CN107954604A - A kind of high-strength transparence germanate devitrified glass and preparation method thereof - Google Patents
A kind of high-strength transparence germanate devitrified glass and preparation method thereof Download PDFInfo
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- CN107954604A CN107954604A CN201711411332.9A CN201711411332A CN107954604A CN 107954604 A CN107954604 A CN 107954604A CN 201711411332 A CN201711411332 A CN 201711411332A CN 107954604 A CN107954604 A CN 107954604A
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- germanate
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- 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
Abstract
The present invention relates to a kind of high-strength transparence germanate devitrified glass and preparation method thereof, the percentage by weight composition of the microcrystalline glass formula is：GeO251~65%, Ga2O310~20%, SiO20~18%, BaO 5~12%, Y2O33~12%, ZrO22~8%, Na2O 0.5~2%.Raw material is prepared into germanate parent glass with conventional melt cooling method after mixing by recipe requirements first, it is heat-treated after parent glass after annealing is processed into suitable specification, while high-temperature heat treatment high-frequency electric field is formed between the upper and lower surface of glass sample, field strength, frequency and the application time of heat treatment temperature, time and high-frequency electric field are adjusted, is obtained after sample cooling and contains the equally distributed high-strength transparence germanate devitrified glass of nanocrystal.Product optical transmittance in 0.3~5.0 μ m is more than 78%, and bending strength is up to 106 ~ 125MPa.
Description
Technical field
The present invention relates to new material technology field, more particularly to a kind of high-strength transparence germanate devitrified glass and its preparation
Method, can be applied to the field such as infrared optical window and other infrared optical elements.
Background technology
Infrared detection technique is one of important way that contemporary society obtains information, with the quick hair of hyundai electronics information
Exhibition, the requirement to infrared detection technique are more and more stringenter.In order to obtain the infrared imaging of high-resolution, must be requested that infrared window material
There are material very wide infrared waves to pass through scope and very high infrared transmittivity, particularly in the field such as infrared guidance and infrared counteraction
It is required that window material is respectively provided with compared with high transmittance in 0.3-5.0 μ ms, and require can high temperature resistant, anti-blown sand invade
The features such as erosion, good mechanical performance.It disclosure satisfy that the material of the condition and few at present, common material includes MgF2、ZnS、
AlON、MgAl2O4, diamond and sapphire etc., wherein MgF2It can become opaque when temperature is higher than 500 DEG C in wet environment,
And produce face crack；ZnS mechanical strengths are low, wear-resisting property is poor, and it is existing that oxidation can occur when temperature in use is more than 300 DEG C
As that will soften more than 500 DEG C；AlON and MgAl2O4Immature in preparation process, its optical transmittance is difficult to meet the requirements；It is blue
Gem processing is difficult, of high cost, and mechanical performance significantly reduces when temperature in use is more than 700 DEG C；Diamond is not only with high costs,
And large-size components can not be prepared, while high-temperature oxydation phenomenon is serious.Therefore strictly speaking, at present still without a kind of preferable
Infrared optical window electromagnetic wave transparent material.
Germanate glass is a kind of new infrared electromagnetic wave transparent material, it has very high optics in 0.3-5.0 μ ms
Transmitance, and chemical stability and resistance to elevated temperatures are good, but its mechanical performance is still difficult to meet actual operation requirements, generally
The bending strength of germanate glass is only 60MPa or so, and uses industrial applications needs at least more than 100MPa, therefore how
The mechanical strength for improving germanate glass material is to realize the premise of its industrial applications.Central South University and Jingdezhen Ceramic university
It is changed into devitrified glass Deng by carrying out heat treatment to germanate glass, be remarkably improved its mechanical strength, however, in heat
Fine-grain formed in processing procedure is easy to growth of reuniting, will be to significantly reducing when crystallite dimension is more than 50 nanometers
To the transmitance of visible ray, so as to influence its actual performance.How formed crystallite is ensured in heat treatment process not
Reunite, it is dispersed be distributed in glass matrix, so as to significantly be carried on the basis of germanate glass optical property is not influenced
Its high mechanical strength is the key for promoting germanate glass practical.
The content of the invention
The technical problem to be solved in the present invention is to provide one kind to solve crystallite in germanate glass controlled micro crystallization heat treatment process
Agglomeration traits, and high-strength transparence germanate devitrified glass of its mechanical strength and preparation method thereof can be significantly improved.
To solve above technical problem, the technical scheme is that：A kind of high-strength transparence germanate devitrified glass, its
Being characterized in that the percentage by weight of the microcrystalline glass formula forms is：GeO251~65%, Ga2O310~20%, SiO20~
18%, BaO 5~12%, Y2O33~12%, ZrO22~8%, Na2O 0.5~2%.
The preparation method of above-mentioned high-strength transparence germanate devitrified glass, it is characterised in that：By weight percentage by crystallite
Frit is weighed, after mixing, through melting, annealing, controlled micro crystallization processing acquisition germanate devitrified glass.
The technological parameter for melting process is that melt temperature is 1300~1550 DEG C, and it is 1.0~3.0 to melt soaking time
Hour.
The technological parameter of the annealing operation is that annealing temperature is 500~650 DEG C, when annealing time is 1.0~2.0 small.
The technological parameter of the controlled micro crystallization treatment process is that nucleation temperature is 650~800 DEG C, and nucleation time is 1.0~2.0
Hour；Crystallization temperature is 900~1100 DEG C, when crystallization time is 1.0~2.0 small；Glass sample applies change in crystallization process
Frequency high voltage electric field, electric field strength are 2000~8000 V/cm, and frequency is 50 Hz, and heating in temperature-fall period with not applying electric field.
The external high-voltage variable frequency power source of electric furnace used in the controlled micro crystallization treatment process, glass sample upper and lower surface 1cm distinguish outside
High temperature resistant positive and negative electrode piece is set, which connects high voltage power supply incoming line respectively, and electric power output voltage can for 0 ~ 50000 V
Adjust, the output of 50 Hz power frequencies or direct current output can be set to, electric field-assisted heat treatment experiment chamber sets vacuum extractor, to prevent air
Intermediate ion causes the air layer between breakdown electrode in high temperature current field condition decentralization conductance.
The present invention, which forms it on the basis of existing germanate glass formula, suitably to be adjusted, while changes heat treatment
Process conditions, the innovative controlled micro crystallization that germanate glass is realized using electric field-assisted heat treatment mode so that germanate glass
The energy source that crystallization activation energy is overcome in high-temperature heat treatment process is not only the thermal energy that high temperature provides, while comes from height yet
The electric field energy of piezoelectric field.Since glass is in high-temperature heat treatment process, the ion in structure can be expanded in a certain range class
Dissipate and migrate, and the ion migrated is to carry electric charge in itself, electric charge will necessarily form directed movement under electric field action.Work as institute
When the electric field of application is electrostatic field, the cation in glass structure will be toward anode direction directional migration.If the and electric field applied
For high-frequency alternating field, then the direction that the direction of motion of ion is influenced and may spread with itself by the direction of electric field it is identical or
On the contrary, it so can promote or suppress diffusion and the migration rate of ion, so as to fulfill the actual control to microcrystalline growth process.
Due to having very strong repulsive force between the ion of two positively chargeds under electric field action, it is difficult under high temperature current field condition " altogether
Retreat ", thus reunion of the nucleus in forming process can be suppressed, the scattered growth of crystal is realized, so as to solve germanate glass
The agglomeration traits of crystallite, are realized on the premise of germanate glass optical property is not significantly affected in glass controlled micro crystallization heat treatment process
Significantly improve its mechanical strength.
The invention has the advantages that：
(1) using the method for the present invention prepare germanate devitrified glass, between visible region, between near-infrared and middle infrared
With good optical transmittance, optical transmittance is more than 78% in 0.3~5.0 μ m；
(2) the germanate devitrified glass prepared using the method for the present invention, its bending strength is up to 106 ~ 125MPa；
(3) crystallite dimension in the high-strength transparence germanate devitrified glass prepared by the present invention is less than 50nm, and crystal grain is in parent
Well dispersed in glass thus small to scatter incident light effect, the optical transmittance of material is improved.
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
Preferred embodiment, to the specific reality according to a kind of high-strength transparence germanate devitrified glass proposed by the present invention and preparation method thereof
Mode, method, step, feature and its effect are applied, is described in detail as follows：
Embodiment one：
The present embodiment is a kind of high-strength transparence germanate devitrified glass and preparation method thereof, its step is as follows：
(1) the germanate parent glass during described in contains following components by weight percent：GeO252%, Ga2O315%, SiO2
15%, BaO 6%, Y2O38%, ZrO23%, Na2O 1%。
(2) the raw material precise of the germanate parent glass of above component, after mixing, melts in electric furnace, its
Melt temperature is 1450 DEG C, when thawing soaking time is 1.5 small；Annealing temperature is 550 DEG C, when annealing time is 2.0 small.
(3) electric field-assisted process of thermal treatment condition is：Nucleation temperature is 720 DEG C, when nucleation time is 1.0 small；Crystallization
Temperature is 950 DEG C, when crystallization time is 1.0 small；Apply high-voltage alternating electric field, frequency in glass sample upper and lower surface at 950 DEG C
For 50 Hz, electric field strength is 5000 V/cm, heat treatment 1 it is small when after stop heating and meanwhile stop apply electric field.
(4) the germanate devitrified glass prepared by, optical transmittance is 79% in 0.3~5.0 μ m（Not hydroxyl
Uptake zone）, bending strength is 112 MPa.
Embodiment two：
The present embodiment is a kind of high-strength transparence germanate devitrified glass and preparation method thereof, its step is as follows：
(1) the germanate parent glass during described in contains following components by weight percent：GeO260.5%, Ga2O312%, SiO2
8%, BaO 7%, Y2O35%, ZrO26%, Na2O 1.5%。
(2) the raw material precise of the germanate parent glass of above component, after mixing, melts in electric furnace, its
Melt temperature is 1520 DEG C, when thawing soaking time is 1.0 small；Annealing temperature is 570 DEG C, when annealing time is 1.5 small.
(3) electric field-assisted process of thermal treatment condition is：Nucleation temperature is 750 DEG C, when nucleation time is 1.5 small；Crystallization
Temperature is 990 DEG C, when crystallization time is 1.5 small；Apply high-voltage alternating electric field, frequency in glass sample upper and lower surface at 990 DEG C
For 50 Hz, electric field strength is 6500 V/cm, heat treatment 1.5 it is small when after stop heating and meanwhile stop apply electric field.
(4) the germanate devitrified glass prepared by, optical transmittance is 81.5% in 0.3~5.0 μ m（Without hydroxyl
Base uptake zone）, bending strength is 124 MPa.
Embodiment three：
The present embodiment is a kind of high-strength transparence germanate devitrified glass and preparation method thereof, its step is as follows：
(1) the germanate parent glass during described in contains following components by weight percent：GeO265%, Ga2O318.5%, SiO2
3%, BaO 8%, Y2O33%, ZrO22%, Na2O 0.5%。
(2) the raw material precise of the germanate parent glass of above component, after mixing, melts in electric furnace, its
Melt temperature is 1350 DEG C, when thawing soaking time is 2.0 small；Annealing temperature is 600 DEG C, when annealing time is 1.5 small.
(3) electric field-assisted process of thermal treatment condition is：Nucleation temperature is 820 DEG C, when nucleation time is 2.0 small；Crystallization
Temperature is 990 DEG C, when crystallization time is 1.5 small；Apply high-voltage alternating electric field, frequency in glass sample upper and lower surface at 910 DEG C
For 50 Hz, electric field strength is 7500 V/cm, heat treatment 2.0 it is small when after stop heating and meanwhile stop apply electric field.
(4) the germanate devitrified glass prepared by, optical transmittance is 83% in 0.3~5.0 μ m（Not hydroxyl
Uptake zone）, bending strength is 120 MPa.
Claims (5)
- A kind of 1. high-strength transparence germanate devitrified glass, it is characterised in that the percentage by weight composition of the microcrystalline glass formula For：GeO251~65%, Ga2O310~20%, SiO20~18%, BaO 5~12%, Y2O33~12%, ZrO22~8%, Na2O 0.5~2%.
- 2. the preparation method of high-strength transparence germanate devitrified glass according to claim 1, it is characterised in that：By weight hundred Ratio is divided to be weighed devitrified glass raw material, after mixing, through melting, annealing, controlled micro crystallization processing acquisition germanate crystallite glass Glass.
- 3. preparation method according to claim 2, it is characterised in that：The technological parameter for melting process is that melt temperature is 1300~1550 DEG C, when thawing soaking time is 1.0~3.0 small.
- 4. preparation method according to claim 2, it is characterised in that：The technological parameter of the annealing operation is that annealing temperature is 500~650 DEG C, when annealing time is 1.0~2.0 small.
- 5. preparation method according to claim 2, it is characterised in that：The technological parameter of the controlled micro crystallization treatment process is coring temperature Spend for 650~800 DEG C, when nucleation time is 1.0~2.0 small；Crystallization temperature is 900~1100 DEG C, crystallization time for 1.0~ 2.0 it is small when；Glass sample applies frequency conversion high voltage electric field in crystallization process, and electric field strength is 2000~8000 V/cm, and frequency is 50 Hz, heating in temperature-fall period with not applying electric field.
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| CN201711411332.9A CN107954604B (en) | 2017-12-23 | 2017-12-23 | High-strength transparent germanate microcrystalline glass and preparation method thereof |
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| CN201711411332.9A CN107954604B (en) | 2017-12-23 | 2017-12-23 | High-strength transparent germanate microcrystalline glass and preparation method thereof |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109678348A (en) * | 2019-02-27 | 2019-04-26 | 西华大学 | A kind of fluorine oxygen ceramic-vitreous material and preparation method thereof |
| CN114133142A (en) * | 2021-12-24 | 2022-03-04 | 海南大学 | Rare earth doped ZnAl2O4Preparation method of nanocrystalline glass |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1872752A (en) * | 2006-06-06 | 2006-12-06 | 青岛大学 | Method for preparing polar microcrystalline glass |
| CN101234852A (en) * | 2008-01-16 | 2008-08-06 | 中南大学 | 0.3-5mum wave range infrared permeation high temperature resistant glass ceramic material and preparing method thereof |
-
2017
- 2017-12-23 CN CN201711411332.9A patent/CN107954604B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1872752A (en) * | 2006-06-06 | 2006-12-06 | 青岛大学 | Method for preparing polar microcrystalline glass |
| CN101234852A (en) * | 2008-01-16 | 2008-08-06 | 中南大学 | 0.3-5mum wave range infrared permeation high temperature resistant glass ceramic material and preparing method thereof |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109678348A (en) * | 2019-02-27 | 2019-04-26 | 西华大学 | A kind of fluorine oxygen ceramic-vitreous material and preparation method thereof |
| CN114133142A (en) * | 2021-12-24 | 2022-03-04 | 海南大学 | Rare earth doped ZnAl2O4Preparation method of nanocrystalline glass |
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| CN107954604B (en) | 2020-07-28 |
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