Polarizing glass and method for producing same

Abstract

Provided is a polarizing glass having excellent mechanical strength and polarizing properties. The polarizing glass comprises the following components in percentage by weight: 35-60% of a cation component Si < 4 + >; 5-18% of B < 3 + >; 5-25% of R < + >; 2 to 14 percent of Al < 3 + >; r < + > is one or more of Li < + >, Na < + > and K < + >; the anion component contains 98 to 99.9 percent of O2 <->; 0.1 to 1 percent of Cl <->; and 0-1% of Br <->. Through reasonable component design, the polarized glass has excellent mechanical strength and polarization property.

Description

Technical Field

[0001] This invention relates to a glass, and more particularly to a polarizing glass with excellent mechanical strength and polarization properties. Background Technology

[0002] Polarizing glass selectively absorbs natural light through its internal dichroic metal particles. Photons vibrating parallel to the length direction of the metal particles are absorbed by the electron-plasma oscillations of the metal particles and converted into heat energy, while photons vibrating perpendicular to the length direction of the metal particles pass through unimpeded. This achieves the conversion of unpolarized light into high-intensity polarized light. Polarizing glass is widely used in polarization-dependent optical isolators, optical modulators, laser printers, and other devices. Secondly, the miniaturization of polarizing glass meets the needs of miniaturization and integration of optical devices, and can be widely used in optical storage and fiber optic sensing.

[0003] In the prior art, the matrix glass used to prepare polarized glass has low mechanical strength. After mechanical stretching, the glass has large stress and is very easy to crack, which does not meet the requirements of subsequent processing and reduction, and cannot produce large-size polarized glass sheets. At the same time, it is not conducive to further improving the polarization performance of polarized glass. Summary of the Invention

[0004] The technical problem to be solved by the present invention is to provide a polarizing glass with excellent mechanical strength and polarization characteristics.

[0005] The technical solution adopted by this invention to solve the technical problem is:

[0006] (1) Polarizing glass, the composition of which is expressed as a weight percentage, the cationic component contains: Si 4+ 35-60%; B 3+ 5-18%; R + 5-25%; Al 3+ 2-14%; Ag + 0.1% to 0.6%, the R + For Li + Na + K + One or more of the following;

[0007] The anionic component contains: O 2- 98-99.9%; Cl - : 0.1-1%; Br - : 0-1%.

[0008] (2) According to the polarizing glass described in (1), its components are expressed as weight percentages, and the cationic component further contains: Zr 4+ 0–8%; and / or Zn 2+: 0-10%; and / or Ti 4+ : 0-7%; and / or Ba 2+ : 0-8%; and / or Cu 2+ : 0-0.3%.

[0009] (3) Polarized glass, the components of which are expressed in weight percent, the cationic component consisting of Si 4+ : 35-60%; B 3+ : 5-18%; R + : 5-25%; Al 3+ : 2-14%; Ag + : 0.1-0.6%; Zr 4+ : 0-8%; Zn 2+ : 0-10%; Ti 4+ : 0-7%; Ba 2+ : 0-8%; Cu 2+ : 0-0.3%, said R + is one or more of Li + , Na + , K + ;

[0010] the anionic component consisting of O 2- : 98-99.9%; Cl - : 0.1-1%; Br - : 0-1%.

[0011] (4) Polarized glass according to any one of (1) to (3), the components of which are expressed in weight percent, satisfying one or more of the following 4 cases:

[0012] 1) Si 4+ / B 3+ is 2.0-6.0, preferably Si 4+ / B 3+ is 3.0-5.0, more preferably Si 4+ / B 3+ is 3.5-4.5;

[0013] 2) Al 3+ / Ti 4+ is 0.5-8.0, preferably Al 3+ / Ti 4+ is 2.0-6.0, more preferably Al 3+ / Ti 4+ is 3.0-4.5;

[0014] 3) B 3+ / (Ti 4+ + Al 3+ ) is 0.5-6.0, preferably B3+ / (Ti 4+ +Al 3+ ) is 1.0 to 4.0, more preferably B 3+ / (Ti 4+ +Al 3+ ) is 1.5 to 3.0;

[0015] 4) R + / (Ba 2+ +Zn 2+ ) is 0.5 to 5.0, preferably R + / (Ba 2+ +Zn 2+ ) is 1.5 to 4.5, more preferably R + / (Ba 2+ +Zn 2 + ) is 2.5 to 3.8, said R + is one or more of Li + , Na + , K + .

[0016] (5) The polar glass according to any one of (1) to (3), the components being expressed in weight percent, wherein: Si 4+ : 40 to 55%, preferably Si 4+ : 45 to 53%; and / or B 3+ : 8 to 15%, preferably B 3+ : 10 to 13%; and / or R + : 10 to 20%, preferably R + : 12 to 18%; and / or Al 3+ : 4 to 12%, preferably Al 3+ : 4 to 9%; and / or Ag + : 0.15 to 0.45%, preferably Ag + : 0.2 to 0.35%; and / or Zr 4+ : 2 to 7%, preferably Zr 4+ : 3 to 6%; and / or Zn 2+ : 2 to 8%, preferably Zn 2+ : 3 to 6%; and / or Ti 4+ : 1.5 to 5%, preferably Ti 4+ : 2 to 4%; and / or Ba 2+ : 1.5 to 6%, preferably Ba 2+ : 2.5 to 4.5%; and / or Cu 2+ : 0.02 to 0.1%, preferably Cu 2+ : 0.05 to 0.1%, said R + is one or more of Li +Na + K + One or more of them.

[0017] (6) The polarizing glass according to any one of (1) to (3), wherein its components are expressed as weight percentages, wherein: O 2- 98.2%–99.5%, preferred O 2- 98.2%–99%; and / or Cl - 0.1-0.6%, preferably Cl - 0.2–0.5%; and / or Br - 0.1-0.7%, preferably Br - : 0.1% to 0.5%.

[0018] (7) The polarizing glass according to any one of (1) to (3), wherein its components are expressed as weight percentages, wherein: Li + 0-5%, preferably Li + 1-4%, more preferably Li + 1.5–3%; and / or Na + 3-16%, preferably Na + 5-13%, more preferably Na + 7-10%; and / or K + 2-13%, K is preferred + 5-12%, preferably K + 6-10%.

[0019] (8) The polarizing glass according to any one of (1) to (3) has a bending strength of 80 MPa or more, preferably 120 MPa or more, more preferably 150 MPa or more; and / or a Young's modulus of 75 GPa or more, preferably 80 GPa or more, more preferably 85 GPa or more; and / or a transmittance of polarizing glass with a thickness of 1.0 mm or less is 80% or more, preferably 85% or more, more preferably 90% or more; and / or an extinction ratio of polarizing glass with a thickness of 1.0 mm or less is 30 dB or more, preferably 40 dB or more, more preferably 50 dB or more; and / or an insertion loss of polarizing glass with a thickness of 1.0 mm or less is 0.60 dB or less, preferably 0.50 dB or less, more preferably 0.30 dB or less.

[0020] (9) Matrix glass, the composition of which is expressed as a weight percentage, the cationic component contains: Si 4+ 35-60%; B 3+ 5-18%; R + 5-25%; Al 3+ 2-14%; Ag + 0.1% to 0.6%, the R+ Li + , Na + , K + , or one or more of these;

[0021] The anion component contains: O 2- : 98-99.9%; Cl - : 0.1-1%; Br - : 0-1%.

[0022] (10) The base glass according to (9), the components of which are expressed in weight percent, the cation component further containing: Zr 4 + : 0-8%; and / or Zn 2+ : 0-10%; and / or Ti 4+ : 0-7%; and / or Ba 2+ : 0-8%; and / or Cu 2+ : 0-0.3%.

[0023] (11) Base glass, the components of which are expressed in weight percent, the cation component consisting of: Si 4+ : 35-60%; B 3+ : 5-18%; R + : 5-25%; Al 3+ : 2-14%; Ag + : 0.1-0.6%; Zr 4+ : 0-8%; Zn 2+ : 0-10%; Ti 4+ : 0-7%; Ba 2+ : 0-8%; Cu 2+ : 0-0.3%, the R + being one or more of Li + , Na + , K + ;

[0024] The anion component consists of: O 2- : 98-99.9%; Cl - : 0.1-1%; Br - : 0-1%.

[0025] (12) The base glass according to any one of (9) to (11), the components of which are expressed in weight percent, satisfying one or more of the following 4 cases:

[0026] 1) Si 4+ / B 3+ : 2.0-6.0, preferably Si 4+ / B 3+from 3.0 to 5.0, more preferably Si 4+ / B 3+ from 3.5 to 4.5;

[0027] 2) Al 3+ / Ti 4+ from 0.5 to 8.0, preferably Al 3+ / Ti 4+ from 2.0 to 6.0, more preferably Al 3+ / Ti 4+ from 3.0 to 4.5;

[0028] 3) B 3+ / (Ti 4+ + Al 3+ ) from 0.5 to 6.0, preferably B 3+ / (Ti 4+ + Al 3+ ) from 1.0 to 4.0, more preferably B 3+ / (Ti 4+ + Al 3+ ) from 1.5 to 3.0;

[0029] 4) R + / (Ba 2+ + Zn 2+ ) from 0.5 to 5.0, preferably R + / (Ba 2+ + Zn 2+ ) from 1.5 to 4.5, more preferably R + / (Ba 2+ + Zn 2 + from 2.5 to 3.8, said R + is one or more of Li + , Na + , K + .

[0030] (13) The glass substrate of any one of (9) to (11), having components in weight percent, wherein: Si 4+ : 40 to 55%, preferably Si 4+ : 45 to 53%; and / or B 3+ : 8 to 15%, preferably B 3+ : 10 to 13%; and / or R + : 10 to 20%, preferably R + : 12 to 18%; and / or Al 3+ : 4 to 12%, preferably Al 3+ : 4 to 9%; and / or Ag + : 0.15 to 0.45%, preferably Ag +: 0.2-0.35%; and / or Zr 4+ : 2-7%, preferably Zr 4+ : 3-6%; and / or Zn 2+ : 2-8%, preferably Zn 2+ : 3-6%; and / or Ti 4+ : 1.5-5%, preferably Ti 4+ : 2-4%; and / or Ba 2+ : 1.5-6%, preferably Ba 2+ : 2.5-4.5%; and / or Cu 2+ : 0.02-0.1%, preferably Cu 2+ : 0.05-0.1%, said R + is one or more of Li + , Na + , K + .

[0031] (14) The glass substrate of any one of (9) to (11), comprising, in percent by weight: O 2- : 98.2-99.5%, preferably O 2- : 98.2-99%; and / or Cl - : 0.1-0.6%, preferably Cl - : 0.2-0.5%; and / or Br - : 0.1-0.7%, preferably Br - : 0.1-0.5%.

[0032] (15) The glass substrate of any one of (9) to (11), comprising, in percent by weight: Li + : 0-5%, preferably Li + : 1-4%, more preferably Li + : 1.5-3%; and / or Na + : 3-16%, preferably Na + : 5-13%, more preferably Na + : 7-10%; and / or K + : 2-13%, preferably K + : 5-12%, more preferably K + : 6-10%.

[0033] (16) The substrate glass according to any one of (9) to (11), wherein the substrate glass has a bending strength of 80 MPa or more, preferably 120 MPa or more, more preferably 150 MPa or more; and / or a Young's modulus of 75 GPa or more, preferably 80 GPa or more, more preferably 85 GPa or more; and / or a transmittance of 80% or more, preferably 85% or more, more preferably 90% or more, for a substrate glass having a thickness of 1.0 mm or less.

[0034] (17) A polarizing element made of the polarizing glass according to any one of (1) to (8).

[0035] (18) An apparatus comprising the polarizing glass according to any one of (1) to (8), or the polarizing element according to (17).

[0036] (19) A method for manufacturing the polarizing glass according to any one of (1) to (8), the method comprising the steps of: 1) forming a substrate glass; 2) heat-treating the substrate glass; 3) stretch-treating the heat-treated substrate glass; and 4) reduction-treating the stretch-treated substrate glass to obtain the polarizing glass.

[0037] (20) The method for manufacturing the polarizing glass according to (19), wherein the forming of the substrate glass comprises the steps of: weighing the glass raw materials according to the content of each component of the substrate glass, mixing and stirring the weighed glass raw materials to obtain a mixture, melting the mixture in a melting furnace, melting the mixture in the melting furnace at a melting temperature of 1200 to 1500 °C for 5 to 20 hours, preferably at a melting temperature of 1250 to 1400 °C, then increasing the temperature to 1300 to 1500 °C for 6 to 8 hours of fining at a fining temperature of 1350 to 1450 °C, and finally cooling and homogenizing the molten glass to form a substrate glass, and annealing the substrate glass at 500 to 600 °C for 6 to 10 hours, and then naturally cooling the substrate glass to obtain the substrate glass.

[0038] (21) The method for manufacturing the polarizing glass according to (19), wherein the heat-treating of the substrate glass is performed at a heat-treating temperature of 500 to 800 °C for a heat-treating time of 10 to 20 hours, and the reduction-treating is performed at a reduction-treating temperature of 200 to 500 °C, preferably at a reduction-treating temperature of 300 to 450 °C, for a reduction-treating time of 10 to 40 hours, preferably for a reduction-treating time of 20 to 30 hours.

[0039] The polarizing glass of the present application has excellent mechanical strength and polarization properties due to the reasonable component design.

[0040] The substrate glass obtained by the present application has high transmittance and other properties, and the mechanical strength of the substrate glass is improved, the cracking problem of the substrate glass during stretching, subsequent processing and reduction is solved, and the polarizing glass with excellent mechanical strength and polarization properties is prepared. DETAILED DESCRIPTION

[0041] Hereinafter, embodiments of the present application will be described in detail, but the present application is not limited to the following embodiments, and can be implemented by making appropriate changes within the scope of the object of the present application. Further, regarding portions described repeatedly, although there are cases where appropriate descriptions are omitted, the gist of the application is not limited thereto, and in the present application, polarizing glass can be simply referred to as glass.

[0042] [Polarizing glass and base glass]

[0043] Hereinafter, ranges of each component (ingredient) constituting the polarizing glass and the base glass of the present application will be described. In the present specification, unless otherwise specified, the content of a cation component is expressed as a weight percentage (wt%) of the cation component with respect to the total cation components, the content of an anion component is expressed as a weight percentage (wt%) of the anion component with respect to the total anion components; the ratio between the contents of cation components is the ratio between the weight percentage contents of the respective cation components; the total content between the contents of cation components is the total value of the weight percentage contents of the respective cation components; and the total content between the contents of anion components is the total value of the weight percentage contents of the respective anion components.

[0044] Unless otherwise indicated in specific cases, the numerical ranges listed herein include the upper and lower limit values, "above" and "below" include the end point values, and all integers and fractions within the range are included, and are not limited to the specific values listed in the defined range. As used herein, "and / or" is inclusive, for example, "A and / or B" means only A, or only B, or both A and B.

[0045] It should be noted that the ion valence of each component described below is a representative value used for convenience, and is not distinguished from other ion valences. There is a possibility that the ion valence of each component in the polarizing glass or the base glass is other than the representative value. For example, Cu is usually present in the state of +2 valence in the polarizing glass and the base glass of the present application, and therefore, "Cu 2+ " is used as the representative value in the present patent, but there is a possibility that it is present in other ion valence states, which is also within the scope of protection of the present patent. It should be particularly noted that the polarizing glass of the present application is obtained by reducing the base glass of the present application by reduction in a reducing atmosphere, so that the long strip or elliptical silver halide clusters on the surface layer of the base glass are reduced to silver single substance, and therefore, the silver ion and the silver single substance involved in the present application are collectively referred to as Ag + .

[0046] [About cation components]

[0047] Si 4+It is an important component of the glass of this invention, and its function is to form a uniform network structure inside the glass, thereby constituting the glass's framework. If Si 4+ When the Si content is below 35%, the mechanical strength, thermal stability, and chemical stability of the glass decrease, therefore Si... 4+ The lower limit of the Si content is 35%, preferably 40%, and more preferably 45%. 4+ When the Si content exceeds 60%, the melting temperature of the matrix glass increases, the viscosity increases, the glass raw material becomes difficult to prepare, and defects such as bubbles and inclusions are easily generated in the glass. Therefore, Si 4+ The maximum content of [the substance] is 60%, preferably 55%, and more preferably 53%.

[0048] B 3+ It is one of the main components of glass, existing in glass in two forms: [BO4] and [BO3]. When present in appropriate amounts, it can act as a flux. B 3+ When present in the form of [BO4], it can form a uniform network structure with silicon-oxygen tetrahedra, improving the chemical stability, thermal stability, and coefficient of thermal expansion of the glass. With the increasing presence of B... 3+ With increasing content, [BO4] transforms into [BO3], causing a phase separation tendency in the glass. Under certain time and temperature, [BO3] gradually aggregates to form a boron-rich phase, which is conducive to the formation and growth of silver halide clusters. Therefore, B 3+ The lower limit for the content is 5%, preferably 8%, and more preferably 10%. However, excessive content of B... 3 + As the [BO3] content further increases, the glass's network structure is disrupted, leading to intensified phase separation. Consequently, the glass's chemical stability, thermal stability, and transmittance deteriorate. Therefore, B... 3+ The maximum content is 18%, preferably 15%, and even more preferably 13%.

[0049] Through extensive experimental research, the inventors discovered that in some implementation methods, by controlling Si 4+ The content of B 3+ The ratio between the contents of Si 4+ / B 3+ Within the range of 2.0 to 6.0, Si is advantageous for controlling the phase separation degree of the matrix glass, promoting the full aggregation of silver halide clusters, and improving the transmittance of both the polarizing glass and the matrix glass. Therefore, Si is preferred. 4+ / B 3+ The value is 2.0 to 6.0, with Si being more preferred. 4+ / B 3+ The Si value is 3.0–5.0, with further optimization. 4+ / B 3+ It ranges from 3.5 to 4.5.

[0050] R + (R + Li + , Na + , K + ) as the network modifier, can play a fluxing role, which is beneficial to reduce the melting temperature and fining temperature of the base glass. By containing more than two kinds of R + , the mixed alkali effect formed helps to improve the weather resistance of the glass. However, too high content of R + will destroy the glass network skeleton, resulting in poor performance of the glass such as strength, chemical stability, thermal stability, etc. Therefore, the content of R + is 5-25%, preferably 10-20%, more preferably 12-18%. In some embodiments, the content of Li + is 0-5%, more preferably Li + is 1-4%, further preferably Li + is 1.5-3%; the content of Na + is 3-16%, more preferably Na + is 5-13%, further preferably Na + is 7-10%; the content of K + is 2-13%, more preferably K + is 5-12%, further preferably K + is 6-10%.

[0051] Al 3+ , together with Si 4+ , constitutes the network structure, which can improve the mechanical strength and chemical stability of the glass, while suppressing the strong phase separation of the base glass. Therefore, the lower limit of the content of Al 3+ is 2%, preferably 4%. When the content of Al 3+ is too high, the viscosity of the base glass increases, the melting temperature is high, and defects such as stones are easily produced, which is not conducive to the precipitation of silver halide particles in the glass. Therefore, the upper limit of the content of Al 3+ is 14%, preferably 12%, more preferably 9%.

[0052] Zr 4+ can suppress the phase separation of the base glass during forming, and can improve the weather resistance of the glass, but if the content of Zr 4+ is too high, it is difficult to melt the raw materials of the glass, it is easy to form stones in the glass, and it suppresses the phase separation of the base glass during heat treatment. Therefore, the content of Zr 4+ is 0-8%, preferably 2-7%, more preferably 3-6%.

[0053] Zn 2+Zn can lower the melting temperature of glass and improve its weather resistance. 2+ It can lengthen the material properties of the matrix glass, increase its Young's modulus, and facilitate process control during stretching. However, excessive Zn content... 2+ This will reduce the transmittance of both the matrix glass and the polarizing glass, affecting the extinction ratio of the polarizing glass. Therefore, Zn 2+ The content is 0-10%, preferably 2-8%, and more preferably 3-6%.

[0054] Ti 4+ It can improve the weather resistance of glass and help suppress photochromism. Ti 4+ It can react with Si during the heat treatment process. 4 + The formation of a continuous network structure significantly improves the strength of the glass. When Ti... 4+ When the content of Ti is too high, it easily promotes violent phase separation in the glass, leading to a decrease in the glass's transmittance and a decline in its polarization characteristics. Therefore, Ti 4+ The content is 0-7%. In some embodiments, the Ti content in the glass can be controlled. 4+ And Al 3+ Coexistence further enhances the mechanical strength of the glass. Therefore, Ti 4+ The content is preferably 1.5% to 5%, more preferably 2% to 4%.

[0055] In some implementations, by controlling Al 3+ The content of Ti 4+ The ratio of Al content 3+ / Ti 4+ Within the range of 0.5 to 8.0, Al is beneficial for controlling the phase separation degree of the matrix glass, improving the flexural strength of both the matrix glass and polarizing glass, and enhancing their mechanical strength. Therefore, Al is preferred. 3+ / Ti 4+ The value ranges from 0.5 to 8.0, with Al being more preferred. 3+ / Ti 4+ The value is 2.0 to 6.0, with Al being further preferred. 3+ / Ti 4+ The value is 3.0 to 4.5.

[0056] In some implementations, by controlling B in the glass 3+ The content of Ti 4+ Al 3+ Total Ti content 4+ +Al 3+ The ratio B between them 3+ / (Ti 4+ +Al 3+Within the range of 0.5 to 6.0, it is possible to achieve high transmittance in both the matrix glass and polarizing glass while improving their bending strength and mechanical strength. Therefore, B is preferred. 3+ / (Ti 4+ +Al 3+ The value is 0.5 to 6.0, with B being more preferred. 3+ / (Ti 4+ +Al 3+ The value is 1.0 to 4.0, with B being the preferred option. 3+ / (Ti 4+ +Al 3+ The value ranges from 1.5 to 3.0.

[0057] Ba 2+ It can lower the melting temperature of glass raw materials and improve the weather resistance of glass. Ba 2+ It can lengthen the material properties of the matrix glass, increase the Young's modulus of both the matrix glass and polarizing glass, and facilitate the adjustment of the stretching process of the matrix glass. However, excessive Ba content can lead to problems. 2+ This will damage the network structure of the glass. Therefore, Ba 2+ The content is 0-8%, preferably 1.5-6%, and more preferably 2.5-4.5%.

[0058] In some implementations, by controlling R + The content of Ba 2+ Zn 2+ Total Ba content 2+ +Zn 2+ The ratio R between + / (Ba 2+ +Zn 2+ Within the range of 0.5 to 5.0, the melting temperature of the matrix glass can be reduced, promoting silver halide precipitation, increasing the Young's modulus of both the matrix glass and polarizing glass, effectively improving their resistance to deformation, and solving the cracking problem during glass stretching. Therefore, R is preferred. + / (Ba 2+ +Zn 2+ The value is 0.5 to 5.0, with R being more preferred. + / (Ba 2+ +Zn 2+ The value of R is 1.5 to 4.5, and R is further optimized. + / (Ba 2+ +Zn 2+ The value ranges from 2.5 to 3.8.

[0059] Ag + Ag is an important component of the glass of this invention, serving as a polarizing agent in the glass. +When the content is too low, the density and size of the polarized particles formed are too small to make the glass surface exhibit polarized properties. Therefore, the lower limit of the content of Ag + is 0.1%, preferably the lower limit is 0.15%, and more preferably the lower limit is 0.2%. However, if the content of Ag + is too high, the glass will lose transparency during melting and forming, and in addition, the silver halide clusters will grow excessively during heat treatment, the distribution density will decrease, and the polarized properties of the glass will decrease. Therefore, the upper limit of the content of Ag + is 0.6%, preferably the upper limit is 0.45%, and more preferably the upper limit is 0.35%.

[0060] Cu 2+ is an optional component in the glass of the present application. The role of Cu 2+ is to prevent Ag + from being reduced during melting. If the glass does not contain Cu 2+ , the polarized properties will decrease significantly. However, if the content of Cu 2+ is too high, the glass will be colored seriously, which will affect the transmittance and polarized properties of the glass. Therefore, the content of Cu 2+ is 0-0.3%, preferably 0.02-0.1%, and more preferably 0.05-0.1%.

[0061] <About the anion component>

[0062] O 2- is the main anion component in the glass of the present application. In order to obtain the excellent properties of the present application, the content of O 2- is 98-99.9%, preferably 98.2-99.5%, and more preferably 98.2-99%.

[0063] The halogen ion components Cl - and Br - form silver halide clusters with silver ions during heat treatment, which is beneficial to the subsequent stretching to form long silver halide clusters. However, excessive halogen ions will cause the matrix glass to be opalized during melting and annealing, which will cause the transmittance and polarized properties of the polarized glass to decrease. In some embodiments, both Cl - and Br - are contained, and the mixed migration ion effect between the two can slow down the diffusion rate of halogen and inhibit the thermal respheroidization of the stretched silver halide clusters. Therefore, the content of Cl - is 0.1-1%, preferably 0.1-0.6%, and more preferably 0.2-0.5%; and the content of Br - is 0-1%, preferably 0.1-0.7%, and more preferably 0.1-0.5%.

[0064] The "does not contain" and "0%" described herein mean that the component is not intentionally added as a raw material to the substrate glass and polarizing glass of the present application; however, as a raw material and / or equipment for producing the substrate glass and polarizing glass, there can be some impurities or components that are not intentionally added and can be contained in a small amount or trace amount in the final substrate glass and polarizing glass, and such a case is also within the scope of the present application.

[0065] Hereinafter, the properties of the substrate glass and polarizing glass of the present application will be described.

[0066] The test methods for each property of the substrate glass and polarizing glass of the present application are as follows:

[0067] <sem>

[0068] The polarized glass is surface treated by HF acid, and after surface spraying of the sample, the phase separation and silver halide precipitation in the polarized glass are determined by scanning electron microscope analysis.

[0069] <Light transmittance>

[0070] The light transmittance in the present application is external transmittance, which can be referred to as transmittance in the present application, and the average light transmittance of 1260-1650 nm is measured by using a Hitachi U-41000 spectrophotometer.

[0071] <Extinction ratio>

[0072] The extinction ratio (ER) of the polarized glass is tested by using an extinction ratio tester, and the extinction ratio (ER 1310nm ) of the polarized glass at 1310 nm and the extinction ratio (ER 1550nm ) at 1550 nm are obtained.

[0073] The extinction ratio tester generates linearly polarized light of a specific direction by using a polarizer, and the sample is placed in an analyzer. As the analyzer rotates, the maximum transmittance T max and the minimum transmittance T min of the sample are obtained. The calculation formula of the extinction ratio is:

[0074]

[0075] <Insertion loss>

[0076] The insertion loss (IR) of the polarized glass is tested by using an extinction ratio tester, and the insertion loss (IR 1310nm ) of the glass at 1310 nm and the insertion loss (IR 1550nm ) at 1550 nm are obtained.

[0077] The incident light amount T in before inserting the sample and the maximum transmittance T max after inserting the sample are obtained by using the extinction ratio tester. The calculation formula of the insertion loss is:

[0078]

[0079] <Flexural strength>

[0080] The flexural strength of the polarized glass is tested by using a method of directly measuring the indentation expansion crack size. The sample specification is 3mmx30mmx40mm, and after chamfering, grinding and polishing, after the sample preparation is completed, a vickers hardness indenter is used to apply a force of 49N on the sample and maintain for 30s, and after the indentation is punched, the flexural strength is measured by using a three-point bending method.

[0081] <Young's modulus>

[0082] Young's modulus (E) is tested by ultrasonic wave to obtain longitudinal wave velocity and transverse wave velocity, and then calculated according to the following formula:

[0083] G = V S 2 p

[0084] In the formula, E is Young's modulus, Pa;

[0085] G is shear modulus, Pa;

[0086] V T is transverse wave velocity, m / s;

[0087] V S is longitudinal wave velocity, m / s;

[0088] p is the density of the glass, g / cm 3 .

[0089] The base glass of the present application has the following properties:

[0090] 1) In some embodiments, the transmittance of the base glass of the present application is 80% or more, preferably 85% or more, more preferably 90% or more, at a thickness of 1.0 mm or less. The thickness of the base glass is preferably 0.05 to 0.8 mm, more preferably 0.1 to 0.5 mm, further preferably 0.2 mm or 0.3 mm or 0.4 mm or 0.5 mm.

[0091] 2) In some embodiments, the flexural strength of the base glass of the present application is 80 MPa or more, preferably 120 MPa or more, more preferably 150 MPa or more.

[0092] 3) In some embodiments, the Young's modulus of the base glass of the present application is 75 GPa or more, preferably 80 GPa or more, more preferably 85 GPa or more.

[0093] The polarized glass of the present application has the following properties:

[0094] 1) In some embodiments, the transmittance of the polarized glass of the present application is 80% or more, preferably 85% or more, more preferably 90% or more, at a thickness of 1.0 mm or less. The thickness of the polarized glass is preferably 0.05 to 0.8 mm, more preferably 0.1 to 0.5 mm, further preferably 0.2 mm or 0.3 mm or 0.4 mm or 0.5 mm.

[0095] 2) In some embodiments, the flexural strength of the polarized glass of the present application is 80 MPa or more, preferably 120 MPa or more, more preferably 150 MPa or more.

[0096] 3) In some embodiments, the Young's modulus of the polarizing glass of the present application is 75 Gpa or more, preferably 80 Gpa or more, more preferably 85 Gpa or more.

[0097] 4) In some embodiments, the extinction ratio of the polarizing glass of the present application is 30 dB or more, preferably 40 dB or more, more preferably 50 dB or more, with a thickness of 1.0 mm or less. The thickness of the polarizing glass is preferably 0.05-0.8 mm, more preferably 0.1-0.5 mm, further preferably 0.2 mm or 0.3 mm or 0.4 mm or 0.5 mm.

[0098] 5) In some embodiments, the insertion loss of the polarizing glass of the present application is 0.60 dB or less, preferably 0.50 dB or less, more preferably 0.30 dB or less, with a thickness of 1.0 mm or less. The thickness of the polarizing glass is preferably 0.05-0.8 mm, more preferably 0.1-0.5 mm, further preferably 0.2 mm or 0.3 mm or 0.4 mm or 0.5 mm.

[0099] The polarizing glass of the present application can be made into a polarizing element due to its excellent performance, and is widely used in devices related to polarization, such as optical isolators, fiber polarizers, spectrophotometers, etc.

[0100] [Manufacturing method]

[0101] The method for manufacturing the base glass of the present application is as follows:

[0102] The glass raw materials, including but not limited to oxides, hydroxides, complex salts (such as carbonates, nitrates, sulfates, etc.), boric acid, elements, etc., are weighed according to the content of each component of the base glass according to the present application, and after being mixed and stirred uniformly according to the conventional method, they are added into a melting furnace (such as a platinum or platinum alloy crucible) for melting, preferably at a melting temperature of 1200-1500°C for 5-20 hours, more preferably at a melting temperature of 1250-1400°C; then the temperature is raised to 1300-1500°C for 6-8 hours of fining, preferably at a fining temperature of 1350-1450°C; finally, after cooling and homogenizing, it is poured into a mold for shaping, and after annealing at 500-600°C for 6-10 h, it is naturally cooled to obtain the base glass.

[0103] The method for manufacturing the polarizing glass of the present application is as follows:

[0104] 1) Forming the base glass: forming the base glass according to the method for manufacturing the base glass described above;

[0105] 2) heat treatment: heat treating the matrix glass at a temperature of 500-800°C for 10-20 hours. By heat treating, silver halide clusters are formed in the interior of the matrix glass, especially at the silver core;

[0106] 3) stretching treatment: stretching the heat treated matrix glass, so that the spherical silver halide clusters in the interior of the matrix glass are stretched into long strip or elliptical clusters with a length-diameter ratio of ≥2:1. Preferably, the surface of the stretched matrix glass can be polished;

[0107] 4) reduction treatment: reducing the stretched matrix glass in a reducing atmosphere, so that the long strip or elliptical silver halide clusters in the surface layer of the glass are reduced into elemental silver, thereby obtaining the polarized glass of the present application. The reduction treatment temperature is preferably 200-500°C, more preferably 300-450°C, and the reduction treatment time is preferably 10-40h, more preferably 20-30 hours.

[0108] [Examples]

[0109] In order to further clarify and explain the technical solutions of the present application, the following non-limiting examples are provided.

[0110] [Matrix glass examples]

[0111] In this example, the matrix glasses with the compositions shown in Tables 1-2 were obtained using the above-mentioned manufacturing method for matrix glass. In addition, the properties of each matrix glass were determined by the test method described in the present application, and the results are shown in Tables 1-2. In the following examples, the thickness of the sample for testing the transmittance of the matrix glass was 0.2mm.

[0112] Table 1.

[0113]

[0114]

[0115] Table 2.

[0116]

[0117]

[0118] [Polarized glass examples]

[0119] The polarizing glass having the composition shown in Tables 3 to 4 was obtained by using the above-mentioned method for manufacturing polarizing glass. In addition, the characteristics of each polarizing glass were measured by the test method described in the present application, and the measurement results are shown in Tables 3 to 4. In the following examples, the thickness of the sample for measuring the transmittance, the extinction ratio, and the insertion loss of the polarizing glass was 0.2 mm.

[0120] Table 3.

[0121]

[0122]

[0123] Table 4.

[0124]

[0125] < / sem>

Claims

1. Polarized glass, characterized in that The components are expressed in weight percent, the cationic component comprising: Si 4+ : 35-60%; B 3+ : 5-18%; R + : 5-25%; Al 3+ : 2-14%; Ag + : 0.1-0.6%, said R + being one or more of Li + , Na + , K + . The anion component contains: O 2- : 98-99.9%; Cl - : 0.1-1%; Br - : 0-1%.

2. The polarizing glass according to claim 1, characterized by of which the components are expressed in percentage by weight, the cationic component also containing: Zr 4+ : 0-8%; and / or Zn 2+ : 0-10%; and / or Ti 4+ : 0-7%; and / or Ba 2+ : 0-8%; and / or Cu 2+ : 0-0.3%.

3. Polarized glass, characterized in that of which the components are expressed in percentage by weight, the cationic component consisting of Si 4+ : 35-60%; B 3+ : 5-18%; R + : 5-25%; Al 3+ : 2-14%; Ag + : 0.1-0.6%; Zr 4+ : 0-8%; Zn 2+ : 0-10%; Ti 4+ : 0-7%; Ba 2+ : 0-8%; Cu 2+ : 0-0.3%, said R + being one or more of Li + , Na + , K + . The anion component consists of O 2- : 98-99.9%; CI - : 0.1-1%; Br - : 0-1%.

4. The polar glass of any one of claims 1-3, wherein, The components are expressed in percentage by weight and satisfy one or more of the following four conditions: 1) Si 4+ / B 3+ is 2.0 to 6.0, preferably Si 4+ / B 3+ is 3.0 to 5.0, more preferably Si 4+ / B 3+ is 3.5 to 4.5; 2) Al 3+ / Ti 4+ is 0.5 to 8.0, preferably Al 3+ / Ti 4+ is 2.0 to 6.0, more preferably Al 3+ / Ti 4+ is 3.0 to 4.5; 3) B 3+ (Ti 4+ + Al 3+ ) is 0.5 to 6.0, preferably B 3+ (Ti 4+ + Al 3+ ) is 1.0 to 4.0, more preferably B 3+ (Ti 4+ + Al 3+ ) is 1.5 to 3.0; 4) R + (Ba 2+ + Zn 2+ ) is 0.5 to 5.0, preferably R + (Ba 2+ + Zn 2+ ) is 1.5 to 4.5, more preferably R + (Ba 2+ + Zn 2+ ) is 2.5 to 3.8, and said R + is one or more of Li + , Na + , K + .

5. The polar glass of any one of claims 1-3, wherein, its components are expressed in weight percent, wherein: Si 4+ : 40-55%, preferably Si 4+ : 45-53%; and / or B 3+ : 8-15%, preferably B 3+ : 10-13%; and / or R + : 10-20%, preferably R + : 12-18%; and / or Al 3+ : 4-12%, preferably Al 3+ : 4-9%; and / or Ag + : 0.15-0.45%, preferably Ag + : 0.2-0.35%; and / or Zr 4+ : 2-7%, preferably Zr 4+ : 3-6%; and / or Zn 2+ : 2-8%, preferably Zn 2+ : 3-6%; and / or Ti 4+ : 1.5-5%, preferably Ti 4+ : 2-4%; and / or Ba 2+ : 1.5-6%, preferably Ba 2+ : 2.5-4.5%; and / or Cu 2+ : 0.02-0.1%, preferably Cu 2+ : 0.05-0.1%, said R + is one or more of Li + , Na + , K + .

6. The polar glass of any one of claims 1-3, wherein, of its components in weight percent, wherein: O 2- : 98.2-99.5%, preferably O 2- : 98.2-99%; and / or Cl - : 0.1-0.6%, preferably Cl - : 0.2-0.5%; and / or Br - : 0.1-0.7%, preferably Br - : 0.1-0.5%.

7. The polar glass of any one of claims 1-3, wherein, its components are expressed in weight percent, wherein: Li + : 0-5%, preferably Li + : 1-4%, more preferably Li + : 1.5-3%; and / or Na + : 3-16%, preferably Na + : 5-13%, more preferably Na + : 7-10%; and / or K + : 2-13%, preferably K + : 5-12%, more preferably K + : 6-10%.

8. The polar glass of any one of claims 1-3, wherein, The polarized glass has a bending strength of 80 MPa or more, preferably 120 MPa or more, more preferably 150 MPa or more; and / or a Young's modulus of 75 Gpa or more, preferably 80 Gpa or more, more preferably 85 Gpa or more; and / or a transmittance of 80% or more, preferably 85% or more, more preferably 90% or more for a thickness of 1.0 mm or less; and / or an extinction ratio of 30 dB or more, preferably 40 dB or more, more preferably 50 dB or more for a thickness of 1.0 mm or less; and / or an insertion loss of 0.60 dB or less, preferably 0.50 dB or less, more preferably 0.30 dB or less for a thickness of 1.0 mm or less.

9. A matrix glass characterized in that, The components are expressed in weight percent, the cationic component comprising: Si 4+ : 35-60%; B 3+ : 5-18%; R + : 5-25%; Al 3+ : 2-14%; Ag + : 0.1-0.6%, said R + being one or more of Li + , Na + , K + . The anion component contains: O 2- : 98-99.9%; CI - : 0.1-1%; Br - : 0-1%.

10. The substrate glass according to claim 9, wherein, of which the components are expressed in percentage by weight, the cationic component also containing: Zr 4+ : 0-8%; and / or Zn 2+ : 0-10%; and / or Ti 4+ : 0-7%; and / or Ba 2+ : 0-8%; and / or Cu 2+ : 0-0.3%.

11. A matrix glass characterized in that, its components expressed in weight percent, the cationic component consisting of Si 4+ : 35-60%; B 3 + : 5-18%; R + : 5-25%; Al 3+ : 2-14%; Ag + : 0.1-0.6%; Zr 4+ : 0-8%; Zn 2+ : 0-10%; Ti 4+ : 0-7%; Ba 2+ : 0-8%; Cu 2+ : 0-0.3% consisting of R + one or more of Li + , Na + , K + . The anion component consists of O 2- : 98-99.9%; CI - : 0.1-1%; Br - : 0-1%.

12. The base glass according to any one of claims 9 to 11, characterized by The components are expressed in percentage by weight and satisfy one or more of the following four conditions: 1) Si 4+ / B 3+ is 2.0 to 6.0, preferably Si 4+ / B 3+ is 3.0 to 5.0, more preferably Si 4+ / B 3+ is 3.5 to 4.5; 2) Al 3+ / Ti 4+ is 0.5 to 8.0, preferably Al 3+ / Ti 4+ is 2.0 to 6.0, more preferably Al 3+ / Ti 4+ is 3.0 to 4.5; 3) B 3+ / (Ti 4+ + Al 3+ ) is 0.5 to 6.0, preferably B 3+ / (Ti 4+ + Al 3+ ) is 1.0 to 4.0, more preferably B 3+ / (Ti 4+ + Al 3+ ) is 1.5 to 3.0; 4) R + (Ba 2+ + Zn 2+ ) is 0.5 to 5.0, preferably R + (Ba 2+ + Zn 2+ ) is 1.5 to 4.5, more preferably R + (Ba 2+ + Zn 2+ ) is 2.5 to 3.8, and said R + is one or more of Li + , Na + , K + .

13. The base glass according to any one of claims 9 to 11, wherein its components are expressed in weight percent, wherein: Si 4+ : 40-55%, preferably Si 4+ : 45-53%; and / or B 3+ : 8-15%, preferably B 3+ : 10-13%; and / or R + : 10-20%, preferably R + : 12-18%; and / or Al 3+ : 4-12%, preferably Al 3+ : 4-9%; and / or Ag + : 0.15-0.45%, preferably Ag + : 0.2-0.35%; and / or Zr 4+ : 2-7%, preferably Zr 4+ : 3-6%; and / or Zn 2+ : 2-8%, preferably Zn 2+ : 3-6%; and / or Ti 4+ : 1.5-5%, preferably Ti 4+ : 2-4%; and / or Ba 2+ : 1.5-6%, preferably Ba 2+ : 2.5-4.5%; and / or Cu 2+ : 0.02-0.1%, preferably Cu 2+ : 0.05-0.1%, said R + is one or more of Li + , Na + , K + .

14. The base glass according to any one of claims 9 to 11, wherein its components are expressed in percentage by weight, in which: O 2- : 98.2-99.5%, preferably O 2- : 98.2-99%; and / or Cl - : 0.1-0.6%, preferably Cl - : 0.2-0.5%; and / or Br - : 0.1-0.7%, preferably Br - : 0.1-0.5%.

15. The base glass according to any one of claims 9 to 11, wherein its components are expressed in weight percent, wherein: Li + : 0-5%, preferably Li + : 1-4%, more preferably Li + : 1.5-3%; and / or Na + : 3-16%, preferably Na + : 5-13%, more preferably Na + : 7-10%; and / or K + : 2-13%, preferably K + : 5-12%, more preferably K + : 6-10%.

16. The base glass according to any one of claims 9 to 11, wherein The base glass has a bending strength of 80 MPa or more, preferably 120 MPa or more, more preferably 150 MPa or more; and / or a Young's modulus of 75 Gpa or more, preferably 80 Gpa or more, more preferably 85 Gpa or more; and / or a transmittance of 80% or more, preferably 85% or more, more preferably 90% or more for a thickness of 1.0 mm or less.

17. A polarizing element characterized by, The polarized glass is made of any one of the polarized glasses of claims 1-8.

18. An apparatus, comprising: The polarized glass is made of any one of the polarized glasses of claims 1-8.

19. The method of producing a polarized glass according to any one of claims 1 to 8, characterized by, The method comprises the following steps: 1) forming a base glass; 2) heat treating the base glass; 3) stretching the heat-treated base glass; 4) reducing the stretched base glass to obtain a polarized glass.

20. The method of claim 19, wherein the polar glass is manufactured by a method comprising: The forming of the base glass comprises the following steps: The glass raw materials are weighed according to the content of each component of the base glass, mixed and stirred uniformly after batching, then added to a melting furnace for melting, melted in a melting furnace with a melting temperature of 1200-1500°C for 5-20 hours, preferably a melting temperature of 1250-1400°C, then heated to 1300-1500°C for 6-8 hours of fining, preferably a fining temperature of 1350-1450°C, finally cooled down after homogenization, poured into a mold, and annealed at 500-600°C for 6-10h and naturally cooled to obtain the base glass.

21. The method of claim 19, wherein the polar glass is manufactured by a method comprising: The heat treatment temperature for the heat treatment of the base glass is 500-800°C, the heat treatment time is 10-20 hours, the reduction treatment temperature for the reduction treatment is 200-500°C, preferably 300-450°C, and the reduction treatment time is 10-40h, preferably 20-30 hours.

Images