High-hardness, colorless and high-transmittance ferrous doped phosphoaluminosilicate energy-saving glass and preparation method thereof

Abstract

The invention discloses high-hardness, colorless and high-transparency ferrous doped phosphoaluminosilicate energy-saving glass and a preparation method thereof, and belongs to the technical field of glass manufacturing, the high-hardness, colorless and high-transparency ferrous doped phosphoaluminosilicate energy-saving glass comprises the following raw materials by weight: 10-80% of SiO2, 5-60% of P2O5, 0.1-5% of FeO, 1-30% of ZnO, 15-30% of Al2O3, 10-40% of MO and 0-30% of MX2; wherein the M element in the MO is selected from one of Mg, Ca, Sr and Ba, and X in the MX2 is one of F, Cl, Br and I. Compared with energy-saving glass of the same type, the prepared high-hardness colorless high-transmittance ferrous doped phosphoaluminosilicate energy-saving glass has the advantages that strong shielding of a near-infrared light area and colorless high transmittance of a visible area are kept, meanwhile, the hardness is higher, the raw materials are cheap and easy to obtain, the preparation process of obtaining the glass from two-time melting is simplified into one-time melting, and the production cost is reduced. The method is more suitable for traffic fields such as automobiles, steamships or aerospace.

Description

Technical Field

[0001] The invention belongs to the technical field of glass manufacturing, and in particular relates to a high-hardness, colorless and high-transmittance ferrous-doped phosphate aluminum silicate energy-saving glass and a preparation method thereof. Background Art

[0002] Glass is a type of silicate non-metallic material made of quartz sand, soda ash and limestone as the main raw materials, through high-temperature melting, homogenization and molding processing. It has excellent properties such as transparency, high temperature resistance, non-combustion, impact resistance and insulation. It is widely used in modern industry and daily life, especially in the field of transportation, such as key components such as windshields and windows. These application scenarios put forward higher requirements on glass. Not only does it need to maintain excellent light transmittance and thermal stability, but it also needs to have strong impact resistance and high hardness to resist flying stone impact and external force impact that may be encountered during driving. However, ordinary glass has a high transmittance to sunlight, especially the near-infrared (NIR, wavelength 780 to 2500nm) shielding rate is extremely low. In summer, a large amount of NIR thermal radiation in sunlight enters the car compartment, which will cause internal overheating, while in winter, the heat of objects in the car compartment is dissipated through the glass, which greatly increases the energy consumption of the vehicle air-conditioning system. Therefore, it is particularly important to develop a glass with high hardness, impact resistance and energy-saving effect for applications in transportation fields such as automobiles, ships or aerospace.

[0003] At present, energy-saving glass mainly includes low-emissivity (Low-E) glass, film glass and ferrous-doped glass. Low-E glass relies on metal coating to achieve infrared shielding effect, but its online product durability is insufficient, and the energy-saving performance of offline products is attenuated due to the easy oxidation of the functional layer, the visible light transmittance is less than 70%, and the manufacturing process is complex and the cost is high. VO2 film glass can adaptively adjust the light transmittance according to the ambient temperature, but its visible light transmittance is less than 70% and its chemical stability is poor, and its service life is limited. Generally, ferrous-doped energy-saving glass (201710474943.1) has a visible light transmittance greater than 70%, but it is blue. The same type of energy-saving glass (20240052065.4) can have a visible light transmittance greater than 80% and is colorless, but its hardness is less than 450, and it contains high-cost elements such as GeO2. Its preparation process requires two melting to obtain glass.

[0004] Based on the above problems, developing a glass with high hardness, low-cost raw materials and simplified preparation process has become the research focus and technological breakthrough direction of energy-saving glass in the transportation field. Summary of the invention

[0005] In order to solve the above technical problems, the present invention proposes a high-hardness, colorless and high-transmittance ferrous-doped phosphate aluminum silicate energy-saving glass and a preparation method thereof.

[0006] To achieve the above object, the present invention provides the following technical solutions:

[0007] One of the technical solutions of the present invention:

[0008] The present invention provides a high-hardness, colorless and high-transmittance ferrous-doped phosphoaluminosilicate energy-saving glass, which comprises the following raw materials by weight percentage: SiO2 10-80%, P2O5 5-60%, FeO 0.1-5%, ZnO 1-30%, Al2O3 15-30%, MO 10-40% and MX2 0-30%;

[0009] The M element in the MO is selected from one of the alkaline earth metals Mg, Ca, Sr and Ba, and the X in the MX2 is one of the halogens F, Cl, Br and I.

[0010] Further, the SiO2 is introduced via silicon dioxide; and / or

[0011] The P2O5 is introduced via phosphorus pentoxide, ammonium hydrogen phosphate or phosphate; and / or

[0012] The raw material of FeO is an iron compound or an iron element; and / or

[0013] The ZnO is introduced via zinc oxide; and / or

[0014] The Al2O3 is introduced via aluminum oxide or phosphate containing Al element; and / or

[0015] The MO is introduced via a carbonate or oxide containing the M element; and / or

[0016] The MX2 is introduced via the corresponding alkaline earth metal halide.

[0017] The iron compound is selected from FeCl2, FeCl3, FeO, Fe2O3 or FeSO4; the FeCl2 is anhydrous ferrous chloride or ferrous chloride hydrate; the FeCl3 is anhydrous ferric chloride or ferric chloride hydrate.

[0018] The second technical solution of the present invention:

[0019] The present invention also provides a method for preparing the above-mentioned high-hardness, colorless and highly transparent ferrous iron-doped phosphate aluminum silicate energy-saving glass, comprising the following steps: mixing the raw materials with the reducing agent, pouring them into a crucible, placing them in a lifting furnace, heating them to the melting temperature, keeping them warm, quenching and forming them, and annealing them to obtain the above-mentioned high-hardness, colorless and highly transparent ferrous iron-doped phosphate aluminum silicate energy-saving glass.

[0020] The reducing agent is a mixture of ammonium salt, carbon powder and silicon powder, and the amount of the reducing agent is 1.2-30% of the total weight of the raw materials.

[0021] The weight ratio of the ammonium salt, carbon powder and silicon powder is (1-15): (0.1-10): (0.1-5).

[0022] The ammonium salt is selected from ammonium chloride, ammonium carbonate or ammonium bicarbonate.

[0023] Before the raw materials and the reducing agent are mixed, the raw materials and the reducing agent are ground for 15 to 120 minutes, and then sieved (100 to 300 mesh sieve) after grinding.

[0024] The melting temperature is 1100-1700° C., the heating rate is 5-10° C. / min, and the insulation time is 1-5 hours.

[0025] The annealing temperature is 400-600° C. and the time is 1-12 hours; and / or

[0026] The temperature of the quenching forming is 300-600°C.

[0027] After annealing, the temperature is lowered to room temperature at a cooling rate of 1 to 10°C / min.

[0028] The present invention realizes the production of energy-saving glass by adopting a simple melting quenching method. Under the premise of not using a sulfur-carbon reducing agent and not requiring a protective atmosphere, the glass melt can quickly wrap the ferrous ions, greatly reducing the direct contact between oxygen and the ferrous ions, and inhibiting the conversion of the ferrous ions into ferric ions. The method of the present invention is applicable to a traditional float glass production line, can greatly reduce the complexity and danger of production, and is helpful to quickly, massively and conveniently produce ferrous heat-absorbing energy-saving glass. At the same time, the colorless and highly transparent ferrous-doped phosphoaluminosilicate energy-saving glass produced can be transparent and colorless to a large extent, and can better respond to ambient light than the original ferrous-doped soda-lime-silicon energy-saving glass, without affecting the transmission of visible light.

[0029] The third technical solution of the present invention:

[0030] The present invention also provides application of the high-hardness, colorless and high-transmittance ferrous-doped phosphate aluminum silicate energy-saving glass in the field of transportation.

[0031] Compared with the same type of energy-saving glass (such as the energy-saving glass in 20240052065.4), the high-hardness, colorless and highly transparent ferrous-doped phosphate-aluminum silicate energy-saving glass prepared by the present invention has greater hardness, cheap and readily available raw materials while maintaining strong shielding in the near-infrared light region and colorless and highly transparent in the visible region. The preparation process is simplified from obtaining glass by melting twice to obtaining glass by melting once. The high-hardness, colorless and highly transparent ferrous-doped phosphate-aluminum silicate energy-saving glass of the present invention is more suitable for use in transportation fields such as automobiles, ships or aerospace.

[0032] Compared with the prior art, the present invention has the following advantages and technical effects:

[0033] (1) Compared with the same type of energy-saving glass (such as the energy-saving glass in 20240052065.4, which has a hardness of less than 450 Hv and contains high-cost elements such as GeO2), the high-hardness, colorless and high-transmittance ferrous phosphate-doped aluminosilicate energy-saving glass prepared by the present invention has a hardness greater than 450 Hv while maintaining strong shielding in the near-infrared light region and colorless and high transmittance in the visible region. The raw materials do not contain high-cost components such as GeO2 and are cheap and easily available.

[0034] (2) The present invention directly mixes raw materials with low-valent iron elements. Compared with the same type of energy-saving glass (such as the energy-saving glass in 20240052065.4), the preparation process is simplified from obtaining glass by two meltings to obtaining glass by one melting, shortening the production cycle. The present invention adopts a melt quenching process, which can be adapted to ordinary float glass production lines. BRIEF DESCRIPTION OF THE DRAWINGS

[0035] The accompanying drawings constituting a part of the present invention are used to provide a further understanding of the present invention. The exemplary embodiments of the present invention and their descriptions are used to explain the present invention and do not constitute an improper limitation of the present invention. In the accompanying drawings:

[0036] Figure 1 10×9×0.6 cm thick ferrous-doped phosphoaluminosilicate energy-saving glass with high hardness, colorless and high transparency prepared in Example 2 of the present invention 3 Large physical map;

[0037] Figure 2 The transmittance spectral performance effect diagram of the colorless and high-transmittance ferrous doped phosphate aluminosilicate energy-saving glass prepared in Examples 1 to 7 of the present invention and Comparative Examples 1 to 2, wherein 1 is Example 1, 2 is Example 2, 3 is Example 3, 4 is Example 4, 5 is Example 5, 6 is Example 6, 7 is Example 7, 8 is Comparative Example 1, and 9 is Comparative Example 2. DETAILED DESCRIPTION

[0038] Various exemplary embodiments of the present invention will now be described in detail. This detailed description should not be considered as limiting the present invention, but should be understood as a more detailed description of certain aspects, features, and embodiments of the present invention.

[0039] It should be understood that the terms described in the present invention are only for describing special embodiments and are not intended to limit the present invention. In addition, for the numerical range in the present invention, it should be understood that each intermediate value between the upper and lower limits of the scope is also specifically disclosed. Each smaller range between the intermediate value in any stated value or stated range and any other stated value or intermediate value in the described range is also included in the present invention. The upper and lower limits of these smaller ranges can be independently included or excluded in the scope.

[0040] Unless otherwise indicated, all technical and scientific terms used herein have the same meanings as those generally understood by those skilled in the art. Although the present invention describes only preferred methods and materials, any methods and materials similar or equivalent to those described herein may also be used in the implementation or testing of the present invention. All documents mentioned in this specification are incorporated by reference to disclose and describe the methods and / or materials associated with the documents. In the event of a conflict with any incorporated document, the content of this specification shall prevail.

[0041] It will be apparent to those skilled in the art that various modifications and variations may be made to the specific embodiments of the present invention description without departing from the scope or spirit of the present invention. Other embodiments derived from the present invention description will be apparent to those skilled in the art. The present invention description and examples are exemplary only.

[0042] The words “include,” “including,” “have,” “contain,” etc. used in this document are open-ended terms, meaning including but not limited to.

[0043] Unless otherwise specified, the room temperature in the present invention is 25±2°C.

[0044] In some embodiments of the present invention, there is provided a high-hardness, colorless, and highly transparent ferrous-doped phosphoaluminosilicate energy-saving glass, which comprises the following raw materials by weight percentage: SiO2 10-80%, P2O5 5-60%, FeO 0.1-5%, ZnO1-30%, Al2O3 15-30%, MO 10-40%, and MX2 0-30%;

[0045] Wherein, the M element in MO is selected from one of the alkaline earth metals Mg, Ca, Sr and Ba, and X in MX2 is one of the halogens F, Cl, Br and I;

[0046] wherein SiO2 is introduced via silicon dioxide; and / or

[0047] P2O5 is introduced via phosphorus pentoxide, ammonium hydrogen phosphate or phosphates; and / or

[0048] The raw material of FeO is an iron compound or iron alone; and / or

[0049] ZnO is introduced via zinc oxide; and / or

[0050] Al2O3 is introduced through aluminum oxide or phosphate containing Al element; and / or

[0051] MO is introduced via a carbonate or oxide containing the M element; and / or

[0052] MX2 is introduced via the corresponding alkaline earth metal halide.

[0053] In some preferred embodiments of the present invention, the iron compound is selected from FeCl2, FeCl3, FeO, Fe2O3 or FeSO4; FeCl2 is anhydrous ferrous chloride or ferrous chloride hydrate; FeCl3 is anhydrous ferric chloride or ferric chloride hydrate.

[0054] The existing technology for preparing colorless, highly transparent ferrous-doped phosphoaluminosilicate energy-saving glass (such as patent 20240052065.4) has a high usage of alkali metals and is combined with more boron oxide and phosphorus oxide. When the usage of alkali metals is at a high level and more boron oxide and phosphorus pentoxide are compounded, the hardness of the glass will decrease. This is mainly attributed to the following factors: First, alkali metals have a large ionic radius and a low charge number. When such metals are introduced in large quantities, alkali metal ions will enter the network gaps of silicon-oxygen tetrahedrons, causing the original covalent bonds to be destroyed, thereby making the glass structure loose; second, boron oxide can strengthen the glass network at low content levels. However, once its content increases, a large number of loose boron-oxygen triangles will destroy the network structure. At the same time, the boron-oxygen bonds will transform into less stable structures; third, the phosphorus-oxygen tetrahedral bond energy formed by phosphorus pentoxide is relatively low, and the connection flexibility is relatively large. When it is integrated into the glass system in large quantities, it will weaken the silicon-oxygen network structure. In addition, its poor thermal stability can easily cause various defects and microcracks in the glass. The combination of the above factors ultimately leads to a decrease in the hardness of the glass.

[0055] The present invention uses alkaline earth metals, reduces the phosphorus content and does not use boron oxide. Alkaline earth metals can achieve the effect of improving the hardness of glass. The internal principle is as follows: on the one hand, alkaline earth metal ions have a relatively high charge number. With this characteristic, alkaline earth metal ions can build a stronger electrostatic force with oxygen ions in the silicon-oxygen tetrahedron network, thereby greatly stabilizing the overall structure of the glass and improving the hardness; on the other hand, in terms of strengthening the network structure, given that the silicon-oxygen tetrahedron network of glass is usually partially incomplete or even broken, alkaline earth metal ions can just participate in the construction process of the glass network structure, and they can form chemical bonds with oxygen atoms in silicon-oxygen tetrahedrons, thereby significantly improving the degree of cross-linking of the network. Taking magnesium ions as an example, after forming chemical bonds with oxygen in silicon-oxygen tetrahedrons, different silicon-oxygen tetrahedrons are closely connected, which makes the overall structure of the glass present a more compact and orderly state, greatly enhancing the ability of the glass to resist external deformation, and finally achieving the effect of improving the hardness of the glass.

[0056] In some embodiments of the present invention, a method for preparing the above-mentioned high-hardness, colorless and highly transparent ferrous iron-doped phosphate aluminum silicate energy-saving glass is provided, comprising the following steps: mixing the raw materials with the reducing agent, pouring them into a crucible, placing them in a lifting furnace, heating them to the melting temperature, keeping them warm, quenching and forming them, and annealing them to obtain high-hardness, colorless and highly transparent ferrous iron-doped phosphate aluminum silicate energy-saving glass.

[0057] In some embodiments of the present invention, the reducing agent is a mixture of ammonium salt, carbon powder and silicon powder, and the amount of the reducing agent is 1.2-30% of the total weight of the raw materials.

[0058] In some embodiments of the present invention, the weight ratio of ammonium salt, carbon powder and silicon powder is (1-15):(0.1-10):(0.1-5).

[0059] In some preferred embodiments of the present invention, the ammonium salt is selected from ammonium chloride, ammonium carbonate or ammonium bicarbonate.

[0060] In some embodiments of the present invention, before the raw material and the reducing agent are mixed, the raw material and the reducing agent are ground. The grinding time is 15 to 120 minutes, and the grinding is followed by sieving (100 to 300 mesh sieve). The ground raw material and reducing agent particles are finer, the surface area is increased, and the contact area with the reaction medium (such as the gas in the lifting furnace) is also increased, which is conducive to the contact and collision between the reactants, accelerates the reaction rate, and improves the reaction efficiency. Grinding can also make the particles of the raw material and the reducing agent more evenly mixed together, reducing the gaps and agglomeration between the particles. Uniform mixing helps the reactants to contact and react more fully at high temperatures, avoiding incomplete local reactions or over-reactions. Small particles are easier to melt. At high temperatures, the contact area between particles increases, making it easier for heat to be transferred to the inside of the particles, reducing the energy required for melting, thereby reducing the overall melting temperature. This helps to save energy and shorten the melting time. Grinding can also reduce the agglomeration of impurity particles and large particles in the raw materials, which are prone to form defects such as bubbles and stones during the glass melting process. Small, uniform particles help reduce these defects and improve the clarity and strength of the glass.

[0061] In some embodiments of the present invention, the melting temperature is 1100-1700°C, the heating rate is 5-10°C / min, and the insulation time is 1-5h. The higher the melting temperature, the faster the melting rate of the glass, the more intense the silicate formation reaction, and the faster the particles melt. Too high a melting temperature will aggravate the erosion of refractory materials, lead to the introduction of impurities into the glass, and affect the transparency and chemical stability of the glass; while too low a melting temperature may cause incomplete melting of the glass and produce defects such as stones. A faster heating rate can make the glass melt quickly reach a molten state, which is conducive to the homogenization of the melt and the discharge of bubbles, and improves the uniformity and transparency of the glass. However, heating too fast may also cause local overheating of the melt, resulting in local stress and uneven melting. The reasonable heating rate of the present invention can effectively utilize energy, reduce energy waste, and improve production efficiency. Appropriate insulation time is conducive to the homogenization and clarification process of the glass melt, so that defects such as streaks and stones in the glass are eliminated to the allowable limit, forming a uniform and integrated glass. Too long a holding time may cause crystallization in the glass melt, forming a crystal structure, and affecting the optical and mechanical properties of the glass. The melting temperature, heating rate, and holding time of the present invention are all suitable, and can ensure that high-hardness, colorless, and highly transparent glass is obtained.

[0062] In some embodiments of the present invention, the annealing temperature is 400-600° C. and the time is 1-12 hours; and / or

[0063] The temperature of quenching forming is 300-600℃.

[0064] In some embodiments of the present invention, after annealing, the temperature is lowered to room temperature at a cooling rate of 1 to 10°C / min. A fast cooling rate is likely to generate thermal stress inside the glass, causing the glass to crack during cooling or use; while a slow cooling rate helps to release stress inside the glass, reduce stress concentration, and improve the mechanical strength and thermal shock resistance of the glass. Different cooling rates will affect the structure and phase change behavior of the glass. The appropriate cooling rate of the present invention can ensure the mechanical strength and thermal shock resistance of the glass.

[0065] The present invention realizes the production of energy-saving glass by adopting a simple melting quenching method. Under the premise of not using a sulfur-carbon reducing agent and not requiring a protective atmosphere, the glass melt can quickly wrap the ferrous ions, greatly reducing the direct contact between oxygen and the ferrous ions, and inhibiting the conversion of the ferrous ions into ferric ions. The method of the present invention is applicable to a traditional float glass production line, can greatly reduce the complexity and danger of production, and is helpful to quickly, massively and conveniently produce ferrous heat-absorbing energy-saving glass. At the same time, the colorless and highly transparent ferrous-doped phosphoaluminosilicate energy-saving glass produced can be transparent and colorless to a large extent. Compared with the original ferrous-doped soda-lime-silicon energy-saving glass, it can better reflect the ambient light and does not affect the transmission of visible light.

[0066] The high-hardness, colorless and high-transmittance ferrous-doped phosphate aluminum silicate energy-saving glass provided by the embodiment of the present invention can be used in the transportation field.

[0067] Compared with the same type of energy-saving glass (such as the energy-saving glass in 20240052065.4), the high-hardness, colorless and highly transparent ferrous-doped phosphate-aluminum silicate energy-saving glass prepared by the present invention has greater hardness, cheap and readily available raw materials while maintaining strong shielding in the near-infrared light region and colorless and highly transparent in the visible region. The preparation process is simplified from obtaining glass by melting twice to obtaining glass by melting once. The high-hardness, colorless and highly transparent ferrous-doped phosphate-aluminum silicate energy-saving glass of the present invention is more suitable for use in transportation fields such as automobiles, ships or aerospace.

[0068] All raw materials used in the examples of the present invention are commercially available.

[0069] It should be pointed out that the matters not described in detail in the present invention are all conventional operating means in the art and are not the focus of the present invention. For example, specific methods such as grinding and screening are all completed by conventional methods.

[0070] The technical solution of the present invention is further illustrated by the following embodiments.

[0071] Example 1

[0072] The high-hardness, colorless and highly transparent ferrous-doped phosphoaluminosilicate energy-saving glass provided in this embodiment has the following raw materials, calculated by weight percentage: 26.89% of aluminum dihydrogen phosphate (Al(H2PO4)3), 1.01% of ferrous chloride (FeCl2·4H2O), 28.96% of silicon dioxide (SiO2), 10.32% of zinc oxide (ZnO), 21.56% of aluminum oxide (Al2O3), and 11.26% of magnesium oxide (MgO).

[0074] In this embodiment, the reducing agent is a mixture of NH4Cl, carbon powder and silicon powder, wherein the silicon powder accounts for 1.50% of the total mass of the raw materials, the carbon powder accounts for 3.50% of the total mass of the raw materials, and the NH4Cl accounts for 5.50% of the total mass of the raw materials.

[0075] The preparation method of the above-mentioned high-hardness, colorless and high-transmittance ferrous-doped phosphoaluminosilicate energy-saving glass is as follows:

[0076] (1) Mixture preparation: grind aluminum dihydrogen phosphate, silicon dioxide, zinc oxide, magnesium oxide, aluminum oxide, ferrous chloride and a reducing agent for 20 minutes respectively, pass through a 300-mesh sieve, and then fully mix to obtain a mixture;

[0077] (2) Preparation of molten glass: Pour the mixture obtained in step (1) into a crucible, place the crucible in a lifting furnace, raise the temperature from room temperature to 1550° C. and keep it for 1.5 h to melt into molten glass;

[0078] (3) Quenching and forming of glass liquid: The glass liquid obtained in step (2) is placed in a preheated mold (temperature is 560°C) for quenching and forming, and then the quenched and formed sample is placed in an annealing furnace at 560°C for annealing for 4 hours, and finally cooled to room temperature at a rate of 5°C / min to obtain a high-hardness, colorless and high-transmittance ferrous-doped phosphoaluminosilicate energy-saving glass.

[0079] The theoretical component contents of the high-hardness, colorless and high-transmittance ferrous-doped phosphoaluminosilicate energy-saving glass prepared from 60g of raw materials in this embodiment are shown in Table 1.

[0080] Table 1 Theoretical component contents of high hardness, colorless and highly transparent ferrous-doped phosphoaluminosilicate energy-saving glass prepared from 60g raw materials

[0081] Components Weight(g) Weight percentage (%) <![CDATA[SiO2]]> 17.38 30.55 <![CDATA[P2O5]]> 10.81 19.00 FeO 0.22 0.39 ZnO 6.20 10.90 <![CDATA[Al2O3]]> 15.52 27.28 MO(MgO) 6.75 11.88 total 56.88 100

[0082] Example 2

[0083] The high-hardness, colorless and highly transparent ferrous-doped phosphoaluminosilicate energy-saving glass provided in this embodiment has the following raw materials, calculated by weight percentage: 25.76% of aluminum dihydrogen phosphate (Al(H2PO4)3), 0.98% of ferrous chloride (FeCl2·4H2O), 27.74% of silicon dioxide (SiO2), 20.65% of aluminum oxide (Al2O3), 14.98% of calcium oxide (CaO), and 9.89% of zinc oxide (ZnO).

[0084] In this embodiment, the reducing agent is a mixture of NH4Cl, carbon powder and silicon powder, wherein the silicon powder accounts for 1.30% of the total mass of the raw materials, the carbon powder accounts for 2.50% of the total mass of the raw materials, and the NH4Cl accounts for 3.50% of the total mass of the raw materials.

[0085] The preparation method of the above-mentioned high-hardness, colorless and high-transmittance ferrous-doped phosphoaluminosilicate energy-saving glass is as follows:

[0086] (1) Mixture ingredients: grind silicon dioxide, zinc oxide, aluminum dihydrogen phosphate, aluminum oxide, calcium oxide and ferrous chloride with a reducing agent for 20 minutes, pass through a 300-mesh sieve, and then fully mix to obtain a mixture;

[0087] (2) Preparation of glass liquid: pour the mixture obtained in step (1) into a crucible, place the crucible in a lifting furnace, raise the temperature from room temperature to 1550° C. and keep it for 2 h to melt into glass liquid;

[0088] (3) Quenching and forming the glass liquid: The glass liquid obtained in step (2) is placed in a preheated mold (temperature is 560°C) for quenching and forming, and then the quenched and formed sample is placed in an annealing furnace at 560°C for annealing for 3 hours, and finally cooled to room temperature at a rate of 5°C / min to obtain a high-hardness, colorless and high-transmittance ferrous-doped phosphoaluminosilicate energy-saving glass.

[0089] The theoretical component contents of the high-hardness, colorless and high-transmittance ferrous-doped phosphoaluminosilicate energy-saving glass prepared from 60 g of raw materials in this embodiment are shown in Table 2.

[0090] Table 2 Theoretical component contents of high hardness, colorless and highly transparent ferrous-doped phosphoaluminosilicate energy-saving glass prepared from 60g raw materials

[0091] Components Weight(g) Weight percentage (%) <![CDATA[SiO2]]> 16.64 29.23 <![CDATA[P2O5]]> 10.28 18.08 FeO 0.20 0.35 ZnO 5.93 10.42 <![CDATA[Al2O3]]> 14.87 26.13 MO(CaO) 8.99 15.79 total 56.91 100

[0092] Example 3

[0093] The high-hardness, colorless and highly transparent ferrous-doped phosphoaluminosilicate energy-saving glass provided in this embodiment has the following raw materials, calculated by weight percentage: 22.86% of sodium dihydrogen phosphate (Al(H2PO4)3), 0.85% of ferrous chloride (FeCl2·4H2O), 24.61% of silicon dioxide (SiO2), 18.32% of aluminum oxide (Al2O3), 24.56% of strontium oxide (SrO), 8.77% of zinc oxide (ZnO), and 0.03% of iron powder.

[0094] In this embodiment, the reducing agent is a mixture of NH4Cl, carbon powder and silicon powder, wherein the silicon powder accounts for 1.50% of the total mass of the raw materials, the carbon powder accounts for 3.50% of the total mass of the raw materials, and the NH4Cl accounts for 5.50% of the total mass of the raw materials.

[0095] The preparation method of the above-mentioned high-hardness, colorless and high-transmittance ferrous-doped phosphoaluminosilicate energy-saving glass is as follows:

[0096] (1) Mixture ingredients: grind aluminum dihydrogen phosphate, silicon dioxide, aluminum oxide, zinc oxide, strontium oxide, ferrous chloride, iron powder and reducing agent for 20 minutes respectively, pass through a 300-mesh sieve, and then fully mix to obtain a mixture.

[0097] (2) Preparation of molten glass: The mixture obtained in step (1) was poured into a crucible, placed in a lifting furnace, and heated from room temperature to 1550° C. and kept at this temperature for 1.5 h to melt into molten glass.

[0098] (3) Quenching and forming of glass liquid: The glass liquid obtained in step (2) is placed in a preheated mold (temperature is 560°C) for quenching and forming, and then the quenched and formed sample is placed in an annealing furnace at 560°C for annealing for 4 hours, and finally cooled to room temperature at a rate of 7°C / min to obtain a high-hardness, colorless and high-transmittance ferrous-doped phosphoaluminosilicate energy-saving glass.

[0099] The theoretical component contents of the high-hardness, colorless and high-transmittance ferrous-doped phosphoaluminosilicate energy-saving glass prepared from 60 g of raw materials in this embodiment are shown in Table 3.

[0100] Table 3 Theoretical component contents of high hardness, colorless and highly transparent ferrous-doped phosphoaluminosilicate energy-saving glass prepared from 60g raw materials

[0101] Components Weight(g) Weight percentage (%) <![CDATA[SiO2]]> 14.76 25.77 <![CDATA[P2O5]]> 9.12 15.92 FeO 0.20 0.35 ZnO 5.26 9.18 <![CDATA[Al2O3]]> 13.19 23.03 MO(SrO) 14.74 25.75 total 57.27 100

[0102] Example 4

[0103] The high-hardness, colorless and highly transparent ferrous-doped phosphoaluminosilicate energy-saving glass provided in this embodiment has the following raw materials, calculated by weight percentage: 20.34% of aluminum dihydrogen phosphate (Al(H2PO4)3), 0.84% ​​of ferrous chloride (FeCl2·4H2O), 22.03% of silicon dioxide (SiO2), 7.84% of zinc oxide (ZnO), 16.38% of aluminum oxide (Al2O3), and 32.57% of barium oxide (BaO).

[0104] In this embodiment, the reducing agent is a mixture of NH4Cl, carbon powder and silicon powder, wherein the silicon powder accounts for 1.5% of the total mass of the raw materials, the carbon powder accounts for 3.50% of the total mass of the raw materials, and the NH4Cl accounts for 5.50% of the total mass of the raw materials.

[0105] The preparation method of the high-hardness, colorless and high-transmittance ferrous-doped phosphoaluminosilicate energy-saving glass in this embodiment is the same as that in Example 1.

[0106] The theoretical component contents of the high-hardness, colorless and high-transmittance ferrous-doped phosphoaluminosilicate energy-saving glass prepared from 60 g of raw materials in this embodiment are shown in Table 4.

[0107] Table 4 Theoretical component contents of high hardness, colorless and highly transparent ferrous-doped phosphoaluminosilicate energy-saving glass prepared from 60 g raw materials

[0108] Components Weight(g) Weight percentage (%) <![CDATA[SiO2]]> 13.20 22.92 <![CDATA[P2O5]]> 8.15 14.15 FeO 0.19 0.33 ZnO 4.70 8.17 <![CDATA[Al2O3]]> 11.79 20.48 MO(BaO) 19.54 33.95 total 57.57 100

[0109] Example 5

[0110] The high-hardness, colorless and high-transmittance ferrous-doped phosphoaluminosilicate energy-saving glass provided in this embodiment has the following raw materials, calculated by weight percentage: 22.41% of aluminum dihydrogen phosphate (Al(H2PO4)3), 0.84% ​​of ferrous chloride (FeCl2·4H2O), 24.19% of silicon dioxide (SiO2), 18.08% of aluminum oxide (Al2O3), 25.86% of calcium fluoride (CaF2), and 8.62% of zinc oxide (ZnO).

[0111] In this embodiment, the reducing agent is a mixture of NH4Cl, carbon powder and silicon powder, wherein the silicon powder accounts for 0.5% of the total mass of the raw materials, the carbon powder accounts for 2.80% of the total mass of the raw materials, and the NH4Cl accounts for 7.50% of the total mass of the raw materials.

[0112] The preparation method of the above-mentioned high-hardness, colorless and high-transmittance ferrous-doped phosphoaluminosilicate energy-saving glass is as follows:

[0113] (1) Mixture preparation: grind aluminum dihydrogen phosphate, silicon dioxide, aluminum oxide, zinc oxide, calcium fluoride, ferrous chloride and a reducing agent for 20 minutes respectively, pass through a 300-mesh sieve, and then fully mix, grind for another 30 minutes, pass through a 200-mesh sieve, and then fully mix to obtain a mixture;

[0114] (2) Preparation of molten glass: Pour the mixture obtained in step (1) into a crucible, place the crucible in a lifting furnace, raise the temperature from room temperature to 1550° C. and keep it for 1.5 h to melt into molten glass;

[0115] (3) Quenching and forming of glass liquid: The glass liquid obtained in step (2) is placed in a preheated mold (temperature is 560°C) for quenching and forming, and then the quenched and formed sample is placed in an annealing furnace at 560°C for annealing for 4 hours, and finally cooled to room temperature at a rate of 5°C / min to obtain a high-hardness, colorless and high-transmittance ferrous-doped phosphoaluminosilicate energy-saving glass.

[0116] The theoretical component contents of the high-hardness, colorless and high-transmittance ferrous-doped phosphoaluminosilicate energy-saving glass prepared from 60 g of raw materials in this embodiment are shown in Table 5.

[0117] Table 5 Theoretical component contents of high hardness, colorless and highly transparent ferrous-doped phosphoaluminosilicate energy-saving glass prepared from 60 g raw materials

[0118] Components Weight(g) Weight percentage (%) <![CDATA[SiO2]]> 15.71 27.47 <![CDATA[P2O5]]> 9.78 17.12 FeO 0.20 0.35 ZnO 5.60 9.79 <![CDATA[Al2O3]]> 14.04 24.58 <![CDATA[MX2(CaF2)]]> 11.82 20.69 total 57.15 100

[0119] Example 6

[0120] The high-hardness, colorless and high-transmittance ferrous-doped phosphoaluminosilicate energy-saving glass provided in this embodiment has the following raw materials, calculated by weight percentage: 24.15% of aluminum dihydrogen phosphate (Al(H2PO4)3), 0.90% of ferrous chloride (FeCl2·4H2O), 26.00% of silicon dioxide (SiO2), 19.36% of aluminum oxide (Al2O3), 12.64% of calcium fluoride (CaF2), 9.27% ​​of zinc oxide (ZnO), and 7.68% of calcium oxide (CaO).

[0121] In this embodiment, the reducing agent is a mixture of NH4Cl, carbon powder and silicon powder, wherein the silicon powder accounts for 0.5% of the total mass of the raw materials, the carbon powder accounts for 2.80% of the total mass of the raw materials, and the NH4Cl accounts for 7.50% of the total mass of the raw materials.

[0122] The preparation method of the above-mentioned high-hardness, colorless and high-transmittance ferrous-doped phosphoaluminosilicate energy-saving glass is as follows:

[0123] (1) Mixture preparation: grind aluminum dihydrogen phosphate, silicon dioxide, aluminum oxide, zinc oxide, calcium fluoride, ferrous chloride and a reducing agent for 20 minutes respectively, pass through a 300-mesh sieve, and then fully mix, grind for another 30 minutes, pass through a 200-mesh sieve, and then fully mix to obtain a mixture;

[0124] (2) Preparation of molten glass: Pour the mixture obtained in step (1) into a crucible, place the crucible in a lifting furnace, raise the temperature from room temperature to 1550° C. and keep it for 1.5 h to melt into molten glass;

[0125] (3) Quenching and forming of glass liquid: The glass liquid obtained in step (2) is placed in a preheated mold (temperature is 560°C) for quenching and forming, and then the quenched and formed sample is placed in an annealing furnace at 560°C for annealing for 4 hours, and finally cooled to room temperature at a rate of 5°C / min to obtain a high-hardness, colorless and high-transmittance ferrous-doped phosphoaluminosilicate energy-saving glass.

[0126] The theoretical component contents of the high-hardness, colorless and high-transmittance ferrous-doped phosphoaluminosilicate energy-saving glass prepared from 60 g of raw materials in this embodiment are shown in Table 6.

[0127] Table 6 Theoretical component contents of high hardness, colorless and highly transparent ferrous-doped phosphoaluminosilicate energy-saving glass prepared from 60g raw materials

[0128] Components Weight(g) Weight percentage (%) <![CDATA[SiO2]]> 15.60 27.31 <![CDATA[P2O5]]> 9.64 16.87 FeO 0.20 0.35 ZnO 5.56 9.73 <![CDATA[Al2O3]]> 13.94 24.40 <![CDATA[MX2(CaF2)]]> 7.58 13.27 MO(CaO) 4.59 8.07 total 57.11 100

[0129] Example 7

[0130] The high-hardness, colorless and highly transparent ferrous-doped phosphoaluminosilicate energy-saving glass provided in this embodiment has the following raw materials, calculated by weight percentage: 22.49% of aluminum dihydrogen phosphate (Al(H2PO4)3), 0.84% ​​of ferrous chloride (FeCl2·4H2O), 24.19% of silicon dioxide (SiO2), 18.00% of aluminum oxide (Al2O3), 8.62% of zinc oxide (ZnO), and 25.86% of calcium chloride (CaCl2).

[0132] In this embodiment, the reducing agent is a mixture of NH4Cl, carbon powder and silicon powder, wherein the silicon powder accounts for 0.40% of the total mass of the raw materials, the carbon powder accounts for 4.00% of the total mass of the raw materials, and the NH4Cl accounts for 7.24% of the total mass of the raw materials.

[0133] The preparation method of the above-mentioned high-hardness, colorless and high-transmittance ferrous-doped phosphoaluminosilicate energy-saving glass is as follows:

[0134] (1) Mixture ingredients: grind aluminum dihydrogen phosphate, silicon dioxide, aluminum oxide, zinc oxide, calcium chloride, ferrous chloride and a reducing agent for 20 minutes respectively, pass through a 200-mesh sieve, and then fully mix to obtain a mixture;

[0135] (2) Preparation of glass liquid: pour the mixture obtained in step (1) into a crucible, place the crucible in a lifting furnace, raise the temperature from room temperature to 1500° C. and keep it for 3 hours to melt into glass liquid;

[0136] (3) Quenching and forming of glass liquid: The glass liquid obtained in step (2) is placed in a preheated mold (temperature is 560°C) for quenching and forming, and then the quenched and formed sample is placed in an annealing furnace at 560°C for annealing for 4 hours, and finally cooled to room temperature at a rate of 8°C / min to obtain high-hardness, colorless and high-transmittance ferrous-doped phosphoaluminosilicate energy-saving glass.

[0137] The theoretical component contents of the high-hardness, colorless and high-transmittance ferrous-doped phosphoaluminosilicate energy-saving glass prepared from 60 g of raw materials in this embodiment are shown in Table 7.

[0138] Table 7 Theoretical component contents of high hardness, colorless and highly transparent ferrous-doped phosphoaluminosilicate energy-saving glass prepared from 60g raw materials

[0139] Components Weight(g) Weight percentage (%) <![CDATA[SiO2]]> 14.51 25.29 <![CDATA[P2O5]]> 9.03 15.74 <![CDATA[MX2(CaCl2)]]> 15.52 27.05 FeO 0.18 0.31 <![CDATA[Al2O3]]> 12.96 22.59 ZnO 5.17 9.02 total 57.37 100

[0140] Comparative Example 1

[0141] In this comparative example, a ferrous-doped colorless, highly transparent silicate energy-saving glass with near-infrared full-band shielding is prepared according to the method recorded in 20240052065.4, wherein the raw materials of the ferrous-doped colorless, highly transparent silicate energy-saving glass with near-infrared full-band shielding are as follows by weight percentage: 25.60% of sodium dihydrogen phosphate (NaH2PO4), 0.88% of ferrous chloride (FeCl2·4H2O), 3.75% of ammonium chloride (NH4Cl), 1.88% of carbon powder, 0.56% of silicon powder, 24.60% of silicon dioxide (SiO2), 7.01% of boron oxide (B2O3), 5.45% of germanium oxide (GeO2), 8.14% of aluminum oxide (Al2O3), 18.65% of sodium carbonate (Na2CO3) and 3.48% of calcium carbonate (CaCO3).

[0142] The preparation method of the above-mentioned near-infrared full-band shielding ferrous-doped colorless high-transparent silicate energy-saving glass is as follows:

[0143] (1) Mixture 1 ingredients: Sodium dihydrogen phosphate, silicon dioxide, boron oxide, germanium oxide, aluminum oxide, sodium carbonate and calcium carbonate were crushed and passed through a 200-mesh sieve respectively, and then fully mixed for 10 minutes to obtain mixture 1 (main raw material);

[0144] (2) Degassing: Pour the mixture 1 obtained in step (1) into a crucible, place the crucible in a muffle furnace, heat it to 600° C. at a heating rate of 10° C. / min in an air atmosphere, keep it at that temperature for 1 h, and then cool it to room temperature (25±2° C.);

[0145] (3) Preparation of glass liquid 1: The crucible containing the degassed mixture 1 obtained in step (2) is preheated at 500° C. for 10 min in an air atmosphere, and then placed in a lifting furnace and kept at 1250° C. for 1 h to melt the mixture 1 into glass liquid 1;

[0146] (4) quenching and forming treatment of the glass liquid 1: placing the glass liquid 1 obtained in step (3) in a cold container for quenching and forming to obtain a cracked glass block and a crucible for storing the residual glass liquid 1 (the glass block is cracked due to internal stress);

[0147] (5) Preparation of glass powder: Grind the glass block obtained in step (4) and pass it through a 300-mesh sieve to obtain glass powder;

[0148] (6) Mixture 2 ingredients: ferrous chloride, ammonium chloride, carbon powder and silicon powder were crushed and passed through a 300-mesh sieve respectively, and then fully mixed for 20 minutes to obtain mixture 2;

[0149] (7) Preparation of glass liquid 2: Add glass powder and mixed material 2 to the crucible storing the residual glass liquid 1 in step (4), preheat at 500° C. for 10 min in an air atmosphere, then place in a lifting furnace and keep at 1250° C. for 2 h to melt into glass liquid 2;

[0150] (8) Quenching and forming the glass liquid 2: The glass liquid 2 obtained in step (7) is placed in a preheated mold (temperature is 430°C) for quenching and forming, and then the quenched and formed sample is placed in an annealing furnace at 430°C for annealing for 12 hours, and finally cooled to room temperature at a cooling rate of 1°C / min to obtain a ferrous-doped colorless, highly transparent silicate energy-saving glass with near-infrared full-band shielding (a high-transmittance, high near-infrared shielding, colorless, heat-insulating and energy-saving glass product).

[0151] The theoretical component contents of the near-infrared full-band shielding ferrous-doped colorless highly transparent silicate energy-saving glass prepared from 100 g of the raw materials in this comparative example are shown in Table 8.

[0152] Table 8 Theoretical component contents of ferrous-doped colorless highly transparent silicate energy-saving glass with near-infrared full-band shielding prepared from 100g of raw materials

[0153] Components Weight(g) Weight percentage (%) <![CDATA[SiO2]]> 25.80 31.72 <![CDATA[P2O5]]> 15.15 18.63 <![CDATA[A2O(Na2O)]]> 17.52 21.54 FeO 0.32 0.38 <![CDATA[B2O3]]> 7.01 8.62 <![CDATA[GeO2]]> 5.45 6.70 <![CDATA[Al2O3]]> 8.14 10.01 CaO 1.95 2.40 total 81.34 100

[0154] Comparative Example 2

[0155] This comparative example provides a near-infrared full-band shielding ferrous iron-doped colorless high-transparent silicate energy-saving glass according to the method recorded in 20240052065.4, wherein the near-infrared full-band shielding ferrous iron-doped colorless high-transparent silicate energy-saving glass is composed of the following raw materials in weight percentage: 15.80% sodium dihydrogen phosphate (NaH2PO4), 0.88% ferrous chloride (FeCl2·4H2O), 3.75% ammonium chloride (NH4Cl), 1.88% carbon powder, 0.56% silicon powder, 30.60% silicon dioxide (SiO2), 7.11% boron oxide (B2O3), 5.35% germanium oxide (GeO2), 8.11% aluminum oxide (Al2O3), 22.45% sodium carbonate (Na2CO3) and 3.51% calcium carbonate (CaCO3).

[0156] The preparation method of the above-mentioned near-infrared full-band shielding ferrous-doped colorless high-transparent silicate energy-saving glass is as follows:

[0157] (1) Mixture 1 ingredients: Sodium dihydrogen phosphate, silicon dioxide, boron oxide, germanium oxide, aluminum oxide, sodium carbonate and calcium carbonate were crushed and passed through a 200-mesh sieve respectively, and then fully mixed for 10 minutes to obtain mixture 1 (main raw material);

[0158] (2) Degassing: Pour the mixture 1 obtained in step (1) into a crucible, place the crucible in a muffle furnace, heat it to 600° C. at a heating rate of 10° C. / min in an air atmosphere, keep it at that temperature for 1 h, and then cool it to room temperature (25±2° C.);

[0159] (3) Preparation of glass liquid 1: The crucible containing the degassed mixture 1 obtained in step (2) is preheated at 500° C. for 10 min in an air atmosphere, and then placed in a lifting furnace and kept at 1250° C. for 1 h to melt the mixture 1 into glass liquid 1;

[0160] (4) quenching and forming treatment of the glass liquid 1: placing the glass liquid 1 obtained in step (3) in a cold container for quenching and forming to obtain a cracked glass block and a crucible for storing the residual glass liquid 1 (the glass block is cracked due to internal stress);

[0161] (5) Preparation of glass powder: Grind the glass block obtained in step (4) and pass it through a 300-mesh sieve to obtain glass powder;

[0162] (6) Mixture 2 ingredients: ferrous chloride, ammonium chloride, carbon powder and silicon powder were crushed and passed through a 300-mesh sieve respectively, and then fully mixed for 20 minutes to obtain mixture 2;

[0163] (7) Preparation of glass liquid 2: Add glass powder and mixed material 2 to the crucible storing the residual glass liquid 1 in step (4), preheat at 500° C. for 10 min in an air atmosphere, and then put into a lifting furnace and keep at 1600° C. for 2 h to melt into glass liquid 2;

[0164] (8) Quenching and forming the glass liquid 2: The glass liquid 2 obtained in step (7) is placed in a preheated mold (temperature is 430°C) for quenching and forming, and then the quenched and formed sample is placed in an annealing furnace at 430°C for 12 hours, and finally cooled to room temperature at a rate of 1°C / min to obtain a ferrous-doped colorless high-transmittance silicate energy-saving glass with near-infrared full-band shielding (high light transmittance, high near-infrared shielding, colorless, heat-insulating and energy-saving glass product).

[0165] The theoretical component contents of the ferrous-doped colorless, highly transparent silicate energy-saving glass with near-infrared full-band shielding prepared from 100 g of the raw materials in this comparative example are shown in Table 9.

[0166] Table 9 Theoretical component contents of ferrous-doped colorless highly transparent silicate energy-saving glass with near-infrared full-band shielding prepared from 100g of raw materials

[0167] Components Weight(g) Weight percentage (%) <![CDATA[SiO2]]> 20.74 25.54 <![CDATA[P2O5]]> 19.54 24.06 <![CDATA[A2O(Na2O)]]> 18.00 22.16 FeO 0.32 0.38 <![CDATA[B2O3]]> 7.07 8.70 <![CDATA[GeO2]]> 5.32 6.55 <![CDATA[Al2O3]]> 8.27 10.18 CaO 1.97 2.43 total 81.22 100

[0168] Effect Example 1

[0169] 10×9×0.6 cm ferrous-doped phosphoaluminosilicate energy-saving glass with high hardness, colorless and high transparency prepared in Example 2 3 See the actual picture of the large piece Figure 1 It can be seen that the ferrous-doped phosphate aluminum silicate energy-saving glass prepared by the present invention is colorless and has high transmittance.

[0170] Effect Example 2

[0171] The visible light transmittance, near-infrared light transmittance, thermal expansion coefficient, glass transition temperature and hardness of the colorless, highly transparent ferrous-doped phosphoaluminosilicate energy-saving glass prepared in Examples 1 to 7 and Comparative Examples 1 to 2 were measured. The results are shown in Table 10.

[0172] (1) Test sample: colorless, high-transmittance ferrous-doped phosphoaluminosilicate energy-saving glass prepared in Examples 1 to 7 and Comparative Examples 1 to 2, with a thickness of 7 to 8 mm.

[0173] (2) Test method: The transmittance was measured using a UV-Visible / NIR spectrophotometer from Japan's HITACHI company. The wavelength range for the visible light transmittance test is 380 to 780 nm, and the wavelength range for the near-infrared light transmittance test is 780 to 2500 nm. The Vickers hardness of the block sample was tested using a microhardness tester, HXD-1000TMC / LCD, from Shanghai Taiming Company, in combination with a diamond indenter. The test force was 25 to 1000 gf and the load was maintained for 15 seconds. The Vickers hardness value and indentation effect of the sample to be tested were measured using the indentation method. The linear thermal expansion coefficient and glass transition temperature were measured using a thermal expansion instrument (DIL 402, Netzsch, Germany) at a heating rate of 5°C / min.

[0174] The transmission spectrum performance effect diagram of the colorless high-transmittance ferrous doped phosphoaluminosilicate energy-saving glass prepared in Examples 1 to 7 and Comparative Examples 1 to 2 is shown in FIG. Figure 2 , wherein 1 is Example 1, 2 is Example 2, 3 is Example 3, 4 is Example 4, 5 is Example 5, 6 is Example 6, 7 is Example 7, 8 is Comparative Example 1, and 9 is Comparative Example 2.

[0175] Table 10 Visible light and near infrared light transmittance and microhardness

[0176]

[0177] It can be seen from Table 10 that the types and proportions of components of the high-hardness, colorless and highly transparent ferrous-doped phosphoaluminosilicate energy-saving glass have a significant impact on the performance of the glass. It can be seen from Comparative Examples 1 to 2 that with the change of the type of alkali metal in the glass matrix, the near-infrared shielding ability changes to a certain extent. Comparative Examples 1, 2, 3, and 4 show that with the change of the radius of the alkaline earth metal ion, the near-infrared shielding ability changes to a certain extent. The larger the ion radius, the weaker the near-infrared shielding ability. Regarding hardness, compared with the energy-saving glass of Comparative Examples 1 and 2, which do not contain alkaline earth metals or have a low alkaline earth metal content and have a microhardness of less than 450Hv, the hardness of the glass sample of the present invention is better, which can be as high as 490Hv. Comparative Examples 1, 2, 3, and 4 show that with the change of the radius of the alkali metal ion, the hardness capacity changes to a certain extent. The larger the ion radius, the harder the hardness decreases from 483Hv to 438Hv, and as the radius of the alkaline earth ion increases, the thermal expansion coefficient also increases, from 0.32×10 -5 / ℃ increased to 0.62×10 -5 / ℃, and the glass transition temperature gradually decreased from 755℃ to 710℃. By comparing Examples 5, 6, and 7, it can be seen that halogen has a certain influence on the near-infrared shielding performance of glass. The larger the ion radius, the weaker the near-infrared shielding performance, the harder the glass is, the smaller the hardness is, from 490Hv to 471Hv, and the thermal expansion coefficient is from 0.58×10 -5 / ℃ reduced to 0.46×10-5 / ℃, the glass transition temperature increases from 685℃ to 750℃, but the visible light transmittance becomes stronger and wider, achieving colorless transparency.

[0178] The above are only preferred specific embodiments of the present invention, but the protection scope of the present invention is not limited thereto. Any changes or substitutions that can be easily thought of by a person skilled in the art within the technical scope disclosed by the present invention should be included in the protection scope of the present invention. Therefore, the protection scope of the present invention should be based on the protection scope of the claims.

Claims

1. A high-hardness, colorless and highly transparent ferrous-doped phosphoaluminosilicate energy-saving glass, characterized in that: The following raw materials are included by weight percentage: SiO2 10~80%, P2O5 5~60%, FeO 0.1~5%, ZnO 1~30%, Al2O315~30%, MO 10~40% and MX2 0~30%; The M element in the MO is selected from one of Mg, Ca, Sr and Ba, and the X in the MX2 is one of F, Cl, Br and I.

2. The high-hardness, colorless and high-transmittance ferrous-doped phosphoaluminosilicate energy-saving glass according to claim 1, characterized in that: The SiO2 is introduced via silicon dioxide; and / or The P2O5 is introduced via phosphorus pentoxide, ammonium hydrogen phosphate or phosphate; and / or The raw material of FeO is an iron compound or an iron element; and / or The ZnO is introduced via zinc oxide; and / or The Al2O3 is introduced via aluminum oxide or phosphate containing Al element; and / or The MO is introduced via a carbonate or oxide containing the M element; and / or The MX2 is introduced via the corresponding alkaline earth metal halide.

3. A method for preparing the high-hardness, colorless and high-transmittance ferrous-doped phosphoaluminosilicate energy-saving glass according to any one of claims 1 to 2, characterized in that: The method comprises the following steps: mixing raw materials with a reducing agent, heating to a melting temperature, keeping the temperature, quenching and forming, and annealing to obtain the high-hardness, colorless, and highly transparent ferrous-doped phosphoaluminosilicate energy-saving glass.

4. The method for preparing the high-hardness, colorless and high-transmittance ferrous-doped phosphoaluminosilicate energy-saving glass according to claim 3, characterized in that: The reducing agent is a mixture of ammonium salt, carbon powder and silicon powder, and the amount of the reducing agent is 1.2-30% of the total weight of the raw materials.

5. The method for preparing the high-hardness, colorless and high-transmittance ferrous-doped phosphoaluminosilicate energy-saving glass according to claim 4, characterized in that: The weight ratio of the ammonium salt, carbon powder and silicon powder is (1-15): (0.1-10): (0.1-5).

6. The method for preparing the high-hardness, colorless and high-transmittance ferrous-doped phosphoaluminosilicate energy-saving glass according to claim 4, characterized in that: The ammonium salt is selected from ammonium chloride, ammonium carbonate or ammonium bicarbonate.

7. The method for preparing the high-hardness, colorless and high-transmittance ferrous-doped phosphoaluminosilicate energy-saving glass according to claim 3, characterized in that: Before mixing the raw material with the reducing agent, the raw material and the reducing agent are ground.

8. The method for preparing the high-hardness, colorless and high-transmittance ferrous-doped phosphoaluminosilicate energy-saving glass according to claim 3, characterized in that: The melting temperature is 1100-1700° C., the heating rate is 5-10° C. / min, and the insulation time is 1-5 hours.

9. The method for preparing the high-hardness, colorless and high-transmittance ferrous-doped phosphoaluminosilicate energy-saving glass according to claim 3, characterized in that: The annealing temperature is 400-600° C. and the time is 1-12 hours; and / or The temperature of the quenching forming is 300-600°C.

10. Application of the high-hardness, colorless and high-transmittance ferrous-doped phosphate-aluminosilicate energy-saving glass according to any one of claims 1 to 2 in the field of transportation.

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