CN111875251B - Infrared transmitting gallate oxyfluoride glass containing gadolinium oxide and preparation method thereof - Google Patents
Infrared transmitting gallate oxyfluoride glass containing gadolinium oxide and preparation method thereof Download PDFInfo
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- 239000011521 glass Substances 0.000 title claims abstract description 94
- LNTHITQWFMADLM-UHFFFAOYSA-N gallic acid Chemical compound OC(=O)C1=CC(O)=C(O)C(O)=C1 LNTHITQWFMADLM-UHFFFAOYSA-N 0.000 title claims abstract description 26
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 229910001938 gadolinium oxide Inorganic materials 0.000 title description 5
- 229940075613 gadolinium oxide Drugs 0.000 title description 5
- CMIHHWBVHJVIGI-UHFFFAOYSA-N gadolinium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[Gd+3].[Gd+3] CMIHHWBVHJVIGI-UHFFFAOYSA-N 0.000 title description 5
- 239000000463 material Substances 0.000 claims abstract description 18
- 229910016036 BaF 2 Inorganic materials 0.000 claims abstract description 6
- 229910052688 Gadolinium Inorganic materials 0.000 claims abstract description 3
- 239000002994 raw material Substances 0.000 claims description 14
- 238000001816 cooling Methods 0.000 claims description 12
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 10
- 238000002844 melting Methods 0.000 claims description 10
- 230000008018 melting Effects 0.000 claims description 10
- 239000007788 liquid Substances 0.000 claims description 9
- 229910052760 oxygen Inorganic materials 0.000 claims description 6
- 239000001301 oxygen Substances 0.000 claims description 6
- 229910001220 stainless steel Inorganic materials 0.000 claims description 6
- 239000010935 stainless steel Substances 0.000 claims description 6
- 238000000137 annealing Methods 0.000 claims description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 5
- 239000000155 melt Substances 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 5
- 229910052757 nitrogen Inorganic materials 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 5
- 229910002056 binary alloy Inorganic materials 0.000 claims description 4
- 229910005191 Ga 2 O 3 Inorganic materials 0.000 claims description 3
- 239000006060 molten glass Substances 0.000 claims description 3
- 238000005303 weighing Methods 0.000 claims description 3
- 230000007704 transition Effects 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims 1
- 230000005540 biological transmission Effects 0.000 abstract description 12
- 238000002834 transmittance Methods 0.000 abstract description 9
- 230000009477 glass transition Effects 0.000 abstract description 5
- 239000011159 matrix material Substances 0.000 abstract description 5
- -1 rare earth ions Chemical class 0.000 abstract description 5
- 229910052761 rare earth metal Inorganic materials 0.000 abstract description 4
- 238000007496 glass forming Methods 0.000 abstract description 3
- 230000003287 optical effect Effects 0.000 abstract description 3
- 238000006467 substitution reaction Methods 0.000 abstract description 3
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 12
- 150000002500 ions Chemical class 0.000 description 8
- AJNVQOSZGJRYEI-UHFFFAOYSA-N digallium;oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Ga+3].[Ga+3] AJNVQOSZGJRYEI-UHFFFAOYSA-N 0.000 description 6
- 229910001195 gallium oxide Inorganic materials 0.000 description 6
- 229910052697 platinum Inorganic materials 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- 239000004615 ingredient Substances 0.000 description 3
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 2
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 230000006399 behavior Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 150000001768 cations Chemical class 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
- 229910052733 gallium Inorganic materials 0.000 description 2
- 229910052746 lanthanum Inorganic materials 0.000 description 2
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 description 2
- 239000003607 modifier Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229910000287 alkaline earth metal oxide Inorganic materials 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910000416 bismuth oxide Inorganic materials 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000004031 devitrification Methods 0.000 description 1
- 238000002059 diagnostic imaging Methods 0.000 description 1
- TYIXMATWDRGMPF-UHFFFAOYSA-N dibismuth;oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Bi+3].[Bi+3] TYIXMATWDRGMPF-UHFFFAOYSA-N 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 238000003682 fluorination reaction Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 1
- 238000004093 laser heating Methods 0.000 description 1
- 229910000464 lead oxide Inorganic materials 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 239000005304 optical glass Substances 0.000 description 1
- 238000012634 optical imaging Methods 0.000 description 1
- 230000005693 optoelectronics Effects 0.000 description 1
- SIWVEOZUMHYXCS-UHFFFAOYSA-N oxo(oxoyttriooxy)yttrium Chemical compound O=[Y]O[Y]=O SIWVEOZUMHYXCS-UHFFFAOYSA-N 0.000 description 1
- YEXPOXQUZXUXJW-UHFFFAOYSA-N oxolead Chemical compound [Pb]=O YEXPOXQUZXUXJW-UHFFFAOYSA-N 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
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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
- C03C4/00—Compositions for glass with special properties
- C03C4/10—Compositions for glass with special properties for infrared transmitting glass
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
- C03B19/00—Other methods of shaping glass
- C03B19/02—Other methods of shaping glass by casting molten glass, e.g. injection moulding
-
- 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
- C03C3/12—Silica-free oxide glass compositions
- C03C3/23—Silica-free oxide glass compositions containing halogen and at least one oxide, e.g. oxide of boron
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
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Abstract
Gd-containing material 2 O 3 The infrared transmitting gallate oxyfluoride glass comprises the following components: ga 2 O 3 :25～45mol％，Gd 2 O 3 :1～20mol％，RO:40～70mol，BaF 2 5 to 20mol% of Gd 2 O 3 Can be partially covered with Y 2 O 3 Alternative, Y 2 O 3 The substitution range of (A) is 0 to 10mol%. The glass transition temperature of the invention is high>650 ℃ and good glass forming performance (delta T: -130 ℃), low phonon energy and good transmittance in the mid-infrared band of 2.5-6 um. The glass has relatively low preparation temperature (below 1450 ℃), good glass forming performance, wider mid-wave infrared high transmittance, better thermal stability and wider mid-infrared transmission window, is particularly suitable for window materials of mid-infrared bands and matrix materials of other mid-infrared optical devices, and can also be used as an ideal matrix doped with high-concentration rare earth ions.
Description
Technical Field
The present invention relates to a Gd-containing polymer having a broad band and excellent thermal stability 2 O 3 The infrared transmitting gallate oxyfluoride glass and the preparation method thereof are characterized in that gallium oxide is used as a glass network forming body and is suitable for medium infrared window materials with high transmission of 2.5-6 um broadband and matrix materials of other medium infrared optical devices.
Background
In recent years, with the rapid development of science and technology, the demand for optical imaging systems is increasing, and especially wide-band transmission window materials have a large gap in the fields of multi-image cameras, endoscopes, biological microscopes, new-generation infrared optoelectronic systems, and the like. Meanwhile, with the trend of high precision in these fields, the requirements such as higher precision and wider detection range are put forward on the window material, which requires that the window material has higher stability and wider transmission waveband window.
Based on the fact that gallium oxide, which is an intermediate oxide in the mid-infrared glass system, has a similar elemental behavior to that of main group alumina, and gallium and aluminum have similar outermost layer electron, ionic radius and electronegativity, researchers have searched for Ga by replacing Al with Ga in the Al — Ca binary system 2 O 3 The impact on glass structure and performance. Early studies showed that gallium, like aluminum, does not form glass by itself, and that by adding suitable modifiers, it is possible to form Ga-based low phonon energy gallate glass without network formers (B, si, P, ge, as) at a certain cooling rate, wherein the modifiers which form stable gallate glass with gallium oxide are mainly alkaline earth oxides (CaO, srO, baO), lanthanum oxide, lead oxide and bismuth oxide with large radii (see Journal of Non-Crystalline Solids 81 (1986) 337-350, journal of Non-Crystalline Solids 80 (1986) 518-526 and Key Engineering Materials Vols.94-95 (1994) pp 257-278).
Gallium oxide has relatively large atomic mass, weak Ga-O bonds, and low phonon energy (670 cm) compared to other conventional network former oxides -1 ) And thus has a wider transmission wavelength. Meanwhile, because of the lack of network formers, gallium oxide has low bond strength, is easy to crystallize and phase-split in the preparation process of glass, the stability of the glass is relatively poor, and binary and ternary systems of the glass only have relatively small generation regions.
Gallium oxide has a wider transmission band and a higher transmittance in an infrared band due to its low phonon energy, and in recent years, is an important point of attention of infrared material researchers, and with the maturity and wide application of a laser heating technology, an extremely high cooling rate is achieved, and some glass systems with high melting points and poor glass formation begin to be attracted by the researchers, wherein a high-melting-point Ga-La system is one of binary systems which are researched more, and the system has lower phonon energy, wider transmission, higher refractive index and high nonlinear optics, and is a high-quality base material for infrared lasers and infrared light waveguides, but the preparation method is limited to a laser pneumatic suspension preparation method, and only 2-3 mm glass can be prepared at present, and the preparation size is too small to be practically used (see sci. Rep.7 (March) (2017) 45600).
Gd and La are in the same period as lanthanum, and have many similarities of physical and chemical behaviors with other elements in the same period, and Gd 2 O 3 The material is widely used as a raw material for preparing infrared transparent ceramics, and shows excellent optical properties in the middle infrared field. La causes a large structural distortion in the gallate network due to its large ionic radius, and causes a large number of non-bridged oxygen bonds, thereby being unfavorable for the stability of the glass network structure, and the introduction amount in the gallate glass is usually less than 10mol%, while
Compared with
Smaller ion radius, higher atomic mass, relatively lower converted phonon energy, and relatively larger Ga in the formation region 2 O 3 In an-RO system, gd with low phonon energy is introduced, so that the infrared transmission of the Gd is expected to be further expanded, and meanwhile, gd 3+ The ion radius is smaller and the ion is easier to enter [ GaO ] 4 ] - The gaps of the tetrahedral network improve the tightness of the network connection, and in addition, gd 3+ Compensation [ GaO ] 4 ] - The local charge of the tetrahedral network is also expected to further improve the thermal stability of the glass.
Fluorine and oxygen have similar ionic radius and electronegativity, occupy the same lattice site in network space, and are added with BaF 2 Fluxing, namely reducing the melting temperature to be between 1400 and 1500 ℃ which is relatively low, realizing the preparation of the infrared optical glass with larger size, and simultaneously carrying out fluorination reaction: f - +OH - →HF↑+O 2- Effectively reducing the influence of hydroxyl at the position of 3um on infrared transmission. Meanwhile, the 2P orbital energy of fluorine is lower than that of oxygen, which can cause short-band intrinsic absorption wavelength blueAnd moving and widening the transmission window.
Disclosure of Invention
The technical problem to be solved by the invention is to provide a Gd-containing glass with wide waveband and high transmittance and better glass stability 2 O 3 Compared with the existing heavy metal gallate oxide and oxyfluorgallate glass, the glass has better thermal stability and wider mid-infrared transmission window.
The technical solution of the invention is as follows:
gd-containing material 2 O 3 Infrared transmitting gallate oxyfluoride glass (Ga) 2 O 3 -Gd 2 O 3 -RO-BaF 2 ) In Ga 2 O 3 Introduction of BaF into-RO binary system gallate glass 2 And Gd 2 O 3 The glass comprises the following components:
r is one or more of Ca, sr and Ba.
The Gd-containing compound 2 O 3 Ga in infrared transmitting gallate oxyfluoride glass 2 O 3 Has an optimum value of 30-40%, gd 2 O 3 The optimal value of (A) is 5-15%, the optimal value of RO is 50-65%, and BaF 2 The most preferable value of (1) is 10 to 15%, wherein Gd is 2 O 3 Can be partially covered with Y 2 O 3 Alternative, Y 2 O 3 The substitution range of (b) is 0 to 10mol%.
Gd-containing material 2 O 3 The melting method of the novel infrared-transmitting gallate oxyfluoride glass comprises the following steps:
(1) calculating the weight percentage of the glass raw materials according to the mol percentage of the glass components as defined in claim 1 or 3, and then weighing each raw material;
(2) putting the mixed batch mixture into an oven at 100-130 ℃, preserving heat for 12-36 h, transferring into a crucible, adding a cover, melting in a resistance furnace at 1400-1450 ℃ for 1-3 h, introducing dry nitrogen or dry oxygen into the melt, cooling to 1300-1350 ℃, stirring for 0.5h, and preserving heat for 0.5h to obtain uniform and clear molten glass;
(3) pouring the molten glass on a stainless steel mold to form glass;
(4) transferring the glass obtained in the step (3) into a glass container heated to the transition temperature (T) g ) Keeping the temperature in a muffle furnace for 3 to 5 hours, annealing to room temperature at the speed of 10 ℃/h, and completely cooling to obtain the Gd-containing material 2 O 3 The infrared transmitting gallate oxyfluoride glass.
Index delta T = T for measuring glass thermal stability x -T g Wherein T is x Is the initial devitrification temperature, T, of the glass g Is the glass transition temperature. And melting peak temperature T m Relevant glass stability parameter H r ＝ΔT/(T m -T x ) Δ T and H r The larger the value, the better the thermal stability of the prepared glass, and the more favorable the preparation of large-size glass. Using the above Gd-containing compound 2 O 3 The measured thermal stability parameter Delta T of the novel infrared transmitting gallate oxyfluoride glass and the glass prepared by the preparation method 2 O 3 The content is 8mol and Gd is simultaneously introduced 2 O 3 And Y 2 O 3 The infrared high-transmittance wave band of the glass is improved obviously at times and is 2.5-6 um.
Compared with the prior art, the invention has the following beneficial effects:
1) The glass prepared by the invention has higher thermal stability than the existing gallate oxide and oxyfluorogallate glass, the preparation method is simple, the cost is low, and the large-size preparation of the glass is facilitated.
2) Gd incorporated in the present invention 2 O 3 Having a low phonon energy, gd 3+ Storage of Ga 3+ Having the same charge, possibly entering the network as an intermediate with Ga 3+ Together forming a glass network structure, possibly filling gaps in the network, to compensate for GaO 4 ]The charges of the structural units form the oxyfluoride glass with low phonon energy and high stability.
3) The inventionIntroducing BaF into 2 The glass melting temperature is reduced, the hydroxyl content in the glass can be effectively reduced, the glass transmission window is widened, the mixed ion effect is formed with other divalent cations in the glass, the crystallization tendency of the glass is reduced, and the stability of the glass is improved.
4) The invention introduces partial substituted Gd 3+ Y of (A) is 3+ Ionic radius of the compound and Gd 3+ Close, equivalent substitution of Gd 3+ Position of ion in glass network, with Gd 3+ 、Ga 3+ Together, a trivalent mixed cation effect is formed, thereby improving the glass forming ability.
5)Gd 3+ Ion phase vs. La 3+ And Y 3+ More amount can be introduced into the gallate glass, a better matrix environment is provided for the ultrahigh doping of the rare earth ions while the stability of the glass is improved, the doping of the ultrahigh concentration rare earth ions is hopefully realized, and more high-field-strength Gd is added 3+ The introduction of ions also greatly improves the chemical stability of the glass.
6) The infrared transmitting gallate oxyfluoride glass prepared by the invention has wider intermediate infrared transmitting waveband (2.5-6 um) and low phonon energy, is not only suitable for window materials in the fields of medical imaging endoscopes, biological research microscopes, military/civil infrared detectors and the like, but also can be used as a matrix material doped with high-concentration rare earth ions.
Drawings
FIG. 1 is a graph of the differential thermal profile of infrared-transmitting glasses of comparative example 1 and example 7 of the present invention.
FIG. 2 is a graph showing the transmittance of comparative example 1 and example 7 glasses according to the present invention.
Detailed Description
The molar compositions of the corresponding glasses and the measured values of the characteristic temperatures and stability parameters of the glasses are given in tables 1 and 2, respectively, and the invention is further illustrated below with reference to specific examples.
TABLE 1
TABLE 2
| Numbering | Tg | T x | T p | T m | ΔT | H r |
| Comparative example 1 | 602 | 721 | 775 | 1120 | 119 | 0.30 |
| Example 2 | 677 | 789 | 809 | 1051 | 112 | 0.42 |
| Example 3 | 709 | 805 | 819 | 1070 | 96 | 0.36 |
| Example 4 | 681 | 800 | 823 | 1077 | 119 | 0.43 |
| Example 5 | 685 | 817 | 841 | 1085 | 132 | 0.49 |
| Example 6 | 683 | 805 | 841 | 1112 | 122 | 0.39 |
| Example 7 | 646 | 799 | 838 | 1091 | 153 | 0.52 |
Comparative example 1:
glass composition of 25Ga 2 O 3 -10BaO-65RO, preparing 100g of raw material, firstly drying the raw material at 100 ℃ for 12 hours, transferring the raw material into a platinum crucible, then putting the platinum crucible containing the ingredients into an electric furnace at 1400 ℃ for melting for 1 hour, simultaneously introducing dry nitrogen into the melt, then cooling to 1300 ℃, stirring for 0.5 hour to make the glass liquid uniform, then preserving heat for 0.5 hour, pouring the clarified glass liquid on a stainless steel template, then rapidly transferring the glass liquid into an annealing furnace at the glass transition temperature, preserving heat for 3 hours, and slowly cooling to room temperature to eliminate the stress in the glass, thereby obtaining the infrared transmitting gallate oxyfluoride glass without gadolinium oxide. By TG/DTA3700 (SIINT), on N 2 The characteristic temperature values measured at a heating rate of 10/min under the atmosphere are shown in Table 2, and the stability parameters Δ T and H are given r 。
Example 2, example 3, example 4, example 5, example 6.
Weighing the components according to the mol percentage listed in table 1 to prepare 100g of raw materials, firstly drying the raw materials at 120 ℃ for 24-36 hours, transferring the raw materials into a platinum crucible, then putting the platinum crucible containing the ingredients into an electric furnace at 1400-1450 ℃ to be melted for 1-2 hours, simultaneously introducing dry nitrogen or dry oxygen into a melt, then cooling to 1350-1300 ℃, stirring for 0.5 hour to make the glass liquid uniform, then preserving heat for 0.5 hour, pouring the clarified glass liquid on a stainless steel template, then rapidly transferring the glass liquid into an annealing furnace which is heated to the glass transition temperature, preserving heat for 4 hours, and slowly cooling to the room temperature to eliminate the stress in the glass to obtain the infrared transmitting gallate oxyfluoride glass of gadolinium oxide, wherein the related characteristic temperature values and stability parameters are listed in table 2, and because Gd is used for 2 O 3 A dual role in the glass structure such thatGd 2 O 3 When a certain amount is added, the stability delta T of the glass is reduced after reaching the extreme value and the melting temperature T is reduced m Related parameter H r Then accompanied by Gd 2 O 3 Is increased.
Example 7.
Adopts glass with the composition of 35Ga 2 O 3 -10BaF 2 -37RO-8Gd 2 O 3 -10Y 2 O 3 Preparing 100g of raw materials, firstly drying the raw materials at 130 ℃ for 36 hours, transferring the raw materials into a platinum crucible, then putting the platinum crucible containing the ingredients into an electric furnace at 1450 ℃ for melting for 1 hour, simultaneously introducing dry nitrogen into the melt, then cooling to 1350 ℃, stirring for 0.5 hour to make the glass liquid uniform, then preserving heat for 0.5 hour, pouring the clarified glass liquid on a stainless steel template, then rapidly transferring the stainless steel template into an annealing furnace which is heated to the glass transition temperature, preserving heat for 5 hours, and slowly cooling to room temperature to eliminate the stress in the glass, thereby obtaining the infrared transmitting gallate oxyfluoride glass containing gadolinium oxide and yttrium oxide. The values of the characteristic temperature and the stability parameters are listed in Table 2, in the case of Gd being introduced 3+ After ionization, Y is introduced 3+ The stability of the glass is obviously improved, the increment is over 30 ℃, the temperature reaches 153 ℃ which is far higher than that of the comparative example 1 without doped trivalent ions, the hydroxyl absorption is obviously reduced, the transmittance is obviously improved, the transmittance is increased by about 10 percent, and the thermal stability and the infrared transmittance are shown in the figure.
Claims (3)
1. Gd-containing material 2 O 3 The infrared transmitting gallate oxyfluoride glass is characterized in that Ga is 2 O 3 Introduction of BaF into-RO binary system gallate glass 2 And Gd 2 O 3 The glass comprises the following components:
composition mol%
Ga 2 O 3 25~45
Gd 2 O 3 8~20
RO 40~70
BaF 2 5~20
Y 2 O 3 5~10
R is one or more of Ca, sr and Ba, gd 2 O 3 And Y 2 O 3 The mixing content of (A) falls within a range of 13 to 20.
2. The Gd-containing of claim 1 2 O 3 The infrared transmitting gallate oxyfluoride glass is characterized in that Ga 2 O 3 30 to 40 percent of Gd 2 O 3 8-15 percent of RO, 45-65 percent of BaF 2 10% -15%.
3. Gd-containing material 2 O 3 The preparation method of the infrared transmitting gallate oxyfluoride glass is characterized by comprising the following steps:
(1) calculating the weight percentage of the glass raw materials according to the mol percentage of the glass components in claim 1, and then weighing the raw materials;
(2) putting the evenly mixed batch materials into a container 100 o C~130 o C, keeping the temperature in an oven for 12h to 36h, moving the oven into a crucible, adding a cover, and placing the crucible into a furnace for 1400 to 1450 o Melting for 1-3h in a resistance furnace of C, introducing dry nitrogen or dry oxygen into the melt, and then cooling to 1300 DEG C o C~1350 o C, stirring for 0.5h, and then preserving heat for 0.5h to obtain uniform and clear glass liquid;
(3) pouring the molten glass on a stainless steel mold to form glass;
will be described in detail
The resulting glass is transferred to a glass which has been raised to a transition temperature (T g ) The muffle furnace is heated for 3 to 5 hours and then heated by 10 DEG o Annealing to room temperature at the speed of C/h, and completely cooling to obtain the Gd-containing material 2 O 3 The infrared transmitting gallate oxyfluoride glass.
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