A high-hardness, colorless, and highly transparent ferrous-doped phosphoaluminosilicate energy-saving glass and its preparation method

Abstract

The present invention discloses a high-hardness, colorless, and highly transparent ferrous-doped phosphoaluminosilicate energy-saving glass and a preparation method thereof. These materials belong to the field of glass manufacturing technology and comprise, by weight, the following raw materials: 10-80% SiO2, 5-60% P2O5, 0.1-5% FeO, 1-30% ZnO, 15-30% Al2O3, 10-40% MO, and 0-30% MX2; wherein the M element in MO is selected from one of Mg, Ca, Sr, and Ba, and X in MX2 is one of F, Cl, Br, and I. Compared to similar energy-saving glasses, the high-hardness, colorless, and highly transparent ferrous-doped phosphoaluminosilicate energy-saving glass prepared by the present invention maintains strong shielding in the near-infrared region and colorless and highly transparent light in the visible region, while exhibiting greater hardness. The raw materials are readily available and inexpensive, and the preparation process is simplified from a double-melt process to a single-melt process, making it more suitable for use in transportation applications such as automobiles, ships, and aerospace.

Description

Technical Field

[0001] The present 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 from quartz sand, soda ash, and limestone through high-temperature melting, homogenization, and molding. It exhibits excellent properties such as transparency, heat resistance, non-flammability, impact resistance, and insulation. It is widely used in modern industry and daily life, particularly in the transportation sector, where it is used in key components such as windshields and windows. These applications place higher demands on glass. Not only must it maintain excellent light transmittance and thermal stability, but it must also possess strong impact resistance and high hardness to withstand flying rocks and external impacts that may occur during driving. However, ordinary glass has a high transmittance to sunlight, and its shielding rate for near-infrared (NIR, wavelength 780 to 2500nm) is particularly low. In summer, a large amount of NIR thermal radiation from sunlight enters the vehicle cabin, causing internal overheating. In winter, heat from objects inside the cabin is dissipated through the glass, significantly increasing the energy consumption of the vehicle's air conditioning system. Therefore, developing a glass that combines high hardness, impact resistance, and energy-saving properties is particularly important for applications in transportation sectors such as automobiles, ships, and aerospace.

[0003] Currently, energy-saving glass primarily includes low-emissivity (Low-E) glass, coated glass, and ferrous-doped glass. Low-E glass relies on a metal coating to achieve infrared shielding, but its online product durability is insufficient, while its offline product energy-saving performance degrades due to the susceptibility of the functional layer to oxidation. Its visible light transmittance is less than 70%, and its manufacturing process is complex and costly. VO2 coated glass can adaptively adjust its light transmittance based on ambient temperature, but its visible light transmittance is less than 70%, its chemical stability is poor, and its service life is limited. Typical ferrous-doped energy-saving glass (201710474943.1) has a visible light transmittance greater than 70%, but appears bluish. The same type of energy-saving glass (20240052065.4) can achieve 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 production process requires two melts to produce the 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 objectives, 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: 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 the 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-doped phosphate aluminum silicate energy-saving glass, comprising the following steps: mixing the raw materials with a reducing agent, pouring them into a crucible, placing them in a lifting furnace, heating them to a melting temperature, keeping them warm, quenching and forming them, and annealing them to obtain the above-mentioned high-hardness, colorless and highly transparent ferrous-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 mixing the raw materials and the reducing agent, the raw materials and the reducing agent are ground for 15 to 120 minutes and then sieved (100 to 300 mesh).

[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 achieves the production of energy-saving glass by adopting a simple melt quenching method. Without using a sulfur-carbon reducing agent and without requiring a protective atmosphere, the glass melt can quickly encapsulate ferrous ions, greatly reducing direct contact between oxygen and ferrous ions and inhibiting the conversion of ferrous ions into ferric ions. The method of the present invention is applicable to traditional float glass production lines, can greatly reduce production complexity and danger, and facilitates the rapid, large-scale, and convenient production of ferrous heat-absorbing energy-saving glass. At the same time, the colorless, 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-silica energy-saving glass, it can better reflect ambient light and does not affect 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 phosphoaluminosilicate energy-saving glass in the field of transportation.

[0031] Compared to similar 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 maintains strong shielding in the near-infrared region and colorless and highly transparent in the visible region, while also being harder, made from inexpensive and readily available raw materials, and simplifying the preparation process from a two-melt process to a single-melt process. This high-hardness, colorless, and highly transparent ferrous-doped phosphate-aluminum silicate energy-saving glass is more suitable for use in transportation applications such as automobiles, ships, and 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 450Hv and contains high-cost elements such as GeO2), the high-hardness, colorless and high-transmittance ferrous phosphate-doped aluminum silicate energy-saving glass prepared by the present invention has a hardness greater than 450Hv 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 uses a direct mixture of raw materials and low-valent iron elements. Compared with similar energy-saving glass (such as the energy-saving glass in 20240052065.4), the preparation process is simplified from two melts to one melt, shortening the production cycle. The present invention adopts a melt quenching process and is compatible with ordinary float glass production lines. BRIEF DESCRIPTION OF THE DRAWINGS

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

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

[0037] Figure 2 These are effect diagrams of the transmittance spectrum performance of the colorless, high-transmittance ferrous-doped phosphoaluminosilicate 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 rather as a more detailed description of certain aspects, features, and embodiments of the present invention.

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

[0040] Unless otherwise indicated, all technical and scientific terms used herein have the same meaning as commonly understood by those skilled in the art. Although only preferred methods and materials are described herein, any methods and materials similar or equivalent to those described herein may also be used in the practice 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 any conflict with any incorporated document, the contents 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 described herein without departing from the scope or spirit of the invention. Other embodiments will be apparent to those skilled in the art from the description of the invention. The description and examples are intended to be illustrative 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 elemental iron; 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] Existing technologies for producing colorless, highly transparent, ferrous-doped phosphoaluminosilicate energy-saving glass (e.g., Patent 20240052065.4) use relatively high amounts of alkali metals, along with high amounts of boron oxide and phosphorus pentoxide. When alkali metal levels are high and high amounts of boron oxide and phosphorus pentoxide are added, the hardness of the glass decreases. This is mainly attributed to the following factors: First, alkali metals themselves have a large ionic radius and a low charge number. When such metals are introduced in large quantities, the alkali metal ions will enter the network gaps of the silicon-oxygen tetrahedron, causing the original covalent bonds to be destroyed, and thus making the glass structure tend to be loose; second, boron oxide can strengthen the glass network at a low content. 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 a less stable structure; third, the phosphorus-oxygen tetrahedral bond energy formed by phosphorus pentoxide is relatively low, and the connection flexibility is relatively large. When it is incorporated 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. Its 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 the 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. They can form chemical bonds with the oxygen atoms in the silicon-oxygen tetrahedron, thereby significantly improving the cross-linking degree of the network. Taking magnesium ions as an example, after forming chemical bonds with the oxygen in the silicon-oxygen tetrahedron, different silicon-oxygen tetrahedrons are closely connected, causing the overall structure of the glass to present a more compact and orderly state, greatly enhancing the ability of the glass to resist external deformation, and ultimately 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-doped phosphate-aluminum silicate energy-saving glass is provided, comprising the following steps: mixing the raw materials with a reducing agent, pouring the mixture into a crucible, placing the mixture into a lifting furnace, heating the mixture to a melting temperature, keeping the mixture warm, quenching and forming the mixture, and annealing the mixture to obtain the high-hardness, colorless and highly transparent ferrous-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 to 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, both the raw materials and the reducing agent are ground before being mixed. The grinding time is 15 to 120 minutes, and the raw materials and reducing agent are screened (100 to 300 mesh) after grinding. The ground raw materials and reducing agent particles are finer, with a larger surface area, and the contact area with the reaction medium (such as the gas in the elevator furnace) is also increased. This facilitates contact and collision between the reactants, accelerates the reaction rate, and improves reaction efficiency. Grinding also allows the raw materials and reducing agent particles to mix more evenly, reducing interparticle gaps and agglomeration. This uniform mixing facilitates more complete contact and reaction between the reactants at high temperatures, avoiding incomplete or overreaction in some areas. Fine particles melt more easily. At high temperatures, the increased contact area between particles allows heat to be transferred more easily to the interior of the particles, reducing the energy required for melting and thus lowering the overall melting temperature. This helps save energy and shortens melting time. Grinding also reduces the agglomeration of impurity particles and large particles in the raw materials, which can easily form defects such as bubbles and stones during the glass melting process. Small and uniform particles help reduce these defects and improve the transparency 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 holding time is 1-5 hours. The higher the melting temperature, the faster the glass melts, the more intense the silicate formation reaction, and the faster the particles dissolve. Excessively high melting temperatures can exacerbate refractory erosion, introduce impurities into the glass, and affect its transparency and chemical stability. Excessively low melting temperatures can lead to incomplete melting of the glass, resulting in defects such as calculi. A faster heating rate allows the glass melt to quickly reach a molten state, facilitating homogenization and the removal of bubbles, thereby improving the uniformity and transparency of the glass. However, heating too quickly can also cause local overheating of the melt, resulting in localized stress and uneven melting. The reasonable heating rate of the present invention effectively utilizes energy, reduces energy waste, and improves production efficiency. An appropriate holding time facilitates the homogenization and clarification of the glass melt, eliminating defects such as streaks and calculi within the glass to acceptable limits, resulting in a uniform, integrated glass. Too long a holding time may cause crystallization in the glass melt, forming a crystalline structure, which affects the optical and mechanical properties of the glass. The melting temperature, heating rate, and holding time of the present invention are all relatively suitable, which can ensure the production of high hardness, colorless, and highly transparent glass.

[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 glass is cooled to room temperature at a cooling rate of 1 to 10°C / min. A rapid cooling rate can easily generate thermal stress within the glass, causing it to crack during cooling or use. A slow cooling rate, on the other hand, helps release stress within the glass, reducing stress concentration and improving its mechanical strength and thermal shock resistance. Different cooling rates can affect the structure and phase transition 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 achieves the production of energy-saving glass by adopting a simple melt quenching method. Without using a sulfur-carbon reducing agent or requiring a protective atmosphere, the glass melt can quickly encapsulate ferrous ions, greatly reducing direct contact between oxygen and ferrous ions and inhibiting the conversion of ferrous ions into ferric ions. The method of the present invention is applicable to traditional float glass production lines, can greatly reduce production complexity and risk, and facilitates the rapid, large-scale, and convenient production of ferrous heat-absorbing energy-saving glass. At the same time, the colorless, highly transparent ferrous-doped phosphoaluminosilicate energy-saving glass produced can be largely transparent and colorless. Compared with the original ferrous-doped soda-lime-silica energy-saving glass, it can better reflect ambient light and does not affect the transmission of visible light.

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

[0067] Compared to similar 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 maintains strong shielding in the near-infrared region and colorless and highly transparent in the visible region, while also being harder, made from inexpensive and readily available raw materials, and simplifying the preparation process from a two-melt process to a single-melt process. This high-hardness, colorless, and highly transparent ferrous-doped phosphate-aluminum silicate energy-saving glass is more suitable for use in transportation applications such as automobiles, ships, and 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 conventional operating means in this field and are not the focus of the present invention. For example, specific methods such as grinding and screening are all completed using conventional methods.

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

[0071] Example 1

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

[0073] 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.

[0074] The preparation method of the above-mentioned high-hardness, colorless and high-transmittance ferrous-doped phosphoaluminosilicate energy-saving glass is as follows:

[0075] (1) Mixture preparation: Grind aluminum dihydrogen phosphate, silicon dioxide, zinc oxide, magnesium oxide, aluminum oxide, ferrous chloride and reducing agent separately for 20 minutes, pass through a 300-mesh sieve, and then fully mix to obtain a mixture;

[0076] (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 at that temperature for 1.5 hours to melt it into molten glass;

[0077] (3) Quenching and forming of glass liquid: The glass liquid obtained in step (2) is placed in a preheated mold (temperature is 560°C) and quenched and formed. The quenched and formed sample is then placed in an annealing furnace at 560°C and annealed for 4 hours. Finally, the temperature is cooled to room temperature at a rate of 5°C / min to obtain a high-hardness, colorless, and highly transparent ferrous-doped phosphoaluminosilicate energy-saving glass.

[0078] The theoretical component contents of the high-hardness, colorless, and highly transparent ferrous-doped phosphoaluminosilicate energy-saving glass prepared from 60 g of raw materials in this embodiment are shown in Table 1.

[0079] Table 1 Theoretical component contents of high-hardness, colorless, and highly transparent ferrous-doped phosphoaluminosilicate energy-saving glass prepared from 60 g of raw materials

[0080] 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

[0081] Example 2

[0082] The high-hardness, colorless, and highly transparent ferrous-doped phosphoaluminosilicate energy-saving glass provided in this embodiment comprises the following raw materials, calculated by weight percentage: 25.76% aluminum dihydrogen phosphate (Al(H2PO4)3), 0.98% ferrous chloride (FeCl2·4H2O), 27.74% silicon dioxide (SiO2), 20.65% aluminum oxide (Al2O3), 14.98% calcium oxide (CaO), and 9.89% zinc oxide (ZnO).

[0083] 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.

[0084] The preparation method of the above-mentioned high-hardness, colorless and high-transmittance ferrous-doped phosphoaluminosilicate energy-saving glass is as follows:

[0085] (1) Mixture preparation: 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;

[0086] (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 2 hours to melt it into molten glass;

[0087] (3) Quenching and forming of glass liquid: The glass liquid obtained in step (2) is placed in a preheated mold (temperature is 560°C) and quenched and formed. The quenched and formed sample is then placed in an annealing furnace at 560°C and annealed for 3 hours. Finally, the temperature is cooled to room temperature at a rate of 5°C / min to obtain a high-hardness, colorless, and highly transparent ferrous-doped phosphoaluminosilicate energy-saving glass.

[0088] The theoretical component contents of the high-hardness, colorless, and highly transparent ferrous-doped phosphoaluminosilicate energy-saving glass prepared from 60 g of the raw materials in this embodiment are shown in Table 2.

[0089] Table 2 Theoretical component contents of high-hardness, colorless, and highly transparent ferrous-doped phosphoaluminosilicate energy-saving glass prepared from 60 g of raw materials

[0090] 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

[0091] Example 3

[0092] The high-hardness, colorless, and highly transparent ferrous-doped phosphoaluminosilicate energy-saving glass provided in this embodiment comprises the following raw materials, calculated by weight percentage: 22.86% sodium dihydrogen phosphate (Al(H2PO4)3), 0.85% ferrous chloride (FeCl2·4H2O), 24.61% silicon dioxide (SiO2), 18.32% aluminum oxide (Al2O3), 24.56% strontium oxide (SrO), 8.77% zinc oxide (ZnO), and 0.03% iron powder.

[0093] 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.

[0094] The preparation method of the above-mentioned high-hardness, colorless and high-transmittance ferrous-doped phosphoaluminosilicate energy-saving glass is as follows:

[0095] (1) Mixture ingredients: Grind aluminum dihydrogen phosphate, silicon dioxide, aluminum oxide, zinc oxide, strontium oxide, ferrous chloride, iron powder and reducing agent separately for 20 minutes, pass through a 300-mesh sieve, and then fully mix to obtain a mixture.

[0096] (2) Preparation of molten glass: The mixture obtained in step (1) was poured into a crucible, placed in a lifting furnace, raised from room temperature to 1550°C and kept warm for 1.5 hours to melt into molten glass.

[0097] (3) Quenching and forming of glass liquid: The glass liquid obtained in step (2) is placed in a preheated mold (temperature is 560°C) and quenched and formed. The quenched and formed sample is then placed in an annealing furnace at 560°C and annealed for 4 hours. Finally, the temperature is cooled to room temperature at a rate of 7°C / min to obtain a high-hardness, colorless, and highly transparent ferrous-doped phosphoaluminosilicate energy-saving glass.

[0098] The theoretical component contents of the high-hardness, colorless, and highly transparent ferrous-doped phosphoaluminosilicate energy-saving glass prepared from 60 g of the raw materials in this embodiment are shown in Table 3.

[0099] Table 3 Theoretical component contents of high-hardness, colorless, and highly transparent ferrous-doped phosphoaluminosilicate energy-saving glass prepared from 60 g of raw materials

[0100] 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

[0101] Example 4

[0102] The high-hardness, colorless, and highly transparent ferrous-doped phosphoaluminosilicate energy-saving glass provided in this embodiment comprises the following raw materials, calculated by weight percentage: 20.34% aluminum dihydrogen phosphate (Al(H2PO4)3), 0.84% ​​ferrous chloride (FeCl2·4H2O), 22.03% silicon dioxide (SiO2), 7.84% zinc oxide (ZnO), 16.38% aluminum oxide (Al2O3), and 32.57% barium oxide (BaO).

[0103] 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.

[0104] 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.

[0105] The theoretical component contents of the high-hardness, colorless, and highly transparent ferrous-doped phosphoaluminosilicate energy-saving glass prepared from 60 g of the raw materials in this embodiment are shown in Table 4.

[0106] Table 4 Theoretical component contents of high-hardness, colorless, and highly transparent ferrous-doped phosphoaluminosilicate energy-saving glass prepared from 60 g of raw materials

[0107] 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

[0108] Example 5

[0109] The high-hardness, colorless, and highly transparent ferrous-doped phosphoaluminosilicate energy-saving glass provided in this embodiment comprises the following raw materials, calculated by weight percentage: 22.41% aluminum dihydrogen phosphate (Al(H2PO4)3), 0.84% ​​ferrous chloride (FeCl2·4H2O), 24.19% silicon dioxide (SiO2), 18.08% aluminum oxide (Al2O3), 25.86% calcium fluoride (CaF2), and 8.62% zinc oxide (ZnO).

[0110] 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.

[0111] The preparation method of the above-mentioned high-hardness, colorless and high-transmittance ferrous-doped phosphoaluminosilicate energy-saving glass is as follows:

[0112] (1) Mixture preparation: grind aluminum dihydrogen phosphate, silicon dioxide, aluminum oxide, zinc oxide, calcium fluoride, ferrous chloride and reducing agent for 20 minutes respectively, pass through a 300-mesh sieve, and then fully mix, grind again for 30 minutes, pass through a 200-mesh sieve, and then fully mix to obtain a mixture;

[0113] (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 at that temperature for 1.5 hours to melt it into molten glass;

[0114] (3) Quenching and forming of glass liquid: The glass liquid obtained in step (2) is placed in a preheated mold (temperature is 560°C) and quenched and formed. The quenched and formed sample is then placed in an annealing furnace at 560°C and annealed for 4 hours. Finally, the temperature is cooled to room temperature at a rate of 5°C / min to obtain a high-hardness, colorless, and highly transparent ferrous-doped phosphoaluminosilicate energy-saving glass.

[0115] The theoretical component contents of the high-hardness, colorless, and highly transparent ferrous-doped phosphoaluminosilicate energy-saving glass prepared from 60 g of the raw materials in this embodiment are shown in Table 5.

[0116] Table 5 Theoretical component contents of high-hardness, colorless, and highly transparent ferrous-doped phosphoaluminosilicate energy-saving glass prepared from 60 g of raw materials

[0117] 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

[0118] Example 6

[0119] The high-hardness, colorless, and highly transparent ferrous-doped phosphoaluminosilicate energy-saving glass provided in this embodiment comprises the following raw materials, calculated by weight percentage: 24.15% aluminum dihydrogen phosphate (Al(H2PO4)3), 0.90% ferrous chloride (FeCl2·4H2O), 26.00% silicon dioxide (SiO2), 19.36% aluminum oxide (Al2O3), 12.64% calcium fluoride (CaF2), 9.27% ​​zinc oxide (ZnO), and 7.68% calcium oxide (CaO).

[0120] 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.

[0121] The preparation method of the above-mentioned high-hardness, colorless and high-transmittance ferrous-doped phosphoaluminosilicate energy-saving glass is as follows:

[0122] (1) Mixture preparation: grind aluminum dihydrogen phosphate, silicon dioxide, aluminum oxide, zinc oxide, calcium fluoride, ferrous chloride and reducing agent for 20 minutes respectively, pass through a 300-mesh sieve, and then fully mix, grind again for 30 minutes, pass through a 200-mesh sieve, and then fully mix to obtain a mixture;

[0123] (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 at that temperature for 1.5 hours to melt it into molten glass;

[0124] (3) Quenching and forming of glass liquid: The glass liquid obtained in step (2) is placed in a preheated mold (temperature is 560°C) and quenched and formed. The quenched and formed sample is then placed in an annealing furnace at 560°C and annealed for 4 hours. Finally, the temperature is cooled to room temperature at a rate of 5°C / min to obtain a high-hardness, colorless, and highly transparent ferrous-doped phosphoaluminosilicate energy-saving glass.

[0125] The theoretical component contents of the high-hardness, colorless, and highly transparent ferrous-doped phosphoaluminosilicate energy-saving glass prepared from 60 g of the raw materials in this embodiment are shown in Table 6.

[0126] Table 6 Theoretical component contents of high-hardness, colorless, and highly transparent ferrous-doped phosphoaluminosilicate energy-saving glass prepared from 60 g of raw materials

[0127] 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

[0128] Example 7

[0129] The high-hardness, colorless, and highly transparent ferrous-doped phosphoaluminosilicate energy-saving glass provided in this embodiment comprises the following raw materials, calculated by weight percentage: 22.49% aluminum dihydrogen phosphate (Al(H2PO4)3), 0.84% ​​ferrous chloride (FeCl2·4H2O), 24.19% silicon dioxide (SiO2), 18.00% aluminum oxide (Al2O3), 8.62% zinc oxide (ZnO), and 25.86% calcium chloride (CaCl2).

[0130] 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.

[0131] The preparation method of the above-mentioned high-hardness, colorless and high-transmittance ferrous-doped phosphoaluminosilicate energy-saving glass is as follows:

[0132] (1) Mixture preparation: Grind aluminum dihydrogen phosphate, silicon dioxide, aluminum oxide, zinc oxide, calcium chloride, ferrous chloride and a reducing agent for 20 minutes, pass through a 200-mesh sieve, and then fully mix to obtain a mixture;

[0133] (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 1500°C and keep it for 3 hours to melt it into molten glass;

[0134] (3) Quenching and forming of glass liquid: The glass liquid obtained in step (2) is placed in a preheated mold (temperature is 560°C) and quenched and formed. The quenched and formed sample is then placed in an annealing furnace at 560°C and annealed for 4 hours. Finally, the temperature is cooled to room temperature at a rate of 8°C / min to obtain a high-hardness, colorless, and highly transparent ferrous-doped phosphoaluminosilicate energy-saving glass.

[0135] The theoretical component contents of the high-hardness, colorless, and highly transparent ferrous-doped phosphoaluminosilicate energy-saving glass prepared from 60 g of the raw materials in this embodiment are shown in Table 7.

[0136] Table 7 Theoretical component contents of high-hardness, colorless, and highly transparent ferrous-doped phosphoaluminosilicate energy-saving glass prepared from 60 g of raw materials

[0137] 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

[0138] Comparative Example 1

[0139] 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, in weight percentage: 25.60% sodium dihydrogen phosphate (NaH2PO4), 0.88% ferrous chloride (FeCl2·4H2O), 3.75% ammonium chloride (NH4Cl), 1.88% carbon powder, 0.56% silicon powder, 24.60% silicon dioxide (SiO2), 7.01% boron oxide (B2O3), 5.45% germanium oxide (GeO2), 8.14% aluminum oxide (Al2O3), 18.65% sodium carbonate (Na2CO3) and 3.48% calcium carbonate (CaCO3).

[0140] The preparation method of the above-mentioned ferrous-doped colorless highly transparent silicate energy-saving glass with near-infrared full-band shielding is as follows:

[0141] (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, and then fully mixed for 10 minutes to obtain mixture 1 (main raw material);

[0142] (2) Degassing: Pour the mixture 1 obtained in step (1) into a crucible, place the crucible in a muffle furnace, and heat it to 600°C at a heating rate of 10°C / min under air atmosphere, keep it at that temperature for 1 hour, and then cool it to room temperature (25±2°C);

[0143] (3) Preparation of glass liquid 1: The crucible containing the degassed mixture 1 obtained in step (2) was preheated at 500° C. for 10 min in an air atmosphere, then placed in a lifting furnace and kept at 1250° C. for 1 h to melt the mixture 1 into glass liquid 1;

[0144] (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, thereby obtaining a cracked glass block and a crucible for storing the residual glass liquid 1 (the glass block is cracked due to internal stress);

[0145] (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;

[0146] (6) Mixture 2: Ferrous chloride, ammonium chloride, carbon powder, and silicon powder were pulverized through a 300-mesh sieve, and then fully mixed for 20 minutes to obtain mixture 2;

[0147] (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 minutes in an air atmosphere, then place in a lifting furnace and keep at 1250°C for 2 hours to melt into glass liquid 2;

[0148] (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 (high-transmittance, high near-infrared shielding, colorless, heat-insulating, energy-saving glass product).

[0149] 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.

[0150] Table 8 Theoretical component content of ferrous-doped colorless, highly transparent silicate energy-saving glass with near-infrared full-band shielding prepared from 100g of raw materials

[0151] 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

[0152] Comparative Example 2

[0153] This comparative example provides a ferrous-doped colorless, highly transparent silicate energy-saving glass with near-infrared full-band shielding 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, 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).

[0154] The preparation method of the above-mentioned ferrous-doped colorless highly transparent silicate energy-saving glass with near-infrared full-band shielding is as follows:

[0155] (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, and then fully mixed for 10 minutes to obtain mixture 1 (main raw material);

[0156] (2) Degassing: Pour the mixture 1 obtained in step (1) into a crucible, place the crucible in a muffle furnace, and heat it to 600°C at a heating rate of 10°C / min under air atmosphere, keep it at that temperature for 1 hour, and then cool it to room temperature (25±2°C);

[0157] (3) Preparation of glass liquid 1: The crucible containing the degassed mixture 1 obtained in step (2) was preheated at 500° C. for 10 min in an air atmosphere, then placed in a lifting furnace and kept at 1250° C. for 1 h to melt the mixture 1 into glass liquid 1;

[0158] (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, thereby obtaining a cracked glass block and a crucible for storing the residual glass liquid 1 (the glass block is cracked due to internal stress);

[0159] (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;

[0160] (6) Mixture 2: Ferrous chloride, ammonium chloride, carbon powder, and silicon powder were pulverized through a 300-mesh sieve, and then fully mixed for 20 minutes to obtain mixture 2;

[0161] (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 minutes in an air atmosphere, then place in a lifting furnace and keep at 1600°C for 2 hours to melt into glass liquid 2;

[0162] (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) and quenched and formed. The quenched and formed sample is then placed in an annealing furnace at 430°C and annealed for 12 hours. Finally, the temperature is cooled to room temperature at a rate of 1°C / min to obtain a near-infrared full-band shielding ferrous-doped colorless high-transmittance silicate energy-saving glass (high transmittance, high near-infrared shielding, colorless, heat-insulating and energy-saving glass product).

[0163] 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 9.

[0164] Table 9 Theoretical component content of ferrous-doped colorless, highly transparent silicate energy-saving glass with near-infrared full-band shielding prepared from 100g of raw materials

[0165] 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

[0166] Effect Example 1

[0167] 10×9×0.6cm high hardness and colorless high transparency ferrous doped phosphoaluminosilicate energy-saving glass 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.

[0168] Effect Example 2

[0169] 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.

[0170] (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.

[0171] (2) Test method: The transmittance was measured using a UV-Visible / NIR spectrophotometer from HITACHI, Japan. The wavelength range for the visible light transmittance test was 380-780 nm, and the wavelength range for the near-infrared light transmittance test was 780-2500 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 25-1000 gf and the load was maintained for 15 s. The Vickers hardness value and indentation effect of the sample 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.

[0172] 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.

[0173] Table 10 Visible light and near infrared light transmittance and microhardness

[0174]

[0175] As can be seen from Table 10, 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 as the type of alkali metal in the glass matrix changes, the near-infrared shielding ability changes to a certain extent. Comparative examples 1, 2, 3, and 4 show that as the radius of the alkaline earth metal ion changes, the near-infrared shielding ability changes to a certain extent. The larger the ion radius, the weaker the near-infrared shielding ability. As for hardness, compared with the energy-saving glass comparative examples 1 and 2 that do not contain alkaline earth metals or have a low alkaline earth metal content, the microhardness of which is 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 as the radius of the alkali metal ion changes, the hardness capacity changes to a certain extent. The larger the ion radius, the harder the glass 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℃. Comparison of Examples 5, 6, and 7 shows that halogen has a certain effect on the near-infrared shielding performance of glass. The larger the ion radius, the weaker the near-infrared shielding performance, the harder the glass, and the lower the thermal expansion coefficient from 0.58×10 -5 / ℃ is 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 and transparent.

[0176] The above are merely preferred embodiments of the present invention, but the scope of protection of the present invention is not limited thereto. Any changes or substitutions that can be easily conceived by a person skilled in the art within the technical scope disclosed in the present invention should be included in the scope of protection of the present invention. Therefore, the scope of protection of the present invention should be based on the scope of protection of the claims.

Claims

1. A high-hardness, colorless, and highly transparent ferrous-doped phosphoaluminosilicate energy-saving glass, characterized in that: Calculated by weight percentage, it includes the following raw materials: SiO2 10~80%, P2O5 5~60%, FeO 0.1~5%, ZnO 1~30%, Al2O3 15~30%, MO10~40% and MX2 0~30%; Wherein, the M element in MO and MX2 is selected from one of Mg, Ca, Sr and Ba, and X in MX2 is one of F, Cl, Br and I; The method for preparing the hard, colorless, and highly transparent ferrous-doped phosphoaluminosilicate energy-saving glass comprises the following steps: mixing raw materials with a reducing agent, heating to a melting temperature, keeping the temperature, and then quenching, forming, and annealing to obtain the hard, colorless, and highly transparent ferrous-doped phosphoaluminosilicate energy-saving glass; 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.

2. The high-hardness, colorless, and highly transparent 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 or phosphate; and / or The raw material of the 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 highly transparent 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 weight ratio of the ammonium salt, carbon powder and silicon powder is (1-15): (0.1-10): (0.1-5).

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 ammonium salt is selected from ammonium chloride, ammonium carbonate or ammonium bicarbonate.

6. 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 materials with the reducing agent, both the raw materials and the reducing agent are ground.

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: The melting temperature is 1100-1700° C., the heating rate is 5-10° C. / min, and the holding time is 1-5 hours.

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 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.

9. Use of the high-hardness, colorless, and highly transparent ferrous-doped phosphoaluminosilicate energy-saving glass according to any one of claims 1 to 2 in the field of transportation.

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