CN109626817B - Application of lead nitrate, intermediate infrared oxyfluoride silicate rare earth doped glass and preparation thereof - Google Patents

Application of lead nitrate, intermediate infrared oxyfluoride silicate rare earth doped glass and preparation thereof Download PDF

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CN109626817B
CN109626817B CN201910019517.8A CN201910019517A CN109626817B CN 109626817 B CN109626817 B CN 109626817B CN 201910019517 A CN201910019517 A CN 201910019517A CN 109626817 B CN109626817 B CN 109626817B
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infrared
rare earth
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孙立忠
裴锦涛
张振
徐昌富
王煜
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Xiangtan University
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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
    • C03C3/00—Glass compositions
    • C03C3/04—Glass compositions containing silica
    • C03C3/076—Glass compositions containing silica with 40% to 90% silica, by weight
    • C03C3/11—Glass compositions containing silica with 40% to 90% silica, by weight containing halogen or nitrogen
    • C03C3/112—Glass compositions containing silica with 40% to 90% silica, by weight containing halogen or nitrogen containing fluorine
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
    • C03B25/00—Annealing glass products
    • 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
    • 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
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    • C03C4/12—Compositions for glass with special properties for luminescent glass; for fluorescent glass

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Abstract

The invention discloses an application of lead nitrate, which is used as an additive and added into mid-infrared oxyfluoride silicate rare earth doped glass, wherein the addition amount of the lead nitrate accounts for 0.2-0.8% of the mole percentage of the mid-infrared oxyfluoride silicate rare earth doped glass. In addition, the invention also discloses intermediate infrared oxyfluoride silicate rare earth doped glass which contains 50-55 mol% of SiO2(ii) a 44-49 mol% of PbF2(ii) a Greater than 0 and less than or equal to 0.6mol% of TmF3(ii) a 0.2 to 0.8 mol% of Pb (NO)3)2. The invention also discloses a preparation method of the glass, which comprises the steps of mixing and grinding the raw material components, and carrying out melting and annealing treatment to prepare the mid-infrared oxyfluoride silicate rare earth doped glass; wherein the melting process is carried out in the air, and the temperature of the melting process is 1200-1400 ℃.

Description

Application of lead nitrate, intermediate infrared oxyfluoride silicate rare earth doped glass and preparation thereof
Technical Field
The invention relates to the technical field of mid-infrared luminescent glass, in particular to application of lead nitrate, mid-infrared oxyfluoride silicate rare earth doped glass and preparation thereof.
Background
Rare earth doped glass is the most commonly used reinforcing material for the intermediate infrared laser at present, OH-in raw materials and the environment is an unavoidable important influence factor in the industrial production process, and trace OH-content in a matrix can absorb the emission spectrum of the waveband to a great extent, so that the intermediate infrared luminous intensity is greatly reduced, and the application of the glass is greatly limited.
At present, the methods for removing hydroxyl groups in the preparation process of rare earth doped glass mainly comprise the following steps: physical dehydroxylation and chemical dehydroxylation. The prior art also has related reports, e.g. officialIn a patent of patent publication No. CN 102557436A, namely, mid-infrared anhydrous tellurate glass and a preparation method thereof, the components of the glass comprise 55-80 mol% of TeO220 to 45 mol% of ZnF25 to 20 mol% of sodium ion compound (Na)2F2Or Na2CO3) Firstly, mixing the components according to a certain ratio, then carrying out vacuum drying, carrying out gradient temperature rise drying at positive pressure of 4-12 kPa and within the range of 200-400 ℃, mixing the materials, and removing physical water molecules; and then heating to 800-900 ℃ in a high-purity oxygen environment, melting for 3h to obtain glass liquid, and performing stress annealing at 200 ℃ to obtain a sample. The patent mainly adopts a physical method to remove hydroxyl, achieves certain hydroxyl removing effect, but has extremely complex preparation process and higher requirements on preparation conditions. For another example, an article at Hunan Tan university, named Removal of hydroxyl radicals enhancing 2.85 μm mid-associated luminescence center in oxyfluorotellite glass with high ZnF2 content, Journal of Non-Crystalline Solids 502,97-105, reports a ZnF2The glass component proportion of the glass is 50TeO2-(45.5-x)PbF2-xZnF2-2.5YbF3-2HoF3(x ═ 0, 10, 20, 30, 45.5) and ZnF2As an additive, replacing PbF in the matrix2And proved that ZnF2Has better dehydroxylation effect, enhances the mid-infrared luminous intensity of 2.85 mu m to a great extent, and has the advantage of ZnF2The non-toxic substance is used as a matrix material, so that the environment is protected. However, ZnF2The introduction of a large amount of (b) tends to cause changes in the matrix of the glass and also adversely affects the phonon energy, thermal stability and the like of the glass.
Disclosure of Invention
In order to solve the problems in the prior art, the invention aims to provide the application of lead nitrate, and aims to greatly reduce the content of hydroxyl groups in the prepared silicate glass by adding trace lead nitrate, so as to improve the luminous intensity of the glass by 3.75 mu m.
In order to achieve the purpose, the invention provides an application of lead nitrate, which is used as an additive and added into mid-infrared oxyfluoride silicate rare earth doped glass to reduce the hydroxyl content in the prepared mid-infrared oxyfluoride silicate rare earth doped glass and improve the luminous intensity of the mid-infrared oxyfluoride silicate rare earth doped glass by 3.75 microns, wherein the addition amount of the lead nitrate accounts for 0.2-0.8 mol% of the mid-infrared oxyfluoride silicate rare earth doped glass.
The addition amount of the lead nitrate is strictly controlled, when the molar doping amount is more than 0.8%, bubbles generated by decomposition of the lead nitrate at high temperature can remain in the glass, the mechanical property of the glass is influenced, the structure in the glass is changed, the optical property of the glass is also influenced, and meanwhile, the hydroxyl removal effect is in a descending trend along with the increase of the addition amount of the lead nitrate; when the mixing amount of the lead nitrate is less than 0.2%, the hydroxyl removal effect is not obviously increased due to the insufficient mixing amount of the lead nitrate.
Preferably, the addition amount of the lead nitrate accounts for 0.4-0.8% of the mol percent of the mid-infrared oxyfluoride silicate rare earth doped glass, and preferably 0.6%.
The inventor researches and discovers that the hydroxyl content of the obtained mid-infrared oxyfluoride silicate rare earth doped glass can be obviously reduced by adopting trace lead nitrate as an additive and adding the trace lead nitrate into the mid-infrared oxyfluoride silicate rare earth doped glass. When the addition amount of lead nitrate is 0.6 percent of the mole percent of the mid-infrared oxyfluoride silicate rare earth doped glass, the hydroxyl content is unexpectedly found to be reduced to the minimum, and the mid-infrared luminescence of 3.75 mu m is strongest.
The invention also provides mid-infrared oxyfluoride silicate rare earth doped glass, which comprises the following components in percentage by mole:
Figure BDA0001940277130000021
preferably, the mid-infrared oxyfluoride silicate rare earth doped glass comprises the following components in mole percent:
Figure BDA0001940277130000022
Figure BDA0001940277130000031
more preferably, the mid-infrared oxyfluoride silicate rare earth doped glass comprises the following components in mole percent:
Figure BDA0001940277130000032
preferably, the mid-infrared oxyfluoride silicate rare earth doped glass can obtain luminescence of a mid-infrared 3.75 μm waveband under the excitation of a 808nm solid laser.
The invention uses SiO2-PbF2As a base material, TmF3The functional substance is Pb (NO) in a trace amount3)2As additives, substituted for PbF therein2The hydroxyl content in the obtained mid-infrared oxyfluoride silicate rare earth doped glass can be obviously reduced, and the luminous intensity of 3.75 mu m of the mid-infrared oxyfluoride silicate rare earth doped glass is improved.
The invention also provides a preparation method of the mid-infrared oxyfluoride silicate rare earth doped glass, which comprises the steps of mixing and grinding the raw material components, and carrying out melting and annealing treatment to prepare the mid-infrared oxyfluoride silicate rare earth doped glass;
wherein the melting process is carried out in the air, and the temperature of the melting process is 1200-1400 ℃.
Preferably, the melting time is 30-40 min.
Preferably, the annealing process is carried out in the air, the temperature of the annealing process is 320-390 ℃, and the time is 1-4 h.
Different from the existing preparation method, based on the raw material components of the oxyfluoride silicate rare earth doped glass, the invention realizes that the oxyfluoride silicate rare earth doped glass with stronger luminous intensity at the position of 3.75 mu m can be obtained by adopting simple melting and annealing treatment processes.
Researches show that the preparation method can be carried out in the air atmosphere without atmosphere protection which is usually adopted in the prior art in the melting process, and the melting temperature needs to be strictly controlled within the range by matching with the air atmosphere and the strict component proportion so as to prepare the transparent infrared luminescent glass with excellent performance.
Compared with tellurate glass, the mid-infrared oxyfluoride silicate rare earth doped glass has lower phonon energy, is beneficial to mid-infrared luminescence, and has better thermal, mechanical and chemical stability. The invention uses SiO2-PbF2As a base material, TmF3The functional substance is Pb (NO) in a trace amount3)2As additives, substituted for PbF therein2The hydroxyl content in the obtained mid-infrared oxyfluoride silicate rare earth doped glass can be obviously reduced. The glass has simple components, the sample does not need a complicated preparation process, only the simplest melting, annealing, grinding and polishing processes are needed, and the glass has stronger mid-infrared luminous intensity at the position of 3.75 mu m.
Has the advantages that:
1. with SiO2-PbF2Compared with tellurate glass, the prepared binary system oxyfluoride glass has lower phonon energy, is beneficial to mid-infrared luminescence, and has better thermal, mechanical and chemical stability;
2. from the Fourier spectrum, it can be seen that Pb (NO)3)2After doping, the glass disclosed by the invention not only has higher infrared transmittance at the middle and far infrared range of about 3-6 microns, but also has trace and efficient hydroxyl removal effect.
3.Pb(NO3)2The addition amount of the (Pb-0.6) is low, the hydroxyl removal effect is good, the content of hydroxyl in the glass (Pb-0.6) matrix is very low, the mid-infrared luminescence at the position of 3.75 mu m reaches the maximum, and the decomposed product can not cause pollution to the environment and has no influence on other properties of the glass.
4. Compared with the traditional preparation method of the mid-infrared luminescent glass, the binary system oxyfluoride rare earth doped silicate glass is prepared in the air atmosphere in the whole process, the process is simple and easy to implement, and the yield is extremely high.
Drawings
FIG. 1 shows the difference in Pb (NO)3)23.75 μm infrared emission spectrum of the glass sample under the doping amount;
FIG. 2 shows the difference in Pb (NO)3)2Fourier infrared transform spectrogram of the glass sample under the doping amount;
FIG. 3 shows the difference in Pb (NO)3)2A Raman spectrogram of the glass sample under the doping amount;
FIG. 4 shows different Pb (NO)3)2A glass sample object graph under the doping amount;
FIG. 5 is a sample diagram of Pb-1.0.
Detailed Description
The present invention will be further described with reference to specific embodiments.
The group distribution of each group of samples is shown in table 1 below:
TABLE 1 group distribution ratio of samples of each group
Figure BDA0001940277130000041
Figure BDA0001940277130000051
The method for preparing the sample by adopting the high-temperature solid-phase reaction method comprises the following steps:
(1) weighing required raw materials respectively according to a molar ratio;
(2) grinding the raw materials in an agate mortar respectively, uniformly mixing, putting into a corundum crucible, calcining at 1250 ℃ for 40min to completely melt the powder mixture, and only carrying out the melting in the air without atmosphere protection during high-temperature melting;
(3) pouring the material in the molten state into a graphite mold preheated in advance in a muffle furnace, performing stress relief annealing treatment for 3 hours at 350 ℃, and then cooling to room temperature along with the furnace;
(4) and taking out the sample from the mold, grinding the sample into block glass with the size of 10mm multiplied by 2mm, and polishing the block glass by using the diamond micro powder solution until the surface of the block glass is mirror smooth.
Performance and spectrum testing: and respectively carrying out infrared emission spectrum test, Fourier infrared spectrum test and Raman spectrum test on the groups of samples.
As shown in FIG. 1, it is understood from the infrared emission spectrum that the emission intensity of the glass sample at 3.75 μm in the mid-infrared region gradually increased with the increase in the content of lead nitrate, wherein the emission intensity of the Pb-0.6 sample was the strongest, while the emission intensity was lower with no addition and excessive addition.
As shown in FIG. 2, it is found from the Fourier infrared spectrum that a significant absorption peak is generated near 2954nm due to the stretching vibration of OH-, which is accompanied by Pb (NO)3)2The content of the lead-free acid increases, the absorption peak of OH-gradually decreases when the lead is Pb (NO)3)2When the content reaches 0.6mol%, the absorption peak reaches the minimum, which shows that the content of OH-in the glass matrix is greatly reduced after partial lead fluoride is replaced by the content of lead nitrate, and the effect of removing hydroxyl groups by Pb-0.6 is optimal. Meanwhile, the glass under the system has better infrared transmittance between 3 and 6 mu m and wider transmission wave band.
As shown in FIG. 3, it can be seen from the Raman spectrum that the phonon energy of the glass in the system of the present invention is relatively low, and the stability of the glass sample is not affected by the addition of lead nitrate, which is also a basic guarantee for infrared luminescence therein.
As shown in figure 4, the glass samples prepared by different adding amounts of lead nitrate have good shapes, no bubbles appear on the surface, and the mechanical property, the optical property and the like of the glass can not be influenced on the premise of ensuring the hydroxyl removal effect by strictly controlling the adding amount of the lead nitrate.
As shown in FIG. 5, in the Pb-1.0 sample diagram, it can be seen that a large number of bubbles were generated on the surface of the glass sample, and not only was the measured mid-infrared emission spectrum intensity reduced, but also the mechanical properties of the glass were adversely affected.

Claims (6)

1. The mid-infrared oxyfluoride silicate rare earth doped glass is characterized in that: comprises the following components in percentage by mole:
SiO2 50~55mol%；
PbF2 44~49mol%；
TmF3 greater than 0, less than or equal to 0.6 mol%;
Pb(NO3)2 0.6mol%；
the Pb (NO)3)2The fluorescent powder is used as an additive and added into the mid-infrared oxyfluoride silicate rare earth doped glass for reducing the hydroxyl content in the prepared mid-infrared oxyfluoride silicate rare earth doped glass and improving the luminous intensity of the mid-infrared oxyfluoride silicate rare earth doped glass, wherein the luminous intensity is 3.75 mu m.
2. The mid-infrared oxyfluoride silicate rare earth doped glass of claim 1, wherein: the mid-infrared oxyfluoride silicate rare earth doped glass comprises the following components in percentage by mole:
SiO2 50mol%；
PbF2 48.8mol%；
TmF3 0.6mol%；
Pb(NO3)2 0.6mol%。
3. the mid-infrared oxyfluoride silicate rare earth doped glass according to any of claims 1-2, characterized in that: can obtain the luminescence of a middle infrared 3.75 mu m wave band under the excitation of a 808nm solid laser.
4. A method of making a mid-infrared oxyfluoride silicate rare earth doped glass according to any of claims 1 to 3, characterized in that: mixing and grinding the raw material components, and performing melting and annealing treatment to obtain the mid-infrared oxyfluoride silicate rare earth doped glass; wherein the melting process is carried out in the air, and the temperature of the melting process is 1200-1400 ℃.
5. The method of claim 4, wherein: the melting time is 30-40 min.
6. The method of claim 4, wherein: the annealing treatment is carried out in the air, the temperature of the annealing treatment is 320-390 ℃, and the time is 1-4 h.
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Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1562833A (en) * 2004-03-19 2005-01-12 中国科学院上海光学精密机械研究所 Tm3+/Yb3+Codoped heavy metal oxyfluoride silicate glass and preparation method thereof
CN101511742A (en) * 2006-09-04 2009-08-19 日本电气硝子株式会社 Process for producing glass

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1562833A (en) * 2004-03-19 2005-01-12 中国科学院上海光学精密机械研究所 Tm3+/Yb3+Codoped heavy metal oxyfluoride silicate glass and preparation method thereof
CN101511742A (en) * 2006-09-04 2009-08-19 日本电气硝子株式会社 Process for producing glass

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
Tm3+离子掺杂Ge-Ga-S-CsI硫卤玻璃近红外及中红外发光特性研究;张鹏君 等;《中国激光》;20100228;第37卷(第2期);第554-559页 *

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