A cut-off glass-ceramic, a method for manufacturing the same and an optical element

Abstract

The application provides a cut-off glass ceramic, a preparation method thereof and an optical element. The cut-off glass ceramic comprises the following components in percentage by weight: SiO2: 40-70%; Al2O3: 5-12%; MgO: 4-15%; CaO: 0-2%; B2O3: 0-4%; Na2O: 5-12%; K2O: 0-6%; Li2O: 0-2%; TiO2: 1-4%; Fe2O3: 8-20%; Co2O3: 2-8%; V2O5: 0-1%. The cut-off glass ceramic has relatively low production cost, is basically not permeable to visible light, has low near-infrared permeability, high mechanical strength and good chemical stability, and is suitable for use in the field of backplane display.

Description

TECHNICAL FIELD

[0001] The present application relates to a cut-off glass-ceramic and a preparation method thereof and an optical element, in particular to a cut-off glass-ceramic with low transmittance in the visible light to near-infrared wave band range, good mechanical strength and chemical stability, a preparation method thereof and an optical element, and belongs to the field of optical glass. BACKGROUND

[0002] The product of the micro-LED has the advantages of high contrast, high resolution, rich color and the like. At present, the backplane display is to directly weld the micro-LED to the PCB circuit board, but the flatness of the PCB board is low, and there are many defects, and the conditions of missing welding and false welding often occur, resulting in low product yield, thereby causing high cost. Directly welding the micro-LED to the black glass can solve the problem of uneven surface of the substrate, and the black glass substrate can also reduce the step of coating black ink in the process of preparing the backplane display, so as to reduce the preparation links and thereby reduce the manufacturing cost.

[0003] Patent application CN113754277A provides a black glass with low transmittance in the visible light and near-infrared region and a preparation method thereof, and the glass has good transmittance performance and chemical stability, but the mechanical strength of the glass cannot meet the processing requirements of the glass wafer.

[0004] Patent application CN101054263A provides a preparation method of black glass with high absorption effect at 200nm-2500nm. However, this patent introduces chromium oxide as one of the colorants, and Cr element in the glass may exist in the form of Cr 6+ , which is a prohibited substance of RoHS directive and belongs to non-environmental protection elements, and does not meet the national environmental protection requirements. SUMMARY

[0005] PROBLEMS TO BE SOLVED BY THE INVENTION

[0006] In view of the problems of low mechanical strength, low chemical stability and high transmittance in the visible light range of the existing glass products, the present application first provides a cut-off glass-ceramic. The cut-off glass-ceramic has low transmittance in the visible light range, low near-infrared transmittance, high mechanical strength, good chemical stability and meets the environmental safety standards, and has important significance for glass substrate materials used in the field of backplane display.

[0007] Further, the present application also provides a preparation method of the cut-off glass-ceramic, which is simple and easy to operate, and the raw materials are easy to obtain, and is suitable for mass production.

[0008] SOLUTIONS FOR SOLVING THE PROBLEMS

[0009] The present application first provides a cut-off glass-ceramic, which comprises the following components in percentage by weight:

[0010] SiO2: 40% to 70%, preferably 45% to 68%, more preferably 50% to 65%;

[0011] Al2O3: 5% to 12%, preferably 5.5% to 11%, more preferably 6% to 10%;

[0012] MgO: 4% to 15%, preferably 4.5% to 14%, more preferably 5% to 13%;

[0013] CaO: 0% to 2%, preferably 0% to 1%, more preferably 0% to 0.5%;

[0014] B2O3: 0% to 4%, preferably 0% to 3%, more preferably 0% to 2%;

[0015] Na2O: 5% to 12%, preferably 5.5% to 11%, more preferably 6% to 10%;

[0016] K2O: 0% to 6%, preferably 0.5% to 5%, more preferably 1% to 4%;

[0017] Li2O: 0% to 2%, preferably 0% to 1%, more preferably 0%;

[0018] TiO2: 1% to 4%, preferably 1.2% to 3.8%, more preferably 1.4% to 3.6%;

[0019] Fe2O3: 8% to 20%, preferably 9% to 19%, more preferably 10% to 18%;

[0020] Co2O3: 2% to 8%, preferably 2.5% to 7.5%, more preferably 3% to 7%;

[0021] V2O5: 0% to 1%, preferably 0% to 0.8%, more preferably 0 to 0.6%.

[0022] The cutoff glass-ceramic according to the application, wherein the sum Li2O+Na2O+K2O of the contents of Li2O, Na2O, K2O, in weight percent, is 5% to 20%, preferably 6% to 17%, further preferably 7% to 14%.

[0023] The cutoff glass-ceramic according to the application, wherein the ratio (SiO2+Al2O3) / (B2O3+Li2O+Na2O+K2O) of the sum of the contents of SiO2 and Al2O3 to the sum of the contents of B2O3, Li2O, Na2O and K2O, in weight percent, is 2.0 to 6.0, preferably 2.2 to 5.5, more preferably 2.8 to 5.0.

[0024] According to the cut-off glass-ceramics, the ratio of the sum of the contents of Li2O, Na2O and K2O to the sum of the contents of Fe2O3 and Co2O3, i.e. (Li2O+Na2O+K2O) / (Fe2O3+Co2O3), is 0.6-0.8, preferably 0.6-0.78, and more preferably 0.6-0.76.

[0025] According to the cut-off glass-ceramics, the cut-off wavelength of the cut-off glass-ceramics is 1500 nm or more when the thickness of the cut-off glass-ceramics is 0.5 mm; and / or,

[0026] The transmittance of the cut-off glass-ceramics at a wavelength of 2000-2200 nm is not more than 2%, and the transmittance at a wavelength of 2200-2400 nm is not more than 5% when the thickness of the cut-off glass-ceramics is 0.5 mm.

[0027] According to the cut-off glass-ceramics, the bending strength of the cut-off glass-ceramics is 100 MPa or more; and / or,

[0028] The elastic modulus of the cut-off glass-ceramics is 90 GPa or more; and / or,

[0029] The acid resistance of the cut-off glass-ceramics is Class 2 or more; and / or

[0030] The water resistance of the cut-off glass-ceramics is Class 2 or more.

[0031] The present application also provides a preparation method of the cut-off glass-ceramics, which comprises uniformly mixing the components of the cut-off glass-ceramics in a certain proportion, melting the mixture, homogenizing, shaping and annealing to obtain the cut-off glass-ceramics.

[0032] The preparation method comprises the following steps:

[0033] The components of the cut-off glass-ceramics are uniformly mixed in a certain proportion to obtain a mixture, and the mixture is then melted to obtain a molten glass;

[0034] The molten glass is homogenized and shaped in a mold to obtain a shaped body;

[0035] The shaped body is annealed to obtain the cut-off glass-ceramics.

[0036] According to the preparation method, the preparation method at least has one of the following conditions:

[0037] The melting temperature is 1300-1500℃;

[0038] The annealing temperature is 700-900℃;

[0039] The annealing time is 2-10h.

[0040] Further, the application also provides an optical element comprising the cutoff glass ceramic according to the application.

[0041] Effects of the application

[0042] The cutoff glass ceramic according to the application has relatively low production cost, is substantially not permeable to visible light, has low near-infrared permeability, high mechanical strength and good chemical stability, and is suitable for use in the field of backplane display.

[0043] Further, the preparation method of the cutoff glass ceramic according to the application is simple and easy to implement, raw materials are easy to obtain, and the method is suitable for mass production. BRIEF DESCRIPTION OF DRAWINGS

[0044] Figure 1 Fig. 1 shows the spectral transmittance curves of the cutoff glass ceramics of Examples 1-3;

[0045] Figure 2 Fig. 4 shows the XRD patterns of the crystalline phases of the cutoff glass ceramics of Examples 1-5. DETAILED DESCRIPTION

[0046] Various exemplary embodiments, features, and aspects of the present application will be described in detail below. The word "exemplary" is used herein to mean "serving as an example, instance, or illustration." Any implementation described herein as "exemplary" is not necessarily to be construed as preferred or advantageous over other implementations.

[0047] In addition, in order to better illustrate the present application, numerous specific details are given in the following detailed description. Those skilled in the art will understand that the present application can be practiced without certain specific details. In some instances, well-known methods, means, instruments and steps have not been described in detail in order to highlight the principles of the present application.

[0048] Unless otherwise specified, the units used in the present specification are international standard units, and the numerical values and numerical ranges appearing in the present application should be understood to include systematic errors that are inevitable in industrial production.

[0049] In the present specification, the meaning of "may" includes both the meaning of performing a certain process and the meaning of not performing a certain process.

[0050] In the present specification, the "some specific / preferred embodiments", "other specific / preferred embodiments", "embodiments", and the like mean that the particular element (for example, a feature, structure, property, and / or characteristic) described in relation to the embodiment is included in at least one of the embodiments described herein, and can be present in other embodiments or can not be present in other embodiments. In addition, it should be understood that the elements can be combined in various embodiments in any suitable manner.

[0051] In the present specification, the numerical range represented by "numerical value A to numerical value B" means a range including the end point numerical values A and B.

[0052] In the present specification, when "ordinary temperature" or "room temperature" is used, the temperature can be 15 to 25°C.

[0053] The "not containing" described herein means that the compound, element, or the like is not intentionally added as a raw material to the glass of the present application, but some impurities or components not intentionally added can be contained in a small amount or a trace amount in the final glass as a raw material and / or equipment for producing the glass, and such a case is also within the scope of the present application.

[0054] The present application first provides a cut-off glass-ceramic, which comprises the following components in weight percentage:

[0055] SiO2: 40 to 70%, preferably 45 to 68%, more preferably 50 to 65%;

[0056] Al2O3: 5 to 12%, preferably 5.5 to 11%, more preferably 6 to 10%;

[0057] MgO: 4 to 15%, preferably 4.5 to 14%, more preferably 5 to 13%;

[0058] CaO: 0 to 2%, preferably 0 to 1%, more preferably 0 to 0.5%;

[0059] B2O3: 0 to 4%, preferably 0 to 3%, more preferably 0 to 2%;

[0060] Na2O: 5 to 12%, preferably 5.5 to 11%, more preferably 6 to 10%;

[0061] K2O: 0 to 6%, preferably 0.5 to 5%, more preferably 1 to 4%;

[0062] Li2O: 0 to 2%, preferably 0 to 1%, more preferably 0%;

[0063] TiO2: 1 to 4%, preferably 1.2 to 3.8%, more preferably 1.4 to 3.6%;

[0064] Fe2O3: 8% to 20%, preferably 9% to 19%, more preferably 10% to 18%;

[0065] Co2O3: 2% to 8%, preferably 2.5% to 7.5%, more preferably 3% to 7%;

[0066] V2O5: 0% to 1%, preferably 0% to 0.8%, more preferably 0% to 0.6%.

[0067] The cut-off glass-ceramics has a bending strength of 100 MPa or more, an elastic modulus of 90 GPa or more, a cut-off wavelength of 1500 nm or more, a transmittance of no more than 2% in a wavelength range of 2000 nm to 2200 nm, and a transmittance of no more than 5% in a wavelength range of 2200 nm to 2400 nm, and is suitable for use in the field of backplane display.

[0068] The raw materials are introduced in the form of oxides in their respective contents. The composition of the optical glass of the present application is described in detail below.

[0069] The present application utilizes the formation of magnesium-aluminum-silicon microcrystals in the glass to improve the mechanical strength of the glass. Among them, MgO, Al2O3 and SiO2 are the basic components for forming cordierite (Mg 0.6 Al 1.2 Si 1.8 O6) microcrystals in the magnesium-aluminum-silicon system.

[0070] SiO2 is a network former and constitutes the skeletal structure of the glass, mainly existing in the form of silicon-oxygen tetrahedra and aluminum-oxygen tetrahedra. If the content of SiO2 is too low, the thermal stability and chemical stability of the base glass will be poor, and the mechanical strength of the glass will be low. If the content of SiO2 is too high, the glass melting process temperature is high, the bubbles in the glass are difficult to eliminate, and the solubility of the coloring components in the glass is reduced, which does not meet the transmittance requirement. Therefore, the content of SiO2 in the present application is 40% to 70% by weight, preferably 45% to 68%, and further preferably 50% to 65%, for example: 42%, 46%, 48%, 50%, 52%, 56%, 58%, 60%, 62%, 66%, 68%, etc.

[0071] Al2O3 is a network intermediate in the glass, which can enter the network framework, making the glass framework more compact, and improving the chemical stability, mechanical properties and thermal stability of the glass. However, when the content of Al2O3 is too high, the glass melting difficulty is increased. When the content of Al2O3 is too low, the corresponding effect cannot be achieved. Therefore, in the present application, the content of Al2O3 is 5% to 12% by weight, preferably 5.5% to 11%, and further preferably 6% to 10%, for example, 5.5%, 6.5%, 7%, 7.5%, 8%, 8.5%, 9%, 9.5%, 10%, 10.5%, 11%, 11.5%, etc.

[0072] MgO is a glass network modifier, which is distributed between the glass network and is one of the important components of the cordierite microcrystal, and can also provide free oxygen to improve the melting efficiency. However, when the content of MgO is too high, the main crystal phase formed in the glass is periclase rather than cordierite microcrystal, and the strength of the glass cannot meet the requirements. If the content of MgO is too low, the cordierite microcrystal is not easily formed in the glass, and the strength of the glass also cannot meet the requirements. In the present application, the content of MgO is 4% to 15% by weight, preferably 4.5% to 14%, and further preferably 5% to 13%, for example, 5%, 6%, 7%, 8%, 9%, 10%, 11%, 12%, 13%, 14%, etc.

[0073] In the present application, the role of CaO in the glass is similar to that of MgO, which can reduce the melting environment and improve the melting efficiency, and the introduction of appropriate amount of CaO can reduce the crystallization temperature of cordierite. When the content of CaO is too high, the crystallization tendency of the system may be changed. In the present application, the content of CaO is 0% to 2% by weight, preferably 0% to 1%, and further preferably 0% to 0.5%, for example, 0.2%, 0.4%, 0.5%, 0.6%, 0.8%, 1%, 1.2%, 1.4%, 1.5%, 1.6%, 1.8%, etc.

[0074] B2O3 is a network intermediate in the glass, which can accelerate the glass melting and fining process. However, when the content of B2O3 is too high, the structure of the glass is changed, B2O3 enters the glass network structure, and the solubility of the coloring component is reduced, affecting the transmission performance. When the content of B2O3 is too low, the corresponding effect cannot be achieved. Therefore, in the present application, the content of B2O3 is 0% to 4% by weight, preferably 0% to 3%, and further preferably 0% to 2%, for example, 0.5%, 1%, 1.5%, 2%, 2.5%, 3%, 3.5%, etc.

[0075] Li2O can effectively reduce the high-temperature viscosity of the glass and the surface tension of the glass, and help to eliminate bubbles in the glass. However, when the content of Li2O is too high, the melting temperature of the glass is increased, and the melting efficiency is reduced. When the content of Li2O is too low, the corresponding effect cannot be achieved. Therefore, in the present application, the content of Li2O is 0% to 2% by weight, preferably 0% to 1.5%, and further preferably 0% to 1%, for example, 0.1%, 0.2%, 0.3%, 0.4%, 0.5%, 0.6%, 0.7%, 0.8%, 0.9%, 1%, 1.1%, 1.2%, 1.3%, 1.4%, 1.5%, etc. +Li2O has strong aggregation effect in glass, and is a kind of nucleating agent. When the content of Li2O is too high, the base glass is prone to crystallization, and the glass forming performance is reduced. Meanwhile, the cost of Li2O is high, and the introduction of glass will increase the manufacturing cost. Therefore, in the present application, the content of Li2O is 0% to 2% by weight, preferably 0% to 1%, and further preferably 0%, for example: 0.2%, 0.4%, 0.6%, 0.8%, 1%, 1.2%, 1.4%, 1.6%, 1.8%, etc.

[0076] Na2O can improve the melting efficiency of glass, reduce the high temperature viscosity of glass, help to eliminate bubbles, and can also regulate the content of free oxygen in glass, so as to ensure that the ratio of Fe 2+ / Fe 3+ is in a reasonable range. When the content of Na2O is too low, the glass melting temperature is high and the fluxing efficiency is low, and the melting is in a partial reducing atmosphere, which will lead to a high ratio of Fe 2+ / Fe 3+ , so that the glass may have transmission in the ultraviolet region. When the content of Na2O is too high, the chemical stability and crystallization performance of the glass are poor, and the melting is in a partial oxidizing atmosphere, which leads to a low ratio of Fe 2+ / Fe 3+ , so that the glass may have transmission in the near infrared region, so as to achieve the effect of 0-1500nm wave band cutoff. Therefore, in the present application, the content of Na2O can be 5% to 12% by weight, preferably 5.5% to 11%, and further preferably 6% to 10%, for example: 5.5%, 6.5%, 7%, 7.5%, 8%, 8.5%, 9%, 9.5%, 10%, 10.5%, 11%, 11.5%, etc.

[0077] In the present application, the effects of Na2O and K2O in glass are similar. In addition, K2O is beneficial to improve the alkalinity of the glass system, so that the coloring ions in the base glass are in a high valence state. If the content of K2O is too high, the solubility of the coloring components in the glass will be reduced, and the intrinsic strength of the glass will also be reduced. In order to comprehensively improve the transmission performance, chemical stability and mechanical properties of the glass, the content of K2O in the present application is controlled to be 0% to 6% by weight, preferably 0.5% to 5%, and further preferably 1% to 4%, for example: 0.5%, 1%, 1.5%, 2%, 2.5%, 3%, 3.5%, 4%, 4.5%, 5%, 5.5%, etc.

[0078] The sum of the contents of Li2O, Na2O and K2O (Li2O+Na2O+K2O) in the glass mainly plays a role in improving the glass melting efficiency and reducing the high-temperature viscosity of the glass. Controlling the sum of the contents within a reasonable range is helpful to improve the glass fining and homogenizing ability and provide free oxygen to adjust the redox atmosphere of the glass to control the valence of the coloring ions, and finally obtain the effect of less than 1% transmittance in the 0-1500 nm wavelength range. When Li2O+Na2O+K2O is too low, the fluxing effect is not obvious, and at the same time, the free oxygen in the glass is not enough, and the smelting process is in an oxygen-deficient atmosphere, which is not conducive to the formation of Fe 3+ . If Li2O+Na2O+K2O is too high, the free oxygen content in the glass increases and destroys the network structure, the glass crystallization performance and chemical stability are poor, and at the same time, the glass is in an oxygen-rich environment, which is not conducive to the formation of Fe 2+ in the glass, and there may be higher transmittance in the 700-1100 nm wavelength range. Therefore, in the present application, the sum of the contents of Li2O, Na2O and K2O (Li2O+Na2O+K2O) is 5%-20%, preferably 6%-17%, and further preferably 7%-14%, for example, 6%, 7%, 8%, 9%, 10%, 11%, 12%, 13%, 14%, 15%, 16%, 17%, 18%, 19%, etc.

[0079] The viscosity of the glass has an important influence on the dissolution of the coloring agent components. In the present application, when the ratio of the sum of the contents of SiO2 and Al2O3 to the sum of the contents of B2O3, Li2O, Na2O and K2O (SiO2+Al2O3) / (B2O3+Li2O+Na2O+K2O) is too high, the glass viscosity is too high, the requirements for the smelting device will also be increased, at the same time, it will lead to the decrease of the solubility of the coloring components, and also affect the redox atmosphere in the glass smelting process, finally lead to the transmittance property of the glass not meeting the standard requirements. When (SiO2+Al2O3) / (B2O3+Li2O+Na2O+K2O) is too low, the stability of the glass is poor and does not meet the design requirements. Therefore, in the present application, (SiO2+Al2O3) / (B2O3+Li2O+Na2O+K2O) is 2.0-6.0, preferably 2.2-5.5, and further preferably 2.8-5.0, for example: 2.5, 3, 3.5, 4, 4.5, 5, 5.5, etc.

[0080] TiO2 is introduced as a crystal nucleus agent, which can reduce the crystallization peak temperature of magnesium-aluminum-silicon glass-ceramics, slow down the crystallization rate, and thus make the whole crystallization process easy to control. When the content of TiO2 is too high, the crystallization rate of the glass is too fast, and the crystallization process is not easy to control. When the content of TiO2 is too low, it cannot play a role in promoting crystallization. Therefore, the content of TiO2 in the present application is 1% to 4% by weight, preferably 1.2% to 3.8%, further preferably 1.4% to 3.6%, for example: 1.5%, 2%, 2.5%, 3%, 3.5%, etc.

[0081] Fe2O3 is one of the coloring components of the present application. In the high-temperature smelting process, Fe elements exist in the glass in the form of Fe 2+ , Fe 3+ , Fe 3+ has a strong light absorption effect mainly in the ultraviolet region, and Fe 2+ has a strong absorption effect in the 700nm-1100nm waveband. Reasonable control of the content of Fe elements in the component ensures the formation of appropriate Fe 3+ / Fe 2+ ratio in the glass to achieve the required transmission performance. When the content of Fe2O3 in the component is too low, Fe mainly exists in the form of Fe 3+ in the glass. When the content of Fe2O3 in the component is too high, it will affect the glass forming performance. Therefore, the content of Fe2O3 in the present application is 8% to 20% by weight, preferably 9% to 19%, further preferably 10% to 18%, for example: 9%, 10%, 11%, 12%, 13%, 14%, 15%, 16%, 17%, 18%, 19%, etc.

[0082] Co2O3 is also one of the coloring components of the present application. In the high-temperature smelting process, Co elements exist in the glass in the form of Co 2+ , Co 3+ . Co 2+ has a strong absorption effect in the 500nm-700nm waveband and at 1400nm in silicate glass. The absorption of Co 3+ mainly concentrates in the near-ultraviolet and blue light regions of 350nm, 425nm and 463nm. When the ratio of Co 2+ in the glass is too high, the transmission performance above 1500nm wavelength will be reduced. Reasonable control of the Co 3+ / Co 2+The content of Co2O3 in the present application is 2% to 8% by weight, preferably 2.5% to 7.5%, further preferably 3% to 7%, for example 2.5%, 3%, 3.5%, 4%, 4.5%, 6%, 6.5%, 7%, 7.5%, etc.

[0083] The atmosphere of the glass melting process has an important influence on the valence state of Fe and Co in the component. The high-temperature melting atmosphere is mainly related to the alkali metal in the glass component. If the ratio of the sum of the contents of Li2O, Na2O and K2O to the sum of the contents of Fe2O3 and Co2O3 (Li2O+Na2O+K2O) / (Fe2O3+Co2O3) is higher, it means that the content of alkali metal in the component is higher, and more free oxygen can be provided in the melting process. However, if (Li2O+Na2O+K2O) / (Fe2O3+Co2O3) is too high, the Fe and Co elements in the component are in a high valence state, which will cause the glass to have a certain transmittance in the wavelength range of 700 nm to 1100 nm, and will also affect the transmittance in the wavelength range of 0 nm to 1500 nm. If (Li2O+Na2O+K2O) / (Fe2O3+Co2O3) is too low, the Fe and Co elements in the component are in a low valence state, which will affect the transmittance in the wavelength range of more than 1500 nm. Therefore, in the present application, (Li2O+Na2O+K2O) / (Fe2O3+Co2O3) is 0.6 to 0.8 by weight, preferably 0.60 to 0.78, further preferably 0.60 to 0.76, for example 0.62, 0.64, 0.66, 0.68, 0.7, 0.72, 0.74, 0.76, 0.78, etc.

[0084] A small amount of V2O5 can also be introduced into the component to strengthen the absorption of the glass in the visible light region. If the content of V2O5 in the glass is too high, the glass will become brittle, making subsequent processing more difficult. Therefore, the content of V2O5 in the present application is 0% to 1% by weight, preferably 0% to 0.8%, further preferably 0% to 0.6%, for example: 0.1%, 0.2%, 0.3%, 0.4%, 0.5%, 0.6%, 0.7%, 0.8%, 0.9%, etc.

[0085] In the present application, when the thickness of the cut-off glass-ceramics is 0.5 mm, the cut-off wavelength is above 1500 nm, preferably above 1600 nm, and more preferably above 1700 nm; when the thickness of the cut-off glass-ceramics is 0.5 mm, the transmittance in the wavelength range of 2000 nm to 2200 nm is not more than 2%, and the transmittance in the wavelength range of 2200 nm to 2400 nm is not more than 5%. The bending strength of the cut-off glass-ceramics is above 100 MPa, preferably above 110 MPa, and more preferably above 120 MPa; the elastic modulus of the cut-off glass-ceramics is above 90 GPa, preferably above 95 GPa, and more preferably above 100 GPa; the acid resistance of the cut-off glass-ceramics is above Class 2, preferably Class 1; and the water resistance of the cut-off glass-ceramics is above Class 2, preferably Class 1.

[0086] In addition, the cut-off glass-ceramics of the present application does not contain components restricted by the RoHS directive, such as Cr2O3 and CdO.

[0087] Further, the present application also provides a preparation method of the cut-off glass-ceramics, which comprises uniformly mixing the components of the cut-off glass-ceramics in proportion, melting, homogenizing, forming and annealing to obtain the cut-off glass-ceramics.

[0088] Specifically, the preparation method of the present application comprises the following steps:

[0089] The components of the cut-off glass-ceramics are uniformly mixed in proportion to obtain a mixture, and then the mixture is melted to obtain a molten glass;

[0090] The molten glass is homogenized and formed in a mold to obtain a formed body;

[0091] The formed body is annealed to obtain the cut-off glass-ceramics.

[0092] In the present application, the preparation method at least has one of the following conditions: the melting temperature is 1300-1500°C; the annealing temperature is 700-900°C; and the annealing time is 2-10 h. When the annealing temperature is 700-900°C and the annealing time is 2-10 h, a large number of Mg 0.6 Al 1.2 Si 1.8 O6 microcrystals are formed in the glass, thereby increasing the mechanical strength of the glass.

[0093] Further, the preparation method of the present application comprises the following steps:

[0094] The components of the cut-off glass-ceramic are mixed in proportion to obtain a mixture, and the mixture is put into a furnace at 1300-1500°C to form a molten glass;

[0095] The molten glass is subjected to homogenization treatment to disperse the components of the glass liquid uniformly and eliminate bubbles in the glass;

[0096] The homogenized molten glass is cast or poured into a mold to form a shaped body;

[0097] The shaped body is put into an annealing furnace and kept at 700-900°C for 2-10h to obtain the cut-off glass-ceramic. Keeping at 700-900°C for 2-10h forms a large number of Mg 0.6 Al 1.2 Si 1.8 O6 crystals in the glass, thereby increasing the mechanical strength of the glass.

[0098] Further, the present application also provides an optical element comprising the cut-off glass-ceramic according to the present application. The optical element can comprise a glass element and a glass preform.

[0099] Specifically, the glass preform can be made by using a means such as grinding processing, or a means such as re-hot press forming, precision press forming, etc. That is, the glass preform can be made by mechanically processing the glass such as grinding and polishing. Or the glass preform can be made by re-hot press forming a preform blank for press forming made of glass, and then grinding processing. Or the glass preform can be made by precision press forming a preform blank made by grinding processing. It should be noted that the means for preparing the glass preform is not limited to the above means.

[0100] Examples

[0101] The embodiments of the present application will be described in detail below with reference to examples, but those skilled in the art will understand that the following examples are only used to illustrate the present application and should not be regarded as limiting the scope of the present application. The specific conditions not mentioned in the examples are carried out according to the conventional conditions or the conditions recommended by the manufacturer. The reagents or instruments not mentioned by the manufacturer are all conventional products that can be obtained by purchase.

[0102] Example 1

[0103] 1) The components in Table 1 are calculated, weighed and mixed in proportion, and put into a platinum-made crucible to be melted at a temperature of 1450°C to form a molten glass;

[0104] 2) The molten glass is stirred and subjected to homogenization treatment to eliminate bubbles in the glass;

[0105] 3) The homogenized molten glass is cast or poured into a mold to form a shaped body;

[0106] 4) The shaped body is placed in an annealing furnace at 700℃ for 6h to obtain a cut-off microcrystalline glass.

[0107] Example 2

[0108] 1) The components in Table 1 are weighed and mixed according to the proportions, and put into a platinum-made crucible to be melted at a temperature of 1450℃ to form a molten glass;

[0109] 2) The molten glass is stirred and homogenized to eliminate bubbles in the glass;

[0110] 3) The homogenized molten glass is cast or poured into a mold to form a shaped body;

[0111] 4) The shaped body is placed in an annealing furnace at 750℃ for 6h to obtain a cut-off microcrystalline glass.

[0112] Example 3

[0113] 1) The components in Table 1 are weighed and mixed according to the proportions, and put into a platinum-made crucible to be melted at a temperature of 1450℃ to form a molten glass;

[0114] 2) The molten glass is stirred and homogenized to eliminate bubbles in the glass;

[0115] 3) The homogenized molten glass is cast or poured into a mold to form a shaped body;

[0116] 4) The shaped body is placed in an annealing furnace at 800℃ for 6h to obtain a cut-off microcrystalline glass.

[0117] Example 4

[0118] 1) The components in Table 1 are weighed and mixed according to the proportions, and put into a platinum-made crucible to be melted at a temperature of 1450℃ to form a molten glass;

[0119] 2) The molten glass is stirred and homogenized to eliminate bubbles in the glass;

[0120] 3) The homogenized molten glass is cast or poured into a mold to form a shaped body;

[0121] 4) The shaped body is placed in an annealing furnace at 850℃ for 6h to obtain a cut-off microcrystalline glass.

[0122] Example 5

[0123] 1) The components in Table 1 are calculated, weighed, mixed in proportion, and put into a platinum-made crucible to be melted at a temperature of 1450°C to form molten glass;

[0124] 2) The molten glass is stirred and homogenized to eliminate bubbles in the glass;

[0125] 3) The homogenized molten glass is cast or poured into a mold to form a shaped body;

[0126] 4) The shaped body is put into an annealing furnace at 900°C for 6h to obtain a cut-off glass-ceramic

[0127] Examples 6-7

[0128] 1) The components in Table 1 are calculated, weighed, mixed in proportion, and put into a platinum-made crucible to be melted at a temperature of 1450°C to form molten glass;

[0129] 2) The molten glass is stirred and homogenized to eliminate bubbles in the glass;

[0130] 3) The homogenized molten glass is cast or poured into a mold to form a shaped body;

[0131] 4) The shaped body is put into an annealing furnace at 800°C for 3h to obtain a cut-off glass-ceramic.

[0132] Examples 8-9

[0133] 1) The components in Table 2 are calculated, weighed, mixed in proportion, and put into a platinum-made crucible to be melted at a temperature of 1450°C to form molten glass;

[0134] 2) The molten glass is stirred and homogenized to eliminate bubbles in the glass;

[0135] 3) The homogenized molten glass is cast or poured into a mold to form a shaped body;

[0136] 4) The shaped body is put into an annealing furnace at 700°C for 8h to obtain a cut-off glass-ceramic.

[0137] Examples 10-12

[0138] 1) The components in Table 2 are calculated, weighed, mixed in proportion, and put into a platinum-made crucible to be melted at a temperature of 1450°C to form molten glass;

[0139] 2) The molten glass is stirred and homogenized to eliminate bubbles in the glass;

[0140] 3) The homogenized molten glass is cast or poured into a mold to form a shaped body;

[0141] 4) Put the shaped body into the annealing furnace at 800℃ for 8h to obtain the cut-off glass-ceramics.

[0142] Examples 13-14

[0143] 1) Calculate, weigh and mix the components in Table 2 according to the proportions, and put them into a platinum-made crucible to be melted at a temperature of 1450℃ to form a molten glass;

[0144] 2) Stir and homogenize the molten glass to eliminate bubbles in the glass;

[0145] 3) Pour or pour the homogenized molten glass into a mold to form a shaped body;

[0146] 4) Put the shaped body into the annealing furnace at 900℃ for 6h to obtain the cut-off glass-ceramics.

[0147] Performance detection

[0148] 1. Glass transmittance

[0149] The transmittance curve of the 0.5mm glass sample was tested according to the method of GB / T 7962.12-2010 using a spectrometer to test the glass at 400nm-2400nm, and the test results are shown in Table 1-2. Figure 1

[0150] 2. Bending strength

[0151] The bending strength σ of the glass was tested according to the method specified in GB / T 6569-2006, and the test results are shown in Table 1-2.

[0152] 3. Elastic modulus

[0153] The elastic modulus E of the glass was tested according to the method specified in GB / T 7962.6-2010, and the test results are shown in Table 1-2.

[0154] 4. Acid resistance stability

[0155] The acid resistance stability (D A ) of the glass (powder method) was tested according to the method specified in GB / T 17129-1997, and the acid resistance stability in the present application is sometimes referred to as acid resistance or acid stability, and the test results are shown in Table 1-2.

[0156] 5. Water resistance stability

[0157] The water resistance stability (D W ​) according to the method specified in GB / T 17129-1997. The water resistance stability in the present application is sometimes referred to as water resistance or water resistance stability, and the test results are shown in Tables 1-2.

[0158] 6. XRD test

[0159] The cut-off glass-ceramics of Examples 1-5 were taken, and the powder X-ray diffraction method was used to test the X-ray diffraction patterns of the cut-off glass-ceramics using CuK α Radiation experimental condition analysis, the peak of the X-ray diffraction pattern of the cut-off glass-ceramics, the results are shown in Figure 2

[0160] Table 1

[0161]

[0162] Table 2

[0163]

[0164] As can be seen from Examples 1-14, the cut-off wavelength of the filter glass of the present application is 1500 nm or more, the transmittance is not more than 2% at 2000-2200 nm, and the transmittance is not more than 5% at 2200-2400 nm when the thickness is 0.5 mm, and the glass material also exhibits good mechanical properties and chemical stability.

[0165] In Examples 1-3, the glass with the same formula was annealed at 700℃, 750℃ and 800℃ for 6h to form glass-ceramics, and Figure 1 and Figure 2 It can be seen that the grain size in the glass increases with the increase of the annealing temperature, the cut-off wavelength of the glass is red-shifted, and the mechanical strength of the glass is increased, but it tends to be balanced after a certain degree of increase.

[0166] It should be noted that although the technical solutions of the present application are introduced by specific examples, those skilled in the art can understand that the present application should not be limited thereto.

[0167] The above has described various embodiments of the present application, and the above description is exemplary, not exhaustive, and is not limited to the disclosed embodiments. Many modifications and changes are obvious to those skilled in the art without departing from the scope and spirit of the described embodiments. The choice of terms used herein is intended to best explain the principles, practical applications or technical improvements in the market of the embodiments, or to enable other ordinary skilled persons in the art to understand the embodiments disclosed herein.​

Claims

1. A cut-off glass-ceramic, characterized in that, It comprises the following components in percentage by weight: SiO2: 40% to 70%; Al2O3: 5% to 12%; MgO: 4% to 15%; CaO: 0% to 2%; B2O3: 0% to 4%; Na2O: 5% to 12%; K2O: 0% to 6%; Li2O: 0% to 2%; TiO2: 1% to 4%; Fe2O3: 8% to 20%; Co2O3: 2% to 8%; V2O5: 0.1% to 1%; The ratio of the sum of the contents of SiO2 and Al2O3 to the sum of the contents of B2O3, Li2O, Na2O and K2O (SiO2+Al2O3) / (B2O3+Li2O+Na2O+K2O) is 2.0 to 6.0 in percentage by weight. The ratio of the sum of the contents of Li2O, Na2O and K2O to the sum of the contents of Fe2O3 and Co2O3 (Li2O+Na2O+K2O) / (Fe2O3+Co2O3) is 0.6 to 0.8 in percentage by weight.

2. The cutoff glass-ceramics according to claim 1, characterized in that, It comprises the following components in percentage by weight: SiO2: 45% to 68%; Al2O3: 5.5% to 11%; MgO: 4.5% to 14%; CaO: 0% to 1%; B2O3: 0% to 3%; Na2O: 5.5% to 11%; K2O: 0.5% to 5%; Li2O: 0% to 1%; TiO2: 1.2% to 3.8%; Fe2O3: 9% to 19%; Co2O3: 2.5% to 7.5%; V2O5: 0.1% to 0.8%.

3. The cutoff glass-ceramics according to claim 2, characterized in that, It comprises the following components in percentage by weight: SiO2: 50% to 65%; Al2O3: 6% to 10%; MgO: 5% to 13%; CaO: 0% to 0.5%; B2O3: 0% to 2%; Na2O: 6% to 10%; K2O: 1% to 4%; Li2O: 0%; TiO2: 1.4% to 3.6%; Fe2O3: 10% to 18%; Co2O3: 3% to 7%; V2O5: 0.1% to 0.6%.

4. The cut-off glass-ceramic according to any one of claims 1 to 3, characterized in that The sum of the contents of Li2O, Na2O and K2O (Li2O+Na2O+K2O) is 5% to 20% in percentage by weight.

5. The cutoff glass-ceramics according to claim 4, characterized in that, The sum of the contents of Li2O, Na2O and K2O (Li2O+Na2O+K2O) is 6% to 17% in percentage by weight.

6. The cutoff glass ceramic according to claim 5, characterized in that The sum of the contents of Li2O, Na2O and K2O (Li2O+Na2O+K2O) is 7% to 14% in percentage by weight.

7. The cut-off glass-ceramic according to any one of claims 1 to 3, characterized in that, The ratio of the sum of the contents of SiO2 and Al2O3 to the sum of the contents of B2O3, Li2O, Na2O and K2O (SiO2+Al2O3) / (B2O3+Li2O+Na2O+K2O) is 2.2 to 5.5 in percentage by weight.

8. The cutoff glass-ceramics according to claim 7, characterized in that, The ratio of the sum of the contents of SiO2 and Al2O3 to the sum of the contents of B2O3, Li2O, Na2O and K2O (SiO2+Al2O3) / (B2O3+Li2O+Na2O+K2O) is 2.8 to 5.0 in percentage by weight.

9. The cut-off glass-ceramic according to any one of claims 1 to 3, characterized in that, The ratio of the sum of the contents of Li2O, Na2O and K2O to the sum of the contents of Fe2O3 and Co2O3 (Li2O+Na2O+K2O) / (Fe2O3+Co2O3) is 0.6-0.

78.

10. The cutoff glass-ceramic according to claim 9, characterized in that, The ratio of the sum of the contents of Li2O, Na2O and K2O to the sum of the contents of Fe2O3 and Co2O3 (Li2O+Na2O+K2O) / (Fe2O3+Co2O3) is 0.6-0.

76.

11. The cut-off glass-ceramic according to any one of claims 1 to 3, characterized in that, When the thickness of the cutoff glass-ceramic is 0.5 mm, the cutoff wavelength of the cutoff glass-ceramic is 1500 nm or more; and / or, When the thickness of the cutoff glass-ceramic is 0.5 mm, the transmittance of the cutoff glass-ceramic at a wavelength of 2000-2200 nm is not more than 2%, and the transmittance at a wavelength of 2200-2400 nm is not more than 5%.

12. The cut-off glass-ceramic according to any one of claims 1 to 3, characterized in that, The bending strength of the cutoff glass-ceramic is 100 MPa or more; and / or, The elastic modulus of the cutoff glass-ceramic is 90 GPa or more; and / or, The acid resistance of the cutoff glass-ceramic is Class 2 or more; and / or The water resistance of the cutoff glass-ceramic is Class 2 or more.

13. A method of producing the cut-off glass-ceramic according to any one of claims 1 to 12, characterized in that, The preparation method comprises the following steps:

14. The method of claim 13, wherein, The preparation method comprises the following steps: The preparation method comprises the following steps: The preparation method comprises the following steps: The preparation method at least has one of the following conditions:

15. The production method according to claim 13 or 14, characterized by, The melting temperature is 1300-1500 ℃; The annealing temperature is 700-900 ℃; The annealing time is 2-10 h.

16. An optical element comprising the cutoff glass-ceramic according to any one of claims 1-12. ​

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