阅读说明：本技术 一种含氧化钆的透红外镓酸盐氧氟玻璃及其制备方法 (Infrared transmitting gallate oxyfluoride glass containing gadolinium oxide and preparation method thereof ) 是由 李家成 崔素杰 张龙 姜雄伟 姜益光 王在洋 于 2020-07-17 设计创作，主要内容包括：一种含Gd<Sub>2</Sub>O<Sub>3</Sub>的透红外镓酸盐氧氟玻璃,组成为：Ga<Sub>2</Sub>O<Sub>3</Sub>:25～45mol％,Gd<Sub>2</Sub>O<Sub>3</Sub>:1～20mol％,RO:40～70mol,BaF<Sub>2</Sub>:5～20mol％,其中,Gd<Sub>2</Sub>O<Sub>3</Sub>可部分被Y<Sub>2</Sub>O<Sub>3</Sub>替代,Y<Sub>2</Sub>O<Sub>3</Sub>的替代范围为0～10mol％。本发明玻璃化转变温度高(>650℃),成玻性能好(ΔT:～130℃),声子能低,在2.5～6um中红外波段具有很好的透过率。具有制备温度相对较低(1450℃以下)、成玻璃性能好和较宽的中波红外高透过性,有更好的热稳定性和较宽的中红外透过窗口,特别适用于中红外波段的窗口材料及其它中红外光学器件的基质材料,同时也可作为高浓度稀土离子掺杂的理想基体。(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 20 mol% of Gd 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 10 mol%. 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. Has relatively low preparation temperature (below 1450 ℃), good glass forming performance, wider mid-wave infrared high permeability, better thermal stability and wider mid-infrared transmission window, and is particularly suitable for window materials of mid-infrared wave bands and other mid-infrared transmission windowsThe substrate material of the optical device can be used as an ideal matrix for doping high-concentration rare earth ions.)

1. Gd-containing material₂O₃The infrared transmitting gallate oxyfluoride glass is characterized in that Ga is₂O₃Introduction of BaF into-RO binary system gallate glass₂And Gd₂O₃The glass comprises the following components:

r is one or more of Ca, Sr and Ba.

2. The Gd-containing of claim 1₂O₃The infrared transmitting gallate oxyfluoride glass is characterized in that Ga₂O₃30 to 40 percent of Gd₂O₃5 to 15 percent of RO, 45 to 65 percent of BaF₂10 to 15 percent.

3. Gd-containing material₂O₃The infrared transmitting gallate oxyfluoride glass is characterized in that Ga is₂O₃Introduction of BaF into-RO binary system gallate glass₂And Gd₂O₃The glass comprises the following components:

r is one or more of Ca, Sr and Ba.

4. Gd-containing material₂O₃The preparation method of the infrared transmitting gallate oxyfluoride glass is characterized by comprising the following steps:

calculating the weight percentage of glass raw materials according to the mol percentage of the glass components in the claim 1 or 3, and then weighing the raw materials;

secondly, placing the uniformly mixed batch in a baking oven at 100-130 ℃, preserving heat for 12-36 h, moving the batch into a crucible, adding a cover, melting the batch 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;

thirdly, pouring the glass liquid on a stainless steel mold to form glass;

fourthly, the glass obtained in the third step is moved into the glass which is heated to the transition temperature (T)_g) Keeping the temperature in a muffle furnace for 3-5 h, annealing to room temperature at the speed of 10 ℃/h, and completely cooling to obtain the Gd-containing material₂O₃The infrared transmitting gallate oxyfluoride glass.

Technical Field

The present invention relates to a Gd-containing polymer having a broad band and excellent thermal stability₂O₃The 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 2.5-6 um wide-band high-transmission intermediate infrared window materials and other substrate materials of intermediate infrared optical devices.

Background

In recent years, with the rapid development of scientific 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 of higher precision, wider detection range and the like are provided for window materials, so that the window materials are required to have higher stability and wider transmission waveband windows.

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 system₂O₃The 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, Ga-based low phonon energy gallate glass can be formed without network formers (B, Si, P, Ge, As) at a certain cooling rate, wherein modifiers that can form stable gallate glass with gallium oxide are mainly alkaline earth oxides (CaO, SrO, BaO) with larger radii, lanthanum oxide, lead oxide and bismuth oxide (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).

Compared with other traditional network formsThe adult oxide, gallium oxide, has a relatively large atomic mass, a weak Ga-O bond, and a low phonon energy (670 cm)^-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 always the focus of attention of infrared material researchers, and with the maturity and wide application of a laser heating technology, an extremely high cooling rate can be 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 laser and infrared light waveguide, 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 Gd₂O₃The 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 10 mol%, while

Compared withThe ion radius is small, the ion mass is high, the converted phonon energy is relatively low, and the ion energy is relatively low in a forming areaLarge Ga₂O₃In 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, Gd³⁺Smaller radius of ion and easier entering of [ GaO ]₄]^-The gaps of the tetrahedral network improve the tightness of network connection, and in addition, Gd³⁺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 BaF₂Fluxing, namely reducing the melting temperature to be relatively low between 1400 and 1500 ℃, so that the infrared optical glass with larger size is prepared, and simultaneously, through a 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, so that the blue shift of the intrinsic absorption wavelength of a short wave band can be caused, and a transmission window is widened.

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 stability₂O₃Compared 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 material₂O₃Infrared transmitting gallate oxyfluoride glass (Ga)₂O₃-Gd₂O₃-RO-BaF₂) In Ga₂O₃Introduction of BaF into-RO binary system gallate glass₂And Gd₂O₃The glass comprises the following components:

r is one or more of Ca, Sr and Ba.

The Gd-containing compound₂O₃Ga in infrared transmitting gallate oxyfluoride glass₂O₃Has an optimum value of 30-40%, Gd₂O₃The optimal value of (A) is 5-15%, the optimal value of RO is 50-65%, and BaF₂The most preferable value of (1) is 10 to 15%, wherein Gd is₂O₃Can be partially covered with Y₂O₃Alternative, Y₂O₃The substitution range of (b) is 0 to 10 mol%.

Gd-containing material₂O₃The melting method of the novel infrared-transmitting gallate oxyfluoride glass comprises the following steps:

calculating the weight percentage of glass raw materials according to the mol percentage of the glass components in the claim 1 or 3, and then weighing the raw materials;

secondly, placing the uniformly mixed batch in a baking oven at 100-130 ℃, preserving heat for 12-36 h, moving the batch into a crucible, adding a cover, melting the batch 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;

thirdly, pouring the glass liquid on a stainless steel mold to form glass;

fourthly, the glass obtained in the third step is moved into the glass which is heated to the transition temperature (T)_g) Keeping the temperature in a muffle furnace for 3-5 h, annealing to room temperature at the speed of 10 ℃/h, and completely cooling to obtain the Gd-containing material₂O₃The infrared transmitting gallate oxyfluoride glass.

Index delta T ═ T for measuring glass thermal stability_x-T_gWherein T is_xIs the initial devitrification temperature, T, of the glass_gIs the glass transition temperature. And melting peak temperature T_mRelevant glass stability parameter H_r＝ΔT/(T_m-T_x) Δ T and H_rThe 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 compound₂O₃The measured thermal stability parameter Delta T of the novel infrared transmitting gallate oxyfluoride glass and the glass prepared by the preparation method₂O₃The content is 8mol andwhen Gd is introduced₂O₃And Y₂O₃The infrared high-transmittance band of the glass is 2.5-6 um.

Compared with the prior art, the invention has the beneficial effects that:

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 invention₂O₃Having a low phonon energy, Gd³⁺Storage of Ga³⁺Having the same charge, possibly entering the network as an intermediate with Ga³⁺Together forming a glass network structure, possibly filling gaps in the network, to compensate for GaO₄]The charges of the structural units form the oxyfluoride glass with low phonon energy and high stability.

3) BaF is introduced into the invention₂The 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) In the invention, partial substituted Gd is introduced³⁺Y of (A) is³⁺Ionic radius of the compound and Gd³⁺Close, equivalent substitution of Gd³⁺Position of ion in glass network, with Gd³⁺、Ga³⁺Together, a trivalent mixed cation effect is formed, thereby improving the glass forming ability.

5)Gd³⁺Ion ratio to La³⁺And Y³⁺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 added³⁺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 a wider intermediate infrared transmitting waveband (2.5-6 um) and low phonon energy, is suitable for window materials in the fields of medical imaging endoscopes, biological research microscopes, military/civil infrared detectors and the like, and 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	Tx	Tp	Tm	ΔT	Hr
							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 25Ga₂O₃-10BaO-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 the temperature for 0.5 hour, pouring the clarified glass liquid on a stainless steel template, then rapidly transferring the glass liquid into an annealing furnace heated to the glass transition temperature, preserving the temperature 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 N₂The 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。