A mid-infrared gallate glass and a preparation method and application thereof

Abstract

The application provides a kind of mid-infrared gallate glass and its preparation method and application, wherein, with oxide mass percentage, the components of the mid-infrared gallate glass include: Ga2O3: 26%~35%; CaO: 39%~47%; Al2O3: 3.1%~6.5%; Y2O3: 0.5%~13%; R: 11%~15%, wherein R is one or more of BaO, SrO, MgO; and M: 1%~5%, M is Na2O and / or K2O. The mid-infrared gallate glass provided by the application has high transmittance, good mechanical properties, high stability and strong adaptability to complex environments.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of optical glass materials, in particular to a mid-infrared gallate glass and a preparation method and application thereof. BACKGROUND

[0002] Mid-infrared glass is a special glass material with infrared transmission performance, which not only has excellent infrared transmission performance, but also has the advantages of good optical uniformity, low manufacturing cost and easy processing into large-size or complex-shaped products. It has always been the focus of research and application of infrared materials. The mid-infrared glasses that have been put into practical use at present include aluminate glass, gallate glass and heavy metal fluoride glass.

[0003] With the rapid development of science and technology, the demand for optical imaging systems is increasing, especially the wide-band transparent window material in the field of new generation of infrared photoelectric systems has a large gap, and higher precision and wider detection range are required for mid-infrared window materials, which requires the window material to have high stability and wide transmission band window. In many mid-infrared glass systems, the existence of weak Ga-O bond in gallate glass makes gallate glass have a wide infrared transmission range, and the infrared cutoff wavelength is red-shifted to 6.5 μm-7.0 μm (the cutoff wavelength of aluminate glass is 5.7 μm), so gallate glass has the potential to become a new generation of infrared photoelectric system wide-band transparent window material. However, the overall stability of the traditional gallate glass system is slightly poor, and its surface is easy to deliquesce and mildew in the actual application environment, which affects its transmission performance and use performance as a window material.

[0004] In order to meet the demand of new generation of infrared photoelectric system field for high-stability and wide-transmission mid-infrared window material, it is of great significance to improve the stability of gallate glass. SUMMARY

[0005] The main purpose of the present application is to provide a mid-infrared gallate glass and a preparation method and application thereof, and to solve the technical problem of how to provide a mid-infrared gallate glass with high transmission, good mechanical properties, high stability and strong adaptability to complex environment, so as to be more suitable for practical use.

[0006] The purpose of the present application and the technical problem are realized by adopting the following technical scheme. According to the present application, a mid-infrared gallate glass is provided, and the components of the glass are as follows in terms of mass percentage of oxides:

[0007] Ga2O3: 26% to 35%;

[0008] CaO: 39% to 47%;

[0009] Al2O3: 3.1% to 6.5%;

[0010] Y2O3: 0.5% to 13%;

[0011] R: 11% to 15%, wherein R is one or more of BaO, SrO, MgO; and,

[0012] M: 1% to 5%, M is Na2O and / or K2O.

[0013] The purposes and technical problems of the present application can also be further achieved by the following technical measures.

[0014] In some embodiments, the aforementioned mid-infrared gallate glass,

[0015] Ga2O3: 29% to 31%; and / or,

[0016] CaO: 42% to 46%; and / or,

[0017] Al2O3: 3.5% to 6.0%; and / or,

[0018] Y2O3: 2% to 10%.

[0019] In some embodiments, the aforementioned mid-infrared gallate glass, BaO: 5% to 7%.

[0020] In some embodiments, the aforementioned mid-infrared gallate glass, the sum of the contents of other alkaline earth metal oxides and M, except for BaO, is 9% to 11%;

[0021] The other alkaline earth metal oxides include SrO and / or MgO.

[0022] In some embodiments, the aforementioned mid-infrared gallate glass, the components further include TeO2, and the content of TeO2 is ≤12%.

[0023] In some embodiments, the aforementioned mid-infrared gallate glass, the components further include Sb2O3.

[0024] The purposes and technical problems of the present application can also be achieved by the following technical solutions. According to the present application, a preparation method of the aforementioned mid-infrared gallate glass is provided, which comprises the following steps:

[0025] After the ingredients are prepared according to the formula, the glass raw materials are obtained, the aforementioned glass raw materials are uniformly mixed, and then are melted at 1450-1500℃ for 6-12h, and are cooled to obtain a primary melting clinker;

[0026] The primary smelting clinker is smelted in a vacuum environment, the smelting temperature is 1450-1550 DEG C, the smelting time is 4-8h, then the middle infrared gallate glass is obtained by shaping, annealing and cooling.

[0027] The purposes and technical problems of the present application can also be further realized by the following technical measures.

[0028] In some embodiments, the vacuum degree of the vacuum environment in the preparation method is ≤3*10 -2 Pa.

[0029] The purposes and technical problems of the present application can also be realized by the following technical measures.

[0030] The purposes and technical problems of the present application can also be further realized by the following technical measures.

[0031] In some embodiments, the device is an infrared detector, an infrared aircraft, a fairing or a head cover.

[0032] The present application has at least the following advantages:

[0033] The present application provides a kind of middle infrared gallate glass and its preparation method and application, wherein, with oxide mass percentage, the components of middle infrared gallate glass include: Ga2O3: 26%-35%; CaO: 39%-47%; Al2O3: 3.1%-6.5%; Y2O3: 0.5%-13%; R: 11%-15%, wherein R is one or more of BaO, SrO, MgO; and, M: 1%-5%, M is Na2O and / or K2O.The middle infrared gallate glass provided by the present application has high transmittance, good mechanical properties, high stability and strong adaptability to complex environment.

[0034] The above description is only a summary of the technical solutions of the present application, in order to more clearly understand the technical means of the present application, and can be implemented according to the content of the specification, as follows. BRIEF DESCRIPTION OF DRAWINGS

[0035] Figure 1 is the scanning calorimetry curve of the middle infrared gallate glass in embodiment 1 of the present application;

[0036] Figure 2 is the 0-8um infrared light transmittance curve of the middle infrared gallate glass in embodiment 1 of the present application;

[0037] Figure 3 is the 700-1900 nm infrared light transmittance curve of the mid-infrared gallate glass in Embodiment 1 of the present application;

[0038] Figure 4 is the scanning calorimetry curve of the mid-infrared gallate glass in Embodiment 2 of the present application;

[0039] Figure 5 is the 0-8 μm infrared light transmittance curve of the mid-infrared gallate glass in Embodiment 2 of the present application;

[0040] Figure 6 is the 700-1900 nm infrared light transmittance curve of the mid-infrared gallate glass in Embodiment 2 of the present application. DETAILED DESCRIPTION

[0041] To further illustrate the technical means and effects taken by the present application to achieve the predetermined purposes, the specific embodiments, structures, features and effects of the mid-infrared gallate glass, the preparation method and the application thereof according to the present application are described in detail as follows in combination with the accompanying drawings and preferred embodiments. In the following description, different "an embodiment" or "embodiments" do not necessarily refer to the same embodiment. In addition, the specific features, structures or characteristics in one or more embodiments can be combined in any suitable form.

[0042] It should be noted that in the description of the present application, unless otherwise specified, the meaning of "a plurality of" is greater than or equal to two; the orientations or positional relationships indicated by the terms "upper", "lower", "left", "right", "inner", "outer" and the like are for the purpose of facilitating the description of the present application and simplifying the description, and do not indicate or imply that the device or element referred to must have a particular orientation, be constructed and operated in a particular orientation, and therefore cannot be understood as limiting the present application. When the absolute position of the described object changes, the relative positional relationship may also change accordingly.

[0043] In addition, "first", "second", and similar words used in the present application do not indicate any order, number or importance, but are only used to distinguish different parts. "Vertical" is not strictly vertical, but within the allowable range of error. "Parallel" is not strictly parallel, but within the allowable range of error. "Include" or "contain" and similar words mean that the elements before the word cover the elements listed after the word, and do not exclude the possibility of also covering other elements.

[0044] It should be noted that in the description of the present application, unless otherwise explicitly specified and limited, the terms "mounting", "connecting", "connection" should be understood in a broad sense, for example, can be fixed connection, can also be detachable connection, or integral connection; can be directly connected, or indirectly connected through an intermediate medium. For those skilled in the art, the specific meaning of the above terms in the present application can be understood according to the specific circumstances. When it is described that a specific device is located between a first device and a second device, there can be or can not be an intermediate device between the specific device and the first device or the second device.

[0045] Techniques, methods, and devices known to those of ordinary skill in the relevant art can not be discussed in detail herein, but should be considered part of the specification where appropriate. The present application provides these embodiments to make the present application thorough and complete, and fully express the scope of the present application to those skilled in the art. It should be noted that: unless otherwise specified, the relative arrangement of components and steps, the composition of materials, numerical expressions and values set forth in these embodiments should be interpreted as merely exemplary, not as limiting.

[0046] The present application provides a mid-infrared gallate glass, the components of which include, in terms of mass percentage of oxides:

[0047] Ga2O3: 26% to 35%;

[0048] CaO: 39% to 47%;

[0049] Al2O3: 3.1% to 6.5%;

[0050] Y2O3: 0.5% to 13%;

[0051] R: 11% to 15%, wherein R is one or more of BaO, SrO, MgO; and,

[0052] M: 1% to 5%, M is Na2O and / or K2O.

[0053] Specifically, Ga2O3 is an important network former of mid-infrared gallate glass, which can improve the glass-forming ability and chemical stability of the glass. The mass fraction of this component is controlled between 26% and 35% in the present application, preferably between 29% and 31%. If the mass fraction of this component is less than 26%, the glass-forming ability of the glass becomes poor; if the mass content of this component exceeds 35%, the elastic modulus and chemical stability of the glass become poor.

[0054] CaO is a component necessary for the mid-infrared gallate glass to have good elastic modulus and chemical stability, the mass fraction of the component is controlled between 39% and 47% in the application, preferably between 42% and 46%, which can promote the compactness of the glass structure and improve the acid resistance of the glass. If the mass fraction of the component is less than 39%, the elastic modulus and chemical stability of the glass are not obviously improved, and if the mass fraction of the component is more than 47%, the glass is difficult to be fully melted, and the glass forming property is poor.

[0055] Al2O3 can form a network structure together with SiO2, so that the glass structure tends to be compact, and the mechanical properties and stability of the glass are improved, the mass fraction of the component is controlled between 3.1% and 6.5% in the application, preferably between 3.5% and 6%. If the content of Al2O3 is less than 3.1%, the internal network structure of the glass is small, and the strength, transmittance and other properties are low, and the network gap is small; if the content is more than 6.5%, the melting temperature required is too high, and defects such as stones are caused.

[0056] Y2O3 is the network outer body of the glass, which is used to reduce the melting temperature of the glass and facilitate the discharge of bubbles in the melting process, the mass fraction of the component is controlled between 0.5% and 13% in the application, preferably between 2% and 10%. If the mass fraction of the component is less than 0.5%, the glass melting temperature is relatively high, the viscosity is increased, the bubbles are not easy to discharge, the glass is difficult to be fully melted, and bubbles and stones are easily generated, and if the mass fraction of the component is more than 13%, the elastic modulus and chemical stability of the glass are poor.

[0057] R is BaO, SrO, MgO, which belongs to alkaline earth metal oxide, is the intermediate body of the glass, and is used to improve the glass forming property. The mass fraction of the component is controlled between 11% and 15% in the application, if the mass fraction of the component is less than 11%, the improvement of the glass forming property is not obvious, and if the mass fraction of the component is more than 15%, the chemical stability of the glass is reduced.

[0058] M is Na2O and / or K2O, Na2O and K2O are the network outer body oxide of the basic glass network body, which can improve the chemical stability and surface tension of the glass, has the effect of high temperature fluxing and accelerating the melting of the glass, and reduces the high temperature viscosity of the glass, which is also beneficial to the fining of the glass. The mass fraction of M is controlled between 1% and 5% in the application. If the content is less than 1%, the expected effect cannot be achieved, and if the content is more than 5%, the glass is prone to crystallization, the thermal expansion coefficient of the glass is too large, the chemical stability and mechanical properties of the glass are reduced, and non-bridge oxygen is generated to affect the transmittance of the glass.

[0059] In some embodiments, the aforementioned mid-infrared gallate glass, BaO: 5% to 7%.

[0060] BaO is a divalent network modifier, which can increase the refractive index, density, luster and chemical stability of the glass. A small amount of BaO can accelerate the melting of the glass, but too much BaO can cause secondary bubble in the glass. When the content of BaO is less than 5%, the effect of accelerating the melting of the glass is not obvious; when the content of BaO is greater than 7%, the crystallization temperature of the glass is increased, the crystallization tendency of the glass is increased, and the reaction between BaO and oxygen is increased, which makes the clarification of the melt difficult.

[0061] In some embodiments, in the aforementioned mid-infrared gallate glass, the sum of the content of other alkaline earth metal oxides and M is 9% to 11%, other than BaO; wherein the other alkaline earth metal oxides include SrO and / or MgO.

[0062] Specifically, within this range, the chemical properties of the glass are more stable, the mechanical properties are stronger, the transmittance is higher, and the glass is easier to melt.

[0063] In some embodiments, in the aforementioned mid-infrared gallate glass, the components further include TeO2, and the content of TeO2 is ≤12%.

[0064] The addition of TeO2 can improve the chemical stability of the glass, and the glass has high mechanical strength, good heat resistance and heat shock resistance. At the same time, the infrared transmittance of the glass is also improved. However, when the content of TeO2 is greater than 12%, the glass-forming property of the glass is affected, and crystallization occurs.

[0065] In some embodiments, in the aforementioned mid-infrared gallate glass, the components further include Sb2O3.

[0066] The Sb2O3 component is used as a defoaming agent for the glass. Preferably, the weight percentage content of the component is controlled to be 0.02% to 0.1%. If the weight percentage content of the component is less than 0.02%, the bubbles in the glass cannot be completely eliminated; if the weight percentage content of the component exceeds 0.1%, the excess clarifier cannot completely react, which reduces the homogenization effect of the glass.

[0067] The present application provides a preparation method of any one of the aforementioned mid-infrared gallate glasses, which comprises the following steps:

[0068] After the ingredients are prepared according to the formula, the glass raw materials are obtained, the aforementioned glass raw materials are uniformly mixed, and the mixture is melted at 1450 to 1500°C for 6 to 12 hours, and then cooled to obtain a primary melting clinker;

[0069] The aforementioned primary melting clinker is melted in a vacuum environment, the melting temperature is 1450 to 1550°C, the melting time is 4 to 8 hours, and then the glass is formed, annealed and cooled to obtain a mid-infrared gallate glass.

[0070] Specifically, ingredients are prepared according to the following formula: Ga2O3: 26% to 35% (in terms of mass percentage of oxides); Al2O3: 3.1% to 6.5%; CaO: 39% to 47%; Y2O3: 0.5% to 13%; R: 11% to 15%, wherein R is one or more of BaO, SrO, and MgO; and M: 1% to 5%, wherein M is Na2O and / or K2O.

[0071] After all raw material components are ground uniformly to form a mixture, the mixture is placed in a crucible and put into a silicon-carbon rod electric furnace at 1450-1500°C for 4-8 hours for melting, and then naturally cooled to obtain a primary melting clinker. If the melting time is less than 4 hours, a homogeneous glass body cannot be obtained; and if the melting time is more than 8 hours, energy is wasted.

[0072] The primary melting clinker is placed in a crucible and added into a vacuum melting furnace, and then heated to 1450-1500°C for melting, and the furnace is vacuumized to a vacuum degree of ≤3×10 -2 Pa; if the melting temperature is lower than 1450°C, the glass cannot be melted into a homogeneous glass body; and if the melting temperature is higher than 1500°C, the equipment cannot withstand the temperature, and preferably, the melting temperature is 1450°C, so that the glass formed after the secondary melting is uniform, without obvious crystallization or stoniness, and the crucible and the equipment are not damaged greatly.

[0073] The glass liquid obtained by the vacuum melting in the above step is poured into a mold for forming, and then annealed and cooled to obtain a mid-infrared gallate glass.

[0074] In some embodiments, in the above preparation method, the vacuum degree of the above vacuum environment is ≤3×10 -2 Pa.

[0075] Specifically, if the vacuum degree is greater than 3×10 -2 Pa, a large amount of hydroxyl groups exist in the glass, which affects the infrared transmission performance of the glass.

[0076] The present application provides a device comprising a window, and the window comprises any of the above mid-infrared gallate glasses.

[0077] In some embodiments, the above device is an infrared detector, an infrared aircraft, a fairing, or a head cover.

[0078] The present application will be further described in conjunction with specific embodiments, but it should not be understood as limiting the scope of protection of the present application. Some non-essential improvements and adjustments to the present application made by those skilled in the art based on the above content of the present application still belong to the scope of protection of the present application.

[0079] Unless otherwise defined, all terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this application belongs. Methods and materials are described herein for use in the present application; other, suitable methods and materials known in the art can also be used. The materials, methods, and examples provided herein are illustrative only and not intended to be limiting.

[0080] In the following examples, the infrared light transmittance spectrum is tested according to the test requirements, the sample after surface grinding and polishing treatment is 2mm thick, the test infrared wavelength range is 1μm~8μm infrared light transmittance; the glass transition temperature test uses a German NETZSCH DSC analyzer, the sample is ground, sieved and tested in powder form, the test temperature range is 100℃~1000℃; the moisture resistance of the sample is tested according to the test standard GB / T6582-1997; the acid resistance of the sample is tested according to the test standard GB / T6581-2007.

[0081] Example 1

[0082] The present embodiment provides a mid-infrared gallate glass and a preparation method thereof.

[0083] According to the corresponding glass components and contents of the formula, the corresponding weights of raw materials are weighed, wherein CaO, BaO, Na2O and K2O are introduced in the form of corresponding carbonates. In terms of mass percentage of oxides, the components of the mid-infrared gallate glass include: Ga2O3: 26.19%; CaO: 41.46%; Al2O3: 4.57%; Y2O3: 11%; BaO: 7.28%; MgO: 6.61%; Na2O: 2.39%; K2O: 0.47%; and Sb2O3: 0.03%. After the raw materials are ground into powder and uniformly mixed, they are melted at 1450℃ for 12h, cooled, and a primary melting clinker is obtained.

[0084] The primary melting clinker is melted in a vacuum environment, the vacuum degree is 2×10 -2 Pa, the melting temperature is 1480℃, the melting time is 8h, after complete melting, the mid-infrared gallate glass is obtained through fining, shaping, annealing and cooling.

[0085] The obtained mid-infrared gallate glass is tested. The heat resistance thereof is tested by differential scanning calorimetry, the differential scanning calorimetry curve thereof is as shown in Figure 1 , and the glass transition temperature thereof is 714.4℃. The infrared transmittance of the mid-infrared gallate glass is detected, the 0~8μm infrared light transmittance curve thereof is as shown in Figure 2 , and the 900~1700nm infrared light transmittance curve thereof is as shown in Figure 3The infrared transmittance curve of the obtained mid-infrared gallate glass is shown in FIG. 3, and the average transmittance of the mid-infrared gallate glass under infrared light with a wavelength of 3.7-4.8 μm is 81.9%, and the average transmittance of the mid-infrared gallate glass under infrared light with a wavelength of 900-1700 nm is 84.7%. The moisture resistance and acid resistance of the mid-infrared gallate glass are detected, and the moisture resistance is A level, and the acid resistance is 3 level.

[0086] Example 2

[0087] The present embodiment provides a mid-infrared gallate glass and a preparation method thereof.

[0088] The raw materials corresponding to the glass components and contents in the formula are weighed according to the corresponding weights, wherein CaO, BaO, Na2O and K2O are introduced in the form of corresponding carbonates. In terms of mass percentage of oxides, the components of the mid-infrared gallate glass include: Ga2O3: 32.19%; CaO: 43.21%; Al2O3: 5.53%; Y2O3: 3.1%; BaO: 6.08%; MgO: 6.99%; Na2O: 1.36%; K2O: 0.51%; TeO2: 1%; and Sb2O3: 0.03%. After the raw materials are ground into powder and uniformly mixed, primary melting clinker is obtained by melting at 1460 ℃ for 12 h and cooling.

[0089] The primary melting clinker is melted in a vacuum environment, the vacuum degree is 2.5×10 -2 Pa, the melting temperature is 1470 ℃, the melting time is 8 h, and after complete melting, the mid-infrared gallate glass is obtained by fining, shaping, annealing and cooling.

[0090] The obtained mid-infrared gallate glass is tested. The heat resistance thereof is tested by differential scanning calorimetry, and the differential scanning calorimetry curve is shown in FIG. 2, and the glass transition temperature thereof is 708.4 ℃. The infrared transmittance of the mid-infrared gallate glass is detected, the 0-8 μm infrared light transmittance curve thereof is shown in FIG. 3, the 900-1700 nm infrared light transmittance curve thereof is shown in FIG. 4, the average transmittance of the mid-infrared gallate glass under infrared light with a wavelength of 3.7-4.8 μm is 82.4%, and the average transmittance of the mid-infrared gallate glass under infrared light with a wavelength of 900-1700 nm is 84.8%. The moisture resistance and acid resistance of the mid-infrared gallate glass are detected, and the moisture resistance is A level, and the acid resistance is 3 level. Figure 4 Figure 5 Figure 6

[0091] ​​​As can be seen from the examples 1-2, the mid-infrared gallate glass provided by the application has high transmittance, the average transmittance under infrared light with a wavelength of 3.7-4.8 μm is greater than 82%, and the average transmittance under infrared light with a wavelength of 900-1700 nm is greater than 84%. Moreover, the mid-infrared gallate glass has high chemical stability and strong adaptability to complex environment, as it has high temperature resistance, moisture resistance reaching A level, and acid resistance reaching level 3.

[0092] The technical features in the claims and / or the specification of the present application can be combined, and the combination manner is not limited to the combination obtained by reference relationship in the claims. The technical solutions obtained by combining the technical features in the claims and / or the specification are also within the protection scope of the present application.

[0093] The above is only the preferred embodiment of the present application, and does not limit the present application in any form. Any simple modification, equivalent change and modification made to the above embodiment according to the technical essence of the present application are still within the scope of the technical solutions of the present application.

Claims

1. A mid-infrared gallate glass characterized in that, In terms of oxide mass percentage, the components include: Ga2O3: 26% to 35%; CaO: 39% to 47%; Al2O3: 3.1% to 6.5%; Y2O3: 0.5% to 13%; R: 11% to 15%, wherein R is one or more of BaO, SrO, and MgO; and M: 1% to 5%, wherein M is Na2O and / or K2O.

2. The mid-infrared gallate glass according to claim 1, wherein, Ga2O3: 29% to 31%; and / or, CaO: 42% to 46%; and / or, Al2O3: 3.5% to 6.0%; and / or, Y2O3: 2% to 10%.

3. The mid-infrared gallate glass according to claim 1, wherein, BaO: 5% to 7%.

4. The mid-infrared gallate glass according to claim 3, wherein The sum of the content of other alkaline earth metal oxides and M, except BaO, is 9% to 11%. The other alkaline earth metal oxides include SrO and / or MgO.

5. The mid-infrared gallate glass according to claim 1, wherein The components further include TeO2, and the content of TeO2 is ≤12%.

6. The mid-infrared gallate glass according to claim 1, wherein The components further include Sb2O3.

7. A method of making the mid-infrared gallate glass of any one of claims 1-6, characterized in that, The method comprises the following steps: After the raw materials are prepared according to the formula, the raw materials are mixed uniformly, melted at 1450 to 1500°C for 6 to 12 hours, cooled, and a primary melting clinker is obtained; The primary melting clinker is melted in a vacuum environment, the melting temperature is 1450 to 1550°C, the melting time is 4 to 8 hours, and then the mid-infrared gallate glass is obtained through shaping, annealing, and cooling.

8. The preparation method according to claim 7, characterized in that, The vacuum degree of the vacuum environment is ≤3×10 -2 Pa.

9. An apparatus, comprising: The device comprises a window, and the window comprises the mid-infrared gallate glass according to any one of claims 1 to 6.

10. The apparatus of claim 9, wherein, The device is an infrared detector, an infrared aircraft, a fairing, or a head cover.

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