CN110183104B - Deep ultraviolet transparent glass and preparation method and application thereof - Google Patents

Deep ultraviolet transparent glass and preparation method and application thereof Download PDF

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CN110183104B
CN110183104B CN201910577996.5A CN201910577996A CN110183104B CN 110183104 B CN110183104 B CN 110183104B CN 201910577996 A CN201910577996 A CN 201910577996A CN 110183104 B CN110183104 B CN 110183104B
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glass
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deep ultraviolet
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CN110183104A (en
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贾金升
张弦
张磊
石钰
李开宇
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China Building Materials Academy CBMA
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    • 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
    • C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
    • C03B5/00—Melting in furnaces; Furnaces so far as specially adapted for glass manufacture
    • C03B5/16—Special features of the melting process; Auxiliary means specially adapted for glass-melting furnaces
    • C03B5/235—Heating the glass
    • 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
    • C03C3/062—Glass compositions containing silica with less than 40% silica by weight
    • C03C3/064—Glass compositions containing silica with less than 40% silica by weight containing boron
    • C03C3/066—Glass compositions containing silica with less than 40% silica by weight containing boron containing zinc
    • 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
    • C03C4/0085—Compositions for glass with special properties for UV-transmitting glass

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Abstract

The invention discloses a deep ultraviolet transmitting glass material, a preparation method and application thereof, wherein the ultraviolet transmitting glass comprises the following components in percentage by weight: 54.0-67.0% P2O5，3.0‑10.0％SiO2，6.0‑13.0％Al2O3，10.0‑25.0％B2O3，4.0‑7.0％ZnO，0‑2.0％Li2O，0‑2.0％Na2O，0‑2.0％K2O, the ultraviolet transmitting glass has a transmittance of 50% or more at 185nm when the thickness is 1.0mm, and a thermal expansion coefficient of (60 + -3). times.10 at 30-300 deg.C‑7The temperature is lower than 500 ℃, and the chemical stability and the chemical resistance are of II level; the deep ultraviolet transmitting glass has the advantages of simple preparation method, environmental protection, no pollution, no introduction of heavy metal ions harmful to the environment and lower melting temperature.

Description

Deep ultraviolet transparent glass and preparation method and application thereof
Technical Field
The invention relates to the technical field of special glass materials and preparation thereof, in particular to deep ultraviolet transmitting glass and a preparation method and application thereof.
Background
Ultraviolet rays are electromagnetic waves commonly existing in nature, rays with the wavelength less than 380nm in the solar spectrum are called Ultraviolet rays (Ultraviolet Radiation), have important effects on the aspects of Ultraviolet sterilization, Ultraviolet authentication, Ultraviolet illumination and the like, and strong Ultraviolet rays can also cause certain damage to human skins, eyes and the like. The ultraviolet rays are divided into three types of UV-A (315-. Because the light emitted by the propeller flames of the aircrafts contains strong 220-280nm band deep ultraviolet light, the 220-280nm ultraviolet light becomes the characteristic light emitted by the aircrafts. The ultraviolet detector is used for judging the threat direction and degree by detecting the characteristic ultraviolet light of the propeller plume of the aircraft, sending alarm information in real time so as to select a proper time, implementing effective interference, taking evasion and other measures, and resisting attack of an enemy. The ultraviolet detection field is a research hotspot in the ultraviolet field in the world at present, the detection wavelength range is 185-280nm, no response is generated to the wavelength above 280nm, and the solar blind ultraviolet characteristic is really realized. Therefore, the method has important significance for detecting signals of deep ultraviolet, particularly in the deep ultraviolet region in the range of 185nm to 280 nm. However, 185-280nm is at the far end of deep ultraviolet, part of which belongs to the vacuum ultraviolet region, the ray capacity is particularly high, according to the theory that the transmission loss of electromagnetic waves in a medium is the shorter the wavelength is, the loss is larger, so that the ultraviolet transmitting materials which can be commercialized in the world are few in variety and the transmittance at 185nm is low.
There have been many studies on ultraviolet-transmitting materials at home and abroad, and these ultraviolet-transmitting materials mainly focus on fluoride single crystals, halide glass and quartz glass materials. Wherein fluoride crystals (e.g. CaF)2、MgF2Crystal) is difficult to grow, process and prepare, expensive because of the single crystal growth, and the crystal has inherent defects because of anisotropy, poor chemical stability, small geometric dimensions, and limited application; the halide glass contains fluoride or chloride, so that the halide can corrode the platinum crucible to a certain extent in the high-temperature melting process of the glass, the cost and the potential safety hazard of production are increased, the preparation condition is strict, and the price is high; although the transmittance of the high-purity quartz glass at 254nm reaches 91%, the quartz glass has high melting temperature, strict requirements on preparation conditions and high price, the difference between the thermal expansion coefficient and the thermal expansion coefficient of the kovar alloy is large, the high-purity quartz glass cannot be directly sealed with the kovar alloy, the application range is limited, and the application of the high-purity quartz glass is also limited.
The ultraviolet-transmitting glass material has good uniformity, high transmittance, controllable geometric shape and low price, and is a preferred material for the fields of national defense science and technology, high technology and the like. In China, ultraviolet-transmitting glass materials have been developed in the last 70 th century, and are widely applied to the aspects of special optical instruments such as power grid safety monitoring, forest fire warning, large-scale integrated circuit photoetching, crop pest control, ultraviolet optical lenses, ultraviolet spectrometers and the like, and the deep ultraviolet-transmitting glass materials used in the field of deep ultraviolet detection are lacked at present. The foreign ultraviolet-transmitting glass material products mainly comprise 8337B Schottky in Germany and American Corning 9471 ultraviolet-transmitting glass materials, the transmittances of the two materials at 200nm are respectively 40% and 35% (the thickness is 1mm), the transmittance at 185nm is lower, and the detection requirement of deep ultraviolet transmission can not be met.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide the low-softening-temperature deep ultraviolet transmitting glass which has high deep ultraviolet transmittance, low softening temperature and excellent chemical stability, and the thermal expansion coefficient of the low-softening-temperature deep ultraviolet transmitting glass can be matched with sealing of kovar alloy.
In order to achieve the purpose, the invention adopts the technical scheme that:
the deep ultraviolet transmitting glass comprises the following components in percentage by weight:
Figure BDA0002112556160000021
Figure BDA0002112556160000031
the alkali metal oxide is selected from Li2O、Na2O and K2At least one of O.
The Li2O、Na2O and K2The weight percentage of O is as follows:
Li2O 0-2.0％
Na2O 0-2.0％
K2O 0-2.0％。
thickness of the ultraviolet-transmitting glassAt a temperature of 1.0mm, the transmittance at 185nm is 50% or more, and the thermal expansion coefficient is (60 + -3) × 10 at 30-300 deg.C-7/° c, the softening temperature is less than 500 ℃.
Transition metal oxide Fe contained in the deep ultraviolet transmitting glass2O3And TiO2Is less than 1 PPm.
The invention also provides a preparation method of the deep ultraviolet transmitting glass, which comprises the following steps:
(1) iron removal and conversion: carrying out iron removal treatment on the raw materials, then proportioning the high-purity raw materials according to the designed components, and converting the weight of each component to obtain the corresponding raw material weight;
(2) pre-melting and high-temperature melting: adding the uniformly mixed powder into a platinum crucible at one time, and pre-melting the mixture in a glass melting furnace at the temperature of 700-850 ℃ for 50-80 minutes; then heating up to carry out high-temperature melting operation, continuously heating up to 1200-1350 ℃ at the heating rate of 5-10 ℃/min, melting for 4-8 hours, and stirring the mixed powder for 2-3 times in the melting process to obtain glass melt; when the mixed powder is melted, adopting a reducing atmosphere for protection and melting;
(3) and (3) casting molding: after the mixed powder is melted uniformly, taking the obtained glass melt out of the glass melting furnace, pouring the glass melt into a heat-resistant steel mold preheated to 450-550 ℃ for casting to a specified specification to obtain the preset formed glass;
(4) annealing treatment: and (3) putting the preset formed glass into an annealing furnace for annealing treatment, and cooling to obtain the colorless, transparent, uniform, bubble-free and stripe-free blocky ultraviolet-transmitting glass material.
The gas in the reducing atmosphere is carbon monoxide, and the obtaining process of the reducing atmosphere of the carbon monoxide gas is to put a small crucible filled with carbon powder or graphite powder into a melting furnace for heat preservation for 1.5 to 2.5 hours.
The invention also provides the application of the deep ultraviolet transmitting glass in sealing and connecting deep ultraviolet detecting window materials, manufacturing ultraviolet lamps, optical windows and ultraviolet spectrometers, optical instruments and pick-up lenses which require high ultraviolet-visible light transmittance.
Compared with the prior art, the deep ultraviolet transparent phosphate glass has the following characteristics:
(1) the glass has excellent deep ultraviolet penetration performance, and the transmittance of glass with the thickness of 1mm at 185nm is more than 50 percent;
(2) has a suitable thermal expansion coefficient of (60 +/-3) multiplied by 10-7/℃；
(3) Has a low softening temperature, the softening temperature is less than 500 ℃;
(4) and has good chemical stability and chemical resistance level II.
In the present invention, P2O5The glass is a main body of a skeleton structure formed by glass, is a component playing a main role in a glass skeleton, and is also a main component for improving ultraviolet transmittance. The phosphate glass system has short ultraviolet absorption cut-off wavelength, has a basic system for developing high-transmittance ultraviolet glass, and is generally double-bonded [ PO ] in the network structure of the glass4]Tetrahedra as units, connected at top angles to each other, P2O554.0-67.0% by weight of P2O5When the content is less than 54%, high transmittance of the ultraviolet glass, P, is not easily obtained2O5When the content is more than 67%, the refractive index of the glass decreases, the expansion coefficient increases, and the chemical resistance of the glass decreases.
SiO2Also, glass forms the main body of the skeleton structure, and is a component which plays a major role in the glass skeleton. SiO 22When introduced in small amounts, [ SiO ]4]Tetrahedron and [ PO ]4]The top angles of the tetrahedrons are connected, so that the network structure is enhanced, and the ultraviolet absorption limit moves to the short wave direction; when the amount of the introduced compound is large, [ PO ]4]The tetrahedra being present essentially as a network, [ SiO ] structure4]Excessive tetrahedra self-connected to each other, SiO2Has an ultraviolet cut-off wavelength of 160nm, B2O3Has an ultraviolet cut-off wavelength of 170nm, P2O5Has an ultraviolet cut-off wavelength of 145nm due to P2O5SiO 22The ultraviolet ray transmitting property of the optical filter is good, so that the phenomenon that the ultraviolet ray absorption limit moves to the long wave direction is generated. SiO 223.0-10.0% by weight of SiO2The content is less than 3.0 percent, ultraviolet glass with high transmittance is not easy to obtain, and the chemical resistance stability of the glass is reduced; SiO 22When the content is more than 10.0%, the high-temperature viscosity of the glass increases, resulting in a decrease in the ultraviolet transmittance of the glass.
B2O3Forming oxides for the glass and also being a constituent of the glass skeleton. Boron oxygen triangle (BO)3]And boron-oxygen tetrahedron [ BO4]Boron may be in the form of a trigonal [ BO ] under different conditions as a structural element3]Or boron-oxygen tetrahedron [ BO4]In the presence of B, it is difficult to form boron-oxygen tetrahedron under high-temperature melting conditions, but B is present only in the form of trihedron under certain conditions at low temperature3+There is a tendency to abstract free oxygen to form tetrahedra, making the structure compact and increasing the low temperature viscosity of the glass, but B is due to2O3The characteristics of reducing the glass viscosity at high temperature and increasing the glass viscosity at low temperature are also main components for reducing the glass refractive index, thereby determining B2O3The content range of (A) is small. P2O5Due to the existence of double bonds, tetrahedral connection at one end of the double bonds is broken, a three-dimensional network cannot be formed, but a layered structure is formed, so that the phosphate glass has poor chemical stability and high expansion coefficient, and B capable of entering the glass network is introduced into the glass2O3And then, the internal broken net structure can be repaired, so that the glass is turned to a three-dimensional framework structure from a two-dimensional layered structure, the chemical stability of the system is improved, and the ultraviolet absorption cutoff is facilitated to move to short wave. B is2O3In an amount of 10.0 to 25.0% by weight, B2O3The content of (b) is less than 10.0%, which may decrease the chemical stability of the glass; b is2O3A content of (b) of more than 25.0% increases the thermal expansion coefficient of the glass, and increases the tendency of the glass to phase separate.
Al2O3Adding Al to phosphate glass as intermediate oxide of glass2O3Then, Al3+Absorbing double bond oxygen in phosphorus-oxygen tetrahedron with [ PO ]4]Tetrahedron form novel [ AlPO ]4]Structure of [ SiO ]4]The tetrahedral structure is very similar to that of the prior art,thus, [ AlPO ]4]The tetrahedra are connected by bridge oxygen and are composed of [ PO ]4]、[AlO4]The overlapping composition strengthens the network structure, not only greatly improves the chemical stability, but also reduces the expansion coefficient, and more expensively, the structure does not reduce the quantity of bridge oxygen, and the ultraviolet absorption limit and the ultraviolet transmittance can be guaranteed. Al (Al)2O36.0-13.0 wt% of Al2O3Less than 6.0%, reduced glass resistance, reduced transition temperature, Al2O3The content of (b) is more than 13.0%, the ultraviolet transmittance is lowered.
The chemical stability can be improved by introducing a small amount of ZnO, the chemical performance of the glass can be improved by introducing a small amount of ZnO, but the ultraviolet transmittance of the glass can be reduced by introducing too much ZnO, so that the ultraviolet cutoff wavelength moves towards the long wave direction, the weight percentage of ZnO is 4.0-7.0%, the chemical resistance of the glass can be reduced when the content of ZnO is less than 4.0%, and the ultraviolet transmittance of the glass can be reduced when the content of ZnO is more than 7.0%.
Li2O、Na2O、K2O is alkali metal oxide, is glass network exo-oxide, mainly plays a role in network bond breaking in a phosphate glass system, generates non-bridge oxygen, the ultraviolet transmittance of the glass is related to the quantity of the bridge oxygen in the glass, if the quantity of the bridge oxygen is large, the ultraviolet transmittance limit moves towards the short wave direction, the transmittance is increased, and otherwise, the transmittance is reduced. But because of the addition of SiO in the phosphate system2And B2O3Added Li2O、Na2O、K2O but first repairs [ PO ]4]、[SiO4]And [ BO ]3]A breaking point therebetween, [ BO3]Transformation of triangular layered structure into [ BO ]4]The tetrahedron strengthens the network connection, increases the number of bridge oxygens, reduces the content of non-bridge oxygens, and shifts the intrinsic absorption of ultraviolet to the short wave direction. The content of alkali metal oxide is 1-5%, and the alkali metal oxide is selected from Li2O、Na2O and K2At least one of O, wherein Li20-2.0% of O and Na20-2.0% of O and K2The content of O in percentage by weight is 0-2.0%. Because of Li+The atomic radius is small, the field is strong, the polarizability is high, but when the content of the weight percentage is more than 2%, the glass liquid seriously erodes the crucible, so that the glass stripes are serious, and the glass quality is influenced; na (Na)2The introduction of O can improve the glass forming range of the glass and reduce the phase separation and crystallization tendency of the glass, but when the content of O is more than 2 percent by weight, the ultraviolet transmittance is greatly reduced.
In order to solve the problems in the prior art, the invention successfully develops the deep ultraviolet transmitting glass with the transmittance of more than 50 percent at the 185nm wavelength of the glass with the thickness of 1mm through the optimization of the design of the glass components, the preparation method of the glass is simple, the glass is environment-friendly and pollution-free, no heavy metal ions are introduced, the melting temperature is lower, the deep ultraviolet region in the range of 185nm to 280nm has the characteristics of high ultraviolet transmittance, proper thermal expansion coefficient, low softening temperature, excellent chemical stability and the like, is suitable for sealing with the kovar alloy, can be used for sealing of a deep ultraviolet detecting window material, and can also be used for manufacturing ultraviolet lamps, ultraviolet optical windows, ultraviolet spectrometers, optical instruments and camera lenses and the like which require high ultraviolet-visible light transmittance.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, embodiments of the present invention are described in further detail below.
The invention provides deep ultraviolet transparent glass which comprises the following components in percentage by weight:
Figure BDA0002112556160000061
Figure BDA0002112556160000071
the deep ultraviolet transmitting glass of the present invention does not substantially contain Cl-、SO3 2-No clarifying agent is introduced in the glass melting process; the melting of traditional glass needs to add a clarifying agent to eliminate bubbles in the glassFor purposes, however, whether As is used2O3、Sb2O3The equivalent elements or F, Cl elements for reducing the viscosity of the glass liquid can seriously absorb far ultraviolet rays or reduce the chemical stability of the glass, and no clarifying agent is introduced in the glass melting process, so that the deep ultraviolet transmitting phosphate glass provided by the invention needs to be prepared by a glass melting process without the clarifying agent.
The deep ultraviolet transmitting glass of the present invention belongs to a phosphate glass system, and does not substantially contain oxides of valence-changing elements, metal oxides harmful to the environment and oxides having a glass coloring function, such As As2O3、Sb2O5、PbO、CdO、Cr2O3、CuO、CoO、NiO、BeO、CeO2、V2O5、WO3、MoO3、MnO2、SnO2、Ag2O、Nd2O3And the like, which have a low electron transition energy, and an electron absorption energy is transited by irradiation of high-energy rays, so that ultraviolet rays are significantly absorbed in an ultraviolet region, particularly in a far ultraviolet region, and thus, the total amount of harmful impurities determines the ultraviolet transmittance and cut-off wavelength of the window glass material. For the glass with the use requirement of 185-band 200nm far-ultraviolet region, the content of the internal impurities such as Cr, Mn and the like is less than 1 ppm.
Preferably, the alkali metal oxide is selected from Li2O、Na2O and K2At least one of O.
Preferably, the Li2O、Na2O and K2The weight percentage of O is as follows:
Li2O 0-2.0％
Na2O 0-2.0％
K2O 0-2.0％。
preferably, when the thickness of the ultraviolet transmitting glass is 1.0mm, the transmittance of the ultraviolet transmitting glass at 185nm is more than 50%, and the thermal expansion coefficient is (60 +/-3) multiplied by 10 in the range of 30-300 DEG C-7Low softening temperature (less than 500 deg.C), good chemical stabilitySex, chemical resistance II grade.
Preferably, the transition metal oxide Fe contained in the deep ultraviolet transmitting glass2O3And TiO2Is less than 1 PPm.
The deep ultraviolet transmitting glass of the invention does not substantially contain transition metal oxide Fe2O3And TiO2Even if the content is contained, the content is caused by impurities in the raw materials, and the total amount is less than 1 PPm; there are many factors affecting the ultraviolet transmittance of deep ultraviolet transparent glass, and in addition to the components of the glass, harmful impurities such as Fe, Ti, etc. are important factors, and even trace impurities seriously affect the ultraviolet transmittance of the glass, so that the pollution of the harmful impurities is prevented in the whole production process of the glass.
The fact that the glass material is substantially free of a specific component means that the glass material is not intentionally added, and the fact that the glass material is incorporated in an extremely small amount due to the inclusion of other glass materials is not excluded to the extent that the glass material is inevitably contaminated with an extremely small amount of impurities from raw material impurities or the like and does not affect desired characteristics, but the content of these variable valence elements is strictly controlled to 1ppm or less when the glass material is incorporated.
The invention also provides a preparation method of the deep ultraviolet transmitting glass, which comprises the following steps:
(1) iron removal and conversion: carrying out iron removal treatment on the raw materials, then proportioning the high-purity raw materials according to the designed components, and converting the weight of each component to obtain the corresponding raw material weight;
the invention carries out iron removal treatment on the main raw material to improve the purity of the glass raw material, and the P in the invention2O5Introducing high-purity phosphoric acid, mixing other raw materials uniformly during the process of mixing, and then weighing the P2O5Slowly adding the mixture into the batch in batches, and slightly and uniformly stirring;
(2) pre-melting and high-temperature melting: adding the uniformly mixed powder into a platinum crucible at one time, and pre-melting the mixture in a glass melting furnace at the temperature of 700-850 ℃ for 50-80 minutes; then heating up to carry out high-temperature melting operation, continuously heating up to 1200-1350 ℃ at the heating rate of 5-10 ℃/min, melting for 4-8 hours, and stirring the mixed powder for 2-3 times in the melting process to obtain glass melt; when the mixed powder is melted, adopting a reducing atmosphere for protection and melting;
due to P2O5The glass has large volatilization amount when being heated, so that the components of the glass are not easy to control, and the invention adopts a one-time feeding and low-temperature premelting technology.
When the glass mixture is melted, the glass mixture is melted by adopting a reducing atmosphere for protection, and the reducing atmosphere is more favorable for obtaining stable high-transmittance far-transmitting ultraviolet glass than an oxidizing atmosphere; stirring with basket-type stirrer to clarify the high-temperature molten glass and eliminate bubbles, and further stirring to eliminate stripes.
(3) And (3) casting molding: after the mixed powder is melted uniformly, taking the obtained glass melt out of the glass melting furnace, and quickly pouring the glass melt into a heat-resistant steel mold preheated to 450-550 ℃ for casting to obtain the specified specification to obtain the preset formed glass;
(4) annealing treatment: and (3) putting the preset formed glass into an annealing furnace for annealing treatment, and cooling to obtain the colorless, transparent, uniform, bubble-free and stripe-free blocky ultraviolet-transmitting glass material.
Preferably, the gas in the reducing atmosphere is carbon monoxide, and the carbon monoxide gas reducing atmosphere is obtained by placing a small crucible filled with carbon powder or graphite powder in a melting furnace and preserving the temperature for 1.5-2.5 hours.
The preparation method is simple, the melting temperature is low, and the prepared deep ultraviolet light transmitting glass material has excellent performance, is suitable for sealing with kovar alloy, can be used for sealing deep ultraviolet detection window materials, can also be used for manufacturing ultraviolet lamps, optical windows, ultraviolet spectrometers, optical instruments and camera lenses which require high ultraviolet-visible light transmittance, and has wide market application prospect.
The invention is further illustrated by the following specific examples:
the glass chemistry (wt.%) and glass properties of the examples are detailed in table 1.
(1) Ultraviolet transmittance T [ λ is transmittance of glass at 185nm ];
(2) coefficient of thermal expansion alpha30/300An average coefficient of thermal expansion alpha of 30-300 DEG C30/300[10-7/℃]。
Wherein, the sample is subjected to surface grinding and polishing treatment according to the test requirements and then is subjected to various physicochemical property tests; the ultraviolet transmittance T of the glass at 185nm is tested by a spectrophotometer; the linear expansion coefficient of 30-300 ℃ is measured by a horizontal dilatometer, expressed as the mean linear expansion coefficient, using the method specified in ISO 7991.
Table 1 chemical composition (wt.%) and glass properties of the examples
Figure BDA0002112556160000091
Example 1
First, a glass raw material was selected in accordance with the glass composition of example 1 of Table 1, and the main raw material of the glass raw material was subjected to an iron removal treatment to increase the purity of the glass raw material, and an oxide of a valence-changing element such as Fe2O3Etc. are strictly controlled to obtain finished glass Fe2O3Less than 1PPm, and mixing with high-purity quartz sand (Fe)2O3The content of boric anhydride is less than 1PPm), boric anhydride (the content of oversize products with the size of 400 mu m is less than 10 percent, the content of undersize products with the size of 63 mu m is less than 10 percent), high-purity phosphoric acid and aluminum acetate (analytically pure) are uniformly mixed, then alkali metal is added to introduce and mix raw materials of lithium carbonate (analytically pure), sodium carbonate (analytically pure) and potassium carbonate (analytically pure) so as to avoid chemical reaction during mixing, the prepared batch does not need to be placed for too long time, and feeding operation is carried out as soon as possible so as to avoid agglomeration caused by reaction of phosphoric acid and the raw materials. The volatilization of the phosphoric acid is large, in order to ensure that the prepared glass is basically consistent with the designed components, the volatile batch materials such as phosphate and the like are melted into glass clinker by adopting a low-temperature premelting method, a closed crucible is adopted during premelting to reduce the volatilization of the components of the glass, the glass melting furnace with the premelting temperature of 800 ℃ is heated for 1 hour, then the temperature is continuously increased to 1300 ℃ at the temperature increasing rate of 8 ℃/minute to melt for 6 hours, and the reducing atmosphere is adopted to protect the glass mixture during meltingMelting, wherein the gas in the reducing atmosphere is carbon monoxide, and the obtaining process of the reducing atmosphere of the carbon monoxide gas is to put a small crucible filled with carbon powder or graphite powder into a melting furnace and keep the temperature for 2 hours. The density difference of various raw materials is large, the phenomenon of uneven concentration is easy to generate, so that the transmittance of the glass is reduced, the glass melt liquid needs to be stirred for 2-3 times in the melting process, the glass is melted uniformly, after the glass is melted, the glass melt liquid is taken out of a furnace and is quickly poured into a heat-resistant steel mold preheated to 500 ℃ to be cast into a specified test product requirement, then the test product requirement is put into an annealing furnace for annealing treatment, and the colorless, transparent, uniform, bubble-free and stripe-free block deep ultraviolet glass material is obtained after cooling. The test performance is shown in table 1, (1) the ultraviolet transmittance reaches 52.1% when the wavelength is 185 nm; (2) average linear expansion coefficient of 63 x 10 at 30-300 DEG C-7/℃。
Example 2
Actual composition of glass referring to table 1, example 2, the basic properties of the samples are shown in table 1, using the same raw materials and raw material requirements as in example 1, and using a melting process regime of heating in a glass melting furnace at a premelting temperature of 700 ℃ for 80 minutes, then continuing to heat to 1350 ℃ at a heating rate of 5 ℃/minute, melting for 4 hours, and casting into prescribed test articles in a heat-resistant steel mold preheated to 550 ℃ and the same test conditions as in example 1. (1) The ultraviolet transmittance reaches 51.2 percent when the wavelength is 185 nm; (2) average linear expansion coefficient of 58 x 10 at 30-300 DEG C-7/℃。
Example 3
Actual composition of glass referring to table 1, example 3, the basic properties of the samples are shown in table 1, using the same raw materials and raw material requirements as in example 1, and using a melting process regime of heating in a glass melting furnace at a premelting temperature of 850 ℃ for 50 minutes, then continuing to heat to 1200 ℃ at a heating rate of 10 ℃/minute for 8 hours of melting, and casting into prescribed test articles in a heat-resistant steel mold preheated to 450 ℃ and using the same test conditions as in example 1. (1) The ultraviolet transmittance reaches 51.4% at the wavelength of 185 nm; (2) average linear expansion coefficient of 59X 10 at 30-300 deg.C-7/℃。
Example 4
Actual composition of the glass referring to table 1, example 4, using the same raw materials and raw material requirements as in example 1, and using the same melting process regime and test conditions, the basic properties of the samples are shown in table 1. (1) The ultraviolet transmittance reaches 52.2 percent when the wavelength is 185 nm; (2) average linear expansion coefficient of 61X 10 at 30-300 deg.C-7/℃。
Example 5
Actual composition of the glass referring to table 1, example 5, using the same raw materials and raw material requirements as in example 1, and using the same melting process regime and test conditions, the basic properties of the samples are shown in table 1. (1) The ultraviolet transmittance reaches 51.2 percent when the wavelength is 185 nm; (2) average linear expansion coefficient of 58 x 10 at 30-300 DEG C-7/℃。
Example 6
Actual composition of the glass referring to table 1, example 5, using the same raw materials and raw material requirements as in example 1, and using the same melting process regime and test conditions, the basic properties of the samples are shown in table 1. (1) The ultraviolet transmittance reaches 52.3 percent when the wavelength is 185 nm; (2) average linear expansion coefficient of 59X 10 at 30-300 deg.C-7/℃。
The invention also provides application of the deep ultraviolet transmitting glass in sealing with kovar alloy, can be used for sealing deep ultraviolet detecting window materials, and can also be used for manufacturing ultraviolet lamps, optical windows, ultraviolet spectrometers, optical instruments and camera lenses which require high ultraviolet-visible light transmittance.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.

Claims (7)

1. The deep ultraviolet transparent glass is characterized by comprising the following components in percentage by weight:
Figure FDA0003210799020000011
when the thickness of the deep ultraviolet transmitting glass is 1.0mm, the transmittance of the deep ultraviolet transmitting glass at 185nm is more than 50 percent, and the thermal expansion coefficient is (60 +/-3) multiplied by 10 within the range of 30-300 DEG C-7/° c, the softening temperature is less than 500 ℃.
2. The deep ultraviolet transparent glass of claim 1, wherein the alkali metal oxide is selected from the group consisting of Li2O、Na2O and K2At least one of O.
3. The deep ultraviolet-transmitting glass according to claim 2, wherein the alkali metal oxide Li is2O、Na2O and K2The weight percentage of O is as follows:
Li2O 0-2.0％
Na2O 0-2.0％
K2O 0-2.0％。
4. the DUV-transmitting glass according to any one of claims 1 to 3, wherein Fe is a transition metal oxide contained in the DUV-transmitting glass2O3And TiO2Is less than 1 PPm.
5. The method for preparing the deep ultraviolet transparent glass according to any one of claims 1 to 4, which is characterized by comprising the following steps:
(1) iron removal and conversion: carrying out iron removal treatment on the raw materials, then proportioning the high-purity raw materials according to the designed components, and converting the weight of each component to obtain the corresponding raw material weight;
(2) pre-melting and high-temperature melting: adding the uniformly mixed powder into a platinum crucible at one time, and pre-melting the mixture in a glass melting furnace at the temperature of 700-850 ℃ for 50-80 minutes; then heating up to carry out high-temperature melting operation, continuously heating up to 1200-1350 ℃ at the heating rate of 5-10 ℃/min, melting for 4-8 hours, and stirring the mixed powder for 2-3 times in the melting process to obtain glass melt; when the mixed powder is melted, adopting a reducing atmosphere for protection and melting;
(3) and (3) casting molding: after the mixed powder is melted uniformly, taking the obtained glass melt out of the glass melting furnace, pouring the glass melt into a heat-resistant steel mold preheated to 450-550 ℃ for casting to a specified specification to obtain the preset formed glass;
(4) annealing treatment: and (3) putting the preset formed glass into an annealing furnace for annealing treatment, and cooling to obtain the colorless, transparent, uniform, bubble-free and stripe-free blocky ultraviolet-transmitting glass material.
6. The method according to claim 5, wherein the gas in the reducing atmosphere is carbon monoxide, and the carbon monoxide gas reducing atmosphere is obtained by placing a small crucible containing carbon powder or graphite powder in a melting furnace and maintaining the temperature for 1.5 to 2.5 hours.
7. The deep ultraviolet transmitting glass as claimed in any one of claims 1 to 4, which is used in sealing of deep ultraviolet detecting window materials, manufacturing of ultraviolet lamps, optical windows, ultraviolet spectrometers, optical instruments and pick-up lenses which require high ultraviolet-visible light transmittance.
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