is ceramic thoroughly for doping, wherein described each component percentage by weight
For：Al2O3：35%-40%, CaO：30%-40%, R：10%-15%, M：9%-10%, TiO2：3%-6%；Wherein, R is
One or more in BaO, SrO, MgO, M is Na2O and/or K2O。
The object of the invention to solve the technical problems is also realized using following technical scheme.According to present invention proposition
TiO2The ceramic preparation method of infrared aluminate glass includes thoroughly for doping：
(1) raw material is weighed, raw material is melted, 1450~1550 DEG C of fusion temperature, fusing time 8~16 hours is cold
But, glass clinker is obtained；The composition of described raw material is：Al2O3：35%-50%, CaO：30%-40%, R：10%-20%,
M：7%-15%, TiO2：3%-6%, wherein, R is the one or more in BaO, SrO, MgO；M is Na2O and/or K2O；
(2) above-mentioned glass clinker is crushed, the clinker after crushing is subjected to vacuum fusion, fusion temperature 1500~1600
DEG C, vacuum 1.0 × 10-3~1.0 × 10-2After Pa, glass melting, clarified, shaping, annealing, cooling obtain TiO2Doping is saturating
Infrared aluminate glass；
(3) above-mentioned glass is incubated at a temperature of 50 DEG C more than the transition temperature (Tg), carries out coring processing, then heat to
The crystallization start temperature (Tx) of glass 0.5~3 hour, is cooled to the transition temperature of glass, insulation annealing 2~3 after Crystallizing treatment
Natural cooling after hour, obtains TiO2Infrared aluminate glass is ceramic thoroughly for doping.
The object of the invention to solve the technical problems can be also applied to the following technical measures to achieve further.
It is preferred that, foregoing TiO2The preparation method of doping infrared aluminate glass ceramics thoroughly, wherein it is described the step of (2)
Described in glass clinker pulverized particles size be 5~10mm；Glass described in step (3) is 50 more than transition temperature (Tg)
4~16 hours are incubated at a temperature of DEG C；Step (3) the above-mentioned glass is incubated at a temperature of more than transition temperature (Tg) 50 DEG C
Heating rate afterwards is 0.5~1 DEG C/min；Rate of temperature fall is 0.8~1 DEG C/minute after above-mentioned Crystallizing treatment described in step (3)
Clock.
It is preferred that, foregoing TiO2The preparation method of the saturating infrared aluminate glass ceramics of doping, to the glass in step (2)
DSC heat analysis is carried out, transition temperature Tg, the crystallization start temperature Tx of glass is tested.
By above-mentioned technical proposal, TiO of the present invention2Infrared aluminate glass ceramics and preparation method thereof at least have thoroughly for doping
There are following advantages：
(1) TiO that the present invention is obtained2Infrared aluminate glass ceramics have in visible region and nearly middle-infrared band thoroughly for doping
There is excellent spectral transmission performance.
(2) TiO that the present invention is obtained2Infrared aluminate glass ceramics have good mechanical performance, experiment card thoroughly for doping
Bright, after glass heat treatment, glass hard (HRC65Yi Shang) is significantly improved.
(3) TiO that the present invention is obtained2Doping thoroughly infrared aluminate glass ceramics preparation method using glassware first into
Shape, then carries out heat treatment and glass ceramics is made, be suitable for carrying out the making of the abnormal complex shape infrared windows such as ball cover.
(4) TiO that the present invention is obtained2Infrared aluminate glass ceramics are former without noble metals such as rare earth, germanium, galliums thoroughly for doping
Expect that cost is low；The toxic components such as fluorine-containing, chlorine, sulphur, lead it are not related in preparation process, environmental safety is good.
Described above is only the general introduction of technical solution of the present invention, in order to better understand the technological means of the present invention,
And can be practiced according to the content of specification, below with presently preferred embodiments of the present invention and coordinate accompanying drawing describe in detail as after.
Brief description of the drawings
Fig. 1 is the DSC curve of glass in embodiment 1,2；
Fig. 2 is TiO in embodiment 12The X ray diffracting spectrum of the saturating infrared aluminate glass ceramics of doping and host glass；
Fig. 3 is the TiO that embodiment 2 is obtained2The infrared transmission of the saturating infrared aluminate glass ceramics of doping and host glass
Spectral line (thickness of sample 5mm).
Embodiment
Further to illustrate the present invention to reach the technological means and effect that predetermined goal of the invention is taken, below in conjunction with
Accompanying drawing and preferred embodiment, to according to TiO2 proposed by the present invention adulterate thoroughly infrared aluminate glass ceramics and preparation method thereof its
Embodiment, feature and its effect, are described in detail as after.In the following description, different " embodiment " or " implementation
What example " referred to is not necessarily same embodiment.In addition, the special characteristic or feature in one or more embodiments can be by any suitable
Form is combined.
Embodiment 1：
Aluminate glass batch 10kg (wt%) is weighed and is mixed by following composition and ratios：40%Al2O3, 36%
CaO, 7%BaO, 4%MgO, 8%Na2O, 5%TiO2, batch melted in silicon molybdenum rod furnace with platinum-rhodium alloy crucible,
Glass metal is cast in cooling in the cast iron die of preheating after fusing and obtained by 1450 DEG C of fusion temperature, fusing time 16 hours
TiO2The saturating infrared aluminate glass clinker of doping.
Insert in platinum-rhodium alloy crucible, enter in vacuum induction melting stove for the clinker of 5~10mm size particles by crushing
Row fusing, 1500 DEG C of fusion temperature, maximum vacuum 1.0 × 10-3Pa.After being completely melt after clarification 1~2 hour, by glass
Liquid is cast in the cast iron die of preheating, and rapid be transferred in electric furnace is annealed after shaping, and water white transparency is obtained after cooling
TiO2The saturating infrared aluminate glass of doping.The test such as DSC heat analysis is carried out to glass, the DSC curve of glass is as shown in figure 1, glass
The transition temperature Tg of glass is 736 DEG C, softening temperature is 796 DEG C, crystallization start temperature Tx is 861 DEG C, Vickers hardness is
7.57GPa, infrared 4.0 mu m waveband 5mm samples transmitance is more than 80%.
Infrared aluminate glass carries out coring and Crystallizing treatment in electric furnace thoroughly for the TiO2 doping that above-mentioned steps are obtained.Glass
The coring at a temperature of 790 DEG C of glass sample is handled 12 hours, is then warming up to 860 DEG C of Crystallizing treatments 3 hours with 1 DEG C/min of speed,
Stove is closed after being cooled to 736 DEG C of insulation annealings 3 hours after Crystallizing treatment with 1 DEG C/min of speed, room temperature is naturally cooled to and obtains TiO2
Infrared aluminate glass is ceramic thoroughly for doping.Fig. 2 is the X ray diffracting spectrum of glass, it can be seen that glass goes out after Crystallizing treatment
Now obvious crystal diffraction peak, shows to there occurs controlled micro crystallization in glass, forms glass ceramic material.After tested, glass ceramics
Material softening temperature is 843.4 DEG C, Vickers hardness is 8.30GPa, and infrared 4.0 mu m waveband 5mm samples transmitance is more than 75%.
Embodiment 2：
Aluminate glass batch 10kg (wt%) is weighed and is mixed by following composition and ratios：45%Al2O3, 30%
CaO, 6%BaO, 6%MgO, 10%Na2O, 3%TiO2, batch melted in silicon molybdenum rod furnace with platinum-rhodium alloy crucible
Change, 1550 DEG C of fusion temperature, fusing time 12 hours, glass metal is cast in into cooling in the cast iron die of preheating after fusing obtains
TiO2The saturating infrared aluminate glass clinker of doping.
Insert in platinum-rhodium alloy crucible, enter in vacuum induction melting stove for the clinker of 5~10mm size particles by crushing
Row fusing, 1600 DEG C of fusion temperature, maximum vacuum 1.0 × 10-3Pa.After being completely melt after clarification 1~2 hour, by glass
Liquid is cast in the cast iron die of preheating, and rapid be transferred in electric furnace is annealed after shaping, and TiO is obtained after cooling2Doping is thoroughly red
Outer aluminate glass.Test analysis is carried out to glass, the DSC curve of glass is as shown in figure 1, the transition temperature Tg for measuring glass is
747 DEG C, softening temperature be 810 DEG C, crystallization start temperature Tx be 871 DEG C, Vickers hardness be 7.60GPa, infrared 4.0 mu m waveband
5mm samples transmitance is more than 80%.
The glass that above-mentioned steps are obtained carries out coring and Crystallizing treatment in electric furnace.Glass sample is at a temperature of 800 DEG C
Coring is handled 16 hours, then 871 DEG C of Crystallizing treatments is warming up to 0.5 hour with 0.5 DEG C/min of speed, with 1 after Crystallizing treatment
DEG C/min speed is cooled to 747 DEG C of insulation annealings and closes stove after 3 hours, naturally cools to room temperature and obtains TiO2The saturating infrared aluminium of doping
Silicate glass ceramics, the infrared spectrum H103 resin of sample and host glass as shown in figure 3, show after controlled micro crystallization, glass
Infrared transmittivity has declined, but still higher, reaches more than 75%, meets window transmission and requires.Glass ceramic material is soft
Change temperature be 856.0 DEG C, Vickers hardness be 8.64GPa, infrared 4.0 mu m waveband 5mm samples transmitance is more than 75%.
Embodiment 3：
Aluminate glass batch 10kg (wt%) is weighed and is mixed by following composition and ratios：35%Al2O3, 40%
CaO, 8%BaO, 2%MgO, 6%Na2O, 3%K2O, 6%TiO2, batch enters in silicon molybdenum rod furnace with platinum-rhodium alloy crucible
Glass metal is cast in the cast iron die of preheating and cooled down by row fusing, 1550 DEG C of fusion temperature, fusing time 8 hours after fusing
Obtain TiO2The saturating infrared aluminate glass clinker of doping.
Insert in platinum-rhodium alloy crucible, enter in vacuum induction melting stove for the clinker of 5~10mm size particles by crushing
Row fusing, 1550 DEG C of fusion temperature, maximum vacuum 1.0 × 10-2Pa.After being completely melt after clarification 1~2 hour, by glass
Liquid is cast in the cast iron die of preheating, and rapid be transferred in electric furnace is annealed after shaping, and TiO is obtained after cooling2Doping is thoroughly red
Outer aluminate glass.Test analysis is carried out to glass, the transition temperature Tg for measuring glass is 731 DEG C, softening temperature is 795 DEG C,
Crystallization start temperature Tx is 853 DEG C, Vickers hardness is 7.57GPa, and infrared 4.0 mu m waveband 5mm samples transmitance is more than 80%.
The glass that above-mentioned steps are obtained carries out coring and Crystallizing treatment in electric furnace.Glass sample is at a temperature of 780 DEG C
Coring is handled 4 hours, then 853 DEG C of Crystallizing treatments is warming up to 2 hours with 0.5 DEG C/min of speed, with 1 DEG C/minute after Crystallizing treatment
Clock rate rate is cooled to 731 DEG C of insulation annealings and closes stove after 3 hours, naturally cools to room temperature and obtains TiO2The saturating infrared aluminate glass of doping
Glass ceramics.Material softening temperature is 837.8 DEG C, Vickers hardness is 8.18GPa, and infrared 4.0 mu m waveband 5mm sample transmitances are more than
75%.
Embodiment 4：
Aluminate glass batch 10kg (wt%) is weighed and is mixed by following composition and ratios：40%Al2O3, 30%
CaO, 10%BaO, 5%SrO, 6%Na2O, 4%K2O, 5%TiO2, batch enters in silicon molybdenum rod furnace with platinum-rhodium alloy crucible
Glass metal is cast in the cast iron die of preheating and cooled down by row fusing, 1450 DEG C of fusion temperature, fusing time 12 hours after fusing
Obtain TiO2The saturating infrared aluminate glass clinker of doping.
Insert in platinum-rhodium alloy crucible, enter in vacuum induction melting stove for the clinker of 5~10mm size particles by crushing
Row fusing, 1600 DEG C of fusion temperature, maximum vacuum 1.0 × 10-3Pa.After being completely melt after clarification 1~2 hour, by glass
Liquid is cast in the cast iron die of preheating, and rapid be transferred in electric furnace is annealed after shaping, and TiO is obtained after cooling2Doping is thoroughly red
Outer aluminate glass.Test analysis is carried out to glass, the transition temperature Tg for measuring glass is 739 DEG C, softening temperature is 805 DEG C,
Crystallization start temperature Tx is 863 DEG C, Vickers hardness is 7.58GPa, and infrared 4.0 mu m waveband 5mm samples transmitance is more than 80%.
The glass that above-mentioned steps are obtained carries out coring and Crystallizing treatment in electric furnace.Glass sample is at 790 DEG C of coring
Reason 12 hours, is then warming up to 863 DEG C of Crystallizing treatments 3 hours, with 1 DEG C/min of speed after Crystallizing treatment with 1 DEG C/min of speed
It is cooled to 739 DEG C of insulation annealings and closes stove after 3 hours, naturally cools to room temperature and obtain TiO2Infrared aluminate glass is made pottery thoroughly for doping
Porcelain, material softening temperature is 848.6 DEG C, Vickers hardness is 8.35GPa, and infrared 4.0 mu m waveband 5mm sample transmitances are more than
75%.
The above described is only a preferred embodiment of the present invention, any formal limitation not is made to the present invention, according to
Any simple modification, equivalent variations and the modification made according to the technical spirit of the present invention to above example, still fall within this hair
In the range of bright technical scheme.
Claims (8)
1. a kind of TiO2Infrared aluminate glass is ceramic thoroughly for doping, it is characterised in that：Each component percentage by weight：
Al2O3：35%-50%,
CaO：30%-40%,
R：10%-20%,
M：7%-15%,
TiO2：3%-6%；
Wherein, R is the one or more in BaO, SrO, MgO；M is Na2O and/or K2O。
2. TiO according to claim 12Infrared aluminate glass is ceramic thoroughly for doping, it is characterised in that described each component
Percentage by weight is：Al2O3：35%-40%, CaO：30%-40%, R：10%-15%, M：9%-10%, TiO2：3%-
6%.
3. a kind of TiO2The preparation method of the saturating infrared aluminate glass ceramics of doping, it is characterised in that：Comprise the following steps：
(1) raw material is taken, raw material is melted, 1450~1550 DEG C of fusion temperature, fusing time 8~16 hours, cooling is obtained
Glass clinker；The composition of described raw material is：Al2O3：35%-50%, CaO：30%-40%, R：10%-20%, M：7%-
15%, TiO2：3%-6%, wherein, R is the one or more in BaO, SrO, MgO；M is Na2O and/or K2O；
(2) by above-mentioned glass clinker crush, by after crushing clinker carry out vacuum fusion, 1500~1600 DEG C of fusion temperature, very
Reciprocal of duty cycle 1.0 × 10-3~1.0 × 10-2Pa, after being completely melt, clarified, shaping, annealing, cooling obtain TiO2Doping is thoroughly infrared
Aluminate glass；
(3) by above-mentioned glass, coring is handled under nucleation temperature, and described nucleation temperature is more than or equal to Tg temperature and adds 50 DEG C；So
The crystallization start temperature (Tx) of glass is warming up to afterwards 0.5~3 hour, the transition temperature of glass is cooled to after Crystallizing treatment, be incubated
Natural cooling after annealing 2~3 hours, obtains TiO2Infrared aluminate glass is ceramic thoroughly for doping.
4. TiO according to claim 32The preparation method of the saturating infrared aluminate glass ceramics of doping, it is characterised in that step
Suddenly the size of the glass clinker pulverized particles described in (2) is 5~10mm.
5. TiO according to claim 32The preparation method of the saturating infrared aluminate glass ceramics of doping, it is characterised in that step
Suddenly coring is handled the glass described in (3) at a temperature of 50 DEG C more than the glass transformation temperature, is incubated 4~16 hours.
6. TiO according to claim 32The preparation method of the saturating infrared aluminate glass ceramics of doping, it is characterised in that step
Suddenly heating rate of (3) the described above-mentioned glass after coring processing is 0.5~1 DEG C/min.
7. TiO according to claim 32The preparation method of the saturating infrared aluminate glass ceramics of doping, it is characterised in that step
Suddenly rate of temperature fall is 0.8~1 DEG C/min after the Crystallizing treatment described in (3).
8. TiO according to claim 32The preparation method of the saturating infrared aluminate glass ceramics of doping, it is characterised in that right
Glass in step (2) carries out DSC heat analysis, tests transition temperature Tg, the crystallization start temperature Tx of glass.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101224949A (en) * | 2008-01-25 | 2008-07-23 | 浙江大学 | Ecological glass-ceramic and preparation method thereof |
| CN101538117A (en) * | 2009-04-24 | 2009-09-23 | 清华大学 | Ferroelectric glass-ceramic dielectric material and preparation method thereof |
| CN101691276A (en) * | 2009-09-29 | 2010-04-07 | 中国建筑材料科学研究总院 | Large-size infrared transmitting calcium aluminate glass |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101224949A (en) * | 2008-01-25 | 2008-07-23 | 浙江大学 | Ecological glass-ceramic and preparation method thereof |
| CN101538117A (en) * | 2009-04-24 | 2009-09-23 | 清华大学 | Ferroelectric glass-ceramic dielectric material and preparation method thereof |
| CN101691276A (en) * | 2009-09-29 | 2010-04-07 | 中国建筑材料科学研究总院 | Large-size infrared transmitting calcium aluminate glass |
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