High-toughness phosphosilicate glass and low-carbon method of making same

Abstract

The application discloses a high-toughness phosphosilicate glass and a low-carbon preparation method thereof, and relates to the technical field of glass manufacturing. The high-toughness phosphosilicate glass comprises the following components in terms of molar percentage: SiO2 10-80%, P2O5 0.5-60%, Al2O3 0.5-60%, B2O3 0.5-60%, ZnO 0.5-30%, M2O 0.5-40%, XO 0.1-30% and Sb2O3 0.1-10%; the M element in the M2O is selected from one or more of Li, Na, K, Rb and Cs; and the X element in the XO is selected from one or more of Mg, Ca, Sr and Ba. The high-toughness phosphosilicate glass has a fracture toughness of 2.28 MPa.m 0.5 , an absorption coefficient less than 0.50 cm ‑1 in a wavelength range of 380-780 nm, and a transmittance greater than 80% in the wavelength range of 380-780 nm. In the preparation process, no carbon-containing material is used, and the glass melting temperature is reduced to 1000-1400 DEG C, thereby greatly reducing carbon dioxide emission and preparation energy consumption compared with traditional glass preparation technology, and realizing low-carbon preparation of the glass.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of glass manufacturing, in particular to a high-toughness phosphosilicate glass and a low-carbon preparation method thereof. BACKGROUND

[0002] Ordinary glass is a silicate non-metallic material prepared by mixing, high-temperature melting, homogenizing quartz sand, soda ash, feldspar, limestone and the like, processing into a shape, and then annealing, and has the characteristics of transparency, non-combustibility, high temperature resistance, impact resistance, non-conductivity, etc., and is widely used in daily life, such as large glass windows in buildings, automobile glass, etc. However, the furnace temperature for manufacturing such common materials is as high as 1500℃, which consumes a large amount of energy and releases a large amount of carbon dioxide into the atmosphere. More importantly, ordinary glass is made of quartz sand, soda ash and limestone, and the latter two materials release carbon dioxide when melted. The large amount of carbon dioxide emitted during the preparation of ordinary glass has a serious adverse effect on the environment, and the demand for low-carbon preparation of glass is increasing year by year. At present, hydrogen or a mixture of hydrogen and methane is generally used as raw material to reduce carbon dioxide emissions of natural gas and other carbon-containing fuels, but it does not solve the carbon emissions of glass raw materials and the high energy consumption required for melting glass. In addition, the fracture toughness of ordinary glass is poor, only 0.72MPa·m 0.5 , which will start to crack under a Vickers hardness indenter load of 0.1kgf, limiting its actual use range. At present, it is reported that glass can be prepared by using anion or cation high-entropy components, and the fracture toughness can reach 1.21-1.52MPa·m 0.5 , but these components are generally not suitable for large-scale production on mature float production lines. Therefore, how to prepare a glass with high toughness or excellent crack resistance by a low-carbon method has become a technical problem that technicians in the field need to solve. SUMMARY

[0003] The purpose of the present application is to provide a high-toughness phosphosilicate glass and a low-carbon preparation method thereof to solve the problems existing in the prior art.

[0004] To achieve the above purpose, the present application provides the following solutions:

[0005] One of the technical solutions of the present application: a high-toughness phosphosilicate glass, comprising the following components in terms of mole percentage: SiO2 10-80%, P2O5 0.5-60%, Al2O3 0.5-60%, B2O3 0.5-60%, ZnO 0.5-30%, M2O 0.5-40%, XO 0.1-30%, and Sb2O3 0.1-10%;

[0006] The M element in the M2O is selected from one or more of Li (lithium), Na (sodium), K (potassium), Rb (rubidium) and Cs (cesium) (M is an alkali metal element); and the X element in the XO is selected from one or more of Mg (magnesium), Ca (calcium), Sr (strontium) and Ba (barium) (X is an alkaline earth metal element).

[0007] In the present application, SiO2 can be used as a rigid glass forming body; P2O5 can be used as a flexible forming body; Al2O3 helps to introduce phosphates in silicate glass; ZnO, B2O3, M2O and XO, etc. can play the role of a dissolving agent; Sb2O3 can play the role of a clarifying agent; in the phosphosilicate glass system, the rigid silicon-oxygen tetrahedral network (SiO4 unit is constructed with Si and O elements as the core) and the flexible chain-like phosphorus-oxygen structure (long chain structure composed of M, X, Zn, P, O elements) are chemically bonded through aluminum-oxygen tetrahedron (AlO4) or boron-oxygen tetrahedron (BO4). The aluminum-oxygen tetrahedron or the boron-oxygen tetrahedron acts as a structural bridging unit, which not only maintains the topological stability of the silicon-oxygen tetrahedral framework, but also effectively embeds the flexibility of the phosphorus-oxygen chain into the rigid matrix through the formation of P-O-Al(B) and Si-O-Al(B) covalent bonds. This multi-scale structure coupling mechanism optimizes the design of the energy dissipation path, realizes the cooperative deformation ability of the glass network under stress, and finally breaks through the brittleness limitation of traditional silicate glass, significantly improving the fracture toughness of the material.

[0008] The high-toughness phosphosilicate glass of the present application has a fracture toughness of up to 2.28 MPa·m 0.5 , a crack resistance to Vickers hardness indenter of up to 10 times that of ordinary soda-lime-silica glass, an absorption coefficient in the wavelength region of 380-780 nm of less than 0.50 cm -1 , and a transmittance in the wavelength region of 380-780 nm of greater than 80%, etc.

[0009] Preferably, the high-toughness phosphosilicate glass has a component composition of, in terms of mole percentage: SiO2 20-40%, P2O5 10-40%, Al2O3 5-15%, B2O3 10-20%, ZnO 5-10%, M2O 15-25%, XO 4.5-9.5%, and Sb2O3 0.5%.

[0010] More preferably, the high-toughness phosphosilicate glass has a component composition of, in terms of mole percentage: SiO2 30%, P2O5 30%, Al2O3 5%, B2O3 10%, ZnO 5%, M2O 15%, XO 4.5%, and Sb2O3 0.5%.

[0011] The second technical solution of the present application is a low-carbon preparation method of the high-toughness phosphosilicate glass described above, comprising the following steps:

[0012] The SiO2 source, the P2O5 source, the Al2O3 source, the B2O3 source, the ZnO source, the M2O source, the XO source and the Sb2O3 source are weighed according to the target molar ratio of each component (i.e. the molar amount of SiO2, P2O5, Al2O3, B2O3, ZnO, M2O, XO and Sb2O3 contained in or provided by the SiO2 source, the P2O5 source, the Al2O3 source, the B2O3 source, the ZnO source, the M2O source, the XO source and the Sb2O3 source is calculated to obtain the molar amount of each raw material required to obtain the target component composition of the phosphosilicate glass), mixed to obtain a mixture; the mixture is degassed, and the degassed mixture is prepared into a glass liquid; the glass liquid is quenched to form the high-toughness phosphosilicate glass.

[0013] The SiO2 source, the P2O5 source, the Al2O3 source, the B2O3 source, the ZnO source, the M2O source, the XO source and the Sb2O3 source all do not contain carbon elements.

[0014] The present application does not use any carbon-containing raw materials in the preparation process, which can avoid the emission of carbon dioxide generated by the raw materials in the preparation process and realize low-carbon preparation of the glass.

[0015] Further, the SiO2 source includes silicon dioxide (SiO2).

[0016] Further, the ZnO source includes zinc oxide (ZnO).

[0017] Further, the Sb2O3 source includes antimony trioxide (Sb2O3).

[0018] Further, the P2O5 source includes diaphosphorus pentoxide (P2O5) or ammonium dihydrogen phosphate (NH4H2PO4).

[0019] Further, the Al2O3 source includes aluminum oxide (Al2O3) or aluminum dihydrogen phosphate (Al(H2PO4)3).

[0020] Further, the M2O source includes a phosphate or silicate containing M elements.

[0021] Further, the XO source includes a phosphate or silicate containing X elements.

[0022] Further, the degassing includes: heat preservation of the mixture at 400-800℃ for 0.5-3.0h.

[0023] Further, the raw materials used for mixing are all powders after crushing and passing through a 200-mesh sieve (i.e. each raw material is crushed and passed through a 200-mesh sieve, and then weighed and mixed according to the molar ratio).

[0024] Further, the preparation of the degassed mixture into a glass liquid comprises: preheating the degassed mixture at 250-500 DEG C for 10-60 min, and then keeping the temperature at 1000-1400 DEG C for 0.5-3.0 h to obtain the glass liquid.

[0025] The present application not only does not use any carbon-containing raw material in the preparation process, but also reduces the glass melting temperature (to 1000-1400 DEG C) by selecting specific raw materials (ZnO source, B2O3 source, M2O source and XO source, etc., which can play the role of a dissolving agent), compared with the traditional glass preparation technology (melting temperature up to 1500-1600 DEG C), not only avoids the carbon dioxide emission generated by the raw materials in the preparation process, but also reduces the carbon dioxide emission caused by the use of fuel to heat, greatly reduces the overall carbon dioxide emission in the glass preparation process, realizes the low-carbon preparation of glass, and the reduction of the glass melting temperature also reduces the energy consumption in the preparation process.

[0026] Further, the quenching forming comprises: placing the glass liquid in a mold preheated to 300-600 DEG C for quenching forming.

[0027] Further, after the quenching forming, the method further comprises the step of annealing the sample obtained after the quenching forming; the annealing temperature is 400-600 DEG C, and the annealing time is 1-6 h.

[0028] The present application realizes the low-carbon preparation of a high-toughness phosphosilicate glass by using a simple melting-quenching method, and can obtain a high-performance phosphosilicate glass with a fracture toughness of 2.28 MPa·m 0.5 , a resistance to Vickers hardness indenter of 10 times or more that of ordinary soda-lime-silica glass, an absorption coefficient of less than 0.50 cm -1 in the wavelength range of 380-780 nm, and a transmittance of more than 80% in the wavelength range of 380-780 nm under the premise of not using carbon-containing raw materials and reducing the glass melting temperature by 100-400 DEG C compared with ordinary glass melting.

[0029] The third technical scheme of the present application is the application of the high-toughness phosphosilicate glass in the fields of building, automobile manufacturing or aerospace.

[0030] The present application has the following technical effects:

[0031] (1) The high-toughness phosphosilicate glass has a fracture toughness of 2.28 MPa·m0.5 The anti-cracking property of the Vickers hardness indenter can reach 10 times or more than that of common soda-lime-silica glass, the absorption coefficient in the wavelength range of 380-780 nm is less than 0.50 cm -1 and the transmittance in the wavelength range of 380-780 nm is greater than 80%, etc.

[0032] (2) The present application does not use any carbon-containing raw materials in the preparation process, and the glass melting temperature is reduced (to 1000-1400℃) through specific raw material selection, compared with the traditional glass preparation technology (melting temperature up to 1500-1600℃), not only the carbon dioxide emission generated by the raw materials in the preparation process is avoided, but also the carbon dioxide emission caused by the use of fuel heating is reduced, the overall carbon dioxide emission in the glass preparation process is greatly reduced, the low-carbon preparation of glass is realized, and the reduction of the glass melting temperature also reduces the energy consumption in the preparation process.

[0033] (3) The high-toughness glass of the present application can be widely used in the fields of building, automobile manufacturing or aerospace, etc. BRIEF DESCRIPTION OF DRAWINGS

[0034] In order to more clearly illustrate the technical solutions in the embodiments of the present application or the prior art, the drawings needed to be used in the embodiments will be briefly introduced as follows. Obviously, the drawings in the following description only constitute some embodiments of the present application, and other drawings can also be obtained by those skilled in the art without creative labor on the basis of these drawings.

[0035] Figure 1 The microhardness instrument indentation effect diagram of the high-toughness phosphosilicate glass prepared in Example 1 and the soda-lime-silica glass prepared in Comparative Example 1.

[0036] Figure 2 The high-toughness phosphosilicate glass prepared in Example 1, wherein (a) is the transmittance change with wavelength, and (b) is the absorption coefficient change with wavelength. DETAILED DESCRIPTION

[0037] Now, various exemplary embodiments of the present application will be described in detail, which should not be considered as a limitation of the present application, but should be understood as a more detailed description of certain aspects, characteristics and embodiments of the present application.

[0038] It is to be understood that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the present application. In addition, where a range of values is provided, it is understood that each intervening value, to the upper and lower limit of the range is also specifically disclosed. Each smaller range between any stated value or intervening value in a stated range and any other stated or intervening value in that stated range is encompassed. The upper and lower limits of these smaller ranges can independently be included or excluded in the range, and are also encompassed by the application, subject to any specifically excluded limit in the stated range. Where the stated range includes one or both of the limits, ranges excluding either or both of the limits are also included.

[0039] Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this application belongs. Although preferred methods and materials are described herein, any methods and materials similar or equivalent to those described herein can be used in the practice or testing of the present application. All documents mentioned herein are incorporated by reference to disclose and describe in detail the methods and / or materials which are related to the present application. In the case of conflict between the present specification and any document incorporated herein by reference, the present specification will control.

[0040] Many modifications and variations of the present application described in the specification are possible without departing from the scope or spirit of the application. Other implementations of the application will be apparent to those skilled in the art from consideration of the specification and practice of the application disclosed herein. The specification and examples are illustrative only.

[0041] As used herein, the terms "comprises", "comprising", "includes", "including", "has", "having", and the like are open-ended terms that are intended to mean including, but not limited to.

[0042] It should be noted that the present application does not describe in detail the conventional operation means in the art, and is not the focus of the present application.

[0043] In the following examples and comparative examples of the present application, if it refers to room temperature, it specifically refers to 20-30°C.

[0044] In the following examples and comparative examples of the present application, each raw material used is a common commercially available product unless otherwise specified.

[0045] Example 1

[0046] A low-carbon preparation method of a high-toughness phosphosilicate glass, the steps are as follows:

[0047] (1) Raw material ratio design: according to the mole percentage, the raw material composition is: silicon dioxide 25.37%, ammonium dihydrogen phosphate 29.85%, aluminum oxide 9.95%, boron oxide 9.95%, zinc oxide 9.95%, sodium phosphate 9.95%, calcium silicate 4.48%, and antimony trioxide 0.50%.

[0048] (2) Preparation of the mixture: The silicon dioxide, ammonium dihydrogen phosphate, aluminum oxide, boron oxide, zinc oxide, sodium phosphate, calcium silicate and antimony trioxide, which were respectively pulverized and passed through a 200-mesh sieve, were weighed according to the molar percentage and mixed for 10 minutes to obtain the mixture.

[0049] (3) Degassing: The mixture obtained in step (2) was poured into a crucible, which was placed in a muffle furnace and heated to 600°C at a temperature increasing rate of 10°C / min under an air atmosphere, and then kept at 600°C for 1 hour, and then cooled to room temperature.

[0050] (4) Preparation of the glass liquid: The crucible containing the degassed mixture obtained in step (3) was preheated at 450°C for 10 minutes under an air atmosphere, and then placed in an elevator furnace and kept at 1250°C for 1 hour to melt the mixture into a glass liquid.

[0051] (5) Quenching of the glass liquid: The glass liquid was placed in a preheated mold (temperature: 450°C) to perform quenching, and then the quenched sample was placed in an annealing furnace at 450°C for annealing for 4 hours, and finally cooled to room temperature at a cooling rate of 1°C / min to obtain a high-toughness phosphosilicate glass.

[0052] Example 2

[0053] The same as in Example 1, except that the raw material composition was, in terms of molar percentage, silicon dioxide 31.94%, ammonium dihydrogen phosphate 20.94%, aluminum oxide 10.47%, boron oxide 10.47%, zinc oxide 10.47%, sodium phosphate 10.47%, calcium silicate 4.71%, and antimony trioxide 0.53%.

[0054] Example 3

[0055] The same as in Example 1, except that the raw material composition was, in terms of molar percentage, silicon dioxide 39.23%, ammonium dihydrogen phosphate 11.05%, aluminum oxide 11.05%, boron oxide 11.05%, zinc oxide 11.05%, sodium phosphate 11.05%, calcium silicate 4.97%, and antimony trioxide 0.55%.

[0056] Example 4

[0057] The same as in Example 1, except that the raw material composition was, in terms of molar percentage, silicon dioxide 19.43%, ammonium dihydrogen phosphate 37.91%, aluminum oxide 9.48%, boron oxide 9.48%, zinc oxide 9.48%, sodium phosphate 9.48%, calcium silicate 4.27%, and antimony trioxide 0.47%.

[0058] Example 5

[0059] The same as Example 1, except that the raw material composition, in terms of mole percent, is: silicon dioxide 14.03%, ammonium dihydrogen phosphate 45.25%, aluminum oxide 9.05%, boron oxide 9.05%, zinc oxide 9.05%, sodium phosphate 9.05%, calcium silicate 4.07%, and diantimony trioxide 0.45%.

[0060] Example 6

[0061] The same as Example 1, except that the raw material composition, in terms of mole percent, is: silicon dioxide 31.68%, ammonium dihydrogen phosphate 4.14%, aluminum oxide 12.42%, boron oxide 12.42%, zinc oxide 12.42%, sodium phosphate 20.70%, calcium silicate 5.59%, and diantimony trioxide 0.63%.

[0062] Example 7

[0063] The same as Example 1, except that the raw material composition, in terms of mole percent, is: silicon dioxide 25.47%, ammonium dihydrogen phosphate 8.28%, aluminum oxide 12.42%, boron oxide 12.42%, zinc oxide 12.42%, sodium phosphate 16.56%, calcium silicate 11.80%, and diantimony trioxide 0.63%.

[0064] Example 8

[0065] The same as Example 1, except that the raw material composition, in terms of mole percent, is: silicon dioxide 28.18%, ammonium dihydrogen phosphate 11.05%, aluminum oxide 11.05%, boron oxide 22.10%, zinc oxide 11.05%, sodium phosphate 11.05%, calcium silicate 4.97%, and diantimony trioxide 0.55%.

[0066] Example 9

[0067] The same as Example 1, except that the raw material composition, in terms of mole percent, is: silicon dioxide 25.37%, ammonium dihydrogen phosphate 29.85%, aluminum oxide 9.95%, boron oxide 9.95%, zinc oxide 9.95%, potassium phosphate 9.95%, calcium silicate 4.48%, and diantimony trioxide 0.50%.

[0068] Example 10

[0069] The same as Example 1, except that the raw material composition, in terms of mole percent, is: silicon dioxide 25.37%, ammonium dihydrogen phosphate 29.85%, aluminum oxide 9.95%, boron oxide 9.95%, zinc oxide 9.95%, sodium phosphate 9.95%, barium silicate 4.48%, and diantimony trioxide 0.50%.

[0070] Example 11

[0071] The same as Example 1, except that the raw material composition, in terms of mole percent, is: silicon dioxide 23.08%, ammonium dihydrogen phosphate 45.25%, aluminum oxide 4.52%, boron oxide 9.05%, zinc oxide 4.52%, sodium phosphate 9.05%, calcium silicate 4.07%, and diantimony trioxide 0.46%.

[0072] Example 12

[0073] The same as Example 1, except that the raw material composition, in terms of mole percent, is: silicon dioxide 28.91%, ammonium dihydrogen phosphate 37.91%, aluminum oxide 4.74%, boron oxide 9.48%, zinc oxide 4.74%, sodium phosphate 9.48%, calcium silicate 4.27%, and diantimony trioxide 0.47%.

[0074] Example 13

[0075] The same as Example 1, except that the raw material composition, in terms of mole percent, is: silicon dioxide 35.32%, ammonium dihydrogen phosphate 29.85%, aluminum oxide 4.98%, boron oxide 9.95%, zinc oxide 4.98%, sodium phosphate 9.95%, calcium silicate 4.48%, and diantimony trioxide 0.49%.

[0076] Example 14

[0077] The same as Example 1, except that the raw material composition, in terms of mole percent, is: silicon dioxide 17.75%, ammonium dihydrogen phosphate 51.95%, aluminum oxide 4.33%, boron oxide 8.66%, zinc oxide 4.33%, sodium phosphate 8.66%, calcium silicate 3.90%, and diantimony trioxide 0.42%.

[0078] Example 15

[0079] The same as Example 1, except that the raw material composition, in terms of mole percent, is: silicon dioxide 12.86%, ammonium dihydrogen phosphate 58.09%, aluminum oxide 4.15%, boron oxide 8.30%, zinc oxide 4.15%, sodium phosphate 8.30%, calcium silicate 3.73%, and diantimony trioxide 0.42%.

[0080] Example 16

[0081] The same as Example 1, except that the raw material composition, in terms of mole percent, is: silicon dioxide 24.17%, ammonium dihydrogen phosphate 37.91%, aluminum oxide 9.48%, boron oxide 9.48%, zinc oxide 4.74%, sodium phosphate 9.48%, calcium silicate 4.27%, and diantimony trioxide 0.47%.

[0082] Example 17

[0083] The same as Example 1, except that the raw material composition, in terms of mole percent, is: silica 25.37%, ammonium dihydrogen phosphate 29.85%, aluminum oxide 14.93%, boron oxide 9.95%, zinc oxide 4.98%, sodium phosphate 9.95%, calcium silicate 4.48%, and antimony trioxide 0.49%.

[0084] Example 18

[0085] The same as Example 1, except that the raw material composition, in terms of mole percent, is: silica 25.37%, ammonium dihydrogen phosphate 29.85%, aluminum oxide 9.95%, boron oxide 14.93%, zinc oxide 4.98%, sodium phosphate 9.95%, calcium silicate 4.48%, and antimony trioxide 0.49%.

[0086] Example 19

[0087] The same as Example 1, except that the raw material composition, in terms of mole percent, is: silica 25.37%, ammonium dihydrogen phosphate 29.85%, aluminum oxide 4.98%, boron oxide 19.90%, zinc oxide 4.98%, sodium phosphate 9.95%, calcium silicate 4.48%, and antimony trioxide 0.49%.

[0088] Comparative Example 1

[0089] A soda-lime-silica glass was prepared by the following steps:

[0090] (1) Raw material ratio design: the raw material composition, in terms of mole percent, is: silica 73.00%, aluminum oxide 1.00%, sodium carbonate 15.00%, calcium carbonate 10.50%, and antimony trioxide 0.50%.

[0091] (2) Mixing of the batch: the silica, aluminum oxide, sodium carbonate, calcium carbonate, and antimony trioxide, which have been respectively pulverized and passed through a 200-mesh sieve, were weighed out in terms of mole percent, and were thoroughly mixed for 10 min to obtain a batch.

[0092] (3) Outgassing: the batch obtained in step (2) was poured into a crucible, and the crucible was placed in a muffle furnace, which was heated to 600°C at a temperature increase rate of 10°C / min under an air atmosphere, and was held at 600°C for 1 h, and was then cooled to room temperature.

[0093] (4) Preparation of the glass liquid: the crucible containing the outgassed batch obtained in step (3) was preheated at 450°C for 10 min under an air atmosphere, and was then placed in an elevator furnace, and was held at 1550°C for 1 h to melt the batch into a glass liquid.

[0094] (5) Glass liquid quenching forming: the glass liquid is placed in a preheated mold (temperature is 600 ℃) to perform quenching forming, then the sample after quenching forming is placed in an annealing furnace at 600 ℃ for annealing for 4 h, and finally the temperature is reduced to room temperature at a rate of 1 ℃ / min to obtain a sodium calcium silicon glass.

[0095] The component compositions (molar proportions) of the phosphosilicate glass products prepared in Examples 1-19 and the sodium calcium silicon glass product prepared in Comparative Example 1 are shown in Tables 1 and 2.

[0096] Effect Example

[0097] The basic physical properties of the phosphosilicate glass products prepared in Examples 1-19 and the sodium calcium silicon glass product prepared in Comparative Example 1, such as the absorption coefficient in the wavelength range of 380-780 nm, the transmittance in the wavelength range of 380-780 nm, and the fracture toughness, are tested, and the testing method is as follows:

[0098] (1) Transmittance and absorption coefficient in the wavelength range of 380-780 nm: the transmittance of the glass sample is measured using a UV-Visible / NIR spectrophotometer of Japan HITACHI company, and the wavelength range for visible light transmittance testing is 380-780 nm. The sample is a bulk sample with a thickness of 4 mm. The absorption coefficient is calculated according to the transmittance.

[0099] (2) Hardness, Young's modulus, and fracture toughness: the sample is a bulk sample with a thickness of 4 mm. The Vickers hardness of the bulk sample is tested using a HXD-1000TMC / LCD microhardness tester of Shanghai Taiming company, and specifically, the Vickers hardness value and microhardness indentation effect of the sample to be tested are measured by indentation method under a test force of 25-1000 gf with a load of 15 s. The Young's modulus of the glass sample is tested using a Bruker Hysitrin TI 980 nanoindenter. The fracture toughness of the sample is obtained in combination with the microindentation results according to the standard GB / T37900-2019.

[0100] (3) Thermal expansion coefficient: the thermal expansion coefficient and glass transition point temperature of the glass sample are tested using a NETZSCH DIL 402CL thermal dilatometer of Germany Netzsch company, and the heating rate is 10 ℃ / min; the sample is a cylindrical sample with a diameter of 4.01 mm and a length of 44.36 mm.

[0101] Figure 1The microhardness indenter effect pictures of the high-toughness phosphosilicate glass prepared in Example 1 and the soda-lime-silicate glass prepared in Comparative Example 1 (wherein the first row is the soda-lime-silicate glass and the second row is the phosphosilicate glass) can be seen that the soda-lime-silicate glass can withstand the pressure of the microhardness tester below 100 gf, and when the pressure is 100 gf, the left and right sides of the indentation crack, while the toughened phosphosilicate glass can withstand the pressure of 1000 gf without cracking, wherein 1000 gf is the upper limit of the pressure of the ordinary microhardness tester, which shows that the bearing capacity of the sample exceeds 1000 gf, which is more than 10 times of the ordinary soda-lime-silicate glass (prepared in Comparative Example 1). It is proved that the toughness performance of the high-toughness phosphosilicate glass of the present application is greatly increased than the soda-lime-silicate glass.

[0102] Figure 2 The ultraviolet-visible-near-infrared transmission and absorption spectrum of the high-toughness phosphosilicate glass prepared in Example 1, wherein (a) is the change of the transmission rate with the wavelength, and (b) is the change of the absorption coefficient with the wavelength. It can be seen that the visible light transmission performance of the toughened phosphosilicate glass of the present application is excellent and the absorption is low, which is close to the ordinary soda-lime-silicate glass (prepared in Comparative Example 1).

[0103] The test results of each example and comparative example are shown in Tables 1-3.

[0104] Table 1 Component composition, 380-780 nm wavelength region average absorption coefficient, 380-780 nm wavelength region average transmission rate and fracture toughness of the phosphosilicate glass products prepared in Examples 1-10

[0105]

[0106]

[0107] Table 2 Component composition, 380-780 nm average absorption coefficient, 380-780 nm average transmission rate and fracture toughness of the phosphosilicate glass products prepared in Examples 11-19 and the soda-lime-silicate glass prepared in Comparative Example 1

[0108]

[0109] Table 3 Basic physical properties of some examples and soda-lime-silicate glass

[0110]

[0111] The component compositions of the phosphosilicate glass products prepared from Examples 1-19 are as follows: the total content of SiO2and P2O5 is controlled at 50% in Examples 1-5, the difference being the respective contents of SiO2and P2O5; the total content of P2O5, M2O and XO is controlled at 39.5% in Examples 1, 6 and 7, the difference being the respective contents of P2O5, M2O and XO; the total content of P2O5 and B2O3 is controlled at 30% in Examples 1 and 8, the difference being the respective contents of P2O5 and B2O3; the difference between Example 1 and Example 9 is only that the alkali metal M is changed from sodium to potassium; the difference between Example 1 and Example 10 is only that the alkaline earth metal X is changed from calcium to barium; the total content of SiO2and P2O5 is controlled at 60% in Examples 11-15, the difference being the respective contents of SiO2and P2O5, and the difference between Example 15 and Example 1 is the content of Al2O3and ZnO; the total content of P2O5, Al2O3and B2O3 is controlled at 45% in Examples 16-19, the difference being the respective contents of P2O5, Al2O3and B2O3.

[0112] As can be seen from Tables 1-3, the component types and proportions of the phosphosilicate glass have a significant effect on the hardness and fracture toughness of the glass. The fracture toughness of all the samples is superior to that of sodium calcium silicate glass. As can be seen from Comparative Examples 1-5, the fracture toughness changes with the change in the contents of phosphorus and silicon in the glass matrix. With the increase in the content of phosphorus and the decrease in the content of silicon, the fracture toughness first increases and then decreases. As can be seen from Examples 1, 6 and 7, the fracture toughness changes with the change in the content of alkali metal (i.e. M) or alkaline earth metal ion (i.e. X). With the increase in the content of alkali metal or alkaline earth metal ion, the fracture toughness decreases. As can be seen from Examples 1 and 8, the fracture toughness changes with the change in the content of boron. With the increase in the content of boron, the fracture toughness decreases. As can be seen from Examples 1, 9 and 10, the fracture toughness changes with the change in the radius of the alkali metal or alkaline earth metal ion. With the increase in the radius of the ion (the radius of potassium > the radius of sodium, and the radius of barium > the radius of calcium), the fracture toughness decreases. As can be seen from Examples 11-15, the hardness and fracture toughness change with the change in the contents of phosphorus and silicon in the glass matrix. With the increase in the content of phosphorus and the decrease in the content of silicon, the hardness decreases and the fracture toughness first increases and then decreases. As can be seen from Examples 16-19, the fracture toughness changes with the change in the contents of aluminum, boron and phosphorus. With the increase in the content of boron, or the decrease in the content of phosphorus or aluminum, the fracture toughness decreases.

[0113] It can also be seen from Table 3 that the component types and proportions of the phosphosilicate glass have obvious effects on the thermal expansion properties and glass transition temperature of the glass. Comparing Example 1, Examples 11-15 and the soda-lime-silica glass, the thermal expansion coefficients of Examples 1, 11-15 are greater than that of the soda-lime-silica glass, but the glass transition temperatures of Examples 1, 11-15 are less than that of the soda-lime-silica glass. Comparing Example 1 and Example 11, the fracture toughness changes with the change of aluminum and zinc elements in the glass matrix. With the increase of aluminum element and the decrease of zinc element, the thermal expansion coefficient of the sample decreases, but the glass transition temperature increases. Comparing Examples 11-15, the thermal expansion coefficient and the glass transition temperature change with the change of phosphorus and silicon elements in the glass matrix. With the increase of phosphorus element and the decrease of silicon element, the thermal expansion coefficient of the sample increases, but the glass transition temperature decreases.

[0114] The above-described examples are merely preferred modes of the present application and are not intended to limit the scope of the present application. Various modifications and improvements to the technical solutions of the present application made by those of ordinary skill in the art without departing from the design spirit of the present application shall fall within the scope of protection of the present application as defined by the claims.

Claims

1. A high-toughness phosphosilicate glass, characterized in that, The composition, by molar percentage, is: SiO2 30%, P2O5 20%, Al2O3 10%, B2O3 10%, ZnO 10%, Na2O 15%, CaO 4.5% and Sb2O3 0.5%. Alternatively, SiO2 30%, P2O5 20%, Al2O3 10%, B2O3 10%, ZnO 10%, K2O 15%, CaO 4.5% and Sb2O3 0.5%; Alternatively, the composition is: SiO2 30%, P2O5 30%, Al2O3 5%, B2O3 10%, ZnO 5%, Na2O 15%, CaO 4.5% and Sb2O3 0.5%; Alternatively, the composition is: SiO2 35%, P2O5 25%, Al2O3 5%, B2O3 10%, ZnO 5%, Na2O 15%, CaO 4.5% and Sb2O3 0.5%; Alternatively, the composition is: SiO2 25%, P2O5 35%, Al2O3 5%, B2O3 10%, ZnO 5%, Na2O 15%, CaO 4.5% and Sb2O3 0.5%; The high-toughness phosphosilicate glass is prepared by a low-carbon preparation method comprising only the following steps: The raw materials SiO2 source, P2O5 source, Al2O3 source, B2O3 source, ZnO source, M2O source, XO source and Sb2O3 source are calculated and weighed according to the target molar ratio of each component, and mixed to obtain a mixture; the mixture is degassed, and the degassed mixture is prepared into a glass melt; the glass melt is quenched and shaped, and the sample obtained after quenching and shaping is annealed to obtain the high-toughness phosphosilicate glass; The SiO2 source, P2O5 source, Al2O3 source, B2O3 source, ZnO source, M2O source, XO source and Sb2O3 source do not contain carbon. The M2O source is a Na2O source or a K2O source, and the XO source is a CaO source; The step of preparing the degassed mixture into glass melt includes: preheating the degassed mixture at 250-500°C for 10-60 minutes, and then holding it at 1000-1400°C for 0.5-3.0 hours to obtain the glass melt; The SiO2 source includes silicon dioxide; The ZnO source includes zinc oxide; The Sb₂O₃ source includes antimony trioxide; The P2O5 source includes phosphorus pentoxide or ammonium dihydrogen phosphate; The Al2O3 source includes aluminum oxide or aluminum dihydrogen phosphate; The M2O source includes phosphates or silicates containing the element M; The XO source includes phosphates or silicates containing the element X.

2. The high-toughness phosphosilicate glass as described in claim 1, characterized in that, The venting process includes: keeping the mixture at 400-800°C for 0.5-3.0 hours.

3. The high-toughness phosphosilicate glass as described in claim 1, characterized in that, The quenching and forming process includes: placing the molten glass in a mold preheated to 300-600°C for quenching and forming.

4. The high-toughness phosphosilicate glass as described in claim 1, characterized in that, The annealing temperature is 400–600°C, and the time is 1–6 hours.

5. The application of the high-toughness phosphosilicate glass as described in any one of claims 1-4 in the fields of construction, automotive manufacturing or aerospace.

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